towards a better understanding of the links between - Idaea

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4th SCARCE
International Conference
TOWARDS A BETTER UNDERSTANDING OF THE LINKS BETWEEN STRESSORS, HAZARD ASSESSMENT AND ECOSYSTEM SERVICES UNDER WATER SCARCITY
25‐26 November 2013
Cádiz, Spain
Esmeralda
Ramos
4th SCARCE International Conference TOWARDS A BETTER UNDERSTANDING OF THE LINKS BETWEEN STRESSORS, HAZARD ASSESSMENT AND ECOSYSTEM SERVICES UNDER WATER SCARCITY 25‐26 November 2013, Cádiz, Spain Scientific Committee •
•
•
•
•
•
Julián Blasco, ICMAN‐CSIC, Puerto Real, Spain Alícia Navarro‐Ortega, IDAEA‐CSIC, Barcelona, Spain Damià Barceló, IDAEA‐CSIC, Barcelona and ICRA, Girona, Spain Ralf Ludwig, Ludwig Maximilians Universität, München, Germany Ignacio Rodríguez Iturbe, Princeton University, New Jersey, USA Klement Tockner, IGB, Berlin, Germany ORGANIZERS INSTITUTO DE CIENCIAS MARINAS
DE ANDALUCÍA
SUPPORTING ORGANIZATIONS Book of abstracts of the 4th SCARCE International Conference
Edition 2012
Editors: Alícia Navarro Ortega and Damià Barceló Cullerés
With contributions of all conference participants
Edited by Asociación Ibérica de Limnología
ISBN 978-84-937882-6-1
This work has been supported by the Ingenio-Consolider 2010 project SCARCE (CSD2009-00065) from the
Spanish Ministry of Economy and Competitiveness.
5 Preface Preface Water scarcity and quality are the main problems of humanity in the current scenarios in
relation to water resources. In a next future, this situation can be even worse, because the
global population is growing and the demand for different water uses are increasing. It should
be taken into account that problems are not only related with the available amount but also
with its quality. To understand the links between stressor, hazard assessment and ecosystem
services, water management must improve to guarantee its supply to everybody in sufficient
amount and quality. Some stressors such as water scarcity can limit biodiversity and economic
activities in entire regions. In addition of being a stressor on its own, water scarcity can drive
the effects of other stressors acting upon river ecosystems. It leads to intermittency in water
flow, and therefore has implications for hydrologic connectivity, negative side-effects on
biodiversity, water quality, and river ecosystem functioning. Water scarcity can amplify the
effects of water pollution by reducing the natural diluting capacity of rivers. Interactions
between stressors may be exacerbated by climate change. For instance, warmer
temperatures and reduced river flows will likely increase the physiological burden of pollution
on the aquatic biota, and biological feedback between stressors (e.g. climate change and
nutrient pollution) may produce unexpected outcomes. Degradation of drainage basins,
destruction of natural habitats, over-exploitation of fish populations and other natural
resources, or the establishment of invasive species, are factors whose impacts combine and
may give rise to synergistic effects, especially during periods of water shortage. The effects
of these stressors are very relevant for the chemical and ecological status of water bodies as
well as for the sustainability of ecosystem services they provide
Water scarcity is a key stressor with direct and indirect effects. The relevance of water
scarcity as a stressor is most important in semi-arid regions such as the Mediterranean basin,
characterized by highly variable river flows and the periodic occurrence of low flows and even
no-flows. Climate change previsions forecast an increase in the frequency and magnitude of
extreme events. Although extremes are part of the normal hydrologic behaviour in
Mediterranean-type rivers, many already show a consistent trend towards decreased
discharge. Finally, we should consider as well that the research to support the management
has to take into account the complexity of the problems, their multi- and interdisciplinary
nature and how to transfer the gathered knowledge to managers and authorities.
The Spanish funded project SCARCE wants to tackle water scarcity in our country. To solve
this problem it will assess and predict the effects of global change on water quantity and
quality and ecosystem services in Mediterranean river basins of the Iberian Peninsula, as well
as their impact on society and economy. The project has assembled a multidisciplinary team
in different fields (hydrology, chemistry, ecology, ecotoxicology, economy and modelling) to
transform the obtained scientific knowledge into effective and sustainable water
management tools. In order to guarantee practical application of the research results, water
authorities and stakeholders are involved in the project. The topic of this project is of great
relevance and reaches beyond national borders. Thus, an international perspective is
fundamental to understand water problems and to find the solutions. These facts give an
international dimension to the project and the meeting.
After the success of the three previous SCARCE International Conferences, which were held,
in Girona (2010), Madrid (2011) and Valencia (2012), this meeting is focused on the
understanding of the links between stressors, hazard assessment and ecosystem services
under water scarcity. The participation of researchers from different disciplines but with an
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 6 Preface integrative approach of water problems will give support to a new vision, tools and strategies
to achieve an oriented solution of current and future water quality problems and the role of
the ecosystem services in management policies.
The topics of this 4th SCARCE International Conference are:
•
Monitoring network for chemical and biological data. Legacy and emerging POPs,
pharmaceuticals and tools for integration and improvement of risk assessment
•
Global change and water
•
Multiple stressors and risk assessment
•
Socioeconomic issues and water management
•
Last FP7 EU call on water resources: multistressors and toxicants
This SCARCE Conference will provide a forum to present and discuss water related issues from
a multi- and interdisciplinary perspective. This meeting encourages communications with an
integrative perspective on issues related to the links between the occurrence of stressors in
water, the hazard assessment and ecosystem services in water scarcity scenarios. The
participation of anyone interested in sharing knowledge about water resources and the
improvement in their management for sustainability is welcome.
The three previous SCARCE International Conferences led to special issues in the
Environmental Science and Pollution Research (19(4) 2012), Science of the Total Environment
(440(1) 2012) and Journal Hazardous Material (2013). A special journal issue associated with
the 4th edition will be published in Science of the Total Environment. All participants are
encouraged to submit their contributions to this special issue.
We are pleased to welcome you to Cadiz. We hope you will have a good experience and your
participation in this meeting will give you the opportunity to share your knowledge and
experience and to interact with colleagues in an exciting environment for science. We would
like to thank the speakers, participants, supporters and sponsors for their contributions that
will make this event an unforgettable meeting. We acknowledge the support of the Spanish
Ministry of Economy and Competitiveness to SCARCE project.
Julián Blasco and Damià Barceló
Cádiz, November 25th, 2013
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain Final Programme
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 9 Final programme Monday, 25th November 2013
9.00 – 9.30
Registration
9.30 – 9.50
Welcome
Eduardo González Mazo1, Marina Villegas2 and Damià Barceló3,4
1
Chancellor of the University of Cadiz, Cadiz, Spain
Deputy Director of Research Projects, Ministry of Economy and Competitiveness,
Government of Spain
3
Water and Soil Quality Research Group, IDAEA-CSIC, Barcelona, Spain
4
Catalan Institute for Water Research (ICRA), Girona, Spain
2
Introduction to global change and water scarcity
Chairperson: Julián Blasco
9.50 – 10.20
Water research and innovation strategy in Horizon 2020, the State Plan
of Spain and the Water JPI
Marina Villegas1,2
1
Deputy Director of Research Projects, Ministry. of Economy and Competitiveness,
Government of Spain
2
President of the Governing Board of the Water JPI, Ministry of Economy and
Competitiveness, Government of Spain
10.20 – 10.50
The Joint Programming Initiative on Water: a Pilot call for proposals
Enrique Playán1
1
Coordinator of the Water JPI, Ministry of Economy and Competitiveness, Government of
Spain
10.50 – 11.10
SCARCE: Snapshots on recent results and achievements Dec2009-Nov
2013
Damià Barceló1,2 and Alícia Navarro-Ortega1
1
2
11.10 – 11.40
Poster session/Coffee break
Session I: Monitoring network for chemical and biological data. Legacy and
emerging POPs
Chairperson: Peter D. Hansen
11.40 – 12.10
Changes in the distributions of persistent organic pollutants and
mercury in freshwater ecosystems under changing climate conditions
Joan O. Grimalt
Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 10 Final programme 12.10 – 12.40
Monitoring Perfluorinated Compounds in the Xúquer River
Julián Campo1, Francisca Pérez2, Ana Masia1, Marinel.la Farré2, Yolanda
Pico1 and Damià Barceló2,3
1
Environmental and Food Safety Research Group, Faculty of Pharmacy, University of
Valencia, Burjassot, Spain
2
3
Catalan Institute of Water Research (ICRA) Girona, Spain
12.40 – 13.00
First report of pyrethroids in river fish: a case study in Iberian river
basins (Spain)
Cayo Corcellas1, Ethel Eljarrat1 and Damià Barceló1,2
1
2
13.00 – 13.20
Priority and emerging pollutants in southern Spain: overview of some
case studies from the Anquimed research group
Irene Aparicio, Julia Martín, Dolores Camacho-Muñoz, Juan Luís Santos and
Esteban Alonso
Department of Analytical Chemistry, Escuela Politécnica Superior, University of Seville,
Seville, Spain
13.20 – 15.00
Lunch
Session II: Monitoring network for chemical and biological data. Pharmaceuticals
and other emerging compounds
Chairperson: Mira Petrovic
15.00 – 15.30
Uptake
and
Bioaccumulation
of
Endocrine
Disruptors
and
Pharmaceutical compounds in Biofilm, Macroinvertebrates, and Fish in
four Mediterranean Rivers
Belinda Huerta1, Victoria Osorio2, Marina Gorga2, Anna Jakimska3, Nuria de
Castro4, Lidia Ponsati1, Isabel Muñoz4, Sandra Pérez2, Mira Petrovic1,5, Sergi
Sabater1, Sara Rodríguez-Mozaz1 and Damià Barceló1,2
1
3
Departmen. of Analytical Chemistry, Chemical Faculty, Gdansk University of Technology,
Gdansk, Poland
4
Department of Ecology, Facultat de Biologia, University of Barcelona, Barcelona, Spain
5
Catalan Institution for Research and Advanced Studies (ICREA), Barcelona, Spain
2
15.30 – 15.50
Methodological challenges for the determination of endocrine disruptor
compounds in the environment. Comparison of different analytical
strategies
Marina Gorga1, Belinda Huerta2, Sara Rodríguez-Mozaz2, Mira Petrovic2,3 and
Damià Barceló1,2
1
3
2
A monitoring survey of pharmaceuticals in wastewater treatment plants
and river water in four Iberian river basins
Victoria Osorio1, Jaume Aceña1, Sandra Pérez1 and Damià Barceló1,2
1
2
16.10 – 16.30
Sediment core analysis as a tool for reconstructing the contamination
history of aquatic systems. Case study: Jamaica Bay (NY)
Pablo A. Lara-Martín1,2, Eduardo González-Mazo1, and Bruce J. Brownawell2
1
Department of Physical Chemistry, Faculty of Marine and Environmental Sciences,
University of Cadiz, Puerto Real, Spain
2
School of Marine and Atmospheric Sciences, Stony Brook University, Stony Brook, New York,
United States
16.30 – 17.00
Session III: Monitoring network for chemical and biological data. Tools for
integration and improvement of risk assessment
Chairperson: Werner Brack
17.00 – 17.30
Chemicals of emerging concern in Iberian rivers. Analysis of sources and
environmental exposure
Mira Petrovic1,2, Maja Kuzmanovic3, Damia Barceló1,3and Antoni Ginebreda3
1
Catalan Institute for Water Research (ICRA), Girona, Spain.
Catalan Institution for Research and Advanced Studies (ICREA), Barcelona, Spain.
3
2
17.30 – 17.50
Occurrence and in-stream attenuation of wastewater derived
pharmaceuticals in Iberian rivers
Vicenç Acuña1, Daniel von Schiller1, María Jesús García-Galán1, Sara
Rodríguez-Mozaz1, Lluís Corominas1, Ignasi Aymerich1, Mira Petrovic1,2,
Manel Poch1,3, Damià Barceló1,4 and Sergi Sabater1,5
1
3
Laboratory of Chemical and Environmental Engineering (LEQUIA). University of Girona,
Girona, Spain
4
5
Institute of Aquatic Ecology, University of Girona, Girona, Spain
2
17.50 – 18.10
Effects of food limitation and pharmaceuticals compounds on the larval
development of a marine invertebrate
Enrique González-Ortegón1, Julián Blasco2, Lewis LeVay1 and Luis Giménez1
1
2
School of Ocean Sciences, Bangor University, Menai Bridge, UK
Instituto de Ciencias Marinas de Andalucía, CSIC, Puerto Real, Spain
Preliminary results of effects of pharmaceuticals on fresh water
organisms
Gabriela V. Aguirre-Martínez1,2,4, C. Okello1,3, María José Salamanca1, C.
Garrido2, T.B. Henry4,5,6, Tomás A. Del Valls1 and María Laura Martín-Díaz1,2
1
Cátedra UNESCO/UNITWIN/WiCop, Facultad Ciencias del Mar y Ambientales, Universidad de
Cádiz, Puerto Real, Spain
2
Andalusian Center of Marine Science and Technology (CACYTMAR), Puerto Real, Spain
3
Integrated Geoscience Research Group (IGRG), Interdepartmental Centre for Environmental
Sciences Research (CIRSA), University of Bologna, Ravenna, Italy
4
School of Biomedical and Biological Sciences/Marine Institute, University of Plymouth,
Plymouth, United Kingdom
5
Center for Environmental Biotechnology, University of Tennessee, Knoxville, USA
6
Department of Forestry, Wildlife and Fisheries, University of Tennessee, Knoxville, USA
18.30 – 18.50
Assessment of the water purification ecosystem service regarding instream pharmaceutical residues: exploring the GREAT-ER model
parameters based on data uncertainty
Laurie Boithias1, Rafael Marcé1, Vicenç Acuña1, Joana Aldekoa2, Vicky
Osorio3, Mira Petrović1,4, Felix Francés2, Antoni Ginebreda3 and Sergi
Sabater1,5
1
Universitat Politècnica de València, Valencia, Spain
3
4
5
2
19.30 – 21.00
Touristic route
21:00
Joint Dinner
Tuesday, 26th November 2013
Session IV: Global change and water
Chairperson: Joan Grimalt
9.00 – 9.30
Climate Change, Water and Security in the Mediterranean - implications
for science and policy (a perspective from the CLIMB project)
Ralf Ludwig and the CLIMB consortium
Department of Geography, Ludwig-Maximilians-Universität Munich, Munich, Germany
9.30 – 10.00
Spring snowfall decadal variability over the Alps
Matteo Zampieri1, Enrico Scoccimarro1,2 and Silvio Gualdi1,2
1
2
EuroMediterranean Center for Climate Change (CMCC), Bologna, Italy
INGV, Bologna, Italy
Analysis of climate change effects on water and sediment cycle in a
Mediterranean catchment
Gianbattista Bussi1, Félix Francés1, José Andrés López-Tarazón2,3and Ramón
J. Batalla3,4,5
1
Research Institute of Water and Environmental Engineering, Universitat Politècnica de
València, Spain
2
School of Natural Sciences and Psychology, Liverpool John Moores University, UK
3
Department of Environment and Soil Sciences, University of Lleida, Spain
4
5
Forest Science Centre of Catalonia, Solsona, Spain
10.30 – 10.50
Sediment dynamics response under global change: Sensitivity Analysis in
a Mediterranean watershed
María Sánchez-Canales1, Alfredo López1, Vicenç Acuña2 and F. Javier Elorza1
1
2
10.50 – 11.20
Measuring wetlands level using historical remot sensing imaginery
Victor Juan Cifuentes Sanchez1, Rosario Escudero Barbero2 and María Jose
Checa Alonso2
1
2
11.20 – 11.50
Univ. Politécnica de Madrid, Escuela Técnica Sup. de Ingenieros de Minas, Madrid, Spain
Confederacion Hidrografica del Gaudalquivir, Sevilla, Spain
Empresa Pública TRAGSATEC, Madrid, Spain
Session V: Multiple stressors and risk assessment
Chairperson: Ralf Ludwig
11.50 – 12.20
From chemical exposure to ecosystem effects: a critical view of the risk
assessment process
Antoni Ginebreda
12.20 – 12.40
Multiple stressor effects on river biofilms. Searching the ruling factor
Lídia Ponsatí1, Mira Petrovic1,2, Yolanda Picó3, Antoni Ginebreda4, Elisabet
Tornés1,5, Natàlia Corcoll1, Helena Guasch5, Damià Barceló1,4 and Sergi
Sabater1,5
1
Catalan Institute for Water Research (ICRA), Girona Spain
3
Laboratori de Nutrició i Bromatologia, Univerisity of València, Burjassot, Spain
4
5
Institue of Aquatic Ecology, University of Girona, Girona, Spain
2
12.40 – 13.00
Ecological screening indicators of stress and risk for the Llobregat river
water
Ramón López-Roldán1, Irene Jubany2, Vicenç Martí2,3, Susana González1 and
Jose Luis Cortina1,3
1
CETaqua, Cornellà, Barcelona, Spain
CTM Technological Centre Foundation, Manresa, Spain
3
Department of Chemical Engineering, BarcelonaTech (UPC), Barcelona, Spain
2
Habitat quality assessment in river basins considering terrestrial and
aquatic threats
Marta Terrado1, Guy Ziv2, Lisa Mandle2, Becky Chaplin-Kramer2, Richard
Sharp2, Sergi Sabater1,3 and Vicenç Acuña1
1
Catalan Institute for Water Research, Girona, Spain
The Natural Capital Project, Woods Institute for the Environment, Stanford Univ, CA, USA
3
Institute of Aquatic Ecology, University of Girona, Spain
2
13.20 – 15.00
Lunch
Session VI: Socioeconomic issues and water management
Chairperson: Antoni Ginebreda
15.00 – 15.30
Evaluation strategy and data processing of indicator values and risk
assessment – a sustainable logic indicator system for planning,
constructions, materials and scenarios in semi arid areas
Peter-D. Hansen1, B. Gabriel2 and R. vom Lehn2
1
TU Berlin (Berlin Institute of Technology - BIT), Dept. Ecological Impact Research and
Ecotoxicology
2
TU-Campus Wedding (TIB), Master´s Programme Real Estate Management, Berlin, Germany
15.30 – 16.00
The role of e-Infrastructures: Linking biodiversity and ecosystems
through the deployment of new water quality technologies in river
basins
Juan Miguel González Aranda1, Antonio José Sáenz Albanés2, Jesús Marco de
Lucas3 and Benjamín Sánchez Gimeno4
1
Ministry of Economy and Competitiveness, Madrid, Spain
Andalusian Institute of Technology-IAT, Seville, Spain
3
Institute of Physics of Cantabria-IFCA, CSIC-UC, Santander, Spain
4
Ministry of Economy and Competitiveness, Madrid, Spain
2
16.00 – 16.20
Integrating Action Assessment and Knowledge Exchange in Combating
Desertification: The PRACTICE Integrated Protocol
Susana Bautista1, Barron J. Orr2, and V. Ramón Vallejo3
1
Department of Ecology, University of Alicante, Alicante, Spain
Office of Arid Lands Studies, University of Arizona, Tucson, USA
3
Departmment of Plant Biology, University of Barcelona, Barcelona, Spain
2
16.20 – 16.40
The use of deliberative scenarios for WES appraisal and identification of
measures in two Mediterranean case studies: Noguera de Tor and Anoia
river basins
Francesc La Roca1, Graciela Ferrer1 and Joserra Díez2
1
University of Valencia, Department for Applied Economics, Valencia, Spain
University of the Basque Country, Department of Mathematics and Experimental Sciences
Didactics, Vitoria-Gasteiz, Spain
2
16.40 – 17.10
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 15 Final programme Session VII: Last FP7 EU call on water resources: multiestressors and toxicants
Chairperson: Damià Barceló
17.10 – 17.40
SOLUTIONS for present and future emerging pollutants in land and
water resources management
Werner Brack
Helmholtz Centre for Environmental Research UFZ, Leipzig, Germany
17.40 – 18.10
Managing Aquatic ecosystems and water Resources under multiple
Stress (MARS)
Christian K. Feld1,2, Sebastian Birk1 and Daniel Hering1,2
1
Depar. of Aquatic Ecology, Faculty of Biology, Univ. of Duisburg-Essen, Essen, Germany
Centre for Water and Environmental Research (ZWU), University of Duisburg-Essen, Essen,
Germany
2
18.10 – 18.40
GLOBAQUA: Managing the effects of multiple stressors on aquatic
ecosystems under water scarcity
Sergi Sabater1, Alícia Navarro-Ortega2 and Damià Barceló1,2
1
2
Final remarks and closure of the meeting
18.40 – 18.50
Final remarks and closure of the meeting
18.50
End of meeting
In italics, invited presentations
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 16 Final programme Posters
Monitoring network for chemical and biological data. Legacy and emerging POPs
1.-
Development and optimization of configuration IT-SPME coupled to UHPLC-MS/MS
to the analysis of organic pollutants in water samples
Ana Masiá1, Yolanda Moliner-Martínez2, María Muñoz-Ortuño2, Yolanda Picó1 and Pilar
Campíns-Falcó2
1
Environmental and Food Safety Research Group, Faculty of Pharmacy, University of Valencia,
Burjassot, Spain
2
Department of Analytical Chemistry, Faculty of Chemistry, University of Valencia, Burjassot, Spain
2.-
Analysis of organic persistent pollutants compounds by gas chromatography
tandem mass spectrometry in biota samples from four spanish rivers
Elena Martínez1, Àngels Quiroga1 and Damià Barceló1,2
1
2
3.-
Stir bar sorptive extraction of 100 micropollutants from aqueous samples and
determination by gas chromatography-mass spectrometry: electrospray
ionization vs atmospheric pressurized gas chromatography
Marina G. Pintado-Herrera1, Eduardo González-Mazo1 and Pablo A. Lara-Martín1
1
Department of Physical-Chemistry, Faculty of Marine and Environmental Sciences, University of Cadiz,
Campus of International Excellence of the Sea (CEI.MAR), Puerto Real, Spain
4.-
Screening of perfluorinated compounds in water, sediment and biota of the
Llobregat River basin (NE Spain)
Julián Campo1, Francisca Pérez2, Yolanda Picó1, Marinel.la Farré2 and Damià
Barceló2,3
1
Burjassot, Spain
2
3
5.-
Occurrence of perfluorinated compounds in Spanish sewage treatment plants and
determination of their removal efficiencies
Julián Campo1, Ana Masiá1, Yolanda Picó1, Marinel.la Farré2 and Damià Barceló2,3
1
Food and Environmental Safety Research Group, Faculty of Pharmacy, University of Valencia,
Burjassot, Spain.
2
3
Catalan Institute of Water Research (ICRA), Girona, Spain
6.-
Seasonal inputs of polyethoxylated compounds to a Mediterranean coastal lagoon
through surface watercourses
Juan M. Traverso-Soto1, Pablo A. Lara-Martín1, Eduardo González-Mazo1 and V. M.
León2
1
Departamento de Química Física, Facultad de Ciencias del Mar y Ambientales, Campus de Excelencia
Internacional del Mar (CEI·MAR), Universidad de Cádiz, Puerto Real, Spain
2
Instituto Español de Oceanografía, Centro Oceanográfico de Murcia, San Pedro del Pinatar, Spain
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 17 Final programme 7.-
Seasonal changes in the concentration of synthetic surfactants in groundwater
from aquifer systems (Cadiz, SW Spain)
Carmen Corada-Fernández1, Nivis Torres-Fuentes1, Pablo A. Lara-Martín1, L. Candela2
and Eduardo González-Mazo1
1
Puerto Real, Spain
2
Department of Geotechnical Engineering and Geosciences, UPC, Barcelona, Spain
8.-
Geographical distribution of pesticides in waters of the river Júcar, Spain
Juan Antonio Pascual Aguilar1,2, Vicente Andreu1, Ana Masiá3 and Yolanda Picó3
1
Environmental forensic and Landscape Chemistry Group, Centro de Investigaciones sobre
Desertificación-CIDE (CSIC-UV-GV), Moncada, Spain
2
Centro para el Conocimiento del Paisaje, Matet, Spain
3
Food and Environmental Safety Research Group, Department of Medicine Preventive, Faculty of
Pharmacy, University of Valencia, Burjassot, Spain
9.-
Study of the occurrence, spatial and temporal distribution of pesticides in water,
sediment and biota from Llobregat River Basin
Ana Masiá, Julián Campo, Cristina Blasco and Yolanda Picó
Environmental and Food Safety Research Group, Faculty of Pharmacy, University of Valencia, Burjassot,
Spain
10.- Occurrence of siloxanes in fish samples from the Júcar River
Josep Sanchís1, Francisca Pérez1, Marinella Farré1 and Damià Barceló1,2
1
2
11.- Study of Silver Nanoparticles in aqueous solutions by Capillary Reversed-Phase
Liquid Chromatography, Transmission Electron Microscopy and UV-Vis techniques
Rodrigo A. Gonzalez-Fuenzalida, Yolanda Moliner-Martínez, Jorge Verdú-Andrés and
Pilar Campíns-Falcó
Department of Analytical Chemistry, University of Valencia, Burjassot, Spain
12.- Cost effective methodology as analytics tools for DEHP and their degradation
products in waters
Neus Jornet-Martinez, María Muñoz-Ortuño, Yolanda Moliner-Martínez, Rosa HerráezHernández, A. Argente-García and Pilar Campíns-Falcó
13.- Incidence and distribution of heavy metals in sediments of the Turia River basin
Vicente Andreu1, Eugenia Gimeno2 and Juan A. Pascual1
1
2
Centro de Investigaciones sobre Desertificación-CIDE (CSIC-UV-GV), Moncada, Spain
Fundación Universidad de Valencia. CIDE, Moncada, Spain
14.- Levels of free and combined chlorine found in indoor swimming pools, both in
bathing water and air
Javier Pla-Tolós1, Carmen Molins-Legua1, Jorge Verdú-Andres1, Yolanda MolinerMartínez1, Rosa Herráez-Hernández1, Pilar Campins-Falcó1 and Salvador Llana2
1
2
Department of Analytical Chemistry, Chemistry Faculty, University of Valencia, Burjassot, Spain
Dpto. de Educación Física y Deportiva, Universidad de Valencia
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 18 Final programme 15.- Development of new supports for in situ estimation of nitrogen containing
compounds in atmospheres of wastewater treatment plants
Neus Jornet-Martinez, Yolanda Moliner-Martínez, Jorge Verdú Andrés, Carmen
Molins-Legua, Rosa Herráez Hernández and Pilar Campíns-Falcó
Department of Analytical Chemistry, Chemistry Faculty, University of València, Burjassot, Spain
16.- Fat determination in effluents of dairy industries by preconcentration in nylon
membranes and ATR-IR
María Muñoz-Ortuño, Yolanda Moliner-Martinez, Rosa Herráez-Hernández and Pilar
Campíns-Falcó
17.- Determination of lactose in effluents of dairy industries
María Muñoz-Ortuño1, Yolanda Moliner-Martinez1, Rosa Herráez-Hernández1, M.T.
Picher2 and Pilar Campíns-Falcó1
1
2
Department of Organic Chemistry, Chemistry Faculty, University of Valencia, Burjassot, Spain
18.- Greenhouse gas emissions in two coastal systems in Cadiz Bay (SW Spain):
relationship with organic matter inputs
Macarena Burgos, A. Sierra, Teodora Ortega and Jesús Forja
CACYTMAR, Dep. Química-Física, Puerto Real, Spain
19.- Anthropogenic effects on greenhouse gas emissions in the Guadalete River
Estuary
CACYTMAR, Dpto. Química-Física, Puerto Real, Spain
Monitoring network for chemical and biological data. Pharmaceuticals and other
emerging compounds
20.- Hourly variations in the occurrence of several pharmaceuticals and surfactants in
urban and industrial wastewater
Dolores Camacho-Muñoz, Julia Martín, Juan L. Santos, Irene Aparicio and Esteban
Alonso
Department of Analytical Chemistry, Escuela Politécnica Superior, University of Seville, Seville, Spain
21.- Multi-residue analysis of pharmaceutically active compounds (PhACs) in aqueous
matrices by liquid chromatography -quadrupole - time-of-flight - mass
spectrometry
Rosa M. Baena-Nogueras, Gabriela Aguirre-Martínez, L. Alves-Maranho, María Laura
Martín-Díaz, Eduardo González-Mazo and Pablo A. Lara-Martín
Departamento de Química Física, Facultad de Ciencias del Mar y Ambientales, Universidad de Cádiz,
Puerto Real, Spain
22.- Sorption of 3 pharmaceuticals in agricultural soils: hydrochlorothiazide,
metoprolol and clarithromycin
Nivis Torres-Fuentes1, Carmen Corada-Fernández1, Eduardo González-Mazo1, Pablo A.
Lara-Martín1 and Diana Álvarez-Muñoz1,2
1
Campus of International Excellence (CEI•MAR), Puerto Real, Spain
2
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 19 Final programme 23.- Evaluation of a simple method for the analysis of pharmaceuticals in seafood
Diana Álvarez-Muñoz1, Belinda Huerta1, Sara Rodríguez-Mozaz1 and Damià Barceló1,2
1
2
24.- High-resolution mass spectrommetry applications in the identification and
detection of transformation products in the aquatic environment
Bozo Zonja1, Sandra Pérez1 and Damià Barceló1,2
1
2
Water and soil quality research group, IDAEA-CSIC, Barcelona, Spain
25.- Pharmaceutical compounds in sludge from different sludge stabilization
processes: occurrence and environmental risk assessment after sludge
application onto soils
Juan L. Santos, Julia Martín, Dolores Camacho-Muñoz, A. Santos, Irene Aparicio and
Esteban Alonso
25b.- Green and cheap alternative for the determination of 5-nitroimidazoles in river
and well waters based on Cation Selective Exhaustive Inyection and Sweeping
Micellar Electrokinetic Chromatography (CSEI-sweeping-MEKC)
Diego Airado-Rodríguez, Maykel Hernández-Mesa, Carmen Cruces-Blanco and Ana M.
García-Campaña
Department of Analytical Chemistry, Faculty of Sciences, University of Granada, Granada, Spain
26.- Temporal trends of illicit drugs in WWTPs in Valencia, Spain
María Jesús Andrés-Costa1, Ana Masiá1, Vicente Andreu2 and Yolanda Picó1
1
Environmental and Food Safety Research Group, Department of Medicine Preventive, Faculty of
Pharmacy, University of Valencia. Burjassot, Spain
2
Reserch Centre of Desertification (CIDE, CSIC-UV-GVA). Moncada, Valencia, Spain
27.- Emerging illicit drugs in waste and surface waters in the Turia River Basin
María Jesús Andrés-Costa1, Ana Masiá1, Cristina Blasco1, Vicente Andreu2 and Yolanda
Picó1
1
Environmental and Food Safety Research Group, Department of Medicine Preventive, Faculty of
Pharmacy, University of Valencia. Burjassot, València, Spain
2
28.- Occurrence and environmental risk assessment of drugs of abuse in four Spanish
river basins
Nicola Mastroianni1, Miren López de Alda1 and Damià Barceló1,2
1
2
28b.- Investigation of drugs of abuse in river water from the Granada Province by
means of UHPLC-MS/MS in combination with dispersive liquid-liquid
microextraction (DLLME) as environmentally-friendly sample treatment
Diego Airado-Rodríguez, Manuel Lombardo-Agüí, Ana M. García-Campaña and Carmen
Cruces-Blanco
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 20 Final programme Monitoring network for chemical and biological data. Tools for integration and
improvement of risk assessment
29.- Assessment of pharmaceutical Diclofenac occurrence in the Llobregat river via
Monte Carlo sensitivity analysis of several parameters using GREAT-ER model
Zoran Banjac1, Laurie Boithias2, Antoni Ginebreda1, Rafa Marce2, Victoria Osorio1,
Sandra Pérez1, Damià Barceló1,2, Sergi Sabater2 and Vicenç Acuña2
1
2
30.- Application of ArcGIS software to display the occurrence and risk of chemical
pollutants
Maja Kuzmanović1, Antoni Ginebreda1, Mira Petrović2,3 and Damià Barceló1,2
1
3
2
31.- Improving the WFD purposes by the incorporation of ecotoxicity tests
Neus Roig1,2, Jordi Sierra1,3, Martí Nadal2, Ignacio Moreno4, Elena Nieto4, Miriam
Hampel4, Julián Blasco , Marta Schuhmacher1,2 and Jose Luis Domingo2
1
Environmental Engineering Laboratory, Departament d'Enginyeria Quimica, Universitat Rovira i Virgili,
Tarragona, Spain
2
Laboratory of Toxicology and Environmental Health, School of Medicine, IISPV, Universitat Rovira i
Virgili, Reus, Spain
3
Laboratori d’Edafologia, Facultat de Farmàcia, Universitat de Barcelona, Barcelona, Spain
4
Departamento Ecología y Gestión Costera, Instituto de Ciencias Marinas de Andalucía (CSIC), Puerto
Real, Cadiz, Spain
32.- A chemical determination of the sediment fluxes at the Barasona Reservoir
José A. López-Tarazón1,2, Pilar López3, Damià Vericat2,4,5 Isabel Muñoz3 and Ramon J.
Batalla2,4,6
1
School of Natural Sciences and Psychology, Liverpool John Moores University, Liverpool, UK
Departament de Medi Ambient i Ciències del Sòl (DMACS), Universitat de Lleida, Lleida, Spain
3
Departament d’Ecologia, Universitat de Barcelona, Barcelona, Spain
4
Centre Tecnològic Forestal de Catalunya, Solsona, Spain
5
Institute of Geography and Earth Sciences, Aberystwyth University, Ceredigion, Wales, UK
6
2
33.-
Exposure to human pharmaceuticals produces differential transcriptome
expression fingerprints in the brain of the seabream, Sparus aurata
Miriam Hampel1,2, Massimo Milan1, Julián Blasco1, Serena Ferraresso1 and Luca
Bargelloni3
1
2
34.-
Instituto de Ciencias Marinas de Andalucía (ICMAN-CSIC), Puerto Real, Spain
Department of Comparative Biomedicine and Food Science, University of Padova, Legnaro, Italy
Environmentally relevant concentrations of three human pharmaceuticals alter
the liver transcriptome of the Atlantic salmon, Salmo salar
Miriam Hampel1, Esteban Alonso2, Irene Aparicio2, James Bron2, Juan Luis Santos2,
John Taggart1 and Michael Leaver1
1
2
Institute of Aquaculture, University of Stirling, Stirling, Scotland, UK
Department of Analytical Chemistry, University of Seville, Seville, Spain
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 21 Final programme 35.-
Temperature forcing and pharmaceuticals occurrence as proxy of global change.
Subtlethal effects (osmoregulatory capacity, ingestion and respiration rates) in
the freshwater crustacean, A. desmarestii
Elena Nieto, Miriam Hampel, Enrique González-Ortegón, Pilar Drake and Julián
Blasco
Institute for Marine Science of Andalusia, Department of Ecology and Coastal Management, Campus
Universitario Rio San Pedro s/n, Puerto Real, Spain
35b.- A comparative study of recirculation and continuous mode for pollutant ions
exchange from pretreated olive mill wastewater
M. D. Victor-Ortega1, J.M. Ochando-Pulido1, G. Hodaifa2 and A. Martínez-Férez1
1
2
Chemical Engineering Department, University of Granada, 18071 Granada, Spain
Molecular Biology & Biochemical Engineering Department, University Pablo de Olavide, 14013 Seville
35c.- Effect of ions concentration on the remediation of sodium and iron from olive
mill effluent by ion exchange technique
M. D. Victor-Ortega1, J.M. Ochando-Pulido1, G. Hodaifa2, L. Martínez-Nieto1 and A.
Martínez-Férez1
1
2
Chemical Engineering Department, University of Granada, Granada, Spain
Molecular Biology & Biochemical Engineering Department, University Pablo de Olavide, Seville
35d.- Comparing different nanofiltration and reverse osmosis membranes for final
remediation of olive mill wastewater
J.M. Ochando-Pulido1, M. D. Victor-Ortega1, G. Hodaifa2, L. Martínez-Nieto1 and A.
Martínez-Férez1
1
2
35e.- Steady-state performance enhancement of a diafiltration reverse osmosis system
for final salinity rejection of olive mill wastewater
J.M. Ochando-Pulido1, M. D. Victor-Ortega1, G. Hodaifa2 and A. Martínez-Férez1
1
2
Global change and water
36.- Freshwater scarcity effects on the different components of a European estuary
from Mediterranean-climate zone
Enrique González-Ortegón1, Alberto Arias1, Francisco Baldó2, José Antonio Cuesta1,
Carlos Fernández-Delgado3, César Vilas4 and Pilar Drake1
1
Instituto de Ciencias Marinas de Andalucía (CSIC), Puerto Real, Spain
Instituto Español de Oceanografía, Cádiz, Spain
3
Departamento Biología Animal, Universidad de Córdoba, Córdoba, Spain
4
IFAPA Centro El Toruño, El Puerto de Santa María, Spain
2
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 22 Final programme Multiple stressors and risk assessment
37.- Effects of stream habitat complexity and biodiversity on leaf litter decomposition
Lorea Flores1, R. A. Bailey2,3, Arturo Elosegi1, Aitor Larrañaga1, B. R. Rall4 and J.
Reiss5
1
Fac. of Science and Technology; University of the Basque Country, Leioa, Spain
Mathematical Sciences Institute, Queen Mary University, London, UK
3
School of Mathematics and Statistics, University of St Andrews, St Andrews, UK
4
J. F. Blumenbach, Institute of Zoology and Anthropology, University of Goettingen, Goettingen,
Germany
5
Dept. of Life Sciences, Whitelands College, Roehampton University, London, UK
2
38.- The effects of a mixture of pharmaceuticals compounds at environmental
concentrations on epilithic biofilms: constant flow vs water intermittency
conditions
Natàlia Corcoll1, Maria Casellas1, Belinda Huerta1, Helena Guasch2, Sara RodríguezMozaz1, Albert Serra2, Damià Barceló1,3 and Sergi Sabater1,2
1
3
2
39.- Invertebrate community response to water and sediment chemical composition in
Mediterranean rivers
Núria de Castro-Català1, Damià Barceló2,3, Sandra Pérez2, Mira Petrovic3, Yolanda
Picó4 and Isabel Muñoz1
1
Department of Ecology, University of Barcelona, Barcelona, Spain.
3
4
Burjassot, Spain
2
40.- Effects of water abstraction on large river ecosystem metabolism
Maite Arroita, Ibon Aristi and Arturo Elosegi
Faculty of Science and Technology, the University of the Basque Country, Bilbao, Spain
41.- Effects of restoring stream dead wood on reach-scale storage and decomposition
of organic matter
Aitor Larrañaga1, Lorea Flores1, Ibon Aristi1, Inmaculada Arostegui1, Maite Arroita1,
Joserra Díez2 and Arturo Elosegi1
1
2
Faculty of Science and Technology, University of the Basque Country, Bilbao, Spain
University college of Teacher Training, University of the Basque Country, Vitoria-Gasteiz, Spain
42.- Effects of WWTP effluent on the metabolism of a Mediterranean river
Ibon Aristi1, Maite Arroita1, Lydia Ponsati2, Sergi Sabater2,3, Daniel von Schiller2,
Arturo Elosegi1 and Vicenç Acuña2
1
3
2
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 23 Final programme 43.- An assessment of environmental factors influencing species distribution in a
temperate estuary: a binomial approach
Enrique González-Ortegón1, César Vilas4, Alberto Arias1, Francisco Baldó2, José
Antonio Cuesta1, Carlos Fernández-Delgado3 and Pilar Drake1
1
3
Dpto Biología Animal, Universidad de Córdoba, Córdoba, Spain
4
2
44.-
Effect of black poplar plantations in the base river flow in a Mediterranean
stream
Núria Ferrer and Albert Folch
Hydrogeology Group, Dept. of Geotechnical Engineering and Geo-Sciences, Universitat Politècnica de
Catalunya-BarcelonaTech, Barcelona, Spain
Socioeconomic issues and water management
45.- Water management in a restored wetland influences trophic links and species
composition in the aquatic macroinvertebrate community
Enrique González-Ortegón1, M.E.M. Walton1, Bushra Moghaddam1, Cesar Vilas2, Ana
Prieto 2, H.A. Kennedy1, J. Pedro Cañavate2 and Lewis Le Vay1
1
2
School of Ocean Sciences, College of Natural Sciences, Bangor University, Menai Bridge, UK
46.- Integrated Water Resources Management and related indicators
Andrea Momblanch, Joaquín Andreu and Javier Paredes
Universitat Politècnica de València
47.-
WaterDiss2.0: Disseminating Water Research across the European Union
Beatriz Medina1, C. Roberts2, T. Simms2, U. Stein3 and G. Nion4
1
Amphos 21, Spain
The Chancellor, masters and Scholars of the University of Oxford, UK
3
Ecologic, Germany, UK
4
Office International del L’Eau, France
2
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 24 Final programme 4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain Oral presentations
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 27 Oral presentations Water research and innovation strategy in Horizon 2020, the State
Plan of Spain and the Water JPI
Marina Villegas1,2
2
1
Deputy Director of Research Projects, Ministry of Economy and Competitiveness, Government of Spain
President of the Governing Board of the Water JPI, Ministry of Economy and Competitiveness, Government of
Spain
Introduction
In this presentation, three research and innovation programmes devoting significant investments to water
research and innovation will be discussed. One of them is the State Plan of Spain, covering the period
2013-2016, while the other two have a European dimension. Horizon 2020 is the successor of the seventh
Framework Programme, and represents a completely new approach to research and innovation in the
period 2014-2020. Finally, the Joint Programming Initiative “Water Challenges for a Changing World”
(the Water JPI) represents an effort of European countries to coordinate efforts in water research and
innovation. All three programmes represent the main funding opportunities for Spanish researchers and
innovators, and use complementary approaches to cover a wide range of activities and to fund actors
located in different points along the knowledge value chain.
In this document, water is referred to in the terms used in the Water Framework Directive, article 1:
“inland surface waters, transitional waters, coastal waters and groundwater”.
Horizon 2020, the research and innovation programme of the European Commission
Horizon 2020 is the financial instrument implementing the Innovation Union, a Europe 2020 flagship
initiative aimed at securing Europe's global competitiveness. Horizon 2020 is part of the political drive to
create new growth and jobs in Europe. Upon its start, on January 1st 2014, the programme will combine
all research and innovation funding currently provided through the Framework Programmes for Research
and Technical Development, the innovation related activities of the Competitiveness and Innovation
Framework Programme (CIP) and the European Institute of Innovation and Technology (EIT).
Horizon 2020 will strengthen the EU’s position in science, strengthen industrial leadership in innovation,
and address major concerns shared by all Europeans by tackling societal challenges. The programme will
help bridge the gap between research and the market. This market-driven approach will include creating
partnerships with the private sector and Member States to bring together the resources needed.
International cooperation will be an important cross-cutting priority of Horizon 2020. Horizon 2020 will
be complemented by further measures to complete and further develop the European Research Area by
2014. These measures will aim at breaking down barriers to create a genuine single market for
knowledge, research and innovation.
Water Research and Innovation (R&I) will be addressed in virtually all areas of Horizon 2020. However,
the area where it will receive dedicated attention is the Societal Challenges. Water issues are partially
addressed under Challenge 2 “food security, sustainable agriculture and forestry, marine and maritime
and inland water research and the bioeconomy”. In this challenge, water issues are considered in areas
such as water and soil biodiversity, low water agricultural production or inland aquaculture.
The most important share of water R&I in Horizon 2020 is under Challenge 5 “climate action,
environment, resource efficiency and raw materials”. One of its objectives is to achieve a water efficient
economy and society. According to the formulation of this challenge, water challenges in the rural, urban
and industrial environments need to be addressed to promote water system innovation and resource
efficiency and to protect aquatic ecosystems. This challenge aims at protecting the environment,
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 28 Oral presentations sustainably managing natural resources, water, biodiversity and ecosystems.
The State Plan for scientific and technological research and for innovation, 2013-2016
This Plan will simultaneously and continuously face the design of interventions aimed at the promotion
and coordination of Research, Development and Innovation (RDI) activities, ranging from the generation
of ideas to market access in the form of new products and / or processes, improving quality of life, citizen
well-being and contributing to economic development. It is addressed to all the agents of the Spanish
Science, Technology and Innovation sector responsible for:
•
RDI execution;
•
RDI management; and
•
RDI deployment for scientific, technological and innovation progress of the entire Spanish
society and economy.
The State Plan is the instrument allowing the implementation of public policies of the General
Administration of Spain addressing the coordination of RDI activities. Therefore, public funds are
awarded through competition processes. The selection of RDI proposals to be funded is made taking into
account technical and scientific criteria. If relevant, internationally validated technological, business and
commercial viability criteria are additionally used. In all cases, standardized and transparent assessment
processes based on peer review are implemented.
The State Plan is aligned with Horizon 2020 - the research and innovation programme of the European
Commission – in order to capitalize synergies and to facilitate the passage of researchers and
technologists from one programme to the other.
The State Plan is divided in State Programmes and Subprogrammes covering a number of areas related to
human resources, blue sky research, support to companies, societal challenges and strategic areas. There
is no specific programme on water, but virtually all programmes are developing activities related to water
research.
The State Programme on RDI supporting societal challenges is the programme most directly related to
Water. This section of the State Plan is in tight coordination with Horizon 2020. Challenge 5 under this
Programme “Climate Change, resource efficiency and raw materials” is the area most directly focusing on
water RDI. Research on societal challenges will be implemented through a series of activities, such as
projects, accompanying measures, and support to Joint Programming Initiatives, such as the Water JPI,
whose activities are described in the next section.
The Water JPI, coordinating the research and innovation efforts of European Countries
In 2008 the European Commission presented a new policy: ‘Towards joint programming in research’ with
the meaningful subtitle ‘Working together to tackle common challenges more effectively”, challenging
countries to develop initiatives on joint programming with the purpose of increasing the efficiency and
impact of national public funding in strategic areas. Joint programming targets public research
programmes first and foremost, which means public-public cooperation in the direction of the definition
and implementation of common research agendas with jointly agreed-upon multi–annual activities and
funding mechanisms. Joint Research Initiatives are a relative new but important mechanism in the
European Research Area. The Joint Programming process is to pool national efforts at a large scale and to
make better use of Europe's RDI resources to tackle major challenges effectively. It is a strategic process
whereby Member States agree, on voluntary basis and in a partnership approach, on common visions and
strategic research agendas. National resources are put together on the basis of collaboration between
national programmes.
The JPI “Water challenges for a changing world” deals with research in the field of water and
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 29 Oral presentations hydrological sciences. The availability of water in sufficient quantities and adequate quality is indeed a
public issue of high priority and addresses a pan-European and global environmental challenge.
The Council of the European Union decided to launch the Joint Programming Initiative “Water
Challenges for a Changing World” on 6 December 2011 as a contribution to the reduction of
fragmentation of efforts by Member States and mobilisation of skills, knowledge and resources, with a
view to strengthening Europe's leadership and competitiveness on water research and innovation.
Europe invests an estimated amount of 500 million € per year to fund public research and innovation
activities in water. While European countries invest 370 million €, the European Commission invests 130
million €. The Joint Programming Initiative will actively cooperate with the European Commission to
provide the European society with the maximum return of these investments. The Initiative responds to
the grand challenge of “Achieving Sustainable Water Systems for a Sustainable Economy in Europe and
Abroad”. No single European country can address this challenge by itself, due to the magnitude of the
needed operations and to the geographical variation of the water problems. Responding to the grand
challenge requires a joint multi-disciplinary approach, since outstanding economic, ecological,
technological and societal challenges are to be addressed.
The objectives of the Water JPI are described in its Vision Document:
•
Involving water end-users for effective RDI results uptake;
•
Attaining critical mass of research programmes;
•
Reaching effective, sustainable coordination of European water RDI;
•
Harmonising National water RDI agendas in Partner Countries;
•
Harmonising National water RDI activities in Partner Countries; and
•
Supporting European leadership in science and technology.
The Strategic Research and Innovation Agenda establishes five research and innovation challenges:
•
Maintaining Ecosystem Sustainability;
•
Developing Safe Water Systems for the Citizens;
•
Promoting Competitiveness in the Water Industry:
•
Implementing a Water-Wise Bio-Based Economy
•
Closing the Water Cycle Gap
These challenges are being implemented through different activities. Calls for proposals for collaborative
projects are an important type of activities in the Water JPI. A pilot call on “Emerging water
contaminants – anthropogenic pollutants and pathogens” has been preannounced and will be published on
November 1st, 2013.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 30 Oral presentations The Joint Programming Initiative on Water: a Pilot call for proposals
Enrique Playán1
1
Coordinator of the Water JPI, Ministry of Economy and Competitiveness, Government of Spain
The Water JPI
The Joint Programming Initiative “Water Challenges for a Changing World” (the Water JPI) started its
development in 2008, and was endorsed by the European Council in December 2011. This is an
intergovernmental initiative, currently formed by 19 partner countries plus the European Commission.
Five additional countries are participating as observers. The Water JPI published its Vision Document in
2011, and its Strategic Research and Innovation Agenda (SRIA) in 2013. The Water JPI SRIA lists five
specific challenges, which are in turn divided into a total of 11 subchallenges. The Water JPI has listed a
number of possible instruments which can be used to address these challenges. Among them, the support
for and use of networks (hubs) of institutions or teams, systematic reviews, think tanks, coordination of
ongoing national or EU projects, calls for proposals on collaborative projects, training and mobility
activities, Public-Private partnerships workshops, conferences, and infrastructure. A Pilot activity has
been formulated by the Water JPI in the form of a call for proposals on collaborative projects.
A Pilot Call for Proposals
The Pilot Call for Proposals was pre-announced on September 20th, 2013, and will be published on
November 1st, 2013. The call topic is “Emerging water contaminants – anthropogenic pollutants and
pathogens”. This topic responds to Water JPI SRIA specific challenge 2 (Developing Safe Water System
for Citizens), and more specifically to subchallenge 2.1 (Emerging Pollutants: Assessing their Effects on
Nature and Humans, their Behaviour and Treatment Opportunities). The deadline for proposal submission
is 19th December 2013 at 12.00 (CET). Funding decisions will be announced by May-October 2014, and
projects are expected to start in autumn 2014. A one-stage application procedure will be used in this call.
Proposals (in English language) must be submitted electronically via the Academy of Finland online
services.
This Pilot Call for proposals aims to enable multi-national, collaborative research, development and
innovation projects. The overarching aim of this Pilot Call of the Water JPI is to identify new ways to
efficiently assess, prevent, control and remove emerging pollutants and pathogens and thereby prevent
human health risks and secure ecological functions of water ecosystems now and in the future. The call
also intends to stimulate mobility of researchers between participating countries, consequently enhancing
European collaborative research during the project life and beyond. Within each selected consortium
funding of the participating researchers will be provided by their respective national funding organisation
according to their normal terms and conditions for project funding. The amount of public funding
available for transnational collaborative research projects through this call is estimated almost up to 9 M
Euros. Funding organizations from 10 countries will contribute to the call: RPF Cyprus; DCSR Denmark;
AKA Finland; ONEMA France; BMBF Germany; EPA Ireland; MIUR Italy; RCN Norway; FCT
Portugal; MINECO and CDTI Spain. In the case of Spain, MINECO and CDTI will support respectively
the participation of public research institutions and industries.
At least one of the following three themes shall be addressed by applicants:
1. Identification and prevention of emerging freshwater contaminants including but not limited to:
•
•
Identification of new contaminants as well as their sources;
Prediction of environmental behaviour in surface water, sediments, soil, groundwater,
aquatic food web, as well as in wastewater or drinking water systems;
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 31 Oral presentations •
•
•
•
•
Assessing the transfer time of the different contaminants between various environmental
compartments as well as understanding the processes suffered during transfer;
Modelling transport and fate of emerging contaminants as well as the propagation of
antimicrobial resistance;
Development of reliable, sensitive, innovative, and rapid analysis and detection systems;
Development of comparable and validated data sets on the prevalence and distribution of
major contaminants in the freshwater environments; and
Assessing the formation of transformation products (TP) and elucidating the processes
leading to these TPs.
2. Control, mitigation and methods for treatment and removal including but not limited to:
•
•
•
•
Development, implementation and evaluation of management measures and technologies
to control and reduce the dispersal and impact of emerging contaminants on water
quality, especially under the aspect of water reuse;
Development of technologies for a more efficient removal of these contaminants at
source or in urban or rural water treatment system;
Evaluation of treatment efficiency and implementation of existing and novel techniques.
Including monitoring/sensor technologies; and
Development, implementation and evaluation of mitigation options.
3. Impacts on ecosystem services and human health including but not limited to:
•
•
•
•
Impact assessment of emerging contaminants on ecosystem services (ecotoxicology) and
human health (toxicology) at different scales, considering short-term and long-term
aspects;
Development of integrated risk assessment methodologies for emerging contaminants;
especially for those acting at sub-lethal level;
Estimation of health risks resulting from new water management practices, such as water
reuse in urban areas; and
Understanding and predicting the environmental behaviour of emerging contaminants in
surface water, sediments, soil, groundwater and in freshwater food webs.
(Bullet points are only meant as examples).
Proposals with duration of 24-36 months may be submitted by Universities, higher education institutions;
public research institutes, industries, companies and SMES. Tackling societal challenges always requires
a multidisciplinary approach. Therefore, all submitted applications should emphasize participation of
stakeholders and dissemination and exploitation of results. Consortia must include a minimum of three
partners from three different Water JPI partner countries contributing to the funding of this call.
Researchers from 1) Water JPI partner countries not funding this call; 2) Water JPI observer countries; or
3) Third countries can participate in the consortia at their own expense.
Further activities
The Water JPI is currently preparing additional activities in cooperation with Horizon 2020. Among
them, a call to be published in 2014 is under preparation on the topic “developing technological solutions
and services for water distribution and measurement, waste water treatment and reuse, desalination,
floods and droughts, etc.” This call for proposals will probably be performed under an ERA-NET from
Horizon 2020, so as to obtain additional funds for selected projects. Information on this and other
forthcoming activities will be published at the Water JPI web site.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 32 Oral presentations SCARCE: Snapshots on recent results and achievements
(Dec2009-Nov 2013)
Damià Barceló1,2 and Alícia Navarro-Ortega1
1
Water and Soil Quality Research Group, Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain
2
The Mediterranean basin is one of the regions of the world most vulnerable to global change (Barceló and
Sabater 2010), and one of the "hot spots" for oncoming problems in water availability (Giorgi and
Lionello 2008). The main panels on climate change predict a future scenario of increasing frequency of
floods and extended droughts in the Iberian Peninsula, mostly in the Mediterranean basin (IPCC 2007).
Low summer flow and large floods in autumn and winter are characteristics of rivers under Mediterranean
climate (Gasith and Resh 1999), but the forecasted scenarios suggest several points of concern, including
decreased hydrological connectivity and increased concentration of pollutants during droughts, changes in
biological communities as a result of harsher environmental conditions, and decreased of biological
processes like nutrient uptake, primary production, or decomposition .In addition, water resources in
Spain are subjected to rising pressures, related to the socioeconomic activities of an increasing human
population, expressed by accelerated land use changes, and the specific climate characteristic of
Mediterranean countries. This will be added to the currently existing problems, and will probably affect
the available water resources, their quality, the functioning of associated ecosystems, especially rivers and
their aquifers, and the ecosystem services they provide.
In such context, SCARCE (Assessing and predicting effects on water quantity and quality in Iberian
Rivers caused by global change – www.scarceconsolider.es), which is a Consolider-Ingenio 2010 project
from the Spanish Ministry of Economy and Competitiveness, aims to describe and predict the relevance
of global change impacts on water availability, water quality and ecosystem services in Mediterranean
river basins of the Iberian Peninsula, as well as their impacts on the human society and economy
(Navarro-Ortega et al. 2012). Hence, the project has assembled a multidisciplinary team of leading
scientists in the fields of hydrology, geomorphology, chemistry, ecology, ecotoxicology, economy,
engineering and modelling, in an unknown effort in the CONSOLIDER framework. The project also
considers the active involvement of Water Authorities and other relevant agents as stakeholders.
SCARCE has two complementary objectives. The first tackles basic research questions and will define
the long-term patterns and the mechanisms that operate in the hydrology, water quality, habitat dynamics,
and ecosystem structure and function of Mediterranean basins. The second objective is related to the
effects of climate and human footprint (taken both as key elements of global change) that provide on the
ecosystem services, rivers and streams, as well as the urgent need to implement and eventually refine the
water management policies demanded by the EU Water Framework Directive (WFD). Therefore, the
project emphasizes linking basic research and management practices in a single framework. The project is
structured in ten thematic work packages (WPs), each of them dealing with one scientific discipline, from
hydrology, chemistry and biology to modelling, economy and river management. Many interactions have
been established between the different WPs in order to allow a complete flow of results between WPs.
The final goals of SCARCE are to complete the monitoring and to advance in modelling of several issues.
Regarding monitoring, WP4 QUALITY analyses the biological and chemical quality through extensive
monitoring campaigns. WP3 MORPH deals with the morphological and sediment characterization of the
river basins. WP5 PROCESS details on the ecosystem responses to hydrological, geomorphological and
chemical disturbances and WP2 HYDRO deals with the hydrology of the selected basins and the
connection to aquifers. These monitoring data and others available from the water authorities (assembled
by WP1 DATA) feed models of WP6 UPSCALE and WP8 SERVICES. Finally socioeconomic scenarios
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 33 Oral presentations are considered in the WP7 ECONOMY.
Four basins have been selected (Llobregat, Ebro, Júcar and Guadalquivir) because of their
representativeness of the different factors operating in the Mediterranean area. Most of these basins were
included in EU projects (the Llobregat in MODELKEY, the Ebro in AquaTerra or the Guadalquivir in
AQUAMONEY and RAMWASS).
Two extensive field campaigns have been undertaken at different flow conditions (high and low-medium)
in 77 sampling sites along the four basins. The levels of over 250 compounds belonging to different
groups have been determined in water, sediments and fish. The macroinvertebrates, diatomees and
biofilm have been studied in all the sites and a morphological characterization of the sites has taken place
together with the characterization of sediments, vegetation, ecosystem processes and impacts. The results
obtained from the sampling campaigns have been related with the historical ones coming from the river
Management authorities and transferred for its use in different models that consider from hydrological
variables to emerging contaminants, water quality management or climate change impacts. The amount of
data generated in the monitoring campaigns, together with the application of a variety of models will
generate attractive management tools aimed to improve the river basin management plans demanded by
the WFD.
SCARCE is a 5-year project that has been active since December 2009. With this international conference
the fourth year of project is closed. The scientific objectives included in the project have been
accomplished as it is reflected in the more than 200 articles published in peer reviewed journals and three
special issues in Environmental Science and Pollution Research, Science of the Total Environment and
Journal of Hazardous Materials respectively. The amount of scientists involved in the project has also
increased from the initial 72 to the present 161 which means more than double the active involvement in
the project. Active participation is visible as well from the number of PhD thesis associated to the
SCARCE. All these indicators reflect the importance of the project and its high impact in the scientific
community by increasing the knowledge of the Mediterranean river basins of the Iberian Peninsula.
Acknowledgements
This work has been supported by the Spanish Ministry of Economy and Competitiveness through the project Consolider-Ingenio
2010 CSD2009-00065. Special thanks to all partners of the Scarce consortium and the peer review panel for ensuring quality
results and good collaboration within the project.
References
Barceló, D. and S. Sabater (2010). "Water quality and assessment under scarcity: Prospects and challenges in Mediterranean
watersheds." Journal of Hydrology 383(1-2): 1-4.
Gasith, A. and V. H. Resh (1999). "Streams in Mediterranean climate regions: Abiotic influences and biotic responses to
predictable seasonal events." Annual Review of Ecology and Systematics 30: 51-81.
Giorgi, F. and P. Lionello (2008). "Climate change projections for the Mediterranean region." Global and Planetary Change 63(23): 90-104.
IPCC (2007). Fourth Assessment Report: Climate Change 2007. Cambridge, UK, Cambridge University Press.
Navarro-Ortega, A., V. Acuña, R. J. Batalla, J. Blasco, C. Conde, A. Elosegi, F. Francés, F. La-Roca, I. Muñoz, M. Petrovic, Y.
Picó, S. Sabater, X. Sanchez-Vila, M. Schuhmacher and D. Barceló (2012). "Assessing and forecasting the impacts of global
change on Mediterranean rivers. The SCARCE Consolider project on Iberian basins." Environmental Science and Pollution
Research 9: 918-933.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 34 Oral presentations Changes in the distributions of persistent organic pollutants and
mercury in freshwater ecosystems under changing climate conditions
Joan O. Grimalt
Department of Environmental Chemistry, IDÆA-CSIC, Barcelona, Spain
Urban, industrial and agricultural processes release to the atmosphere toxic substances such as
organochlorine compounds (OCs) such as polychlorobiphenyls (PCBs), hexachlorobenzene (HCB),
hexachlorocyclohexanes (HCHs) and DDTs, which are semi-volatile, chemically stable and largely
hydrophobic, a group of properties that define these compounds as persistent organic pollutants (POPs).
Polycyclic aromatic hydrocarbons (PAHs) and some trace metals (e.g. mercury, cadmium and lead) are
also released to the atmosphere as consequence of these activities. After emission, these pollutants are
dispersed widely and are deposited onto waterbodies (Tables 1-3). They can enter the food web where
they bioaccumulate and become toxic to aquatic and terrestrial organisms. Many of the diverse aspects of
climate change (e.g. temperature increase, variations in rainfall, wind patterns and dust deposition) affect
the distribution and mobility of toxic substances in freshwater systems.
Table 1 Concentrations of OCs in waters from remote sites (mean ± standard deviation; pg L-1) (from
Vilanova et al., 2001a; Fernandez et al., 2005)
Location
HCB
α-HCH
γ-HCH
Ladove Lake Sept. 2000
8.5 ± 3.2 68 ± 35
139 ± 89
Lake Redon May 2000
6.0 ± 2.4 313 ± 120 1760 ± 606
Lake Redon (1996-8)
8.4 ± 11 410 ± 220 2500 ± 1090
Lake Gossenkölle (1996-7) 4.0 ± 1.8 64 ± 53 930 ± 850
Øvre Neådalsvatn (1998)
6.2 ± 1.0 110 ± 52 200 ± 76
Amituk Lake (1994, Arctic)
630
169
Sea water (Antarctica)
3.4
0.7
Arctic Ocean (1990, 1992-4) 14-18 870-4700 180-700
Lake Malawi (1996-8)
4.4 ± 1.6 9.8 ± 6.2
14 ± 8.7
Bow Lake (2000)
21
210
130
Kananaskis (2000)
15
160
140
α-Endosulfanß-Endosulfan
nd
207 ± 88
60 ± 38
44 ± 28
nd
28
nd
157 ± 51
84 ± 46
28 ± 24
nd
2.0-7.2
3.3 ± 6.2
19
15
0.35-5.3
Endosulfan
sulfate
280 ± 65
1246 ± 293
1000 ± 540
92 ± 72
120 ± 16
23
17
Table 2 Concentrations of PCBs and DDTs in waters from remote sites (mean ± standard deviation)
(from Vilanova et al., 2001a; Fernandez et al., 2005)
Location
Lake Redon Nov. 2000
Lake Redon May 2000
Lake Redon (1996-8)(a)
Lake Gossenkölle (1996-7)
Amituk Lake (1994, Arctic)
Arctic Ocean (1990, 1992-4)
Easthwaite Water Lake (1996-7)
Lakes in Southern Sweden (1997)
PCBs (pg L-1)
DDTs (pg L-1)
Total Particulate Dissolved % in SPM
Total
64 ± 30
33 ±8
31 ± 31 59 ± 19
12 ± 3
79
53
26
67
9.6
56 ± 11
28 ± 8
29 ± 8
7.1 ± 2.9
62 ± 44
16 ± 28
110 ± 64
14 ± 6.3
26 ± 5.4
0.59 ± 0.40
372
27
1.0 ± 0.30*
680±190
8-144
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 35 Oral presentations Although many toxic substances introduced into the environment by human activity have been banned or
restricted in use, many persist, especially in soils and sediments, and either they remain in contact with
food webs or can be eventually re-mobilised and taken up by aquatic biota (Catalan et al., 2004; Vives et
al., 2005). The high levels of metals (e.g Hg) and OCs in the tissue of freshwater fish in arctic and alpine
lakes (Grimalt et al., 2001; Vives et al., 2004a) attest to the mobility and transport of these substances in
the atmosphere (Figure 1; Carrera et al., 2002; Fernandez et al., 2002; 2003; van Drooge et al., 2004) and
their concentration in cold regions (Fernandez and Grimalt, 2003).
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 36 Oral presentations Figure 1 Geometric mean concentrations of various OCs in gas phase (bars) compared to mean ambient
temperature (points). The warmest periods generally correlate with higher concentrations of the
compounds in the gas phase. This trend is clearest for the least volatile compounds and at the site of
lowest temperatures (Skalnate Pleso) (based on van Drooge et al., 2004).
Table 3 Concentrations of PAHs in waters from remote sites (mean ± standard deviation) (from Vilanova
et al., 2001b; Fernandez et al., 2005).
Location
Lake Redon May 2001
Lake Redon (1996-8)
Lake Gossenkölle (1996-7)
Esthwaite Water Lake
Raritan Bay (New Jersey)
Hamilton Harbour (Lake
Ontario)
Niagara River
Danube Estuary
Northern Chesapeake Bay
Southern Chesapeake Bay
Hampton (urban)
York River (semiurban)
Elizabeth River (industrial)
Baltic Sea
PAH
particulate
8.5 ± 0.7
0.18 ±0.03
0.41 ± 0.13
0.57 ± 0.34
0.50 ± 0.08
7.0 – 7.1
PAH
PAH total
dissolved
3.4 ± 0.4
12 ± 1.0
0.58 ± 0.2 0.77 ± 0.20
0.27 ± 0.19 0.70 ± 0.21
0.35 ± 0.19 0.86 ± 0.44
0.56 ± 0.06 1.1 ± 0.1
92 ± 32
3.2 – 7.4
10 – 15
45 ± 4
17 ± 5
0.13 – 1.25 0.18 – 0.21
8.7 – 14
3.2
2.9
5.2
5.2
43
23
0.07 – 0.33 0.57- 0.74
0.64 – 1.08
The IPCC (2007) predicts that precipitation will increase in northern Europe and decrease in the
Mediterranean zones by 10 to 20% due to climatic change, and will become more unpredictable
(Cristensen et al., 2007). This translates to an increase in the frequency of extreme hydrological
phenomena such as major droughts and flash floods. These changes in precipitation patterns will
influence the transport and distribution of pollutants as well as their impact on aquatic environments.
For OCs, greater deposition is observed for volatile contaminants (primarily HCH, HCB, and the most
volatile congeners of PCBs, DDEs and DDTs) at higher levels of wet deposition as exemplified in at
Teide in Tenerife (Fig. 8.11) (van Drooge et al., 2001). These results are consistent with the differences in
atmospheric deposition observed in other sites such as Redon Lake, Øvre Neadålsvatn and Gossenkölesee
(Fig. 8.7) (Carrera et al., 2002). Hence, any future decrease in precipitation would imply a drop in the
amounts of these contaminants that enter water bodies.
In contrast, PAH deposition is primarily controlled by particle settling, followed by wet precipitation, and
lastly, air temperature. The two first aspects are fundamental for high molecular weight hydrocarbons,
whereas temperature is most important for the low molecular weight ones (Fernandez et al., 2003).
Volatile heavy metals and POPs present much more cryptic problems than those of habitat change,
acidification or eutrophication. Their effects on communities are largely unknown and difficult to trace,
because they are generally sub-lethal. Health implications for fish and their human consumers are
nonetheless clear and the volatility and condensation effects make it very likely that a warmer climate in
particular will increase their transfer to polar and mountain regions. One of the more poignant
observations of recent years has been that of the widespread contamination even of Antarctic ecosystems
with these substances (Borghini et al., 2005; Bargagli 2008).
However, in the areas closer to emission sites, warmer temperatures may result in higher concentrations
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 37 Oral presentations of these compounds in air than at present. This change will increase the dispersion capacity of
hydrophobic organic pollutants and mercury, leading to higher rates of toxification of humans and higher
organisms through respiration. This effect will also be important for PAHs although in this case the
ultimate environmental impact will depend on the balance between improved combustion sources and
future energy demands, which may increase following population and wealth growth. The implications of
increased temperatures will be similar for mercury. Transformation into methylmercury may be enhanced
at higher temperatures due to increased microbial activity. Higher temperatures in Arctic and northern
environments, where cold conditions currently limit methylation and mercury mobility, are of concern. In
Scandinavia, thousands of lakes have fish with mercury levels above the health guidelines. The projected
decreases in atmospheric precipitation, e.g. rain and snow may further increase these levels due to higher
proportions of groundwater percolating through mercury-rich soils.
Acknowledgements
Financial support was provided by the EU Projects EUROLIMPACS (GOCE-CT-2003-505540) and ArcRisk (FP7-ENV-2008-1226534) and GRACCIE (CSD2007-00067). Financial support from the Generalitat de Catalunya (Research Group
2009SGR1178) is also acknowledged.
References
Bargagli, R. (2008) Environmental contamination in Antarctic ecosystems. The Science of the Total Environment 400, 212-26.
Carrera, G., Fernandez, P., Grimalt, J.O. et al. (2002) Atmospheric deposition of organochlorine compounds to remote high
mountain lakes of Europe. Environmental Science and Technology 36, 2581-2588.
Catalan, J., Ventura, M., Vives, I. & Grimalt, J.O. (2004) The roles of food and water in the bioaccumulation of organochlorine
compounds in high mountain lake fish. Environmental Science and Technology 38, 4269-4275.
Christensen, J.H., Hewitson, B., Busuioc, A. et al (2007) Regional Climate Projections. In: Climate Change 2007: The Physical
Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate
Change [Solomon, S., Qin, D., Manning, M. et al. (eds.)]. Cambridge University Press, Cambridge, United Kingdom and New
York, NY, USA.
Fernandez, P. & Grimalt, J.O. (2003) On the global distribution of persistent organic pollutants. Chimia 57, 514-521.
Fernandez, P., Carrera, G. & Grimalt, J.O. (2005) Persistent organic pollutants in remote freshwater ecosystems. Aquatic
Sciences 67, 263-273.
Fernandez, P., Carrera, G., Grimalt, J.O. et al. (2003) Factors governing the atmospheric deposition of polycyclic aromatic
hydrocarbons to remote areas. Environmental Science and Technology 37, 3261-3267.
Fernandez, P., J.O. Grimalt & R.M. Vilanova (2002) Atmospheric Gas-Particle Partitioning of Polycyclic Aromatic
Hydrocarbons in High Mountain Regions of Europe. Environmental Science and Technology 36, 1162-1168.
Grimalt, J.O., Fernandez, P., Berdié, L. et al. (2001) Selective trapping of organochlorine compounds in mountain lakes of
temperate areas. Environmental Science and Technology 35, 2690-2697.
van Drooge, B.L., Grimalt, J.O., Torres-García, C.J. & Cuevas, E. (2001) Deposition of semi-volatile organochlorine compounds
in the free troposphere of the Eastern North Atlantic Ocean. Marine Pollution Bulletin 42, 628-634.
van Drooge, B.L., Grimalt, J.O., Camarero, L., Catalan, J., Stuchlik, E. & Torres Garcia, C.J. (2004) Atmospheric semivolatile
organochlorine compounds in European high-mountain areas (Central Pyrenees and High Tatras). Environmental Science and
Technology 38, 3525-3532.
Vilanova, R., Fernández, P., Martinez, C. & Grimalt, J.O. (2001a) Organochlorine pollutants in remote mountain lake waters.
Journal of Environmental Quality 30, 1286-1295.
Vilanova, R.M., Fernandez, P., Martinez, C. & Grimalt, J.O. (2001b) Polycyclic aromatic hydrocarbons in remote mountain lake
waters. Water Research 35, 3916-3926.
Vives, I., Grimalt, J.O., Catalan, J., Rosseland, B.O. & Battarbee, R.W. (2004a) Influence of altitude and age in the accumulation
of organochlorine compounds in fish from high mountain lakes. Environmental Science and Technology 38, 690-698.
Vives, I., Grimalt, J.O., Ventura, M. & Catalan, J. (2005) Distribution of polycyclic aromatic hydrocarbons in the food web of a
high mountain lake, Pyrenees, Catalonia, Spain. Environmental Toxicology and Chemistry 24, 1344-1352 (2005)
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 38 Oral presentations Monitoring Perfluorinated Compounds in the Xúquer River
Julián Campo1, Francisca Pérez2, Ana Masia1, Marinel.la Farré2, Yolanda Pico1 and Damià
Barceló2,3
1
2
Environmental and Food Safety Research Group, Faculty of Pharmacy, University of Valencia, Burjassot, Spain
3
Introduction
Perfluorinated compounds (PFCs) are synthetic chemicals with long fluorocarbon chains headed by
different functional groups (carboxylic, sulfonate, sulphonamide, alcohol, etc). Their chemical properties
provide them strong water and oil repellency, thus, PFCs and their precursors are widely used in
industrial and commercial applications, such as electrical wire insulation, specialist circuit boards,
plumbers tape, waterproof membranes for garments (such as Gore-Tex), surgical implants, dental floss,
engine protector additives, non-stick coatings, moulded parts and coatings for use in a wide range of
chemically hostile environments (Liu et al. 2013, Pico et al. 2011). The strength of the carbon-fluorine
bonds confer to PFCs high thermal and chemical stabilities making them highly persistent in the
environment, where they can bio-accumulate and potentially produce adverse effects on human beings
and wildlife (Xu et al. 2013). Because of this, compounds such as perfluorooctane sulfonate (PFOS) and
its precursor, Perfluorooctyl sulfonyl fluoride (POSF), were the first group of PFCs included as Persistent
Organic Pollutants by the Stockholm Convention. The European Union also published a Directive
prohibiting its use since June 2008 (Liu et al. 2013).
Although the International and European Legislations attempt to decrease PFCs levels in the
environment, a clear declining trend in their pollution has not been observed since there is a still growing
demand for substances with their unique properties. However, other short-chain PFCs are replacing
PFOS. Over the last decade, advances in analytical techniques have resulted in studies describing the
occurrence of PFCs in water (including drinking water), sediments, air, organisms, and even in ice caps
(Llorca et al. 2010, 2011, 2012a, Wang et al. 2013). Contamination of aquatic ecosystems with PFCs
results from a combination of point and non-point sources. Some reports suggest that non-point inputs are
responsible for much of the pollution, other state that the most important contribution are point sources
such as sewage treatment plant discharges, as these plants appear to be ineffective eliminating PFCs
(Llorca et al. 2012a, Pico et al 2012).
The aim of the present study was to determine the distribution of 21 PFCs in water, sediments and biota
samples collected in the Xúquer River (East of Spain) to describe the current quality of this Spanish
Mediterranean basin in order to understand the possible effects of global change on ecosystem services.
This river basin host large cities (Cuenca, Requena, Valencia) and, until recently, has suffer uncontrolled
wastewater discharge of both, industrial and human origin.
Experimental
Screened PFCs were chosen after a thorough study of the existing literature considering their solubility
and their possible presence in the matrices analysed. Twenty-one PFCs were selected including 14
perfluorocarboxylic acids (from 4 to 18 carbons), 6 perfluorosulfonates (from 4 to 10 carbons) and one
perfluorosulfonamide. The Júcar basin was designated as a European Pilot River Basin for the
implementation of the WFD and is located in the east of Spain. It has an area of 21,632km2, a main
stream length of approximately 500 km, and an average precipitation of 510 mm/year. Urban water use is
118.64hm3/year for 1,030,979 people, and irrigated area is 187,855ha, consuming 1,394hm3/year. It is a
much regulated basin, with a total reservoir capacity of 2,643hm3. Main industry located in the basin
includes several sectors (automotive, furniture, tiles, etc.).
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 39 Oral presentations Fig.1. Location of the sampling points at the Jucar River Basin
Grab water and sediment samples were collected. PFCs were extracted from sediments with acidified
methanol by ultrasonication and cleaned up by solid-phase extraction (SPE) and from water by SPE using
STRATA X reversed mode cartridges and methanol as eluent (Picó et al. 2012). The chromatographic
instrument was an HP1200 series LC combined with an Agilent 6410 triple quadrupole (QQQ) mass
spectrometer, equipped with an electrospray ionization (ESI) interface working in negative ionization
mode. For fish extraction, the sample was digested using potassium hydroxide in methanol on an orbital
shaker at room temperature. Samples were then centrifuged, and supernatants were directly injected into
the turbulent flow chromatographic system that uses two columns in tandem for clean-up (Llorca et al.
2012b). The triple quadrupole mass spectrometer Thermo Scientific TSQ Vantage (Thermo Fisher
Scientific, San Jose, CA), equipped with a Turbo Ion Spray source was used for analytical purposes.
The recoveries were in the range of 69–110%, 62–103% and 87-110 % for water, sediment and biota with
RSDs (%) ≤ 20 %. LOQs ranged from 0.01 to 2 ng/L for water, from 0.04 to 8 ng/g for sediments, and
from 0.02 to 2.26 pg/µL for biota. A strict quality control was carried out to check the results. So, every
15 samples analysed a procedural blank and a positive control sample were injected. Each water, sludge
and biota samples were analyzed in triplicate and the average concentration is reported
Results and discussions
In terms of detection frequency, most of the PFCs were detected at least once. From the 21 analytes
included in this study, 11 were detected in water and sediment and 14 in biota samples. PFOS,
perfluoropentonic acid (PFPeA) and the perfluorobutanoic acid (PFBA) were the most frequent, being the
sulfonate present in all the biota samples and the acid in all the sediment samples. In fact all samples were
contaminated with at least one PFC. Table 1 summarizes the results of the water monitoring. Of the 21
analytes screened, 10 were not detected. Most of the PFCs were found in less of 30% of the samples.
However, PFBA, PFPeA and perfluoroctanoic acid (PFOA) showed high frequencies (≥ 50 %). PFBA,
perfluorodecanoic acid (PFDA) and PFOS showed concentrations higher than 100 ng/L, as the 644.19
ng/L of PFBA. Also, in the case of the sediments, 10 compounds were not detected. PFBA, PFPeA,
PFOA, perfluorobutane sulfonate (PFBS), PFOS were in more than 50 % of the samples. Concentrations
were from 0.05 ng/g d.w. for PFHxs to 29.19 ng/g d.w. for perfluorobutane sulfonate (PFBS). The
partition coefficients of PFCs between sediment and surface water were estimated using the concentration
of PFCs in the sediment and in the overlaying water at the same sampling sites always that possible
showing an appropriate correlation as previously described (Pico et al. 2012).
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 40 Oral presentations Table 1. Minimum and maximum concentration, mean levels and frequency of PFCs in waters of the
Xúquer River Basin.
Perfluorinted compounds
Min
a
Concentration ng/L
Max
Mean b
Frequency (%)
Mean
c
Perfluorocarboxilic acids (PFA)
Pefluorobutanoic acid (PFBA)
5,21
644,19
49,87
83,12
60
Pefluoropentanoic acid (PFPeA)
0,08
2,82
0,38
0,64
60
Perfluorohexanoic acid (PFHxA)
1,44
18,74
3,82
9,55
40
Pefluoroheptanoic acid (PFHpA)
0,64
20,14
2,22
5,55
40
Perfluoroctanoic acid (PFOA)
0,07
52,15
4,36
8,18
53
Perfluorononanoic acid (PFNA)
0,85
19,80
2,31
8,67
27
Pefluorodecanoic acid (PFDA)
0,09
213,01
14,21
71,06
20
Perfluoroundecanoic acid (PFUdA)
0,62
0,62
0,04
0,62
7
Perflurotridecanoic acid (PFTrDA)
0,04
0,04
0,00
0,04
7
Perfluorotetradecanoic acid (PFTeDA)
0,03
0,04
0,01
0,04
13
Perfluorosulfonates
Perfluorohexane sulfonate (L-PFHxS)
12,07
36,70
3,25
24,38
13
Perfluoroctane sulfonate (L-PFOS)
0,01
127,98
11,29
28,23
40
a
Values different from zero
Considering non-detected as zero
c
Considering only positive results
b
In biota, PFOA was the prevalent compound, it was found in 56% of the samples and also it was at a
higher concentrations ranging from 26 to 151 ng/g wet weight. Other compounds found in the majority of
the fish samples were PFOS and PFHxA.
A
B
Figure 1. Cumulative concentrations of PFCs in each sampling point of the Xúquer River Basin (A)
sediment and (B) water
On the spatial distribution of PFCs in the Júcar River, Figure 1 shows the cumulative concentration in
each sampling point for water and sediment. The highest concentrations in water were at the points
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 41 Oral presentations located in main cities such as Cuenca (JUC2) and Sueca (JUC8), both characterized by the presence of
industrial belts. PFOS was important in water only at the point JUC7 and JUC8, suggests localized
sources that are unique to the study region at this time. Concentrations of PFCs measured in Júcar River
Basin (all ng/L level) did not approach the numerical water quality criteria (all > several μg/L), viz. either
the criteria maximum concentration (CMC) or criteria continuous concentration (CCC) values
The pattern in sediments was different. There is an accumulation of perfluorinated sulfonates in
comparison with water. The accumulation of PFCs in sediments is related to the TOC (Pico et al. 2012),
which ranges from 0.64 (JUC8) to 3,685 (MAG2). The Magro tributary has been historically affected by
regular and episodic sewage inputs (domestic and industrial) on the water quality.
Perfluorosulfonates in biota were at concentrations similar to those found in sediments. The mean value
for PFOS in fish was 46 ng/g wet weight. The values of perfluorosulfonates were also higher than the
values for perfluocarboxylic acids, such as PFOA with a mean concentration of 33 ng/g wet weight.
In summary, all compartment examined in this survey contained measurable concentrations of PFCs.
PFBA, PFBS and PFPeA were typically the most abundant PFC across all sample types.
Conclusion
Methodologies used in this research proved to be feasible and efficient ways for systematic PFCs
determination in different matrices. All samples were contaminated with at least one PFC, 11 were
detected in water and sediment and 14 in biota samples. The higher concentrations in the water samples
located at the most highly inhabited cities, offers some support to the idea that a proportion of the PFC
contamination in Spanish cities is likely to arise from the use and disposal of consumer goods containing
these compounds. Despite the fact that production of L-PFOS ceased in 2002, the results of this study
indicate that it still exists in the marketplace and is actively used. PFCs were detected in different
compartments of the ecosystem where they are bio-accumulating and, potentially, would produce adverse
effects on humans
Acknowledgements
This work has been supported by the Spanish Ministry of Economy and Competitiveness through the projects Consolider-Ingenio
2010 CSD2009, and CGL2011-29703-C02-02.
References
Liu, C.H., Chang, V.W.C. and Gin K.Y.H. Environmental toxicity of PFCs: An enhanced integrated biomarker assessment and
structure-activity analysis. Environ. Toxicol. Chem.. (2013) 32, 2226-2233.
Llorca, M., Farre, M., Pico, Y., Teijon, M.L., Alvarez, J.G. and Barcelo, D. Infant exposure of perfluorinated compounds: Levels
in breast milk and commercial baby food. Environ.Int. (2010) 36, 584-592.
Llorca, M., Farre, M., Pico, Y. and Barcelo, D. Analysis of perfluorinated compounds in sewage sludge by pressurized solvent
extraction followed by liquid chromatography-mass spectrometry. J. Chromatogr. A (2011) 1218, 4840-4846.
Llorca, M., Farre, M., Pico, Y., Muller, J., Knepper, T.P. and Barcelo, D. Analysis of perfluoroalkyl substances in waters from
Germany and Spain. Sci. Total Environ. (2012a) 431, 139-150.
Llorca, M., Pérez, F., Farré, M., Agramunt, S., Kogevinas,M. and Barceló, D. Analysis of perfluoroalkyl substances in cord
blood by turbulent flow chromatography coupled to tandem mass spectrometry. Sci. Total Environ. (2012b) 433, 151-160
Pico, Y., Farre, M., Llorca, M. and Barcelo, D. Perfluorinated Compounds in Food: A Global Perspective. Crit. Rev. Food Sci.
Nut. (2011) 51, 605-625.
Pico, Y., Blasco, C., Farre, M., Barcelo, D. Occurrence of perfluorinated compounds in water and sediment of L'Albufera
Natural Park (Valencia, Spain). Environ. Sci. Pollut. Res. (2012), 19, 946-957.
Wang SL, Wang H, Deng WJ. Perfluorooctane sulfonate (PFOS) distribution and effect factors in the water and sediment of the
Yellow River Estuary, China. Environ. Monit. Assess. (2013) 185,8517-8524.
Xu J, Tian YZ, Zhang Y, et al. Source apportionment of perfluorinated compounds (PFCs) in sediments: Using three
multivariate factor analysis receptor models. J. Hazard. Mat. (2013), 260, 483-488
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 42 Oral presentations First report of pyrethroids in river fish: a case study in Iberian river
basins (Spain)
Cayo Corcellas1, Ethel Eljarrat1 and Damià Barceló1,2
2
Introduction
Pyrethrins are natural insecticides produced by certain species of chrysanthemum. In order to increase
their stability in the environment, some different derivates have been synthesized. These semi-synthetic
compounds are named pyrethroids. They contain 2-3 chiral centers depending on their structure, so each
pyrethroid could contain 2 or 4 enantiomer pairs and different diastereoisomers.
In last decades the usage of pyrethroids has increased widely in the indoor as household insecticides,
insect-control products, pet shampoos and lice treatments, and in the outdoor as agricultural pesticides
and for pest control. Because of that, they are almost ubiquitous and, as long as they are dumped
continuously, they will be always present in the environment. Some authors have already determined
levels of pyrethroid in rivers, in both water and sediment. (Feo, Ginebreda, Eljarrat, & Barcelo, 2010;
Rocha, Ribeiro, Cruzeiro, Figueiredo, & Rocha, 2012).
Despite the assumption that these insecticides are converted to non-toxic metabolites by hydrolysis in
mammals, recent studies showed their presence in dolphins or even in human breast milk (Alonso et al.,
2012; Corcellas et al., 2012). These studies point out a potential bioaccumulation of these insecticides.
Besides, even when their toxicity was supposed low for non-target organisms, it is known the high
toxicity in fish (Feo, Eljarrat, & Barcelo, 2010).
With that background, our study involves for the first time the determination of pyrethroid in fishes and
their isomeric characterization. The fishes were collected from four different Iberian River Basins, e.g.
the Ebro, the Llobregat, the Júcar and the Guadalquivir.
Sampling and methodology
48 samples of different fish species and different size were collected at selected sampling points along
each basin river. Inside each river basin, one selected species of fish was monitored in four, five or even
six sampling points along the river. Besides, diverse species were fished in each sampling point in order
to have more information about that point. The analyzed species were barbels (Luciobarbus sclateri, L.
graellsii, Barbus guiraonis), carps (Cyprinus carpio), trouts (Salmo trutta), gudgeons (Gobio Lozanoi)
and catfishes (Silurus glanis).
Whole fishes were analysed. Each sample corresponded to pool of individuals. Pool samples were
homogenized, freeze-dried and stored until analyses at -20ºC. Sample preparation consisted in an
extraction with hexane:dichloromethane (2:1) and a tandem SPE cleanup with alumina and C18
cartridges. Finally, pyrethroids were determined by a GC-MS-MS system working with negative
chemical ionization. The analytical method included 12 different pyrethroids: bifenthrin, cifluthrin,
cypermethrin, cyhalothrin, deltamethrin, fluvalinate, fenvalerate, permethrin, phenothrin, resmethrin,
tetramethrin and tralomethrin. The samples were analysed twice, first with an achiral GC column and
second with a chiral one.
Results
The first remarkable result was that pyrethroids were detected in all the tested samples, indicating the
bioavailability and bioaccumulation of these pesticides by river fish. Concentrations of pyrethroids in
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 43 Oral presentations fishes ranged between 12 and 4938 ng/g lipid weight (lw), with the highest levels being found in areas
with greater agricultural impact. Table 1 summarizes the general results obtained.
Table 1: Pyrethroid levels in fishes from Iberian river basins (ng/g lw).
River basin
(N)
Ebro (5)
Monitored species
Other species
Species
Range
Mean
C. carpio
46-1017
307
Llobregat
(5+1*)
C. carpio
Guadalquivir
(4)
L. sclateri
20-843
608
Júcar (5)
G. Lozanoi
114-670
327
152-1508
Species (N)
Mean
L. graellsii (4)
114
Silurus glanis (2)
238
L. graellsii (2+1*)
356
Salmo trutta (1*)
4938
C. carpio (1)
140
B. guiraonis (2)
68
Salmo trutta (2)
481
551
N: number of sampling points.
* This sampling point corresponds to a reservoir.
Moreover, these river basins are in different geographical areas, so the pyrethroid usage is assumed to be
different. In that sense, we considered important to evaluate and characterize the individual presence of
each analysed pyrethroid. Generally, the most abundant pyrethroids were permethrin and cypermethrin,
with a maximum contribution of 75 and 72% to the total pyrethroid contamination. In contrast,
fluvalinate, phenothrin and resmethrin were never detected. The following Figure 1 shows the pyrethroid
distribution for each river basin. It is easy to check the different pattern for each river basin, even when
for Ebro and Llobregat were similar. For instance, permethrin is the most abundant pyrethroid in Ebro
and Llobregat basins but cypermethrin is in Guadalquivir and tetramethrin in Júcar River Basin.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 44 Oral presentations Figure 1: Distribution of pyrethroids through each River Basin.
Since pyrethroid isomerism could affect toxicology, isomeric and enantiomeric studies have been also
carried out in order to determine potential isomeric- and/or enantiomeric-selective accumulation
processes by fish. For that purpose, an additional analysis through a chiral GC column was performed.
Some differences between species were found in the enantiomer distribution in samples from the same
sampling point. Figure 2 shows an example of that fact. In it, cypermethrin chromatogram with a chiral
column is represented for a sample of catfish and a sample of barbel both corresponding to the same
sampling point of the Ebro river. It is clear that the trans- isomers (the two not-shadowed peaks) represent
less than the 10% of the total cypermethrin but the cys- isomers (the four shadowed peaks) present
different profiles. Concretely in this case, the first two enantiomers are in an almost racemic mixture in
barbels but catfishes bioaccumulate more of one of these enantiomers.
As a result of this characterization, we could conclude that these enantiomeric profiles depended on the
species but not so much on the sampling point or even the river sampled. That means that there is a
selective accumulation in each species.
Conclusions
This report evaluates for the first time the presence of pyrethroids in fishes. The levels reached up to 4938
ng/g lw. There are significative differences in the distribution pattern of the 13 pyrethroids among river
basins and even among species from the same sampling point. Different enantiomeric profiles were
described for each species. This could imply a selective accumulation depending on the species.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 45 Oral presentations a)
b)
Figure 2: Chromatograms of the enantiomeric separation of cypermethrin in a) barbel sample and b)
catfish sample of the Ebro River. (cys-isomers shadowed)
Acknowledgements
This research was founded by the Spanish Ministry of Science and Innovation through the project SCARCE (Consolider Ingenio
2010 CSD2009-00065). This work has also been partly funded by the Generalitat de Catalunya (Consolidated Research Group
Water and Soil Quality Unit 2009-SGR-965).
References
Alonso, M. B., Feo, M. L., Corcellas, C., Vidal, L. G., Bertozzi, C. P., Marigo, J., Barcelo, D. (2012). Pyrethroids: A new threat
to marine mammals? Environment International, 47, 99-106. doi: 10.1016/j.envint.2012.06.010
Corcellas, C., Feo, M. L., Paulo Torres, J., Malm, O., Ocampo-Duque, W., Eljarrat, E., & Barcelo, D. (2012). Pyrethroids in
human breast milk: Occurrence and nursing daily intake estimation. Environment International, 47, 17-22. doi:
10.1016/j.envint.2012.05.007
Feo, M. L., Eljarrat, E., & Barcelo, D. (2010). Determination of pyrethroid insecticides in environmental samples. Trac-Trends in
Analytical Chemistry, 29(7), 692-705. doi: 10.1016/j.trac.2010.03.011
Feo, M. L., Ginebreda, A., Eljarrat, E., & Barcelo, D. (2010). Presence of pyrethroid pesticides in water and sediments of Ebro
River Delta. Journal of Hydrology, 393(3-4), 156-162. doi: 10.1016/j.jhydrol.2010.08.012
Rocha, M. J., Ribeiro, M. F. T., Cruzeiro, C., Figueiredo, F., & Rocha, E. (2012). Development and validation of a GC-MS
method for determination of 39 common pesticides in estuarine water - targeting hazardous amounts in the Douro River estuary.
International Journal of Environmental Analytical Chemistry, 92(14), 1587-1608. doi: 10.1080/03067319.2011.581366
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 46 Oral presentations Priority and emerging pollutants in southern Spain: overview of some
case studies from the Anquimed research group
Irene Aparicio, Julia Martín, Dolores Camacho-Muñoz, Juan Luís Santos and Esteban Alonso
Introduction
Nowadays, thousands of organic compounds end up into the environment as a result of their production,
applications or consumption rates. Some of these compounds, such as polycyclic aromatic hydrocarbons,
pesticides and polychlorinated biphenyls, have been classified as priority pollutants and are regulated by
legislation. However, there is less information about of other compounds, which are also continuously
discharged to the environment, mainly due to the lack of analytical methodologies for their determination
at low concentrations in complex matrices. Among the emerging contaminants are pharmaceutically
active compounds, surfactants such as linear alkylbenzene sulfonates and nonylphenol ethoxylates,
perfluorinated compounds and flame retardants.
Since its founding in 2004, the research group "Análisis Químico Industrial y Medioambiental"
(Anquimed) from the University of Seville has focused its studies on the occurrence of priority and
emerging contaminants in the environment. The main activities of the group are the development of
analytical methods, environmental monitoring studies, degradation studies and the evaluation of
wastewater treatments in the removal of emerging pollutants.
Development of analytical methods
One of the main challenges, to obtain information about the presence of emerging pollutants in the
environment, is to develop analytical methodologies that allow their determination at low concentration
levels in the complex environmental matrices. Our research group has contributed to this field in three
ways: (i) the development of reliable analytical methods that combine appropriate analytical properties
and low-cost for the routine determination of emerging contaminants in the environment, (ii) the
development of analytical methods for the determination of new groups of significant pollutants, of great
environmental concern, for which the availability of analytical methods is still limited and (iii) the
development of novel sample treatment methods.
The methodologies developed for the routine determination of emerging pollutants involved solid-phase
extraction, for aqueous samples, and ultrasonic-assisted extraction, for solid samples, and determination
by liquid chromatography with diode-array and fluorescence detectors. These methods allowed the
determination of 17 of the most significant pharmaceutically active compounds in wastewater and surface
water (Camacho-Muñoz et al., 2009) and in sewage sludge, soils and sediments (Martín et al., 2010), as
well as the determination of some of the most problematic emerging pollutants (linear alkybenzene
sulfonates, nonylphenol ethoxylates and di(2-ethylhexyl)phthalate) in sewage sludge and in sludgeamended soil (González et al., 2010). The developed methodologies allowed high recoveries (up to 123 %
for aqueous samples and up to 107 % for solid samples) and low limits of quantification (lower than 1
μg/L in aqueous samples and lower than 360 μg/kg in solid samples).
The methods developed of the determination of novel pollutants employed liquid chromatography
coupled to triple-quadrupole-mass spectrometry for the analysis of cytostatic drugs (Martín et al., 2011a)
and liquid chromatography coupled to quadrupole time-of-flight mass spectrometry for the analysis of
classical and novel antidibetic drugs (Martín et al., 2012a). Due to their low consumption rates, these
compounds are present in the environment at low concentrations so the use of advanced analytical tools is
necessary for their determination. The limits of quantitation of the developed methods were 0.1 ng/L and
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 47 Oral presentations 0.4 ng/L, for the analysis of the cytostatic and antidiabetic drugs, respectively. The developed methods
are suitable to be applied to the evaluation of the occurrence and the ecotoxicological risk of these
problematic compounds in aqueous environmental samples such as wastewater or surface water.
The evaluation and development of alternative sample treatment techniques to solid-phase extraction was
studied in order to improve the speed, economy and efficiency of sample treatment and to reduce
interferences from the matrix. Dispersive liquid–liquid microextraction was evaluated showing to be a
useful tool for the determination of organic pollutants in aqueous samples (Martín et al., 2013) with
recoveries up to 80 %. The main advantages of the proposed method, with regards to SPE methods, are
that sample management is facilitated because of the low sample and solvent volumes required, and the
treatment is easier and faster to perform.
Environmental monitoring studies
The analytical methods developed by the group have been applied to the monitorization of emerging
pollutants in several environmental compartments such as wastewater, surface water, sludge, soil and
sediment in order to evaluate their occurrence not only in the aquatic and terrestrial environment but also
in the main sources of releasing emerging pollutants into the environment: urban and industrial
wastewater.
Among the natural systems studied are the unique ecosystems of Doñana National Park (Camacho et al.,
2010a; 2010b; Camacho-Muñoz et al., 2013a)) and Guadalquivir River basin (Martín et al., 2011b). These
studies showed the presence of pharmaceutically active compounds at concentrations up to 4.55 μg/L and
52 μg/kg in surface water and sediments, respectively, from Doñana National Park and up to 0.75 μg/L in
surface water from Guadalquivir River. The antiinflammatory drugs were the therapeutic group at the
highest concentrations, followed by lipid regulators, nervous stimulant and antiepileptic drugs. This
distribution is similar to that observed in effluent wastewater, so effluent wastewater discharges can be
considered as the main source of these compounds to Doñana National Park and Guadalquivir River.
Pharmaceutically active compounds had been monitored in wastewater treatment plants during one-year
period (Santos et al., 2009). The seasonal evolution of the concentrations observed, conditioned to the
therapeutic group, could be related with their human consumption. The potential industrial and urban
sources of pharmaceutically active compounds and other emerging contaminants to the environment have
been studied through their monitorization in wastewater collection systems (Camacho-Muñoz et al.,
2014). This study showed that urban activities were the main source of pharmaceutically active
compounds and linear alkylbenzene sulfonates to the environment while industrial activities contributed
significantly to the discharges of nonylphenol ethoxylates and salicylic acid. Different discharge patterns
were observed: while pharmaceutically active compounds were present at their highest concentration at
the first hours in the morning others, such as linear alkylbenzene sulfonates, nonylphenol ethoxylates and
salicylic acid, showed an hourly distribution similar to water consumption.
Anquimed research group has also carried out monitorization studies of several emerging contaminants in
sewage sludge from wastewater treatment plants (Aparicio et al., 2009; Martín et al., 2012b, 2012c;
González et al., 2010). These studies, carried out in more than 20 wastewater treatment plants from
Andalusia region, showed the presence of linear alkylbenzene sulfonates and nonylphenol ethoxylates at
high concentrations, being, in most of the studied sludge samples, higher than the limit values set by the
European Union Sludge Directive draft published in April 2000 (higher than 78 % in the case of
nonylphenol ethoxylates).
Degradation studies
Degradation studies are of great concern since they do not only provide information about the distribution
of the contaminants in the environment, but also about their persistence in different environmental
compartments. Our research group has performed degradation studies of anionic and non-ionic surfactants
in a typical Mediterranean soil amended with sewage sludge applying winter (12.7 ºC) and summer (22.4
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 48 Oral presentations ºC) conditions (González et al., 2012). The results showed the influence of the temperature in the
degradation of these compounds. The half-life time of linear alkylbenzene sulfonates were lower than 14
days at 12.7 ºC and lower than 7 days at 22.4 ºC. The concentrations were reduced to 5% of the initial
concentration 49 and 21 days after sludge-application to the soil at 12.7 ºC and 22.4 ºC, respectively. In
the case of nonylphenol ethoxylates, an increase of the concentration was observed during the first days
of the experiment as consequence of the degradation of the nonylphenol polyethoxylate compounds.
Their concentrations were reduced to 5% after 63 and 70 days at 12.7 ºC and 22.4 ºC, respectively.
Wastewater treatment evaluation
After their use or consumption, emerging contaminants are discharged to wastewater treatment plants
through sewer systems. The knowledge about their occurrence in wastewater treatments is of great
interest in order to assess the entry of these contaminants into the environment and their potential
environmental effects. Our research group has evaluated the removal of emerging pollutants in different
wastewater treatment systems including conventional (Santos et al., 2009), low-cost (Camacho-Muñoz et
al., 2012a) and tertiary processes (Camacho-Muñoz et al., 2012b).
The occurrence of pharmaceutically active compounds, linear alkylbenzene sulfonates and nonylphenol
ethoxylates has been studied in 17 wastewater treatment plants based on conventional activated sludge
processes (n=4), oxidation ditches (n=8), trickling filter beds (n=1), lagooning (n=2) and constructed
wetlands (n=2) (Camacho-Muñoz et al., 2012a), as well as, in membrane bioreactor technologies
operating with flat sheet, hollow fibre membranes and with reverse osmosis (Camacho-Muñoz et al.,
2012b). Mean removal rates of pharmaceutically active compounds in conventional wastewater
treatments were slightly higher (64%) than those achieved in low-cost treatments (55%). Ibuprofen,
naproxen, salicylic acid and caffeine were the pharmaceutical compounds most efficiently removed,
regardless the wastewater treatment applied, with removal rates up to 99%. Anaerobic lagooning was the
less effective treatment for the removal of the most persistent compounds: carbamazepine and
propranolol.
Mean removal rates of pharmaceutical compounds achieved by membrane bioreactor technologies were
ranged between 7 % (carbamazepine after flat sheet membranes) and 97 % (caffeine after flat sheet
membranes). No significant difference in effectiveness was found among flat sheet and hollow fibre
membranes. However, improvement was obtained for most of the studied organic compounds with the
addition of a reverse osmosis module. In comparison to conventional activated sludge process, membrane
bioreactor technologies allowed higher removal rates for all the studied compounds, except for linear
alkylbenzene sulfonates homologues.
Nowadays, the research of Anquimed group in the topic of wastewater treatments is focused in the
evaluation of new treatment technologies for the removal of emerging pollutants from wastewater. These
technologies include a combination of integrated fixed-film activated sludge and membrane bioreactor
technology followed by reverse osmosis for the achievement of a high-quality effluent, as well as
environmental and sustainable technologies for the removal of emerging contaminants of great
environmental concern from hospital residues.
References
Aparicio, I., Santos, J.L., Alonso, E. Limitation of the concentration of organic pollutants in sewage sludge for agricultural
purposes: a case of study in south Spain. Waste Management (2009), 29, 1747–1753.
Camacho-Muñoz, D., Martín, J., Santos, J.L., Aparicio, I., Alonso, E. An affordable method for the simultaneous determination
of the most studied pharmaceutical compounds as wastewater and surface water pollutants. Journal of Separation Science
(2009), 32, 3064-3073.
Camacho-Muñoz, D., Martín, J., Santos, J.L., Aparicio, I., Alonso, E. Occurrence, temporal evolution and risk assessment of
pharmaceutically active compounds in Doñana Park (Spain). Journal of Hazardous Materials (2010a), 183, 602-608.
Camacho-Muñoz, D., Santos, J.L., Aparicio, I., & Alonso, E. Presence of pharmaceutically active compounds in Doñana Park
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 49 Oral presentations (Spain) main watersheds. Journal of Hazardous Materials (2010b), 177, 1159-1162.
Camacho-Muñoz, D., Martín, J., Santos, J.L., Aparicio, I., Alonso, E. Effectiveness of conventional and low-cost wastewater
treatments in the removal of pharmaceutically active compounds. Water, Air and Soil Pollution (2012a), 223, 2611-2621.
Camacho-Muñoz, D., Martín, J., Santos, J.L., Alonso, E., Aparicio, I., De La Torre, T., Rodriguez, C., Malfeito, J.J. Effectiveness
of three configurations of membrane bioreactors on the removal of priority and emergent organic compounds from wastewater:
comparison with conventional wastewater treatments. Journal of Environmental Monitoring (2012b), 14, 1428-1436.
Camacho-Muñoz, D., Martín, J., Santos, J.L., Aparicio, I., Alonso E. Distribution and risk assessment of pharmaceutical
compounds in river sediments from Doñana Park (Spain). Water, Air and Soil Pollution (2013a), 224, 1665-1679.
Camacho-Muñoz, D., Martín, J., Santos, J.L., Aparicio, I., Alonso, E. Occurrence of surfactants in wastewater: Hourly and
seasonal variations in urban and industrial wastewaters from Seville (Southern Spain). Science of the Total Environment (2014),
468–469, 977-984.
González, M.M., Santos, J.L., Aparicio, I., Alonso, E. Method for the simultaneous determination of the most problematic
families of organic pollutants in compost and compost-amended soil.Analytical and Bioanalytical Chemistry (2010a), 397, 277285
González, M.M., Martín, J., Santos, J.L., Aparicio, I., Alonso, E. Occurrence and risk assessment of nonylphenol and
nonylphenol ethoxylates in sewage sludge from different conventional treatment processes. Science of the Total Environment
(2010b), 408, 563-570.
González, M.M., Martín, J., Camacho-Muñoz, D., Santos, J.L., Aparicio, I., Alonso, E. Degradation and environmental risk of
surfactants after the application of compost sludge to the soil. Waste Management (2012), 32, 1324-1331.
Martín, J., Santos, J.L., Aparicio, I., Alonso, E. Multi-residue method for the analysis of pharmaceutical compounds in sewage
sludge, compost, and sediments by sonication-assisted extraction and LC determination. Journal of Separation Science (2010) 33,
1760-1766.
Martín, J., Camacho-Muñoz, D., Santos, J.L., Aparicio, I., Alonso, E. Simultaneous determination of a selected group of
cytostatic drugs in water using high-performance liquid chromatography-triple-quadrupole mass spectrometry. Journal of
Separation Science (2011a), 34, 3166-3177.
Martín, J., Camacho-Muñoz, D., Santos, J.L., Aparicio, I., Alonso, E. Monitoring of pharmaceutically active compounds on the
Guadalquivir River basin (Spain): occurrence and risk assessment. Journal of Environmental Monitoring (2011b), 13, 20422049.
Martín, J., Buchberger, W., Santos, J.L., Aparicio, I., Alonso, E. High-performance liquid chromatography quadrupole time-offlight mass spectrometry method for the analysis of antidiabetic drugs in aqueous environmental samples. Journal of
Chromatography B, (2012a), 895-896, 94-101.
Martín, J., Camacho-Muñoz, D., Santos, J.L., Aparicio, I., Alonso, E. Occurrence of pharmaceutical compounds in wastewater
and sludge from wastewater treatment plants: removal and ecotoxicological impact of wastewater discharges and sludge
disposal. Journal of Hazardous Materials (2012b), 239-240, 40-47.
Martín, J., Camacho-Muñoz, D., Santos, J.L., Aparicio, I., Alonso, E. Distribution and temporal evolution of pharmaceutically
active compounds alongside sewage sludge treatment. Risk assessment of sludge application onto soils. Journal of Environmental
Management (2012c), 102, 18-25.
Martín, J., Camacho-Muñoz, D., Santos, J.L., Aparicio, I., Alonso, E. Determination of priority pollutants in aqueous samples by
dispersive liquid–liquid microextraction. Analytica Chimica Acta (2013), 773, 60-67.
Santos, J.L., Aparicio, I., Callejón, M., Alonso, E. Occurrence of pharmaceutically active compounds during 1-year period in
wastewaters from four wastewater treatment plants in Seville (Spain). Journal of Hazardous Materials (2009), 164, 1509-1516.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 50 Oral presentations Uptake and Bioaccumulation of Endocrine Disruptors and
Pharmaceutical compounds in Biofilm, Macroinvertebrates, and Fish in
four Mediterranean Rivers
Belinda Huerta1, Victoria Osorio2, Marina Gorga2, Anna Jakimska3, Nuria de Castro4, Lidia
Ponsati1, Isabel Muñoz4, Sandra Pérez2, Mira Petrovic1, 5, Sara Rodríguez-Mozaz1 and Damià
Barceló 1,2
1
2
3
Department of Analytical Chemistry, Chemical Faculty, Gdansk University of Technology, Gdansk, Poland
4
Departament d’Ecologia, Facultat de Biologia, Universitat de Barcelona (UB), Barcelona, Spain
5
Introduction
Many contaminants have been detected in wastewater effluents and surface water in recent years,
including pharmaceuticals (PhACs) and endocrine disrupting compounds (EDCs). Many of these
compounds are not completely removed in the wastewater treatment plants (WWTPs) and are released to
the environment (Gros et al., 2006; Halling-Sørensen et al., 1998; Kolpin et al., 2002; Osorio et al., 2012).
This situation is of special concern in Mediterranean regions, where the WWTP effluents may represent a
high percentage of some streams flow, particularly under water scarcity (Coogan et al., 2007). In surface
waters heavily impacted by WWTP effluents PhACs and EDCs may be present at concentrations that
might cause adverse effects in the aquatic organisms (Garcia et al., 2012). Moreover, as they are
continuously introduced into surface waters, chronic exposure of the affected biota may occurs during a
complete life cycle, and in some cases, in successive generations (Pascoe et al., 2003). PhACs are
designed to modify physiological or biochemical functions in target organisms but the exposure to them
by non-target organisms could also have severe consequences. In the case of EDCs, they are already
defined as compounds able to disrupt endocrine system in many organisms and may also have unexpected
effects in non-target organisms. A better understanding of how these compounds are transferred from
water to biota could help to determine the potential of ecosystem damage associated with the discharge of
WWTP effluent containing these contaminants (Kinney et al., 2008).
It is generally accepted that substances with octanol-water partition coefficient (log KOW) values higher
than or equal to 3 have the potential to bioaccumulate in biological tissues. Many PhACs and EDCs have
a log KOW < 3, and thus, are not expected to bioaccumulate. However, some of these compounds are
lipid soluble and therefore potentially bioaccumulative in the environment (Howard and Muir, 2011).
Moreover, when considering bioaccumulation of PhACs and EDCs in aquatic organisms, one must take
other factors into consideration, such as the different rates of metabolism in various organisms, the
accumulation behaviour of their metabolites, and the uptake and depuration kinetics.
This work describes the presence and bioaccumulation of PhACs and EDCs in aquatic organisms from
different trophic levels – biofilm (basal resource), two macroinvertebrates: Hydropsyche sp, (collectorfilterer insect larvae) and Dreissena polymorpha (zebra mussel), and fish – collected from four rivers
basins in Spain: Ebro, Llobregat, Júcar and Guadalquivir.
Materials and methods
Sampling was performed in 5 points in each of four rivers with Mediterranean fluvial regime (Ebro,
Llobregat, Júcar and Guadalquivir) to achieve a pollution gradient, from the upper points to the lower
points of the rivers. A total of 20 sites were sampled during the summer of 2010 for the analysis of up to
43 multi-class pharmaceuticals and 21 EDCs in aquatic organisms from different trophic levels: biofilm,
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 51 Oral presentations insect larvae, mussels and fish (see Table 1). Samples were homogenized, composited into a single
sample, freeze-dried and kept at minus 20 °C until analysis.
Table 1. Total number of biota samples collected in 2010.Fish sampling included several species in site
(number indicated in parenthesis)
EBRO
LLOBREGAT
JÚCAR
GUADALQUIVIR
Biofilm
4
5
-
-
Insect larvae
2
4
3
3
Zebra mussel
2
-
-
-
Fish (nº species)
20 (3)
20 (2)
20 (7)
20 (2)
Biofilm samples were extracted according to the method developed by Huerta et al (in preparation).
Briefly, 200 mg of freeze-dried sample was extracted in an automated solvent extractor system
(ASE® 350, Dionex), using a mixture of acetonitrile/citric buffer (pH=4) (1:1, v/v) as extraction solvent.
Extracts were further purified using solid phase extraction (SPE) with Oasis HLB cartridges (6 ml, 200
mg).
Macroinvertebrate samples were extracted according to the method developed by Huerta et al (in
preparation). Briefly, samples (200 mg) were placed in a 50-mL Falcon tube with 3 ml of methanol and
vortexed. A sonication tip was applied in 3 cycles of 120 s, with amplitude (intensity) of 30 %. Extracts
were centrifuged at 11000 rpm, for 5 min. Supernatant was collected and 1.5 ml of the extract was taken
for further purification. Extracts were redissolved in 750 μl of H2O/ACN (1:3, 1 % HCOOH, v/v).
OstroTM 96-well plate was placed in a manifold and wells were added 750 of fresh solvent and then
carefully mixed with the extract in the well. After extraction by vacuum, purified extracts were collected.
Fish and mussel samples were extracted according to the method developed by Huerta et al (Huerta et al.,
2013) for the analysis of pharmaceuticals Briefly, approximately 1 g and 0.5 g, respectively, of freezedried sample was extracted in an automated solvent extractor system (ASE® 350, Dionex), using
methanol as extraction solvent. Extracts were evaporated to 1 ml and then 250 μl was passed through a
preparative column in a gel permeation chromatography system for lipid removal. For the analysis of
EDCs a QuEChERS procedure developed by Jamiska et al was applied (Jakimska et al., 2013). Briefly,
0.5 g of homogenized and freeze-dried sample was transferred to a 50-mL centrifuge tube and vortex for
30 s. Then a ceramic homogenizer and water was added and vortexed for 30 s. After vortexing for 1 min
with subsequent addition of ACN, an extraction salt was added directly to the tube and then the mixture
was immediately manually shaken for 1 min. Samples were centrifuged at 11,000 rpm for 4 min. The
ACN layer was transferred to the polypropylene tube containing dSPE sorbents, vortexed for 1 min and
centrifuged for 15 min at 5000 rpm. Supernatant was collected and evaporated to dryness.
Final extracts were collected and redissolved in methanol/water (10:90 (PhACs), 50:50 (EDCs)) for the
analysis by ultra-rapid liquid chromatography tandem mass spectrometry (LC/MS/MS) with electrospray
ionization (ESI) operating in both positive and negative ion mode, according to the method developed by
Gros et al (Gros et al., 2012) for pharmaceuticals and Jakimska et al (Jakimska et al., 2013) for EDCs.
Ultra performance liquid chromatography (UPLC Acquity, Waters, Mildford, USA) coupled to a
QTRAP® 5500 (AB SCIEX, Framingham, USA) was used for instrumental analysis.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 52 Oral presentations Results and Discussion
In the case of EDCs, 12 compounds, out of 18 detected in water and sediment, were also found in biota
samples. Table 2 shows the number of compounds detected in each river basin and organism in relation to
the number of compounds analyzed for each sample’s type. Bisphenol A, propylparaben, TCEP and
triclosan were detected in all the biofilm samples analyzed, TBEP compound in all the macroinvertebrate
samples, and in 95 % of the fish samples. These compounds are also some of the most prevalent
compounds in water and sediment (detected in more than 70 % samples). Compounds like caffeine and
tolyltriazole, although persistently detected in water at considerable concentration in the majority of the
sampling points (up to 572.2 ng/L and 874.9 ng/L, respectively), was only detected in one biota sample at
very low concentration.
Table 2. Number of EDCs detected in aquatic organisms from four Mediterranean rivers.
Compounds detected (compounds analyzed)
EBRO
LLOBREGAT
JÚCAR
GUADALQUIVIR
Biofilm
7 (17)
7 (14)
-
-
Insect larvae
2 (21)
3 (21)
4 (21)
3 (21)
Zebra Mussels
2 (19)
-
-
-
Fish
7 (19)
5 (19)
7 (19)
7 (19)
In the case of PhACs, 20 compounds, out of 77 found in water and sediment, were also detected in
aquatic organisms. Table 3 illustrates the number of compounds detected in each river basin and trophic
level in relation to the number of compounds analyzed for each sample’s type. Most prevalent compound
in biofilm was the antibiotic azythromycin, found in 44 % of the samples. In contrast, the antiinflammatory drug diclofenac was the most ubiquitous compound in fish, as it was detected in different
fish species and in all the river basins. Compounds frequently detected in water, such as acetaminophen
and ibuprofen, with concentrations around 150 ng/L in some sampling sites, were not detected in any
aquatic organism.
Table 3. Number of PhACs detected in aquatic organisms from four Mediterranean rivers.
Compounds detected (compounds analyzed)
EBRO
LLOBREGAT
JÚCAR
GUADALQUIVIR
Biofilm
0 (43)
15 (43)
-
-
Insect larvae
1 (41)
1 (41)
1 (41)
1 (41)
Zebra Mussels
3 (20)
-
-
-
Fish
4 (20)
2 (20)
2 (20)
1 (20)
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 53 Oral presentations Acknowledgements
This study has been co-financed by Spanish Ministry of Economy and Competitiveness through the project SCARCE
(Consolider-Ingenio 2010 CSD2009-00065) the EU Project ECSafeSEAFOOD [FP7-KBBE 311820] and by the European Union
through the European Regional Development Fund (FEDER). This work was partly supported by the Generalitat de Catalunya
(Consolidated Research Group: Water and Soil Quality Unit 2009-SGR-965).
References
Coogan MA, Edziyie RE, La Point TW, Venables BJ. Algal bioaccumulation of triclocarban, triclosan, and methyl-triclosan in a
North Texas wastewater treatment plant receiving stream. Chemosphere 2007; 67: 1911-1918.
Garcia SN, Foster M, Constantine LA, Huggett DB. Field and laboratory fish tissue accumulation of the anti-convulsant drug
carbamazepine. Ecotox. Environ. Safe. 2012; 84: 207-211.
Gros M, Petrovic M, Barceló D. Development of a multi-residue analytical methodology based on liquid chromatographytandem mass spectrometry (LC-MS/MS) for screening and trace level determination of pharmaceuticals in surface and
wastewaters. Talanta 2006; 70: 678-690.
Gros M, Rodríguez-Mozaz S, Barceló D. Fast and comprehensive multi-residue analysis of a broad range of human and
veterinary pharmaceuticals and some of their metabolites in surface and treated waters by ultra-high-performance liquid
chromatography coupled to quadrupole-linear ion trap tandem mass spectrometry. J. Chromatogr. A 2012; 1248: 104-121.
Halling-Sørensen B, Nors Nielsen S, Lanzky PF, Ingerslev F, Holten Lützhøft HC, Jørgensen SE. Occurrence, fate and effects of
pharmaceutical substances in the environment: A review. Chemosphere 1998; 36: 357-393.
Howard PH, Muir DC. Identifying new persistent and bioaccumulative organics among chemicals in commerce II:
pharmaceuticals. Environ Sci Technol 2011; 45: 6938-46.
Huerta B, Jakimska A, Gros M, Rodriguez-Mozaz S, Barcelo D. Analysis of multi-class pharmaceuticals in fish tissues by ultrahigh-performance liquid chromatography tandem mass spectrometry. J Chromatogr A 2013; 1288: 63-72.
Jakimska A, Huerta B, Barganska Z, Kot-Wasik A, Rodriguez-Mozaz S, Barcelo D. Development of a liquid chromatographytandem mass spectrometry procedure for determination of endocrine disrupting compounds in fish from Mediterranean rivers. J
Chromatogr A 2013; 1306: 44-58.
Kinney CA, Furlong ET, Kolpin DW, Burkhardt MR, Zaugg SD, Werner SL, et al. Bioaccumulation of pharmaceuticals and
other anthropogenic waste indicators in earthworms from agricultural soil amended with biosolid or swine manure. Environ Sci
Technol 2008; 42: 1863-70.
Kolpin DW, Furlong ET, Meyer MT, Thurman EM, Zaugg SD, Barber LB, et al. Pharmaceuticals, Hormones, and Other Organic
Wastewater Contaminants in U.S. Streams, 1999-2000: A National Reconnaissance. Environ. Sci. Technol. 2002; 36: 1202-1211.
Osorio V, Marcé R, Pérez S, Ginebreda A, Cortina JL, Barceló D. Occurrence and modeling of pharmaceuticals on a sewageimpacted Mediterranean river and their dynamics under different hydrological conditions. Sci.Total Environ. 2012; 440: 3-13.
Pascoe D, Karntanut W, Müller CT. Do pharmaceuticals affect freshwater invertebrates? A study with the cnidarian Hydra
vulgaris. Chemosphere 2003; 51: 521-528.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 54 Oral presentations Methodological challenges for the determination of endocrine
disruptor compounds in the environment. Comparison of different
analytical strategies
Marina Gorga1, Belinda Huerta2, Sara Rodríguez-Mozaz2, Mira Petrovic2,3, Damià Barceló1,2
1
2
3
Introduction
The Mediterranean river basins are one of the most vulnerable regions of the world to the global change
due to their climatic conditions and their characteristic topographical regions1. Moreover, the high activity
close to the Mediterranean rivers, either industrial or agricultural, intensive use of the water resources,
and the high population density in these zones, are the principals arguments to evaluate the water quality
of these rivers. Focusing our attention on the group of endocrine disruptor compounds (EDCs), during the
last 3 years and within the multipurpose SCARCE project, the occurrence, spatial distribution and
partitioning of this organic contaminants has been evaluated in four river basins of the Iberian Peninsula.
In the literature, there are several analytical methodologies already available for the determination of
EDCs and related organic contaminants in different matrices with acceptable limits of detection (LODs).
These techniques involve different preconcentration or extraction approaches and multi-step clean-up
protocols. Moreover, the analysis of EDCs or related groups of organic micropollutants, combines the
offline analysis with online instrumental techniques in order to minimize the time of analysis, sample
manipulation or reduce the ion suppression.
The objective of this work was the evaluation and comparison of the different techniques used for the
analysis of EDCs in the principal matrices analyzed under the multidisciplinary SCARCE project with
high number of samples and matrices; river water and sediment, waste water and sewage sludge and fishtissue samples.
First approach consisted of an automated online method using Thermo Scientific EQuan/TurboFlowTM
liquid chromatography coupled to a triple quadrupole mass spectrometer (TSQ Vantatge) with an ESI
source for mass spectrometry detection in tandem (LC-LC-MS/MS). EQuanTM methodology2 was used as
a preconcentration technique in less complex water samples (such as groundwater or surface water),
allowing to inject high volumes of samples decreasing considerably the detection limits. TurboFlowTM
technology was used as a purification approach in the case of water samples where the matrix effects
were important (such as waste water or effluents). This methodology is also applied as a clean-up step in
the case of solid matrices, specifically in sediments, sewage sludge and fish.
For the analysis of EDCs in fish a QuEChERS procedure developed by Jakimska et al.3 (2013) was
applied. The performance of this method was compared to the one developed by Huerta4 (2013) et al. for
the analysis of pharmaceuticals in fish and based on a gel permeation chromatography (GPC).
Therefore, a thorough comparison of different approaches was performed in order to select the most
appropriate method for the analysis of EDCs in different types of environmental samples. Figure 1
showed a schematic diagram of the different techniques for the preconcentration or extraction and clean
up applied for the analysis of EDCs in different matrices.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 55 Oral presentations Water samples
Dirty water samples
Solid samples
Preconcentration
Solid Phase
Extraction (SPE)
Extraction
EQuanTM
technique
Purification
River water
River water
Effluent water
Effluent water
Influent waste water
Influent waste water
M1
M2
UltraSonic
Extraction
(USE)
Pressurized
Liquid
Extraction
(PLE)
QuEChERS
method
Purification
Fish
M7
TurboFlowTM
technique
Solid Phase
clean up
Gel Permeation
chromatography
(GPC)
Sediment
Sediment and
sludge
M4
Influent
waste water
M3
M6
Sediment and
sludge
Fish
M8
M5
Analysis by liquid chromatography separation coupled to mass spectrometry detection
(LC-MS/MS)
Methods applied for the analysis of EDCs in the different matrices
Alternative methods applied for the analysis of EDCs in the different matrices
Methods tested and discarded for the analysis of EDCs in the different matrices
Figure 1. Schematic diagram of the different techniques applied for the preconcentration or extraction
and clean up analysis of EDCs in different matrices
Sample collection and methods
River water and sediment samples were collected during two sampling campaigns (2010 and 2011) at 77
sites from Iberian rivers: 24, 14, 15 and 24 sampling points in Ebro, Llobregat, Júcar and Guadalquivir
river basins, respectively. Wastewater and sludge samples were collected during two sampling campaigns
(2010 and 2011) from 16 wastewater treatment plants (WWTPs): 6, 3, 2 and 5 major WWTPs in Ebro,
Llobregat, Júcar and Guadalquivir river basins, respectively. Fish sampling was performed in 5 point in
each of four rivers. A total of 20 sites were samples during the summer of 2010.
The methodology applied for the simultaneous determination of EDCs in water samples is a fully
automated method based on column switching using EQuanTM columns (M2) for an integrated sample
preconcentration and liquid chromatography coupled to tandem mass spectrometry (LC-LC-MS/MS).
A Hypersil GOLDTM Aqua and a C18 reversed-phase column were used as preconcentration and analytical
columns respectively. The injection volume was set at 5mL for river water and 2 mL in the case of
wastewater. The flow-rate through loading column was 1.75 mL/min during the charge step and in the
transfer step its flow rate down to 0.3 mL/min. Chromatographic separation of compounds detected under
NI conditions was performed under gradient elution condition using water and methanol. Compounds
detected under PI conditions were separated with the same gradient program used above and solvents
were water-methanol with 20 mM of ammonium formiate and 0.1% of acetic acid. For a comparison an
offline preconcentration method based on a classical solid phase extraction (SPE) was performed (M1).
For the determination of EDCs in sediments, sewage sludge and fish samples 2g, 1g and 1g of dried
weight (dw) samples were extracted using a pressurized liquid extraction (PLE) fully automated ASE 200
system (Dionex, Sunnyvale, CA, USA). The extraction solvent employed was water:methanol:acetone
(1:2:1) mixture, the temperature 50ºC and the pressure reached 1500 psi. The resulting extract volume
was about 20 mL. This extract was reduced and re-dissolved with 1mL of methanol in the case of
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 56 Oral presentations sediment samples, for sludge and fish samples the redissolution was with 10 mL of methanol. Then, 20 µl
of these extracts were injected into the LC-LC-MS/MS system. In parallel a UltraSonic Extraction (USE)
with the same solvents was used for sediment samples (M4).
For the purification of these samples, an online TurboFlowTM system was applied (M5). Consisted of two
LC columns, one for purification of the sample (Cyclone) and the second for the analytical separation.
The Aria™ TLX system was programmed to control the loading and eluting pump and the LC-LC
conditions for the sample purification and subsequent separation of the target compounds. Furthermore,
an off-line solid phase purification of the extracts of sediment and sludge samples with an SPE oasis
HLB cartridges was also performed for comparison purposes (M6).
As a modification of the technique explained above, a purification online technique for the analysis of
water samples was applied. During the loading step 250 µl of sample was directly injected onto the
TurboFlowTM column at 1mL/min, and the analytes were retained. The other steps were similar to the
others presented before (M3).
Finally, different methodologies developed for the analysis of fish were compared. M7 was based on the
method adapted for the determination of EDCs using a QuEChERS procedure developed by Jamiska et al.
(2013), where 0.5 g of dw sample was transferred to a 50-mL centrifuge tube and vortex for 30 s. Then a
ceramic homogenizer and water was added and vortexed for 30 s. After vortexing with subsequent
addition of ACN, an extraction salt was added directly and shaken for 1 min, samples were centrifuged
and ACN layer was transferred to the polypropylene tube containing dSPE sorbents, vortexed for 1 min
and centrifuged for 15 min at 5000 rpm. Supernatant was collected and evaporated to dryness. Final
extracts were collected and redissolved in methanol/water (50:50, v/v) for the analysis by ultra-rapid-LCMS/MS with an Ultra performance liquid chromatography (UPLC Acquity, Waters, Mildford, USA)
coupled to a QTRAP® 5500 (AB SCIEX, Framingham, USA). This method was compared to the one
developed by Huerta et al. for the analysis of pharmaceuticals in fish (M8).
Results
The new online methodologies (M2, M5, and M3) showed lower limits of detection than the classical
approaches (M2, M5 and M3) for the determination of EDCs in environmental matrices, minimizing the
matrix effects and the time of analysis. Moreover, in general the on-line methodology was capable of
improving the recoveries for all the target compounds analyzed.
Focusing in water samples and comparing the two different online methodologies (M2 and M3), lower
LODs and LOQs were obtained with EQuanTM methodology in the case of river water samples for all
compounds, confirming that this preconcentration technique was appropriate for samples without
complex matrices. For wastewater samples, the best online methodology was the TurboFlowTM approach,
except for: E2 (influent), E1 (influent, effluent), TCC (influent), BPA (influent), OP1EC (effluent,
influent). Table 1 showed LODs of these techniques.
For the analysis of EDCs in water samples an EQuanTM (M2) approach was applied during two
campaigns. Water TurboFlowTM methodology was only applied during the sampling campaign in 2011 in
waste water. Comparing M2 and M3, in general, the results were in the same range, in addition we
detected about 7% more positive results in waste water (2011) due to the lower limit of detection of this
technique.
Fish samples were analyzed using QuEChERS procedure, but applying the TurboFlowTM approach with
lower limits of detection for important EDCs compounds such as hormones, except for E1, a new
complementary results could be obtained, depending of the target compound analyzed and the species of
fish. Table 1 showed LODs of these techniques.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 57 Oral presentations Table 1. LODs for the determination of EDCs in wastewaters and in different species of fish
Compound
M2 EQuan (ng/L)
Surface
river
water
Effluent
water
M3 TurboFlow (ng/L)
Influent
water
Surface
river
water
Effluent
water
Influent
water
QuEChERS M7 (ng/g)
Barbus
graellisii
Cyprinus
carpio
Silurus
glanis
M5 PLE
extraction/TurboFlow
purification (ng/g)
Silurus glanis
Natural and synthetic estrogens and conjugates
Estradiol (E2)
0.037
0.59
5.4
0.61
0.62
3.5
3.09
2.77
0.34
0.36
Estrone (E1)
0.05
0.14
0.14
0.25
0.27
0.28
0.35
0.34
0.06
0.45
Estriol (E3)
0.17
2.3
3.1
0.59
0.63
0.57
3
2.88
2
0.62
Ethinylestradiol (EE2)
0.14
3.8
4.2
0.34
0.45
1.8
0.62
0.81
0.6
0.49
Diethylstilbestrol (DES)
0.043
1.2
2.7
0.57
0.72
0.84
0.01
0.02
0.03
0.015
Estrone 3-sulfate (E1-3S)
0.0038
0.21
0.35
0.054
0.054
0.12
Estriol 3-sulfate (E3-3S)
0.03
0.75
0.99
0.15
0.18
0.18
Estradiol 17-glucuronide (E2-17G)
0.46
2.9
4.2
0.58
0.61
4.3
Estrone 3-glucuronide (E1-3G)
0.056
0.96
3.1
0.2
0.24
0.57
Estriol 16-glucuronide(E3-16G)
0.059
2
7.5
0.42
0.42
0.47
0.27
0.3
0.25
0.22
0.064
Antimicrobials/Disinfectants
Triclosan (TCS)
0.17
1.5
2.1
0.39
0.45
0.46
Triclorocaraban (TCC)
0.036
0.14
0.18
0.16
0.18
0.22
Methylparaben (MeP)
0.2
0.59
1.5
0.23
0.25
0.27
0.04
0.04
0.005
Ethylparaben (EtP)
0.27
1.2
1.4
0.084
0.10
0.16
0.04
0.05
0.004
0.11
Propylparaben (PrP)
0.021
0.35
0.94
0.075
0.10
0.1
0.004
0.01
0.002
0.098
Benzylparaben (BeP)
0.031
0.12
1
0.15
0.2
0.37
0.01
0.02
0.003
0.027
Bisphenol A (BPA)
0.11
0.69
1.4
0.57
0.61
1.7
0.01
0.01
0.003
0.087
Preservatives
Alkylphenolic compounds
Octylphenol (OP)
0.14
1.6
2.9
0.41
0.44
1.1
Nonylphenol (NP)
0.013
0.3
0.71
0.44
0.55
0.59
Octylphenol monocarboxylate (OP1EC)
0.065
0.64
0.87
0.28
0.34
0.4
Nonylphenol monocarboxylate (NP1EC)
0.034
0.076
0.11
0.052
0.06
0.068
Octylphenol monoethoxylate (OP1EO)
17
20
33
37
18
27
Nonylphenol monoethoxylate (NP1EO)
62
125
187
89
105
135
Octylphenol diethoxylate (OP2EO)
0.011
0.092
0.2
0.087
0.091
0.097
Nonylphenol diethoxylate (NP2EO)
0.013
0.11
0.12
0.075
0.084
0.093
1H-Benzotriazole (BT)
0.072
0.16
0.54
0.16
0.17
0.17
0.1
0.06
0.04
0.029
Tolytriazol (TT)
0.013
0.1
0.21
0.082
0.1
0.14
0.12
0.15
0.09
0.0057
0.0024
0.0025
0.034
0.053
0.063
0.098
0.082
0.55
0.36
0.041
0.11
0.084
0.045
0.13
0.091
0.071
0.14
0.35
0.06
0.5
0.1
0.45
0.09
0.25
0.02
0.2
0.13
0.0075
0.0011
0.0034
Anticorrosives
Organophosphorus flame retardants
Tris(butoxyethyl) phosphate (TBEP)
Tris(chloroisopropyl) phosphate (TCPP)
Tris(2-chloroetyhl) phosphate (TCEP)
Acknowledgements
This work was supported by the Spanish Ministry of Economy and Competitivity through the Consolider-Ingenio 2010
CSD2009-00065 project and SGR 2009-SGR00796 of Generalitat de Catalunya. Marina Gorga acknowledges the European
Social Fund and AGAUR (Generalitat de Catalunya, Spain) for their financial support through the FI pre-doctoral grant. Thermo
Scientific and Merck are acknowledged for the gift of LC columns. Marina Gorga acknowledges Alícia Navarro Ortega
(SCARCE project manager) for your coordination of sampling campaigns that it has made possible this study.
References
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Mediterranean rivers. TrAC Trends in Analytical Chemistry (2011) 30(8), 1269-1278.
2. Gorga, M., Petrovic, M., Barceló, D. Multi-residue analytical method for the determination of endocrine disruptors and
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 58 Oral presentations related compounds in river and waste water using dual column liquid chromatography switching system coupled to mass
spectrometry. J Chromatogr A 2013; 1295: 57-66
3. Jakimska A, Huerta B, Barganska Z, Kot-Wasik A, Rodriguez-Mozaz S, Barcelo D. Development of a liquid chromatographytandem mass spectrometry procedure for determination of endocrine disrupting compounds in fish from Mediterranean rivers. J
Chromatogr A 2013; 1306: 44-58.
4. Huerta B, Jakimska A, Gros M, Rodriguez-Mozaz S, Barcelo D. Analysis of multi-class pharmaceuticals in fish tissues by
ultra-high-performance liquid chromatography tandem mass spectrometry. J Chromatogr A 2013; 1288: 63-72.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 59 Oral presentations A monitoring survey of pharmaceuticals in wastewater treatment
plants and river water in four Iberian river basins
Victoria Osorio1, Jaume Aceña1, Sandra Pérez1 and Damià Barceló1,2
1
2
Introduction
There are 3,936 different pharmaceutically active compounds (PhACs) approved in the worldwide market
for human medicine. The majority of them enter into the aquatic environment from two main routes: the
excretion by humans and the direct disposal through domestic wastewater. Despite its previous treatment
in wastewater treatment plants (WWTPs), depending on the efficiency and chemical properties of the
compound, PhACs are able to reach surface and ground waters. Therefore, PhACs are widespread
pollutants. More than 150 PhACs have been detected in the aquatic environment at levels in the ng/L
range. However, little attention has been paid to the behaviour of PhACs in surface waters.
Iberian river basins are characterized by high flow variability, which is strongly influenced by seasonal
rainfall. High levels of emerging organic contaminants have been detected for instance in the Llobregat
river, in which a trend of rising concentrations was paralleled by an increasing number of WWTP outlets
and increasing population density when approaching the river mouth. As a result of global hydrological
change, when water scarcity periods occur, water flow and dilution capacity of the river are reduced and
consequently wastewater effluent constitutes large percentage of the total river flow. On the other hand,
floods contribute to remobilization of pollutants from sediments. As a consequence of both events, the
potential environmental risk of pollutants is expected to increase[1].
Objectives
In this context, the goals of this work were (a) to study the role of WWTPs in PhACs removal, (b) to
assess the importance of WWTPs as source of contaminants in the aquatic environment, (c) to determine
the occurrence of the contaminants at river basin scale and, (d) to investigate their distribution between
water and solid phase. Two extensive field campaigns have been undertaken at different flow conditions
(high and low-medium). Surface waters and sediments were taken in 77 sampling sites along four
representative basins (Llobregat, Ebro, Júcar and Guadalquivir), together with influent and effluent
sewage water from 15 WWTPs. The levels of over 70 pharmaceuticals belonging to different therapeutic
groups were determined. Based on published literature about occurrence and distribution in the aquatic
environment, a list of 70 prescription drugs was defined, classified by its different therapeutic activity
namely, analgesics and anti-inflammatories, histamine H1 and H2 receptor antagonists, b-blockers, antiplatelet agents, treatment of asthma, anticoagulants, lipid regulators, antibiotics, diuretics, psychiatric
drugs, anti-hypertensives, anti-diabetics, x-ray contrast agents and veterinary treatment.
Experimental
To investigate on the fate and distribution of the pollutants in the river basins, surface and sediment
samples were analyzed in both sampling campaigns. Analysis of the pharmaceuticals was performed with
a method adapted from Gros et al.[2] using a multi-residue method based on liquid chromatography
coupled to mass spectrometry after solid-phase extraction. Quantification of pharmaceuticals was carried
out in Multiple Reaction Monitoring (MRM) mode monitoring two transitions per analyte.
Results
Levels of PhACs were detected in the range of ng/L in surface waters, low ng/g range in sediment and
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 60 Oral presentations ng/L to µg/L range in wastewaters. It was observed that the highest levels PhACs were determined in the
Llobregat river basin, followed by the Ebro, Guadalquivir and Júcar. The most widespread and abundant
therapeutic groups in the surface water and sediment samples were analgesics and anti-inflammatories,
followed by diuretics, psychiatric drugs and veterinary pharmaceuticals. Representativeness of
therapeutic groups was different among the four river basins indicating patterns of consumption in the
different areas of study (Figure 1).
Figure 1: Occurrence of PhACs in surface water of the four Iberian river basins
Conclusions
Concerning the elimination study of PhACs in the WWTPs, most of the compounds were detected both in
influent and effluent wastewater. The elimination rates varied largely and were strongly compounddependent but cumulative levels indicate that the water treatment did not completely eliminate the
contaminants and some compounds remain in significant concentrations in the treated effluents.
Considering WWTPs as emission source of PhACs in the Iberian river basins, these compounds were
quantified in surface water and sediment samples in order to gain further insight of the fate and behaviour
of these compounds from the emission source to the control point.
Acknowledgements
Authors would like to thank the Spanish Ministry of Economy and Competitiveness for its financial support through the projects
SCARCE (Consolider-Ingenio 2010 CSD2009-00065). SP acknowledges the contract from the Ramón y Cajal Program of the
Spanish Ministry of Economy and Competitiveness.
References
[1] V. Osorio, S. Pérez, A. Ginebreda, D. Barceló, Environmental Science and Pollution Research 19 (2012) 1013.
[2] M. Gros, S. Rodríguez-Mozaz, D. Barceló, Journal of Chromatography A 1248 (2012) 104.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 61 Oral presentations Sediment core analysis as a tool for reconstructing the contamination
history of aquatic systems. Case study: Jamaica Bay (NY)
Pablo A. Lara-Martín1,2, Eduardo González-Mazo1, and Bruce J. Brownawell2
1
Department of Physical Chemistry, Faculty of Marine and Environmental Sciences, University of Cadiz, Puerto
Real, Spain
2
School of Marine and Atmospheric Sciences, Stony Brook University, Stony Brook, New York, United States
1. Introduction
Aquatic systems are often subjected to the influence of urban and/or industrial wastewater discharges,
which may contain significant amounts of organic contaminants. In spite of their low concentration in the
water column (often sub-ppb levels), these chemicals may cause damage to the ecosystem in the long
term due to chronic exposure. Among them, personal care products and pharmaceutically active
compounds (PPCPs) and some other emerging contaminants have been the focus of many researchers
within the last decade. Most of these studies deal with the identification and distribution of these
chemicals in water bodies [1,2]. Data on the presence of PPCPs in particulate matter and sediments are
still scarce mainly because further analytical method development is required and the sorption capacity of
many of these compounds is very low. In this sense, the present study deals with the identification,
distribution and fate of PPCPs in the sedimentary column; this offers a new insight that allows
reconstructing the history of the contamination of an aquatic system by these compounds.
2. Materials and methods
Sediment sampling was carried out in Jamaica Bay, located on the Southwestern shore of Long Island,
NY. Six waste water treatment plants (WWTPs) discharge roughly 1.1x109 L/day biologically treated
sewage, constituting by far the largest input of freshwater to the Bay. Tidal exchange of water in this
estuarine embayment is restricted by the single opening
to the greater New York Bight. Nine surface sediment
samples were collected from stations A to I (Fig. 1). A
sediment core was sampled in 2008 in the deepest area of
the Bay (up to 15 m) (station B), which is characterized
by high rates of sediment deposition (1-2 cm/year), as
well as the highest levels of organic wastewater
contaminants within Jamaica Bay in both sediments and
overlying waters [2-4]. The sediment core was sectioned
at 2 cm intervals, dried in an oven at 35 °C, and stored at
room-temperature pending analysis. 137Cs, derived from
global fallout from atmospheric testing of nuclear
weapons was used for dating. 7Be, a short-lived (t1/2 = 53
days) natural radionuclide, was detected only in the
surface (0-2 cm) sample indicating deposition within
about a year of core collection. The bottom of the core
dated to approximately 1948.
Figure 1: location of sampling stations (A-I)
at Jamaica Bay (NY). Sediment cores were
collected at station B.
70 different pharmaceutically active compounds (PhACs) were analyzed in these samples, including a
variety of different analgesics, antiimflammatories, antihypertensives, lipid regulators, antibiotics and
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 62 Oral presentations psichyatric drugs. Linear alkylbenzene sulfonate (LAS), an anionic surfactant widely used in personal
care products and cleaners, was also considered, as well as polyethyleneglycols (PEGs), widely used in
all kind of household products and as an excipient in medicine. The analytical protocol, modified from
ref. 5, includes the extraction and purification of PPCPs in sediment samples in order to perform a later
identification and quantification by liquid chromatography – tandem mass spectrometry (LC-MS-MS).
Briefly, samples (1 g) are extracted by pressurized liquid extraction (PLE) using water/methanol 2:1 as
solvent. Three extraction cycles (5 min each) are performed at 100ºC. Later, the extracts (25-30 mL) are
evaporated and redissolved in 100 mL of HPLC water. Solid phase extraction (SPE) is carried out then,
using Oasis HLB cartridges and methanol (10 mL) as eluting solvent. Recoveries are usually above 70%
for most compounds, except those which are most hydrophobic (and therefore harder to be eluted, e.g.,
some antibiotics such as tamoxifen) or those which are too polar to be properly retained in the SPE
sorbent. Limits of detection were usually below 0.1 ng/g.
3. Results and discussion
Analysis of surface samples showed that highest levels of target compounds belonged to stations A and B,
up to 80 ng/g of PhACs and 9.5 mg/kg of LAS. Therefore, station B was selected to sample the sediment
core. First, the vertical distribution of LAS along the sedimentary column was investigated in order to
confirm the dating of the sediment core by radionuclides (Fig. 2), and also to study changes over time in
the WWTP efficiencies and inputs. Sediments from the sampling area (Jamaica Bay) are characterized by
very high burial rates, virtually no benthic infauna, and little biological or physical mixing, with anoxic or
hypoxic conditions prevailing in the near-bottom waters that favour preservation of LAS and other
potentially labile organic contaminants such as pharmaceuticals in these sediments. The vertical profile
for LAS concentration indicates a first appearance of this compound in the sediment record around 1960,
when it started replacing the poorly biodegradable branched alkylbenzene sulfonates (BAS) [7] (also
detected in the sediment core from 1954 to 1967). Two different maxima are observed in the time history
of LAS concentration corresponding to the mid-late-1980s (75 μg/g), and the mid-1960s (250 μg/g).
These changes over time are attributed to upgrades in treatment performance of the local Jamaica WWTP
that occurred in 1963 and 1978 [3]. The profile of LAS concentration remains fairly stable following
1978, so any changes in the concentration of any other organic contaminants are interpreted as resulting
primarily from changing inputs to the WWTPs surrounding Jamaica Bay, which cover largely residential
portions of Queens and Brooklyn Boroughs of New York City.
Figure 2: vertical profiles showing the distribution of radionuclides and anionic surfactants (LAS and
BAS) in sediment cores from station B.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 63 Oral presentations With respect to pharmaceuticals, their concentrations are much lower (< 100 ng/g) than those for anionic
surfactants (up to 250 µg/g) in the same samples, mainly as a consequence of their lower production and
consumption. However, PhACs, as well as PEGs, show a growing trend over the last decades, in
agreement with the continuous increase in the production and use of these chemicals (Fig. 3). Only 16 of
the 70 pharmaceuticals that were analyzed could be detected. Their sediment records are consistent with
first use dates for pharmaceuticals. Some examples are illustrated in Fig. 3. Thus, ibuprofen is an antiinflammatory drug that was first sold in 1974, and it has been very popular since then, so its presence can
be observed in sediments from that date until today showing an average concentration of 10 ng/g. Betablockers such as metoprolol and propanolol are used for hypertension treatment. Propanolol was the first
beta-blocker successfully developed in the 1960s, but then it was replaced during the 1980s for more
effective compounds such as metoprolol (developed in 1978). This is in agreement with the concentration
profiles that we can observe for both compounds along the sediment core. Thus, concentration of
propanolol increases to 3 ng/g from 1977 to 1985, and then it decreases towards the surface of the core.
Moreover, metoprolol became a generic product in 2006, which improved its sales recently and can
explain the exponential increase in its concentration from 5 to 35 ng/g over the last decade. This is true
also for some other pharmaceuticals, such as the antibiotic clarithromycin, developed in 1991 and gone
generic in 2005 (its maximum concentration was detected in the core surface, being 16 ng/g). Psychiatric
drugs, such as carbamazepine or fluoxetine, which are slowly biodegraded in the water column, can be
also detected in sediments in spite of their high solubility. Carbamazepine was released in 1974 and it is
still widely used in epilepsy treatment (average concentration in sediment is 2 ng/g), whereas fluoxetine
(Prozac) is among the most popular antidepressants. It went generic in 2001 and, although their sales have
decreased over the last decade, it is still widely used despite the availability of newer agents (its
concentration is above 10 ng/g in recent sediments).
Figure 3: concentration vertical profiles showing the distribution of PEGs and pharmaceuticals in
sediment cores from station B.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 64 Oral presentations 4. Conclusions
Surfactants and some pharmaceuticals undergo sorption onto sediments and can be preserved under
anoxic conditions in the sedimentary column. In this study, 16 of 70 pharmaceuticals were detected in
sewage impacted marine sediments, reaching concentrations up to 97 ng/g. Concentrations for LAS and
PEG were significantly higher (> 100 µg/g) due to their more extensive use. Analyzing PPCPs in dated
sediment cores collected from sewage polluted areas allows obtaining historical records of these
contaminants. This can be considered as a powerful tool for monitoring the exposure of aquatic systems
to PPCPs during several decades, an also reflects any changes that may occur in their use and
consumption by nearby populations.
Acknowledgements
The authors thank the funds provided by fellowships from the Marie Curie FP7 Program (ref. 228616, BADEPAS) and from the
Spanish Ministry of Science and Education / Fulbright Commission
References
[1] Kolpin DW, Furlong ET, Meyer MT, Thurman EM, Zaugg SD, Barber LB, Buxton HT. 2002. Pharmaceuticals, hormones,
and other organic wastewater contaminants in U.S. Streams, 1999-2000: a national reconnaissance. Environ Sci Technol 36:
1202-1211.
[2] Benotti MJ, Bronwawell BJ. 2007. Distributions of pharmaceuticals in an urban estuary during both dry- and wet-weather
conditions. Environ Sci Technol 41: 5795-5802.
[3] Ferguson PL, Bopp RF, Chillrud SN, Aller RC, Brownawell BJ. 2003. Biogeochemistry of nonylphenol ethoxylates in urban
estuarine sediments. Environ Sci Technol 37: 3499-3506.
[4] Lara-Martín PA, Li X, Bopp RF, Brownawell BJ. 2010. Occurrence of alkyltrimethylammonium compounds in urban
estuarine sediments: behentrimonium as a new emerging contaminant. Environ Sci Technol 44: 7569-7575.
[5] Jelic A, Petrovic M, Barceló D. 2009. Multi-residue method for trace level determination of pharmaceuticals in solid samples
using pressurized liquid extraction followed by liquid chromatography/quadrupole linear ion trap mass spectrometry. Talanta 80:
363-371.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 65 Oral presentations Chemicals of emerging concern in Iberian rivers. Analysis of sources,
environmental exposure and risk
Mira Petrovic1,2, Maja Kuzmanovic3, Damia Barcelo1,3 and Antoni Ginebreda3
1
3
2
Introduction
The identification and determination of emerging contaminants in the aquatic environment has seen a
dramatic progress in recent years along with a rapid development of new analytical techniques. Several
extensive national and multinational monitoring programs have been launched in the last few years in
order to provide comprehensive reconnaissance of the occurrence of various contaminants, with a special
emphasis on pharmaceuticals, hormones and other polar organic wastewater contaminants. Within the
project SCARCE an extensive sampling of water, sediment and biota from four Iberian river basins has
been undertaken in two monitoring campaigns (2010 and 2011). A total of 77 samples of water, 75
sediments, and 63 pools of fish were collected for chemical characterization. At selected locations in the
Llobregat, Ebro, Jucar and Guadalquivir River Basins the levels of over 300 compounds belonging to
different groups of priority (polycyclic aromatic hydrocarbons, organochlorine pesticides, and
alkylphenols), and emerging contaminants (pharmaceuticals, drugs of abuse, personal care products, polar
pesticides, perfluorinated compounds, endocrine disrupting compounds, halogenated flame retardants,
and nanoparticles) have been determined using advanced analytical techniques based on gas
chromatographytandem mass spectrometry and liquid chromatographytandem and hybrid mass
spectrometry.
This work presents a synthesis and critical evaluation of levels for 244 organic emerging contaminants
found in water phase and provides a basis for assessing the risk of exposure to these contaminants. In
order to get better insight into the spatial distribution of contaminants and to pinpoint hot spots impacted
by human and agricultural waste sources, a site-specific Geographical Information Systems (GIS) model
was created, combining sampling site locations and analytical data from each of those sampling points.
ArcMap Software, as the main component of Esri's ArcGIS suite of geospatial processing programs has
been used to create the maps which show the occurrence of organic pollutants along 77 sites located in 4
Iberian river basins measured in SCARCE project, well as their risk to ecosystem at given locations.
Results
156 of the 244 targeted organic chemicals were detected in at least one water sample. The most frequently
detected chemicals (all detected at more than 80% sampling points) were contaminants of industrial
origin phosphate flame retardants and anticorrosive agents benzotriazols, followed by personal care
products parabens, degradation products of industrial detergents alkyphenol exthoxylates, some
pharmaceuticals such as azitromycin, valsartan, gemfibrozil and desloratidine, and pesticides
chlorphyriphos and diazinon, as shown in Fig. 1.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 66 Oral presentations Fig 1. Frequency of detection (at all sampling points)
Typically >50 compounds were detected per site indicating that the targeted chemicals generally occur in
mixtures in the environment and likely originate from a variety of animal and human uses and waste
sources.
Fig. 2. Compounds detected at the highest average concentrations
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 67 Oral presentations In terms of concentrations the compounds found at the highest average concentrations were: nonylphenol
monocarboxylate (NP1EC), tolyltriazole (TT), tris(chloroisopropyl)phosphate (TCPP) found at average
concentrations above 100 ng/L, followed by other 5 contaminants found at average concentrations higher
than 50 ng/L: perfluorobutanoate (PFBA), 1H-benzotriazole, tris(butoxyethyl) phosphate (TBEP),
diuretic hydrocholorthiazide and imazalil, a fungicide widely used in agriculture, particularly in the
growing of citrus fruits (see Fig. 2).
Regarding the spatial distribution of organic emerging contaminants, the Llobregat river was found to be
the most contaminated river basin, showing clear and significant increase in concentrations downstream
the river being the sites near the mouth of the river the ones with the highest contaminants load, as shown
in Fig. 3. In the Ebro river basin several hot spots can be identified, such as sited downstream of main
cities Zaragoza, Pamplona and Vitoria where effluents from wastewater treatment plant are discharged
into the river or its smaller tributaries. Of four studied river basin, Jucar showed to be the least
contaminated.
Fig. 3. Spatial distribution of total organic contaminants
Risk posed by chemical pollutants, expressed in terms of hazard quotient (HQ), by referring
concentrations to acute EC50 (Daphnia, fish, algae) is also estimated. This allows to identifying both hot
spots and priority compounds. Fig. 4. shows spatial distribution of sampling points and corresponding
total HQ for algae distributed among four main group of contaminants (pesticides, pharmaceuticals,
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 68 Oral presentations endocrine disrupters and related compounds and perfluorinated compounds). At majority of sampling
sites pesticides contribute to the major extent to the overall HQ, with the exception of lower Llobregat
where significant contribution from perfluorinated compound and smaller from pharmaceuticals is
observed and several points at Guadalquivir with significant contribution from EDCs of industrial origin
(such as alkylphenols).
Fig. 4. Hot spots: Sampling sites with highest HQ
In terms of individual compounds posing the highest risk several contaminants were identified showing
HQ>1 (for algae) such as prochloraz, an imidazole fungicide, herbicide diuron and triclosan an
antibacterial and antifungal agent.
In summary, this study confirmed the presence of complex mixtures of unregulated contaminants of
various origins in Iberian rivers, thus raising concern about their potential interactive effects.
Acknowldegment
Authors would like to thank the Spanish Ministry of Economy and Competitiveness for its financial support through the project
SCARCE (Consolider-Ingenio 2010 CSD2009-00065)
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 69 Oral presentations Occurrence and in-stream attenuation of wastewater derived
pharmaceuticals in Iberian rivers
Vicenç Acuña1, Daniel von Schiller1, María Jesús García-Galán1, Sara Rodriguez-Mozaz1, Lluís
Corominas1, Ignasi Aymerich1, Mira Petrovic1,2, Manel Poch1,3, Damià Barceló1,4 and Sergi
Sabater1,5
1
3
Laboratory of Chemical and Environmental Engineering (LEQUIA). University of Girona, Girona, Spain
4
5
2
A multitude of pharmaceuticals enter surface waters mainly via discharges of wastewater treatment plants
(WWTPs), and many rise environmental and health concerns (Schwarzenbach et al. 2006, Gros et al.
2007, Pal et al. 2010). Chemical fate models predict the pharmaceutical concentrations along river
networks using estimates of mass loading, dilution and in-stream attenuation (Huset et al. 2008, Alder et
al. 2010). However, current comprehension of the attenuation rates remains a limiting factor for the
development and calibration of predictive models.
We assessed in-stream attenuation of 75 pharmaceuticals in 4 river segments affected by WWTPs and
differing in environmental factors, aiming to characterize the effects of both physicochemical properties
of pharmaceuticals and local environmental factors on the attenuation rates. The study sites encompassed
considerable ranges in terms of hydrogeomorphological and physicochemical characteristics (Table 1).
To estimate the in-stream attenuation rates of nutrients and pharmaceuticals, we calculated the masstransfer coefficient (vf) for each compound at each site following the intrinsic tracers approach (O’Conner
et al. 1988, Writer et al. 2011).The vf is a scale-free parameter accounting for discharge and water depth
differences among sites which has units of length / time and may be thought of as the theoretical velocity
at which a solute moves towards the location of immobilization (i.e., the water / sediment interface;
Stream Solute Workshop 1990).
Table 1. River segments characteristics and impact of the WWTP on them, as ratios of flow and load of
NH4+ between the WWTP effluent (e) and the upstream river station (u). Note that means and standard
deviations are based on 4 locations (d1-d4).
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 70 Oral presentations Our results revealed that in-stream attenuation was highly variable among pharmaceuticals and river
segments (Figure 1). The variability among vf values might be attributed to both the physicochemical
properties of the pharmaceutical compounds and the local environmental variables. The first was reflected
in differences in the mean values among pharmaceutical as well as on the differences among river
segments, and the second in the variability of vf among river segments for each pharmaceutical (Figure 1).
Figure 1: Mean and standard deviations of the mass transfer coefficients (vf) of 34 pharmaceuticals plus
TDN, TDP and DOC (n = 4, study river segments).
Thus, differences in the mean values of vf among pharmaceuticals highlight the relevance of their
physicochemical properties on their in-stream attenuation rates, but none of the considered
physicochemical properties of pharmaceuticals proved to be relevant in determining the mean attenuation
rates. Instead, log Kow influenced the variability of rates among river segments (Figure 2). A plausible
explanation for such a behaviour is that in the case of hydrophobic compounds (with higher log Kow)
sorption to suspended particles and sediment is a dominant process leading to in-stream attenuation
(reduction of concentration in the aqueous phase along the water segment) and as such those compounds
are less exposed to other biotic (biodegradation) and abiotic (photolysis, volatilization) transformation
processes and therefore become the least affected by the variation of environmental conditions. Despite
the low number of river segments included in this study, the environmental differences among sites
introduced large variability in vf values of the pharmaceuticals. Thus, the differences between sites in vf of
pharmaceuticals with low to mid log Kow were mainly driven by phosphorus indicating a coupling to
phosphorus attenuation.
Following results from our first survey, we more thoroughly investigated the in-stream attenuation of a
selection of pharmaceuticals in one of the river segments (Puigcerdà) using a more sophisticated
mechanistic-modelling approach that integrates both the WWTP and the receiving river. Results from this
study allowed us to better comprehend the linkages among biogeochemical and attenuation processes as
well as the role of the mixing zone in water purification.
Together, our results urge scientist to consider in-stream attenuation in rivers driven by processes other
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 71 Oral presentations than dilution, which should be considered in models when aiming to predict loads and concentrations of
pharmaceuticals.
Figure 1: Linear regression between coefficient of variation of the mass transfer coefficients and log Kow.
Dotted lines indicate 95% confidence intervals.
Acknowledgements
This research was supported by a Marie Curie European Reintegration Grant (PERG07-GA-409 2010-259219) and by a Marie
Curie Career Integration Grant (PCIG9-GA-2011-293535) within the 7th European Community Framework Programme, as well
as by the Spanish Ministry of Economy and Competitiveness through the projects SCARCE (Consolider-Ingenio 2010 CSD200900065) and ENDERUS (CTM-2009-13018), and the postdoctoral grants “Juan de la Cierva” (jci-2009-05604 and jci-201006397), and by the European Union through the European Regional Development Fund (FEDER). This work was partly
supported by the Generalitat de Catalunya (Consolidated Research Group: Water and Soil Quality Unit 2009-SGR-965). Prof.
Barceló acknowledges King Saud University for his visiting professorship.
References
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micropollutants in aquatic systems. Science (2006), 313, 1072–1077.
Gros, M., Petrović, M. and Barceló, D. Wastewater treatment plants as a pathway for aquatic contamination by pharmaceuticals
in the Ebro basin (Northeast Spain). Environmental toxicology and chemistry (2007), 26, 1553–1562.
Pal, A., Gin, K. Y.-H., Lin, A. Y.-C. and Reinhard, M. Impacts of emerging organic 436 contaminants on freshwater resources:
review of recent occurrences, sources, fate and effects. The Science of the Total Environment (2010), 408, 6062–6069.
Huset, C. A., Chiaia, A. C., Barofsky, D. F., Jonkers, N., Kohler, H.-P. E., Ort, C., Giger, D. W. and Field, J. A. Occurrence and
mass flows of fluorochemicals in the Glatt Valley watershed, Switzerland. Environmental Science & Technology (2008), 42,
6369–6377.
Alder, A. C., Schaffner, C., Majewsky, M., Klasmeier, J. and Fenner, K. Fate of betablocker human pharmaceuticals in surface
water: comparison of measured and simulated concentrations in the Glatt Valley Watershed, Switzerland. Water Research
(2010), 44, 936–948.
Writer, J. H., Keefe, S. K., Ryan, J. N., Ferrer, I., Thurman, M. E. and Barber, L. B. Methods for evaluating in-stream attenuation
of trace organic compounds. Applied Geochemistry (2011), 26, 344–345.
O’Conner, D. J. Models of sorptive toxic substances in freshwater systems. I. Basic equations. Journal of Environmental
Engineering (1988), 114, 507–532.
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American Benthological Society (1990), 9, 95–119.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 72 Oral presentations Effects of food limitation and pharmaceuticals compounds on the
larval development of a marine invertebrate
Enrique González-Ortegón1, Julián Blasco2, Lewis LeVay1 and Luis Giménez1
2
1
School of Ocean Sciences, Bangor University, Menai Bridge, UK
Instituto de Ciencias Marinas de Andalucía, CSIC, Puerto Real, Spain
We studied the combined effects of pharmaceutical compounds and food limitation on growth,
development and body mass of larval stages of the marine shrimp Palaemon serratus. Effects of emergent
compounds on growth and development of early life stages may be stronger when organisms are under
some additional stress (González-Ortegón et al 2013). Coastal marine organisms such as the marine
shrimp Palaemon serratus develop in a heterogeneous environment characterised by variations in food
conditions (Mann & Lazier 2006). Under food limited conditions larvae of this marine species developed
through an increased number of stages, especially in warmer waters, resulting in increased duration of
development (González-Ortegón and Giménez 2013).
For practical reasons, investigations of pollution effects on larvae are conducted without taking into
account environmental variability. However, multiple-stressor approaches are necessary to study and
model the effect of emergent compounds on larvae of marine coastal species. Previous results on larvae of
Palaemon serratus under different combinations of temperature and salinity conditions demonstrate that
the effects on survival and larval growth were compound-specific and depended on salinity (GonzálezOrtegón et al 2013). Following the multiple-stressor approach, we now studied the effect of three
common pharmaceuticals (Diclofenac, Clofibric Acid and Clotrimazole) on larval development under
food limitation. We hypothesised that the previous effects of these pharmaceuticals on larval survival,
growth and development should be magnified under food limited conditions.
The pharmaceuticals compounds tested were the anti-inflammatory and analgesic Diclofenac Sodium
(DS), the lipid regulator Clofibric Acid (CA) and the fungicide Clotrimazole (CLZ). The larvae were
exposed to concentrations 2 times higher than found in natural habitats (validated concentrations: DS: 70
µg/l, CA: 40 µg/l and CLZ: 0.07 µg/l) and also concentrations 20 times higher than those found in nature
(700, 400 and 4 µg/l, respectively). Larvae were reared at 24˚C and full salinity seawater (32 PSU). ).
Freshly hatched Artemia sp. nauplii was added and removed with the culture water after a period of 4 h
(food limited condition) or 24 hours (permanent access to prey).
Clotrimazole had toxic effect at lower concentrations than the others two compounds. Survival varied
between 56 and 96% and was reduced by 30% under the combined effect of food limitation and all
pharmaceuticals treatments (exception: Clofibric Acid at low concentration). The duration of larval
development and number of instars required to reach the juvenile stage was affected by feeding condition.
While food limitation doubled the larval duration of development, the pharmaceuticals did not have any
significant effect. By contrast, the number of stages tended be fewer in larvae exposed to all tested
pharmaceuticals especially in those growing under food limitation. Significant reductions (31%) in the
number of stages were found when larvae were exposed to Clotrimazole at high concentration and to
Clofibric Acid at high concentration under food limitation. The reduction in the number of stages without
any significant variation in the developmental time in larvae exposed to Clotrimazole can be explained by
an increment in the intermoult duration. Growth rate was reduced by Clotrimazole at high concentrations.
However, the significant increase in the intermoult duration under the exposure of Clotrimazole with
respect the rest of treatments explained why juvenile body mass was not affected.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 73 Oral presentations Feeding 24 hours
Feeding 4 hours
High doses
100
100
80
80
60
60
40
40
20
20
60
60
50
50
40
40
30
30
20
20
10
10
14
14
12
*
*
12
10
10
*
8
8
6
6
4
4
Body mass (mg)
-1
Specific growth rate (day )
Number of stages
Duration of development (days)
Survival (%)
Low doses
0.7
0.6
0.5
0.4
0.3
0.2
0.1
*
*
0.7
0.6
0.5
0.4
0.3
0.2
0.1
1.5
1.5
1.2
1.2
0.9
0.9
0.6
0.6
Control
AC
DS
CLZ
Control
AC
DS
CLZ
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 74 Oral presentations CA Low
CA High
DS Low
DS High
CLZ Low
CLZ High
2.2
2.0
1.8
Feeding 24h
1.6
1.4
1.2
Days
1.0
0.8
Feeding 4h
2.2
2.0
1.8
1.6
1.4
1.2
1.0
0.8
1
2
3
4
5
6
7
8
Larval stage
In conclusion, the study identifies the toxic effects of Clotrimazole in the marine environment and shows
that the effects of emergent compounds on larval survival appear to be stronger under food limitation.
Acknowledgements
This work was carried out while E. González-Ortegón was in the tenure of a Marie Curie Pstdoctoral Fellowship from the
European Comission.Furhter financial support was provided by SCARCE (Consolider-Ingenio 2010 CSD2009-00065).
References
González-Ortegón, E., Blasco, J., Le Vay, L. and Giménez, L. A multiple stressor approach to study the toxicity and sublethal
effects of pharmaceutical compounds on the larval development of a marine invertebrate, J. Hazard. Mater. (2013),
http://dx.doi.org/10.1016/j.jhazmat.2013.09.041
González-Ortegón, E. and Giménez, L Environmentally-Mediated Phenotypic Links And Performance In Larvae of a Marine
Invertebrate, Marine Ecology Progress Series (submitted).
Mann, K.H. and Lazier, J.R.N. Dynamics of Marine Ecosystems: Biological–Physical Interactions in the Oceans, (2006)
Blackwell Publishing.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 75 Oral presentations Preliminary results of effects of pharmaceuticals on fresh water
organisms
Gabriela V. Aguirre-Martínez1,2,4, C. Okello1,3, María José Salamanca1, C. Garrido2, T.B.
Henry4,5,6, Tomás A. Del Valls1 and María Laura Martín-Díaz1,2
1
Cátedra UNESCO/UNITWIN/WiCop. Facultad Ciencias del Mar y Ambientales, Universidad de Cádiz, Puerto Real,
Cádiz, Spain
2
Andalusian Center of Marine Science and Technology (CACYTMAR), Puerto Real. Cádiz. Spain
3
Integrated Geoscience Research Group (IGRG), Interdepartmental Centre for Environmental Sciences Research
(CIRSA), University of Bologna, Ravenna, Italy
4
School of Biomedical and Biological Sciences/Marine Institute, University of Plymouth, Plymouth, United Kingdom
5
Center for Environmental Biotechnology, University of Tennessee, Knoxville, USA
6
Department of Forestry, Wildlife and Fisheries, University of Tennessee, Knoxville, USA
Pharmaceuticals are designed with the intention of performing a biological effect to target organisms
(Henschel et al., 1997), a concept that cannot be ignored on the fate and effect of these compounds
towards non-target organisms in the environment that continue to be exposed (Fent et al., 2006). The
continuous entry of pharmaceuticals into the aquatic media via sewage treatment plants (STP) might
cause adverse effects to non-target micro and macro organisms from different taxa. The aim of this
research was to evaluate the effect of six drugs of common occurrence in STPs including caffeine (CAF),
ibuprofen (IBU), carbamazepine (CBZ), novobiocin (NOV), methotrexate (MTX) and tamoxifen (TMX)
on freshwater biota. The toxicity of these compounds were examined in the laboratory to assess acute and
chronic toxicity using as bioindicators the freshwater microalgae Selenastrum capricornotum
(Clorophyta), the clam Corbicula fluminea (Mollusca), and the fish Danio rerio (Chordata) in order to
assess potential sublethal responses after short and long-term exposure to different concentrations of these
drugs (environmental and no-environmental concentrations), including growth inhibition in microalgae,
lysosomal membrane stability (LMS) measured in clams and cyp1a gene expression in zebrafish larvae.
Growth inhibition test using S. capricornutum was performed following the methodology described by
Garrido et al. (2008). Microalgae was exposed to pharmaceutical concentrations of 0.000001, 0.00005,
0.00001, 0.00005, 0.0005, 0.001, 0.005, 0.15, 0.05, 0.5, 5, 50, 100 and 500 mg·L-1. The experiment was
perfomed in triplicate under laboratory conditions. The optical density at a width length of 690 nm was
checked at 0, 24, 48, 72, 96, 120, 144, 168 and 240 hour marks to measure the absorbance signifying
growth. LMS was analyzed in clams heamolymph after 21 days of exposure in laboratory controled
conditions to CAF (0.1, 5, 15, 50 µg·L-1), IBU (0.1, 5, 10, 50 µg·L-1), CBZ, NOV and MTX (0.1, 1, 10, 50
µg·L-1), using the methodology described by Martín-Díaz et al.,(2008). LMS was evaluated using the
neutral red retention time assay (NRRA) following the methodology reported in detail by MartínezGómez et al. (2008) and adapted to the species used in this study. Gene expression analysis was
performed in zebrafish larvae from age 72 to 168 hour post fertilization. Larvae was exposed to CAF,
IBU, CBZ (0.05 and 5 μM) and TMX (0.003 and 0.3 μM) during 96 h in triplicate. Total RNA was
extracted from 30-35 larvae per beaker following q-RT-PCR gene expression analysis (Reinardy et al.,
2013). The relative fold change in cyp1a expression was calculated following Livak and Schmittgen
(2001).
Results indicated that growth rate of S. capricornutum (Fig. 1) was barely affected by CBZ, IBU,
NOV,CAF, TMX and MTX at environmental concentrations.However, CAF at 500 mg·L-1 and MTX at
100 and 500 mg·L-1 affected significantly microalgal growth (p < 0.01). Significant inhibition was also
observed when S. Carpicornotum was exposed to TMX at 50, 100 and 500 mg·L-1 (p < 0.01) being this
drug the most toxic tested. Nevertheless the concentration that provoked an adverse effect on growth rate
on this species of microalgae are not likely to occur in the environment. The EC50 calculated is indicated
in table 1. Results of LMS are shown in figure 2. No diferences were observed between control (120 min)
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 76 Oral presentations and solvent control DMSO (115 min). Environmental concentrations of CAF, IBU, NOV, CBZ and TMX
reduced significantly the NRRT compared with controls and DMSO treatment. At the end of 21 days of
the experiment LMS in C. fluminea was reduced up to 42 % when exposed to 50 μg L-1 of CAF; 53 %
when exposed to 50 μg L-1 of IBU; 58,3 % when exposed to CBZ at 10 and 50 μg L-1; 55 % when
exposed to 0.1 and 10 μg L-1of NOV and 65 % when exposed to 1 μg L-1 of TAM. In addittion, clams
exposed to CBZ and TMX at 1,10 and 50 μg·L-1 were considered to present a diminished health status
(retention time < 45 min). Regarding zebrafish larvae exposed to pharmaceuticals (Fig. 3), it was
observed a significant down-regulation of cyp1a gene expression when larvae were exposed to CAF,
CBZ, and IBU at environmental range (0.05 μM) and at higher concentration range (5 μM) compared to
controls organisms (p < 0.05)(Fig. 2). cyp1a gene expression was also significantly down regulated in
zebrafish exposed to TMX at 0.003 and 0.03 μM.
To conclude, environmental concentrations of selected pharmaceuticals are able to excert adverse effect
in C. fluminea and D. rerio larvae. On the other hand, only high concentrations of pharmaceuticals in the
range of mg·L-1 had an effect in S. capricornotum growth rate. Furthermore endpoints applied in this
study showed the necessity of using more sensitive responses such as LMS and gene expression analysis,
when assessing risk of pharmaceuticals in freshwater environments, since endpoints applied in current
guidelines such as growth inhibition may not be suitable.
Caffeine
Optical density (690nm)
1.4
0
0.00005
0.0005
0.001
0.005
0.015
0.05
0.5
5
50
100
500
1.2
1
0.8
0.6
0.4
Ibuprofen
1.6
1.4
1.6
0.2
0
0.00005
0.0005
0.001
0.005
0.015
0.05
0.5
5
50
100
500
1.2
1
0.8
0.6
0.4
0.2
0
0
24
48
72
96
120
144
168
0
240
0
24
48
72
Time (hrs)
Carbamazepine
1.4
120
144
168
240
0
0.00005
0.0005
0.001
0.005
0.015
0.05
0.5
5
50
100
500
1.2
1
0.8
0.6
0.4
Novobiocin
1.6
1.4
1.6
0
0.00005
0.0005
0.001
0.005
0.015
0.05
0.5
5
50
100
500
1.2
1
0.8
0.6
0.4
0.2
0.2
0
0
0
24
48
72
96
120
144
168
0
240
24
48
72
Time (hrs)
96
120
144
168
240
Time (hrs)
Methotrexate
1.6
Tamoxifen
1.6
0
0.00005
0.0005
0.001
0.005
0.015
0.05
0.5
5
50
100
500
1.2
1
0.8
0.6
0.4
0.2
1.4
1.4
96
Time (hrs)
0
0.000001
0.000005
0.00001
0.00005
0.0005
0.001
0.005
0.015
0.05
0.5
5
50
100
500
1.2
1
0.8
0.6
0.4
0.2
0
0
24
48
72
96
120
144
168
Time (hrs)
240
0
0
24
48
72
96
120
144
168
240
Time (hrs)
Figure 1: Growth inhibition of Selenastum Capricornotum exposed 240 h to selected drugs.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 77 Oral presentations Table 1. EC50 of S. Caprocornutum exposed to selected drugs. (nc= no calculated)
Pharmaceutical
EC 50
Caffeine
290.6 mg L-1
Ibuprofen
≈ 300 < mg L-1
Carbamazepine
nc
Novobiocin
nc
Methotrexate
210 mg L-1
Tamoxifen
26.4 mg L-1
140
140
*
NRRT (min)
100
120
*
*
*
80
60
*
*
100
NRRT (min)
120
*
80
*
60
40
40
20
20
*
0
0
Control
DMSO
0.1
5
15
Control
50
DMSO
0.1
5
15
140
140
120
120
100
*
*
*
*
60
NRRT (min)
100
*
80
50
Ibuprofen concentration (µg/L)
Caffeine concentration (µg/L)
NRRT (min)
*
*
*
60
40
40
20
20
0
*
80
0
Control
DMSO
0.1
1
10
Carbamazepine concentration (µg/L)
50
Control
DMSO
0.1
1
10
Novobiocin concentration (µg/L)
50
140
120
NRRT (min)
100
*
80
*
*
60
*
40
20
0
Control
DMSO
0.1
1
10
Tamoxifen concentration (µg/L)
50
Figure 2: Neutral red retention time (NRRT) analysed in Corbicula fluminea exposed to selected
pharmaceuticals. Asterisks indicate significant differences with control (n = 6; p < 0.05).
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 78 Oral presentations Relative fold change (2-ΔΔCt)
2
1.5
1
0.5
*
*
*
*
*
IBU
0.05
IBU
5
*
*
*
0
Control
CAF
0.05
CAF
5
CBZ
0.05
CBZ
5
TMX
0.003
TMX
0.3
Pharmaceutical concentration (µM)
Figure 3: cyp1a gene expression in D. rerio larvae exposed to caffeine (CAF), carbamazepine (CBZ),
tamoxifen (TMX) and ibuprofen (IBU) at a low and high environmental relevant concentration. Asterisks
indicate significant differences with control (n = 2; p < 0.05).
Acknowledgements
This work was conducted under the framework of the project P09-RNM-5136 (Government of Andalusia, Spain),. Gabriela
Aguirre-Martínez would like to thank the financial support from BECAS CHILE (Government of Chile) and Junta de Andalucia
(Govenrment of Andalucia Spain)
References
Fent, K., Weston, A.A., Caminada, D. Ecotoxicology of human pharmaceuticals, Aquatic Toxicology, (2006), 122-159.
Garrido-Perez, M. C., Perales-VargasMachuca, J. A., Nebot-Sanz, E. & Sales-Marquez, D. Effect of the test media and toxicity of
LAS on the growth of Isochrysis galbana, Ecotoxicology, (2008), 17 (8), 738-746.
Henschel, K.,P.,. Wenzel, A., Diedrich, M., Fliedner, A. Environmental Hazard Assessment of Pharmaceuticals. Regulatory
Toxicology and Pharmacology, (1997), 25, 220–225.
Livak, K.J., Schmittgen, T.D. Analysis of relative gene expression data using real-timequantitative PCR and the 2(T) (−Delta
Delta C) method. Methods, (2001, )25, 402–408.
Martín-Díaz M.L., Jiménez-Tenorio N., Sales D., DelValls T.A. Accumulation and histopathological damage in the clam
Ruditapes philippinarum and the crab Carcinus maenas to assess sediment toxicity in Spanish ports. Chemosphere, (2008) 71,
1916–1927
Martínez-Gómez, C., Benedicto, J., Campilloa, J.A. and Moore M. Application and evaluation of the neutral red retention (NRR)
assay for lysosomal stability in mussel populations along the Iberian Mediterranean coast. Journal of Environmental Monitoring,
(2008), 10, 490-499.
Reinardy, H.C., Scarlett, A.G., Henry, T.B., West, C. E., Hewitt, L.M., Frank, R.A., Rowland, S.J. Aromatic Naphthenic Acids in
Oil Sands Process-Affected Water, Fully Resolved by GCxGC-MS, Weakly Induce the Gene for Vitellogenin Production in
Zebrafish (Danio rerio) Larvae. Environmental Science and Technology, (2013),47 (12), 6614–6620
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 79 Oral presentations Assessment of the water purification ecosystem service regarding instream pharmaceutical residues: exploring the GREAT-ER model
parameters based on data uncertainty
Laurie Boithias1, Rafael Marcé1, Vicenç Acuña1, Joana Aldekoa2, Vicky Osorio3, Mira
Petrović1,4, Felix Francés2, Antoni Ginebreda3 and Sergi Sabater1,5
1
3
2
Universitat Politècnica de València, Valencia, Spain
4
5
Introduction
The attenuation of pharmaceutical residues contamination in the aquatic environment depends on various
complementary processes such as dilution, sorption to sediments, and degradation (i.e. photodegradation
and biodegradation). One of the environmental parameters driving the attenuation of pharmaceutical
contamination is therefore water flow (Petrović et al., 2011). Water scarcity thus poses not only a water
quantity hazard (Boithias et al., 2013), but also a water quality risk, as contaminants become more
concentrated. The removal of pharmaceutical residues within waste water treatment plants (WWTP)
(Gros et al., 2010, 2007; Jelic et al., 2012, 2011; Radjenović et al., 2009, 2007) and the assessment of the
risk posed by pharmaceutical residues in rivers (e.g. Ginebreda et al., 2014, 2010) are already extensively
documented. Very little literature exists that describes the transport and the fate of pharmaceuticals in
surface waters and river networks (Aldekoa et al., 2013; Osorio et al., 2012). Consequently, little is
known about the ability of aquatic ecosystem to provide the water purification ecosystem service which
concerns to pharmaceutical residues removal, included the impact of water scarcity. The objective of this
preliminary study is to assess the ability of the steady-state spatially explicit GREAT-ER model (Boeije
and Koormann, 2003) to simulate the concentration of 5 ubiquitous pharmaceutical compounds
(ketoprofen, diclofenac, carbamazepine, naproxen and acetaminophen) throughout the Llobregat basin in
two contrasted hydrological conditions. Using an uncertainty analysis approach, we evaluated the ability
of the GREAT-ER model when using a 3-parameters model (WWTP and river removal rates, annual
emissions).
Material and method
Study area
The Llobregat River is located in NE Spain, draining an area of 4948 km2. Altitude ranges from 1260 m
at its source in the Pyrenees to 0 m at its mouth in the Mediterranean Sea after a 156 km course. Two
main tributaries join the Llobregat: the Cardener and the Anoia Rivers (Fig. 1). Mean annual precipitation
is 3330 hm3, and mean annual discharge is 693 hm3, the mean discharge at the catchment outlet being
19 m3 s-1. Throughout the basin, the grey water of 59 waste water treatment plants (WWTP) flow into the
river network, together with the effluents of several industrial plants such as potash-mining activities in
the Cardener River (137 hm3 yr-1, 92% coming from the WWTP), therefore sometimes constituting a
significant part of the river flow. The lower course flows through the densely populated area of Barcelona
(>3 million inhabitants), which human-use water is supplied from diverting water from the Cardener and
the Llobregat upstream river courses. To ensure water supply during low flow periods three dams were
built in the upstream sections of the Cardener and the Llobregat rivers (Fig. 1). About 30% of the mean
annual flow in the Llobregat basin is diverted for human uses (Aldekoa et al., 2013; Ginebreda et al.,
2010).
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 80 Oral presentations Fig. 1 Study area (from Aldekoa et al., 2013)
Discharge and pharmaceutical data
Two extensive field campaigns were carried out at different flow conditions in September 2010 and 2011
(with high and low-medium river flow respectively). Daily flow discharges were gathered from the
Catalan Water Agency for 14 gauging stations throughout the basin and for entry and exit flows from the
three reservoirs in the catchment, and for each campaign. Water flow values were calculated for every
river stretch through a water balance considering measured flow levels in 14 points, discharged water
from WWTPs, extracted water for supplying drinking or irrigation water, and the natural water
contribution. Velocity values in every stretch were calculated relating water flow, slope and drained area
with Manning empirical formula using geomorphologic information supplied by the Catalan Water
Agency and from Aguilera et al. (2012). Samples were collected at the 14 gauged sites throughout the
basin. Water sampling and pharmaceutical laboratory analysis were performed as described by Aldekoa et
al. (2013). In addition, pharmaceutical data were gathered from Gros et al. (2010, 2007) and Jelic et al.
(2011) to calculate both the compound removal efficiency in WWTP and the annual emission per
inhabitant (percentiles and average; Table 1).
Table 1 Uncertainty ranges of ketoprofen, diclofenac, carbamazepine, naproxen and acetaminophen
annual emission and WWTP removal rate (REwwtp) in North-Eastern Spain; literature uncertainty range
of the removal rates of the 5 molecules in aquatic environment (REriver)
Emission (kg cap-1 yr-1)
Percentiles
0.025 0.5
0.975
REriver (h-1)
REwwtp (%)
mean
n
Percentiles
0.025 0.5
0.975
mean
n
Percentiles
0.025
0.5
0.975
mean
n
Ketoprofen
0E+00 8E-05 3E-04 1E-04 40
6
84
100
78
36
3E-04
7E-02 1E+00 3E-01
11
Diclofenac
5E-06
6E-05 2E-04 7E-05 40
5
51
100
54
31
1E-03
5E-02 3E+00 4E-01
20
Carbamazepine 1E-06
1E-05 1E-04 2E-05 40
1
25
84
31
20
6E-05
4E-04 6E-02
4E-05
3E-04 9E-04 3E-04 40
35
91
100
83
38
1E-03
5E-03 3E+00 5E-01
12
2E-03 6E-03 2E-03 7
100
100
100
100
6
3E-03
2E-02 6E-02
10
Naproxen
Acetaminophen 2E-04
10E03
2E-02
15
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 81 Oral presentations Modelling approach for pharmaceutical fate modelling
GREAT-ER embeds the spatially explicit flow data previously described. For this exploratory study, we
selected the model “0” of GREAT-ER, where only 3 parameters are involved: the annual emission, and
the WWTP and river rates of pharmaceutical removal (respectively REwwtp and REriver).
Uncertainty analysis and calibration
The uncertainty analysis was performed by propagating the minimal and the maximal values from the
ranges reported in Table 1 for the 5 compounds’ annual emission, REwwtp and REriver. The minimal value
was calculated as the 0.025 percentile whereas the maximal value was calculated as the 0.975 percentile.
The Root Mean Square Error (RMSE) was calculated to quantify the goodness-of-fit between simulated
and observed data at the 14 sampling sites.
Results and discussion
The range of values of the simulated concentrations at the 14 gauging sites varies depending on the inputs
(Fig. 2 and Table 2). The RMSE values highlight that in general for the 5 compounds, the emission value
probably ranges between the median (similar to mean except for naproxen) and the 0.025 percentile.
RMSE differences also appear between 2010 and 2011. As we assume that emission doesn’t change
depending on the climate conditions, the possible calibration levers are REwwtp and REriver whose
efficiencies change with hydraulic retention time (HRT) in WWTP and rivers (Sui et al., 2011). The
RMSE is not sensitive to REwwtp because REwwtp is expressed as a fraction, and changes are therefore
linear.
Table 2 Root Mean Square Error (RMSE, in ng L-1) of the simulated concentrations of ketoprofen,
diclofenac, carbamazepine, naproxen and acetaminophen compared to observed concentrations. Grey
boxes corresponds either to Emission = 0 or to REwwtp = 100%: outputs are null in both cases.
KETOPROFEN DICLOFENAC CARBAMAZEPINE NAPROXEN ACETAMINOPHEN
Case
Emission
#
RE wwtp
RE river
2010
2011
2010
2011
2010
2011
2010
2011
2010
2011
0.5 perc.
0.5 perc.
0.5 perc.
16
122
16
84
14
29
155
616
70
3
1
0.025 perc.
0.025
perc.
0.025
perc.
48
44
38
74
856
1
11
61
120
599
2
0.025 perc.
0.025
perc.
0.975
perc.
48
44
41
82
560
1
26
34
80
408
3
0.025 perc.
0.975
perc.
0.025
perc.
48
44
41
83
856
1
27
36
70
1
4
0.025 perc.
0.975
perc.
0.975
perc.
48
44
41
83
560
1
27
36
70
1
5
0.975 perc.
0.025
perc.
0.025
perc.
208
44
122
516
64
303
642
34
67
15
6
0.975 perc.
0.025
perc.
0.975
perc.
49
44
26
84
35
198
71
36
68
10
7
0.975 perc.
0.975
perc.
0.025
perc.
48
44
41
83
64
303
27
36
70
1
8
0.975 perc.
0.975
perc.
0.975
perc.
48
44
41
83
35
198
27
36
70
1
MEAN
MEAN
MEAN
24
127
24
91
9
47
90
36
69
4
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 82 Oral presentations Fig. 2 Simulated and observed pharmaceutical concentrations (ng L-1) in 2010 and 2011 campaigns for
the cases described in Table 2. Limits Of Quantifications (LOQ) are also reported.
Concluding remarks and future work
This preliminary study showed that it is relevant to parameterize the GREAT-ER “0” model using the
median values of gathered parameter data for most of the compounds. The next step will be to estimate
the weight of both the WWTP and the aquatic ecosystem in attenuating the pharmaceutical
concentrations, depending on hydrological conditions. Therefore, a sensitivity analysis will be performed.
To generalize the conclusion, the study will also include several additional pharmaceutical compounds.
Acknowledgments
This project was funded by the Spanish Ministry of Science and Innovation (Consolider-Ingenio 2010 CSD2009-00065), and by
a Marie Curie European Reintegration Grant (PERG07-GA-2010-259219) within the 7th European Community Framework
Programme.
References
Aguilera, R., Sabater, S., Marcé, R., 2012. In-Stream Nutrient Flux and Retention in Relation to Land Use in the Llobregat River
Basin, in: Sabater, S., Ginebreda, A., Barceló, D. (Eds.), The Llobregat. Springer Berlin Heidelberg, Berlin, Heidelberg, pp. 69–
92.
Aldekoa, J., Medici, C., Osorio, V., Pérez, S., Marcé, R., Barceló, D., Francés, F., 2013. Modelling the emerging pollutant
diclofenac with the GREAT-ER model: Application to the Llobregat River Basin. J. Hazard. Mater.
Boeije, G., Koormann, F., 2003. GREAT-ER II : Chemical Fate Models. 39p.
Boithias, L., Acuña, V., Vergoñós, L., Ziv, G., Marcé, R., Sabater, S., 2013. Assessment of the water supply-demand ratios in a
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 83 Oral presentations Mediterranean basin under different global change scenarios and mitigation alternatives. Sci. Total Environ. In Press.
Ginebreda, A., Kuzmanovic, M., Guasch, H., de Alda, M.L., López-Doval, J.C., Muñoz, I., Ricart, M., Romaní, A.M., Sabater,
S., Barceló, D., 2014. Assessment of multi-chemical pollution in aquatic ecosystems using toxic units: Compound prioritization,
mixture characterization and relationships with biological descriptors. Sci. Total Environ. 468-469, 715–723.
Ginebreda, A., Muñoz, I., de Alda, M.L., Brix, R., López-Doval, J., Barceló, D., 2010. Environmental risk assessment of
pharmaceuticals in rivers: Relationships between hazard indexes and aquatic macroinvertebrate diversity indexes in the Llobregat
River (NE Spain). Environ. Int. 36, 153–162.
Gros, M., Petrović, M., Barceló, D., 2007. Wastewater treatment plants as a pathway for aquatic contamination by
pharmaceuticals in the Ebro river basin (northeast Spain). Environ. Toxicol. Chem. 26, 1553–1562.
Gros, M., Petrović, M., Ginebreda, A., Barceló, D., 2010. Removal of pharmaceuticals during wastewater treatment and
environmental risk assessment using hazard indexes. Environ. Int. 36, 15–26.
Jelic, A., Fatone, F., Di Fabio, S., Petrovic, M., Cecchi, F., Barceló, D., 2012. Tracing pharmaceuticals in a municipal plant for
integrated wastewater and organic solid waste treatment. Sci. Total Environ. 433, 352–361.
Jelic, A., Gros, M., Ginebreda, A., Cespedes-Sánchez, R., Ventura, F., Petrović, M., Barceló, D., 2011. Occurrence, partition and
removal of pharmaceuticals in sewage water and sludge during wastewater treatment. Water Res. 45, 1165–1176.
Osorio, V., Marcé, R., Pérez, S., Ginebreda, A., Cortina, J.L., Barceló, D., 2012. Occurrence and modeling of pharmaceuticals on
a sewage-impacted Mediterranean river and their dynamics under different hydrological conditions. Science of The Total
Environment 440, 3–13.
Petrović, M., Ginebreda, A., Acuña, V., Batalla, R.J., Elosegi, A., Guasch, H., López de Alda, M., Marcé, R., Muñoz, I.,
Navarro-Ortega, A., Navarro, E., Vericat, D., Sabater, S., Barceló, D., 2011. Combined scenarios of chemical and ecological
quality under water scarcity in Mediterranean rivers. TrAC Trends in Analytical Chemistry 30, 1269–1278.
Radjenović, J., Petrović, M., Barceló, D., 2007. Analysis of pharmaceuticals in wastewater and removal using a membrane
bioreactor. Anal. Bioanal. Chem. 387, 1365–1377.
Radjenović, J., Petrović, M., Barceló, D., 2009. Fate and distribution of pharmaceuticals in wastewater and sewage sludge of the
conventional activated sludge (CAS) and advanced membrane bioreactor (MBR) treatment. Water Res. 43, 831–841.
Sui, Q., Huang, J., Deng, S., Chen, W., Yu, G., 2011. Seasonal Variation in the Occurrence and Removal of Pharmaceuticals and
Personal Care Products in Different Biological Wastewater Treatment Processes. Environmental Science & Technology 45,
3341–3348.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 84 Oral presentations Climate Change, Water and Security in the Mediterranean implications for science and policy (a perspective from the CLIMB
project)
Ralf Ludwig and the CLIMB consortium
Ludwig-Maximilians-Universität Munich, Department of Geography, Munich, Germany
The Mediterranean region is experiencing a broad range of threats to water security. According to latest
climate projections, as published in the 5th Assessment Report of the Intergovernmental Panel on Climate
Change (IPCC 2013) or the European Environmental Agency (EEA 2012), the region is at risk due to its
pronounced susceptibility to changes in the hydrological budget and extremes, which is expected to have
strong impact on the management of water resources and on key strategic sectors of regional economies.
Related developments have the capacity to exacerbate tensions, and intra- and inter-state conflict among
social, political, ecological and economic actors. Effective adaptation and prevention policy measures call
for multi-disciplinary analysis and action.
In order to better assess the manifold consequences and uncertainties in climate impact on manenvironment systems, a coordinated topic has been programmed in EU-FP7, bringing together the three
projects CLICO (SSH), WASSERMed (ENV) and CLIMB (ENV) to establish the research cluster
CLIWASEC (Climate Change, Water and Security; www.cliwasec.eu), to improve scientific synergy and
policy outreach.
The current state of the art on climate change research for the Mediterranean region shows large scientific
consensus that climate change is impacting the area in a manifold and distinct fashion. Recently observed
trends and projections from climate model ensembles indicate a strong susceptibility to change in
hydrological regimes, an increasing general shortage of water resources and consequent threats to water
availability and management. Our comprehensive summary highlights threats resulting from decreasing
groundwater resources, strongly increasing drought risk for flash floods, advancing sea-level rise, and
their impact on key strategic sectors of regional economies with consequent macroeconomic and social
implications. It shows that the magnitude of change contains a strong capacity to aggravate tensions that
may lead into conflict among different socio-economic actors. However, it must be clearly stated that
current uncertainties in climate projections and subsequent (hydrological) model chains, a yet incomplete
understanding of the impact of a climate change signal on (micro- and macro-) economic mechanisms,
and the lack of an elaborate and integrated human security conceptual framework are imposing strong
limitations on water-related decision-making under conditions of climate change. This is particularly true
due to the general lack of regional data and the yet unresolved mismatch of spatial and temporal scales of
operation from different scientific perspectives (Ludwig et al. 2011).
The clustering of projects can help push forward current understanding of the interactions of climate
change impacts on ecological, economic and social components of human-environment systems. This is
essential for advancing towards optimized regional solutions for water resources management under
climate change.
The findings from the three projects clearly indicate that climate change is progressing at an
unprecedented pace, increasing the pressures of water scarcity on ecological, economic and social levels.
The cluster approach of working in multiple case studies around the Mediterranean, the Middle East and
Sub-Saharan Africa provides substantial knowledge about the heterogeneity and variability of climate
change impacts. Triggered mostly by a strong increase in temperature and a moderate to strong reduction
and seasonal re-distribution of precipitation, impacts will mostly be felt in water resources management,
agriculture, tourism and its consequent implications on security. Further, CLIMB and the CLIWASEC
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 85 Oral presentations cluster have made substantial progress in assessing the uncertainties in climate change research. An
example for interdisciplinary CLIWASEC research will be illustrated for the common case study in the
Lower Nile Delta, Egypt (Susnik et al. 2013).
The presentation will highlight on a Joint Policy Position Paper, recently published by the three projects,
and intended to discuss and exchange on related implications on policy and decision making from
international, national and regional perspectives. The presentat summarizes the findings of the cluster and
provides recommendations for an improved adaptation to climate change and related threats to water
security in the region.
Finally, CLIMB will launch its GeoPortal, a web-based, public platform to access CLIMB results and
interpretations. The GeoPortal will provide decision makers with a specifically designed tool to better
assess local and regional climate change impacts and related threats to security in high resolution.
Acknowledgements
The contribution from all partners in the CLIMB consortium (GA: 244151), the WASSERMed project (GA: 244255) and the
CLICO project (GA: 244443) is gratefully acknowledged.
References
European Environmental Agency (2012): Climate Change, Impact and Vulnerability in Europe. EEA Report No 12/2012. 304 p.
Intergovernmental Panel on Climate Change (2013): Climate Change 2013. The Physical Science Basis. Summary for Policy
Makers.Working Group 1 contribution to the IPCC Fifth Assessment Report (WG1 AR5). [Stocker, T. F., D. Qin, G.-K. Plattner,
M. Tignor, S. K. Allen, J. Boschung, A. Nauels, Y. Xia, V. Bex and P. M. Midgley (eds.)]. Cambridge University Press,
Cambridge, United Kingdom and New York, NY, USA, in press.
Ludwig, R., Roson, R., Zografos, C. and G. Kallis (2011): Towards an inter-disciplinary research agenda on climate change,
water and security in Southern Europe and Neighbouring countries. In: Environmental Science and Policy.
doi:10.1016/j.envsci.2011.04.003
Susnik, J., Vamvakeridou-Lyroudia, L., Gebert, N., Kloos, J., Renaud, F., Lajeunesse, I., Mabrouk, B., Savic, D., Kapelan, Z.,
Ludwig, R., Fischer, G., Roson, R. and C. Zografos (2013): Interdisciplinary assessment of water-related climate change impacts
on the Lower Nile River, Egypt. Proceedings of the 13th Int. Conf. on Env. Sc. and Tech., Athens; CEST2013.ref: cest13_0382.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 86 Oral presentations Spring snowfall decadal variability over the Alps
Matteo Zampieri1, Enrico Scoccimarro1,2 and Silvio Gualdi1,2
1
EuroMediterranean Center for Climate Change (CMCC), Bologna, Italy
2
INGV, Bologna, Italy
Introduction
The Alps are often called the ‘water towers’ of Europe. In fact, they are the most important freshwater
supply of continental Europe: the Rhine, Po, Rhone and several tributaries of the Danube originate here.
Due to their high elevation, the hydrological cycle of the Alps is largely affected by snow, with important
repercussions for the environment and society (Beniston 2012, Barnett et al 2005). In fact, snow acts as
an insulator of the underlying soil (Clark et al 1999), determining the vegetation distribution and
phenology (Keller et al 2005) and reducing the surface temperature by reflecting solar radiation
(Groisman et al 1994). In the Alps, snow is present from late autumn to spring at a wide range of
altitudes, allowing ski-related tourism (Toeglhofer et al 2011) and determining the seasonality of
hydropower production through the runoff originating from the spring snowmelt (Hanggi and
Weingartner 2012). In the past, potential factors determining snowfall and snow cover variations have
been extensively studied. Temperature variations can alter the partition of solid to liquid precipitation
(Serquet et al 2011, Eccel et al 2012) and the spring snowmelt timing, determining the length of the
snowy season (Laternser and Schneebeli 2003). Therefore, long-term global warming is likely responsible
for the observed reduction of snowfall (Serquet et al 2011) and for the possible continuation of this trend
in the future (Beniston 2012). The potential economic damage to the tourism-related industry could be
quite significant (Elsasser and Messerli 2001). Moreover, climate change can alter the seasonality of
hydropower generation (Finger et al 2012) and hazard related risks (Marty and Blanchet 2012).
Decadal variations in teleconnections considerably complicate the interpretation of the climate change
signal. Therefore, the snowfall trend computed over a few decades can be larger than the effects that
might be attributed solely to climate change. This was evidenced in connection with the retreat of glaciers
in the tropics (Francou et al 2003, Kaser et al 2004). In the Alps, the recent rapid warming and the
associated circulation change have largely contributed to the general reduction of snowfall amount and
snow cover duration observed in the past few decades (Hantel and Hirtl-Wielke 2007, Serquet et al 2011).
The change of circulation affecting winter snowfall over the Alps is well known. In fact, the recent
tendency toward a predominantly positive phase of the North Atlantic Oscillation (NAO; Hurrell 1995)
corresponded to high-pressure, warm and dry weather conditions unfavorable to snow over the Alps,
which has decreased particularly since the 1980s at elevations below 1500–2000 m (see e.g. Bartolini et
al 2001, Beniston 1997, Laternser and Schneebeli 2003, Marty 2008, Durand et al 2009, Valt and
Cianfarra 2010). In this short paper we focus on spring snowfall, which determines the length of the
snowy season. We show that spring snowfall low-frequency (multi-decadal) variability over the Alps is
modulated by the Atlantic Multi-decadal Oscillation (AMO; Schlesinger and Ramankutty 1994). In fact,
the AMO has been recently identified as one of the main natural drivers of the low-frequency variability
of the European climate in spring, summer and autumn (Sutton and Dong 2012) and of the mass balance
of Alpine glaciers (Huss et al 2010). Similarly, we report the occurrence of synchronous shifts of the
AMO phase and spring snowfall amount.
Results
Figure 1 shows the long-term anomalies of temperature (first column), total precipitation (second column)
and solid precipitation (third and fourth columns) related to the AMO phase transitions (displayed in the
different rows) computed on the HISTALP dataset (Auer et al. 2007, Brunetti et al. 2009, Chimani et al.
2011) In each row we list the periods over which we computed the differences, which correspond to
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 87 Oral presentations period of positive (warm) and negative (cold) AMO phase (Suttom and Dong 2012, Einfeld et al 2001).
As for temperature (first column), statistically significant changes are found in the shifts toward warm
AMO in the 1990s and around 1930 (first and third rows of figure 1, respectively). These transitions
correspond to warming of the Alps, more marked on the western side. The largest warming, of about 1.5
C, is recorded during the last AMO transition. Warm to cold AMO transitions that occurred in the early
1960s and around 1900 are displayed in the second and fourth rows, respectively.
Figure 1: From left to right: differences of HISTALP spring temperature, total precipitation observations
and spring snowfall reconstruction (in absolute values and in percentage) due to the four AMO
transitions that occurred in the past 150 years. The periods over which we computed the differences are
listed in each row of the plot. Shading is applied over areas where the statistical significance of the
differences is below the 95% threshold level according to the Mann–Whitney test.
The same analysis conducted for precipitation is shown in the second column of figure 1. With respect to
temperature, precipitation is not characterized by a significant long-termtrend. Despite the larger spatial
variability, the precipitation variations show a relatively similar pattern in every transition. In fact, every
AMO- to AMO+ change (both forward an backward in time) is characterized by a reduction of total
precipitation up to 1 mm/day in the western Alps, i.e, over the French and Swiss territory and
northwestern Italy. A similar signal is found for the southeastern Alps, but with smaller amplitude and not
always statistically significant. In particular, the difference in precipitation is less significant in the last
AMO transition (top panel), most likely because of the shorter period available to compute the averages.
Snowfall (third and last columns) offers the most consistent picture. In fact, snowfall changes are quite
similar for every AMO phase shift. In the cold to warm transition, especially in the last episode, snowfall
inherits the statistical significance of the temperature change. In fact, the temperature rise occurring
during the cold to warm transitions produces statistically significant snowfall reduction at low altitudes.
On the other hand, the snowfall increase, passing from warm to cold AMO periods, is more confined at
higher elevations. Again, the most significant and robust changes of spring snowfall due to AMO shifts
are in the western Alps, where the associated pattern is characterized by a reduction (increase) of about 1
mm/day passing from cold to warm (warm to cold) periods, corresponding to 20–30% of the mean spring
snowfall. The signal is weaker and less significant going back in time, but always consistent in terms of
the spatial pattern.
Sutton and Dong (2012) show that spring precipitation anomalies connected to the AMO in the last two
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 88 Oral presentations transitions were due to a change of circulation, consisting of a ridge of high mean sea level pressure
(MSLP) over central Europe, sandwiched between two troughs (low MSLP) over the northeast Atlantic
Ocean and northeastern Europe. Here, we explore this dynamical link and its physical consequences over
Western Europe for all the AMO transitions in the past 150 years using the 20th Century Reanalysis
(Compo et al. 2011).
Figure 2: Same as figure 1, but computed on the 20th Century Reanalysis 2 meters temperature,
precipitation, mean sea level pressure and cloudiness, plotted on a larger area (30W–30E, 35N–65N).
Figure 2 shows the anomalies of temperature, precipitation, MSLP and cloudiness associated with each
shift. Results for temperature and precipitation are consistent with HISTALP, particularly in the western
Alps, and they confirm the presence of a teleconnection pattern between the North Atlantic basin and the
European continent, which, affecting the atmospheric circulation, contributes to the low-frequency
changes of precipitation. It is worth noting that our results appear to beless significant and stable from the
statistical point of view in the case of the oldest transition. Sutton and Dong (2012) attributed the
temperature anomalies in Western Europe mainly to advection of Northern Atlantic air. In addition to this
effect, we report statistical significant cloudiness anomalies that might explain a portion of the surface
temperature variability related to the AMO.
Althought. It is not possible to extrapolate this results for the future, the next AMO shift could be
expected for the 2020s and it migh profoundly affect the climate of Alps and of Europe.
Acknowledgements
This research has been funded by the Italian Ministry of Education, University and Research and the Italian Ministry of
Environment, Land and Sea under the GEMINA and NEXTDATA projects
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4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 89 Oral presentations Bartolini E, Claps P and D’Odorico P 2001 Connecting European snow cover variability with large scale atmospheric patterns
Adv. Geosci. 26 93–7
Beniston M 1997 Variations of snow depth and duration in the Swiss Alps over the last 50 years: links to changes in large-scale
climatic forcings Clim. Change 36 281–300
Beniston M 2012 Is snow in the Alps receding or disappearing? Wiley Interdiscip. Rev. Clim. Change 3 349–58
Brunetti M, Lentini G, Maugeri M, Nanni T, Auer I, Böhm R and Schöner W 2009 Climate variability and change in the
Greater Alpine Region over the last two centuries based on multi-variable analysis Int. J. Climatol. 29 2197–225
Chimani B, Böhm R, Matulla C and Ganekind M 2011 Development of a longterm dataset of solid/liquid precipitation Adv. Sci.
Res. 6 39–43
Clark M P, Serreze M C and Robinson D A 1999 Atmospheric controls on Eurasian snow extent Int. J. Climatol. 19 27–40
Compo G P et al 2011 The twentieth century reanalysis project Q. J. R. Meteorol. Soc. 137 1–28
Durand Y, Giraut G, Laternser M, Etchevers P, Merindol L and Lesaffre B 2009 Reanalysis of 47 years of climate in the French
Alps (1958–2005): climatology and trends for snow cover J. Appl. Meteorol. Climatol. 48 2487–512
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analysis in Alpine regions Theor. Appl. Climatol. 110 345–58
Elsasser H and Messerli P 2001 The vulnerability of the snow industry in the Swiss Alps Mt. Res. Dev. 21 335–9
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Groisman P Y, Karl T R and Knight R W 1994 Observed impact of snow cover on the heat balance and the rise of continental
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Manag. 26 1231–52
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4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 90 Oral presentations Analysis of climate change effects on water and sediment cycle in a
Mediterranean catchment
Gianbattista Bussi1, Félix Francés1, José Andrés López-Tarazón2,3 and Ramón J. Batalla3,4,5
1
Research Institute of Water and Environmental Engineering, Universitat Politècnica de València, Spain
2
School of Natural Sciences and Psychology, Liverpool John Moores University, UK
3
Department of Environment and Soil Sciences, University of Lleida, Spain
4
5
Forest Science Centre of Catalonia, Solsona, Spain
Introduction
In the last years, the analysis of climate change impact on water resources has been a key environmental
research target. A broadly shared conclusion is that, in Mediterranean areas, average temperature is
expected to increase while average precipitation is expected to decrease. Extreme events are also expected
to increase their magnitude and frequency (Alpert et al., 2002). Nevertheless, little is known about the
impact of climate change on water and sediment cycles at the catchment scale. Past studies focused this
problem, although climate change impact quantification is still a quite difficult task. Given the high
complexity of rainfall – runoff transformation, soil detachment and sediment transport phenomena,
physically based distributed hydrological and environmental modelling is proposed as a tool to estimate
the effect of climate change on water and sediment cycle. In this study, the TETIS hydrological and
sedimentological model (Francés et al., 2007; Bussi et al., 2013) is coupled with climatological model
scenarios in order to obtain climate change-affected series of several hydrological and sedimentological
variables, which are later analysed in order to understand the impact of future climatological evolutions
on hydrology and sediment transport of a highly erodible Mediterranean catchment.
Methods
The TETIS model was implemented at the Ésera River catchment, a medium size catchment (1510 km2)
draining to the Barasona reservoir (storage volume 92.2 Hm3). It is located in the Central Southern
Pyrenees (Spain), in an area characterized by high reliefs and slopes (Fig. 1). Main land uses are pine
forest, shrubland, and arable land. The climate is strongly influenced by the Mediterranean Sea, with dry
winters and torrential rainfall episodes in summer.
Figure 1: Ésera River catchment location
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 91 Oral presentations The catchment is defined as a highly erodible catchment (López-Tarazón et al., 2009), as it shows
frequent badlands areas in its central part. Due to this characteristic, the Barasona reservoir is
experiencing severe siltation since its building (1932). Several bathymetries were carried out since 1984
in order to control the reservoir storage volume. Flushing and dredging operation were also carried out
along the reservoir life, although the extracted volume is unknown.
The TETIS model was implemented at the Éserva River catchment. Meteorological data (precipitation
and temperature) was taken from Spain02 gridded dataset (Herrera et al., 2010). The hydrological submodule was calibrated by adjusting simulated water discharge at the Capella station (Fig. 1) in order to
reproduce observed water discharge records provided by the CEDEX (Experimental Studies Centre). The
hydrological sub-model showed a satisfactory behaviour, as calibration Nash and Sutcliffe efficiency was
0.72 and spatio-temporal validation at the Barasona reservoir obtained an efficiency of 0.71.
The sediment sub-model was calibrated by adjusting simulated total load in order to reproduce the
sediment volume accumulated at the bottom of the Barasona reservoir. The sediment trap efficiency of
the Barasona reservoir was taken into account by using the Brune curves, which provided trap efficiency
raging between 82% and 88%. The deposit dry bulk density was computed by means of the Miller
formula, using Lane and Koelzer coefficients, and validated with measured density values. The chosen
calibration period was from 1998 to 2008. During this period, three bathymetries were carried out,
allowing splitting this period into two sub-series, one used for calibration and the other for validation. The
results are shown in Fig. 2. The model obtained a validation volume error of 23%.
Figure 2: observed vs simulated evolution of the reservoir storage capacity.
The TETIS model was subsequently coupled with meteorological output (precipitation and temperature)
produced by the ARPEGE atmospheric regional model in the framework of the PRUDENCE project
(Christensen et al., 2007). Three climatological scenarios were simulated: a control scenario (1961-1990),
representing the current climate, A2 scenario (2071-2100) and B2 scenario (2071-2100), both
representing two different future climate evolution (elaborated within the Special Report on Emissions
Scenarios). A2 scenario forecasts a stronger temperature increase and precipitation decrease tan B2.
Previous to their use, climatological precipitation and temperatura were corrected in order to reproduce
more precisely the Ésera River catchment climate. The correction was done base on quantiles plots (q-q
plots), as suggested, for example, by Déqué (2007). The results are presented as follows.
Results and conclusions
The Ésera River catchment TETIS model was run using as input the daily temperature and precipitation
series produced by the ARPEGE model. TETIS provided daily series of several hydrosedimentological
variables, such as mean catchment precipitation and temperature, water and sediment discharge, mean
catchment soil moisture and water-equivalent snow depth. Results, presented in Tab. 1, show that
precipitation tends to decrease and temperature tends to increase, as expected. The variation is more
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 92 Oral presentations pronounced for A2 scenario, which is more pessimistic than B2 scenario. These variations cause a strong
decrease in both soil saturation and snow depth. All these hydrometeorological variables affect total water
yield, which is expected to decrease by 40% under A2 scenario and by 35% under B2 scenario.
Nevertheless, sediment yield does not follow the same trend, as it is expected to strongly decrease under
A2 scenario and to increase under B2 scenario. Given the highly non-linear relationship between water
and sediment discharge, an analysis of extreme values is needed in order to understand this apparent
contradiction.
Table 1: model results, averaged on the whole 31-year series and over the entire catchment.
Variable
Precipitation (mm/year)
Temperature (ºC)
Soil saturation (%)
Snow depth (mm eq.)
Water yield (Hm3/year)
Sediment yield (ton/ha/year)
Control
686
7.99
74
49
690
6.33
A2
B2
variation variation
596
12.06
54
15
418
3.62
607
11.01
57
19
446
7.04
In Fig.3 the Gumbel distribution functions of annual maximum of daily precipitation, water discharge and
sediment discharge are shown. They show that extreme values do not behave accordingly to mean values
observed in Tab. 1. This is because extreme precipitation is expected to increase (i.e. precipitation is
expected to become more torrential, as pointed out for example by Alpert et al., 2002). This increase is
not sufficient to obtain increasing values of extreme water discharge, given that the decrease in soil
moisture compensates this effect. Nevertheless, extreme sediment discharge values show an increase
under B2 scenario and a decrease under A2 scenario. This is because B2 scenario is more torrential than
A2 scenario, as can be seen in the extreme daily precipitation plot in Fig. 3.
Figure 3: Gumbel distribution functions of annual maximum daily precipitation, water discharge and
sediment discharge.
Another interesting phenomenon, which can be noted analysing the model results, is the time
compression alteration. Time compression describes the contribution of largest events to the total load. In
this case study, the 5 largest events accounted for 39.6%, 36.9% and 49.8% of total sediment yield for
control, A2 and B2 scenario respectively, the 10 largest events for 52.7%, 54.8% and 65.1% and the 20
largest events for 62.0%, 70.2% and 78.8%. This indicates that time compression is expected to increase,
following model results, and, as a consequence, the Ésera River sediment cycle is expected to become
more large event-dependent in the future, regardless of total sediment load.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 93 Oral presentations Another interesting feature that model results allow analysing is the spatial variation of soil erosion (Fig.
4). The most affected zones are located in the northern part of the catchment, due to high slopes and
badland presence. Soil erosion is expected to expand under B2 scenario and to reduce under A2 scenario.
The main sources of sediments are located in the badland areas in the central part of the catchment for all
scenarios, although for scenario B2 the surface of badland zones appears to increase and for scenario A2
to decrease.
Figure 4: spatial variation of soil erosion (from left to right: control period, A2 scenario and B2
scenario).
Acknowledgements
This study was funded by the research projects SCARCE-CONSOLIDER (ref. CSD2009-00065) and ECOTETIS (ref.
CGL2011-28776-C02-01). Meteorological data was provided by the Spanish Meteorological Agency (AEMET).
References
Alpert, P., Ben-Gai, T., Baharad, A., Benjamini, Y., Yekutieli, D., Colacino, M., Diodato, L., Ramis, C., Homar, V., Romero, R.,
Michaelides, S., Manes, A. The paradoxical increase of Mediterranean extreme daily rainfall in spite of decrease in total values.
Geophysical Research Letters (2002), 29(11), 1536, doi:10.1029/2001GL013554.
Bussi, G., Rodríguez-Lloveras, X., Francés, F., Benito, G., Sánchez-Moya, Y., and Sopeña, A. Sediment yield model
implementation based on check dam infill stratigraphy in a semiarid Mediterranean catchment. Hydrology and Earth System
Sciences (2013), 17(8), 3339–3354, doi:10.5194/hess-17-3339-2013.
Christensen, J. H., Carter, T. R., Rummukainen, M., and Amanatidis, G. Evaluating the performance and utility of regional
climate models: the PRUDENCE project. Climatic Change (2007), 81(S1), 1–6, doi:10.1007/s10584-006-9211-6.
Déqué, M. Frequency of precipitation and temperature extremes over France in an anthropogenic scenario: Model results and
statistical correction according to observed values (2007). Global and Planetary Change, 57(1-2), 16–26,
doi:10.1016/j.gloplacha.2006.11.030.
Francés, F., Vélez, J.I., and Vélez, J.J.. Split-parameter structure for the automatic calibration of distributed hydrological
models. Journal of Hydrology (2007), 332(1-2), 226–240, doi:10.1016/j.jhydrol.2006.06.032.
Herrera, S., Gutiérrez, J.M., Ancell, R., Pons, M.R., Frías, M.D., and Fernández, J.. Development and analysis of a 50-year highresolution daily gridded precipitation dataset over Spain (Spain02). International Journal of Climatology (2010), 32, 74–85,
doi:10.1002/joc.2256.
López-Tarazón, J.A., Batalla, R.J., Vericat, D., and Francke, T., Suspended sediment transport in a highly erodible catchment:
The River Isábena (Southern Pyrenees). Geomorphology (2009), 109, 210–221, doi:10.1016/j.geomorph.2009.03.003.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 94 Oral presentations Sediment dynamics response under global change: Sensitivity Analysis
in a Mediterranean watershed
María Sánchez-Canales1, Alfredo López1, Vicenç Acuña2 and F. Javier Elorza1
1
Universidad Politécnica de Madrid, Escuela Técnica Superior de Ingenieros de Minas, Calle Ríos Rosas 21, 28003
Madrid, Spain
2
Erosion and sediment transport processes are sensitive to Global change, because of their close links to
land cover use and the hydrology of a river basin, both climate and land cover change and to a wide range
of human activities influence erosion and sediment mobilisation and transport (Walling, 2008). The
sediment transport in a watershed is controlled by many factors, including precipitation patterns,
variations in land uses or/and soil characteristics, and slope patterns of erosion and sediment runoff.
We carry out a research concerning the different factors implied in sediment dynamics and their
importance in order to try to deduce the most effective mitigation strategies to respond to global change
effects, with respect to sedimentation, in Mediterranean areas. To address this, we perform a sensitivity
analysis of the InVEST Sediment Retention model (Tallis et al., 2013) in the Llobregat basin (a
Mediterranean region basin in northeastern Spain) for total sediment export and also for total sediment
retained with two different benefits (avoided reservoir sedimentation and water quality).
The service erosion protection, which is the relative contribution of the different parts of the landscape to
sediment retention, is estimated considering the land use patterns that affect sedimentation in downstream
reservoirs. The function sediment retention is calculated as the difference from received (from upstream
cells) and exported sediment. Eroded soil from each cell is estimated using the Universal Soil Loss
Equation (USLE) (Wischmeier & Smith 1978), while the retained amount of sediment by each cell is a
function of the retention coefficients associated to vegetation covers.
After the model is calibrated (Terrado et al., 2012 and briefly description in section ‘supplementary
information’) it is essential to make the model sensitivity analysis. The sensitivity analysis used here is
the Morris method (Morris, 1991), which is a one-at-a-time (OAT) sensitivity analysis method that aims
at isolating the influential parameters from a large number of input parameters. As all SA methods, the
goal of the Morris screening method is to determine the relative influence of each input (xi) on the output
(y). To achieve this, it determines the statistical information of the random variable ∂y/∂xi and uses the
mean (μ) and standard deviation (σ) of ∂y/∂xi at several points in the sample space to deduce the
sensitivity of y to xi. In an extension of the base Morris approach a different sensitivity measure was
defined by Campolongo et al. 2007, it is μ*.
With the sensitivity analysis of the model, we determine which factors of the sediment retention model
are more relevant for the outcome of the model through a sensitivity analysis in order to know which
factors involved in global change affect more sediment dynamics at the Mediterranean basin of Llobregat.
The evaluation of these factors is essential at highly pressured basins in semi-arid Mediterranean area. We
were interested in determining which factors should have more adjusted data to feed the model and above
all, in which ones human management can mitigate sediment erosion.
The results show that, in all cases, any change in climate factors (such as precipitation erosivity or soil
erodibility factors) leads to significant changes in sediment dynamics. However, changes in other factors
as crop-vegetation and management factor or support practice factor, in some cases, might make it
possible to totally or partly compensate the changes in sediment dynamics due to climate change.
References
Campolongo F, Cariboni J and Saltelli A. An effective screening design for sensitivity analysis of large models. Environmental
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 95 Oral presentations Modelling & Software 22 (2007) 1509-1518.
Morris MD, Factorial sampling plans for preliminary computational experiments. Technometric 33 (1991), 161-174.
Tallis HT, Ricketts T, Guerry AD,Wood SA, Sharp R, Nelson, E, Ennaanay D, Wolny S, Olwero N, Vigerstol K, Pennington D,
Mendoza G, Aukema J, Foster J, Forrest J, Cameron D, Arkema K, Lonsdorf E, Kennedy C, Verutes G, Kim CK, Guannel G,
Papenfus M, Toft J, Marsik M, Bernhardt J and Griffin R. InVEST 2.4.2 User’s Guide. The Natural Capital Project, Stanford
(2013).
Terrado M, Honey-Rosés J, Acuña V, Sabater S. Ecosystem Services in an Impacted Watershed. The Handbook of
Environmental Chemistry 21 (2012) 347-368.
Walling DE. Studying the impact of Global Change on erosion and sediment dynamics: current progress and future challenges.
Discussion document. ISI Workshop, IRTCES, Beijing (2008).
Wischmeier WH and Smith DD. Predicting rainfall erosion losses-a guide to conservation planning. Vol 537. U.S. Department of
Agriculture (1978).
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 96 Oral presentations Measuring wetlands level using historical remot sensing imaginery
Victor Juan Cifuentes Sanchez1, Rosario Escudero Barbero2 and María Jose Checa Alonso2
1
Confederacion Hidrografica del Gaudalquivir, Sevilla, Spain 2 Empresa Pública TRAGSATEC, Madrid, Spain
Level recorder devices are the equivalent in lakes of gauge stations. However, lake measuring networks
have been neglected until recently. As a result, data is incomplete and fragmentarian. Problem arises
when a "reference hydrogram" is required in order to determine if present oscillations are in the range of
natural varation.
A possible approach, tested in the present work, is making use of historical images of the LANDSAT
program, which are easily available, often in the files of institutions.
The aim of the study is to determinate the level of accuracy which can be attained by calculating lake
level from the the water surface using historical images, in lakes where the level was measured and
recorded and then comparing the field and the remote sensing measured data.
As test area, the lagoons of South of Cordoba have been used. This group of lagoons have recorded level
series up to thirty years long. Most of them are included in the Ramsar List.
Figure 1: Extension of the water layer (Laguna de los Jarales)
The works compress the selection of reliable algorithms that make possible to discrimite between water
and dry terrain, and more difficult indeed, between vegetation on dry terrain and vegetation on flooded
terrain (Figure 1).
The results shows that remote sensing can be an useful and reliable tool that can be used to recover never
recorded data and in order to generate sintetical historical series (Figure 2).
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 97 Oral presentations Comparativa Profundidades (Rincón)
6.0
y = 1.0151x + 0.1527
R2 = 0.9245
Profundidad campo (m)
5.0
4.0
3.0
2.0
1.0
0.0
0.0
1.0
2.0
3.0
4.0
5.0
6.0
Profundidad teledetección (m)
Figure 2. Historical vs Remote Sensing measured data
Acknowledgements
To the managers and staff of the Reserva Natural de lagunas del sur de Cordoba, specially to Baldomero Moreno and Rafael
Vega,
References
Lei Ji, Li Zhang y Bruce Wylie. Analysis of Dynamic Thresholds for the Normalized Difference Water Index. Photogrammetric
Engineering & Remote Sensing 2009.
J. Bustamante; R, Diaz-Delgado y D. Aragonés. Determinación de las características de masas de aguas someras en las marismas
de Doñana mediante teledetección. XI Congreso Nacional de Teledetección. Puerto de la Cruz 2005.
Lic.Gloria Y. Bolívar Durán, Dr. Manoel Araújo de Sousa Junior, MSc. Silvia Midori Saito. Uso de Técnica Tasseled Cap y de
los índices NDWI y MNDWI para la delimitación de áreas propensas a inundación _ Estado Guárico, Venezuela.
Emilio Chuvieco y Stijn Hantson, 2010. PNT de Media Resolución. Procesamiento de imágenes Landsat. Documento técnico de
algoritmos a aplicar.
José A. Torres Esquivias. Lagunas del sur de Córdoba. Córdoba 2004. Ed. Diputación de Córdoba.
Aljibe (Consultores s.l.l.). Estudio hidrogeológico de las lagunas del Sur de Córdoba. Lagunas del Rincón y Santiago, Lagunas
Amarga y Dulce. Net 291875/1.Diciembre 2005. Life-Naturaleza conservación y restauración de humedales andaluces. Life Nat
03/E/000055.
José Manuel Moreira (coord.). Caracterización ambiental de humedales de Andalucía. Consejería de Medio Ambiente. 2005.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 98 Oral presentations From chemical exposure to ecosystem effects: A critical view of the
risk assessment process
Antoni Ginebreda1, Maja Kuzmanovic1, Mira Petrovic2 and Damià Barceló1,2
1
Water and Soil Research Group, Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain
2
Pollution in surface waters is considered one of the main causes of impairment of aquatic ecosystems and
biodiversity loss [1]. Risk could be broadly defined [2] as the combination of a probability of occurrence
of some event multiplied by its hazard effects:
RISK = OCCURRENCE x ECOSYSTEM EFFECTS
Estimating the risk posed by chemical pollution to the ecosystem thus requires paying attention to both
factors, i.e., the exposure to chemicals and the potential or actual effects caused.
‘Occurrence’ or environmental exposure is usually expressed in terms of environmental
concentration.Advances in environmental chemistry [3] have shown that typical environmental scenarios
are characterised by continuous exposure to many contaminants. This is due not only to the high number
of chemicals used that can potentially be released into the environment (In the European Union there are
more than 100 000 registered chemicals listed by EINECS of which 30 000 to 70 000 are in daily use) [4],
but also to the biotic and abiotic transformations that they may undergo once there. Therefore, parent
compounds, transformation products and other non-targeted compounds yield complex mixtures whose
composition can only be partially identified by monitoring, while a substantial proportion essentially
remains unknown [5].
As regards to ‘effects’, two approaches are typically used (Fig. 1): Adverse effects to the ecosystem, can
be indirectly estimated through some intrinsic properties of the pollutants concerned, typically their
Ecotoxicity (but also their Persistence and Bioaccumulation), and assuming that they are translated into
ecosystem effects. On the other hand, effects of pollution can be perhaps more realistically considered by
direct measurement of ecological descriptors covering both structural and functional ecosystem aspects.
Whereas indirect methods can be better related to each single pollutant, their extrapolation to the whole
ecosystem is not straightforward. On the other hand, direct ecological measurements provide a better
insight on the actual ecosystem status but conversely, the role played by every specific chemical remains
largely unknown. The situation is even more complicated if one considers that in addition to pollution,
other geographic and hydrologic factors are also and simultaneously concurring.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 99 Oral presentations Figure 1: Direct vs. Indirect estimation of ecosystem effects
Overall, and quoting Hendriks [6], we are facing a complex scenario in which “>100,000 compounds ×
>100,000 end points × >100,000 sites” should be considered together. This is a big scientific challenge
that calls for new and imaginative approaches.
Depending on which part of the problem we want to focus, the three blocks of variables can be treated on
a detailed basis or instead on an integrative or global form.
Here we argue that the method of choice in the risk assessment process will strongly depend on the
question we are interested to answer. If, for instance, we wish to focus our study on what are the most
relevant chemicals (prioritization) or what are the most sensitive species to pollution on a given site, a
detailed description of the part concerned is required, while others can be handled as global.
Along the presentation we will discuss, with the aid of specific examples, different possible
methodological alternatives, showing their advantages and drawbacks, as well as, some ongoing new
research possibilities.
References
1. Vorosmarty, C.J. ; McIntyre, P.B. ; Gessner, M.O. ; Dudgeon, D.; Prusevich, A.; Green, P.; Glidden, S. ; Bunn, S.E. ; Sullivan,
C.A.; Liermann, C.R. ; Davies; P.M.. Nature, 2010, 468, 334
2. D. Guillén , A. Ginebreda, M. Farré, R.M. Darbra, M. Petrovic, M. Gros, D. Barceló. Prioritization of chemicals in the aquatic
environment based on risk assessment:Analytical, modeling and regulatory perspective. Science of the Total Environment 440
(2012) 236–252
3. D. Barceló; M. Petrovic. Challenges and achievements of LC-MS in environmental analysis: 25 years on. Trends Anal. Chem.
2007, 26(1), 2-11
4. D.C.G Muir, P.H. Howard. Are there other persistent organic pollutants? A challenge for environmental chemists. Environ Sci
Technol 2006;40:7157–66.
5. Daughton, C.G. Non-regulated water contaminants: emerging research. Env. Imp. Assess. Res. 2004, 24, 711-732.
6. A.J. Hendriks. How to deal with 100,000+ Substances, Sites and Species: Overarching Principles in Environmental Risk
Assessment. Env. Sci. Technol. 2013; 47, 3546-3547
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 100 Oral presentations Multiple stressor effects on river biofilms. Searching the ruling factor
Lídia Ponsatí1, Mira Petrovic1,2, Yolanda Picó3, Antoni Ginebreda4, Elisabet Tornés1,5, Natàlia
Corcoll1, Helena Guasch5, Damià Barceló1,4 and Sergi Sabater1,5
1
3
Laboratori de Nutrició i Bromatologia, Univerisity of València, Burjassot, Spain
5
2
4
Introduction
Increasing concentrations of nutrients and contaminants (organic and inorganic) are progressively
detected in river waters enhancing the potential toxicity risk on epilithic biofilms (Sabater et al., 2007;
Ricart et al., 2010; Corcoll et al., 2012). Concentrations in water are variable in time and space depending
on the source of pollution (diffuse or point sources), hydrological conditions, and their transformation
processes. Chemical compounds from point sources can be diluted during high flows, while those from
diffuse sources such as watershed runoff may increase (Guasch et al. 2010; Boithias et al. 2011).
Mediterranean rivers have large floods in autumn and winter (Gasith and Resh 1999). Forecasted
scenarios of climate change predict an increase of droughts and flood episodes (IPCC 2007). Also dams,
that are ubiquitous structures on many rivers, may alter the natural hydrological dynamics of rivers
(Cazaubon et al., 1999). Natural conditions determine the biomass dynamics of river biofilms (Bouletreau
et al., 2006; Uehlinger et al., 1996) and may be altered by high water flows (Cazaubon et al., 1999;
Robinson et al., 2004). These structural changes may also modulate the biofilm sensitivity to toxicants,
and mature and thick biofilms may perform as a barrier against chemical toxicity, reducing the
accessibility to chemicals (Ivorra et al., 2000; Guasch et al., 2003). The present study evaluates the
respective relevance of environmental factors (light, temperature, water flow) and chemical stressors
(nutrients, pharmaceuticals, endocrine disruptors, pesticides, perfluorinated compounds and heavy metals)
in the structure and functioning of epilithic biofilms in four Mediterranean watersheds. Stressors co-occur
and interact in specific manners, and the respective relevance of one or another in the response of the
biota may be altered also by the flow regime.
Material and Methods
The study was conducted in four Mediterranean river basins: Llobregat, Ebro, Júcar and Guadalquivir.
Five locations were selected in each river according an up- to downstream pollution gradient in each
basin. Sampling was performed in two different hydrological periods, expecting differences in water
flow: autumn 2010 (C1, with high flow or flood events) and autumn 2011 (C2, with basal or constant
flow). Water samples were taken for physical (e.g. discharge, temperature, light) and chemical analysis.
Chemical analyses included nutrients such as dissolved inorganic nitrogen (DIN), total phosphorus (TP)
and dissolved organic carbon (DOC), heavy metal concentrations (including Cu, Zn, Co, Ni, Cd, Pb and
As), and organic priority and emerging compounds (including 175 compounds grouped in 4 groups:
pesticides, pharmaceuticals, endocrine disrupters and perfluorinated compounds).
The biofilm was analyzed for its community composition (based on diatom species), the algal biomass
(Chl-a), photosynthetic capacity (Ymax), non-photochemical quenching (NPQ), the bacterial density
(Bacteria), and the extracellular enzymatic activity alkaline phosphatase (AP). Attribution of main
stressors on biofilm response was carried out by means of variance partition analysis (Redundancy
analysis), therefore differentiating specific responses of biofilms in each watershed and period.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 101 Oral presentations PCA (diatoms)
J1c1
G1c2
E1c1
J1c2
E1c2
ABIA
L6c2
L6c1
AX2 (14%)
AMIN
CATO G4c1 NSAP
RABB
NSBM
L7c2
GPUM
NGRE
G3c1 L7c1
NRCS
CPED G2c2
NDIS
L5c2
CMIC
NINC
GMIN
G3c2 E4c2
NERI
NPAL CPLI
E5c1 G4c2 G2c1
G1c1
NIFR
CAEX
E5c2 L5c1 NVEN CPLE
J2c1
E4c1
NCPR
L3c2 L4c2 ALFR
NTPT J6c2 J4c1
FBRE
NMEG FPIN J4c2
Llobregat
NMINJ7c2
L3c1 NCTE J6c1
E2c2
NSOC
L4c1
Ebro
J2c2
NSEM
E3c2 ASCL
Júcar
AINA
Guadalquivir
C1 Æ2010
C2 Æ2011
-1.0
The first axis of the principal component
analyses (PCA) performed with the diatom
communities separated sensitive vs tolerant
species to pollution. The scores were later used
for further RDA analyses. The first axis of PCA
explained the highest (38 % of the variance) and
separated upstream sites of Júcar, Ebro and
Guadalquivir rivers (on the right site) to
downstream sites of Llobregat, Ebro and
Guadalquivir rivers (on the left site). The species
composing communities of upstream sites
(Achananthes minutissima, A. biasolettiana or
Cymbella microchephala) were associated to
good water quality conditions. In contrast, those
composing communities from downstream sites
(Navicula subminuscula, N. recens, Nitzchia
insconspicua, N. palea or N. frustulum) are
tolerant to pollution. The second PCA axis
explains less variance (14%), separates mainly
upstream sites (in positive sites) to downstream
sites (negative positions) of the Júcar River. The
diatoms assemblage in this river was of higher
water quality than that of other rivers.
1.0
Results and Discussion
E3c1
J7c1
-1.0
APED
E2c1
1.0
AX1 (38%)
Figure 1. Principal component analysis
(PCA) based on diatom species
abundance
An RDA was performed that could predict the biofilm variables (including the diatoms) from the
environmental variables (the main physical and chemical descriptors, heavy metals, and priority and
emerging contaminants) for all four watersheds studied (Fig.2). According to partitioning variance
analyses, most of the variance was explained by physicochemical factors (17.2%). Conductivity, DIN and
TP were the most significant. Other pollution sources explained a 5.1% of the variance, being endocrine
disruptors and metals the most significant toxicants. The first axis of RDA (Fig.2) showed a gradient of
1.0
E5c1
Llobregat
Ebro
Júcar
Metals
Bacteria
Total Phosphorus
G1c1
E2c1
Guadalquivir
C1 Æ2010
C2 Æ2011
J2c2
J1c1
L7c1 E3c2G2c1 NPQ
E2c2 L7c2 G3c1
Chla
J4c1J6c1
E1c1
J7c1
J2c1 AP
G4c1
J1c2
Endocrine Disruptors
E4c1
E4c2 Ymax
L5c1
L3c2
G4c2
G3c2
E5c2
E3c1
J6c2
L4c2 L6c2
L4c1 DIN
L6c1
L5c2 G2c2
Conductivity
L3c1
Total variance 100%
Diatoms
Explained 36.6%
G1c2
J7c2
Non
explained
63.4%
-1.0
J4c2
E1c2
-1.0
AX1 (33.7%)
PC(Cond
DIN, TP)
17.2%
Tox
(ED’s )
5.1%
Share 14.3%
1.0
Figure 2. Redundance analyses (RDA) based on biofilm structural and functional metrics and
environmental factors, including physicochemical parameters and toxicants.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 102 Oral presentations pollution, where sites with higher conductivity, presence of endocrine disruptors and high phosphorus
(downstream sites in the Ebro, Guadalquivir and Llobregat rivers) contrasted with sites in the Júcar River.
In the former, higher levels of pollution co-occur with more tolerant diatom communities. These sites
had algal communities with a higher photosynthetic capacity, mostly green-algae. Biofilm communities
were made up of species sensitive to pollution, showed high algal biomass and high alkaline phosphatase
activity.
High flows characterized the summer-autumn 2010 hydrology (Fig. 3A), particularly in the Llobregat
River. Instead, summer 2011 had conditions close to basal flow. The RDA based on Llobregat river data
(Fig. 3B) defines the two sampling campaigns in the first axis (29.1% variance), while the second axis
(17.4% of variance) represents a gradient of pollution. During high flows, algal biomass was low and
bacteria abundance high, as it corresponds to initial stages of biofilm development. Probably, new biofilm
colonization was occurring after the flood event. Pharmaceutical pollution was the most relevant type of
pollution in this situation. Their inputs can be associated to waste water treatment plant effluents. During
basal flows biofilm communities had higher algal biomass, characteristic of mature communities. In this
situation, pesticides concentration was higher than in summer 2010. Dominant pesticides in the Llobregat
were probably derived from urban activities, and pesticides can be more concentrated in the water
column. Diatom sensitive species characterized the upstream sites of Llobregat River, however, pollution
tolerant ones, were typical of downstream sites. Both the type of toxicants pollution detected in Llobregat
River (pharmaceuticals and urban pesticides) and the observed up- to downstream increasing gradient of
pollution, may be explained by the high proportion of urban land uses in downstream sites of this
watershed.
Discharge (m3/s)
60
40
Llobregat
2010
20
0
100
2011
80
sampling
60
Pharmaceuticals
L7c2
L7c1
sampling
Bacteria
AX1 (17.4%)
80
Llo3
Llo4
Llo5
Llo6
Llo7
1.0
B)
100
L6c1
Chla
L5c1
Pesticides
NPQ
L6c2
AP
40
L4c2
-0.6
A)
20
0
15 days bef ore sampling (in Autumn)
L3c2
-1.5
L4c1
L5c2
Diatoms
AX1 (29.1%)
L3c1
1.0
Figure 3. A) Discharge for the Llobregat river in samplings of autumn 2010 and 2011. B) RDA analyses
of Llobregat river based on biofilm structural and functional metrics and environmental factors,
including physicochemical parameters and toxicants. Nonte: c1 (sampling autumn 2010) and c2
(sampling autumn 2011).
RDA analyses based on Ebro River data showed that biofilm responses were mainly linked to an excess
of nutrients (dissolved inorganic nitrogen) and agricultural pesticides in water. The increasing pollution
up to downstream was parallel to co-occurring increasing agricultural land uses. Pesticides concentrations
in water were higher during high flow (summer 2010) than with basal flow (summer 2011), supporting
that pesticide inputs were coming from the agricultural areas runoff. In the Ebro structural biofilm
responses to water flow were comparable to those observed in Llobregat River (Fig. 3B).
Redundancy analyses based on Guadalquivir River data showed that biofilm responses were mainly
attributed to an excess of organic matter (DOC) and endocrine disruptors occurrence, increasing from upto down-stream sites, related to the increasing agricultural and urban land uses in downstream sites. In
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 103 Oral presentations summer 2010, slightly high flow was detected in this river when comparing to summer 2011. During
basal flow, endocrine disruptors were higher indicating their origin of point sources (such as WWTP).
Biofilm responses of Guadalquivir River to changes in water flow were comparable to those observed in
the Llobregat River (Fig. 3B). The sensitivity of diatoms species to water pollution also allowed
characterize up- and donwnstream sites of the Guadalquivir River according to a gradient of pollution.
Redundancy analyses based on Júcar River data showed that biofilm responses were mainly attributed to
a joint gradient increasing conductivity, total phosphorus, and metals from up- to downstream sites. This
gradient of pollution co-occurs with an increasing gradient of agricultural areas from up- to downstream
sites. No significant differences in water flow were detected among sampling campaigns, since hydrology
in this river is highly regulated by dams. Biofilm communities from upstream sites presented a higher
abundance of diatoms species sensitive to pollution and a higher abundance of bacteria than those from
downstream sites. The biofilm also showed a higher non-photochemical quenching and alkaline
phosphatase activity in the upstream sites, indicating their higher efficiency than those from downstream
sites.
Acknowledgements
This study was financed by Spanish Ministry of Economy and Competitiveness through the project SCARCE (ConsoliderIngenio 2010 CSD2009-00065) and by the European Union through the European Regional Development Fund (FEDER).
References
Boithias, L., Sauvage, S., Taghavi, L., Merlina, G., Probst, J.-L., & Pérez, J. M. S. 2011. Occurrence of metolachlor and
trifluralin losses in the Save river agricultural catchment during floods. Journal of hazardous materials196, 210–9.
Bouletreau, S., Garabetian, F., Sauvage, S., Sanchez-Perez, J.-M., 2006. Assessing the importance of a self-generated detachment
process in river biofilm models. Freshwater Biology 51, 901–912.
Cazaubon, A., Giudicelli, J., Continentales, E., 1999. Impact of the residual flow on the physical characterics and benthic
community (algae, invertebrate) of a regulated Mediterranean river: the Durance, France. Regulated Rivers: Research and
Management 461, 441–461.
Corcoll, N., Bonet, B., Morin, S., Tlili, A., Leira, M., Guasch, H., 2012. The effect of metals on photosynthesis processes and
diatom metrics of biofilm from a metal-contaminated river: A translocation experiment. Ecological Indicators 18, 620–631.
Gasith, A. and V. H. Resh. 1999. Streams in Mediterranean climate regions: Abiotic influences and biotic responses to preditable
seasonal events. Annual Review of Ecology and Systematics 30:51-81.
Guasch, H., Admiraal, W., Sabater, S., 2003. Contrasting effects of organic and inorganic toxicants on freshwater periphyton.
Aquatic Toxicology 64, 165–175.
Guasch, H., Güluzar, A., Bonet, B., Corcoll, N., Leira, M., Serra, A. 2010. Discharge and the response of biofilms to metal
exposure in Mediterranean rivers. Hydrobiologia 657:143–157.
Ivorra, N., Bremer, S., Guasch, H., Kraak, M.H.S., Admiraal, W., 2000. Differences in the Sensitivity of Benthic Microalgae To
Zn and Cd Regarding Biofilm Development and Exposure History. Environmental Toxicology and Chemistry 19, 1332.
IPCC, 2007. Fourth Assessment Report: Climate Change 2007. Cambrigde UK, Cambridge University Press.
Ricart, M., Guasch, H., Barceló, D., Brix, R., Conceição, M.H., Geiszinger, A., Alda, M.J.L. De, López-Doval, J.C., Muñoz, I.,
Postigo, C., Romaní, A.M., Villagrasa, M., Sabater, S., 2010. Primary and complex stressors in polluted mediterranean rivers:
Pesticide effects on biological communities. Journal of Hydrology 383, 52–61.
Robinson, C.T., Uehlinger, U., Monaghan, M.T., 2004. Stream ecosystem response to multiple experimental floods from a
reservoir. River Research and Applications 20, 359–377.
Sabater, S., Guasch, H., Ricart, M., Romaní, A., Vidal, G., Klünder, C., Schmitt-Jansen, M., 2007. Monitoring the effect of
chemicals on biological communities. The biofilm as an interface. Analytical and bioanalytical chemistry 387, 1425–34.
Uehlinger, U.R.S., Bu, H., Federal, S., Science, E., Eawag, T., Du, C.-, 1996. Periphyton dynamics in a floodprone prealpine
river: evaluation of significant processes by modelling 249–263.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 104 Oral presentations Ecological screening indicators of stress and risk for the Llobregat
river water
Ramón López-Roldán1, Irene Jubany2, Vicenç Martí2,3, Susana González1 and Jose Luis
Cortina1,3
1
CETaqua, Cornellà, Barcelona, Spain
CTM Technological Centre Foundation, Manresa, Spain
3
Department of Chemical Engineering, Universitat Politècnica de Catalunya, BarcelonaTech (UPC), Barcelona,
Spain
2
Abstract
The objective is to develop and apply several simple and rough indicators for river aquatic ecosystems
assessment in order to screen potential chemical stressors. Several indicators, based on toxicity (PNEC)
and on legislation levels (EQS) have been developed. All these indicators are ratios that were calculated
by using public and private data of concentrations of a large list of compounds during a period of five
years, including metals and organic compounds in the lower part of the Llobregat River basin at the
intake of the Drinking Water Treatment Plant. Additionally, new campaigns were executed for increasing
the information available on the presence of compounds not routinely analysed, such as some other
pesticides and pharmaceuticals. In the case of inorganic pollutants, the indicators obtained in this river
section showed significant risk especially for zinc, but also for copper, nickel and barium. For organic
pollutants, the pesticides terbuthylazine, diazinon, 2-methyl-4-chlorophenoxyacetic (MCPA), and in a
few cases, chlorpyrifos and lindane, also showed indexes above the threshold. Among the
pharmaceuticals, the antibiotics clarithromycin and ciprofloxacin were the only ones with risk indicators
adverse to ecosystems.The specific values of the indexes obtained rely on the quantity and quality of the
data available, so their interpretation should take into account that some values can be high due to the use
of too conservative toxicological information.
Introduction
Degradation of water bodies has been a key issue in Europe during last years. Water Framework Directive
(WFD, Directive 2000/60/EC) (1) imposes the achievement of good ecological status of water bodies.
Environmental objectives should preserve quality of water bodies beyond the potential uses for industry,
agriculture, urban and recreational uses, integrating preservation of the health of ecosystems, their
functioning and structure. Indexes for physico-chemical and biological status are relatively easy to
implement. Measurements are based in data that can be obtained by analysis or by identification and
counting of species.
National administrations, like River Basin authorities, should deal with indexes that could be easily used
to give an indication of the good chemical, hydromorphological and biological status of each specific
water body according to their local characteristics.
The idea of establishing comprehensive indexes is to provide indicators on water quality for the
environmental managers. This effort of simplicity can be very useful but the information on the impact on
single parameters is lost. Present work is focusing on giving simple indicators on the impact on every
pollutant that are can be found in Llobregat river waters, considering its effect on aquatic and vertebrate
organisms.
Case study
The proposed ratios were calculated using data of concentrations of a list of contaminants in the Llobregat
river water. The Llobregat river basin is situated in Catalonia (NE, Spain) and covers a catchment area of
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 105 Oral presentations about 5000 km2 but in the present study, a specific location has been selected close to the mouth of the
river, just before the intake of the biggest DWTP supplying water to the Barcelona Metropolitan. The site
has been selected for two main reasons. As it is in the lower part of the Llobregat basin, the river is
receiving discharges from urban and industrial wastewater treatment plants, sewer overflows and diffuse
pollution from agricultural fields, being the area with the highest impact along the river. The location
before the DWTP gives information on potential impact on health for consumers. This location is not only
advantageous for this double objective of protecting environmental and human health, but for the higher
intensity of existing monitoring programmes.
Ecological screening risk indicators
New indexes have been proposed for the calculation of environmental risk for a large list of compounds
commonly found in the Llobregat River. Those indexes are based on analytical results on the
concentration of these compounds on surface water (Predicted Environmental Concentration, PEC) and
reported effects (Predicted Non Effect Concentration, PNEC). For those compounds with no PNEC
reported, calculations for obtaining PNEC values have been performed based on available data. The
methodology for deriving these standards is based, among others, on the concepts of Ecological Risk
Assessment (ERA) based on PNEC and PEC (2).
Taking PECj as the concentration of a contaminant j measured in water, a risk indicator of aquatic
organisms, I ao,j is defined as follows:
I ao , j =
PEC j
PNEC j
PNECj is derived from toxicological values in water, basically NOEC (No Observed Effect
Concentration) of crustaceans, algae, and fishes, and the proper safety factor (assessment factor, AF).
For the list of priority substances, according to Directive 2008/105/CE, Environmental Quality Standars
(EQS) are defined to give a concentration that supposes impact on aquatic media. In these cases, where
threshold concentration for pollutants is legislated, an indicator of aquatic impact Iam,j can be calculated
replacing the PNEC by the legislative value EQS (CREF,j):
I am , j =
PEC j
C REF j
The protection of terrestrial vertebrates (mammals and birds) that are predators of aquatic organisms are
also part of the aquatic ecosystem and could be assessed by comparing concentration of contaminants in
aquatic organisms (PECfood) with the value of PNEC expressed in food basis. PECfood,j could be expressed
by using the transference Bioconcentration Factor (BCF) that measures the ratio concentration of
contaminant in small aquatic organisms (considered food) (PECfood, j) divided by the concentration of
contaminant in water (PECj). In this way, an indicator of terrestrial vertebrates risk, Itv,j could be obtained
with the following expression:
I tv , j =
PEC j
PNEC food , j / BCF j
BCFj values could be obtained from empirical studies or, in case of organic compounds, from correlations
with log Kow (Octanol-Water Partition Coefficient).
The above mentioned expressions show that, having the concentration of the contaminants in water
(PECj), the calculation of all the exposed indicators can be performed. For all these indicators, a target
value of 1 was taken as the limit of correct environmental situation.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 106 Oral presentations Results
Up to date, new indexes have been calculated for ecological risk assessment. Risk indicators for aquatic
organisms give significant values (index value above 1) for all metals studied, in this case, barium,
copper, nickel and zinc. Figure 1 shows indexes based on Water Catalan Agency data. Concerning
organic compounds, the most significant indexes for aquatic organisms are referred to the herbicide
terbuthylazine, a chlorotriazine, and the nonsystemic organophosphate insecticide diazinon. For terrestrial
vertebrates, as seen in Figure 2, the only compound showing an impact according to the index calculated
is zinc. The indexes calculated for terrestrial vertebrates for these organic compounds are showing no
significant impact.
Figure 1: Monthly risk indicators for aquatic organisms at selected site of Llobregat River (2006-2010)
for metals (left) and organic compunds (right) based on Water Catalan Agency (ACA) data bases
Figure 2: Monthly risk indicators for terrestrial vertebrates at selected site of Llobregat River (20062010) for organic compunds based on Water Catalan Agency (ACA) data bases
Uncertainty of indicators is mainly due to PNEC values derivation. As mentioned, contaminants that have
few representative data have a high value of AF and use deterministic approach, and thus PNEC values
could be very conservative, giving indicators of one order of magnitude or more respect to the case when
many representative data have been used. When the derived PNEC is based in distributed approach has
less uncertainty than in the case of deterministic approach. In the case of these metals with the range of
confidence interval and range of AF (1 to 5) a variation of less than order of magnitude in PNEC is
obtained.
As a general tendency, risk indexes calculated for aquatic organisms tends to be higher than those indexes
calculated for terrestrial organisms for the same compounds as BCF are considered in the second ones. As
both indexes are based on the same PEC, monthly variations of those indexes follow the same pattern.
Concerning extra campaigns for pesticides (3) and pharmaceutical compunds (4), the indexes shown in
Figure 3 have been calculated on average concentrations for each compound on each campaign. The only
pesticides showing indexes above 1 are diazinon, MCPA and terbuthylazine. The indexes for the former
three compounds have been calculated using very low reference values. This is one of the reasons why
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 107 Oral presentations non-regulated pesticides show higher risk indexes than the legislated ones.
In pharmaceutical compunds, the antibiotics clarithromycin and ciprofloxacin the index is above 1 posing
a risk to ecosystems. If indexes based on maximum concentration values are observed, the antiinflammatory drug diclofenac, the lipid regulators gemfibrozil and fenofibrate, and the antibiotics
enrofloxacin and sulfamethoxazole, presents values between 1 and 10.
Figure 3. Risk indicators for pesticides (a) and pharmaceutical compounds (b) at selected site of
Llobregat River (special campaigns 2009-2010)
Conclusions
The combination of several indicators is crucial for the assessment of the river pressure based on
chemical contaminants, but still there is a lack of information on reliable PNEC values. PNEC values are
usually very conservative if they are not derived with the proper quantity and quality data, even though
they allow establishing the possibility of rejecting the negative effect of some contaminants if they do not
exceed the target value.
New studies in the future will lead to more information on toxicological effects of substances that will
lead to more accurate PNEC calculations and toxicological information on new compounds not available
nowadays. After this initial diagnosis, more detailed studies on the effect of the potential chemicals that
pose risk need to be performed in order to establish cause-effect relationships.
Acknowledgements
This work was supported by the Spanish Ministry of Economy and Competitiveness through WATMATIN project (CTM201021182) and the former Spanish Ministry of Environment through the VIECO project (MARM009/RN08/01.1). AGBAR is
acknowledged for the data supplied.
References
(1) Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000 establishing a framework for
Community action in the field of water policy
(2) Joint Research Centre, Technical Guidance Document on Risk Assessment in support of Commission Directive 93/67/EEC
on Risk Assessment for new notified substances Commission Regulation (EC) No 1488/94 on Risk Assessment for existing
substances Directive 98/8/EC of the European Parliament and of the Council concerning the placing of biocidal products on the
market Part II, 2003
(3) Köck-Schulmeyer, M., Ginebreda, A., González, S., Cortina, J.L., de Alda, M.L. and Barceló, D. Analysis of the occurrence
and risk assessment of polar pesticides in the Llobregat River Basin (NE Spain), Chemosphere (2012), 86, 8-16.
(4) Osorio, V., Marcé, R., Pérez, S., Ginebreda, A., Cortina, J.L. and Barceló, D. Occurrence and modeling of pharmaceuticals
on a sewage-impacted Mediterranean river and their dynamics under different hydrological conditions, Sci. Total Environ.
(2012) 440, 3-13.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 108 Oral presentations Habitat quality assessment in river basins considering terrestrial and
aquatic threats
Marta Terrado1, Guy Ziv2, Lisa Mandle2, Becky Chaplin-Kramer2, Richard Sharp2, Sergi
Sabater1,3 and Vicenç Acuña1
2
1
Catalan Institute for Water Research, Girona, Catalunya, Spain
The Natural Capital Project, Woods Institute for the Environment, Stanford University, CA, USA
3
Institute of Aquatic Ecology, University of Girona, Catalunya, Spain
Introduction
The loss and degradation of natural habitat quality constitutes a primary cause of the loss of biodiversity
(Fuller et al., 2007). Land use change is considered the most severe driver of change in biodiversity (Sala
et al., 2000), but other threats such as the construction of infrastructure (i.e., roads, hydropower
generation plants, wastewater treatment plants), or the introduction of exotic species, are also responsible
of biodiversity decline (Gleick, 2003, Ricciardi and Rasmussen, 1999). Mediterranean ecoregions host
exceptional species diversity, but are poorly protected, highly degraded, and exposed to multiple
persistent threats. Consequently, they have been ranked among the world’s highest conservation priorities
(Myers et al., 2000).
Efforts to preserve biodiversity in the European Union (EU) have been directed towards the designation
of protected areas under the Habitats Directive (92/43/ECC). Aquatic habitats are also regulated under the
EU Water Framework Directive (WFD, 2000/60/EC), which aims to attain the good ecological status for
all EU water bodies by year 2015. Both Directives require that EU Member States evaluate the
conservation status of the protected areas and species listed every six years. Our goal is to provide a tool
that could be used by environmental managers to better assess the effects of ongoing threats and
management actions on habitat quality- biodiversity.
Methods
We used the ecosystem service tool InVEST or Integrated Valuation of Environmental Services and
Tradeoffs (Kareiva et al., 2011; Tallis et al., 2011), which has a biodiversity module to assess terrestrial
habitat quality combining information on land use-land cover (LULC) and threats to biodiversity
(anthropogenic pressures). We modified the existing terrestrial habitat quality module for it to be able to
simultaneously assess aquatic habitat quality. The idea behind the followed approach is that areas with
high quality habitat will better support all levels of biodiversity, and that decreases in habitat extent and
quality mean a decline in biodiversity persistence and resilience. The model runs in a gridded map in
which each cell is assigned a habitat type. Considering biodiversity in general, each type of habitat can
provide habitat for a different number of species, meaning that it has higher or lower habitat suitability
(Hj) for biodiversity. Ten habitat types were considered in the Llobregat river basin (Figure 1a). Four
terrestrial and five aquatic threats were included in the model (Figure 1b-j). The source of each threat was
mapped on a raster in which the value of the grid cell, normalized between 0 and 1, indicated the intensity
of the threat within the cell. Whereas terrestrial threats were considered to be able to impact all habitat
types, aquatic threats only affected aquatic habitat types. The impact of threats on the habitat in a grid cell
was mediated by three factors: i) the distance between the cell and the threat’s source (to account for that,
a maximum distance over which the threat affected habitat quality was defined); ii) the relative weight of
each threat (importance of one threat referred to the others); and iii) the relative sensitivity of each habitat
type to the threat. Land-originated threats could initially propagate in all directions of the landscape.
However, the behavior of aquatic threats needed to be defined differently, since the sense of propagation
should follow the direction of the flow. The more sensitive a habitat type was to a threat, the more
degraded it would be by the threat. Eventually, the sum of the total threat level in a grid cell gave a
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 109 Oral presentations degradation score for the cell which could be translated into a score of habitat quality.
We validated the model results with available biodiversity data from the area of study. Macroinvertebrate
diversity data from the Catalan Water Agency (ACA) for years 2010-2011 was used to validate aquatic
habitat quality, whereas an index of floral richness from the Barcelona’s Council accounting for the
number of species of vascular plants per habitat was used for terrestrial habitat quality.
Figure 1: Maps of habitat types (a) and location and magnitude of the terrestrial (b-e) and aquatic (f-j)
threats in the Llobregat river basin. Considered threats: (b) urbanization, (c) agriculture, (d) roads, (e)
mines, (f) dams, (g) wastewater treatment plants, (h) water abstractions, (i) channelling, (j) invasive
species.
Results
Habitat quality in the Llobregat river basin was heterogeneously distributed (Figure 2a). According to the
obtained results, urban settlements are one of the main environmental drivers of habitat degradation in the
basin. Even though some threats already exist in the Northern part, the lowest habitat quality is mostly
detected in the South of the basin, where two factors interact: the higher presence of urban settlements,
and an accumulation of threats from upstream. Scores displayed in Figure 2 are relative values
differentiating areas according to their higher or lower habitat quality and, therefore, to their higher or
lower capacity to host biodiversity. Values are relative because they are referred to forest as the
potentially best habitat for terrestrial ecosystems, and to the highest-order streams as the potentially best
habitat for aquatic ecosystems.
In general terms, aquatic habitat in the Llobregat basin tended to be more degraded than terrestrial habitat
(Figure 2b). We already expected that since aquatic habitat is affected by a higher number of
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 110 Oral presentations threats.Moreover, habitat quality scores were more heterogeneous for terrestrial than for aquatic habitat,
the latter with values of habitat quality mainly concentrated around 0.5. Low habitat scores [0.1-0.5]
occurred majorly in aquatic ecosystems, whereas high habitat scores [0.6-0.9] were more frequent in
terrestrial ecosystems. Only were habitat quality scores < 0.1 more important for terrestrial ecosystems.
Figure 2: Habitat quality in the Llobregat river basin: (a) landscape distribution of habitat quality; (b)
histogram of aquatic and terrestrial habitat quality.
Habitat quality in the study area was related to biodiversity (Figure 3). Terrestrial habitat quality appeared
to be strongly related to the index of floral richness. Less vascular plant species were found in areas of
low habitat quality, and the number of plant species increased as habitat quality improved (Figure 3a).
Aquatic habitat quality was also related to macroinvertebrate diversity in water (Figure 3b). Even though
the relationship was weaker in this case, it was still significant (p<0.0001). Aquatic habitat quality was in
accordance with the assessment of threats performed periodically by the Catalan Water Agency in water
bodies (ACA, 2005). A decreasing trend in aquatic habitat quality was observed when the level of total
threats increased. Habitat quality was always high when the level of threats was low, but their values were
more dispersed as habitat quality became lower as a result of threats increase.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 111 Oral presentations Figure 3: Relationship between biodiversity and predicted habitat quality in the Llobregat river basin:
(a) floral richness versus terrestrial habitat quality; (b) macroinvertebrate Shannon diversity (H’) versus
aquatic habitat quality.
Here we improved the existing habitat quality assessment tool of InVEST by including the assessment of
aquatic habitats, and we tested its reliability by comparing the results of the model with terrestrial and
aquatic biodiversity values in a case study basin affected by multiple threats. We also propose a tool to be
used for environmental managers to better assess the effects of ongoing threats and management actions.
Acknowledgements
This research was supported by the Spanish Ministry of Science and Innovation through the project SCARCE (ConsoliderIngenio 2010 CSD2009-00065), by the Spanish Ministry of Education and Science through the Juan de la Cierva program
(JC2011-09116 – to M Terrado), by a Marie Curie European Reintegration Grant within the 7th European Community
Framework Programme (PERG07-GA-2010-259219), as well as by the European Union through the European Regional
Development Fund (FEDER).
References
ACA (Catalan Water Agency). Characterization of water bodies and analysis of the risk of non-accomplishment of the objectives
of the Water Framework Directive (2000/60/CE) in Catalunya (Catalan). Department of Environment and Housing, Catalan
Government (2005).
Fuller, T., Sanchez-Cordero, V., Illoldi-Rangel, P., et al. The cost of postponing biodiversity conservation in Mexico. Biol
Conserv (2007), 134, 593-600.
Gleick, P.H. Global freshwater resources: soft-path solutions for the 21st century. Science (2003), 302, 1524-28.
Kareiva, P., Tallis, H., Ricketts, T., et al. Natural Capital: Theory and practice of mapping ecosystem services. Oxford
University Press, New York (2011).
Myers, N., Mittermeier, R.A., Mittermeier, C.G., et al. Biodiversity hotspots for conservation priorities. Nature (2000), 403, 85358.
Ricciardi, A. and Rasmussen, J.B. Extinction rates of North American freshwater fauna. Conserv Biol (1999), 13, 1220-22.
Sala, O.E., Chapin III, F.S., Armesto, J.J., et al. Global biodiversity scenarios for the year 2100. Science (2000), 287, 1770-74.
Tallis, H., Ricketts, T., Guery, A.D., et al. InVEST 2.4.4 User's Guide. The Natural Capital Project, Stanford, CA (2011).
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 112 Oral presentations Evaluation strategy and data processing of indicator values and risk
assessment – a sustainable logic indicator system for planning,
constructions, materials and scenarios in in semi arid areas
Peter-D. Hansen1, B. Gabriel2 and R. vom Lehn2
1
TU Berlin (Berlin Institute of Technology - BIT), Dept. Ecological Impact Research and Ecotoxicology
2
TU-Campus Wedding (TIB), Master´s Programme Real Estate Management, Berlin, Germany
Executive Summary
Process orientated Indicator values are helpful tools for net working, visualization and for understanding
of complex systems. A evaluation and monitoring system is internationally needed and accepted
according to the International Standards and Indicators used by the BNB/DGNB, BREEAM, LEED,
African Green City Index (GCI), Asian GCI, European GCI, ESTIDIMA (Pearls), GREEN Pyramids.
The newly established Eva.S evaluation tool represents a challenge as much as a competent opportunity
and toolbox for project development, assessment and management of the project progresses.
A comprehensive strategy is necessary to enable a relevant, scientific monitoring to capture and assess
qualitative and quantitative effects related indicators of the measures planned and/or realized the first time
by Eva.S and the YC-Project. The YC-project working phases were attended during data mining by
evaluation matrices and visualization of results by so-called radar diagrams from the beginning on.
The development and realization of a project is a process in several distinct project-phases and this will
certainly not end with its implementation. Sectorial considerations and therefore possibly inefficient
measures in case of changes in the project can be prevented because the presented interaction and feed
back effects in a within the evaluation and monitoring strategy is integrated from the beginning on of the
project with the focus on the analysis of work flow and rating checks.
The now available evaluation tool Eva.S serves as an instrument for the project participants to handle and
present their dimensions (fields of action), categories i.e. CO2, energy efficiency, sustainability, work
packages and finally to present the overall results in a clear and manageable way. Because of the
numerous projects and possibilities of Eva.S and its multiple applications and visualization of the
processes for interpretation and competent communication to public the indicators values and the
investigated evaluation strategy are of significant relevance and acceptance for planning, construction and
process orientated monitoring as well as “grade of achievements” for Megacities, New Towns and New
Urban Settlements.
Data sets, handling of data and the data bank
The project relevant data are processed in a format of quantitative and qualitative indicators selected in
categories like CO2, Energy, Water, Air Quality, Water and Land Use, Socio-cultural, Economy,
Environmental Management. The sustainability has to be proved by social-cultural quality, ecological
quality and economic quality after the classical technical qualities of sustainability. This operation is
resulting in a set of project specific Indicators. The effect related indicators and measures selected are
finally proved and visualized as results and rated in a radar diagram. The indicator concept includes a
rating system 1-10.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 113 Oral presentations Tab. 1: Rating level 1-10
___________________________________________________________________
Definition 1-2 = best practice
Definition
5 = accepted average value
Definition 8-9 = most worse rating
Definition 10 = failure / criteria to prove a failure
The rating 3, 4, 6, 7 reflects to project specific refinements
___________________________________________________________________
The rating system is similar to the common rating tables of the International Standards (ISO, CEN) to
demonstrate in particular the “grade of achievement” of the measures.
Original data sets were mined and organized in a matrix by the topics: strategic dimensions, work
packages (WP), objectives, measures, impact, input Indicators (data of initial situation), objective
indicators, target values (qualitative and quantitative) and measuring methods. At this time the data bank
contains 135 original data sets. In the individual data sets the project rating is always implemented. The
26 Dimensions were condensed and evaluated according to three fields of action (FoA): Reduction of
Resources - Consumption, Energy and Climate and Sustainability. For feeding and editing Eva.S a solid
data base of the dimensions and a set of relevant and productive evaluation criteria for the field of actions
is of fundamental importance. The mining of the data was in close connection to the given objectives as
well as to the work packages of the YC project and feed back by the project teams.
The work flow for managing the data:
Step
1: data mining, organization project data in matrices and Indicator sheets
Step
2: data feeding the Eva.S evaluation tool by project data sets
Step
3: data check by a multi array grid (processor) for sustainability criteria
Step
4: monitoring and decision loop, resulting products and alternative strategies
Step
5: dissemination of results, rating of results and visualization
The Eva.S evaluation tool is working in the background linked to the data bank and the given objectives
and achievements of the project progress. This can be monitored and demonstrated at any time and at any
place / location in the web: http://yc.liebrenz.info/refina/index.php
In this YC-example the results in the three fields of actions “Reduction of Resources Consumption”,
“Energy and Climate” and “Sustainability” are visualized by a radar diagram
(Fig. 1, 2, 3).
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 114 Oral presentations Figure 1: Dissemination of Project Results. Field of Action: Reduction of Resource – Consuption
Figure 2: Dissemination of Project Results. Field of Action: Energy and Climate
Figure 3: Dissemination of Project Results. Field of Action: Sustainability
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 115 Oral presentations Conclusion
The Eva.S evaluation tool was developed in the Young Cities Project by the Evaluation and Monitoring
group. But from the first beginning on it was designed also for other applications and potential projects
and test runs were consequently performed. Because the YC-project data bank was build up slowly but
constantly. Finally we discussed proved applications of Eva.S at the communal authorities level. There
will be a training and application of Eva.S for legal frame work.
The risk analysis and monitoring studies (Hansen 1983, 1997, 2007, Hansen et al 2013) were an added
values for the project development, evaluation and monitoring according to the well accepted
International Standards.The risk analysis part of Eva.S was tested and optimized by the “MORIX
feasibility studies” in the REM (Real Estate Management) Master Courses of the Technische Universität
Berlin (BIT – Berlin Institute of Technology). Many new aspects and directions for future applications
and new perspectives of Eva.S are discussed in ZIA (2013) and will be certainly applied in the near
future. The YC-databank and Eva.S are present in the web by the following address:
http://yc.liebrenz.info/refina/index.php
Summary
1. Eva.S data bank is serving (administrate) the Megacity - YC-project by 135 data sets, 3 Fields of
Action (FoA: Reduction of Resources - Consumption, Energy and Climate and Sustainability) and 25
Work Packages.
2. Eva.S is easy to feed by a Drop-Down menu.
3. Eva.S is Open Source / Microsoft Office
4. Eva.S is not an E-book – it is a evaluation tool
5. Eva.S is from now on a
http://yc.liebrenz.info/refina/index.php
web
based
application
and
has
access
world
wide:
6. The Eva.S project data are evaluated by qualitative and quantitative project specific indicators proved
by the classical dimensions of sustainability: socio-cultural quality, economic and ecological quality.
7. The dynamic and constantly up-dated Eva.S evaluation tool has many potential applications in the field
of evaluation and monitoring. Stakeholders are project developer, political decision maker of municipal
authorities.
Acknowledgements
The authors thanks the Young Cities Project Center of the world wide Megacities project for data mining and updating of the data
sets. We thank the members of the Evaluation Working Group of the YC Project for competent contributions in stimulating many
frontiers approaches and evaluation concepts. The authors gratefully acknowledge the BMBF for funding the Young Cities
Project – research for sustainable development of the megacities of tomorrow – energy and climate-efficient structures in urban
growth centres
References
Hansen, P.-D. 1983. Regulatory Significance of Toxicological Monitoring by Ed. Mervyn Richardson, VCH Publishers, New
York 1993
Hansen, P.-D. 1997. Ecotoxicology and Landscape Planning. Quality Assurance, 5,3 231-241
Hansen, P.-D. 2007. Risk assessment of emerging contaminants in aquatic systems. Trends Anal. Chem. (TRAC), Vol. 26, No
11, 1095-1099
ZIA 2013 Real Estate Industry Perspectives – Sustainability, 3rd Revised and Amended Edition – March 2013
Hansen, P.-D. Gabriel, B., Liebrenz, H., Herig, S. and vom Lehn, R. 2013, A sustainable logic indicator system for planning,
constructions, materials and scenarios, uwf UmweltWirtschaftsForum- Springer, in press.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 116 Oral presentations The role of e-Infrastructures: Linking biodiversity and ecosystems
through the deployment of new water quality technologies in river
basins
Juan Miguel González Aranda1, Antonio José Sáenz Albanés2, Jesús Marco de Lucas3 and
Benjamín Sánchez Gimeno4
1
Ministry of Economy and Competitiveness-MINECO, Madrid, Spain
2
Andalusian Institute of Technology-IAT, Seville, Spain
3
Institute of Physics of Cantabria-IFCA, CSIC-UC, Santander, Spain
4
Ministry of Economy and Competitiveness-MINECO, Madrid, Spain
Rationale
Biodiversity Ecosystem Functioning (BEF) is one of the “Big Five” Hot Ecological Topics, jointly with
Climate Change, Habitat Fragmentation/loss, Species Invasions, and Compound Impacts. This “Big Five”
develops within a global worldwide context, where several high level initiatives aim to deepen into these
issues through: (a) The creation of the Intergovernmental Science-Policy Platform on Biodiversity and
Ecosystems Services (IPBES, doing what IPCC did for Climate Change for Biodiversity); (b) The
definition of the Nagoya 2010 CBD Targets in order to take effective and urgent action to halt the loss of
Biodiversity in order to ensure that by 2020 ecosystems are resilient and continue to provide essential
services; and (c) the fundamentals of the Economics of Ecosystems and Biodiversity (TEEB-2010),
among others. It is clear that all these topics meet in River Basins, where Decision Makers, Researchers,
different socio-economic Stakeholders (mainly from Agro-food, Water and Energy sectors) and rest of
Citizens (in general terms), come together as members of Communities of Practice sharing these common
concerns (González-Aranda et al., 2006) not only at their regional/local river basin, but also at
international level (González-Aranda, 2010). Monitoring, modelling and understanding River Basins is a
real challenge that requires the experience and knowledge cumulated along many decades, but today it
can greatly benefit of the new streams of information, like high resolution satellites images, or real time
monitoring sensors, and also from more complex and accurate models covering from global climate to
local hydrological and water quality predictions. Therefore, the provision of proper service-oriented eInfrastructures, integrating the whole chain from instrumentation and databases to supercomputers where
models can be executed, taking benefift of the “state-of-art” of the Information Society Tecnologies, will
support to understand the environmental limits, ecosystem resilience and relationship between
Biodiversity & Essential Ecosystem Services. This contribution shows a set of on-going case studies and
initiatives based on the framework of the ESFRI LIFEWATCH, putting in practice many of these
concepts.
About the ESFRI LIFEWATCH e-Infrastructure
The European Strategy Forum on Research Infrastructures (ESFRI) is a strategic instrument to develop
the scientific integration of Europe and to strengthen its international outreach. The competitive and open
access to high quality Research Infrastructures supports and benchmarks the quality of the activities of
European scientists, and attracts the best researchers from around the world. Environmental sciences are
also considered in ESFRI, through initiatives such as LIFEWATCH “Infrastructure for Research on the
Protection, Management and Sustainable Use of Biodiversity”. LIFEWATCH is a distributed eInfrastructure as it is cooperating with “distributed” Centres in European Union cooperating countries. In
fact, Spain (Seville) is the Statutory Seat, responsible of the ICT Core developments and coordinator and
manager of the distributed construction operations of this e-Infrastructure. These Centres (initially, the
Common facilities also located in Italy, The Netherlands and Belgium) are developing and operating
virtual and physical media and other components that give access to (1) distributed observatories/sensor
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 117 Oral presentations networks; (2) interoperable databases & warehouses; (3) existing (data-)networks, using accepted
standards; (4) computational power; (5) software & tools for visualization, analysis and modelling. Their
main aim is to address new research fields, test innovative hypothesis, deepen scientific knowledge and
above all, to provide solutions for environmental policy and management issues (see Figure 1).
Figure 1: LIFEWATCH ESFRI connecting Science with Environmental policy & management
Therefore, the proper operation of this e-Infrastructure demands that the development of new “toolboxes”
and users’ interfaces is adequately planned. The application of these principles may be exemplified within
the context of the research and management of river basin areas as can be derived from the conceptual
layer-based Architecture shown in Figure 2. This conceptual framework will provide policy makers, river
basin-related managers and other users with available research data, analyses and lessons learned from
particular cases, specially those involving multi- and inter-disciplinary work across different research
lines. This information will help decision-making processes related with water quality, biodiversity and
ecosystem protection, or land and adaptive management.
Figure 2: LIFEWATCH ESFRI distributed e-Infrastructure conceptual Architecture
Thus, such an e-infastructure should ensure in first place the access to validated data from monitoring
activities and other reliable sources of data, by establishing and strengthening its relationships with
existing scientific and data provider bodies. For instance, a new generation of smarter complex sensing
platforms are already integrating water quality measurements and many other relevant environmental
measurements (atmospheric variables, solar radiation and spectrum) with high sampling frequency and
mobility plus profiling capability (Coterillo, 2012). In addition, the e-infrastructure should enable the
integration of accurate hydrological models describing baseline conditions (like thermocline evolution)
with those models that could predict relevant events like algae bloom (Monteoliva, 2013). The access to
harmonized and consolidated data, such as those systematically provided by river basin authorities
(Lassaletta et al., 2009) and integrated modelling will enable the researchers on water-related issues to
establish interlinkages with other environmental drivers, such as climate change or anthropic impacts, and
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 118 Oral presentations even to work at different temporal and spatial scales (Aguilera el al., 2013 a and b; Lassaletta et al., 2010
and 2013). Finally, the new knowledge built from the use of those tools will provide a new set of criteria
for policy makers and environmental managers that will enable them to take decisions based on the
best available scientific knowledge.
AQUALIFE Advanced Surveillance Environmental & Decision Support System for River Basins
The LIFEWATCH e-Infrastructure based AQUALIFE (Sáenz-Albanés, 2013) initiative involves the
design, construction and maintenance of an
Advanced Surveillance Environmental & Decision
Support System for River Basins. Its testing pilot
prototypes are being developed in the scenario of
the Guadalquivir River Basin (including the Doñana
Natural Area), under the auspices of the
Guadalquivir River Basin Authorities Body
(“Confederación Hidrográfica del Guadalquivir”CHG), and in tightly cooperation with the
Andalusian Institute of Technology (IAT). It is
structured in 5 Work Packages, where “cuttingedge” technologies on Remote Sensing (Satellite
Images,etc.), sensor networks, interoperability and
semantics of big (meta-) data resources and decision
support systems (including the so-called “virtual
labs”) are initially foreseen to be put at the disposal
of the Managers & Decision Makers, Researchers
and Citizens dealing with Guadalquivir River Basin
area and then, to be opened-up to the rest of ESFRI
LIFEWATCH Community of Practice.
Figure 3: AQUALIFE - LIFEWATCH funcionalities
& planned e-services features
The expected impacts of AQUALIFE developments in regards to the Public Administration will be
especially focused on the establishment of a new generation Organizational Knowledge and Information
Management System which allows to coordinate and manage into both “in real time” and “on-demand”
ways, the (e-) services requested by the River Basins users. These (e-) services are schematically shown
in Figure 3. Moreover, the expected improvement of the coordination among River Basin managers at
regional, national and international level, which are sharing common EC Directives (e.g., Water
Framework Directive, Directive 2007/60/EC on the assessment and management of flood risk,etc.), River
Restoration practices, etc. Moreover, a big impact in Agro-food sector is also expected, as this system
will provide with cost and energy saving recommendations, as well as other useful informations related to
crops. Moreover, citizens will be aware of their active participation on River Basin Integrated Water
Resource Management process, mainly by transmitting their opinions and suggestions in regards to water
conflict, gender, and River Basin preservation and restoration. All these, by means of the establishment of
proper dissemination mechanisms, though the use of the so-called mobility devices (smartphones, etc.),
and portal web public areas (see Figure 4).
In summary, these systems will be ideal instruments to support River Basin Authorities for the adaption,
application and monitoring of the river basins, including efficient early risk management subsystems, the
setting of territory plans and to guarantee a proper dissemination strategy of their activities.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 119 Oral presentations Figure 4: Conceptual Frame of the AQUALIFE - LIFEWATCH Information System Architecture
References
Aguilera, E., Lassaletta, L., Sanz-Cobena, A., Garnier, J. & Vallejo, A., 2013a. The potential of organic fertilizers and water
management to reduce N2O emissions in Mediterranean climate cropping systems. A review. Agriculture, Ecosystems &
Environment 164, 32-52.
Aguilera, E., Lassaletta L., Gattinger A. & Gimeno B.S. 2013b. Managing soil carbon for climate change mitigation and
adaptation in Mediterranean cropping systems. A meta-analysis. Agriculture Ecosystems & Environment 168, 25-36.
Coterillo et al. 2012. Integrating a Multisensor Mobile System in the Grid Infrastructure, in Remote Instrumentation for EScience
and Related Aspects. Springer, 2012.
EMoSEM Ecosystem models as support to eutrophication management in the North Atlantic Ocean Project
era.eu/np4/20.html.
http://www.seas-
González-Aranda, J.M., Rodríguez-Clemente, R., Lozano S. 2010. E-Research in International Cooperation Networks in Science
& Technology Research. Pags. 167-199. Chapter in book: E-Research Collaboration: Theory, Techniques and Challenges.
Springer. 2010. ISBN 978-3-642-12256-9.
González-Aranda, J.M. 2006. Creating and nurturing the MELIA (Mediterranean Dialogue on Integrated Water Management)
Community of Practice: A strategic Coordination Action for the establishment of an Information and Knowledge Management,
Sharing and Dissemination Platform for IWRM in the Mediterranean Area. In Book of Abstracts of “EUROPE International
Network of Basin Organizations - INBO 2006”, Megève (France) September 2006.
Lassaletta, L., García-Gómez, H., Gimeno, B.S., Rovira, J.V. 2009. Agriculture-induced in nitrate concentrations in stream
waters of a large Mediterranean catchment over 25 years (1981-2005). Science of the Total Environment: 407: 6034-604; IF
(2009).
Lassaletta, L., García-Gómez, H., Gimeno, B.S., Rovira J.V. 2010. Headwater streams: neglected ecosystems in the EU Water
Framework Directive. Implications for nitrogen pollution control. Environmental Science and Policy 13: 423-433.
Lassaletta, L., Billen, G., Romero, E., Garnier, J. & Aguilera, E. 2013. How changes in diet and trade patterns have shaped the N
cycle at the national scale: Spain (1961–2009). Regional Environmental Change. Accepted DOI 10.1007/s10113-013-0536-1.
Monteoliva, A. et al., 2013-2015, ROEM+ Project: http://www.roemplus-life.eu/.
Sáenz-Albanés, A.J., 2013. AQUALIFE Technical Annex. Andalusian Institute of Technology, Seville, Spain.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 120 Oral presentations Integrating Action Assessment and Knowledge Exchange in Combating
Desertification: The PRACTICE Integrated Protocol
Susana Bautista1, Barron J. Orr2 and V. Ramón Vallejo3
1
Department of Ecology, University of Alicante, Alicante, Spain
Office of Arid Lands Studies, University of Arizona, Tucson, USA
3
Departmment of Plant Biology, University of Barcelona, Barcelona, Spain
2
Introduction
There is an increasing demand for the development and implementation of appropriate assessment
methods to measure progress on managingdrylands and combating desertification (UNCCD 2009). The
adoption of best management practices requires a good use of the existing scientific and local knowledge,
as well as improved understanding on the impacts of the strategies and techniques applied on the target
socio-ecological systems. Both requirements can be met through the systematic and participatory
evaluation of the actions applied and further dissemination of the results.
Approaches to the assessment and monitoring of dryland management range from those that focus on
particular biophysical properties of the system (e.g., soil erosion) to those that emphasize socioeconomics (e.g., cost-benefit analysis). In recent years, focus has shifted to socio-ecological assessment,
which recognizes the complex and dynamic relationships between humans and ecosystems (MA 2005).
Particular challenges are the integration of biophysical and socio-economic fields; the identification and
selection of a set of indicators that capture key sustainability issues, that are manageable and simple
enough to be applied consistently and affordably in different regions over long periods of time, but also
relevant for each specific ecological and socio-economic context assessed; and the development of
participatory approaches that integrate scientific and local knowledge, as well as the variety of
stakeholder perspectives (Bautista and Alloza 2009).
The participation of stakeholders and the incorporation of local knowledge in the assessment of
environmental problems and potential solutions have been increasingly demanded by international
institutions. Conventional environmental assessments tend to be expert-led, top-down activities that
generate knowledge for understanding the impacts of management actions. However, these approaches
suffer poor adoption rates in part because the engagement of local stakeholders is unidirectional and often
limited to defining the context at the beginning and delivering the findings upon completion. Participatory
assessment has the potential to engender social learning among all stakeholders, including scientists,
which then has the potential to increase collaboration (Reed et al. 2008). Assessment approaches that
promote the identification and selection of assessment criteria by the stakeholders, ensure a link between
stakeholder perspectives and what is measured and create the demand on the part of the stakeholder for
accurate and representative data that are relevant to their local realities and constraints.
PRACTICE integrated assessment protocol, IAPro
PRACTICE IAPro links the evaluation of management actions with knowledge exchange and social
learning through a participatory process. IAPro is based on (1) key common indicators that represent key
ecosystem services in drylands, and that are also relevant for the objectives of CBD and UNFFC, and (2)
site-specific indicators identified by local stakeholders that are relevant to the objectives and the
particular context conditions.
IAPro provides guidance on how to engage a comprehensive and representative set of stakeholders
interested in actions to combat desertification. It provides a means to capture baseline stakeholder
perspectives on management actions and assessment indicators, and then facilitates knowledge exchange
and social learning among stakeholders.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 121 Oral presentations The basic assumptions underlying IAPro evaluation method are: (1) Participatory assessment increases
adoption. (2) Assessment improves by linking scientific and local knowledge. (3) Assessment must be
supported by accurate monitoring data. (4) There are not absolute best practices. Evaluation of practices
depends on tradeoffs between criteria, individual stakeholder perspectives and interests, as well as
dynamic socio-environmental contexts. (5) Dryland social-ecological systems are coupled, and therefore
the assessment of management options must simultaneously consider both biophysical and socioeconomic attributes.
IAPro is structured as a sequence of steps that offers a path for knowledge exchange among the variety of
stakeholders and between scientists and stakeholders. Some of the modules are full participatory activities
(Steps 1 to 3 and 6), while Steps 4 and 5 represent scientific and technical work to be performed by the
local assessment team (Fig. 1).
1. SHP
Identification &
engagement
2. Baseline evaluation
of actions & selection
of site-specific
indicators
Science-based suite
of general (common)
indicators
5. Integrating data
and perspectives.
MCDA
3. Integrating &
weighting general and
site-specific indicators
Social learning
4. Data
gathering
6. Collective
integrated
assessment
Figure 1: IAPro structure. Flowchart of the protocol steps
The suite of science-based criteria and indicators in IAPro aims to represent a well-balanced basket of
ecosystem services, covering the four broad categories of provisioning, regulatory, supporting, and
cultural services, and focusing on key services in drylands (MA, 2005). Table 1 summarizes the criteria
proposed, including potential indicators for their assessment. These criteria and indicators, which aim to
capture the overall functioning of dryland systems, are combined with additional site-specific indicators
identified by local stakeholders that are relevant to the objectives and the particular context conditions.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 122 Oral presentations Table 1. Science-based common criteria and indicators for the assessment of management and
restoration actions to combat land degradation in drylands.
Criteria
Indicators
Income; personal/family wealth
Provisioning Services: Goods (food, fiber, timber, forage..)
Regulating & Supporting
Services:
Water and soil conservation
Carbon sequestration
Cultural Services: Landscape and cultural heritage
Biodiversity
Site-specific
Productivity; Productivity value
Plant cover and pattern; Soil surface condition
Soil organic carbon; Above-ground biomass
Site specific (e.g., aesthetic value; spiritual
l )
Diversity of vascular plants
The protocol begins with the identification and engagement of the site-specific stakeholder platform (Step
1). This step aims to identify and involve a comprehensive and representative set of stakeholders who can
contribute to the evaluation process. It is essential not to assume a priori knowledge of all stakeholders.
The stakeholder identification method to be used is a form of “chain referral” where initial key
respondents (potential stakeholders) are interviewed to obtain information and referrals of other potential
stakeholders.
Step 2 aims to capture the baseline stakeholder perspectives on (1) the actions applied to combat
desertification and (2) the site-specific indicators for the assessment of these and other potential actions.
This step provides two crucial elements for participatory assessment and social learning. On the one hand,
it captures and makes explicit the individual stakeholder baseline perspectives, which can be later
contrasted with monitoring data and other stakeholders’ perspectives, leading eventually to the production
of new knowledge and learning. On the other hand, it provides stakeholders the opportunity for
participating in the definition of the assessment method itself, by proposing site-specific indicators that
are relevant for the local conditions.
Step 3 aims to establish both individual and integrated stakeholder perspectives on the relative importance
of the indicators selected in previous steps. Step 3 is designed to gather information on stakeholder
preferences on both the indicators suggested by different stakeholders and the common indicators
suggested by IAPro. Therefore, Step 3 offers opportunities for social learning and the integration of
scientific and local knowledge. The final outcome from Step 3 is a set of collective weights for the list of
selected indicators. The weights elicited are then incorporated (See Step 5) into a Multi-Criteria Decision
Analysis (MCDA) applied to the data collected for each indicator and action assessed. There are several
approaches and methods available for weighting indicators and criteria. IAPro proposes a revised version
of a procedure known as SIMOS procedure (Figueira and Roy 2002). It is an exercise that uses a ‘card
playing’ format in which different criteria (indicators) are classified and ranked.
Step 4 addresses the collection of data for each of the indicators proposed in previous IAPro steps. Data
gathering must rely on the expertise of local researchers and technicians, who are responsible for
choosing the most appropriate metrics and survey methods, yet participation of stakeholders in the
process is desirable and encouraged.
IAPro Step 5 applies MCDA to integrating the stakeholder perspectives on the assessment method
(through the selection of indicators and definition of their relative importance) and the data gathered for
each of the selected indicators. The final result of the procedure is a partial or ordinal ranking of options,
which helps visualize the alternatives that perform at least as good as the others in most of the criteria.
Step 6 represents the end of a process where the combination of science and local knowledge, monitoring
data and stakeholder perspectives converge into a collective evaluation of the actions implemented to
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 123 Oral presentations combat land degradation. This step brings what scientists have learned from the stakeholders from
previous steps back to them and brings the science (the approach and the data) to the stakeholders so that
they can make a more informed assessment of the management actions through social learning and other
forms of informal learning. Step 6 is conducted in a framework of a workshop with the SHP that targets
the integrated evaluation of the management actions to combat land degradation.
Policy oriented recommendations
Sustainable management can benefit from participatory assessment methods that incorporate the
knowledge and perspectives of scientists and the stakeholder community. Participatory assessments that
promote social learning have a great potential to increase adoption of good practices. Methods that result
in social learning also result in engagement, a necessary precursor to collaborative decision making and
collective action.
Implementation of IAPro facilitates knowledge exchange and learning through the participatory
assessment of management actions to combat desertification. This approach has been successfully tested
in 18 dryland sites distributed across eleven countries, demonstrating its potential for the consistent but
also adaptive assessment of a large variety of management actions to combat desertification. The
PRACTICE-IAProl can be used at larger scales, for instance, to help identifying best policies at a national
level. Spatial and temporal scale would be determined by the stakeholder platform and the actions and
programmes being evaluated. Since IAPro indicators are also Sustainable Land Management (SLM)
indicators, the protocol can be used to SLM assessment. Similarly, the participatory approach could be
adjusted for a priori exploration of alternatives.
Dissemination of lessons learned among local communities, and among different sites and the larger
desertification community is crucial to further promote knowledge exchange and learning. PRACTICE
Netweb (http://practice-netweb.eu/) is a place where people involved in or affected by actions to combat
desertification/land degradation can connect, share their stories and learn from each other.
Acknowledgements
The authors thank the collaborative work done by the partnership of PRACTICE Project, funded by the European Commission
under the FP7-ENV Program, which greatly contributed to the development and testing of PRACTICE Protocol.
References
Bautista S. and Alloza, J.A. Evaluation of forest restoration. In S. Bautista, S., Aronson, J., Vallejo, V.R. (eds), Land Restoration
to Combat Desertification. Innovative Approaches, Quality Control and Project Evaluation. Fundación CEAM, Paterna, Spain
(2009), pp. 47-72.
Figueira, J. and Roy, B. Determining the weights of criteria in the ELECTRE type methods with a revised Simos’ procedure.
European Journal of Operational Research (2002), 139, 317–326.
Millennium Ecosystem Assessment, MA. Ecosystems and Human Well-being: Synthesis. Island Press, Washington, DC. (2005).
Reed, M.S., Dougill, A.J. and Baker, T.R. Participatory indicator development: what can ecologists and local communities learn
from each other? Ecological Applications (2008), 18, 1253-1269.
Steins, N.A. and Edwards, V.M. Platforms for collective action in multiple-use common pool resource management. Agriculture
and Human Values (1999), 16, 241-255.
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Combat Desertification (2009), http://www.unccd.int/en/programmes/Science/Conferences/Pages/1st-Scientific-Conference.aspx
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 124 Oral presentations The use of deliberative scenarios for WES appraisal and identification
of measures in two Mediterranean case studies: Noguera de Tor and
Anoia river basins
Francesc La Roca1, Graciela Ferrer1 and Joserra Díez2
2
1
University of Valencia, Department for Applied Economics, Valencia, Spain
University of the Basque Country, Department of Mathematics and Experimental Sciences Didactics, VitoriaGasteiz, Spain
Introduction
In the last decades, human activities have intensified the use of natural resources giving rise to deep
transformations of ecosystems and natural processes (Vitousek, 1994; IPPC, 2007). Fresh water
ecosystems are particularly vulnerable to these changes, specially, in arid zones like the Mediterranean
(CBD, 2010; EEA 2010). The state of water ecosystems is seriously affected by the combined effect of
climate change and a wide range of human’s pressures and impacts –e.g. pollution, channelling, flow
regulation, loss of riparian forests (Sabater, 2008). The deterioration of water ecosystems impairs their
capacity for supplying natural resources and services which are basic for human wellbeing (MEA, 2005).
Implementing mitigation and adaptation measures to deal with the causes and effects of global change
requires a shared diagnosis of local issues and identification of context adapted actions (Ostrom et al.,
2007) to conserve ecosystem services (ES) in the medium and long run. Participation of users and
interested parties in such activities is necessary due to the complex and uncertain nature of the issues to
be dealt with (Funtowicz and Ravetz, 1990; WFD-CIS, 2002) and the necessary involvement of such
actors in measures implementation for reducing pressures on the environment (WFD-CIS, 2002).
Our interest is to explore how global environmental change affects water ecosystem services (WES) at
local scale now and for the 2050 horizon, and to understand how society appraises them. This implies the
articulation of a plurality of points of views, values and interests to understand complex relationship
among different knowledge domains, spatial scales and time-horizons, as well as anticipatory and
strategic thinking (Kay et al., 1999). In this context, we propose the development of deliberative scenarios
in small scale case studies as an interesting research tool, as they are suitable instruments for articulation
of a plurality of views –including lay people- and fruitful thinking around complex issues, tackling
uncertainty, and allow reflection on a concrete socio-economic and spatial context (Pahl-Wostl, 2008;
Lebel et al., 2005). In this paper we present the results obtained in the two case studies where we applied
this methodology.
Methods
Selection of case studies
The two case studies selected were Noguera de Tor river basin (Ebro river basin) and Anoia river basin
(Llobregat river basin). Noguera de Tor is a small mountain river basin (312 km2) located in the
southwest Catalan Pyrenees (1800 – 850 m.o.s.l). Its main channel is Noguera de Tor (30 km length, 244
hm3/year), a third order tributary to the Ebro river. The valley has a low population density and the main
economic activities are hydropower generation and residential and familiar tourism linked to snow and
active sports, nature and historical heritage. Ecosystems have a good status of conservation –a main part
of the river basin is included in the National Park “Aigüestortes i Llac de Sant Maurici”- although fluvial
ecosystems suffer from high hydromorphological pressures due to intense intervention –dam, weirs,
diversions, etc.- on the fluvial channels and over river flows to produce electricity.
Anoia is a river basin (930 km2) located near to the Metropolitan Area of Barcelona. The stream (65 km
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 125 Oral presentations length, 60 hm3/year) flows from the Catalan Central Depression (700 m.o.s.l.) through the Prelitoral
mountain to Sant Sadurní d’Anoia, to join the Llobregat river in Martorell (56 m.o.s.l.). In natural
conditions, the Anoia supplies the 9% of Llobregat river’s water resources. Population concentrates in
middle sized cities (Igualada and Martorell) close to the main river channel in the middle river basin and
in the confluence of Anoia and Llobregat rivers. Main economic activities are industry and services.
Industrial activities –paper, tanneries, textile, automotive, etc.- have a long tradition in the area (Anoia
county), historically taking advantage from water and potential energy of Anoia’s river and from pumping
Carme-Capellades’ groundwater. Since the mid-eighties traditional industrial sectors have declined
influenced by market globalization, however population living in the basin has increased as a result of the
Barcelona’s urban sprawl. Non-irrigated agriculture is important in the lower basin (Alt Penedès county),
where vineyards are predominant and the production of cava is concentrated. Surface water bodies do not
reach good chemical and ecological status due to industrial and urban pollution, hydromorphological
alterations –channelling, weirs, and agricultural and urban occupation of fluvial banks. Groundwater
bodies are in bad status due to overpumping and chemical pollution. Water provisioning for an important
part of urban and industrial uses depends on water transfers from Ter-Llobregat system.
The deliberative scenarios exercise
A deliberative scenarios exercise has been developed to explore the impacts of global environmental
change on WES at the local scale for the horizon 2050, and values hold by the local society around WES.
It consist of a set of three workshops per case study aimed to define (1) the present situation of WES at
the local scale; (2) plausible future situations of WES at local scale taking into account the foreseen
impacts of climate change on the hydrological cycle and two alternative socio-economic and institutional
contexts –one market driven and another socio-environmental friendly; and, (3) policy actions that should
be taken to retain WES in the future situation (La Roca et al., 2011b).
The first workshop was devoted to contrasting the project team identification of WES with local people
(La Roca et al., 2011a), and to the identification of WES trade-off derived from current socio-economic
activities in each case study river basin.
In a second workshop a scenario of qualitative expected effects of climate change on the hydrological
cycle was presented to participants in each case study, taking as reference the downscaling of climate
change effects over climatic variables for Catalonia (Barrera-Escoda and Cunillera, 2011). In this context
participants identified the most vulnerable current uses and WES. Then, they worked in two groups
imagining how their river basin would be in the next 40 years, introducing two contextual socio-economic
and institutional scenarios in form of story-lines: one where development is understood as mere economic
growth (called “Economic competence”); and the other, where development implies a balance among
social values, environmental restrictions and economic growth (called “Socio-environmental
integration”). These narratives are based on the global scenario story lines “Market first” and
“Sustainability first” of the GEO-4 Report (UNEP 2007) and “Global Orchestration”, “Adapting Mosaic”
and “Techno-Garden” of the Millenium Ecosystem Assessment (Cork, Peterson, et al., 2005). Finally,
they identified the most relevant WES for future local wellbeing, whatever the contextual socio-economic
scenario will be.
In the third workshop participants were asked to select and propose the measures they identified as the
relevant ones for future local wellbeing through the conservation or improvement of WES. They
identified opportunities and drawbacks for their implementation.
Methodologies applied for the development of workshops included the presentation and contrast of
information collected through desk research, structured debate around proposed questions and group work
to build up schematic representations of future visions –forecasting approach- and measures –backcasting
approach (Van Notten et al., 2003). Each workshop session took between 2 to 3 hours throughout 20122013. In each case study interested parties were identified and contacted –telephonically and via e-mailto invite them to participate. After each workshop, a report on the development and contents treated
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 126 Oral presentations during the workshop was sent to participants.
Results
Attendance to workshops was irregular, noting a very low participation in the Anoia case study. In
Noguera de Tor there was predominant participation of local actors with environmental sensitivity and the
absence of the main economic users of water. In Anoia, there was a scarce participation of local and
county authorities and representatives of economic users of water, and a bias to environmentally aware
participants.
Identification of current WES uses and trade-offs
Participants in the Noguera de Tor case study identified the highly intense provision of water for energy
production as the main source of deterioration of ES (hydrological regime, maintenance the ecosystem
integrity, recreational and aesthetic services and provisioning of water for livestock farming).
Participants in the Anoia workshop highlighted the overuse of the provisioning service of water for
domestic uses and for industrial activities and the overuse of self-purification service as the main cause of
deterioration of regulation, habitat, and cultural/aesthetic services. Such overuse has required the import
of these services through Ter-Llobregat system. Participants also stressed that this situation is aggravated
by urban, infrastructural or agricultural occupations of fluvial space that deteriorates services of
protection against extreme climatic events, soil and sediment dynamics and hydrological regime, which in
turn, reduce the provision of habitat, recreational and aesthetic services.
Identification of the most vulnerable uses and WES to climate change
As consequence of climate change expected changes in the case study’s river basins are reductions of
surface and groundwater resources, increase of evapotranspiration, a reduced number of snow days –in
the case of Pyrenees zone-, and the alteration of the fluvial metabolism, affecting the ecosystem’s ability
for fluvial self-purification and for biodiversity support (ACA, 2009).
In the Noguera de Tor, participants considered traditional ranching and snow tourism the most vulnerable
current uses; while they consider hydropower generation highly resilient because of existence of room for
efficiency improvements and the strong firm’s negotiation power. Participants underlined new economic
options: new climate adapted crops and re-orientation of touristic offer towards summer tourism. As a
consequence, increased pressure on provisioning and regulation WES is expected. Growing conflicts
among water for hydropower production and competing provisioning services are foreseen.
In the case of Anoia river basin, participants identified non-irrigated agriculture, small irrigated gardens,
industrial uses and livestock farming as the most vulnerable current uses. Drinking and domestic uses of
water is not considered vulnerable because its institutional highest priority of supply. An increase of
pressures on all currently used and affected WES is expected, as well as growing dependence on external
resources for supplying water provision services to urban and industrial uses.
Identification of WES considered as the most important for the future
In the case of Noguera de Tor, participants considered that the most important WES for local people in
the future will be provisioning of water for livestock farming and for other economic activities –tourism,
in particular- and the provision of recreational and educational and scientific services. For enjoying these
services, they considered the conservation of hydrological regime and the maintenance of ecosystem
integrity services as a strategic issue.
In the case of Anoia, participants considered that the most important WES for local people in the future
will be the provisioning of water for drinking and domestic purposes, the hydrological regime and the
maintenance of ecological integrity, together with self-purification.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 127 Oral presentations 1
Suggested mix of measures for conserving or recovering WES
In the case of Noguera de Tor, participants identified five action lines: (1) political coordination; (2) land
planning integration; (3) water use rationalization; (4) economic instruments; (5) knowledge & education.
In the case of Anoia, participants identified six action lines: (1) water use rationalization; (2) land and
urban planning integration; (3) economic instruments; (4) transparency and knowledge; (5) pollution
prevention; (6) ecological restoration.
Discussion
Identification of ES is a useful tool to conceptually frame the mapping of human-ecosystem evolving
relationship. It enriches the reflection on natural resources management making evident the
interdependence of direct uses of natural resources and services with ecological processes and functions
that provide them.
Participants perceived provisioning and cultural/aesthetic ES as direct services from ecosystem, with a
direct effect on human wellbeing. However, the ES approach allowed people to easily realize that the
enjoyment of such ES implies a double relationship with regulation and habitat ES. On the one hand,
intensification of provisioning and cultural/aesthetic services can erode the capacity of ecosystem for
supplying regulation and habitat ES. On the other hand, provisioning and cultural/aesthetic services
heavily depend on the capacity of ecosystems for providing regulation and habitat services. This fact
makes people value regulation and habitat ES not only from the perspective of an environmental abstract
responsibility but also from a material linkage between human wellbeing to ecosystem health. One of the
results of this experience is that workshop’s participants identified regulation and habitat ES as
cornerstones for future human wellbeing and, accordingly, a main part of measures they suggested were
addressed to improve or guarantee the ecosystems capacity to provide them. This approach is promising
to communicate and get social support to measures addressed to achievement of environmental goals in
water management –e.g. good status of water bodies under the WFD.
Distributional issues emerged repeatedly in both case studies. Spatial or temporal asymmetries between
ES production and use were made evident. Participants pointed out the asymmetry between who assumes
the costs for ES production (in form of trade-offs) and who enjoy the benefits. They stressed the need for
a more equitable regulation of natural commons –including economic compensations and use restriction’s
thresholds- that accounts for local people wellbeing and avoids or minimizes spatial or temporal
transference of impacts. The integration of ES conservation as a goal in sector oriented policies –
rationalization of demands- and the need of coordination among different political and administrative
scales and policies was emphasized as a necessary requirement to effectively conserve or improve ES.
The use of scenarios in a deliberative way allowed participants’ creative and strategic thinking under high
uncertainty –the future under global change conditions. Deliberative scenarios are a useful tool for
dealing with complexity, addressing multidimensional aspects, their interdependencies and the
articulation of mix of measures. Participatory techniques give the opportunity for mutual learning and
shared reflection, however participatory processes are time consuming for participants and promoters.
Low participation is a weakness in our experiment. Willingness to participate is much related to potential
participants’ personal motivation. The lack of practical outcomes in terms of influence on decision
making discouraged the attendance of economic and political actors, while introduced an environmental
bias as a majority of participants in workshops had an environmentalist sensibility. This fact reduced the
inclusiveness of discourses.
Acknowledgment
This research has been developed in the framework of the SCARCE Project (Consolider-Ingenio 2010 Project CSD2009-00065),
1
Annex 1 contains an example of the expected effects of suggested measures on the capacity of Noguera de Tor river basin’s water ecosystems
for providing selected WES. The case of Anoia is not included due to space limitations.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 128 Oral presentations funded by the Spanish Ministry of the Economy and Competitiveness.
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UNEP, Malta.
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Annex 1.
Table 1. Expected effects of participant’s measures on the capacity of Noguera de Tor river basin’s water ecosystems for
providing selected WES (grey cells indicate the participant’s selection of WES to be retained for the future wellbeing of river
basin inhabitants). Source: own elaboration based on the III Workshop.
Measures
Voluntary agreement for WES protection
Land use limitations
Ecosystems connectivity
Review of water use rights
Ecological flows
Payment for water provision for hydropower generation
Payment for self-purification and provision of good quality water
Payment for recreational uses of protected areas
Research on impacts of global change on biodiversity
Knowledge transfer
Environmental education
(1)
-
(2)
+
+
-
+
(3)
+
+
-
+
(4)
+
+
+
(5)
+
+
+
+
+
+
+
+
+
+
+
+
(6)
+
+
+
+
+
+
+
+
+
+
(7)
+
+
+
+
+
+
+
+
+
+
Notes: (1) Water for hydropower generation; (2) Water for livestock farming; (3) Water for other economic activities (tourism); (4) Recreational
services; (5) Educational and scientific services; (6) Hydrological regime; (7) Maintenance of ecosystem integrity.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 129 Oral presentations SOLUTIONS for present and future emerging pollutants in land and
water resources management
Werner Brack
Helmholtz Centre for Environmental Research UFZ, Leipzig, Germany
There is evidence that many European surface waters will not achieve the good ecological and chemical
status till 2015 as required by the Water Framework Directive (WFD). Many studies suggest that the
contamination with chemicals significantly contribute to this problem, while it is getting more and more
obvious that priority substances alone do not explain this phenomenon. So-called emerging pollutants
play an important role. They lack regulation but often also appropriate tools for their detection and
understanding and models for exposure, effect and risk assessment.
The large scale FP7 Collaborative Project SOLUTIONS addresses this problem. Starting in October 2013
with 39 partners from all over Europe, but also with partners from China, Australia and Brazil, the 5 years
project wants to provide solutions for the early detection, identification, prioritization, assessment and
abatement of emerging pollutants.
Overall concept
While the chemical status of WFD considers only 33 priority substances together with 8 other chemicals,
we are confronted with a dramatically diverse chemosphere. At present more than 70 million chemicals
are registered in the Chemical Abstract System (CAS), about 14 million chemicals are commercially
available and in typical environmental samples we are able to detect ten thousands of compounds. Thus, it
is not astonishing that priority substances often do not explain observed effects. However, despite the
multitude of chemicals in general, typically much smaller numbers of chemicals are causing the majority
of toxicity, if we focus on distinct toxicological endpoints, organisms or populations. This was shown by
Kortenkamp & Faust (SOLUTIONS proposal) for anti-androgenic effects. Based on monitoring data from
2005 they could show that only 5 chemicals including heterocyclic fungicides, butylparabene and
plasticizers were responsible for 80 % of anti-androgenicity. Only one of them is a priority substance
according to WFD. It is obvious that proper risk assessment has to be well informed on the chemicals that
actually cause a risk. These chemicals however, may be highly variable on the time scale, e.g. due to the
enormous dynamics in the chemicals market. This holds for example for pesticides, such as the fungicides
mentioned above, which are frequently replaced by others because they lose their registration or because
pest become resistant. To properly reflect these dynamics, SOLUTIONS provides an exhaustive
conceptual framework for legacy chemicals, chemicals that are presently in use but also future chemicals.
This framework integrates effect-based and chemical monitoring tools for the early detection and
identification of hazardous chemicals that already accumulated in the environment with modeling tools
based on compound structure, properties and emission data to predict exposure and risks of chemicals in
use. This approach will be also used for future chemicals on the basis of scenarios and predictions. Large
scale case studies are performed to demonstrate the novel tools and models and to mutually validate them.
Tools and Models
SOLUTIONS will provide analytical tools for high-sensitivity determination of chemicals with low
PNECs including novel passive and active sampling tools and advanced methods for sample preparation
and analysis. A second focus is on the development of non-target workflows for compound identification
and structure elucidation based on LC-MS/MS techniques in combination with computer tools. Effectdirected analysis integrating chemical information and effect patterns via fractionation or multivariate
statistics will help to identify those chemicals that cause measurable effects. The development of multiendpoint effect-based monitoring tools for the early detection of hazardous chemicals in the aquatic
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 130 Oral presentations environment is a key issue in SOLUTIONS. Effect-based tools follow the concept of Adverse Outcome
Pathways (AOP) and strive to provide appropriate tools for different levels of biological organization.
Effect-based monitoring tools will be supplemented with trait-based ecological tools to detect ecosystem
degradation that may be caused by toxicants.
An integrated system of models and databases will be established to understand and predict exposure to
emerging pollutants and related risks. Emission estimation modeling will be combined with multicompartment modeling of fate and transport and distributed modeling on a basin scale in order to estimate
pollutant concentrations in European surface waters. Key factors will be together with spatial data for
river basin characterization the physico-chemical properties of the compounds that determine exposure.
Structure-based modeling of substance properties will fill the significant data gaps. A specific focus is
given on ionic, polar and multifunctional compounds where traditional approaches e.g. based on log KOW
fail. Mode-of-action specific toxicity prediction and mixture effects modeling will be interlinked with
exposure modeling to predict ecosystem and human health risks.
Case studies
SOLUTIONS tools will be demonstrated in three case studies including the Danube basin, the Rhine
basin and the river basin under SCARCE. The major focus of the Danube basin case study is on the
establishment of River Basin Specific Pollutants. The SOLUTIONS investigations are closely linked to
Joint Danube Survey 3, which provides SOLUTIONS with samples and data and will benefit from the
new evaluation tools. The Rhine case study will have a specific focus on abatement options in waste and
drinking water management. The case study in Spanish rivers will evaluate SOLUTIONS tools under
water scarcity conditions and will integrate and evaluate SCARCE and SOLUTIONS approaches.
Products
Solutions for prioritization, assessment and management of emerging pollutants will include
•
•
•
•
•
•
user-friendly guidelines for innovative monitoring and modeling tools
a solution-oriented computer tool to support decisions
abatement options in waste and drinking water management
a common knowledge base on a wide range of toxicants
scenarios and solutions for upcoming risks and
potential opportunities and obstacles for cooperation of WFD with other policies
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 131 Oral presentations Managing Aquatic ecosystems and water Resources under multiple
Stress (MARS)
Christian K. Feld1,2, Sebastian Birk1 and Daniel Hering1,2
1
2
Department of Aquatic Ecology, Faculty of Biology, University of Duisburg-Essen, Essen, Germany
Centre for Water and Environmental Research (ZWU), University of Duisburg-Essen, Essen, Germany
Summary
Managing Aquatic ecosystems and water Resources under multiple Stress (MARS) is an Integrated
Research Project, funded by the European Union within the Seventh Framework Programme. MARS will
have a duration of four years and will start on February 1st, 2014. Within MARS, nearly 100 scientists and
practitioners, representing 24 partner institutions in 16 European countries, will address the effects of
multiple stressors in surface water and groundwater bodies and its management.
The MARS workplan is organised at the scales of water bodies, river basins and all-Europe, with a direct
link to water authorities and decision makers at each scale. Nested within this spatial structure, the project
will employ a suite of flume and mesocosm experiments to gain a better understanding of the effects of
selected stressors and its combinations, with one focus on hydrological and thermal extremes. This
research will lead to a Europe-wide overview of environmental stressors, their present and future impact
on ecological status and aquatic ecosystems services.
MARS is composed of eight workpackages addressing the development of tools, concepts and scenarios
for river basin management under multiple stressors, and synthesising the empirical research findings
across experimental, river basin and all-Europe scales. To transfer MARS’ research findings into applied
river basin management, amongst others a wiki information system will be set up to disseminate the
MARS outcome among different groups of end users. Eventually, MARS will frequently communicate
the outcome with representatives of river basin districts and the Common Implementation Strategy (CIS)
groups and will advise the WFD revision.
Multiple stressors are largely unaddressed in operational monitoring
Multiple stressors impact Europe’s water resources and aquatic ecosystems (Schinegger et al. 2012), with
often complex effects on ecological and chemical status, water quantity and ecosystem functions and
services. Many existing assessment methods (Birk et al. 2012) focus on the assessment of
hydromorphological degradation, which itself is composed already of multiple hydrologic (flow, water
abstraction, habitat), hydraulic (sheer stress) and morphological (straightening, barriers, damming, bank
fixation) impairments (ETC-ICM 2012). In recent years, agricultural land use at the catchment scale has
increasingly been addressed in bio-indication (e.g. Feld 2013), yet this particular land use actually bears a
cocktail of ‘pollution’ stressors, composed of nutrient pollution (from fertilisers), fine sediment pollution
(from surface run-off) and toxic pollution (from pesticides).
While present indicator systems usually detect these combined effects of the stressors, they fail at
disentangling the hierarchy and effects of the various stress components. Knowledge of the latter,
however, is fundamentally important to manage river basins, i.e. to reduce and mitigate the individual
stressors in order of their importance for the overall ecological status. Further, there is knowledge already
from previous research that multiple stressors may interact synergistically or antagonistically (Wagenhoff
et al. 2011). Therefore, the investigation of the effects of multiple stressors on ecological status, but also
on ecosystem functions and services is timely and urgently required to inform the management of
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 132 Oral presentations Europe’s waters.
Objectives of MARS
In a pre-project survey of Europe’s river basin management plans, MARS identified a set of major
obstacles with regard to multiple stressors:
•
Little is known about the combined effects of multiple stressors—although the majority of water
bodies in Europe is affected by more than one stressor.
•
Simple dose-response relationships between stress intensity and biological effects are not
sufficient under multiple-stress conditions for developing appropriate management measures.
•
There is a weak understanding of how multiple stressors affect degradation and restoration.
•
There is a weak knowledge of the order of importance of individual stressors. This knowledge is
required to prioritise restoration and mitigation measures.
Further, the implementation of measures requires convincing arguments beyond the concept of ecological
status, in order to better inform society about the need for—and the benefits of—restoration. The value of
ecological restoration is difficult to communicate to policy and decision makers and to the public in
general, especially in times of the economic crisis in Europe. Therefore, supplementary indicators
targeting ecosystem services are required to inform the public about the benefits of ecologically intact
ecosystems.
MARS aims at overcoming these obstacles and filling these gaps in river basin management. New
research as well as the synthesis of existing knowledge will be conducted to disentangle the impacts of
multiple stressors on three response categories: i) ecological status ii) functions and iii) services of surface
and ground waters in Europe. New indicators will be developed to predict the implications of river basin
management on the three response groups. The outcome will feed into a toolbox to provide end users with
an enhanced understanding of the ecosystem processes underlying degradation and recovery. This will
help end users quantify the links between the status of aquatic ecosystems and their functioning and
services. The MARS tools will make use of existing prototypes and aim to contribute to the toolbox
proposed in the Blueprint to Safeguard Europe’s Water Resources.
Conceptual approach
Alike the spatial organisation of river basin management plans, the MARS research activities are
organised at different spatial scales. At the water body scale, mesocosm and flume experiments will help
enhance the mechanistic understanding of how stressors interact and impact upon water resources. This
new experimental data will allow to identify threshold responses to optimise stress reductions. A focus
will be on the effect of extreme climate events such as heavy rainfall, heatwaves, water scarcity and the
effects of environmental flows.
At the river basin scale, relationships between multiple stressors and ecological responses, functions,
services and water resources will be identified. The effects of land use change and mitigation scenarios
will be predicted. Altogether, 16 river basins in Europe, chosen to represent a wide range of multiple
stress conditions, will be investigated based on existing data from the catchments (Table 1).
At the European scale, the relationships among stress intensity, ecological status and service provision
will be investigated, with a special focus on large, transboundary rivers, lakes and fish as sentinels of
multiple stressor impacts on biodiversity and direct providers of ecosystem services.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 133 Oral presentations Table 1. River basin case studies of MARS including data availability.
30
31
89
16
28
597
428
100
140
400
140
400
15
30
30
37
30
31
3
300
180
30
20
100
300
40
200
2
10
20
37
30
31
80
18
250
1192
113
300
1600
40
400
5
10
20
37
70
31
80
18
900
1003
40
45
50
12
50
5
10
20
27
30
31
2
18
20
117
27
90
50
12
100
8
8
20
37
Water category
Plankton/ phytobenthos
EFSW
RS
HSW
FRS
FR
EFSW
S
RW
FW
SW
EFH
FRSW
HRS
FHR
HRWS
FRW
Macrophytes
3
3
3
3
3
2
2
2
2
2
2
1
1
1
1
1
Invertebrates
Ecosystem services
Multiple stressor group
Stressors
EHLMT
EMT
EHLMT
EHL
EHIM
EHILT
EHLM
EHMT
EHM
EHMT
HM
EHLMT
EIT
HILT
EHMT
EFHT
Fish
South
South
South
South
South
Central
Central
Central
Central
Central
Central
North
North
North
North
North
Physico-chemistry
Sorraia
Nervion Ibaizabal
Pinios
Beysehir
Lower Danube
Thames
Regge and Dinkel
Odense
Elbe
Ruhr
Drava
Welsh basins
Vansjø-Hobøl
Otra
Kokemäenjoki
Võrtsjärv
Region
Basin name
Stressors: E=Eutrophication/Organic pollution, F=Fisheries, H=Hydrology/Water scarcity, I=Invasives/Pathogens
L=Temperature/Light, O=Morphology/Shipping, T=Toxics. Multiple stressor groups: 1=Hydrology/temperature, 2=Hydrology,
morphology, nutrients, 3=Water scarcity, flow alterations. Ecosystem Services: E=Ecological Flows, F=Fisheries,
H=Hydropower, R=Recreation, S=Water supply, W=Water purification. Water category: L=Lake, G=Groundwater,
T=Transitional water, R=River. Numbers in columns six to ten indicate the number of samples available for each quality
element..
LGT
T
L
LG
R
LGT
G
LT
G
R
R
R
L
R
LG
L
The MARS model
MARS establishes a framework that explicitly links the assessment of risk, status and ecosystem services
within the framework of RBMPs, therefore providing a close integration of stressors, ecosystems and
services (Fig. 1). Risk assessment combines the level of a single stressor—or of a combination of
stressors—with an indicator’s response sensitivity to the stressor(s). The ecological status assessment
centrally fits into the Driver-Pressure-State-Impact-Response (DPSIR) framework: Drivers (e.g. society’s
food demand) cause Pressures (equivalent to stressors, e.g. land use) and consequently affect water body
State (e.g. through enhanced nutrient levels). This has Impacts on ecological State and ecosystem
functioning (e.g. loss of filter feeding taxa and its related filtering of particulate organic matter) and can
cause the reduction or entire loss of ecosystem services (e.g. the self-purification capacity of a stream
section). Eventually, society’s Response is required, for example through environmental regulation
policies (e.g. restoration). Ecosystem services are generally considered through the ‘cascade model’,
which links the structure, functions and processes of ecosystems to a specific service. The service may be
translated into societal benefits or values associated to human well-being. Indicators link between the
three frameworks (Fig. 1). Further, management decisions (Response) are not only based on the StateImpact chain through the DPSIR model, but must consider ecosystem service values, too. MARS will use
this linked model to support management decisions and scenario-testing.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 134 Oral presentations Figure 1. The MARS conceptual model for an integrated assessment framework.
Dissemination of MARS outcome
MARS will officially start on February 1st, 2014 and will be kicked off at the first consortium meeting in
mid-February. A detailed description of MARS and frequent updates on its progress will be provided
soon at www.mars-project.eu. A blog will complement the project website to more frequently address
project features and invite the public to discuss those with members of the MARS consortium. The
MARS Wiki will provide more detailed information and background knowledge on both the impacts of
multiple stressors on the aquatic environment and suited measures to address their management.
Acknowledgements
Managing Aquatic ecosystems and water Resources under multiple Stress (MARS) is a EU-funded integrated project within
Framework Programme 7, Theme ENV.2013.6.2-1: Water resources management under complex, multi-stressor conditions
(contract No. 603378).
References
Birk, S., Bonne, W., Borja, A., Brucet, S., Courrat, A., Poikane, S., Solimini, A., van de Bund, W., Zampoukas, N. and Hering,
D. Three hundred ways to assess Europe's surface waters: An almost complete overview of biological methods to implement the
Water Framework Directive. Ecological Indicators (2012), 18, 31–41.
ETC-ICM. Hydromorphological alterations and pressures in European rivers, lakes, transitional and coastal waters. ETCICM
Technical Report 2/2012, European Topic Centre on Inland, Coastal and Marine waters, Prague.
Feld, C.K. Response of three lotic assemblages to riparian and catchment-scale land use: implications for designing catchment
monitoring programmes. Freshwater Biology (2012), 58, 715–729.
Schinegger, R., Trautwein, C., Melcher, A. and Schmutz, S. Multiple human pressures and their spatial patterns in European
running waters. Water and Environment Journal (2012), 26, 261–273.
Wagenhoff, A., Townsend, C.R., Philipps, N. and Matthaei, C.D. Subsidy-stress and multiple-stressor effects along gradients of
deposited fine sediment and dissolved nutrients in a regional set of streams and rivers. Freshwater Biology (2011), 56, 1916–
1936.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 135 Oral presentations GLOBAQUA: Managing the effects of multiple stressors on aquatic
ecosystems under water scarcity
Sergi Sabater1, Alícia Navarro-Ortega2 and Damià Barceló1,2
2
1
Water and Soil Quality Research Group, Department of Analytical Chemistry, IDAEA-CSIC, Barcelona, Spain
Introduction
Water is the most essential of all natural resources and consequently water and water-related services are
major components of the human wellbeing and major factors of socio-economic development in Europe.
Nowadays, freshwater ecosystems are under threat due to a great variety of stressors that can have
deleterious effects on them, including organic and inorganic pollution, geomorphological alterations, land
cover change, water abstraction, invasive species and pathogens and water scarcity (Vörösmarty et al.,
2010). Most of our current knowledge is based on the effects of single stressors on the chemical and
ecological status (Maltby, 1999) and ecosystem functionality. This limits our capacity to understand
ecosystem responses to multiple stressors. Water scarcity is a structural, persistent drought affecting
resources and aquatic ecosystems, with implications in water quality and societal needs, that occurs when
water demand exceeds the water resources exploitable under sustainable conditions (Sabater and Barceló,
2010). It can be a stressor on its own because of its structural character but it can also drive the effects of
other stressors (e.g., increasing concentrations of pollutants in rivers resulting from a constant input of
pollution and decreasing water availability (Petrovic et al., 2011)). Water scarcity is therefore a key
stressor because of its direct and indirect effects in terms of the chemical and ecological status, but also in
terms of the sustaining of ecosystem services
(Heathwaite, 2010). Water scarcity is among the main
problems to be faced by many societies in the 21st
century because water use has been growing at more
than twice the rate of population increase in the last
century. In particular water scarcity has long formed
an integral part of the Mediterranean environment, but
today exponential demographic growth, climate
change and pollution form a growing threat to the
resource. As a semi-arid region, water scarcity is
present in natural conditions in the Mediterranean are
due to the characteristic highly variable river flows and
occurrence of low flows of the Mediterranean climate.
In addition, the Mediterranean basin is one of the most
sensitive areas of the world regarding possible
consequences of the present climate change (Barceló
and Sabater, 2010) as well as one of the most impacted
because of human water demand. Water scarcity is not
only a simple matter of available resources for the
human necessities. The natural systems also need good
quality to guarantee their viability and functioning. To
forget their necessities increases the danger in their
existence but also in the quality of the services that
they deliver.
Fig 1. Conceptual links considered in the projects
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 136 Oral presentations In order to properly address the effect of stressors in policy terms, a coordinated effort on the research
that considers multiple perspectives is needed. A range of national and EU-funded research projects are
directly or indirectly supporting water and climate policies, in particular the scientific challenges posed by
the EU Water Framework Directive (WFD) and other policies. Within this context GLOBAQUA project
has assembled a multidisciplinary team of leading scientist in the fields of hydrology, chemistry, ecology,
ecotoxicology, economy, sociology, engineering and modelling in order to study the interaction of
multiple stressors within the frame of strong pressure on water resources. The aim is to achieve a better
understanding on how current management practices and policies could be improved by identifying the
main drawbacks and alternatives (Fig. 1).
GLOBAQUA project
As one of the last FP7 projects (European Commission), GLOABAQUA, with the full title “Managing
the effects of multiple stressors on aquatic ecosystems under water scarcity” is a 5-year project that will
start on February 2014 as a follow up of SCARCE project. The consortium is composed of 21 European
partners from 8 countries (including 1 SME) and 2 non-EU partners from Morocco and Canada. The
institutional experience of the Consortium covers a range of disciplines: chemistry, biology, ecology,
geomorphology, hydrology, economics and sociology, including hydrological, biophysical and ecological
modelling, socio-economics and governance science, knowledge brokerage and policy advocacy.
Scientific management of the project is carried out by the Water and Soil Quality Research Group of the
Institute of Environmental Assessment and Water Research of the Spanish Council for Scientific
Research of Barcelona (IDAEA-CSIC). The GLOBAQUA team includes practitioners and policymakers
(Stakeholder Panel) who will ensure that the project is highly relevant to end-user needs. By bringing
together researchers with strong international experience and end-users with key expertise in the region, a
critical mass of experience and knowledge will be mobilized to carry out the project activities. The
partnership is a result of cooperation of several initiatives, existing networks and research projects.
GLOBAQUA has two major complementary objectives. The first objective deals with fundamental
research questions: improvement of our knowledge on relationships between multiple stressors, to
identify potentially synergistic linkages and to assess how these interactions might determine changes in
the chemical and ecological status. In this sense, special attention will be given to the role of water
scarcity as a central stressor and to the relationships between biota (different level of biological
organization) and stressors. This envisages a holistic approach that would range from the assessment of
effects on water quality, organisms and ecosystems to the effects on socio-economical regional
development. Our aim is to establish cause-effect relationships between multiple levels using integrative
modelling. The second objective address the urgent need to improve water management practice and
policies by taking into consideration the influence of multiple stressors; this should especially comprise
the WFD (2000/60/EC) and other related regulations. The objective will be performed through analysis of
current policies and scenario analysis of alternative management practices and policies.
Structure of GLOBAQUA
To answer the integrated questions posed within GLOBAQUA, a cross-scale approach will be applied in
several representative basins. The basic research element will be the kilometre-scale river reach, including
the river channel, the alluvial plain and associated groundwater. GLOBAQUA structure offers a strong
interdisciplinary team, facilitating the knowledge transfer between the research and stakeholder sectors.
The project is organised through highly integrated fourteen WPs, which are grouped in five main
Modules (Fig. 4):
•
Module STRESSORS: is defined to understand the mechanisms behind the multiple stressors acting
in each case study, WP1-DATA will collect existing data from basin authorities and previous
research projects, and will gather experimental data generated within the project. WP2-SCENARIOS
will generate climatic, socioeconomic and land-use scenarios to provide drivers for the impact
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 137 Oral presentations modelling. Its results will set the boundary conditions for the subsequent modelling WPs. WP3HYDROL, WP4-GEOMORPH and WP5-QUALITYCHEM will analyse surface and groundwater
hydrological patterns, sediment and pollutant transport, and quality of the physical habitat and the fate
of inorganic and organic pollutants, respectively.
STRESSORS
WP1-DATA
WP2-SCENARIOS
REC EPTORS
WP3-HYDROL
WP6-BIOL
WP5-QUALITYCHEM
WP7-ECOSYSTEM
IMPLICATIONS
WP8-SERVICES
ENV.
MGT
COORD.
DISSEM.
WP4-GEOMORPH
WP14-MANAGE
WP9-SOCIOECON
WP10-VALUATION
WP1- INTEGRATION
WP12-POLICY
WP13-DISSEMINATION
Fig 4. GLOBAQUA project structure and interaction between WPs
•
Module RECEPTORS: will analyse the effects of the stressors on biodiversity (WP6-BIOL) and
ecosystem functioning (WP7-ECOSYSTEM). Research will be based on manipulative laboratory
experiments using artificial streams, reach-scale measurements, and basin-scale surveys, aiming to
understand effects of single and multiple stressors at different scales and to feed models dealing with
the data at either the reach or basin scales. Results at the lab and reach-scale will be used to feed
mechanistical models at the reach scale, whereas basin-scale results will be used to feed statistical
integrative models at the basin scale.
•
Module IMPLICATIONS: On one hand, WP8-SERVICES will integrate the information generated
by WP6-BIOL and WP7-ECOSYSTEM on the effects of stressors on receptors (biodiversity and
ecosystem functioning) into integrative models at the reach or basin scales. These models will
therefore relate changes in stressors with changes in diversity and ecosystem functioning and, in turn,
with ecosystem services in biophysical terms. On the other hand, WP9-SOCIOECON will
characterize the socioeconomical setting of case-study basins to support the ecosystem services
valuation performed by WP10-VALUATION. Finally, impact of the changes in ecosystem services in
economic terms on the socioeconomic development will be assessed by WP10-VALUATION. This
will help to identify environmentally and socioeconomically sustainable management of water
resources.
•
Module ENVIRONMENTAL MANAGEMENT: includes two WPs dealing with relevant issues
associated to the impact of multiple stressors on water quality, quantity, and ecosystems, as well as on
the potential implementation of the major findings on European policy. Therefore, WP11INTEGRATION will develop a model framework to assess scenarios affecting availability, quality
and demand of water at the European scale. This WP will integrate the most relevant results of the
previous WPs in other modules to define a manageable perspective on the multistressor consequences
for European river basins. The implications of the stressors interactions and their opportunities for the
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 138 Oral presentations related policy making will be analyzed in WP12-POLICY. Therefore this WP is defined as a real
interface between the scientific results obtained all along the project with their policy definition and
development.
•
Module PROJECT COORDINATION AND DISSEMINATION: these WPs (WP13DISSEMINATION and WP14-MANAGE) will run during the whole project duration to guarantee (i)
communication of the results to specific target groups (researchers, policy makers, water managers,
land planners, …), stimulation of their use through relations with stakeholders and end-users, training
programs for different end-users, screening of IPR potential and (ii) efficient coordination of all
activities, day-to-day technical management, overall financial and administrative management of the
GLOBAQUA consortium and cooperation with stakeholder and scientific panels.
Study basins
Three representative basins from the Mediterranean European region, where water scarcity is the main
problem, as well as one Southern Mediterranean basin (North Africa), have been selected to obtain a
complete Mediterranean perspective and an expanded vision of the water scarcity implications. In order to
achieve a full European dimension, one Alpine and one UK river basin, where scarcity is a growing issue,
have been also included among the case studies. In total six basins have been selected, in which several
studies will take place in order to answer the integrated questions that have been put forward in
GLOBAQUA. Based on the use of both surface and groundwater resources, the selected basins
encompass a rich set of socio-ecological conditions (forested mountainous areas, highly populated
watersheds relying on water transfers, agricultural areas and industrial clusters), and a complete
geographic coverage, therefore facilitating the necessary vision to understand the European reality on the
combined effects of multiple stressors on ecosystems and humans. The effect of multiple stressors on
water availability and quality, and their effects on the chemical and ecological status will be examined,
and the existing dysfunctions identified. Each basin will focus on a specific set of stressors to illustrate
different management scenarios. The selected river basins for GLOBAQUA are: Ebro (Spain), Sava
(Slovenia, Croatia, Bosnia and Herzegovina and Serbia), Evrotas (Greece), Souss Massa (morocco),
Anglian (UK) and Adige (Italy) (Fig. 5). In four of them (Adige, Sava, Ebro and Evrotas) an extensive
field work will be done in order to collect information on different stressors (pollution, pathogens,
invasive species, geomorphological and flow regime alterations), while in two of them (Anglian river
basin district and Souss Massa) the existing data will be used to evaluate different management scenarios.
Fig. 5 The six Basins studied in GLOBAQUA
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 139 Oral presentations Final remarks
GLOBAQUA aims at addressing the fundamental need of connecting the occurrence of multiple stressors
in a situation of water scarcity with the policy implementation in European river basins bringing together
a large group of researchers, stakeholders and policy makers across a wide range of disciplines. This
challenge is met by communication tools including an Internet Platform for data Exchange but also many
scientific meetings among the various groups. The structure of the project into WPs allows sharing
responsibilities between researchers who are specialists in their respective fields. The work performed by
the different WPs expands through different scales, starting from the monitoring and modeling studies to
the river basin scale. The achievement of an overall good status of European water bodies until 2015
(according to the WFD timetable demands) poses a crucial challenge not only to water management
agents but also to policy makers on different scales, the scientific community and the society in general.
Management approaches to tackle EU water challenges will only work in the framework of cross border
actions integrating all relevant stakeholders and by making use of cutting-edge scientific knowledge. The
added value of this collaboration lies in the possibility of addressing the problems arising from the
scarcity and multiple stressors pressures and their effects on the ecosystem services, and the overall
effects of global change. Taking into account the interaction between all main environmental
compartments and processes involved, a complete picture of the situation can be obtained, and possible
solutions are visualized at different levels. Other benefits are mutual enrichment, methodological
knowledge transfer, etc. Overall, the synergy of the different groups arises from their different expertise
that complements each other to get a holistic picture of the problem, as well as potential solutions.
Acknowledgements
This work has been supported by the Spanish Ministry of Science and Innovation through the project SCARCE of ConsoliderIngenio 2010 program (CSD2009-00065). It has also received funding from the European Comunities 7th Framework Programme
under Grant Agreement No. 603629-ENV-2013-6.2.1-Globaqua. Special thanks are due to all partners of the SCARCE and
GLOBAQUA consortium and the peer review panels for ensuring quality results and fruitful collaboration within the projects.
References
Barceló D, Sabater S. Water quality and assessment under scarcity: Prospects and challenges in Mediterranean watersheds.
Journal of Hydrology 2010;383: 1-4
Heathwaite AL. Multiple stressors on water availability at global to catchment scales: understanding human impact on nutrient
cycles to protect water quality and water availability in the long term. Freshwater Biology 2010;55: 241-257
Maltby L. Studying stress: The importance of organism-level responses. Ecological Applications 1999;9: 431-440
Petrovic M, Ginebreda A, Acuna V, Batalla RJ, Elosegi A, Guasch H, Lopez de Alda M, Marce R, Munoz I, Navarro-Ortega A,
Navarro E, Vericat D, Sabater S, Barcelo D. Combined scenarios of chemical and ecological quality under water scarcity in
Mediterranean rivers. Trac-Trends in Analytical Chemistry 2011;30: 1269-1278
Sabater S, Barceló D (2010). Volume preface. Water Scarcity in the Mediterranean. Perspectives Under Global Change. Sabater
S, Barceló D, Springer Berlin Heidelberg
Vörösmarty CJ, McIntyre PB, Gessner MO, Dudgeon D, Prusevich A, Green P, Glidden S, Bunn SE, Sullivan CA, Liermann CR,
Davies PM. Global threats to human water security and river biodiversity (vol 467, pg 555, 2010). Nature 2010;468: 334-334
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 140 Oral presentations 4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain Poster sessions
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 143 Poster sessions Development and optimization of configuration IT-SPME coupled to
UHPLC-MS/MS to the analysis of organic pollutants in water samples
Ana Masiá1, Yolanda Moliner-Martínez2, María Muñoz-Ortuño2, Yolanda Picó1 and Pilar
Campíns-Falcó2
1
2
Department of Analytical Chemistry, Faculty of Chemistry, University of Valencia, Burjassot, Spain
In-Tube Solid Phase Microextraction (IT-SPME) is a mode of SPME which typically uses a GC capillary
column with a proper coating to extract the analytes, becoming a useful approach for on-line enrichment
of analytes without any previous sample treatment [1]. The aim of this work was to couple IT-SPME with
UHPLC-MS/MS system, reaching the selectivity and sensitivity necessary to determine organic pollutants
at sub-µg/L level in water samples according to the maximum concentration levels established in the
legislation.
For this configuration, two six port valves were used for sample preparation to prevent the high back
pressures of the UHPLC column, which could negatively affect the IT-SPME system. Water samples (4.0
mL) were passed through the capillary in valve 1 by means of a 1.0 mL precision Hamilton syringe. Then,
40 µL of methanol were injected in valve 1 to desorb the analytes from the extractive phase of the GC
capillary, and the second valve was manually rotated to INJECT position, so the analytes were transferred
to the analytical column by the mobile phase for separation and detection (see Figure 1)
Water sample +
µl methanol
VALVE 1
INJECTION
LOAD
VALVE 2
Open Capillary column
TRB-35
LOAD
Pump
VALVE 1
Water sample +
µl methanol
DESORPTION
LOAD
VALVE 2
Waste
Internal
loop 5µl
Analytical column
INJECT
Open Capillary column
TRB-35
MS/MS
Pump
Internal
loop 5µl
Analytical column
MS/MS
Figure 1: Configuration of IT-SPME-UHPLC-QqQ-MS/MS
Separation was carried out on a UHPLC C18 column (1.7 µm, 2.10 × 50 mm) using a gradient elution
profile of mobile phase consisting of 10 mM ammonium formate in both methanol and water. Then,
analytes were detected with a mass spectrometer using an electrospray ionisation (ESI) source in positive
mode. The two most intense precursor ion → product ion transitions were monitored to obtain
unambiguous confirmation of the compound identity, excepting for trifluoralin.
The described method offers good accuracy and reproducibility and a high enrichment factor (ca. 15),
lineal answer (r > 0.99) and precision (RSD < 20%) are reached, suitable to control the surface water
quality for different pollutants. Moreover, this technique allows simplifying the sample preparation, to
diminish the sample volume needed, the number of off-line steps and the amount of solvents employed.
Acknowledgements
This work has been supported by the Spanish Ministry of Economy and Competitiveness through the projects SCARCE
(CSD2009-665), CGL2011-29703-C02-02 and CTQ 2011-26760. YM-M expresses her gratitude for the JdC (Ministerio de
Ciencia e Innovación) research contract
References
Masiá, A., Moliner-Martínez, Y., Muñoz-Ortuño, M., Picó, Y. and Campíns-Falcó, P. Multiresidue analysis of organic pollutants
by in-tube solid phase microextraction coupled to ultra-high performance liquid chromatography-electrospray-tandem mass
spectrometry, J. Chromatogr. A (2013), 1306, 1-11.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 144 Poster sessions Analysis of organic persistent pollutants compounds by gas
chromatography tandem mass spectrometry in biota samples from four
Spanish rivers
Elena Martínez1, Àngels Quiroga1 and Damià Barceló1,2
1 1
2
In this work, legacy organic persistent pollutants (POPs), such as organochlorinated compounds (OCs)
have been studied in fish samples collected in four Spanish rivers: Ebro, Llobregat, Guadalquivir and
Jucar.
The extraction and clean-up was performed using a multi-residue method based on homogenization and
lyophilisation of the samples followed by ultrasonic assisted extraction and purification via acidic attack
with H2SO4conc. The final extracts were obtained by liquid-liquid extraction with hexane, concentration
under a nitrogen stream and reconstitution to a final volume of 300 μl. The potentials losses during this
step were corrected by the use of labelled subrogate internal standards.
The extracts were subsequently analysed by gas chromatography coupled to tandem mass spectrometry
(GC-MS/MS) using a triple quadrupole analyser (QqQ) working in selected reaction monitoring (SRM)
mode. Separation was achieved using a capillary column HP-5MS of 30m x 0.25 mm i.d. with 0.25 µm
film thicknesses from J&W Scientific (Folsom, CA, USA).
The limits of detection (LODs) and limits of quantification (LOQs) of the method were calculated by
analysis of spiked biota with minimum concentrations of each individual compound at a signal-to-noise
ratio of 3 and 10, respectively.
The optimized method showed an adequate sensitivity and robustness to be applied in the analysis of
selected compounds in complex samples as biota. The method limit of detection and quantification
(MLODs and MLOQs) in biota these were in the range between 0.075 and 0.600ng/g and between 0.600
and 8ng/g, respectively. The recovery ranges were between 65% and 102% for all the compounds.
The results of this study showed that the group of DDTs were the predominant compounds and were in
general detected in the range between the MLOQ and 15 ng/gw.w.
Acknowledgements
2010 CSD2009-00065 and CGL2011-29703-C02-02. We also thank the persons of IDAEA and ICMAN for taking the samples.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 145 Poster sessions Stir bar sorptive extraction of 100 micropollutants from aqueous
samples and determination by gas chromatography-mass spectrometry:
electrospray ionization vs atmospheric pressurized gas
chromatography
Marina G. Pintado-Herrera1, Eduardo González-Mazo1 and Pablo A. Lara-Martín1
1
Department of Physical-Chemistry, Faculty of Marine and Environmental Sciences, University of Cadiz, Campus of
International Excellence of the Sea (CEI.MAR), Puerto Real, Spain
This work presents the development, optimization and validation of a new multi-residue method (100
analytes) for the simultaneous determination of emerging contaminants, such as fragrances, UV filters,
repellents, endocrine disruptors and biocides (40 analytes) and regulated pollutants (polycyclic aromatic
hydrocarbons (PAH), polychlorinated biphenyls (PCB), organochlorine and organophosphorus pesticides,
triazines and pyrethroids) (60 analytes) in aqueous matrices. Water samples were processed using the stir
bar sorptive extraction technique (SBSE). Several parameters were optimized for this technique, such as
extraction time, ionic strength, presence of organic modifiers, pH, concentration of humic acids, and
volume of the derivatization agent. Briefly, 10 mm stir bars coated with polydimethylsiloxane (PDMS)
were placed in a flask containing water samples (100 mL) with acetic anhydride, sodium carbonate and
sodium chloride, and stirred for 5-6 hours at room temperature. Target compounds were extracted from
the bars either by thermal (TD) or by liquid desorption (LD) using a reduced amount of solvent (200 μL).
Water samples were analyzed then by means of gas chromatography coupled to two different mass
spectrometry analyzers, therefore comparing their sensitivity and selectivity: single quadrupole (GC-MS)
and time of flight (GC-ToF-MS). Two types of ionization sources were also tested: electronic impact (EI)
and atmospheric pressure gas chromatography (APGC). The optimized protocol showed acceptable
recovery percentages (50-100%) for most of the analytes, and limits of detection were often below 1
ng/L. Several micropollutants were identified and quantified in several environmental aquatic
compartments, such as seawater, sewage effluent, river and groundwater. Additionally, using unique
features provided by GC-APGC-ToF-MS, several non-target compounds such as new emerging
organophosphorus flame retardants were identified. This is the first time that this technique has been
applied for the analysis of contaminants in environmental matrices, showing significant advantages over
more widely used EI such as “soft” ionization and accurate mass measurement of molecular ions and their
fragments.
Acknowledgements
This study was carried out within the two projects funded by the Consejería de Innovación, Ciencia y Empresa de la Junta de
Andalucía (RNM 5417 and RNM 6613)
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 146 Poster sessions Screening of perfluorinated compounds in water, sediment and biota
of the Llobregat River basin (NE Spain)
Julián Campo1, Francisca Pérez2, Yolanda Picó1, Marinel.la Farré2 and Damià Barceló2,3
1
2
2
PFCs present significant thermal and chemical stability being persistent in the environment, where they can
bio-accumulate and adversely affect humans and wildlife (Llorca et al., 2012). Human exposure to PFCs is
of concern since PFCs tend to be associated with fatty acid binding proteins in the liver or albumin proteins
in blood, and have been detected in human serum, urine, saliva, seminal plasma and breast milk (Sundstrom
et al., 2011). This study is aimed at the screening of 21 perfluorinated compounds (PFCs) in environmental
samples by high-performance liquid chromatography tandem mass spectrometry (LC-MS/MS). The main
objective is to identify target compounds at low levels in water, sediments and biota of the Llobregat River
(2010), second longest river in Catalonia and one of Barcelona’s major drinking water resources. PFCs were
extracted from water samples by Solid Phase Extraction (SPE); from sediment by ultrasonication with
acidified methanol followed by an off-line SPE procedure (Picó et al., 2012), and from biota (fish) with
alkaline digestion, clean-up by TurboFlow™ on line technology coupled to LC-MS/MS (Llorca et al., 2012).
The limits of detection (LODs) and limits of quantification (LOQs) of the method were calculated by
analysis of spiked river water, sediment, and biota with minimum concentrations of each individual
compound at a signal-to-noise ratio of 3 and 10, respectively. The LODs and LOQs of the method in river
water ranged between 0.004 and 0.8 ng L−1 and between 0.01 and 2 ng L−1, respectively. In sediment
LODs were 0.013-2.667 ng g−1 dry weight (dw) and LOQs were 0.04-8 ng g−1 dw, meanwhile in biota
these were 0.006-0.7 pg μL-1 and 0.02-2.26 pg μL-1, respectively. Recoveries ranged between 65% and
102% for all target compounds. The method was applied to study the spatial distribution of these
compounds in the Llobregat River basin. For this, a total of 40 samples were analysed (14 water, 14
sediments, 12 fishes). Of the 21 target compounds, 13 were identified in water samples (PFBA, PFDA,
PFHpA, PFHxA, PFHxDA, PFNA, PFOA, PFPeA, PFTrDA, PFUdA, L-PFBS, L-PFHxS and L-PFOS),
and their concentrations ranged between 0. 1 ng L−1 (PFNA) and 2709 ng L−1 (L-PFOS). Similarly,
PFBA, PFDA, PFDoA, PFHpA, PFNA, PFOA, PFPeA, PFTrDA, PFUdA, L-PFBS, L-PFHxS, L-PFOS
and PFOSA were identified in sediments samples, with concentrations ranging from 0.147 ng g−1 dw (LPFOS) to 13 ng g−1 dw (PFBA). In biota similar PFC were detected, with values between 0.03 and
1738.06 ng g−1. According to this study, PFCs were detected in different compartments of the ecosystem
where they are bio-accumulating and, potentially, would produce adverse effects on humans.
Acknowledgements
2010 CSD2009-00065 and CGL2011-29703-C02-02. We also thank the persons of IDAEA for taking the samples.
References
Llorca, M., Farre, M., Pico, Y., Muller, J., Knepper, T. P., Barcelo, D., 2012. Analysis of perfluoroalkyl substances in waters
from Germany and Spain. Sci. Total Environ. 431, 139-150.
Llorca, M., Pérez, F., Farre, M., Agramunt, S., Kogevinas, M., Barceló, D., 2012. Analysis of perfluoroalkyl substances in cord
blood by turbulent flow chromatography coupled to tandem mass spectrometry. Sci. Total Environ. 433, 151-160.
Pico, Y., Blasco, C., Farre, M., Barcelo, D., 2012. Occurrence of perfluorinated compounds in water and sediment of L'Albufera
Natural Park (Valencia, Spain). Environ.Sci.Pollut.Res. 19, 946-957.
Sundstrom, M., Ehresman, D. J., Bignert, A., Butenhoff, J. L., Olsen, G. W., Chang, S. C., Bergman, A., 2011. A temporal trend
study (1972-2008) of perfluorooctanesulfonate, perfluorohexanesulfonate, and perfluorooctanoate in pooled human milk samples
from Stockholm, Sweden. Environ. Inter. 37, 178-183.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 147 Poster sessions Occurrence of perfluorinated compounds in Spanish sewage treatment
plants and determination of their removal efficiencies
Julián Campo1, Ana Masiá1, Yolanda Picó1, Marinel.la Farré2 and Damià Barceló2,3
1
Food and Environmental Safety Research Group, Faculty of Pharmacy, University of Valencia, Burjassot, Spain
2
2
1. Introduction
Sewage treatment plant (STP) effluents are currently reused with different purposes (agricultural and
industrial purposes, to recharge aquifers or it can be directly discharged into rivers or the sea). However,
STPs seem to be ineffective removing non-regulated so-called emerging contaminants, among which the
presence of perfluorinated compounds (PFCs) is causing high environmental concern (Arvaniti et al.,
2012). In fact, PFCs as Perfluorooctane sulfonate (L-PFOS) and its synthetic starting material,
perfluorooctyl sulfonyl fluoride (L-POSF), were the first PFCs to be listed as persistent organic pollutants
at the Stockholm Convention, (United Nations Environment Programme, 2010) and the EU also
published a directive prohibiting their use after June 2008 (European Parliament and Council, 2006).
Monitoring data are available worldwide, indicating that municipal sewage discharges are significant
sources of these compounds to the aquatic environment, potentially reaching treated water for human
consumption (Ma and Shih, 2010). PFCs are now considered as persistent, bio-accumulative and toxic,
which make them a potential hazard to human health. However, there are very few peer-reviewed articles
analysing concentrations of PFCs in Spanish wastewaters (Llorca et al., 2011; 2012), and even less
reporting their removal efficiency. Accordingly, the main objective of this study is to improve the
knowledge about the causes of aquatic environment pollution considering the STPs as point sources of
PFCs in some Spanish Mediterranean basins.
2. Materials and methods
2.1. Description of the study area and sampling
The Ebro, Guadalquivir, Jucar and Llobregat rivers are between the 15 longest rivers in Spain (928, 657,
498 and 170 Km) and were selected because of their economic and environmental importance. This work
presents the results of an extensive survey carried out in 2010 in STPs of Ebro (6), Guadalquivir (5),
Jucar (2) and Llobregat (2) Rivers (Figure 1). A total of 21 PFCs have been monitored, among which
there are 14 perfluorocarboxylates (PFCAs), 6 perfluorosulfonates (PFASs) and 1 perfluorosulfonamide
(PFSAs) (Table 1). PFCs concentrations have been analysed in influent, effluent and dehydrated sludge
samples of these STPs and removal efficiencies have been calculated.
2.2. Sample preparation and instrumental analysis
An off-line solid-phase extraction (SPE) procedure was used for the pre-concentration of fortified water
samples (Pico et al., 2012), using STRATA-X Polymeric Reversed Phase cartridges (previously
preconditioned). Cartridges were air-dried and analytes eluted. Extracts were evaporated to dryness, reconstituted and analysed.
Sludge samples were homogenized, vortexed, ultra-sounded and centrifuged using different acidified
solvents, and recovering the supernatants according to Pico et al. (2012). The extraction was completed
following the process described in the section 2.2.1. Moisture content was also calculated to report
concentrations in dry weight.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 148 Poster sessions Figure 1. Location of the STPs along the course of the different Rivers
Table 1. PFCs selected in this study, their family, acronym, CAS number and formula
Family
Perfluorocarboxylic
acids
Compound
Acronym
CAS Nº
Formula
PFBA
PFPeA
PFHxA
PFHpA
PFOA
i,p-PFNA
PFNA
PFDA
PFUdA
PFDoA
PFTrDA
PFTeDA
PFHxDA
PFODA
PFAS
L-PFBS
L-PFHxS
L-PFHpS
L-PFOS
i,p-PFNS
375-22-4
2706-90-3
307-24-4
375-85-9
335-67-1
C3F7COOH
C4F9COOH
C5F11COOH
C6F13COOH
C7F15COOH
375-95-1
335-76-2
2058-94-8
307-55-1
72629-94-8
376-06-7
67905-19-5
16517-11-6
C8F17COOH
C9F19COOH
C10F21COOH
C11F23COOH
C12F25COOH
C13F27COOH
C15F31COOH
C17F35COOH
375-73-5
355-46-4
375-92-8
1763-23-1
C4F9SO2O
C6F13SO2O
C7F15SO2O
C8F17SO2O
L-PFDS
PFSA
PFOSA
335-77-3
C10F21SO2O
754-91-6
C8F17SO2NH2
PFCA
Perfluorobutanoic acid
Perfluoropentanoic acid
Perfluorohexanoic acid
Perfluoroheptanoic acid
Perfluorooctanoic acid
Perfluoro-7-methyloctanoic acid
Perfluorononanoic acid
Perfluorodecanoic acid
Perfluoroundecanoic acid
Perfluorododecanoic acid
Perfluorotridecanoic acid
Perfluorotetradecanoic acid
Perfluorohexadecanoic acid
Perfluorooctadecanoic acid
Perfluorosulfonates
Perfluorobutane sulfonate
Perfluorohexane sulfonate
Perfluoroheptane sulfonate
Perfluorooctane sulfonate
Perfluoro-7-methyloctane
sulfonate
Perfluorodecane sulfonate
Perfluoro sulfonamides
Perfluorooctane sulfonamide
The chromatographic instrument was an HP1200 series LC - with an automatic injector, a degasser, a
quaternary pump and a column oven- combined with an Agilent 6410 triple quadrupole (QqQ) mass
spectrometer, equipped with an electrospray ionization (ESI) interface (Agilent Technologies,
Waldbronn, Germany). Data were processed using a MassHunter Workstation Software for qualitative
and quantitative (internal standard methodology based on peak areas) analysis (A GL Sciences, Tokyo,
Japan).
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 149 Poster sessions In water samples, recoveries ranging from 55 to 94%, with relative standard deviations between 8%-18%
were obtained; and low limits of quantification (0.01-2.00 ng L-1) were achieved for all selected PFCs.
For sludge samples, recoveries were between 79 and 111 % and, relative standard deviation was in all
cases below 20 % at the limits of quantification (0.04-8.00 ng g-1). Calibration curves were prepared daily
obtaining R2 >0.98.
3. Results and discussion
From 21 analytes screened, 15 were found in influent and effluent samples. In fact, the waste-waters of all
STPs were contaminated with at least one PFC. The PFCAs most frequent were PFBA, PFNA and
PFPeA, and the PFAS, L-PFOS and L-PFBS. In the Ebro STPs, the maximum concentration in the
influent samples was observed for L-PFOS with 689.20 ng L-1. Among the PFCAs, the highest value was
for PFBA (86.72 ng L-1). The concentration of these analytes in the effluent samples was reduced between
30 and 70%, with values of 501.10 ng L-1 and 26.29 ng L-1 for L-PFOS and PFBA, respectively (Figure
2). These decreases could be attributed to their sorption onto the activated sludge, which could explain
their high concentrations those samples.
Figure 2. Maximum PFCs concentration detected in Ebro STPs influent (IN) and effluent (OUT) samples
IN
OUT
Maximum concentration (ng L-1 )
400
689/501
350
300
250
200
150
100
2010
PFUdA
PFTrDA
PFTeDA
PFOA
PFPeA
PFNA
PFHxA
PFHxDA
PFDoA
PFHpA
PFBA
PFDA
PFOSA
i,p-PFNS
PFODA
L-PFOS
L-PFHxS
L-PFDS
L-PFHpS
L-PFBS
PFUdA
i,p-PFNA
PFTrDA
PFTeDA
PFOA
PFPeA
PFNA
PFHxA
PFHxDA
PFDoA
PFHpA
PFBA
PFDA
PFOSA
i,p-PFNS
PFODA
L-PFOS
L-PFHxS
L-PFDS
L-PFBS
i,p-PFNA
0
L-PFHpS
50
2011
The highest concentration was measured in the Guadalquivir basin, with 5600.00 ng L-1 of PFHxA in
Cordoba’s influent. Concentration of other analytes as L-PFOS (24.88 ng L-1) and PFBA (23.39 ng L-1)
were lower. In the effluent samples, PFBA (27.02 ng L-1) kept similar concentration, meanwhile PFHxA
and L-PFOS showed decreased values (around 1.00 ng L-1). The Jucar STP samples presented the lowest
PFCs concentrations, up to 150.00 ng L-1. The highest value detected was for the PFDA, which reached
128.40 ng L-1 in influent and 102.90 ng L-1 in effluent, followed by L-PFOS with 52.50 and 35.10 ng L-1,
respectively. In the Llobregat STPs, the highest concentration in the influent samples was for L-PFOS
(213.49 ng L-1), followed by PFOA (51.49 ng L-1). Their maximum concentrations in the effluent samples
were 31.44 and 55.42 ng L-1, respectively.
Regarding the sludge samples, 13 PFCs were detected. The PFCAs most frequently detected were PFBA
and PFPeA, and the PFAS, L-PFOS and L-PFBS. PFCs were not detected in Guadalquivir sludge
samples, while those of the Llobregat STPs presented high concentrations, showing 1790.25 ng g-1 in dry
weight (dw) of L-PFOS, and 149.34 ng g-1 dw of PFBA. The concentration of PFASs in the influent was
high. Their adsorption onto the activated sludge (which always presented high concentrations) accounted
for its apparent decrease in the effluent. According to Schultz et al. (2006), there is no known
biodegradation pathway for this class of fluorochemicals. The PFC residue levels in the STPs of the Jucar
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 150 Poster sessions River were low, reaching the highest level at 175.44 ng g-1 dw (L-PFBS). In the Ebro STP sludge
samples, the highest concentration detected was for PFBA (442.38 ng g-1 dw), followed by that of LPFOS (57.01 ng g-1 dw).
The removal efficiency of PFCs was calculated from the analyte concentration in influent (Cin) and
effluent (Cef) : [(Cin-Cef)/Cin] x 100%. According to this equation, the elimination of PFCAs ranged
from -557% (PFNA) to 100% (PFPeA, PFUdA), meanwhile the removal of PFASs was in the range 0%
(L-PFBS, L-PFHxS and L-PFHpS) to 100% (L-PFOS). The less efficient STP in the Ebro River was
Logroño, with 0% of PFBA, PFPeA and L-PFBS elimination, and the most efficient was Tortosa, with
99% of i,p-PFNS removal (Fig. 3). In the Guadalquivir basin, Ranilla showed very low (-557% of PFNA)
and very high (100% of PFPeA) elimination efficiencies, although removals of 100% were also calculated
for L-PFOS in Loja and Copero. In the Jucar River STPs, the efficiencies were between -121% of PFBA,
in Alzira, and 82% of PFOA, in Cuenca. Finally, in the Llobregat basin, the removal ranged from -11% of
PFHpA to 100% of PFPeA and PFUdA, all in Manresa.
4. Conclusions
Wastewater samples of all STPs contained at least one PFCs residue. Up to 15 PFCs were found in
influent and effluent, and 13 in sludge samples. The PFCs most frequently detected were PFBA, PFNA,
PFPeA, L-PFOS and L-PFBS, with concentrations up to 5600 ng/L of PFHxA in the samples of
Guadalquivir’s STPs, 128 ng/L of PFDA in those of Jucar River and 689 ng/L and 213 ng/L of L-PFOS
in those of Ebro and Llobregat Rivers. 67% of PFCs removal efficiencies analysed in this study do not
achieve the 50%. All these data confirm that most of the PFCs are only partially eliminated during the
secondary treatment, commonly used in Spanish STPs, suggesting that they can constitute a focal point of
contamination to the rivers, where they can bio-accumulate and, potentially, produce adverse effects on
humans.
Acknowledgements
2010 CSD2009-00065 and CGL2011-29703-C02-02. We also thank the persons of IDAEA and ICMAN for taking the samples.
References
Ahrens, L., Felizeter, S., Sturm, R., Xie, Z., Ebinghaus, R., 2009. Polyfluorinated compounds in waste water treatment plant
effluents and surface waters along the River Elbe, Germany. Mar. Pollut. Bull. 58, 1326-1333.
Arvaniti, O. S., Ventouri, E. I., Stasinakis, A. S., Thomaidis, N. S., 2012. Occurrence of different classes of perfluorinated
compounds in Greek wastewater treatment plants and determination of their solid-water distribution coefficients. J. Hazard.
Mater. 239-240, 24-31.
European Parliament and Council, 2006. Directive 2006/122/ECOF.
Ma, R., Shih, K., 2010. Perfluorochemicals in wastewater treatment plants and sediments in Hong Kong. Environ. Pollut. 158,
1354-1362.
Llorca, M., Farre, M., Pico, Y., Barcelo, D., 2011. Analysis of perfluorinated compounds in sewage sludge by pressurized solvent
extraction followed by liquid chromatography-mass spectrometry. J. Chromatogr. A 1218, 4840-4846.
Llorca, M., Farre, M., Pico, Y., Muller, J., Knepper, T. P., Barcelo, D., 2012. Analysis of perfluoroalkyl substances in waters
from Germany and Spain. Sci. Total Environ. 431, 139-150.
United Nations Environment Programme, 2010. New POPs SC-4/17: listing of perfluorooctane sulfonic acid, its salts and
perfluorooctane sulfonyl fluoride. United Nations Envrioment Programme: Stockholm Convention on Persistent Organic
Pollutants (POPs), Geneva, Switzerland.
Pico, Y., Blasco, C., Farre, M., Barcelo, D., 2012. Occurrence of perfluorinated compounds in water and sediment of L'Albufera
Natural Park (Valencia, Spain). Environ.Sci.Pollut.Res. 19, 946-957.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 151 Poster sessions Seasonal inputs of polyethoxylated compounds to a Mediterranean
coastal lagoon through surface watercourses
Juan M. Traverso-Soto1, Pablo A. Lara-Martín1, Eduardo González-Mazo1 and V. M. León2
1
Departamento de Química Física, Facultad de Ciencias del Mar y Ambientales, Campus de Excelencia
Internacional del Mar (CEI·MAR), Universidad de Cádiz, Puerto Real, Spain
2
Instituto Español de Oceanografía, Centro Oceanográfico de Murcia, San Pedro del Pinatar, Spain
Nowadays, alcohol ethoxylates (AEOs) are the most important group of nonionic surfactants, being used
in a wide range of applications such as household cleaners and detergents. Commercial AEOs consist of a
mixture of several homologues of varying carbon chain length (Cn) and degree of ethoxylation (EOm).
The major disposal route of these compounds is down the drain to municipal wastewater treatment plants,
where they are efficiently removed. In spite of that, significant amounts of AEOs and their metabolites
(polyethylene glycols, PEGs, which are nonionic synthetic water-soluble polymers of ethylene oxide that
are also used in many other applications) reach the aquatic environments, being eliminated from the water
column by degradation and sorption processes. In this work we have monitored the seasonal occurrence,
levels and behavior of AEOs and PEGs in waters and sediments from Mar Menor Lagoon (SE, Spain), as
well as in a wastewater treatment plant (WWTP) that discharges in this area. Determination of the
concentration of the analytes in both aqueous and particulate phases has been carried out by liquid
chromatography-mass spectrometry (LC-MS) after accelerated solvent and solid phase extractions.
Regarding the WWTP, there were significant differences in the concentrations of the target compounds
depending on the season and the day of the week, with maximum values being detected during the
weekend. Average AEO and PEG concentrations in the lagoon were 0.07 and 8.8 mg kg-1 for sediments,
and 0.35 and 5 μg/L in water, respectively. Levels for both compounds were significantly higher in
samples collected near the shore than those measured inside the lagoon itself. The distribution of AEOs
and PEGs could be better explained due to a combination of multiple sources, not only due to discharges
from the nearby WWTP, but also from the surrounding populations, small creeks which flow directly into
the Mar Menor after collecting treated and untreated urban wastewaters, the input of surfactants used such
as adjuvants in pesticides through surface and groundwaters, and/or from cleaning products used in ports.
Data on these analytes are the first ever known in this area and it is remarkable that concentrations of
PEGs, which are relatively polar metabolites, exceeded by two orders of magnitude those found for AEOs
in sediment samples. In this sense, the highest concentrations were detected close to the San JavierMurcia airport, where PEGs are commonly used in aircraft cleaning products.
Acknowledgements
This work was supported by Petroquímica Española S.A. (ref. OT2008/071) and the Spanish Inter-Ministerial Science and
Technology Commission “DECOMAR” Project (CICYT, CTM2008-01832).
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 152 Poster sessions Seasonal changes in the concentration of synthetic surfactants in
groundwater from aquifer systems (Cadiz, SW Spain)
Carmen Corada-Fernández1, Nivis Torres-Fuentes1, Pablo A. Lara-Martín1, L. Candela2 and
Eduardo González-Mazo1
1
Department of Physical-Chemistry, Faculty of Marine and Environmental Sciences, University of Cadiz, Puerto
Real, Spain
2
Department of Geotechnical Engineering and Geosciences, UPC, Barcelona, Spain
Nowadays, soil and groundwater contamination is a worldwide environmental problem with disastrous
consequences. As a consequence of this and other environmental issues (e.g., biomagnification), the use
and production of some of the most dangerous contaminants, such as pesticides and polychlorinated
biphenyls (PCBs) are regulated in most developed countries. However, there are thousands of different
chemical products that have not being studied yet, many of them known as “emerging contaminants”,
which are also being discharged into aquatic and terrestrial environments. In this work we have
determined the presence and temporal distributions of synthetic surfactants (mostly used in the
formulation of detergents, personal care products, industrial processes, pesticide adjuvants…) in
groundwater samples from two aquifers: Jerez de la Frontera (062.009) and Alluvial Guadalete (062.008).
These hydrogeological units are located surrounding the urban area of Jerez de la Frontera (207.500
inhabitants, 2009) in Andalusia (SW, Spain). The aquifers are affected by agricultural pollution sources,
as nitrate concentrations up to 65.8 mg L-1 and several pesticides (chlorfenvinphos, chlorpyriphos,
prometryn and triazines) have been detected in a previous study (Perez-Carrera et al., 2009). The
proximity of several urban areas that may discharge non-treated urban wastewater in the system (CoradaFernández et al., 2011, 2013) is also relevant. We carried out two different sampling campaigns in the
area during dry season (summer) and rainy season (winter). 25 wells were selected, measuring
temperature (T), pH, conductivity (E.C.), dissolved oxygen (D.O.) and redox potential (Eh). Water
samples were taken from these wells for later analysis of 4 surfactants: linear alkylbenzene sulfonate
(LAS) and alkyl ethoxysulfates (AES) (anionics), and alcohol polyethoxylates (AEOs) and nonylphenol
polyethoxylates (NPEOs) (non-ionics) (Lara-Martín et al., 2006). In both aquifers, oxic conditions
prevailed and pH ranges were between 6.5 and 9. Surfactants were found in a range between 5-165 and 1665 μg L-1 for LAS and AES, respectively, and, for AEOs and NPEOs, between 4-140 and 2-6 μg L-1,
respectively. Highest surfactant concentrations were detected in those wells directly affected by urban
sewage infiltration and during the rainy season. Those homologues/ethoxymers being most hydrophilic
were predominant. Presence of anionic surfactants was attributed to the irrigation of crops with river
water mixed with wastewater from Jerez de la Frontera sewage treatment plant, as well as to the
application of sludge from that plant. The distribution of nonionic surfactants, however, was better related
to the use of pesticides in the area.
Acknowledgements
This study has been supported by the CICYT Projects (CGL2008-05598 and CGL2011-27349), and with the help of a FPI
fellowship from the Spanish Ministry of Education (ref. BES/2006/12304).
References
Corada-Fernández, C., Lara-Martín, P.A., Candela, L. and González-Mazo E. Tracking sewage derived contamination in riverine
settings by analysis of synthetic surfactants, J. Environ. Monit.(2011), 13, 2010-2017.
Corada-Fernández, C., Lara-Martín, P.A., Candela, L. and González-Mazo E. Vertical distribution profiles and diagenetic fate of
synthetic surfactants in marine and freshwater sediments, Sci. Tol. Environ. (2013), 461-462, 568-575.
Lara-Martín, P.A., Gómez-Parra, A. and González-Mazo, E. Development of a method for the simultaneous analysis of anionic
and non-ionic surfactants and their carboxylated metabolites in environmental samples by mixed-mode liquid chromatographymass spectrometry, J.Chromatogr.A (2006), 1137, 188-197.
Perez-Carrera, E. Distribution and reactivity of regulated and emerging organic pollutants in surface and groundwater systems,
PhD., University of Cadiz (2009).
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 153 Poster sessions Geographical distribution of pesticides in waters of the river Júcar,
Spain
Juan Antonio Pascual Aguilar1,2, Vicente Andreu1, Ana Masiá3 and Yolanda Picó3
1
Environmental forensic and Landscape Chemistry Group, Centro de Investigaciones sobre Desertificación-CIDE
(CSIC-UV-GV), Moncada, Spain
2
Centro para el Conocimiento del Paisaje, Matet, Spain
3
Food and Environmental Safety Research Group, Department of Medicine Preventive, Faculty of Pharmacy,
University of Valencia, Burjassot, Spain
Among emerging contaminants the group of pesticides is associated to farming activities (Richardson,
2012). Research to large basin scale is needed to understand surface waters transport and hydrological
connectivity of contaminants. The working hypothesis of this research is that at large geographical scale
pesticides and herbicides are related to major landscape land use-cover types.
The methodological framework developed consisted on the application of environmental forensic criteria
(Taylor, 2004) combining laboratory analytical water samples and cartographic analysis using
Geographical Information Systems (GIS). For the first case, the sampling strategy consisted in the
collection of 15 water samples distributed alongside the River Júcar and its two main tributaries (River
Cabriel and Magro), located in the River Júcar drainage Basin. After selective sample extraction, 50
pesticides were identified and quantified by liquid chromatography coupled to tandem mass spectrometry
(LC-MS/MS) (Masiá et al., 2013). Geographical analysis were performed after geo-location of sampling
points analytical results and integration in the GIS environment using CORINE land use-cover layers for
the year 2006.
Out of 50 pesticides 20 were identified and 18 presented concentrations higher than the Limits of
Quantification. Values ranged from 0.04 ng·L-1 (Terbuthylazine-2 Hydroxy) to 79.39 ng·L-1
(Carbendazim), 150.75 ng·L-1 (Thiabenzadole) and 222.45 ng·L-1 (Imazalil). Contaminants identified
more frequently were Chlorpyriphos, Ethion, Chlorfenvinphos and Imazalil, found in 15, 13, 12 and 10
sites respectively. There is a clear geographical trend in the number of pesticides found and their
concentrations. Three main land use-cover areas where stablished, according to the dominant vegetation
cover: natural surfaces, rainfed agriculture and intensive irrigation farming. The number of pesticides
incrise from natural areas (28 incidencies in 6 sites) to rainfed (37 detections in 5 sites) and irrigation
agriculture (50 incidencies in 4 sampling points). Higher levels of concentrations area also found in the
sector with intensive irrigation agriculture.
Acknowledgements
This work was supported by the Spanish Ministry of Science and Innovation through the project CONSOLIDER-INGENIO 2010
(CSD2009) and by the Ministry and the European Regional Development Fund (ERDF) (projects CGL2011-29703-C02-00,
CGL2011-29703-C02-01, CGL2011-29703-C02-02).
References
Masiá, A., Ibáñez, M., Blasco, C., Sancho, J.V., Picó, Y. and Hernández, F. Combined use of liquid chromatography triple
quadrupole mass spectrometry and liquid chromatography quadrupole time-of-flight mass spectrometry in systematic screening
of pesticides and other contaminants in water samples. Analytica Chimica Acta (2013), 761, 117-127.
Richardson, S.D. Environmental mass spectrometry: emerging contaminants and current issues. Analytical Chemistry (2012),
84, 747–778.
Taylor, D.A. Environmental forensic files. Environmental Health Perspectives (2004), 112, a88–a88.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 154 Poster sessions Study of the occurrence, spatial and temporal distribution of
pesticides in water, sediment and biota from Llobregat River Basin
Ana Masiá, Julián Campo, Cristina Blasco and Yolanda Picó
The Llobregat River emerges in the Eastern Pyrenees in North West of Catalonia (Spain), at 1400 m of
altitude and flows during approximately 160 km coming into the Mediterranean Sea. It is one of the main
water source of the metropolitan area of Barcelona and its surroundings, and it receives the effluent
discharges from more than 30 WWTPs. Moreover, it is influenced by industrial and agricultural activities
(vineyards) at lower-medium course. Thus, a broad range of organic pollutants have been detected along
the river [1,2]. This work presents the results of 43 currently used pesticides monitoring that was carried
out from the end of September to the middle of October 2010 and 2011 in water, sediments and biota
from Llobregat River Basin. Water samples were taken into amber glass bottles of 2.5 L. Sediment
samples were taken using a Van Veen grab sampler and transferred to an aluminum box. Finally, fish
samples were collected using electro-fishing to stun them before they are caught with a net and after died
stored in a clean plastic bag. Once at laboratory, pesticides were extracted from water by solid-phase
extraction (SPE) and from sediment and fish by QuEchERS. The resulted extract was then analyzed by
LC-ESI-MS/MS in positive mode. Separation was carried out on a Luna C18 column (150 × 2.0 mm, 3
µm) using a gradient elution profile with mobile phase consisting of water-methanol both, 10 mM
ammonium formate. The two most intense precursor ion → product ion transitions were monitored to
obtain unambiguous confirmation of the compound identity.
The levels of total pesticides in all matrices were compared in both sampling periods. In water samples,
the most frequent pesticides were imazalil, chlorpyriphos and diazinon which appeared in 93 % of the
samples during 2010 campaing; and the highest concentration was for malathion (320,3 ng/L).
Nevertheless, in 2011 campaign, chlorpyriphos (80 %) and terbuthylazine-2-hydroxy (70 %) were the
most ubiquitous, and the maximum concentrations were detected for carbendazim (up to 697 ng/L) and
diuron (up to 160 ng/L). Regarding the spatial distribution, the highest concentration in 2010 was found
near of the source in LLO1. On the contrary in 2011, there was a concentration gradient of pesticides
through the mouth that is particulary marked in the Anoia tributary. In sediments, metolachlor,
chlorpyriphos, diazinon and diuron were found in 2010 at low ng/g d.w. level. Differently, in the 2011,
carbendazim, thiabendazole, chlorpyriphos, diazinon, dichlofenthion, terbumeton, terbuthylazine-2hydroxy, terbuthryn and tebuconazole were detected. Some of these compounds were not analyzed in the
previos campaign. The concentrations of pesticides were also higher this year. The highest concentration
was for chlorpyriphos (130 ng/g d.w.) at the CAR4 (where the Cardener River flows into the Ebro).
Finally, pesticides were not detected in fish samples.
Acknowledgements
2010 CSD2009, and CGL2011-29703-C02-02. We would also like to thank the persons of the research group from IDAEA for
taking the samples.
References
Gonzalez, S., López-Roldán, R. and Cortina, J.L. Presence and biological effects of emerging contaminants in Llobregat River
Basin: a Review, Environ. Pollut. (2012), 161, 83-92.
Kuser, M., López de Alda, M.J., Hernando, M.D., Petrovic, M., Martín-Alonso, J. and Barceló, D. Analysis and occurrence of
pharmaceuticals, estrogens, progestrogens and polar pesticides in sewage treatment plant effluent, river water and drinking
water in the Llobregat river basin (Barcelona, Spain), J. Hydrol. (2008), 358, 112-123.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 155 Poster sessions Occurrence of siloxanes in fish samples from the Júcar River
Josep Sanchís1, Francisca Pérez1, Marinella Farré1 and Damià Barceló1,2
1
2
Cyclic and linear volatile dimethylsiloxanes (cVMS and lVMS respectively) are low molecular weight
organosilicon compounds with intensive use in domestic (personal care products, coatings, paints...) and
industrial products. Their emission to the environment has been observed in several recent publications
reporting their occurrence in wastewater [1, 2], river environments [1-3], soils [4, 5] and atmosphere [6,
7]. Moreover, cVMS are endocrine disruptors [8, 9] and bioaccumulate in aquatic organisms [10, 11].
Because of all these threats, although they are still not considered in any environmental legislation,
volatile dimethylsiloxanes are currently under revision by statal agencies in North America and by the
European Comission. Analysis of cVMS and lVMS is challenging because of their high volatility and
because of the many sources of contamination in laboratory indoor environment and analytical
instrumentation. We have developed and validated an analytical method based on ultrasounds assisted
extraction followed by GC-MS/MS. Quantification trustness is ensured by statistically assessing the
contamination of a significant number of procedural blanks (minimum 1 blank per sample), which are
analyzed in parallel with the real samples, and substracting the background signal. A total of sixteen fish,
sampled from the Júcar River in the frame of the SCARCE project, have been analyzed. cVMS have been
detected in all but one sample at concentrations between 50 pg/g and the 9.4 ng/g while lVMS have been
detected in 75% of the samples at concentrations 6.17 and 69.0 pg/g. As far as our knowledge goes, this is
the first study of the occurrence of these compounds in river fish from the Iberian Peninsula. The
observed concentrations are consistant with the physico-chemical properties of these compounds
(solubility in the low μg/L order, extremely high KOW and high Henry’s constant) in a water environment:
cVMS and lVMS will rapidly partition (1) to the atmosphere, where they will distribute globally, (2) to
the lipidic content of biota and (3) to the river sediments. Siloxanes concentrations are in the same range
than perches analyzed in Scandinavian lakes [11]. On the other hand, their profiles are similar than those
observed in sea fish from Barcelona markets while the concentrations here presented are about one order
of magnitude lower. This can be explained by the exposure of market fish to indoor environments, were
cVMS concentrations have been reported to reach the μg/m3 order, after their capture.
Acknowledgements
This work has been supported by the Spanish Ministry of Science and Innovation through the projects SCARCE (ConsoliderIngenio 2010 CSD2009-00065) and Nano-Trojan (CTM-2011-24051).
References
[1] Sanchís J., Martínez E., Ginebreda A., Farré M. and Barceló D., Occurrence of linear and cyclic volatile methylsiloxanes in
wastewater, surface water and sediments from Catalonia. Science of The Total Environment (2013), 443, 530-538.
[2] Sparham C., Van Egmond R., O’Connor S., Hastie C., Whelan M., Kanda R. and Franklin O., Determination of
decamethylcyclopentasiloxane in river water and final effluent by headspace gas chromatography/mass spectrometry. Journal of
Chromatography A (2008), 1212, 124-129.
[3] Sparham C., van Egmond R., Hastie C., O’Connor S., Gore D. and Chowdhury N., Determination of
decamethylcyclopentasiloxane in river and estuarine sediments in the UK. Journal of Chromatography A (2011), 1218, 817-823.
[4] Sánchez-Brunete C., Miguel E., Albero B. and Tadeo J.L., Determination of cyclic and linear siloxanes in soil samples by
ultrasonic-assisted extraction and gas chromatography–mass spectrometry. Journal of Chromatography A (2010), 1217, 70247030.
[5] Companioni-Damas E.Y., Santos F.J. and Galceran M.T., Analysis of linear and cyclic methylsiloxanes in sewage sludges and
urban soils by concurrent solvent recondensation - large volume injection - gas chromatography-mass spectrometry. Journal of
Chromatography A (2012), 1268, 150-156.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 156 Poster sessions [6] Lu Y., Yuan T., Yun S.H., Wang W., Wu Q. and Kannan K., Occurrence of Cyclic and Linear Siloxanes in Indoor Dust from
China, and Implications for Human Exposures. Environmental Science & Technology (2010), 44, 6081-6087.
[7] Genualdi S., Harner T., Cheng Y., MacLeod M., Hansen K.M., van Egmond R., Shoeib M. and Lee S.C., Global Distribution
of Linear and Cyclic Volatile Methyl Siloxanes in Air. Environmental Science & Technology (2011), 45, 3349-3354.
[8] He B., Rhodes-Brower S., Miller M.R., Munson A.E., Germolec D.R., Walker V.R., Korach K.S. and Meade B.J.,
Octamethylcyclotetrasiloxane exhibits estrogenic activity in mice via ERα. Toxicology and Applied Pharmacology (2003), 192,
254-261.
[9] Sousa J.V., McNamara P.C., Putt A.E., Machado M.W., Surprenant D.C., Hamelink J.L., Kent D.J., Silberhorn E.M. and
Hobson J.F., Effects of octamethylcyclotetrasiloxane (OMCTS) on freshwater and marine organisms. Environmental Toxicology
and Chemistry (1995), 14, 1639-1647.
[10] Kierkegaard A., van Egmond R. and McLachlan M.S., Cyclic Volatile Methylsiloxane Bioaccumulation in Flounder and
Ragworm in the Humber Estuary, Environmental Science & Technology (2011), 45, 5936-5942.
[11] Kierkegaard A., Bignert A. and McLachlan M.S., Bioaccumulation of decamethylcyclopentasiloxane in perch in Swedish
lakes. Chemosphere (2012), 93, 789-793.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 157 Poster sessions Study of Silver Nanoparticles in aqueous solutions by Capillary
Reversed-Phase Liquid Chromatography, Transmission Electron
Microscopy and UV-Vis techniques
Rodrigo A. Gonzalez-Fuenzalida, Yolanda Moliner-Martínez, Jorge Verdú-Andrés and Pilar
Campíns-Falcó
Silver is known for its antimicrobial action and relative low toxicity in humans. Therefore, silver
nanoparticles combine silver’s and NP’s properties enhancing the interest of understanding its behaviour
and developing methods for its identification and determination. They are used in consumer products,
food technology, textiles/fabrics, medical products and devices. This will increase silver exposure to the
general population [1] and the impact in the environment in terms of toxicity. Consequently, AgNPs may
be considered as a potential emerging contaminant in different matrix such as water.
The objective of this work is to study the response and behaviour of AgNPs which differ in synthesis
methods, colours, sizes in aqueous solutions by using multiple techniques in order to establish a reliable
analytical method of quantification. At the same time stability of these particles were tested in terms of
degradation, organic environment exposure, photochemical radiation, reagents of synthesis functions.
TEM was used to estimate AgNPs concentrations by means of particle size diameters; UV-Vis measures
allowed to study surface plasmon properties and its variation under the various conditions previously
mentioned; Capillary Reversed-Phase Liquid Chromatography provided a highly sensitive (LODs 10-2
nM with 2 μL sample volume injection), concentration responding (linear, R2>0.99) and yet, AgNPs
stability dependent signals.
TEM image of AgNPs and AgNP Chromatogram (0.62 nM, at 400 nm)
Acknowledgements
The authors are grateful to the Spanish MICINN (MAT2007-51584 and CSD2007-00010), MINECO (project CTQ2011-26760)
and to the GV (Prometeo Program)
References
[1] Wijnhoven, S., Peijnenburg, W., Herberts, C., Nanotoxicology 2009, 3, 109-138
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 158 Poster sessions Cost effective methodology as analytics tools for DEHP and their
degradation products in waters
Neus Jornet-Martinez, María Muñoz-Ortuño, Yolanda Moliner-Martínez, Rosa HerráezHernández, A. Argente-García and Pilar Campíns-Falcó
Di-(2-ethylhexyl) phthalate (DEHP) is widely used as plasticizer as well as in a broad range of industrial
and consumer products. Due to its extensive use and possible migration -phthalates are not chemically
bonded to the plastic polymer- is nowadays considered as ubiquitous environmental pollutant [1].
Numerous studies indicated that DEHP can be degraded by bacteria and fungi under different
environment conditions [2].
We proposed a new cost-effective method for the separation and quantification of the main DEHP
degradation products: (2-ethylhexyl) phthalate (MEHP), diethyl phthalate (DEP) and dibutyl phthalate
(DBP). The method combines in-tube solid-phase micro extraction (IT-SPME) with capillary liquid
chromatography and UV diode array [3]. Aliquots of 4 mL of acidified water samples were on-line
processed into the IT-SPME extractive capillary, which was used in in-valve configuration. After sample
loading, the analytes were desorbed with the mobile-phase and transferred to a monolithic capillary
column for separation and detection. No pre-treatment is needed. Therefore, the risk of background
contamination by phthalates during sample treatment is drastically reduced. The reliability of the
proposed method has been tested by analysing several water samples with different matrix. Figure 1
shows the chromatogram given by a positive sample.
Figure 1: Photograph of the IT-SPME – capillary LC system used and chromatogram corresponding to a
washing water.
Acknowledgements
The authors are grateful to the Spanish Ministerio de Economía y Competitividad (project CTQ2011-26760) and to The
Government of the Generalitat Valenciana (projects ACOMP/2013/155 and PROMETEO 2012/045).
References
[1] Liang D-W. Zhang T. and H. P. Fang. Phathalates biodegradation in the environment. Appl. Microbiol Biotechnol (2008) 80,
183-198.
[2] Barnabé, S,. Beauchesne, I., Cooper, D.G., Nicell, J. A., Phosphate removal by mineral-based sorbents used in filters for
small-scale wastewater treatment. Water Res. (2008) 42, 153-162.
[3] Moliner-Martínez, Y., Molins-Legua, C., Verdú-Andrés, J., Herráez-Hernández, R., Campíns-Falcó, P. Advantages of
monolithic over particulate columns for multiresidue analysis of organic pollutants by in-tube solid-phase microextraction
coupled to capillary liquid chromatography. J. Chromatogr. A (2011) 1218, 6256-6262.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 159 Poster sessions Incidence and distribution of heavy metals in sediments of the Turia
River basin
Vicente Andreu1, Eduardo Gimeno2 and Juan A. Pascual1
1
Centro de Investigaciones sobre Desertificación-CIDE (CSIC-UV-GV), Moncada, Spain.
2
Fundación Universidad de Valencia. CIDE, Moncada, Spain
Rivers are one of the mainsources of freshwater to population but, in the same way, receive both point
source and difuse pollution, usually frorm wastewaters and agriculture. However, rivers are not
independent bodies but they influence different associated ecosystems that compound the catchment. In
this sense the fluvial sedimentary phase can act as a sink of pollutants Sediments can act as resevoirs that
accumulate contaminants fixing them or allowing their decomposition or metabolization. However,
environmental changes oor human induced ones, shuch as variations in water pH, increases in the
turbulence or intensity of the water flow, etc.could favour their release to the environment.
In this work, the incidence and distribution of seven heavy metals was monitored in the sediments of the
Turia River. Along the river course, 22 zones were selected for sampling according different lithologies,
land uses, size of populations and the proximity to waste waters treatment plants (WWTPs), from the
headwaters to the mouth. The selected metals (Cd, Co, Cr, Cu, Pb, Ni and Zn) were analysed to determine
its total and extractable contents in the sediments. Total content of metals was extracted by microwave
acid digestion and the extractable fraction by treatment with EDTA. Atomic Absorption Spectrometry,
using graphite furnace when necessary, was used for the determination of all metals.
Highest values were mainly observed in zones 10 and 22, close to urban areas, reaching values of 172.86
mg/kg for Pb, or 58.34 mg/kg for Cr. However, zone 2 near in the headwaters of the Alfambra River and
supposedly of reference for the River authorities shows the highest values of zinc with 96.96 mg/kg.
Regarding the available/extractable fraction of the metals, Cd, Co and Cr were under the detection
limitswith maximum values in zone 22 too, reching in the case of Pb 59.60 mg/kg. The percentage of
available metal in the sediments of the studied zones vary between 15 and 40% for Cu, Pb and Zn, being
the higher than 60% for Pb and Zn in zone 8 near the city of Teruel.
The organic matter content of the sediments is the parameter most strongly related with all the forms of
metals, mainly for Cu, Ni, Pb and Zn, and is a key factor in the availability of them. It has to be noted that
the textural distribution of the sediments, particularly the clay content, also influences this last factor in
the case of Ni.
A strong tendency towards enrichment of the sediments in heavy metals is observed in the Turia River
from North to South, from the headwater to the stuary, with the exception of the possible existence of a
contamination source in zone 2.
Acknowledgements
This work has been supported by the Spanish Ministry of Science and Innovation and the European Regional Development
Funds (ERDF) through the coordinating project MEFTURIA (CGL2011-29703-C02-00), and its subprojects EFAMED and
EMEFOR (CGL2011-29703-C02-02), and the project CONSOLIDER-INGENIO 2010 (CSD2009).
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 160 Poster sessions Levels of free and combined chlorine found in indoor swimming pools,
both in bathing water and air
Javier Pla-Tolós1, Carmen Molins-Legua1, Jorge Verdú-Andres1, Yolanda Moliner-Martínez1,
Rosa Herráez-Hernández1, Pilar Campins-Falcó1 and Salvador Llana2
1
2
Dpto. de Educación Física y Deportiva, Universidad de Valencia
Swimming activity is a source of exposure to disinfection by- products (DBP), which are potentially
toxic. The disinfection in bathing water is mainly carried out by chlorination. Thus, the aim of this study
was to analyse the levels of free chlorine and combined chlorine (monochloramine: NH2Cl, dichloramine:
NHCl2 and trichloramine: NCl3) in water and air samples in indoor swimming pools as function of the
disinfection treatment and the characteristic of the installation (chlorination and UV). The analytical
procedure for the determination of combined chlorine in water samples was the DPB (N,N- diethyl-1,4phenylendiamine) method. The analysis of total chlorine (free and combined chlorine) in air samples was
based on the spectrophotometric determination of iodine after the reaction with the chlorine oxidable
species in air [1].
The results showed that chlorination leads to the formation of chloramines in bathing water samples,
mainly mono- and dichloramine. However, UV-treated swimming pool free chlorine was the predominate
specie owing to the absence of organic matter. The level of total chlorine increased as function of the
swimming activity in swimming pools with chlorination treatment. In the case of UV-treatment, this
content was constant and any significative variation was found with the swimming activity. Similar
results were found in air samples, with an increase of the total chlorine as function of the swimming
activity in the case of chlorinated swimming pools. In addition, the quality of the installation has been
proved an important variable in the exposure of the swimmers to chlorine species. The lower quality of
the installation resulted in a higher content of total chlorine, especially in air samples and therefore a
higher exposure of the swimmer to DBP.
Figure 1. Comparison of the level of total chlorine in air (mg/m3) and water samples (mg/l) in three swimming pools
with chlorinated disinfection procedure (A and B) and with UV-vis treatment C
Acknowledgements
The authors are grateful to the Generalitat Valenciana (Prometeo Program 2012/045) and MINECO: DEP2011-15805-E)
References
[1] Santa Marins, L, Ibarluzea, J., Basterrechea, M., Goñi, F., Ulibarrena, E., Artieeda, J., Orruño, I. Contaminación del aire
interior y del agua de baño en piscinas cubiertas de Guipúzcoa. Gac.Sanit (2009) 23, 115-120.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 161 Poster sessions Development of new supports for in situ estimation of nitrogen
containing compounds in atmospheres of wastewater treatment plants
Neus Jornet-Martinez, Yolanda Moliner-Martínez, Jorge Verdú Andrés, Carmen Molins-Legua,
Rosa Herráez Hernández and Pilar Campíns-Falcó
Departmento de Química Analítica, Facultad de Química, Universidad de Valencia, Burjassot, Spain
Reduced nitrogen-containing compounds such as volatile aliphatic amines are important atmospheric
pollutants due to their odorous and toxic characteristics. Malodorous emissions from wastewater
treatments plants affect negatively quality of life and are a significant contribution to the degradation of
ecosystems. However, the determination of nitrogen-containing compounds in such kind of atmospheres
has received a limited attention, and to date, most analytical procedures proposed to establish time and
space patterns emissions from wastewater treatment plants are focused in sulphur, chlorinated and
aromatic hydrocarbons. Therefore, the development of reliable methods for the determination of ammonia
and volatile aliphatic amines in atmospheres of wastewater treatment plants is of clear interest [1].
The main aim of the present study was to develop an in-situ sensor for sampling and detection of reduced
nitrogen-containing compounds in atmospheres of wastewater treatment plants to estimate both,
inmission and emission concentrations. We present a passive dispositive for in situ analysis of treatment
plant atmospheres Primary and secondary volatile amines presented different color (figure 1). The
dispositive was obtained through easy and direct synthesis by the derivatization reagent 1,2naphotquinone-4-sulphonate (NQS) embedded in polydimethylsiloxane (PDMS) [2]. The sensor did not
need any external source for amine detection, the energy cost is zero, is stable and not toxic. In
conclusion, we report a cost-effective amine sensor, being respectful to environment. The detection limit
achieved was 3 mg m-3 for dimethylamine, which is in the list of prioriotary pollutants in Europe, being
the legislated value for working atmospheres of 3.8 - 9.4 mg m-3 [3].
Figure 1: NQS embedded PDMS a) before vaporous amine exposure and b-e) after amine exposure (50
mg m-3 in 8h): b) diethylamine, c) dimethylamine, d) ethylamine and e) methylamine.
Acknowledgements
The authors are grateful to Generalitat Valenciana (PROMETEO program project 2012/045); N. J-M and Y. M-M expresses their
grateful for a PROMETEO grant and a JdC research contract (Ministerio de Ciencia e Innovación of Spain), respectively.
References
[1] Ge, X., Wexler,S.A. and Clegg, S. L. Atmospheric amines. Atmos. Environ., (2011), 45, 524-546.
[2] Patent P201300436. P. Campíns-Falcó, Y. Moliner-Martínez,R., R. Herráez-Hernández, C. Molins-Legua, J. Verdú-Andrés,
N. Jornet-Martinez.
[3] European Directive 2000/39/CE, Brussels, 6/8/2000.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 162 Poster sessions Fat determination in effluents of dairy industries by preconcentration
in nylon membranes and ATR-IR
María Muñoz-Ortuño, Yolanda Moliner-Martinez, Rosa Herráez-Hernández and Pilar CampínsFalcó
At the present, there is an increasing demand for rapid and cost-effective methods for characterizing
industrial effluent, not only for environmental purposes but also for reducing the production and
maintenance costs. In this study, a method by attenuated total reflectance infrared spectroscopy (ATR-IR)
mode has been developed for the detection and quantification of fat in effluents generated by the dairy
industry, because the fat content has been extensively used in the evaluation of the environmental impact
of the effluents produced by company of milky [1]. 1 mL of samples or stock solutions, which were
manually filtered using a luer-lock glass syringe of 10 mL connected to a 13 mm diameter stainless steel
filter holder, was processed. Filtration was performed by passage through the nylon membranes (13 mm
of diameter and 0.45 µm of pore diameter) mounted in the filter holder. After extraction, the nylon
membranes were then removed from the holder, and placed on the spectrometer so that the upper side of
the membrane was in contact with the ATR crystal. The fat content is then determined by measuring the
absorbance of the band at 1745cm-1.
The proposed method can be directly applied to quantify fat in effluents within the 2- 12 mg/L range with
adequate reproducibility. The intraday precision (CVs) were ≤ 11%, whereas the interday were ≤ 20%.
The limit of detection was 0.5 mg/L. The most relevant features of this process are simplicity and speed
as the samples can be characterized in a few minutes. Furthermore, in this study an in-situ assay with
Sudan III was also developed for detecting visually the fat.
0.08
0.7
0.07
0.06
Absorbance
0.05
0.6
0.04
0.03
0.02
0.01
0.5
0
1780
1760
1740
1720
1700
Absorbance
Wavelenght (cm‐1)
0.4
0.3
0.2
0.1
0
3600
3100
2600
2100
Wavelenght (cm‐1)
1600
1100
600
Figure 1: Spectra recorder for different quantities of fat (2 mg/L, 10 mg/L and 20 mg/L)
Acknowledgements
The authors are grateful to the Generalitat Valenciana (Prometeo Program 2012/045, ACOMP/2013/155) and to Spanish
MINECO (project CTQ2011-26760).
References
[1] Brião, V.B. and Granhen-Tavares, C.R. Effluent generation by the dairy industry: preventive attitudes and opportunities. Braz
J Chem Eng. (2007), 24, 487-497.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 163 Poster sessions Determination of lactose in effluents of dairy industries
María Muñoz-Ortuño1, Yolanda Moliner-Martinez1, Rosa Herráez-Hernández1, M.T. Picher2 and
Pilar Campíns-Falcó1
1
2
Department of Organic Chemistry, Chemistry Faculty, University of Valencia, Burjassot, Spain
The dairy industry, like most other agro-factories, generates strong wastewaters, moreover, this kind of
factory is one of the largest sources of industrial effluents in Europe. The main contributors to the dairy
waste effluents are carbohydrates, fats, minerals and proteins from the milk. Also, the decomposition of
these contaminants caused discomfort to the surrounding population due to the bad smell released. The
aim of research presented in this work was to estimate the concentration of lactose in dairy wastewaters
because it is a major component of milk and milk whey. In the case of whey, the contain is about 77-80%
of carbohydrates, mainly lactose (1).
A colorimetric method was proposed for in-situ estimation of the quantity of lactose in effluents of dairy
industries. Also the response can be measured by a UV-Vis spectrophotometer equipped with a remote
diffuse reflection accesory. 20 drops of samples or stock solutions were deposited in silica gel layer.
After, the silica gel layer was sopping with a solution of thymol (0.05 g Thymol in 95 mL of EtOH and
5mL H2SO4) and after, the silica gel layer was heated with a hand dryer for 1.5 min in order to develop de
color. Finally, the difusse reflectances of samples and stock solutions were also measured. Figure 1 shows
the results obtained in function of the concentration. The achieved limit of detection was 5 mg/L. This
value was much lower than the usual concentration of lactose in samples of wastewaters (0.5-5.3 g/L in
assayed samples provided by several dairy factories).
0.7
0.6
0.5
Absorbance
0.5g /L
0.4
0.1g /L
0.05g/L
0.3
0.01g/L
0.2
0.005gL
0.1
0
200
300
400
500
600
700
800
Wavelenght (nm)
Figure 1: UV-Vis spectrophotometer absorbance of different quantities of lactose and real image of silica
gel
Acknowledgements
The authors are grateful to the Generalitat Valenciana (Prometeo Program 2012/045, ACOMP/2013/155) and to Spanish
MINECO (project CTQ2011-26760).
References
Muangrat, R., Onwudili, J.A. and Williams, P.T. Alkaline subcritical water gasification of dairy industry waste. Bioresource
Technology (2011), 102, 6331-6335.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 164 Poster sessions Greenhouse gas emissions in two coastal systems in Cadiz Bay (SW
Spain): relationship with organic matter inputs
CACYTMAR, Dep. Química-Física, Puerto Real, Spain
Coastal areas are subject to a great anthropogenic pressure because more than half of the world’s
population lives in its vicinity, causing organic matter inputs, which intensifies greenhouse gas emissions
into the atmosphere. Greenhouse gas concentrations (CO2, CH4 and N2O) have been estimated in two
aquatic systems of Cadiz Bay Natural Park: Rio San Pedro Creek and Sancti Petri Channel.
Water renewal in Rio San Pedro Creek is tidally controlled. Due to its little freshwater input, the Creek is
essentially a marine system. Several fish farms are distributed on its banks discharging effluents without
previous treatment. Nine sampling stations are distributed along this system 12 Km length. Sancti Petri
Channel is a flow channel-ebb tides extending from the inner Cadiz Bay to the Atlantic Ocean along 17
Km. Organic matter pollution sources in this enviroment are straggly. There exist anthropogenic inputs
such as aquaculture’s effluents and sewage discharges coming through Iro River, which flows into the
Channel central part. In addition there are natural organic matter inputs from surrounding marshes. It has
been established 11 sampling stations crossing this system.
Sampling was conducted seasonally during 2013. Partial pressure of CO2 was obtained through total
alkalinity and pH measurements. CH4 and N2O concentrations were acquired using a gas chromatograph
connected to an equilibration system.
Greenhouse gas values vary between 410.5 and 1272.3 µatm, 24.0 and 295.5 nM and 16.1 and 27.8 nM
for pCO2, CH4 and N2O, respectively. Gas concentrations increase close to the fish farm effluent in Rio
San Pedro Creek, and next to Iro River in Sancti Petri tidal Channel. Both environments act as greenhouse
gas sources into the atmosphere, showing seasonal variations. It has been estimated mean fluxes of 6.8
mmol m-2 d-1 of CO2, 75.3 μmol m-2 d-1 of CH4 and 31.9 μmol m-2 d-1 of N2O.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 165 Poster sessions Anthropogenic effects on greenhouse gas emissions in the Guadalete
River Estuary
CACYTMAR, Dpto. Química-Física, Puerto Real, Spain
CO2, CH4 and N2O are responsible for 88% of the atmospheric radiation absorption and they affect
(directly and indirectly) the planet climate. Currently, there exist a social concern and an important
scientific effort of quantifying the human activities impact on carbon, nitrogen and phosphorus natural
cycles. Eutrophization and the increased greenhouse gas atmospheric emissions from coastal areas are
evidences of a continuous contamination process, which is able to alter ecosystem functions, and element
fluxes to other Earth compartments.
Guadalete River empties into the Cadiz Bay, located in the southwestern Spanish coast. The River has
been intensely contaminated since 1970. Currently it receives wastewater effluents from cities and direct
discharges from nearby agriculture crop. Eight sampling stations have been established along 18 Km of
the Estuary.
Water surface concentrations of CO2, CH4 and N2O were estimated seasonally during 2013. Partial
pressure of CO2 was obtained through total alkalinity and pH measurements, while CH4 and N2O
concentrations were acquired using a gas chromatograph connected to an equilibration system. Additional
parameters such as organic matter, dissolved oxygen, nutrients and chlorophyll were determinate as well,
in order to understand the relationship between physicochemical and biological processes.
Gas concentrations increase from the River mouth toward the inner part, closer to the anthropogenic
pollution inputs, with values varing widely within 193.1 and 3778.3 µatm for pCO2, 14.8 and 1859.0 nM
for CH4, 17.4 and 134.6 nM for N2O. Greenhouse gas emissions into the atmosphere show seasonal
variability; however, the Guadatete River Estuary acts as greenhouse gas source during the whole year
with mean fluxes of 12.3 mmol m-2 d-1, 91.2 μmol m-2 d-1 and 40.8 μmol m-2 d-1 for CO2, CH4 and N2O,
respectively.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 166 Poster sessions Hourly variations in the occurrence of several pharmaceuticals and
surfactants in urban and industrial wastewater
Dolores Camacho-Muñoz, Julia Martín, Juan L. Santos, Irene Aparicio and Eduardo Alonso
The presence of a broad spectrum of organic pollutants in the environment has been widely recognized as
a potential environmental threat (Santos et al., 2010). After their use or application they usually end up in
the sewer system reaching wastewater treatment plants, being its source industrial and urban activities.
Concentrations of these organic pollutants in influent wastewater can exhibit seasonal, weekly and diurnal
variations (Plósz et al., 2010). However, only a few studies have paid attention to spatial temporal
evolution of these compounds in the influent loads.
In this work twenty one pharmaceutically active compounds belonging to different therapeutic classes
including six non-steroidal antiinflammatory drugs (acetaminophen, diclofenac, ibuprofen, ketoprofen,
naproxen and salicylic acid), five antibiotics (ciprofloxacin, norfloxacin, ofloxacin, sulfamethoxazole and
trimethoprim), a β-blocker (propranolol), three lipid regulators (bezafibrate, clofibric acid, and
gemfibrozil), an antiepileptic drug (carbamazepine), four estrogens (17α-ethinylestradiol, 17β-estradiol,
estriol and estrone) and a nervous stimulant (caffeine); and seven surfactants including four linear
alkylbenzene sulfonates (LAS C10-C13) and a nonylphenol (NP) and its mono- and diethoxylate
derivatives (NP1EO and NP2EO) were analyzed in urban and industrial wastewater collected every hour
during 24 h periods. Temporal evolution of the studied compounds, their different sources (domestic and
industrial) and their seasonal variations were evaluated.
The highest concentrations of pharmaceutically active compounds were found in urban wastewater,
especially in the case of the anti-inflammatory drugs (up to 220 µg L-1) and caffeine (up to 72.4 µg L-1),
although the highest concentractions of salicylic acid were quantified in industrial wastewater (3295 µg L1
). Concentrations of LAS ranged from 12.1 µg L-1 to 2981µg L-1, and from below limit of detection to
171 µg L-1 in urban and industrial wastewater respectively, whereas the concentrations of nonylphenol
ethoxylates were significantly lower.
Pharmaceutically active compound were seasonal-dependent whereas LAS and nonylphenol ethoxylates
showed a similar pattern in both seasons. Pharmaceutically active compounds showed a distribution in
corcondance with the consumption and excretion pattern in the case of urban wastewater and with the
schedule of greater industrial activity in the case of industrial wastewater. Temporal evolution of LAS
showed peak of concentrations in urban wastewater whereas in industrial wastewater concentrations held
steady during all day.
Acknowledgements
This work has been carried out in collaboration with Empresa Metropolitana de Abastecimiento y Saneamiento de Aguas de
Sevilla (EMASESA), financed by Corporación Tecnológica de Andalucía (CTA) and Agencia de Innovación de Andalucía
(IDEA) and supported by the ERDF.
References
Santos, L.H.M.L.M., Araújo, A., Fachini, A., Pena, A., Deleure-Matos, C. and Montenegro, M.C.B.S.D.M. Ecotoxicological
aspects related to the presence of pharmaceuticals in the aquatic environment. Journal of Hazardous Materials (2010), 175, 4595.
Plósz, B.G., Leknes, H., Liltved, H., Thomas, K.V. Diurnal variations in the occurrence and the fate of hormones and antibiotics
in activated sludge wastewater treatment in Oslo, Norway. Science of the Total Environment (2010), 408, 1915-1924.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 167 Poster sessions Multi-residue analysis of pharmaceutically active compounds (PhACs)
in aqueous matrices by liquid chromatography -quadrupole - time-offlight - mass spectrometry
Rosa M. Baena-Nogueras1, Gabriela Aguirre-Martínez1, L. Alves-Maranho1, María Laura MartínDíaz1, Eduardo González-Mazo1 and Pablo A. Lara-Martín1
1
Departamento de Química Física, Facultad de Ciencias del Mar y Ambientales, Universidad de Cádiz, Puerto Real,
Spain
This work presents the optimization of a method for the simultaneous determination of 97
pharmaceuticals including antibiotics and biocides (62), and other groups of different PhACs (35) such as
anti-inflammatories, antihypertensives, lipid regulators, histamine receptor antagonists and psychiatric
drugs in aqueous matrices. Target compounds were extracted from water by solid-phase extraction (SPE)
using HLB cartridges. SPE was optimized testing the influence of pH, different elution solvents and
modifiers (such as formic acid, ammonium formiate and EDTA). Once optimized, we decided to use
methanol with 1% of formic acid as extraction solvent, lowering the pH of the samples to 2 and also
adding 1 g of EDTA before SPE. The optimized protocol showed acceptable recovery percentages (51100%) for most of the analytes. Identification and quantification of target (and also non-targey)
compounds was performed by liquid chromatography –quadrupole - time-of-flight - mass spectrometry
(LC-Q-ToF-MS). The method was used to measure concentrations of PhACs in surface water samples
collected from Rio San Pedro and Guadalete River (SW Spain) during both summer and winter seasons.
High concentrations were detected for some drugs such as acetaminophen (650 ppt) and caffeine (14
ppb). Those antibiotics detected at highest concentrations were azithromycin (30 ppt), a macrolide, and
enrofloxacin (49 ppt), a quinolone. Moreover, several non-target chemicals, mostly surfactants such as
linear alkylbenzene sulfonates (LAS) and polyethoxylated alcohols (AEOs), and other personal care
products (PCPs) (e.g., polyethylene glycols) were also identified within the same samples.
Acknowledgements
This study was carried out within the two projects funded by the Consejería de Innovación, Ciencia y Empresa de la Junta de
Andalucía (RNM 5417 and RNM 6613)
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 168 Poster sessions Sorption of 3 pharmaceuticals in agricultural soils:
hydrochlorothiazide, metoprolol and clarithromycin
Nivis Torres-Fuentes1, Carmen Corada-Fernández1, Eduardo González-Mazo1
Pablo A. Lara-Martín1 and Diana Álvarez-Muñoz1,2
1
Department of Physical-Chemistry, Faculty of Marine and Environmental Sciences, University of Cadiz, Campus of
International Excellence (CEI•MAR), Puerto Real, Spain
2
Catalan Institute for Water Research (ICRA), Parc Científic i Tecnològic de la Universitat de Girona, Girona, Spain
Nowadays, a wide range of contaminants have been identified in the environment. In the case of
pharmaceuticals and personal care products (PPCPs) their presence in surface waters is mainly due to
treated and untreated discharges from sewage treatment plants. The use of digested sewage sludge or
biosolids as sources of nutrients in agricultural soils jeopardizes not only surface waters but also
groundwater and soils. Thus, there is a significant risk that amended soils may be contaminated and, later,
pollutants are transported to surface waters by runoff and to groundwater through leaching. This is
especially important when we consider persistent contaminants that may last many years after their
application (e.g., DDT), or biologically active substances such as pharmaceuticals. The present study
deals with the sorption of three pharmaceuticals that have been previously found by our research group in
soils from the Cadiz area: hydrochlorothiazide (HCTZ), metoprolol (MTP), and clarithromycin (CLTM).
Soil samples were collected from the soils over the aquifer of Jerez de la Frontera (code 062.009).
Physico-chemical properties of these soils were determined in the laboratory: pH, organic carbon content,
water holding capacity and texture. Sorption was determined using the batch equilibrium method
according to OECD guideline 106. Briefly, 80 mL tubes were filled with HPLC water (50 mL),
agricultural soils (0.5 – 1 g) and several concentrations of the target compounds (0.1 to 500 ng/L). After
agitation (48 h), both phases were separated by centrifugation and determination of the concentration of
the analytes was carried out by liquid chromatography - time-of-flight - mass spectrometry (LC-ToF-MS)
after solid phase and pressurized liquid extractions, respectively. Data for each pharmaceutical were fitted
to a Freundlich isotherm model, calculating their respective sorption coefficients. Freundlich constants
(Kf) for the selected compounds were: 45.4 L/kg (HCTZ), 43.4 L/kg (MTP) and 3043 L/kg (CLTM),
respectively. The correlation factors (r2) obtained were 0.9574 (HCTZ), 09767 (MTP) and 0.7565
(CLTM). In spite of showing relatively low octanol-water partition coefficients (log Kow < 3), all target
compounds showed moderate to high sorption capacities onto soils due the presence of positively charged
groups in their molecular structures, which enhance their interaction with clays in soils.
Acknowledgements
This study was carried out within the project PERCOLA (ref. CGL2011-27349), funded by the Ministerio de Economía y
Competitividad
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 169 Poster sessions Evaluation of a simple method for the analysis of pharmaceuticals
in seafood
Diana Álvarez-Muñoz1, Belinda Huerta1, Sara Rodríguez-Mozaz1 and Damià Barceló1,2
2
1
Seafood has traditionally been a popular part of the diet in many parts of the world and in some countries
constituted the main supply of animal protein. Its quality is of major concern to general public and health
authorities and seafood safety, like any other food type, has become an important issue. Priority contaminats in
seafood as a result of environmental contamination need to be assessed and for this purpose a simple and
accessible analytical method is required.
Pharmaceutically active compounds (PhACs) are among the contaminats that need to be monitored. They are
often detected in aqueous compartments and one of the main concerns is their potential to biaccumulate in
biota. Even very low concentrations (ng/l or pg/l) can be toxicologically relevant and may provoke long-term
toxic effects not only to wild life but also to human health.
Due to their high consume and commercial valor an oyster (Crassostea gigas) has been chosen as target specie
for the method evaluation. Bivalves are natural filters feeders and any dissolved or suspended contaminants
present in the water can be easily incorporated into the organism. Besides, this mollusk can be eaten raw
requiring an exhaustive quality control. A simple and routinary extraction method was implemented based on
pressurized liquid extraction (PLE) and solid phase extraction (SPE) clean-up. For the method evaluation the
oysters were spiked at 10 and 100 ng/g of dry weight with a mixture of selected PhACs containing analgesics,
anti-inflamatories, lípido regulators, psychiatric drugs, β-blockers and antibiotics between others. The samples
were analysed using PLE with methanol: water (1:2) as extraction solvent, followed by a SPE on oasis HLB
cartridges, and finally identified and quantified by Ultra Performance Liquid Chromatography - tandem Mass
Spectrometry. The method has been critically compared with one previously published (Huerta et. al. 2013)
and the advantages and disvantages have been pinpointed.
Acknowledgements
This study has been co-financed by Spanish Ministry of Economy and Competitiveness through the project SCARCE
(Consolider-Ingenio 2010 CSD2009-00065) the EU Project ECSafeSEAFOOD [FP7-KBBE 311820] and by the European Union
through the European Regional Development Fund (FEDER). This work was partly supported by the Generalitat de Catalunya
(Consolidated Research Group: Water and Soil Quality Unit 2009-SGR-965)
References
Huerta, B., Jakimska, A., Gros, M., Rodríguez-Mozaz, S., Barceló, D. Analysis of multi-class pharmaceuticals in fish tissues by
ultra-high-perfomance liquid chromatography tandem mass spectrometry. Journal of Chromatography A (2013), 1288, 63-72.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 170 Poster sessions High-resolution mass spectrometry applications in the identification
and detection of transformation products in the aquatic environment
Bozo Zonja1, Sandra Pérez1 and Damià Barceló1,2
1
2
Platforms with high-resolution MS analyzers such as Orbitrap, are the mostly and widely used analyzers
in the structural elucidation of TPs of emerging organic pollutants using LC-MS tecniques. It is now
generally recognized that high-resolution instruments afford the most straightforward route towards the
reliable characterization of TPs because they allow for the determination of elemental formulae based on
the measurement of exact masses with accuracies better than 1-2 ppm in relative mass errors. The high
resolving power of the MS- on some instruments now exceeding even 100,000- enables the determination
of accurate masses even in complex samples containing potentially interfering compounds with identical
nominal masses. Apart from hardware performance, (semi)automated data analysis and interpretation are
becoming increasingly important to assist in the elucidation process. Software developments in the field
of peak finding, construction of fragmentation trees and prediction of fragmentation patterns assist the
analytical chemist to streamline the identification of TPs (Zonja et al. in press).
Classical approach for transformation products (TPs) structure elucidation would be to simulate a certain
environmental process in lab scale, determine its transformation products, synthetize the standards or
even isolate them from the degradated samples with semipreparative LC and later on searching them in
the real environment. This procedure was applied for the identification of photoTPs of the antiviral
zanamivir. Structural identification of the TPs was done on LTQ-Orbitrap Velos using different software
Sieve (Thermo Scientific) in order to ease the elucidation part. Finally four mayor TPs were identified
and its formation mechanistically explained.
A bit different approach and more usefull is the application of suspect analysis for detection of TPs which
implies a fast checking of real environmental samples and evaluating if some TPs occure or not. This
approach was applied for the detection and structural characterisation of Iodinated contrast media’s
(ICMs) photolysis products.. Five ICM – iomeprol, iohexol, iopamidol, iodixanol and diatrizoate were
degraded in river water samples at lab-scale conditions using Suntest (simulated sunlight apparatus).
Masses of the newly found transformation products were determined and they were tentatively identified.
The determination of parent compounds and their TPs in real water samples was performed with data
dependant screening with LTQ-Orbitrap-Velos using a different approach to the one used for the work of
zanamivir presented previously.This methodology allowed us to have several identification points to the
targeted mass (accurate mass, fragmentation pathway and isotope composition – if applicable). The TPs
were separated form their parent compounds on a HPLC-semipreparative column. After purification, the
compounds were analyzed in NMR in order to additionaly confirm their structure. Purified compounds
served as analytical standards allowing us to quantify the presence of these compounds in the aquatic
environment.
Acknowledgements
BZ acknowledges the Marie Curie Actions ITN CSI:Environment PITN-GA-2010-264329 for the Early Stage Researcher
contract and funding. SP acknowledges the contract from the Ramón y Cajal Program. This work was partly supported by
Spanish Ministry of Economy and Competitiveness [64551/HID and Consolider-Ingenio 2010 Scarce CSD2009-00065] and the
Generalitat de Catalunya (Consolidated Research Group: Water and Soil Quality Unit 2009-SGR-965).
References
Zonja et al., Transformation Products of Emerging Contaminants: Analytical challenges and Future needs, Wiley books, in press
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 171 Poster sessions Pharmaceutical compounds in sludge from different sludge
stabilization processes: occurrence and environmental risk assessment
after sludge application onto soils
Juan L. Santos, Julia Martín, Dolores Camacho-Muñoz, A. Santos, Irene Aparicio and Esteban
Alonso
The production of sewage sludge generated as a by-product in wastewater treatment plants (WWTPs) is
continuously increasing. Agricultural use is the most popular disposal route of this sludge, since it not
only represents the cheapest option for sludge disposal, but also constitutes a useful fertilizer and soil
conditioner material (Kelessidis and Stasinakis et al., 2012).
The possible threats, for the environment and human health, of the presence of pharmaceutical
compounds in sludge used in agricultural lands have also been reported (Sabourin et al., 2012). These
compounds are toxic for aquatic and terrestrial organisms and some of them (diclofenac, 17αethinylestradiol and 17β-estradiol) have been proposed as priority substances in the field of water policy
(Annex 1 of the proposal for a Directive) (EC, 2011). However, no regulation about their presence in
sewage sludge is found in the European Union.
The aims of this work were to evaluate the occurrence of twenty-two pharmaceutically active compounds
belonging to different therapeutic groups in different sludge stabilization technologies and estimate the
environmental risks of the application of the final product of these technologies onto soils due to the
presence of pharmaceutical compounds. The types of sludge evaluated were primary, secondary, mixed,
aerobically-digested and dehydrated, anaerobically-digested and dehydrated, compost and lagoon sludge.
Nineteen of the twenty-two pharmaceuticals monitored were detected in sewage sludge. The most
contaminated samples were primary, secondary and mixed sludge (average sum of pharmaceuticals: 179
µg/kg dry matter (dm), 310 µg/kg dm and 142 µg/kg dm, respectively). Average concentration, in the
other types of sewage sludge, were: 8 µg/kg dm in anaerobically-digested sludge, 70 µg/kg dm in
aerobically-digested sludge, 63 µg/kg dm in lagoon sludge and 12 µg/kg dm in compost. The antibiotics
ciprofloxacin and norfloxacin were the pharmaceuticals at the highest concentration levels in most of the
samples (mean values 1.9 and 3.5 mg/kg, respectively). Anaerobic-digestion treatment reduced the
concentration of most of the pharmaceutical compounds more significant than aerobic-digestion
(especially in the case of bezafibrate and fluoroquinolones) and anaerobic stabilization ponds (in the case
of acetaminophen, atenolol, bezafibrate, carbamazepine, 17α-ethinylestradiol, naproxen and salicylic
acid).
Risk quotients, expressed as the ratio between the predicted environmental concentration and the
predicted non-effect concentration, were lower than 1 for all the pharmaceuticals so no significant risk is
expected to occur due to the application of sewage sludge onto soils, except for 17α-ethinylestradiol when
chronic toxicity data were used.
References
Kelessidis, A., Stasinakis, A.S. Comparative study of the methods used for treatment and final disposal of sewage sludge in
European countries. Waste Management (2012), 32, 1186-95.
Sabourin, L., Duenk, P., Bonte-Gelok, S., Payne, M., Lapen, D.R., Topp, E. Uptake of pharmaceuticals, hormones and parabens
into vegetables grown in soil fertilized with municipal biosolids. Scince of the Total Environment (2012) 431, 233-236.
EC, 2011. European Commission, COM(2011) 876. Proposal for a Directive of the European Parliament and of the Council
amending Directives 2000/60/EC and 2008/105/EC as regards priority substances in the field of water policy.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 172 Poster sessions Green and cheap alternative for the determination of 5nitroimidazoles in river and well waters based on Cation Selective
Exhaustive Inyection and Sweeping Micellar Electrokinetic
Chromatography (CSEI-sweeping-MEKC)
Diego Airado-Rodríguez, Maykel Hernández-Mesa, Carmen Cruces-Blanco and Ana M. GarcíaCampaña
The presence of antibiotics in environmental waters is a concerning issue and the development of
sensitive and selective methods to control it is a must. 5-Nitroimidazole derivatives (5-NDZs) are human
antibiotics mainly employed for treating illness due to anaerobia microbes. 5-NDZs are characterized by
their high polarity and low biodegradability, which increases their bioaccumulation in waters.
A novel capillary electrophoresis (CE) method has been developed for 5-NDZ determination in water
samples based in the combination of cation-selective exhaustive injection with sweeping micellar
electrokinetic chromatography (CSEI-sweep-MEKC). This methodology combines two on-line
preconcentration techniques, namely field-enhanced sample injection and sweeping, which implies high
sensitivity. On the other hand, the use of electrokinetic injection involves an enhancement of selectivity
associated to the injection step.
Dispersive liquid liquid microextraction (DLLME) has been proposed for sample treatment prior to CSEIsweep-MEKC. This is a novel microextraction technique, initially developed by Rezaee et al [1].
Basically it consists in the rapid injection of an appropriate mixture of an extractive solvent plus a
disperser agent, into an aqueous sample, resulting in the formation of a cloudy solution. Analytes of
interest are extracted into the extractive solvent droplets. As far as we know this is the first time that this
novel microextraction technique has been coupled with CSEI-sweeping-MEKC. In this case,
dibromomethane and 2-butanol were employed as extraction solvent and dispersive agent, respectively.
The extraction was assisted by salting out effect through by the addition of 16% (w/v) NaCl to water
samples. After DLLME performance and evaporation to dryness of the obtained organic extracts, those
were redissolved in a low conductivity solvent (5mM phosphoric acid with 5% of methanol) and it was
electrokinetically injected at 9.8 KV for 632 s in a bare fused-silica capillary (57.2 cm, 50 µm I.D.). Prior
to the injection, the capillary was rinsed with 50 mM phosphate buffer pH 2.5, followed by a plug of a
higher conductivity buffer (100 mM phosphate pH 2.5, 50 mbar, 264 s) and a plug of water (50 mbar, 2
s). Separation was carried out applying -30 KV at 20 ºC in 44 mM phosphate buffer pH 2.5, containing 8
% tetrahydrofurane and 123 mM SDS. Analytical signals were monitored at 276 nm.
Validation was performed in river and well waters, obtaining satisfactory results in terms of linearity,
precision and trueness. LODs ranged from 0.57 to 4.26 µg/L. The combination of DLLME with the
proposed CE methodology constitutes a simple, sensitive and cheap alternative for 5-NDZ determination,
in accordance with the aims of green chemistry.
Acknowledgements
This work was supported by the Project P08-AGR-4268 (Excellence Project, Junta de Andalucía). DA-R thanks the Spanish
Ministry of Science and Innovation for a “Juan de la Cierva” contract. MHM thanks the Plan Propio of the University of Granada
for a predoctoral grant.
References
1- Rezaee, M., Assadi, Y., Milani Hosseini, M.R., Aghaee, E., Ahmadi, F. and Berijani, S. J. Chromatogr. A (2006), 1116, 1-9
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 173 Poster sessions Temporal trends of illicit drugs in WWTPs in Valencia, Spain
María Jesús Andrés-Costa1, Ana Masiá1, Vicente Andreu2 and Yolanda Picó1
1
Environmental and Food Safety Research Group, Department of Medicine Preventive, Faculty of Pharmacy,
University of Valencia. Burjassot, Spain
2
The presence of drugs of abuse in the aquatic environment has been recognized as an important issue for
the ecosystem due their possible negative effect on it (Richardson, 2011). Incomplete removal of these
substances during wastewater treatment could be one of the causes of their release in the environment
(Zuccato and Castiglioni, 2009). Pollution by illicit drug residues at very low concentrations is
generalized in populated areas, with potential risks for human health and the environment (Zuccato, 2008;
Castiglioni et al 2007). In addition, back-calculation from the concentration of illicit drug in the influents
of wastewater treatment plants (WWTPs) provides an important tool for estimating its local consumption
(Daughton 2001).Samples were collected at the WWTPs of Quart-Benager and Pinedo I and II. These
plants treat most of the residual water from Valencia city sampling campaigns were in three years, 2011,
2012 and 2013. In March 2011 were collected influent samples for seven consecutive days. In April 2012
were collected influent and effluent samples for fifteen consecutive days and in March 2013 were
collected influent and effluent samples for seven consecutive days.
Illicit drugs were extracted using solid phase extraction (SPE) and determined by liquid chromatography
tandem mass spectrometry (LC-MS/MS) in positive ionization with an electrospray ionization source
(ESI). Compounds were quantified in wastewater and surface water as parent drugs were cocaine (COC),
amphetamine (AMP), methamphetamine (MAMP), ecstasy (MDMA) and ketamine (KET).
Benzoylecgonine (BE), 6-acethylmorphine (6-MAM), and 11-nor-9-carboxy-delta9-tetrahydrocannabinol
(THC-COOH) were the main urinary metabolites for cocaine, heroin and cannabis respectivelyThe
determination of illicit drugs in the influent of the selected WWTP shows that cocaine is the drug present
at highest concentrations in the wastewater followed by cannabis and amphetamine in 2011, 2012 and
2013. The temporal variation of the illicit drugs shows little variation from one year to other showing a
quite stable consumption in Valencia city, even through there is a clear increase in the cannabis
consumption during this last sampling without any clear explanation. The results from the concentration
levels quantifying in the influent and the effluent demonstrated that the treatment plants eliminate these
compounds in a high percentage, fully comparable to other studies on removal efficiency carried out in
other European countries as Belgium, United Kindown, Italy or France.
Acknowledgements
This work has been supported by the Spanish Ministry of Economy and Competitiveness trough the project SCARCE-CDS 20090065, CGL 2011-29703-C02-01 and GCL CGL 2011-29703-C02-02. MJ Andrés Costa also acknowledges to this Ministry the
FPI grant to perform her PhD.
References
Castiglioni S, Zuccato E. Chiabrando C., Faneli R., Bagnati R. Detecting illicit drugs and metabolites in wastewater usin high
performance liquid chromatography-tandem mass spectrometry. Spectroscopy Europe (2007), 19, 7-9
Daughton CG In: Daughton CG., Jones-Lepp TL., editors Pharmaceuticals and personal care products in the environment.
Scientific and regulatory issues. Washington: Americal Chemical Society (2001), 348-164.
Richardson SD. Environmental Mass Spectrometry: Emerging Contaminants and Current Issues. Anal Chem (2011), 84, 747778.
Zuccato E., Castiglioni S., Illicit drugs in the environment. Philos Trans R Soc A (2009), 367, 3965-3978.
Zuccato E., Castiglioni S., Bagnati, R., Chiabrando C., Grassi P., Fanelli R. Illicit drugs a novel group of environmental
contaminats. Water Res (2008), 42, 961-968.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 174 Poster sessions Emerging illicit drugs in waste and surface waters in the Turia River
Basin
María Jesús Andrés-Costa1, Ana Masiá1, Cristina Blasco1, Vicente Andreu2 and Yolanda Picó1
1
Environmental and Food Safety Research Group, Department of Medicine Preventive, Faculty of Pharmacy,
University of Valencia. Burjassot, Spain
2
The phenomenon of new psychoactive substances is dynamic. A total of 24 new psychoactive substances
were officially notified for the first time in the EU in 2009 through the EWS (Early Warning System), up
from 41 in 2010, 49 in 2011 and 73 in 2012 (EMCDDA, 2013). Narcotics substances may be excreted
through urine or faeces, as parent compound or as secondary metabolites. Then, they can arrive to sewage
plants and subsequently to environmental compartments (Boles and Wells, 2010). The aim of this study is
to supply a pattern of emerging illicit drugs consumed by analyzing these compounds at the influent and
effluent of sewage treatment plants and to estimate their environmental contamination possibly by
analyzing samples of surface water in the Turia River Basin.
Samples were collected at 25 sites through the Turia River Basin and wastewater samples were collected
from the influent and effluent of three wastewater treatment plants (WWTPs) in Valencia. The 8
emerging illicit drugs selected for this study were α- pyrrolidinopropiophenone (PVP), α- pyrrolidinopentiophenone (PPP), 4’-methyl- α-pyrrolidinohexanophenone (MPHP), 4’-methyl- α- pyrrolidinobutiophenone (MPBP), belong to pyrrolidinophenone group, Mephedrone (4MMC), Dibutylone
(bk-MMBDB), 4-Methoxyphencyclidine (4-MeO-PCP) and Bufotenine (BUF).
Illicit drugs were extracted from 250 ml of water by solid phase extraction (SPE) and determined by
liquid chromatography triple quadruple mass spectrometry (LC-QqQ-MS/MS) using an electrospray
ionization source (ESI) in positive ionization mode. The method detection limits ranged from 0.01 to 1.54
ng L-1 and the recoveries from 57 to 127 % with relative standard deviations ≤ 20 % The feasibility of this
method was demonstrated by analyzing spiked water samples.
Their application to determine new illicit drugs in the influent of the selected WWTP shows the presence
of BUF in all samples (at concentrations up to 325.3 ng L-1) and 4-MeO-PCP in 23.8 % (at concentration
up to 240.3 ng L-1). However, BUF and 4MEO-PCP were not detected in the effluent of these WWTPs.
Also, these illicit drugs were detected at 7 sampling points of the Turia River Basin at concentrations
ranging from 3.8 to 66.8 ng L-1 for BUF and 37.6 ng L-1 for 4-MeO-PCP. The others illicit drugs analyzed,
αPVP, MPHP, MPBP, PPP, 4MMC and bk-MMBDB, were not detected in the analyzed samples. To our
knowledge, this is the first time that these drugs were detected and monitored in River Basins. This study
also highlights the need of future research regarding these drug’s transformation pathways and their
ecotoxicological effects.
Acknowledgements
This work has been supported by the Spanish Ministry of Economy and Competitiveness trough the project SCARCE-CDS 20090065, CGL 2011-29703-C02-01 and CGL 2011-29703-C02-02. MJ Andrés Costa also acknowledges to this Ministry the FPI
grant to perform her PhD.
References
Boles TH, Wells MJM. Analysis of amphetamine and methamphetamine as emerging pollutants in wastewater and wastewaterimpacted streams. Journal of Chromatography A (2010), 1217, 2561-2568.
European Monitoring Centre for Drugs and Drug Addiction (EMCDDA). EU drug markets report: a strategic analysis.
EMCDDA, Lisbon, January 2013.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 175 Poster sessions Occurrence and environmental risk assessment of drugs of abuse in
four Spanish river basins
Nicola Mastroianni1, Miren López de Alda1 and Damià Barceló1,2
1
2
Based on the last World Drug Report recently published by the United Nation Office on Drugs and Crime
(UNODC), around 230 million people (5% of the world’s adult population, aged from 15 to 64 years) has
used an illicit drug at least once in 2010 [1].
After consumption, pharmaceutical and drugs of abuse are metabolized and different proportions of the
parent compound and/or the metabolic products are excreted into the sewage system. Incomplete removal
of these compounds during wastewater treatment results in their release in the aquatic environment where
they have been detected at ng/L levels [2]. Occurrence of illicit/abused drugs in surface waters is a wellestablished issue worldwide, but their potential ecotoxicological effects have been hardly investigated and
are basically still unknown. Additionally, these effects may be more significant in those aquatic
ecosystems that suffer from severe and variable climate conditions and anthropogenic pressures in terms
of water demand and water pollution, such as those existing in Mediterranean river basins.
Direct estimation of effects caused by environmental pollutants on ecosystems is not a straightforward
task, and in the case of illicit drugs the lack of experimental toxicological data makes this approach even
more difficult.
Ecological risk can be estimated numerically using the Hazard Quotients (HQ) approach, where the HQ is
defined as the ratio between the compound measured environmental concentration (PEC) and its chronic
toxicity, usually expressed as the no observed effect concentration (NOEC) or the predicted non-effect
concentration (PNEC). When NOEC values are not available, EC50 or LC50 (50% effect concentration
or 50% lethal concentration, respectively) values from standard ecotoxicological tests can be used
eventually after correction by an assessment factor (AF) [3]. If a Hazard Quotient is calculated to be equal
or greater than one harmful effects cannot be ruled out, while HQ<1 indicate no risk.
In this context, the main objective of the present work was to study the occurrence of 22 illicit drugs and
metabolites in surface water collected along four different Mediterranean river basins of the Iberian
Peninsula (Ebro, Llobregat, Jucar and Guadalquivir river basin) and to estimate their potential
ecotoxicological risk to the aquatic environment. In the considered basins, a total of 77 samples were
collected as grab sample during two consecutive years. The compounds analysed belong to five different
chemical groups, namely cocainics, amphetamine like compounds, opiates and opioids, benzodiazepines,
lysergic acid diethylamide (LSD) and cannabinoids.
Based on the results collected during the monitoring periods, both spatial and temporal differences were
assessed, the locations with the largest loads of drugs were identified, and the HQ corresponding to three
different trophic levels (algae, cladocerans and fish) were calculated. When no experimental toxicity data
was available, predicted toxicity values from (Quantitative) Structure-Activity Relationship ((Q)SAR)
models were selected from the available literature or estimated with the U.S. EPA Ecological Structure
Activity Relationships (ECOSAR) Class Program (v1.11).
Acknowledgments
This work has been financially supported by the Spanish Ministry of Economy and Competitiveness through the project
SCARCE (Consolider-Ingenio 2010 CSD2009-00065), by the European Commission through the project SOLUTIONS (contract
no. 603437), and by the Generalitat de Catalunya (Consolidated Research Group: Water and Soil Quality Unit 2009-SGR-965). It
reflects only the author's views. The Community is not liable for any use that may be made of the information contained therein.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 176 Poster sessions Investigation of drugs of abuse in river water from the Granada
Province by means of UHPLC-MS/MS in combination with dispersive
liquid-liquid microextraction (DLLME) as environmentally-friendly
sample treatment
Diego Airado-Rodríguez, Manuel Lombardo-Agüí, Ana M. García-Campaña and Carmen CrucesBlanco1
In this work, an ultra high performance liquid chromatography - electrospray ionization - tandem mass
spectrometry (UHPLC-ESI-MS/MS) method is presented for the detection, identification and quantitation
of 20 representative multiclass drugs of abuse, including opiates, cannabinoids, amphetamines, and
hallucinogenic compounds. The separation has been achieved in 10 min, using a Kinetex XB-C18 column
(100 x 2.1 mm and 1.7 µm particle size), in gradient mode with a mobile phase of 0.013 % aqueous
formic acid and acetonitrile with 0.013 % formic acid. Parameters affecting the MS/MS detection by
using triple quadrupole were optimized and the corresponding product ions for quantification and
confirmation were selected.
The proposed UHPLC-ESI-MS/MS method has been validated in terms of linearity, sensitivity (limits of
detection and quantification), trueness (through recovery assays) and precision (repeatability and
intermediate precision), and successfully applied to water samples from Riofrío river (Granada).
Dispersive liquid-liquid microextraction (DLLME) is a novel microextraction technique, initially
developed by Rezaee et al [1], and based on ternary solvents. Basically it consists in the rapid injection of
an appropriate mixture of extractive solvent plus a disperser agent, into an aqueous sample, resulting in
the formation of a cloudy solution. Analytes of interest are extracted into the extractive solvent droplets.
The compatibility of the proposed UHPLC-ESI-MS/MS methodology with DLLME has been
demonstrated for water samples. Experimental design and response surface methodology have been
employed for the optimization of critical variables related to DLLME.
Thus, the proposed methodology combines the advantages of DLLME as microextraction technique
(cheap, simple and environmentally friendly) with the high sensitivity, selectivity, rapidness and
identification capability of UHPLC-MS/MS, showing its usefulness for the simultaneous monitoring of a
great variety of abused drugs in environmental water samples, which could be very useful for routine
analysis.
Acknowledgements
DA-R thanks the Spanish Ministry of Science and Innovation for a “Juan de la Cierva” contract.
References
1- Rezaee, M., Assadi, Y., Milani Hosseini, M.R., Aghaee, E., Ahmadi, F. and Berijani, S. J. Chromatogr. A (2006), 1116, 1-9
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 177 Poster sessions Assessment of pharmaceutical Diclofenac occurrence in the Llobregat
river via Monte Carlo sensitivity analysis of several parameters using
GREAT-ER model
Zoran Banjac1, Laurie Boithias2, Antoni Ginebreda1, Rafa Marce2, Victoria Osorio1, Sandra
Pérez1, Damià Barceló1,2, Sergi Sabater2 and Vicenç Acuña2
1
2
Llobregat River basin is heavily exploited by human activities, including urban, industrial and agricultural
uses that transfer into both point and diffuse pollution. The biggest contamination comes from 59
WWTPs located throughout the Llobregat river basin.This river manifests typical Mediterranean
hydrological pattern, characterized by acute flow fluctuations (between 1 and more than 100 m3
/s).During drought periods WWTP effluents may represent major part of the river flow which is one of
the reasons contaminants show in bigger concentration due to less dilution which makes their effects on
ecosystem uncertain.
The objective of the ongoing research is to model the environmental occurrence of pharmaceuticals in the
Llobregat basin [1] using the GREAT-ER (Geo-referenced Regional environmental Exposure Assessment
Tool for European Rivers) [2-3] steady-state model and to assess its sensitivity respect to some of the
parameters used. The sensitivity analysis will be performed using Monte Carlo simulation in the statistical
software of choice [4] coupled with the GREAT-ER. The anti-inflammatory Diclofenac is selected as a
representative and relevant case study, since it has been recently included in the “watch list” set by the
new Directive 2013/39/EU (“daughter” of the Water Framework Directive). The first testing exercise will
be done for 3 parameters: annual consumption, removal in the WWTP and removal in river. The
sensitivity analysis is based on previously assessed uncertainty ranges of these parameters [5]. The
uncertainty is captured in statistical frequency distributions. In each Monte Carlo ‘shot’, discrete samples
are taken from these distributions, and used as input for the deterministic fate models. The simulation
outputs are statistical distributions of predicted environmental concentrations (PECs) for each river
stretch. This study will provide (1) the sensitivity of each involved parameters and (2) a reliable
assessment of the parameter set, by comparing the outputs of each model iteration with the observed
concentrations of Diclofenac at 14 sampling sites throughout the Llobregat river and its tributaries. Such a
calibrated model may be potentially extended to assess the environmental occurrence of other
pharmaceuticals under a wide range of hydrological flow conditions and WWTP treatment processes.
References
1 The Handbook of Environmental Chemistry. Volume 21, (2012). The Llobregat: The Story of a Polluted Mediterranean River,
Eds. S. Sabater, A. Ginebreda and D. Barceló, Springer-Verlag, Heidelberg Berlin
2 Boeije, G., Vanrolleghem, P. & Matthies, M. (1997). A geo-referenced aquatic exposure prediction methodology for ‘downthe-drain’ chemicals. Water Science and Technology, 36(5), 251-258.
3 Boeije, G. & Schowanek, D. (1997). Prediction and visualization of the environmental
concentration of consumer chemicals: the GREAT-ER project. Study Day on Global Environmental
Impact, IAWQ - Belgian Committee, Brussels, June 6, 1997
4. Guiding principles for the Monte Carlo analysis,Risk Assessment Forum,U.S. Environmental Protection Agency,Washington,
DC 20460, EPA/630/R-97/001,1997
5. BOITHIAS L, MARCÉ R, ACUÑA V, ALDEKOA J, OSORIO V, PETROVIĆ M, FRANCES F, GINEBREDA A,
SABATER S, 2013, Assessment of the water purification ecosystem service regarding in-stream pharmaceutical residues:
exploring the GREAT-ER model parameters based on data uncertainty, In preparation.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 178 Poster sessions Application of ArcGIS software to display the occurrence and risk of
chemical pollutants
Maja Kuzmanović1, Antoni Ginebreda1, Mira Petrović2,3 and Damià Barceló1,2
1
2
3
The increasing contamination of aquatic systems with numerous man-made and natural chemicals is one
of the key environmental problems. Although most of these chemicals are present at low concentrations,
many of them may pose ecotoxicological concerns especially when occurring as components of chemical
mixtures. In the EU there are more than 100000 registered chemicals listed by EINECS of which many
are in daily use. One approach for identifying potentially dangerous compounds is screening of the
environment for a large set of chemicals together ith an assessment of the potential toxicity of the
observed concentrations, which can be done by use of measured or predicted effect concentrations for
standard test species. Moreover, combined biological and chemical-analytical approaches provide an
important progress in identification of those toxicants that are relevant for site-specific risk and towards
an estimation of the portion of an effect that can be explained by analysed chemicals.
The main objective of this work was to display the data of occurrence and risk of chemical pollutants in
specific geospatial frame of four river basins (Llobregat, Ebro, Jucar and Guadalquivir).
In this study we used ArcMap Software which is the main component of Esri's ArcGIS suite of geospatial
processing programs, and it is used primarily to view, edit, create, and analyze geospatial data. ArcMap
allows exploration of data within a data set, symbolize features accordingly and create maps.
We used ArcMap to display the distribution of occurrence of 81 pharmaceuticals 42 pesticides 31
endocrine disrupting compounds(EDCs) 21 perfluorinated compounds(PFCs) and 21 illicit drugs along 77
sites located in 4 Iberian river basins (Llobregat, Ebro, Jucar and Guadalquivir) measured on SCARCE
project. We have identified the “hot spots” of pollution in each of 4 rivers. The occurrence of chemical
pollutants was put in context of potential sources as agriculture, urbanization, wastewater discharges etc.
Furthermore, according to frequency of detection and total content of chemical we have identified the
most important pollutants in terms of occurrence.
Moreover, we have assessed the ecological risk for the same chemicals by calculating toxic units (TU) for
algae, Daphnia sp. and fish for each of measured chemicals. Pesticides were the group of compounds
with highest risk to ecosystem. Finally, the risk maps were created by adding the risk data to maps and the
risk “hot spots” were identified mostly around big cities along the rivers where besides pesticides,
pharmaceuticals, EDC’s and PFC’s risk was increased.
Acknowledgements
The authors wish to acknowledge the financial support provided by the Spanish Ministry of Science and Innovation through the
projects SCARCE (Consolider-Ingenio 2010 CSD2009-00065) and CEMAGUA (CGL2007-64551/HID) HID), and the
Generalitat de Catalunya (Grup Consolidat de Recerca: Unitat de Qualitat de l'Aigua i Sòls, 2009SGR965.). Maja Kuzmanovic
acknowledges AGAUR fellowship
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 179 Poster sessions Improving the WFD purposes by the incorporation of ecotoxicity tests
Neus Roig1,2, Jordi Sierra1,3, Martí Nadal2, Ignacio Moreno4, Elena Nieto4, Miriam Hampel4,
Julián Blasco , Marta Schuhmacher1,2 and Jose Luis Domingo2
1
Environmental Engineering Laboratory, Departament d'Enginyeria Quimica, Universitat Rovira i Virgili, Tarragona,
Spain
2
Laboratory of Toxicology and Environmental Health, School of Medicine, IISPV, Universitat Rovira i Virgili, Reus,
Spain
3
Laboratori d’Edafologia, Facultat de Farmàcia, Universitat de Barcelona, Barcelona, Spain
4
Departamento Ecología y Gestión Costera, Instituto de Ciencias Marinas de Andalucía (CSIC), Puerto Real, Cadiz,
Spain
The approval of the European Water Framework Directive (WFD) supposed a big step regarding aquatic
ecosystems protection. According to this Directive, assessment of ecological status is based on three
quality elements: biological, physicochemical and hydromorphological, but ecotoxicological status is still
not included. Some studies have observed that biological status is not always in coherence with
physicochemical status, maybe due to the adaptation mechanisms of aquatic organisms under chronic
chemical exposure. In these situations, ecotoxicity tests could be useful to obtain a better characterisation
of these specific ecosystems.
The general aim of this work is to add a battery of ecotoxicity tests to the current analyses defined by
WFD in order to obtain a better ecological characterization of freshwater systems. The specific aims of
this work are: (1) to compare the effectiveness and viability of different ecotoxicity tests performed with
freshwater sediments (directly and with pore water) taking as target organisms different aquatic species,
and (2) to evaluate the relationship between stream pollutants concentrations (organic pollutants and
metals), biological and hydromorphological status and sediments ecotoxicity. For this purpose, thirteen
sampling sites within the Ebro river watershed were selected. Data about priority pollutants in water,
sediment and fish as well as biological and hydromorphological status of each sampling point will be
achieved. Moreover, in each sampling reach, composite samples of sediment were collected by using a
Van Veen grab. Sediment samples were stored at 4ºC prior to the ecotoxicity analyses.
The ecotoxicity of pore water was evaluated by different bioassays (Vibrio fischeri, Pseudokirshneriella
subcapitata and Daphnia magna) while the ecotoxicity of whole sediment was evaluated in Vibrio
fischeri, Nitzschia palea and Chironomus ripariusIn addition, the concentration of total heavy metals and
metal bioavailability was calculated by a sequential extraction according to the Community Bureau of
Reference (BCR) method. To distinguish the potentially toxic fraction associated to heavy metals burden
of sediments, an analysis of acid-volatile sulphide (AVS) and simultaneously extracted metals (SEM) was
performed. Complementary sediment variables as humidity, porosity, percentages of fines (<63 µm)
organic carbon and organic matter were determined.
This study expect to demonstrate that the integration of chemical, biological and ecotoxicological
analyses could be crucial to understand the hazard of pollutants in aquatic ecosystems, especially, in
freshwater sediments. Future research in this area is needed in order to obtain more data and be able to
establish a tree decision of freshwater analyses evaluation. The poster will present the methodology
purposed for this study as well as the first preliminary results obtained from ecotoxicity tests.
Acknowledgements
Authors would like to thank the Spanish Ministry of Economy and Competitiveness for its financial support through the project
SCARCE (Consolider-Ingenio 2010 CSD2009-00065). Moreover, authors would like to thank especially Confederación
Hidrográfica del Ebro as well as United Research Services, S.L.U. for their collaboration with the sediment sampling campaign.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 180 Poster sessions A chemical determination of the sediment fluxes at the Barasona
Reservoir
José A. López-Tarazón1,2, Pilar López3, Damià Vericat2,4,5 Isabel Muñoz3 and Ramon J.
Batalla2,4,6
1
2
School of Natural Sciences and Psychology, Liverpool John Moores University, Liverpool, UK
Departament de Medi Ambient i Ciències del Sòl (DMACS), Universitat de Lleida, Lleida, Spain
3
Departament d’Ecologia, Universitat de Barcelona, Barcelona, Spain
4
Centre Tecnològic Forestal de Catalunya, Solsona (Lleida), Spain
5
Institute of Geography and Earth Sciences, Aberystwyth University, Ceredigion, UK
6
Reservoir siltation compounds problems and negative impacts on both environmental and socioeconomical issues. The first is focused mainly on macrophyte communities, invertebrate biodiversity, fish
habitat and contamination by pollutants accumulation, whilst the latter refers especially to reservoir
sedimentation, causing water quality issues and, specially, a progressive reduction in dam impoundment
capacity, which creates serious problems for water management. Thus, Water Authorities and managers
should paid special attention to this question. The Barasona Reservoir (i.e., responsible of the irrigation of
more than 70,000 ha in Aragon and Catalunya) experiences acute siltation problems threatening its longterm impoundment capacity. Sediment load mainly come from Eocene marls located in the middle part of
its draining basin (i.e., Ésera and Isábena rivers). Within this context a study is being carried out within
SCARCE with the aim of studying the transfer of sediments and its chemical characteristics through the
Barasona Reservoir to accomplish two main objectives: i) establishing the basic chemical characteristics
of the fine sediment that is deposited in the reservoir and flows out through the dam and, ii) studying the
retention of C, N and P associated to fine particle sedimentation. In the present work we present the
results obtained after the first chemical analyses (C and N) of the sediment inputs (i.e., Ésera and Isábena
rivers) and outputs (i.e., sediment sluiced down through the dam) to evaluate the effects of the hydrology
on the transport of these elements and to quantify the total sediment load (together with C and N) that
enters and goes out the reservoir. For this, we established an integrated sediment monitoring strategy to
control the sediment input to the reservoir, by means of sampling (by using an ISCO 3700 automatic
sampler) at the outlet of the Rivers Ésera and Isábena, and the output from the reservoir itself. To observe
the effects of the hydrology over sediment (and elements) transport, sampling was set up with the
objective of obtaining water samples at 3 different discharge ranges (i.e., low, medium and high flows)
established according the long-term discharge registers of the sampling sites. This way, we had samples
for all the discharge classes, obtaining integrated averaged samples at each sampling point at a given flow
strength. Total C, and N were determined through dry material using an elemental CN auto-analyzer,
whereas organic C was determined after acid treatment of bulk sample and further analysis for total
carbon. Finally, to help in the interpretation of the results, grain size distribution for all samples were also
determined, with a Beckman-Couter LS 230 particle analyzer in two aliquots, one aliquot was analysed
directly after dispersion with pyrophosphate and ultrasound, and the other was treated for organic matter
elimination by adding H2O2. Main results show that, for absolute values, the highest concentrations of
both C (total and organic) and N are always transported by the medium-high flows, a fact that could be
considered as obvious if we take into account that is during these flows when the highest suspended
sediment loads are transported. However, it is remarkable that when we analyse the relative values of dry
weight, this pattern turns around being the low flows which, in proportion to the total load, transport the
highest concentrations of both total and organic C (not so clear for N), Finally, the highest C/N ratios (up
to 130) are observed during low-flows again, pointing out that sediments transported during low-flows are
mainly organic; on the other hand, small-very small ratios are observed during medium-high flows,
probably influenced by the huge amounts of inorganics sediments that are transported during flood
events.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 181 Poster sessions Exposure to human pharmaceuticals produces differential
transcriptome expression fingerprints in the brain of the seabream,
Sparus aurata
Miriam Hampel1,2, Massimo Milan1, Julián Blasco1, Serena Ferraresso1 and Luca Bargelloni3
2
1
Instituto de Ciencias Marinas de Andalucía (ICMAN-CSIC), Puerto Real, Spain
Department of Comparative Biomedicine and Food Science, University of Padova, Legnaro, Italy
Abstract
Pharmaceuticals are pseudo persistent aquatic pollutants
with unknown effects at environmentally relevant
concentrations. Gilthead seabream (Sparus aurata) were
exposed to Acetaminophen (APAP): 31.90 ± 11.07;
Atenolol (AT): 0.95 ± 0.38 and Carbamazepine (CBZ):
6.95 ± 0.13 µg•L-1 for 28 days to (1) determine whether
exposure to environmentally relevant concentrations of the
pharmaceuticals alters the brain transcripome; and (2)
identify different expression profiles and treatment specific
modes of action and pathways. After APAP, AT and CBZ
treatment, 411, 7 and 612 differently expressed transcripts
were identified, respectively. Out of these, 248 features
were common between APAP and CBZ and one between
CBZ and AT. Two features were common across all
treatments.
Figure 1. Venn diagram representation of
differentially expressed genes in the brain of
APAP, AT and CBZ -treated seabream. Venn
diagram shows the overlaps of differentially
expressed genes based on at least a 1.5-fold
filter change with a p≤0.05.
Gene set enrichment analysis revealed effects on several biological process-, cellular compartment- and
molecular function-related GO terms indicating towards known mechanisms from human and rodent
exposures. Lysosome pathway, and androgen and estrogen metabolism were altered by APAP and CBZ,
respectively. These data suggest (1) that exposure to environmentally relevant concentrations of the
pharmaceuticals alters the brain’s gene expression profile of the seabream; (2) the existence of treatment
specific processes that may be useful for biomarker development; and (3) that many responses observed
in seabream are similar to humans.
Acknowledgements
This study was funded by a Marie Curie European Reintegration Grant (Proposal N° 239325-ERA4PHARM, FP7-PEOPLEERG-2008), the project SCARCE, funded by the Spanish Ministry for Sciences and Innovation (Consolider-Ingenio 2010
CSD2009-00065) and the project I2TEP for Cross Border Research and Technology Transfer between Spain and Portugal funded
by the European Community (Interreg EU). The stay of M. Hampel at the University of Padua was funded by a mobility aid
from the Spanish National Council for Scientific Research (CSIC).
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 182 Poster sessions Environmentally relevant concentrations of three human
pharmaceuticals alter the liver transcriptome of the Atlantic salmon,
Salmo salar
Miriam Hampel1, Esteban Alonso2, Irene Aparicio2, James Bron2, Juan Luis Santos2, John
Taggart1 and Michael Leaver1
1
2
Institute of Aquaculture, University of Stirling, Stirling, UK
Department of Analytical Chemistry, University of Seville, Seville, Spain
Abstract
The combination of increasing consumption rates and limited elimination under conventional waste water
treatment practices of many pharmaceutical compounds has now led to their detection in aquatic
environments. Three of the most frequently detected pharmaceuticals in the environment are
Acetaminophen (APAP), Atenolol (AT) and Carbamazepine (CBZ). Atlantic salmon (parr) was exposed
to environmentally relevant levels of APAP (54.77 ± 34.67 µg•L-1), AT (11.08 ± 7.98 µg•L-1) and CBZ
(7.85 ± 0.13 µg•L-1). Gene expression was analyzed in liver tissues using a 16K GRASP (University of
Victoria, Canada) cDNA microarray revealing a significant (p<0.05) up- or down-regulation of 938, 548
and 497 features after APAP, AT and CBZ treatment, respectively. Candidate gene lists for each
treatment were submitted to Blast2Go and Kegg for functional annotation and to analyze for induced
pathways, respectively. Both analyses revealed several common features but also identified treatment
specific processes which in many cases were similar to those observed in humans or rodents. The
ontologic analysis indicated that different pathways were changed; suggesting that salmon may be
affected by environmentally relevant doses of the selected pharmaceutical compounds.
Acknowledgements
This work was supported by a Marie Curie Fellowship to MH (Proposal N° EIF-039691-SALMONPHARM, FP6-2005Mobility-5).
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 183 Poster sessions Temperature forcing and pharmaceuticals occurrence as proxy of
global change. Subtlethal effects (osmoregulatory capacity, ingestion
and respiration rates) in the freshwater crustacean,
A. desmarestii
Elena Nieto, Miriam Hampel, Enrique González-Ortegón, Pilar Drake and Julián Blasco
Institute for Marine Science of Andalusia, Department of Ecology and Coastal Management, Puerto Real, Spain
Many studies have been published on the occurrence and fate of pharmaceutical compounds in different
matrices such as ground water (Daughton and Ternes, 1999; Kolpin et al., 2002), surface water (Ternes,
1998; Kolpin et al., 2002) and sediment (Silva et al., 2011). However, there is a lack of information about
climate change effects on toxicity of chemical compounds. In order to improve the knowledge about this
subject, we performed a series of toxicity tests on the freshwater shrimp Atyaephyra desmarestii as model
organism. A. desmarestii is widely distributed in clean freshwater bodies and has been successfully
employed in pharmaceuticals ecotoxicity tests (Nieto et al., 2013). Selected sublethal endpoints were
osmoregulatory capacity and ingestion- and respiration rate as indicators of physiological changes.
The shrimps were exposed to three pharmaceutical compounds with high comsumption rates worldwide:
Diclofenac (DF) and Ibuprofen (IB) which belong to the group of non-steroidal anti-inflammatory drugs
(NSAIDs) and Carbamazepine (CBZ), an anticonvulsant at two different temperatures (20 and 25ºC).
Sublethal responses were monitored at environmental relevant concentrations, ranging between 1070µg·L-1 for the three selected compounds. No significant differences were found between controls and
treatment (Dunnett´s test p<0.05) in organisms exposed at 20º C and only for DF there was a decrease in
respiration rate close to statistical significance under conditions of severe anoxia (1 mg O2·L-1). Similar
results were found in the organisms exposed at 25º C where no significant differences were found
between control and treatment for osmoregulatory capacity and ingestion rate. In the case of respiration
rate, a significant difference with respect to the control (Dunnett´s test p>0.05) was found in CBZ
exposed organisms under conditions of moderate hypoxia (3 mg O2·L-1) and well oxygenated water (5 mg
O2·L-1). These results indicate that the presence of CBZ even at relatively low concentrations may
produce respiratory defiencies in exposed organisms in well oxygenated water under increasing
temperature conditions. This fact underlines the possibility to use the presence of contaminants and the
increase of temperature as proxy for ecological risk assessment in the context of global change.
Acknowledgements
This study was sponsored by the Consolider-Ingenio 2010 project SCARCE (Consolider-Ingenio 2010 CSD2009-00065) from the
Spanish Ministry of Sciences and Innovation. We would like to thank the support of the Intramural CSIC project 201230E034.
References
Daughton, C.G., Ternes, T.A. 1999. Pharmaceuticals and Personal Care Products in the Environment: Agents of Subtle Change?.
Environmental Health Perspectives. 6, 907-938.
Kolpin, D.W, Furlong, E.T, Meyer, M.T, Thurman, E.M, Zaugg, S.D, Barber, L.B, Buxton, H.T, 2002, Pharmaceuticals,
hormones, and other organic wastewater contaminants in U.S. Streams, 1999-2000: a national reconnaissance, Environ Sci
Technol. 36, 1202-1211.
Nieto, E., Blasco, J., González-Ortegón, E., Drake, P., Hampel, M., 2013. Is Atyaephyra desmarestii a useful candidate for lethal
and sublethal toxicity test on pharmaceutical compounds?, Journal of Hazardous Materials, in press.
Silva, B.F.d.. Jelic, A., López-Serna, R., Mozeto, A.A., Petrovic, M., Barceló, D. 2011, Occurrence and distribution of
pharmaceuticals in surface water, suspended solids and sediments of the Ebro river basin, Spain, Chemosphere. 85, 1331-1339.
Ternes, T.A., 1998. Ocurrence of pharmaceuticals in German sewage treatment plants and rivers. Water Res. 32, 3245-3260.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 184 Poster sessions A comparative study of recirculation and continuous mode for
pollutant ions exchange from pretreated olive mill wastewater
M. D. Victor-Ortega1, J.M. Ochando-Pulido1, G. Hodaifa2 and A. Martínez-Férez1
2
1
In this research work, a comparative study of recirculation and continuous mode was carried out to evaluate
the performance of ion exchange (IE) process for the removal of main pollutant ions present in olive mill
wastewater (OMW). This industrial effluent, which is highly contaminant, was previously treated by means
of chemical oxidation based on Fenton's reagent, flocculation-sedimentation and filtration through olive
stones [1]. Sodium, iron, chloride and phenolic compounds are the main pollutants in this wastewater [2].
The aim of this study was to reduce as much as possible concentration of the mentioned ions in pretreated
OMW for its reuse in the olive oil production process. In this sense, the Drinking Water Directive, Council
Directive 98/83/EC sets the maximum concentration in drinking water at 200 µg L-1 for iron, 200 mg L-1 for
sodium and 250 mg L-1 for chloride [3]. Although phenols level is not established by any directive, it is
important to avoid it as much as possible due to its toxicity. IE process using Dowex Marathon C and
Amberlite IRA-67 resins was investigated at laboratory scale for these ions removal. Recirculation and
continuous mode experimental studies were conducted to evaluate the effect of resins disposition and
temperature.The relative position of both IE resins was firstly studied and it was found that the optimum
arrangement consisted on the cation exchange resin (Dowex Marathon C) followed by the anion exchange
one (Amberlite IRA-67). Moreover, concentrations of the assayed pollutants were below the maximum
levels established by the legislation, both in recirculation and in continuous mode, under the optimized
conditions. Finally, it was probed that both IE resins have good application potential for the removal of iron,
sodium, chloride and phenolic compounds from pretreated OMW.
A)
B)
Figure 1: Flow diagrams of Ion exchange process for purification of pretreated OMW: A) Recirculation
mode experiments; B) Continuous mode experiments.
Acknowledgements
Spanish Ministry of Science and Innovation is acknowledged for funding the project CTQ2010-21411: Depuration of wastewater
from olive oil industry for reuse in the process.
References
[1] Martínez Nieto, L. Hodaifa, G., Rodríguez Vives, S., Giménez Casares, J.A. and Ochando, J. Degradation of organic matter in
olive oil mill wastewater through homogeneous Fenton-like reaction, Chem. Eng. Journa (2011), 173 (2), 503-510.
[2] Garrido Hoyos, S.E., Martínez Nieto, L., Camacho Rubio, F., Ramos Cormenzana, A. Kinetics of aerobic treatment of olive
mill wastewater (OMW) with Aspergillus terreus, Process Biochem., 37 (10) (2002) 1169–1176.
[3] European Commission. 1998. Council Directive 98/83/EC of 3 November 1998 on the quality of water intended for human
consumption.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 185 Poster sessions Effect of ions concentration on the remediation of sodium and iron
from olive mill effluent by ion exchange technique
M. D. Victor-Ortega1, J.M. Ochando-Pulido1, G. Hodaifa2, L. Martínez-Nieto1 and A. MartínezFérez1
2
1
The sorption of sodium and total iron from synthetic pretreated olive mill wastewater (OMW) was
investigated by using a gel strong acid cation exchange resin, which is based on a styrene-divinyl benzene
copolymer matrix with sulfonate functional groups (Dowex Marathon C). OMW has very high chemical
oxygen demand (COD) and elevated concentration of organic matter [1]. Furthermore, inorganic
compounds such as several salts of potassium, calcium, iron, magnesium, sodium and copper are presents
in OMW [2]. In this research study, a semibatch Ion Exchange (IE) system is proposed as an efficient
alternative for purification of OMW pretreated by means of chemical oxidation based on Fenton's
reagent, followed by a coagulation–flocculation step and a filtration in series through three different kinds
of adsorbent materials [3].
Batch sorption experiments were carried out to evaluate the removal of sodium and iron, which are
principal metal cations in this effluent, from synthetic water simulating pretreated OMW at varying these
pollutant ions initial concentrations and contact time. Initial concentrations of 250, 500, 750 and 1000
mg/L, and 0.400, 1.00, 2.50 and 5.00 mg/L were fixed for sodium and iron ions respectively, since these
are typical ranges in real olive mill effluents. The results show that concentrations of sodium and total
iron were considerably reduced with increasing contact time. In addition, the equilibrium was obtained in
about 45 min for theses ions and from this point forward concentrations were lower than the maximum
levels established by the Drinking Water Directive (DWD) [4]. The uptake of sodium and total iron ions
by the assayed resin was reversible and so it has good potential for the removal of the mentioned ions
from pretreated OMW.
Properties
Type
Matrix
Ionic form
as shipped
Particle size
Effective pH
range
Total exchange
capacity
Shipping
weight
Dowex
Marathon C
Strong-acid
cation
StyreneDVB, gel
H+
0.55-0.65 nm
0-14
1.80 eq/L
800 g/L
Figure 1: Physicochemical properties of Dowex Marathon C resin.
Acknowledgements
References
[2] Rozzi, A., Limoni, N., Menegatti, S., Boari, G., Liberti, L. and Passino, R. Influence of Na and Ca alkalinity on UASB
treatment of olive mill effluents. Part 1. Preliminary results. Process Chem. (1988), 23, 86-90.
[3] Martínez Nieto, L. Hodaifa, G., Rodríguez Vives, S., Giménez Casares, J.A., Ochando, J. Flocculation-sedimentation combined
with chemical oxidation process, Clean – Soil, air and water, 39 (10) (2011) 949-955.
[4] European Commission. 1998. Council Directive 98/83/EC of 3 November 1998 on the quality of water intended for human
consumption.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 186 Poster sessions Comparing different nanofiltration and reverse osmosis membranes for
final remediation of olive mill wastewater
J.M. Ochando-Pulido1, M. D. Victor-Ortega1, G. Hodaifa2, L. Martínez-Nieto1 and A. MartínezFérez1
2
1
The present study focuses on the management of OMW in order to achieve the quality to recirculate the
final effluent to the manufacture process or at least to the olives washing machines to finally close the
loop. With this goal, membrane processes were conducted on laboratory scale on real fresh OMW
samples. To preserve the membranes from deleterious fouling phenomena commonly encountered in all
membrane facilities, OMW was conducted to a pretreatment comprising Fenton-like advanced oxidation,
flocculation-sedimentation and filtration through olive stones in series. One nanofiltration (NF) and two
rather different reverse osmosis (RO) polymeric membranes were tested for the ulterior OMW
purification. Membranes performances in terms of productivity and permeate quality were confronted and
discussed, and the suitability of the Fenton-like process as pretreatment step regarding OMW depuration
by membranes was evaluated [1, 2].
An average-sized olive oil factory produces 10-15 m3/day of olive mill wastewater (OMW). Low pH,
extremely high concentration of suspended and dissolved solids, as well as heavy organic load is
characteristic of OMW. Among the latter, the high concentration of phenols and tannins commonly
present in this effluent confers OMW phytotoxic and antimicrobial properties and low biodegradability
that hinder conventional biological treatments. Inorganic compounds including chloride, sulfate and
phosphoric salts of potassium, calcium, iron, magnesium, sodium, copper and traces of other elements are
also present in OMW [3].
Membrane technologies have been demonstrated to be an effective vehicle for removing most organic and
inorganic compounds and microorganisms in regard to wastewater reclamation in the last years.
Nevertheless, membranes fouling inhibition and control are currently ones of the main challenges of
membrane technology. Membrane fouling depends on hydrodynamics as well as solute concentration and
nature in the feedstock, among other factors [4]. Pretreatment of the feedstock has been underlined as key
regarding fouling inhibition strategies [5].
Acknowledgements
References
[2] Martínez Nieto, L. Hodaifa, G., Rodríguez Vives, S., Giménez Casares, J.A., Ochando, J. Degradation of organic matter in olive
oil mill wastewater through homogeneous Fenton-like reaction, Chem. Eng. Journal, 173 (2) (2011) 503-510.
[4] Stoller, M. On the effect of flocculation as pretreatment process and particle size distribution for membrane fouling
reduction, Desalination. 240 (2009) 209-217.
[5] Stoller, M., Chianese, A. Optimization of membrane batch processes by means of the critical flux theory, Desalination, 191
(2006) 62-70.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 187 Poster sessions Steady-state performance enhancement of a diafiltration reverse
osmosis system for final salinity rejection of olive mill wastewater
J.M. Ochando-Pulido1, M. D. Victor-Ortega1, G. Hodaifa2 and A. Martínez-Férez1
2
1
This work aims to modeling the impacts on concentration polarization and fouling resistances driven by
recirculating a fraction of the permeate stream on a thin-film composite reverse osmosis (RO) membrane
(polyamide/polysulfone) for the final purification of OMW previously pretreated by means of chemical
oxidation based on Fenton's reagent, flocculation-sedimentation and filtration through olive stones [1, 2].
In this regard, optimum operating pressure and cross-flow velocity were found in our former experiments
to be equal to 25 bar and 5.1 m/s respectively, whereas operating temperature of 15 °C was chosen to
simulate the temperature conditions close to the ones experienced on average during the olive oil
production campaign, when OMW is derived and should be managed [3]. Upon those fixed operating
conditions, influence of permeate recirculation fraction (0 - 30%) on membrane performance was studied
in diafiltration (semicontinuous) mode. Results were analyzed by the resistances-in-series and critical flux
models to check for the influence of the permeate recirculation ratio on concentration polarization and
fouling build-up on the membrane.
Olive mill wastewater (OMW) is a heavy polluted liquid stream characterized by an acid pH value, black
color, very high chemical oxygen demand (COD) and a high concentration of microbial growth inhibiting
compounds, such as phenolic compounds and tannins. Also inorganic compounds such as chloride,
sulfate and phosphoric salts of potassium, calcium, iron, magnesium, sodium, copper and traces of other
elements are present in OMW [4].
Still scarce are the studies addressing the depuration of (OMW) by means of membrane technology, and
there are still some unresolved problems related to membrane fouling that slow down large-scale
applications. Membrane fouling reduces the performances of membranes over time and depends on
hydrodynamics and solute concentration in the feedstock, among other factors. Proper feedstock
pretreatment and operating conditions are essential in fouling inhibition strategies [5, 6].
Acknowledgements
References
1] Martínez Nieto, L. Hodaifa, G., Rodríguez Vives, S., Giménez Casares, J.A., Ochando, J. Degradation of organic matter in olive
oil mill wastewater through homogeneous Fenton-like reaction, Chem. Eng. Journal, 173 (2) (2011) 503-510.
[3] Ochando-Pulido, J.M., Rodriguez-Vives, S., Martinez-Ferez, A. The effect of permeate recirculation on the depuration of
pretreated olive mill wastewater through reverse osmosis membranes, Desalination, 286 (2012) 145-154.
[5] Stoller, M. On the effect of flocculation as pretreatment process and particle size distribution for membrane fouling
reduction, Desalination. 240 (2009) 209-217.
[6] Stoller, M., Chianese, A. Optimization of membrane batch processes by means of the critical flux theory, Desalination, 191
(2006) 62-70.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 188 Poster sessions Freshwater scarcity effects on the different components of a European
estuary from Mediterranean-climate zone
Enrique González-Ortegón1, Alberto Arias1, Francisco Baldó2, José Antonio Cuesta1, Carlos
Fernández-Delgado3, César Vilas4 and Pilar Drake1
1
2
3
Departamento Biología Animal, Universidad de Córdoba, Córdoba, Spain
4
In the Mediterranean-climate zone, the recurrent drought events and the increasing water demand are
usually leading to a decreased freshwater input to estuaries that threat their proper function as nursery
areas. In this study, all the published results of the Guadalquivir estuary related to this topic were
analysed to provide integrated and valuable insights on the effects of water scarcity on the different
components of the estuaries from this climate zone.
During drought events, the estuary is totally flood-dominated, with the consequent alteration of its
environmental conditions: decreasing the suspended particulate matter (SPM) and nutrients inputs and
thus the turbidity, but increasing their residence time and the salinity intrusion. As the estuarine primary
production (PP) is usually light-limited, the water scarcity (lower turbidity) is usually linked to an
increase of the autochthonous primary production; conversely, the low river inflow causes a reduction of
the allochthonous input of Chl a to the estuary. Among species using the estuary as a nursery area, marine
species tend to hold a more steady position within the salinity gradient (limited osmoregulatory capacity);
thus, the extended seawater intrusion during drought events favours the entrance of straggler marine
species and increase the abundance of marine migrants. However, high dam discharge water after drought
may lead to a persistent increase in the SPM and turbidity. Such unusual situation seems to cause: low
autochthonous PP and low densities of some key species, as the common prey Mesopodopsis slabberi and
the predators Engraulis encrasicolus and Pomadasys incisus; and a shift in the distribution of the most
euryhaline prey Neomysis integer and the predators species Dicentrarchus punctatus and Crangon
crangon, towards more saline waters, causing an increase in the inter-specific competition (for
food/habitat) within the estuarine nursery area.
The estuarine flushing generates: a turbidity plume, which acts as an estuarine cue for some species, as
glass eels; and a net nutrient input to adjacent sea water, causing an enrichment of its PP and favouring its
role as spawning and nursery grounds for marine species (fish and decapod crustaceans). However, under
a scenario of freshwater scarcity, there is a reduction of the estuarine plume extend (decreased
recruitment of some marine species) and of the fertilization of the adjacent coast (loss of its function as
spawning and nursery grounds).
In conclusion, freshwater scarcity is causing currently transitory changes in the estuarine communities,
but a quick reestablishment (strong resilience) is observed together with the recovery of environmental
conditions. However, if the decreasing trend in freshwater input persists, more extreme and persistent
unhealthy physical conditions can be expected and, beyond a certain threshold, the estuarine communities
may become less resilient (more persistent or even permanent community changes). Simirlarly, the
adjacent sea water area could loss its function as spawning and nursery grounds for marine species.
Acknowledgements
The study was co-funded by the Spanish Ministry of Economy and Competitiveness, and the EU Fishery Grant through the
projects SCARCE (Consolider-Ingenio 2010 CSD2009-00065).
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 189 Poster sessions Effects of stream habitat complexity and biodiversity on leaf litter
decomposition
Lorea Flores1, R. A. Bailey2,3, Arturo Elosegi1, Aitor Larrañaga1, B. R. Rall4 and J. Reiss5
1
Fac. of Science and Technology; University of the Basque Country, Leioa, Spain
2
Mathematical Sciences Institute, Queen Mary University, London, UK
3
School of Mathematics and Statistics, University of St Andrews, St Andrews, UK
4
J. F. Blumenbach, Institute of Zoology and Anthropology, University of Goettingen, Goettingen, Germany
5 Dept. of Life Sciences, Whitelands College, Roehampton University, London, UK
Biodiversity affects ecosystem functioning, especially when multiple processes are considered
simultaneously. Most of the information on the relationship between biodiversity and ecosystem
functioning is derived from field or laboratory experiments which typically neglect that the performance
of organisms can be modulated by abiotic factors that may influence interactions of organisms, and by the
horizontal and vertical linkages among organisms, for example within a food web. Therefore the
objectives of this study were to test 1) the effects of biodiversity on leaf decomposition with the
combinations of three crustacean species; 2) if habitat complexity influenced the interactions of these
three species and leaf decomposition; and 3) if the functional response of a predator changed with habitat
complexity.
To test these objectives we performed two laboratory experiments. To simulate habitat complexity we
added structures made of artificial plastic plants and we constructed a total of 4 levels of habitat
complexity using different numbers and arrangements of rings. In the first experiment, three invertebrate
detritivore species were used: the amphipod Gammarus pulex (L.), the isopod Asellus aquaticus (L.) and
the copepod Cyclops viridis (Jurine, 1820). Species were assembled in mono-, di- and tricultures and leaf
mass loss and generation of fine organic matter were measured after 29 days. In the second experiment,
the predator Ischnura elegans (Vander Linden, 1820; Zygoptera, Odonata) was exposed to prey densities
(Asellus aquaticus) ranging from 1 to 120. Prey consumption was measured after 24 h and predation
values were fitted to functional response curves to elucidate if habitat complexity affected the shape of
the functional response.
Preliminary results showed that different assemblages of consumers performed similarly when they had
the same biomass, i.e. we observed no biodiversity effects. However, habitat complexity had an effect on
the response with leaf consumption being lower at higher habitat complexity. In addition, although habitat
complexity seemed not to affect the shape of the functional response of the predator, predation rates
tended to be lower with higher habitat complexity. So far, these results showed that habitat complexity is
an important factor modulating organism interactions and ecosystem functioning.
Acknowledgements
This project was funded by the Spanish Ministry of Economy and Competitiveness (Consolider-Ingenio CSD2009-00065). L.
Flores also acknowledges a predoctoral grant from the Spanish Ministry of Education, Culture and Sports. We also want to thank
Nigel Reeve, the head of Ecology of the Richmond park (London) and John Arbon and Richard Bullock from the London
Wetland Centre for giving the permission to sample organisms.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 190 Poster sessions The effects of a mixture of pharmaceuticals compounds at
environmental concentrations on epilithic biofilms: constant flow vs
water intermittency conditions
Natàlia Corcoll1, Maria Casellas1, Belinda Huerta1, Helena Guasch2, Sara Rodríguez-Mozaz1,
Albert Serra2, Damià Barceló1,3 and Sergi Sabater1,2
1
3
Water and Soil Quality Research Group, Department of Environmental Chemistry, IDEA-CSIC, Barcelona, Spain
2
The occurrence of complex mixtures of pharmaceutical compounds in river ecosystems (from ng/L to few
µg/L) has increased in the last decades, but their potential toxicity on non-target organisms, such as algae
and bacteria composing epilithic biofilms, still remain poorly studied. In Mediterranean basins, temporary
rivers are abundant (Larned et al. 2010). Climate change-runoff models predict an increase in the
occurrence and frequence of water intermittency periods (Kundzewicz et al. 2008). This physical factor
alters the functioning and biomass of biofilm communities (Timoner et al. 2012), and in consequence may
alter their sensitivity to toxicants (Proia et al. 2013). This study aims to evaluate the effects of a chronic
exposure of a mixture of pharmaceutical compounds at environmental concentrations on the structure and
metabolic processes of biofilms. Biofilm communities exposed to a strong dry period (one week without
flow) may have, or may have not, a different sensitivity to pharmaceuticals exposure in comparison to
those under constant flows. In order to address these issues, an experiment was performed in facility of
artificial streams (ESF, ICRA) consisting of 12 channels. The experimental design had four treatments
with 3 replicates (channels) for treatment, resulting in a bifactorial design: i) Flow continuous_Non
pharmaceuticals exposure, ii) Flow continuous_Pharmaceuticals exposure, iii) Flow intermittency_Non
pharmaceuticals exposure and iv) Flow intermittency_Pharmaceuticals exposure. Treatments including
the pharmaceuticals exposure were reached by exposing biofilm communities for six weeks to a mixture
of 9 pharmaceuticals (from 6 different therapeutic families), selected from those more commonly found
in polluted sites of Mediterranean rivers at environmental concentrations (Osorio et al. 2012). In
treatments including a flow intermittency period, when biofilm was 3 weeks old, the water flow was
stopped for 1 week to simulate a dry period, and was restablished during 2 weeks more, named the
rewetting period. Biofilms of all treatmens were sampled during the rewetting period. Biofilm responses
to stressors (pharmaceuticals exposure and water intermittency) were determined based on their structure,
metabolic processes, sensitivity to pharmaceuticals (short-term dose-response tests) and pharmaceuticals
accumulation capacity. The obtained results showed that a chronic exposure of a mixture of
pharmaceuticals at environmental concentrations inhibits slightly algal biomass, cyanobacteria
abundance, alters the structure of bacterial community (based on DGGE analyses) and enhances
metabolic process (such as primary production and community respiration). Bacteria community showed
a lower EC50 to a short-term pharmaceuticals exposure than the algal community, suggesting a higher
sensitivity to pharmacetuticals exposure in bacteria than in algae. In addition, it was observed that the
effects of pharmaceuticals on biofilms were stronger in those communities exposed to water
intermittency. Metabolic processes markedly increased in those communities exposed both to
pharmaceuticals and water intermiitency. Algal community exposed to water intemittency became more
sensitive to short-term exposure of pharmaceuticals (lower EC50 value) than those growing under constant
flow. These results support the hypothesis that the observed decrease in algal biomass and biofilm
thickness due to flow intermittency enhances the diffusion of chemicals from the water column and
increase their potential toxicity on algae (Ivorra et al. 2000; Guasch et al. 2003). In contrast, the bacteria
community previously exposed to water intermittency became more tolerant to short-term exposure of
pharmaceuticals (higher EC50) tha those under constant flow. This finding confirms the hypothesis that
bacterial species tolerant to water intermittency may result also more tolerant to pharmaceutical exposure
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 191 Poster sessions than those dominating under constant flow conditions (co-tolerance phenomena). Our results may
contribute to better predict the potential effects of mixtures of pharmaceutical compounds on biofilms in
natural conditions, and also to better understand the role of water intermittency periods on
pharmaceuticals toxicity on algae and bacteria communities composing biofilms.
Acknowledgements
The authors thank Dr. Carles Borrego for his advice during bacterial molecular analyses. This study was financed by Spanish
Ministry of Economy and Competitiveness through the project SCARCE (Consolider-Ingenio 2010 CSD2009-00065), by the
European Union through the European Regional Development Fund (FEDER) and by the Generalitat de Catalunya (Consolidated
Research Group: Water and Soil Quality Unit 2009-SGR-965).
References
Guasch, H., Admiraal, W., Sabater, S. 2003. Contrasting effects of organic and inorganic toxicants on freshwater periphyton.
Aquatic Toxicology 64, 165–175.
Kundzewicz, Z. W., Mata, L.J., Arnell, N.W., Döll, P., Jimenez, B., Miller, K., Oki, T., Sen, Z., Shiklomanov, I. 2008. The
implications of projected climate change for freshwater resources and their management. Hydrological Sciences Journal 53, 3-10.
Larned, S. T., Datry, T., Arscott, D. B., Tockner, K. 2010. Emerging concepts in temporary-river ecology Freshwater Biology
55, 717–738.
Ivorra, N., Bremer, S., Guasch, H., Kraak, M.H.S., Admiraal, W. 2000. Differences in the Sensitivity of Benthic Microalgae To
Zn and Cd Regarding Biofilm Development and Exposure History. Environmental Toxicology and Chemistry 19, 1332.
Osorio, V., Marcé, R., Pérez, S., Ginebreda, A., Cortina, J.L., Barceló, D. 2012. Occurrence and modeling of pharmaceuticals on
a sewage-impacted Mediterranean river and their dynamics under different hydrological conditions. The Science of the total
environment 440, 3–13.
Proia, L., Vilches, C., Boninneau, C., Kantiani, L., Farré, M., Romaní, A. M., Sabater, S., Guasch, H. 2013. Drought episode
modulates the response of river biofilms to triclosan. Aquatic toxicology 127, 36–45.
Timoner, X., Acuña, V., Von Schiller, D., Sabater, S. 2012. Functional responses of stream biofilms to flow cessation,
desiccation and rewetting. Freshwater Biology 57, 1565–1578.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 192 Poster sessions Invertebrate community response to water and sediment chemical
composition in Mediterranean rivers
Núria de Castro-Català1, Damià Barceló2,3, Sandra Pérez2, Mira Petrovic3, Yolanda Picó4 and
Isabel Muñoz1
1
Department of Ecology, University of Barcelona, Barcelona, Spain
Water and Soil Quality Research Group, Department of Environmental Chemistry, IDEA-CSIC, Barcelona, Spain
3
4
2
River water is used for agricultural, industrial and domestic purposes that lead to water contamination
with numerous natural and synthetic compounds. Emerging pollutants are a large and previously
unknown group of compounds that are not totally removed by wastewater treatment plants (WWTPs) and
can be found ubiquitously in natural waters. Although most of these compounds are present at low
concentrations, many of them raise considerable ecotoxicological concerns, particularly when present as
components of complex mixture (Loos et al., 2009). However, there is little information on their effects
in freshwater communities.
The objective of this study was to check the relationships between invertebrate communities and the
presence of different groups of emerging pollutants in the water and in the sediment of 4 Iberian basins
(Llobregat, Júcar, Guadalquivir, and Ebro).
Four to six sites were sampled in each river during two consecutive years (2010, 2011) in early autumn.
Five sediment samples (10–15 cm in depth) were collected randomly with a core in each sampling site to
study the invertebrate community in the sediment. More than 800 pollutants, including pharmaceuticals,
pesticides, metals, illicit drugs, perfluorinated compounds and endocrine disrupting compounds were
measured in water and sediment matrix.. Physicochemical parameters were also measured in each site.
A preliminary analysis based on Spearman’s rank correlations was performed to check the relationship
between pollutants, physicochemical data and invertebrate community composition.
Negative significant relationships were found between the abundances of invertebrate taxa and chemical
concentrations. Pharmaceuticals and pesticides were the two families of pollutants which were repeatedly
correlated with different genera, both in the water and in the sediment matrix. For pesticides the response
of invertebrates was similar in the water and in the sediment, specifically for those which have endocrine
disrupting effects (e.g. Tolytriazole). Significant relationships were also found for some flame retardants
and alkylphenols. The invertebrates which defined these correlations were some Chironomidae (midges,
e.g. Polypedilum spp.) and some Oligochaeta (worms, e.g. Lumbriculus spp.). The response pattern of
pharmaceuticals was different depending on the matrix (water vs. sediment). Analgesics and antiinflammatory, histamine receptor antagonists and lipid regulators showed significant relationships with
most of the invertebrate taxa only in the water. However, in the sediment matrix the response was more
variable depending on the species and the group of compounds. Nutrients (PO4- and NO3-) were also
negatively correlated with most of the taxa, showing the general effect of nutrient enrichment in the
studied basins. Additional statistical analyses are in process in order to detect particular patterns for each
basin.
References
Loos, R., Gawlik, B.M., Locoro, G., Rimaviciute, E., Contini, S., Bidoglio, G.. EU-wide survey of polar organic persistent
pollutants in European river waters. Environ. Poll. (2009), 157, 561-568.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 193 Poster sessions Effects of water abstraction on large river ecosystem metabolism
Maite Arroita, Ibon Aristi and Arturo Elosegi
Faculty of Science and Technology, the University of the Basque Country, Bilbao, Spain
Water abstraction is increasing worldwide to satisfy the rising demand of energy and water, what
dramatically affects the hydrology of streams and rivers. Being discharge one of the major factors
controlling river ecosystems, these changes caused by water abstraction can have important consequences
for whole-system metabolism (production and respiration), which are fundamental indicators of
ecosystem functioning. Still, the impacts of water abstraction on ecosystem metabolism have been little
studied. Besides, most studies are limited to low-order streams, being measurements in large rivers very
rare. Therefore, the aim of this study was to assess the effects of water abstraction on large river
ecosystem metabolism.
The experiment was performed in three sections of the Aragon River (tributary of River Ebro) affected by
hydropower schemes: Santacara, Mélida and Caparroso (Navarre). All three hydropower schemes have a
maximum diversion capacity of 70 m3·s-1, slightly higher than the annual mean flow (68.6 m3·s-1). Two
reaches were selected at each section: a Control reach not affected by diversion, and an Impact reach in
the short-circuited reach. At the top and the bottom stations of each river reach dissolved oxygen, water
temperature, water level and conductivity were measured continuously for 24 hours. Gross primary
production (GPP) and ecosystem respiration (ER) were calculated following the two-station open-channel
method. Nominal travel time and water velocity were determined using a slug addition of Bromide as
KBr.
More than the 50 % of the discharge was abstracted during the study period, what led to narrower and
shallower river reaches, as well as slower water velocities. These alterations caused an increase in the
amplitude of the diurnal changes in dissolved oxygen in Santacara and Mélida. At these two sites GPP
and ER were higher in Impact reaches, leading to a higher ecosystem flux. The opposite happened in
Caparroso, where the amplitude, GPP, ER and ecosystem flux were lower in river reaches affected by
water abstraction. In spite of these differences, all reaches were autotrophic.
Overall, our results suggest that water abstraction affects river ecosystem metabolism, although the
direction of change can depend on site-specific features.
Acknowledgements
This work has been supported by the Spanish Ministry of Science and Innovation through the project Consolider-Ingenio
CSD2009-00065 and the project ABSTRACT CGL2012-35848.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 194 Poster sessions Effects of restoring stream dead wood on reach-scale storage and
decomposition of organic matter
Aitor Larrañaga1, Lorea Flores1, Ibon Aristi1, Inmaculada Arostegui1, Maite Arroita1, Joserra
Díez2 and Arturo Elosegi1
2
1
University college of Teacher Training, University of the Basque Country, Vitoria-Gasteiz, Spain
Stream channel complexity affects physical structure, biotic communities, and functioning of stream
ecosystems. Large wood is a key element in the creation and maintenance of physically complex stream
channels in forested areas, but human activities often reduce the loading of instream wood reducing its
ecological contribution. In an attempt to enhance stream habitat and ecosystem functioning, large wood
was experimentally introduced into 4 mountain streams in the Basque Country (northern Spain) (Flores et
al., 2011). The restoration modified the area covered by the three main benthic habitats: whereas gravel
and organic matter jams incremented their cover, cobble decreased it. To increment the accuracy of the
estimates we stratified the sampling and measured the storage and breakdown rate of organic matter in
each of the three habitats. We tested for the effect of our intervention at the reach level with a novel
approach based on a combination of permutation and bootstrap. We estimated total benthic organic matter
and decomposition at the stream reach level from the samples taken in the different habitats and published
processing rates of different materials (Arroita et al., 2012). In the biggest stream the effect of restoration
on organic matter storage and decomposition revealed to be non-significant. Nevertheless, considering all
four streams together, the experimental reaches displayed significantly higher values of organic matter
storage and decomposition than control stream reaches after the restoration (between 36 and 400 %
higher, Fig. 1). These relative increments seemed to be explained by the amount of wood added.
Similarly, total decomposition was between 10 and 300% higher in the experimental than in the control
reaches. Therefore, restoring wood loading is related to a tendency to increase the capacity to store and
decompose organic inputs at the reach level.
Figure 1: distribution of the estimates of
the total benthic organic matter at the
control and the experimental reaches
after the restoration. Vertical line
represents median of each distribution.
Acknowledgements
This project was funded by the EU (project LIFE NAT/E/000067) and by the Spanish Ministry of Economy and Competitiveness
(projects CGL2007-65176/HID and Consolider-Ingenio CSD2009-00065) and also benefited by support from the Basque
Government (Project IT-422-07), the University of the Basque Country (project GIU0538), the Province Government of
Guipuscoa and the Municipalities of Oiartzun and Renteria.
References
Arroita, M., Aristi, I., Flores, L., Larrañaga, A., Díez, J., Mora, J., Romaní, A.M. and Elosegi, A. The use of wooden sticks to
assess stream ecosystem functioning: Comparison with leaf breakdown rates, Science of the Total Environment, 440, 115-122.
Flores, L., Larrañaga, A., Díez, J. and Elosegi, A. Experimental wood addition in streams: effects on organic matter storage and
breakdown, Freshwater Biology, 56, 2156-2167.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 195 Poster sessions Effects of WWTP effluent on the metabolism of a Mediterranean river
Ibon Aristi1, Maite Arroita1, Lydia Ponsati2, Sergi Sabater2,3, Daniel von Schiller2, Arturo
Elosegi1 and Vicenç Acuña2
1
2
3
Humans are largely increasing the number of pollutants in the environment, and the contamination of
both surface and subsurface waters has become a serious problem (Schwarenbach et al., 2006). This led
legislators to establish new protection goals and regulatory approaches for environmental management
such as the water framework directive (WFD, EC 2000), and managers to build and operate many waste
water treatment plants (WWTP). Nowadays, over 13,000 WWTP have been constructed in Spain. Sewage
waters are generally a mixture of domestic and industrial wastewater, and often include rainwater run-off
from roads and other paved areas, and although the efficiency of WWTP has improved thanks to
technological advances, they are unable to eliminate all the pollutants they receive. Thus, effluents from
WWTP are a source of nutrients and pollutants that can affect ecosystem processes in the receiving river
reaches. Nutrients from WWTP can produce eutrophication, affecting primary producers (algae,
macrophytes) and microbial heterotrophs (bacteria, fungi), as they can use dissolved nutrients (e.g. Stelzer
et al 2003). On the other hand, WWTP effluents include pollutants such as pharmaceuticals, pesticides,
etc., which can impact aquatic ecosystems (Brunberg & Blomqvist, 2001). Nowadays there is little
information on how WWTP effluents affect ecosystem functioning and the self-purification capacity of
receiving river reaches. To assess this issue, we studied the impact of the effluents from Puigcerdà
WWTP on the carbon components and ecosystem metabolism of the receiving Segre River. We
established a control (C) reach upstream, and an impact (I) reach downstream the effluent with 4
consecutive sites starting at 500 m distance. In all of them, nutrient and pollutant concentrations were
measured, at midday and midnight, and suspended particulate organic matter (SPOM) and benthic organic
matter (BOM) analysed. Finally, ecosystem metabolism was measured for each site using the doublestation open-channel method. Ecosystem respiration (ER), gross primary production (GPP), net
ecosystem metabolism (NEM), ecosystem flux (EF) and production vs. respiration ratio (P/R) were
calculated. Nutrient and pollutant concentrations decreased downstream as a consequence of both dilution
and self-purification. SPOM also decreased downstream, but BOM did not. Ecosystem metabolism
increased below the WWTP, but there were no clear spatial trends downstream, suggesting that
ecosystem functioning did not recover natural values in the studied reach.
References
Brunberg, AK. & Bromqvist, P. Quantification of anthropogenic threats to lakes in a lowland country of Central Sweden. Ambio
(2001), 30, 127-134.
Stelzer, RS., Heffernan, J. & Likens, GE. The influence of dissolved nutrients and particulate organic matter quality on
microbial respiration and biomass in a forest stream. Freshwater Biol. (2003), 48, 1925-37.
Schwarenbach, R., Escher, BJ., Fenner, K., Hoffstetter, TB., Johnson, CA., von Gunten, U. & Wehrli, B. The challenge of
micropollutants in aquatic systems. Science (2006), 313, 1072-1077.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 196 Poster sessions An assessment of environmental factors influencing species
distribution in a temperate estuary: a binomial approach
Enrique González-Ortegón1, César Vilas4, Alberto Arias1, Francisco Baldó2, José Antonio
Cuesta1, Carlos Fernández-Delgado3 and Pilar Drake1
1
2
3
Dpto Biología Animal, Universidad de Córdoba, Córdoba, Spain
4
The analysis of species–environment relationship has always been a central issue in ecology. Presence and
absence data allow us to estimate the probability of occurrence of the species and the optimum and tolerance
range (the realized niche) for the environmental variable of interest. Under a scenario of water scarcity,
freshwater discharges (FSW) to estuaries and, accordingly, estuarine salinity are expected to be remarkably
altered (González-Ortegón and Drake 2013). The aim of this study was to identify which environmental
variables influences the choices of nursery grounds for the marine species and reduce the presence of
estuarine species in the Guadalquivir estuary. Data used in this study were the presence and absence of a
subset of 40 species (among fish and crustaceans) in the Guadalquivir estuary (SW Spain). Because of the
presence-absence nature of the response variables and non-linear effect of some explanatory variables, the
most appropriate technique for these analyses was GAM using a binomial model (Zuur et al., 2009).
Salinity and mysids were the main factors explained the presence of marine species in the Guadalquivir
estuary. 75% of these models included salinity as a main factor to explain the occurrence of species. FSW
from the dam to the estuary during 4 days decreased the presence of marine species and increased the
presence of estuarine invertebrates and diadrom species. By contrast FSW during 15 days triggered the
absence in all studied species.These relationships between presence-absence and environmental factors were
in the most of cases linear, especially for temperature and salinity; but in other cases, especially freshwater
discharges, the responses show a bell-shaped curve which indicated an optimal threshold for the prevalence
of the target species. In spite of all these species inhabit the same ecosystem, each binomial model is
specific and temporal-dependent: none species share an identical model. Similar behaviour at different
seasons could explain the elevated number of species (200) collected in this estuary by now.
Methodologicaly, this study confirm that presence–absence models are affected systematically by the
prevalence (i.e. the frequency of occurrence) of the target organism (Manel et al 2001). With the
exception of some estuarine species, presence-absence models are not useful for species with a low
prevalence (<20%; common for occasional species e.g. Parapleustes asimilis) or with a high prevalence
(>90%; common for estuarine species e.g. Pomatoschistus minutus). Conversely, just in a 23% of studied
species, the binomial models explained a 50% or more of their variances. Most of these species were
marine species with a presence ranging from 50 to 80% in the Guadalquivir estuary. This could reveal the
importance of this kind of model in marine species which enter estuaries seasonally from open sea.
Acknowledgements
The study was co-funded by the Spanish Ministry of Economy and Competitiveness, and the EU Fishery Grant through the
projects SCARCE (Consolider-Ingenio 2010 CSD2009-00065).
References
González-Ortegón, E.and Drake P. Effects of freshwater inputs on the lower trophic levels of a temperate estuary: physical,
physiological or trophic forcing? Aquat Sci (2012), 74, 455–69.
Manel, S., Williams, H. C. and Ormerod, S.J. Evaluating presence–absence models in ecology: the need to account for
prevalence, Journal of Applied Ecology (2001), 38, 921–931.
Zuur, A.F., E.N. Ieno, N.J. Walker, A.A. Saveliev, and G.M. Smith..Mixed effects models and extensions in ecology with R.
(2009), New York: Springer.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 197 Poster sessions Effect of black poplar plantations in the base river flow in a
Mediterranean stream
Núria Ferrer and Albert Folch
Hydrogeology Group, Dept. of Geotechnical Engineering and Geo-Sciences, Universitat Politècnica de CatalunyaBarcelonaTech, Barcelona, Spain
This study aims to assess the effect of poplar plantations in the base river flow of Santa Coloma River
basin (290 km2) located at the N of Barcelona city. To do it a numerical flow model (Visual Moflow 4.5)
has been constructed to simulate the shallow aquifers in the area (Folch et al. 2010) and the streamaquifer interaction for several years.
As in other areas around the world, in this basin the poplar roots tend to reach the water table of shallow
aquifers increasing evapotranspiration (ET) mainly during the summer months. This direct ET from de
aquifer has been included in to the model mass balance based in the study of Meiresonne et al. (1999) for
the period between June and September. Then, a direct ET of the aquifer of 4 mm/day has been added for
the dry days while a value of 2 mm/day has been included for days with precipitation and the day after.
The mass balance shows that poplar extracts an average of 2.66 hm3, a 20% of the total recharge of the
modeled area. This effect reduces the groundwater flow to the stream and in other areas increase
infiltration from the stream to the aquifer. As a result, there is a reduction in the stream flow by 47 % on
average compared a model without poplar plantations.
This reduction in flow occurs mainly in the summer months when the river is more sensitive drying the
river more often than it would happen with other land uses.
References
FOLCH, A., CASADELLÀ, L., ASTUI, MENCIÓ, A., O., MASSANA, J., VIDAL-GAVILAN, G., PÉREZ-PARICIO, A. i
MAS-PLA, J. (2010). Verifying conceptual flow models ina river-connected alluvial aquifer for management purposes using
numerical modeling. En: XVIII International Conference on Water Resources (CMWR 2010), Barcelona, Spain.
MEIRESONNE, L., NADEZHDIN, N., i CERMAK, J. (1999). Measured sap flow and simulated transpiration from a poplar
stand in Flanders ( Belgium ). Agricultural and Forest Metereology, 96, 165–173.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 198 Poster sessions Water management in a restored wetland influences trophic links and
species composition in the aquatic macroinvertebrate community
Enrique González-Ortegón1, M.E.M. Walton1, Bushra Moghaddam1, Cesar Vilas2, Ana Prieto2,
H.A. Kennedy1, J. Pedro Cañavate2 and Lewis Le Vay1
1 School of Ocean Sciences, College of Natural Sciences, Bangor University, Menai Bridge, UK
2 IFAPA Centro El Toruño, El Puerto de Santa María, Spain
Water regulation modifies the natural flood regime, salinity and temperature of aquatic ecosystems, and
hence community composition and structure. Invasions by non-indigenous species can also cause
significant change in the native populations and habitats. However, little is known about how ecological
impacts such as water regulation and invasive species affect food webs and other ecological processes.
This study explores how water management in reconstructed wetlands and introduction of the shrimp
Palaemon macrodactylus affects the trophic niche of the native Palaemonetes varians. Reconstructed
wetlands of Veta La Palma (VP) (west bank of the Guadalquivir estuary, SW Spain) comprise a total
extension of 3000 ha with 70 ha unit ponds dedicated to extensive and semi-extensive aquaculture. Water
is managed by different regimes of water exchange (E) with the Guadalquivir estuary, depending on
whether extensive (E=1% d-1) or mixed (E=5% d-1) aquaculture is performed. These ponds offer an
excellent opportunity to study how water regulation influences species composition in the aquatic
community. We estimated density of aquatic fauna, studied stomach contents of the two shrimps species
and analysed food web faunal and source samples for stable isotope analysis (SIA).
P. varians was found at similar average density in both the extensive (6.14 g m-2 of dry weight) and
mixed (6.77 g m-2) ponds, while P. macrodactylus was found only almost entirely only in mixed ponds
(10.20 g m-2). A low dissimilarity (33.2 %) was found for the aquatic community and water management
was the main factor contributing to dissimilarity. Mysids and copepods were the most abundant species in
mixed ponds, while ostracods and chironomids were more abundant in extensive ponds. Isotopic
signatures of potential prey of P. varians and P. macrodactylus were significantly different between
winter and summer (R=0.43, p=0.01) and between mixed and extensive ponds (R= 0.3-0.5, p<0.01). This
separation by carbon sources might be due to a different origin of primary production and organic matter
(allochthonous from the estuary vs. autochthonous).
A combined analysis of stomach contents and isotopic composition of P. macrodactylus and P. varians
showed that although there is some dietary overlap, the shrimp species have different trophic niches: P.
macrodactylus is more pelagic-carnivorous (main preys are mysids, copepods and exclusively
amphipods), while P. varians is mainly benthonic (consuming mainly isopods, ostracods, polychaetes and
sediment). Although, native P. varians is able to diversify to pelagic preys (mysids and copepods) in the
mixed ponds, where these prey densities are higher, in spite of the presence of the non-native P.
macrodactylus. Analysing the isotopic composition of P. varians across ponds and seasons showed a
significant effect of water regulation (R=0.7, p<0.01), with 76% of this difference being explained by
higher 15N values for P. varians in mixed (15.3 ‰) versus extensive (12.8 ‰) ponds.
In conclusion, the feeding of P. varians appears not to be affected by the presence of P. macrodactylus,
remaining benthonic and in fact diversifying to include P. macrodactylus prey items when these prey
densities increase, resulting in some dietary overlap. Differences in the trophic ecology identified in
stomach contents and isotopic signature of both species are clearly explained by water management.
Acknowledgements
The study was Co-funded by the European Union Atlantic Area Transnational Programme (2007 - 2013) through the SEAFARE
project. Financial support to E. González-Ortegón was given by Marie Curie fellowship with European funds. Others financial
support through SCARCE (Consolider-Ingenio 2010 CSD2009-00065).Merck and Biotage are acknowledged for the gift of LC
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 199 Poster sessions columns and SPE cartridges, respectively. Nicola Mastroianni acknowledges the JAE Program (CSIC-European Social Funds).
References
1. UNODC, 2013. World drugs report 2013, United Nation Office on Drugs and Crime. available
http://www.unodc.org/unodc/secured/wdr/wdr2013/World_Drug_Report_2013.pdf, accessed on September 20, 2013.
at
2. Pal, R., et al., Illicit drugs and the environment — A review. Science of the Total Environment, 2013. 463–464(0): p. 10791092.
3. Ginebreda, A., et al., Environmental risk assessment of pharmaceuticals in rivers: Relationships between hazard indexes and
aquatic macroinvertebrate diversity indexes in the Llobregat River (NE Spain). Environment International, 2010. 36(2): p. 153162.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 200 Poster sessions Integrated Water Resources Management and related indicators
Andrea Momblanch, Joaquín Andreu and Javier Paredes
Universitat Politècnica de València
Current trends at international level, and specifically at European level, advance towards sustainable and
efficient management of natural resources. This current is expressed in the “European Water Framework
Directive” (EP, 2000), the strategies “Europe 2020” (EC, 2010) and “EU biodiversity strategy to 2020”
(EC, 2011), and in “A Blueprint to safeguard Europe’s Water Resources” (EC, 2012), among other
official documents. Moreover, as population grows and other water demanding sectors develop the issue
of water allocation has become more complex (Andreu et al., 2012). This is why, simulation models need
to be adapted to consider the sustainable management of water resources (Loucks, 2000), inside the
broader objective of sustainable development. This has brought about simulation models to evolve
towards new approaches like Decision Support Systems, experts systems, collaborative planning and
management, and dynamic decision systems, among others (Solera, 2003). In line with the
abovementioned concepts, the Integrated Water Resources Management is a process which promotes the
coordinated development and management of water, land and related resources in order to maximise the
resultant economic and social welfare in an equitable manner without compromising the sustainability of
vital ecosystems, as defined by the Global Water Partnership (2000). From this definition, it is clear that
in order to cover so many water and ecosystems related aspects the use of integrative models is
increasingly necessary. In this work, a methodology comprised of five coordinated modules is used to
integrate aspects of water resources evaluation, diffuse pollution evaluation, water allocation, water
quality, and habitat suitability for aquatic species. These five modules are part of the AQUATOOL DSS
Shell for integrated water planning and management (Andreu et al., 1996) and have been designed for
more than 20 years following well established methodologies for water resources systems analysis.
AQUATOOL allows analysing the effect of multiple management alternatives and scenarios on the
relevant variables in a river basin. Thus, it is easier to conduct tradeoff analysis, risk evaluations, and
other useful processes which provide data for informed decision making.
INTEGRATED WATER RESOURCES MANAGEMENT METHODOLOGY
Water resources evaluation model
EVALHID
RIVER BASIN MANAGEMENT
Natural runoff
Natural runoff
350
300
250
CABECERA
CORNEJA
STA TERESA
200
ALHANDIGA
Hm 3
ALMAR
150
VALMUZA
TORMES_VALMUZA
100
ALMENDRA
DESAGUE
50
Jul‐03
Jul‐04
Jan‐04
A pr‐03
A pr‐04
Oct‐03
Jul‐00
Jul‐01
Jul‐02
Jan‐03
A pr‐02
Oct‐02
Jul‐99
Jan‐01
Jan‐02
Jan‐99
Jan‐00
A pr‐00
Oct‐00
A pr‐01
Oct‐01
A pr‐99
Oct‐99
Jul‐95
Jul‐96
Jul‐97
Jul‐98
Jan‐96
Jan‐97
Jan‐98
A pr‐96
Oct‐95
A pr‐97
Oct‐96
A pr‐98
Oct‐97
Oct‐98
Jul‐92
Jul‐93
Jul‐94
Jan‐92
Jan‐93
Jan‐94
Jan‐95
A pr‐92
Oct‐94
A pr‐95
Oct‐91
A pr‐93
Oct‐92
Oct‐93
A pr‐94
0
Water management model
SIMGES
WATER RESOURCES MANAGEMENT
Diffuse pollution evaluation model
CARFU
Volume in reservoirs
Volumes in reservoirs
Flows in rivers
Flows in rivers
Pollutants load into Pollutants load to water bodies
water bodies
50 0.0
600
16
45 0.0
14
500
40 0.0
12
35 0.0
400
' "Rio t1"; " r. Tormes 545_c";"Caudal"'
10
30 0.0
'Rio T3;" r. Tormes 504_c_g"; "Caudal"'
Hm3 300
Hm 3 25 0.0
'"Rio t1";" r. Tormes 503_a";"Caudal"'
' "Rio t1"; " r. Tormes 546_a";"Caudal"'
Sta Te resa
Ammonium
Kg 8
Nitrates
Villagonzalo
20 0.0
Phosphorus
6
'Rio t1;" r. Tormes 502_b"; "Caudal"'
200
15 0.0
'Rio t1;" r. Tormes 504_a";"Caudal"'
4
10 0.0
100
2
50.0
Habitat suitability model
CAUDECO
Habitat Time Series (%)
Habitat Time Series
Large Luciobarbus
Medium Luciobarbus
Small Luciobarbus
Large Pseudochondrostoma
Medium Pseudochondrostoma
Jun‐04
Oct‐03
Jun‐03
Aug‐04
Jun‐02
Oct‐02
Apr‐04
Feb‐04
Aug‐03
Dec‐03
Jun‐01
Oct‐01
Apr‐03
Feb‐03
Dec‐02
Aug‐02
Jun‐00
Oct‐00
Apr‐02
Feb‐02
Dec‐01
Aug‐01
Jun‐99
Oct‐99
Apr‐01
Feb‐01
Dec‐00
Aug‐00
Jun‐98
Oct‐98
Apr‐00
Feb‐00
Dec‐99
Aug‐99
Apr‐99
Feb‐99
Dec‐98
10
8
4
6
3
4
Ammonium
Disolved oxygen
Jun‐07
Jun‐06
Oct‐06
Oct‐05
Feb‐07
Feb‐06
Jun‐05
Jun‐04
Oct‐04
Feb‐05
Jun‐03
Oct‐03
Oct‐02
Feb‐04
Feb‐03
Jun‐02
Jun‐01
Jun‐00
Jun‐99
Oct‐01
Oct‐00
Oct‐99
Feb‐02
Feb‐01
0
Feb‐00
0
Jun‐98
2
Small Squalius carolitertii
Jun‐97
1
Oct‐98
2
Large Squalius carolitertii
Oct‐97
Small Pseudochondrostoma
Oct‐96
jul‐05
dic‐05
oct‐06
feb‐05
ago‐07
mar‐07
may‐06
abr‐04
sep‐04
jun‐03
nov‐03
ene‐03
jul‐00
dic‐00
oct‐01
feb‐00
sep‐99
ago‐02
mar‐02
may‐01
abr‐99
nov‐98
jun‐98
ago‐97
ene‐98
0
14
12
6
5
Feb‐99
20
oct‐96
Water quality (mg/L)
Water quality in rivers/reservoirs
7
Feb‐98
60
40
Feb‐97
80
mar‐97
Water quality model
GESCAL
8
100
Aug‐98
Jun‐97
Oct‐97
Oct‐96
Apr‐98
Feb‐98
Dec‐97
Aug‐97
Apr‐97
Feb‐97
Ju l‐04
Ju l‐03
Ju l‐02
Jan‐04
Jan‐03
Oct‐03
Oct‐02
Apr‐04
Apr‐03
Apr‐02
Ju l‐01
Ju l‐00
Ju l‐99
Ju l‐98
Jan‐02
Jan‐01
Jan‐00
Jan‐99
Oct‐01
Oct‐00
Oct‐99
Oct‐98
Apr‐01
Apr‐00
Apr‐99
Ju l‐97
Jan‐98
Oct‐97
Apr‐98
Ju l‐96
Ju l‐95
Ju l‐94
Jan‐97
Oct‐96
Apr‐97
Ju l‐93
Jan‐96
Oct‐95
Apr‐96
Ju l‐92
Jan‐95
Jan‐94
Jan‐93
Jan‐92
Oct‐94
Oct‐93
Oct‐92
Apr‐95
Oct‐91
Apr‐94
Apr‐93
Apr‐92
Dec‐96
0
0 .0
Jul‐04
Jul‐03
Jul‐02
Jan‐04
Jan‐03
Oct‐03
Oct‐02
Apr‐04
Apr‐03
Jul‐99
Jan‐02
Oct‐01
Apr‐02
Jul‐98
Jul‐01
Jan‐01
Oct‐00
Apr‐01
Jul‐97
Jul‐00
Jan‐00
Oct‐99
Apr‐00
Jul‐96
Jan‐99
Apr‐99
Jul‐95
Jan‐98
Oct‐98
Apr‐98
Jul‐94
Jan‐97
Oct‐97
Apr‐97
Jul‐93
Jan‐96
Oct‐96
Apr‐96
Jul‐92
Jan‐95
Jan‐94
Jan‐93
Oct‐95
Apr‐95
Jan‐92
Oct‐94
Oct‐93
Oct‐92
Oct‐91
Apr‐94
Apr‐93
Apr‐92
0
Scenario and trade‐off analysis for DECISION MAKING
Figure 1: Diagram of the Integrated Water Resources Management methodology.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 201 Poster sessions Figure 1 shows the information flow through the different models. It makes evident that the management
of the river basin impacts on the available water resources and the water quality of runoff. Moreover,
water resources allocation decisions impact all the basin uses, including the environmental uses and the
water quality (Paredes-Arquiola et al., 2013). With this methodology, it is easy to conduct tradeoff
analyses that help to balance the different significant issues in a whole river basin. The influence of
different environmental flow regimes on water quality and habitat suitability have been analysed in
previous studies (Paredes-Arquiola et al., 2013). But, the new methodology presented here also allows
relating changes in the land uses of the river basin to, for instance, changes in water quality or habitat
suitability, maintaining the same management rules. So, the potential of the effective linkage of these
tools is very broad.
In this work, the proposed methodology for Integrated Water Resources Management is applied to the
Tormes Water Resources System, in Spain. The period of analysis goes from October 1996 to September
2007, which includes a critical period related to a drought event. The potential of jointly analysing
different aspects of a water resources system are exemplified. Some indicators and graphics are proposed
to synthesise all the relevant information for decision making, which explicitly show the gains and losses
of each objective in diverse scenarios. Based on this, a tradeoff analysis is proposed to present the
evolution of water quality, satisfaction of demands and habitat availability, as environmental flows
change in several points of the water resources system. The results are analysed through graphics that can
be easily understood by decision makers and stakeholders, supporting sound and informed decisions.
Acknowledgements
The autor would like to thank the Spanish Ministry of Economy and Competitiveness for its financial support through the
projects SCARCE (Consolider-Ingenio 2010 CSD2009-00065) and NUTEGES (VI Plan Nacional de I+D+I 2008-2011,
CGL2012-34978). Besides, I show gratitude to the European Commission for financing the projects SIRIUS (FP7-SPACE-20101, 262902), DROUGHT-R&SPI (programa FP7-ENV-2011, 282769) and ENHANCE (FP7-ENV-2012, 308438).
References
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Andreu, J., Momblanch, A., Paredes, J., Pérez, M.A. and Solera, A. Potential role of standardized water accounting in Spanish
basins. In: Godfrey J. and Chalmers K. (eds.) International Water Accounting: Effective Management of a Scarce Resource.
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modelling and water quality at basin scale and environmental flow assessment: case study of Tormes River, Spain. Hydrological
Science Journal (in press).
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cuencas de los ríos Tajo y Júcar. PhD Thesis (2003) – Universitat Politècnica de València.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 202 Poster sessions WaterDiss2.0: Disseminating Water Research across the European
Union
Beatriz Medina1, C. Roberts2, T. Simms2, U. Stein3 and G. Nion4
2
1
Amphos 21, Spain
The Chancellor, masters and Scholars of the University of Oxford
3
Ecologic, Germany, UK
4
Office International del L’Eau, France
The outcomes of research into water resource problems funded by the European Union have often been
very slow to be taken up by practitioners; typically, almost a decade can pass between the start of a
project, and any subsequent impact on policymakers, industry or communities. Moreover, some projects
seem never to produce results that are of value to potential users. The WaterDiss2.0 project is a
collaboration between partners in France, the UK, Germany, Italy, Spain, Poland and Romania, to review
FP6 and FP7 projects, and to consider the most effective ways of promoting dissemination and uptake of
research findings.
Over 70 projects, some completed and some still in progress, have been reviewed (through questionnaire,
text analysis, interviews) in conjunction with their Principal Investigators, and agreements have
encouraged specific forms of dissemination for particular outputs. Projects were grouped into
unambiguous water-related themes such as flooding, river restoration, water resources, drought, water
treatment processes, and pollution control. The projects’ own intended dissemination methodologies were
evaluated, and some new methods of engagement have been suggested for adoption, and then trialled.
Potential dissemination methods include not only traditional conference papers, or publications in peerrefereed journals but workshops, videos, magazine articles, summer schools for young scientists, staff
exchanges, one-to-one meetings with policymakers or industry specialists and a variety of other
innovative techniques.
The WaterDiss2.0 analysis shows that successful uptake usually occurs when project outcomes are
developed in conjunction with practitioners at the start of the research programme, and when specific and
early attention is paid to the dissemination process itself. Engagement with key stakeholders needs to be
sustained over extended periods. The mutual expectations of funders and the recipients of research
funding are crucial when considering dissemination, and must be clarified at the beginning of a
programme. Impact is most likely when the potential users of research are personally engaged,
enthusiastic and knowledgeable about a specific topic area; multiple presentations of research findings on
a broad variety of themes are likely to be ineffective, even if potential audiences are very large. Beyond
this, more active styles of engagement, such as interactive workshops rather than conferences, appear
most effective at prompting take up and genuine learning for application. This allows trust to develop
between all the participants. Failure to observe these elementary priorities can lead to researchers
effectively ‘walking away’ from projects at the end of the funded programme, and important outcomes
languishing only in unread publications.
On reflection, some of the challenges faced by water researchers are also mirrored in the encounters
experienced in participating in the WaterDiss2.0 project itself. Multinational and multilingual working,
and the development of cross-disciplinary European understanding can be as equally problematic for this
project team, as for broader research communities.
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain List of participants
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 205 List of participants List of participants
A
Aceña Sanchez, Jaume
Department of Environmental Chemistry
IDAEA-CSIC
Jordi Girona, 18-26
08034 Barcelona, Spain
(+34) 93 400 61 00
[email protected]
Andreu Álvarez, Joaquin
Instº Ingeniería del Agua y Medio Ambiente
Universidad Politécnica de Valencia
Camino de Vera s/n
46022 Valencia, Spain
(+34) 96 387 70 00
[email protected]
Acuña, Vicenç
Resources and Ecosystems
Catalan Institute for Water Research (ICRA)
Emili Grahit, 101 - Edifici H2O - PCiT
17003 Girona, Spain
(+34) 972 18 33 80
[email protected]
Andreu Perez, Vicente
Degradación y Conservación de Suelos
Centro de Investigaciones sobre
Desertificación-CIDE (CSIC)
Ctra. Moncada-Naquera Km 4.5
46113 Moncada, Spain
(+34) 963 42 41 62
[email protected]
Aguirre, Gabriela
Department of Physical-Chemistry
University of Cádiz
Poligono Rio San pedro
11510 Cadiz, Spain
(+34) 677 32 21 67
[email protected]
Airado-Rodríguez, Diego
Department of Analytical Chemistry
Univesity of Granada
Avda Fuentenueva S/N
18071 Granada, Spain
(+34) 605183233
[email protected]
Alvarez, Diana
Chemical Contamination of Water Bodies
17003 Girona, Spain
(+34) 972 18 33 80
[email protected]
Andrés-Costa, María Jesús
Preventive Medicine
University of València (UV)
Av. Vicent Andrés Estellés, s/n
46100 Burjassot, Spain
(+34) 963 54 41 18
[email protected]
Aparicio, Irene
Analytical Chemistry
University of Seville
Virgen de Africa, 7
41011 Seville, Spain
(+34) 655 67 09 35
[email protected]
Arias, Alberto M.
Dept. of Ecology and Coastal Management
Inst. for Marine Science of Andalusia (ICMAN-CSIC)
Av. República Saharaui, s/n
11519 Puerto Real, Spain
(+34) 956 83 26 12
[email protected]
Aristi, Ibon
Ecology
University of the Basque Country (UPV/EHU)
PO Box 644
48080 Bilbao, Spain
(+34) 615 00 54 14
[email protected]
Arroita, Maite
Plant Biology and Ecology
PO Box 644
48080 Bilbao, Spain
(+34) 946 01 59 39
[email protected]
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain B
Baena-Nogueras, Rosa María
Av. República Saharaui s/n
(+34) 956 01 65 31
[email protected]
Banjac, Zoran
IDAEA-CSIC
Jordi Girona 18-26
(+34) 93 400 61 00
[email protected]
Baldó, Francisco
Instituto Español de Oceanografía
Puerto Pesquero, Muelle de Levante s/n
11006 Cádiz, Spain
(+34) 647356608
[email protected]
Barceló, Damià
IDAEA-CSIC
Jordi Girona, 18-26
(+34) 93 400 61 00
[email protected]
Biel Maeso, Miriam
Dep. Physical-Chemistry
University of Cadiz
(+34) 651426543
[email protected]
Blasco, Julian
(+34) 956 83 26 12
[email protected]
Boithias, Laurie
17003 Girona, Spain
(+34) 972 18 33 80
[email protected]
Brack, Werner
Department Effect-Directed Analysis
Helmholtz-Zentrum für Umweltforschung GmbH
- UFZ
Permoserstraße, 15
4318 Leipzig, Germany
(+49) 341 235 1531
[email protected]
Burgos Martín, Macarena
(+34) 617 57 50 35
[email protected]
Bautista, Susana
Department of Ecology
University of Alicante
Apdo. 99
03080 Alicante, Spain
(+34) 965 90 34 00 ext.3372
[email protected]
C
Cabello Villarejo, Violeta
Human geography
University of Sevilla
Maria de Padilla s/n
41004 Sevilla, Spain
(+34) 955549526
[email protected]
Calvo, José Luis
Instituto Andaluz de Tecnología
Leonardo Da Vinci 2. Pct Cartuja
(+34) 954 46 80 10
[email protected]
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 207 List of participants Camacho Muñoz, María Dolores
University of Sevilla
Virgen de África, 7
(+34) 677131036
[email protected]
Corada-Fernandez, Carmen
Campus Río San Pedro, s/n
(+34) 646 70 18 22
[email protected]
Campo, Julián
Food and Environmental Safety Research Group
University of València
Av. Vicent Andrés Estellés s/n
(+34) 963 54 49 58
[email protected]
Corcellas i Carramiñana, Cayo
IDAEA-CSIC
Jordi Girona 18-26
(+34) 93 400 61 00
[email protected]
de Castro, Núria
University of Barcelona
Avda. Diagonal, 643
(+34) 93 402 15 07
[email protected]
Corcoll, Natàlia
17003 Girona, Spain
(+34) 972 18 33 80
[email protected]
Cifuentes Sánchez, Víctor Juan
Confederación Hidrogràfica del Guadalquivir
Plaza de España, Sector II y Sector III
(+34) 955 63 75 02
[email protected]
D
Diez, Joserra
Mathematics and Experimental Sciences Didactics
Juan Ibáñez de Sto. Domingo, 1
1006 Vitoria-Gasteiz, Spain
(+34) 945 01 40 20
[email protected]
Durán Lalaguna, Concha
Area de Calidad de Aguas
Confederación Hidrográfica del Ebro
Paseo Sagasta 24-28
50007 Zaragoza, Spain
(34) 976 71 10 00 ext 22321
[email protected]
Drake, Pilar
(+34) 956 83 26 12
[email protected]
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 208 List of participants E
Elosegi, Arturo
PO Box 644
48080 Bilbao, Spain
(+34) 946 01 55 14
[email protected]
Elorza Tenreiro, Francisco
Matemática Aplicada y Métodos Informáticos
UPM - Escuela Técn. Superios de Ingenieros de
Minas
CALLE RíOS ROSAS, 21
28003 Madrid, Spain
(+34) 913367066
[email protected]
Enjuanes, Antoni
Departament d’Agricultura, Alimentació i Acció
Rural
Generalitat de Catalunya
Gran Via de Les Corts Catalanes, 612-614
(+34) 93 304 67 00 ext. 6726
[email protected]
F
Farré, Marinel.la
IDAEA-CSIC
Jordi Girona 18-26
(+34) 93 400 61 00
[email protected]
Flores, Lorea
PO Box 644
48080 Bilbao, Spain
(+34) 946 01 59 69
[email protected]
Feld, Christian K.
Department of Aquatic Ecology
University of Duisburg-Essen
Universitaetsstrasse, 5
45141 Essen. Germany
(+49) 201 183 43 90
[email protected]
Folch, Albert
Department of Geotechnical Engineering and
Geosciences
Technical University of Catalonia
Jordi Girona, 31
08034 Barcelona
(+34) 93 401 180 60
[email protected]
Fernández Delgado, Carlos
Zoology
University of Córdoba
Campus Universitario de Rabanales
14014 Córdoba, Spain
(+34) 957 21 86 05
[email protected]
Ferrer Matvieychuc, Graciela
Economia Aplicada
Universitat de València
Av. Taronger s/n – Ed. Facultat d Economia, 2a
46022 València, Spain
34963828418
[email protected]
Francés, Félix
Research Institute of Water and Environmental
Engineering (IIAMA)
Technical University of València (UPV)
Camino de Vera s/n
(+34) 963 87 76 12
[email protected]
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 209 List of participants G
Ginebreda, Antoni
Environmental Chemistry
IDAEA-CSIC
Jordi Girona, 18-26
(+34) 93 400 61 00
[email protected]
González-Fuenzalida, Rodrigo
University of Valencia
Dr Moliner, 50, Building E. 2nd floor
(+34) 963 54 43 34
[email protected]
González Aranda, Juan Miguel
Spanish Ministry of Economy and
Competitiveness
Paseo de la Castellana, 162
28046 Madrid, Spain
(+34) 915 836 040
[email protected]
Gorga, Marina
IDAEA-CSIC
Jordi Girona, 18-26
(+34) 93 400 61 00
[email protected]
Gonzalez-Ortegon, Enrique
(+34) 956 83 26 12
[email protected]
Grimalt Obrador, Joan
IDAEA-CSIC
Jordi Girona, 18-26
(+34) 93 400 61 00
[email protected]
H
Hampel, Miriam
(+34) 956832612
[email protected]
Hidalgo López, Arturo
Technical University of Madrid (UPM)
Ríos Rosas, 21
28003 Madrid, Spain
(+34) 91 336 32 33
[email protected]
Hansen, Peter D.
Ecological Impact Research and Ecotoxicology
Berlin Institute of Technology (BIT)
Ernst-Reuter-Platz, 1
10587 Berlin, Germany
(+49) 314 289 99
[email protected]
Huerta Buitrago, Belinda
17003 Girona, Spain
(+34) 972 18 33 80
[email protected]
Hernández García, Marta
Alternative Water Resources
CETaqua
Carretera d'Esplugues, 75
08940 Cornellà de Llobregat, Spain
(+34) 93 312 48 00
[email protected]
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 210
List of participants
J
Jornet-Martínez, Neus
University of Valencia
Dr Moliner, 50, Building E. 2nd floor
46100 Burjassot , Spain
(+34) 963 54 43 34
[email protected]
Johns, Joseph Babadi
Dir. of Policy, Programmes, Research and
Development, Masianday Foundation
16th Street, Fajaranjula Golf Course Road
22099 Banjul, Gambia
(+220) 790 63 08
[email protected]
K
Kaptan, Kubilay
Disaster Education, Application and Research
Center (AFAM)
Istanbul Aydin University
Inonu Caddesi, 38, sefakoy
34295 Istanbul, Türkiye
(+90) 533 813 29 97
[email protected]
Kuzmanovic, Maja
Water and Soil Quality Research Group
IDAEA-CSIC
Jordi Girona, 18-26
(+34) 93 400 61 00
[email protected]
Kersting, Teresa
Water, Economic and Society
CETaqua
(+34) 93 312 48 62
[email protected]
L
La- Roca, Francesc
Economia Aplicada
Universitat de Valencia
Campus dels Tarongers, Oriental 2F05
(+34) 96 382 8418
[email protected]
Lara Martin, Pablo Antonio
(+34) 956 01 61 59
[email protected]
Larrañaga, Aitor
Department of Plant Biology and Ecology
PO Box 644
48080 Bilbao, Spain
(+34) 946 01 79 54
[email protected]
Lerdo de Tejada, Francisco
Confederación Hidrográfica del Guadalquivir
Av. República Argentina, 43 acc. 1ª planta
(+34) 95 563 75 31
[email protected]
López de Alda, Miren
IDAEA-CSIC
Jordi Girona 18-26
(+34) 93 400 61 00
[email protected]
López Benito, Alfredo
Ríos Rosas, 21
28003 Madrid, Spain
(+34) 913363233
[email protected]
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 211 List of participants López-Roldán, Ramón
Environment and Health
CETaqua
(+34) 93 312 48 86
[email protected]
Ludwig, Ralf
Department of Geography
Ludwig-Maximilians-Universitaet München
Luisenstrasse 37
80333 Munich, Germany
(+49) 89 2180 6677
[email protected]
M
Marcé, Rafael
17003 Girona, Spain
(+34) 972 18 33 80
[email protected]
Mastroianni, Nicola
IDAEA-CSIC
Jordi Girona, 18-26
(+34) 652 54 97 65
[email protected]
Jesus Marco de Lucas
IFCA-CSIC
Juan Jorda, Avda de los Castros s/n
39005 Santander, Spain
(+34) 660573808
[email protected]
Medina, Beatriz
Environmental Communications
AMPHOS 21
Passeig garcia i faria, 49-51
08019 Bbarcelona, Spain
(+34) 93 583 05 00
[email protected]
Martín-Díaz, M.Laura
Dep. Chemical Physical
University Of Cadiz
Poligono Rio San Pedr S/N
(+34) 607 93 32 90
[email protected]
Martínez, Elena
IDAEA-CSIC
Jordi Girona, 18-26
(+34) 93 400 61 00
[email protected]
Masia Reyes, Ana
(+34) 963 54 49 58
[email protected]
Momblanch Benavent, Andrea
Ingeniería Hidráulica y Medio Ambiente
Universidad Politécnica de Valencia
Camino de Vera s/n
(+34) 96 387 70 00
[email protected]
Moreno-Garrido, Ignacio
(+34) 956 83 26 12
[email protected]
Muñoz, Isabel
University of Barcelona
Avda. Diagonal, 643
(+34) 93 402 15 12
[email protected]
Muñoz Ortuño, María
Doctor Moliner, 50
(+34) 963 54 43 34
[email protected]
N
Naber, Sawsan
Faculty of Agriculture
University of Jordan
P.O. Box 13042
11942 Amman, Jordan
(+962) 777 48 44 60
[email protected]
Navarro-Ortega, Alícia
IDAEA-CSIC
Jordi Girona, 18-26
(+34) 93 400 61 00
[email protected]
Navarro, Enrique
Instituto Pirenaico de Ecología
Av. Montañana 1005
50059 Zaragoza, Spain
(+34) 636 35 93 58
[email protected]
Nieto Cristóbal, Elena
(+34) 956 83 26 12
[email protected]
P
Pascual Aguilar, Juan Antonio
Degradación y Conservación de Suelos
Centro de Investigaciones sobre
Desertificación-CIDE (CSIC)
Ctra. Moncada-Naquera Km 4.5
46113 Moncada, Spain
(+34) 963 42 42 17
[email protected]
Pérez, Sandra
IDAEA-CSIC
Jordi Girona, 18-26
(+34) 93 400 61 00
[email protected]
Petrovic, Mira
17003 Girona, Spain
(+34) 972 18 33 80
[email protected]
Pico Garcia, Yolanda
(+34) 963 54 30 92
[email protected]
Pintado Herrera, Marina
(+34) 956016531
[email protected]
Pla Tolós, Javier
Doctor Moliner, 50
(+34) 963 54 43 34
[email protected]
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 213 List of participants Playán, Enrique
The Joint Programming Initiative on water
Ministry of Economy and Competitiveness
Albacete 5, 2ª planta Este
28027 Madrid
(+34)976 71 60 87
[email protected]
Q
Quiroga, Angels
IDAEA-CSIC
Jordi Girona, 18-26
(+34) 93 400 61 00
[email protected]
R
Roig Montserrat, Neus
Department of Chemical Engineering
Rovira i Virgili University
Paisos Catalans, 26
43007 Tarragona, Spain
(+34) 977 55 85 53
[email protected]
Rodríguez Mozaz, Sara
17003 Girona, Spain
(+34) 972 18 33 80
[email protected]
S
Sabater, Sergi
17003 Girona, Spain
(+34) 972 18 33 80
[email protected]
Sànchez-Vila, Xavier
Department of Geotechnical Engineering and
Geosciences, Technical University of Catalonia
Jordi Girona, 31
08034 Barcelona
(+34) 93 401 180 60
[email protected]
Saenz, Antonio
Instituto Andaluz De Tecnología
Leonardo da Vinci 2, PCT Cartuja
(+34) 954 46 80 10
[email protected]
Sanchez Gimeno, Benjamin
Secretaria General de Ciencia y Tecnología
MINECO
C/ Albacete 5
28028 Madrid, Spain
(+34) 619 43 34 93
[email protected]
Sánchez Canales, María
Escuela Técn. Superios de Ingenieros de Minas
Ríos Rosas, 21
28003 Madrid, Spain
(+34) 91 336 70 47
[email protected]
Sanchís Sandoval, Josep Àngel
IDAEA-CSIC
Jordi Girona 18-26
(+34) 649 23 79 76
[email protected]
Santos, Juan Luis
University of Seville
Virgen de África
(+34) 954 55 62 50
[email protected]
Shatanawi, Muhammad
Land, Water and Environment
Univeristy of Jordan
P.O. Box 13042
11942 Amman, Jordan
(+962) 777 48 44 99
[email protected]
von Schiller, Daniel
17003 Girona, Spain
(+34) 972183380
[email protected]
Sierra, Jordi
Chemical Engineering, ETSQ
University Rovira i Virgili (URV)
Països Catalans, 26
(+34) 977 55 8553
[email protected]
Schuhmacher, Marta
Rovira i Virgili University
Paisos Catalans, 26
(+34) 977 55 96 53
[email protected]
Siirila, Erica
Ingeniería del Terreno
Technical University of Catalunya.
BarcelonaTECH
Jordi Girona, 1-3
(+34) 93 401 18 60
[email protected]
T
Terrado Casanovas, Marta
17003 Girona, Spain
(+34) 972 18 33 80
[email protected]
Torres-Fuentes, Nivis
11510 Cadiz, Spain
(+34) 691 34 63 10
[email protected]
Traverso Soto, Juan Manuel
(+34) 956 01 61 59
[email protected]
V
Víctor-Ortega, María Dolores
Univesity of Granada
Avda Fuentenueva S/N
18071 Granada, Spain
(+34) 655 19 46 25
[email protected]
Villegas, Marina
Subdirección General de Proyectos de
Investigación
Ministry of Economy and Competitiveness
Albacete 5, 2ª planta Este
28027 Madrid
[email protected]
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain 215 List of participants Z
Zampieri, Matteo
Climate Services Division
Centro Euro Mediterraneo sui Cambiamenti
Climatici
Viale Aldo Moro, 44
40127 Bologna, Italy
(+39) 051 378 26 07
[email protected]
Zonja, Bozo
IDAEA-CSIC
Jordi Girona 18-26
(+34) 93 400 61 00
[email protected]
4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain

towards a better understanding of the links between - Idaea

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