td1105 eea raulin - European Network on New Sensing

td1105 eea raulin - European Network on New Sensing

European Network on New Sensing Technologies for Air Pollution
Control and Environmental Sustainability - EuNetAir
COST Action TD1105
INTERNATIONAL WG1-WG4 MEETING on
New Sensing Technologies and Methods for Air-Pollution Monitoring
European Environment Agency - EEA
Copenhagen, Denmark, 3 - 4 October 2013
Action Start date: 01/07/2012 - Action End date: 30/06/2016 - Year 2: 2013-2014 (Ongoing Action)
DEVELOPMENT OF A FORMALDEHYDE CHEMICAL SENSOR FOR
INDOOR AIR QUALITY MONITORING AND ANALYSIS IN PASSIVE
MODE
Dr Katarzyna RAULIN
COST is supported
by the EU Framework Programme
WG4 member: Protocols & Standardisation Methods
ETHERA / France
ESF provides the COST Office
through a European Commission contract
ETHERA created in 2010
Saclay
R&D and Production
Our markets
Indoor Air Quality
Industrial Hygiene
Environment Code
Labour Code
Grenoble
Headquarter
Commercial & Marketing
Public buildings
Private buildings
Industry
IAQ monitoring
LEED building assessment
Personal Exposure Limits
assessment to chemical risk
2
Indoor chemical pollution status
2-butoxy-éthylacétate
25
1-méthoxy-2propylacétate
styrène
Concentration µg/m3
Mediim Concentration
trichloroéthylène
20
Acroléine
Formaldéhyde
tétrachloroéthylène
2-butoxyéthanol
15
1 méthoxy2propanol
hexaldéhyde
Benzène
Éthylbenzène
Acétaldéhyde
o-xylène
10
1,2,4-triméthylbenzène
1,4-dichlorobenzène
Aldehydes +
BTEX
=
> 80% of total
chemical pollution
n-décane
5
m/p xylène
acroléine
n-undécane
Acétaldéhyde
toluène
0
Intérieur
Indoor
Extérieur
Outdoor
Hexaldéhyde
Formadéhyde
Source: French Indoor Air Quality Observatory 2006 –
Campaign based on 600 French representative dwellings
3
ETHERA R&D
Development,
validation
and industrialisation of
new chemical sensors
for the measurement of
indoor air pollutants
Development of new
devices for indoor air
quality control
especially
formaldehyde and
trichloramine
Development of new
devices for the
purification of indoor air
4
ETHERA research based on an innovative
technology for IAQ measurement and treatment
A nanoporous Sol-Gel
material like a « sponge »
Probe molecule integration
Pollutant filtration and
concentration
Polluant
MEASURE
EPURATION
Direct optical detection
Direct ultra-sensitive
measurement of pollutant
concentration without lab
analysis
Specific reaction with the
pollutant creating a colorimetric
reaction
A Simple, Sensitive and
Selective technology
•
Manufacturing from an industrial
Sol-Gel process
•
Protected with 5 international
patents
•
A operational pilot production line
High trapping capacities
Selective and efficient
treatment of the pollutant with
integrated saturation indicator
5
Profil’air® product range : a modular approach
Badge for individual dosimetry
PA-SDIxxx
Dynamic exposure module
PA-MEX001
• Personal Exposure Limits
(STOEL 15min)
• Short-term ambiant
measurements
• Personal Exposure
Limits (TWA 8h)
Sensor
Active
sampling
Passive
sampling
Ambiant diffuser
PA-DFSxxx
Optical reader
module
PA-MRF421
Pump module
PA-MPO201
• Personal Exposure Limits
(STOEL 15min)
• Short-term ambiant
measurements
• Long-term ambiant
measurements
Emission measurement chamber
PA-CMExxx
6
• Emission source research
Main research equipments

Passive measure development in controlled environments
in laboratory
Generation of calibrated gas
mixtures in environmental
chamber
• [HCHO]
• T° (10 - 40°C),
• RH (20 – 80 %)
• Air velocity (0.1 - 2 m/s)

Generation of calibrated gas
mixtures
Validation of the passive measure in real conditions:
measure campaigns in nurseries and schools of Grenoble7
Phase : Calibrated conditions
1,8
2,5E-04
1,6
2,0E-04
active sampler
~107 ppb
1,4
2: y = 2,48E-06x
R² = 9,97E-01
100,7ppb
1,5E-04
Correction coefficient
1,0E-04
K
5,0E-05
DO
time  [HCHO]
1
107,1ppb
y = 0,00025x + 0,18751
R² = 0,999
y = 0,00024x + 0,18297
R² = 0,995
1,2
DO
Reaction rate (min-1)
1: y = 2,35E-06x
R² = 1,00E+00
~50 ppb
0,8
y = 0,00013x + 0,14356
R² = 0,998
0,6
y = 0,00012x + 0,10883
R² = 0,999
107,0ppb
0,4
55,3ppb
49,1ppb
0,2
50,9ppb
0
0,0E+00
0
20
40
60
80
0
100
1000
3000
4000
5000
Time (min)
Concentration (ppb)
 Linearity : sensor response is linear as
a function of time (1, 2, 3 and 4,5 days)
 Correlation passive/active : Very good
correlation between passive and active
ETHERA measures
Concentration passive sampling
(ppb)
 Linearity : sensor response is linear
as a function of the formaldehyde
concentration of 4.5 days
2000
120
y = 0,989x
R² = 1,000
100
y = 0,969x
R² = 0,997
80
60
40
20
0
0
20
40
60
80
100
120
8
Concentration active sampling /DNPH (ppb)
Phase : Calibrated conditions
6,0E-06
K *106 (min-1.ppb-1)
Air speed
• Passive exposition on 1 day
• 50 % RH, 20°C, [HCHO] = 24 ppb
 Low effect of the speed from 0.1 to
0.5 m/s
CV = 3%
5,0E-06
4,0E-06
3,0E-06
2,0E-06
1,0E-06
0,0E+00
0,1
0,3
0,5
Air speed (m/s)
Variable relative humidity
6,0E-06
1,0
100
5,0E-06
0,8
80
0,6
60
0,4
40
0,2
20
1,0E-06
0
0,0E+00
0,0
0
1
2
Time (day)
3
K (ppb-1.min-1)
20%
HR (%)
 Little disruption of
moisture on sensors
120
1,2
DO (420nm)
• 4.5 days à 28ppb de
HCHO
• 20°C, 0,1 m/s à
• 20, 50 et 80% RH
50%
4,0E-06
3,0E-06
2,0E-06
4
9
80%
Phase : Calibrated conditions
Study of potential interfering gaz
In presence of 50 ppb formaldehyde or not of:
•
•
•
•
Toluene (500 and 2000 ppb)
Acetaldehyde / Acroleine / Hexanal
Acetone (some ppm in static)
(other vapors: HNO3, acetic acid, H2O2…)
 No effect on measure with a mixture of acetaldéhyde, acroleine, hexanal in
the presence of formaldehyde except with acetaldehyde >100 ppb
 No significant influence of toluene and acetone on the measure in the
presence of formaldehyde
10
Phase : Real conditions
The passive sensor ETHERA was calibrated in real situations compared
with the Radiello® measures according to the humidity
 Good correlation for the campaign
between Radiello ®/ ETHERA :
average = 21%
Absolute deviation < 5 ppb
 Standard deviation inter-laboratory on
Radiello ®: approximately 18 %
 Low standard deviation variation (CV = 8
%) according to the humidity
Passive sampling concentration (ppb)
120
100
y = 1,0015x
R² = 0,8493
80
60
40
20
0
0
20
40
60
DNPH concentration (ppb)
80
100
Performance of the method
Result
Reproductibility (45 ppb, 50% RH, 24
hrs)
3.6%
Repeatability (45 ppb, 50% RH, 24
hrs)
1.9%
Detection limit (4.5 days of
exposition)
0.2 ppb
Quantification limit (4.5 days of
exposition)
0.8 ppb
Average accuracy / DNPH or
ETHERA active measure
3%
Performance comparable to a chromatographic analysis
 Selective
 Sensitive(ppb)
 Simple
 Non destructive
12
Profil’air roadmap : planned activities
A progressive gas
extension
BTEX
Ambiant
diffuser
Aldehydes
Badge for personal
exposures
Chamber for emission
measurements
CO2, T°, HR
Trichloramine
Formaldehyde
13