Degradación por Fotólisis Directa del Verde Malaquita. Análisis de

Transcription

WASTEWATER REUSE APPLICATIONS AND
CONTAMINANTS OF EMERGING CONCERN
13-14 September 2012, Cyprus
Extensive analytical evaluation of
advanced tertiary treatments for water
reuse purposes
Ana Agüera
Department of Analytical Chemistry
University of Almería
Ana Agüera
University of Almeria
Analytical Chemistry Dpt.
Pesticide Residues Research Group
Ana Agüera
Analytical evaluation of water treatment processes (1999-2012)
Pesticide Residues Research Group
Solar Treatment of Water Research Group
Plataforma Solar de Almería (CIEMAT)
Ana Agüera
OBJECTIVES
● Understanding of degradation mechanisms:
identification of TPs
● Combination of chemical and toxicological
analysis: interpretation of toxicity and
biodegradability results
● Detection of undesirable compounds
● Comparison of efficiency of different
treatments: applicability as tertiary treatments
● Design and optimization of the process
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UNDERSTANDING OF DEGRADATION MECHANISMS: IDENTIFICATION OF TPS
N
H3C
Mineralization
N(CH2CH3) 2
CO2 + H2O + HX
N
OP(OCH3) 2
S
Pirimiphos-methyl
TPs
DIFFICULTIES:
OZONIZATION

Concentration (mg/L)
25
TOC
20
H3C
15
N
TPs
10
5

N(CH2CH3) 2
N

OP(OCH3) 2
S
PM
disappearance

0
0
20
40
60
80
100
120
time ( min)
Technical product
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Total organic carbon
140
160
Large amount of unknown
compounds
Different physical-chemical
properties
Wide range of concentrations
Absence of analytical
standards for an accurate
identification/quantification
IDENTIFICATION OF TPs: ANALYTICAL REQUIREMENTS
High identification capability:
structural information
High sensitivity in “full-scan”
GC-MS
 non polar
compounds
 volatile compounds
 thermally stable
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LC-MS
 polar
compounds
 low volatility
 thermally unstable
IDENTIFICATION OF TPs: ANALYTICAL REQUIREMENTS
Accurate mass measurements
LC-TOF-MS
Elemental composition of parent and
fragment ions
Very high sensitivity in “full-scan”
Low concentration intermediates
No limitations in the type and amount of compounds
that can be simultaneously analyzed
Complex reaction mixtures
LC-QTOF-MS/MS
Increased structural information
MS/MS spectra
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UNDERSTANDING OF DEGRADATION MECHANISMS: IDENTIFICATION OF TPs
NH2
Photodegradation of trimethoprim
N
Hydroxylation
N
H2N
N
OCH3
N
H2N
N
O
TMP
HO
EXPERIMENTAL CONDITIONS:
NH2
N
N
N

N
H2N
OH
OH
O
OCH3
H2N
HO
OH
HO

HO
N
NH2
O CH3
C H 3O
N
Hydrolysis
OH
OH
CH3O
OCH3
H 2N
OH
OH
O
NH2
OH
CH3O
OCH3
OH
P19
299 m/z
OH
OCH3
N
N
H2N
P16 and P18
295 m/z
P13
307 m/z
CH3O
Not real conditions !!!
NH2
N
N
P24
141 m/z
H 2N
N
N
H 2N
OH
OCH3
P21
281 m/z
P15
277 m/z
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OH
OH
HO
OCH3
OH
NH2
HO
O
OH
N
H 2N
OH
HO
HO
OH
N
H2N
OH
P25
197 m/z
NH2
N
OH
CH3O
OH
H3CO
OH
OCH3
P12 and P14
309 m/z
P11 and P20
341 m/z
N
P22
139 m/z
NH2
N
H2N
N
N
H2N
O
OCH3
OCH3
OH
NH2
NH2
N
P10
279 m/z
HO
P23
155 m/z
O
OCH 3
P 1 , P 2 , P 4 , P 5 , P 6 an d P 7
3 2 3 m /z
N
HO
NH2
N
N
H 2N
N
OH
Individual compounds
Pure water
High initial concentrations
HO
C H 3O
NH2
H 2N
P9
307 m/z

Demethylation/Hydroxylation
NH2
O CH3
C H 3O
OCH3
CH3O
OCH3
OC H3
OCH3
P3
305 m/z
HO
HO
OCH3
N
H 2N
OH
OH
OCH3
CH3O
N
H 2N
HN
OCH3
CH3O
N
N
N
NH2
N H2
NH2
NH2
OBJECTIVES
treatments: applicability as tertiary treatments
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Vibrio fischeri
Microalgae
CONCLUSIONS:
 The disappearance of the target compounds
do not assure the detoxification of treated
water: Formation of toxic TPs
TiO2

As toxicity is a biological response, the values
TiO2
obtained by a single toxicity assay can be
insufficient. Consequently, a battery of
bioassays is recommended.
Photo-Fenton
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Photo-Fenton
Daphnia magna
DETECTION OF UNDESIRABLE COMPOUNDS
Toxicity evolution of a 4-MAA solution during photolysis
ACCUTE TOXICITY TEST
% Inhibition (48h)
49 h
50%
Daphnia Magna
Initial solution
After photolysis
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4-MAA PHOTODEGRADATION PATHWAY
N
N
O
N
N
O
O
Mol.Wt.:150
P4
O
O
O
O
NH
Mol.Wt.:220
P3
Mol.Wt.:249
P7
N
N
NH
O
Mol.Wt.:164
P10
N
N
N
H
N
H
HN
Mol.Wt.:135
P8
O
O
Mol.Wt.: 217
4-MAA
OH HO
N
N
N
N
O
Mol.Wt.:188
P11
HO
HN
N
O
Mol.Wt.:204
P9
O
HO
HN
O
HO
HO
Mol.Wt.:209
P5
Mol.Wt.:163
P12
O
N
M.J. Gómez et al. Water Res. 2008, 42, 2698
Ana Agüera
HO
O
Mol.Wt.:191
P6
O
Mol.Wt.:151
P13
TIME EVOLUTION OF THE MAIN TPs OF 4-MAA UNDER UV-TREATMENT
6
1,2x10
N- fenilacetamide
HN
8
1,6x10
O
6
1,0x10
8
1,4x10
5
N
8,0x10
N
O
O
8
1,0x10
O
NH
5
6,0x10
7
8,0x10
7
5
6,0x10
4,0x10
OH HO
N
7
4,0x10
O
5
HO
2,0x10
7
2,0x10
0,0
P5
0
20
40
60
P7
80
Time (h)
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0,0
P8
100
120
140
160
P7 Area (counts)
P5 and P8 Area (counts)
8
1,2x10
N- fenilacetamide or Acetanilide
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OBJECTIVES
treatments: applicability as tertiary treatments.
Real conditions !!!
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CHARACTERIZATION OF URBAN WASTEWATER EFFLUENTS
Rapid
Sensitive
Selective
Broad range of compounds
Accurate confirmation
(ng-μg/L)
INCOMPLETE
REMOVAL
EMERGING CONTAMINANTS
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CHARACTERIZATION OF WASTEWATER EFFLUENTS: MULTIRESIDUE METHODS
Antibiotics
1. Metronidazole
2. Sulfamethoxazole
3. Trimethoprim
4. Ciprofloxacin
5. Cefotaxime
6. Ofloxacin
7. Erythromycin
8. Tetraciclyne
9. Norfloxacin
10. Clarithromycin
11. Lincomycin
12. Sulfamethazine
13. Sulfapyridine
14. Sulfadiazine
15. Sulfathiazole
16. Azithromycin
17. Simvastatin
Analgesic/
Anti-Inflammatory
18. Acetaminophen
19. Indomethacine
20. Fenoprofen
21. Codeine
22. Mefenamic Ac.
23. Ibuprofen
24. Ketorolac
25. Naproxen
26. Diclofenac
27. Ketoprofen
28. Propyphenazone
29. Urbason
Contrast media
30. Iopromide
31. Iopamidol
UV Filters
67. Benzophenone-3
68. Camphor
69. Cinnamate
70. Octocrylene
Flame retardant
71.TCPP oekanal
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Metabolites
72. 4-Acetoaminoantipyrine
73. 4-Formylaminoantipyrin
74. 4-Methylaminoantipyrine
75. 4-Dimethylaminoantipyrine
76. 4-Aminoantipyrine
77. Paraxanthine
78. Carbamaz.10,11-epoxide
79. Antipyrine
80. Fenofibric Acid
81. Clofibric acid
82. Cotinine
83. Salicilic acid
Beta Blockers
Antidepressants
32. Atenolol
33. Propranolol
34. Sotalol
35. Metoprolol
36. Nadolol
44. Fluoxetine
45. Paroxetine
46. Venlafaxine
47. Citalopram
48. Amitriptyline
49. Clomipramine
Antihistamines
Lipid regulators
37. Famotidine,
38. Lansoprazole
39. Ranitidine
40. Omeprazole
41. Loratadine
58. Carbamazepine
59. Diazepan
60. Primidone
50. Fenofibrate
51. Bezafibrate
52. Gemfibrozil
53. Pravastatin
54. Mevastatin
55. Simvastatin
Diuretics
Antineoplastics
61. Ifosfamide
62. Cyclophosphamide
63. Tamoxifen
Anesthetics
64. Mepivacaine
Sympathomimetics
42. Furosemide
43. Hydrochlorothiazide
Antiepileptic
Psychiatric drug
56. Salbutamol
57. Terbutaline
Coricosteroides
65. Methylprednisolone
Anti-Infective
66. Clotrimazole
Pesticides
84. Atrazine
85. Clorpyriphos
86. Clorfenvinphos
87. Diuron
88. Isoproturon
89. Simazine
90. Permetrina
91. Endosulfan
Disinfectants
Fragances
93. Biphenylol
94. Chlorophene
95. Triclosan
98. Celestolide
>120
Others
96. Nicotine
97. Caffeine
Plastic additives
92. Bisfenol-A
99. Phantolide
100.Traseolide
101.Galaxolide
102.Ketone
103.Tonalide
104.Musk xilene
105.Musk ketone
Antioxidants
106.BHT
PAHs
107.Acenaphtene
108.Acenaphtilene
109.Anthracene
110.Benzo[a]anthracene
111.Benzo[a]fluoranthene
112.Benzo[a]pyrene
113.Benzo[k]fluoranthene
114.Crysene
115.Fluoranthene
116.Fluorene
117.Naphtalene
118.Phenantrene
119.Pyrene
CHARACTERIZATION OF URBAN WASTEWATER EFFLUENTS
1.- ALMERIA- El Ejido (urbana/agrícola)
2.- MADRID- Alcalá de Henares (urbana)
3.- MADRID- Alcalá140000
de Henares (urbana/industrial)
4.- CANTABRIA- Vuelta Ostrera (urbana)
5.- BARCELONA- Baix Llobregat (urbana)
Otros
140000
120000
Otros
81
120000
Cafeina
Paraxanthine
100000
Cafeina
Furosemide
FurosemideDiclofenac
100000
80000
Carga total ng/L
Paraxanthine
80000
60000
69
Diclofenac
Ofloxacin
Ofloxacin
Ciprofloxacin
Ciprofloxacin
4-FAA
4-FAA
60000
40000
83
60
4-AAA
67
4-AA
40000
20000
Gemfibrozil
0
1
N=16
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4-AA
Hydrochlorotiazide
Hydrochlorotiazide
20000
0
4-AAA
Atenolol
1
2
N=12
2
3
N=18
3
4
N=6
4
5
N=8
5
Galaxolide
Gemfibrozil
Atenolol
Galaxolide
COMPARISON OF TREATMENTS EFFICIENCY IN REMOVING ECs
APPLICABILITY AS TERTIARY TREATMENTS
20,000.0
CONCLUSIONS:
 Both alkaline and hydrogen peroxide
Others
ozonation provide >90% removal of ECs Hydrochlorothiazide
97%
 But only TOC removal is able to ensure the4AAA
4FAA
absence of reaction intermediates
Naproxen
99%
Atenolol
700.0
700.0
600.0
600.0
500.0
500.0
400.0
300.0
200.0
100.0
100.0
-
-
5,000.0
EFFLUENT
EFFLUENT
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79%
O33
O
91%
O
3/H
OO
3/H
2O22 2
Treate
effluent
(O3/H2O2)
200.0
Hydrochlorothiazide
Hydrochlorothiazide
4AAA
4AAA
4FAA
4FAA
Naproxen
Naproxen
Atenolol
Atenolol
Ciprofloxacin
Ciprofloxacin
Caffeine
Caffeine
Treated
Treate
(O3)
effluent
effluent
(O3/H2O2)
300.0
Others
Urban
Treated
WWTP
(O3)
effluent
effluent
10,000.0
400.0
Urban
WWTP
effluent
15,000.0
Total charge (ng/l)
Others
Total charge (ng/l)
Total charge (ng/l)
25,000.0
Ciprofloxacin
Caffeine
COMPARISON OF TREATMENTS EFFICIENCY IN
REAL CONDITIONS
t 30W
)
1
C o n ta m
in an ts
(n g/L)
)
14
1 1 17
12 13 14 5 6
1
1
1
9
0
8
5 6 7
2 3 4
( m in
( m in
7
0
3
6
10
15
25
60
1
C on centratio n
0
0.2
3.5
T im e
600
0
400
0
200
0
180
00
160
00
140
00
120
00
100
00
800
0
600
0
400
0
200
0
Ozonization
C on centratio n
Solar photo-Fenton, Fe 5 mg/L
180
00
160
00
140
00
120
00
100
00
800
0
(n g/L)
> 90% removal of micropollutants
1 1 17
12 13 14 5 6
1
1
1
9
0
8
5 6 7
2 3 4
C o n ta m
in an ts
1-Bisphenol A; 2-Ibuprofen; 3-Hidroclorotiazide; 4-Diuron; 5-Atenolol; 6-4-AA; 7-Diclofenac; 8-Ofloxacin;
9-Trimethoprim; 10-Gemfibrozil; 11-4-MAA; 12-Naproxen; 13-4-FAA; 14-C; 15-4-FAA; 16-Caffeine; 17Paraxanthine).
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COMPARISON OF TREATMENTS EFFICIENCY IN REAL CONDITIONS
ECONOMICAL STUDY
Costs of solar photo-Fenton and ozonation tertiary treatments for 90% and 98%
elimination of micropollutants
Solar Photo-Fenton
3
3
€/m€/m
Ozonation
€/m3
Reagent
90%
0.04
98%
0.074
90%
0.16
98%
0.22
Labour
Electricity
Investment
Total
0.03
0.004
0.09
0.164
0.05
0.01
0.15
0.284
0.05
0.035
0.78
1.025
0.05
0.042
0.90
1.212
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DESIGN AND OPTIMIZATION OF PROCESSES
TREATMENT OF INDUSTRIAL EFFLUENTS
PHARMACEUTICAL INDUSTRY
NALIDIXIC ACID
Industrial
Wastewater
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Photo-Fenton
Biological treatment
Reclaimed
Water
INDUSTRIAL WASTEWATER CHARACTERIZATION
O
O
OH
N
N
Nalidixic acid
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Parameter
pH
Conductivity
TOC
COD
Nalidixic acid
TSS
Cl
PO43SO42Na+
Ca2+
Amount
3.98
7 mS.cm-1
775 mg.L-1
3420 mg.L-1
-1
45 mg.L
-1
0.407 g.L
-1
2.8 g.L
0.01 g.L-1
0.16 g.L-1
2 g.L-1
0.02 g.L-1
TratamientoTreatment
Biológico (IBR)
Biological
Photo-Fenton Treatment
600
Proceso Fotoquímico (foto-Fenton)
500
900
200
400
300
120
30
20
80
10
200
Degradación del ácido
0
0
100
0
160
50
100 150 200
nalidíxico (<1 mg/L)
H O consumido: 70 mM
2
0
100
2
200
t
30W
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40
(min)
300
0
400
Initial
sample
300
200
100
0
0
20
40
60
80
100
120
140
Tiempo de tratamiento (horas)
93%
100
% reducción del contenido orgánico
-1
NXA (mg L )
DOC (mg/L)
500
2
DOC (mg/L)
2
40
H 2O 2 consumido (mM)
H O consumido
700
600
400
DOC
800
80
DOC
73%
60
40
20
0
20%
AOP
BIO
AOP+BIO
Final
sample
PHOTO-FENTON + BIOTREATMENT
photo-Fenton
biotreatment
NXA
Area (Counts)
2.5x10
8
P2
P7
P30
P5
P33
0.8
8
0.6
2.0x10
8
5.00x10
7
2.50x10
7
0.4
Acido Nalidixico
Industrial
Wastewater
0.00
Ana Agüera
0
Photo-Fenton
Biological
Treatment
1
2
40
t30W (h)
Biological
Treatment
Photo-Fenton
60
80
100
NXA/NXA0
3.0x10
1.0
0.2
0.0Reclaimed
120
time (h) Agua tratada
Water
Photo-Fenton Treatment
Biological Treatment
35
40
• Nalidixic acid: 38 mg/L
600
• Initial TOC: 725 mg/L
500
30
400
20
300
200
10
100
Nalidixic acid (mg/L)
700
TOC (mg/L)
50
TOC
Nalidixic acid
Nalidixic acid (mg/L)
800
biotreated WW
30
25
• Nalidixic acid: 13 mg/L
20
• Initial TOC: 22 mg/L
15
10
5
0
0
0
0
1
2
3
4
0
5
10
15
20
t30W (min)
Time (days)
• 96% TOC removal
• Nalidixic acid persists (~15 mg/L)
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• Total removal of Nalidixic acid and TPs
LC-TOF-MS ANALYSIS
OH
O
O
O
O
O
O
OH
OH
OH
O
O
OH
O
O
O
O
N
N
N
N
OH
N
N
OH
N
N
HO
Initial wastewater
IBR
IBR + photo-Fenton
P17
O
N
N
P4
O
P34
O
O
O
OH
O
OH
OH
N
N
HO
O
N
OH
OH
N
O
P7
N
O
P5
O
O
P3
P2
Cl
N
NXA
N
N
O
H
N
O
OH
N
P22
O
P11
OH
O
OH
O
O
OH
N
OH
O
OH
N
P27
O
N
N
OH
N
O
OH
N
P14
NH
P9
P12
OH
O
N
OH
OH
N
NH
P15
O
O
OH
N
N
N
H
N
N
OH
P6
P1
P13
No DPs
10
20
30
40
Retention time (min)
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Time (min)
50
NH
ANALYTICAL EVALUATION FOR REUSE PURPOSES
BIOLOGICAL TREATMENTS
PURIFIED WATER
TERTIARY TREATMENTS
REUSE
RECLAIMED WATER
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Reuse of treated urban wastewater (secondary treatment) in industrial
crops (tobacco) to obtain products of interest in industry
GREENHOUSE
R
CONCLUSIONS:

TOBACCO CULTURE

From productive
point of
view, the use of urban
WW
WW
wastewater (secondary treatment) is feasible for
industrial crop irrigation
STORATION
FILTRATION
IRRIGATION
The content of N and P in WW is higher: lower
Biomass production (kg·m-2)
dose of fertilizers
% Hydrosoluble proteins
R
% Sugars
% Starch
Compounds of market value
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% Nicotine
% Solanesol
Accumulation of contaminants in the soil
Concentration (mg/kg)
Compounds
Uncultivated
Cultivated soil
CONCLUSIONS:
soil
Lead
0.2725
8.1450
metalspollutants and heavy metals were detected in
 Heavy
Organic
Cadmium
0.0150
0.0600
Priority
the soil, so control
is necessary to prevent
their
pollutants
Pyrene
0.0010
0.0033
PAHs
Phenanthrene
0.0005
0.0019
accumulation in soil
and groundwater contamination.
Carbamazepine
0.0004
0.0003
 The cultivation extracted
contaminants of the
soil.
Hydrochlorothiazide
0.0010
Pharmaceuticals
Clarithromycin
0.0001
0.0001
Industrial crops reduce
the risk of accumulation
of
Emerging
Caffeine
0.0098
0.0007
contaminants
contaminants in Nicotine
soil, leaching and groundwater
3.7571
1.0938
Synthesized
in plant and
Cotinine
0.0119
0.0017
contamination
pose no risk to the consumer
Salicylic Acid
0.0093
 E. coli and suspended solids levels can exceed
10,0000
OMS
Maximum tolerable
concentration in soil
Cadmium: 4 mg·kg-1
Lead: 84 mg·kg-1
0,0800
maximum allowable Pb
values (RD 1620/2007)
0,0700
Nicotine
8,0000
Salicilic Acid
6,0000
Hydrochlorothiazide
4,0000
Clarithromycin
Cotinine
2,0000
Carbamazepine
0,0000
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Suelo sin
Uncultivated
soil
cultivo
Suelo con
Cultivated
soil
cultivo
Caffeine
Cd
Salicilic Acid
0,0600
0,0500
0,0400
0,0300
0,0200
0,0100
0,0000
Hydrochlorothiazide
Clarithromycin
Cotinine
Carbamazepine
Caffeine
Cd
Suelo sin
Uncultivated
soil
cultivo
Suelo con
Cultivated
soil
cultivo
Pireno
Aditionals technical difficulties
Shutter of the irrigation system
Limited storage capacity
Frequent maintenance
of the filters
Need for additional treatment !
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Reuse of reclaimed urban wastewater by
solar photo-Fenton in horticultural crops: zucchini
Irrigation water:
T1: Purified water by secondary
treatment
T2: Reclaimed water by solar photoFenton
PILOT PLANT
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pH 
Solar photo-Fenton pH=3
1. The treatment was effective in the
removal of contaminants
2. An early damage was observed in
the crop
T1
T2
C.E.(25 ºC)
mmhos/cm
1,55
3,66
Sales Totales g/l
1571
3727
Sulfatos mg/l
203
1141
Cloruros mg/l
543
1068
Sodio mg/l
265
675
E. Coli UFC/g
<10
10
Ana Agüera
No pH adjustment
49
COMPOUNDS
38
COMPOUNDS
Ana Agüera
ANALYSIS OF SUBSTRATE
Sustrato (µg/kg)*
Compuestos
T0
T1
4-AAA
32,55
24,09
4-FAA
9,21
1,54
Atenolol
5,48
0,04
Cafeína
1,36
1,29
Carbamazepina
0,91
0,74
Mepivacaina
0,11
0
Nicotina
4,13
0
Trimetoprim
2,67
1,07
1,56
0,54
Velafaxime
T0 SECONDARY TREATMENT
T1 MILD PHOTO-FENTON
Ana Agüera
9
COMPOUNDS
7
COMPOUNDS
5
COMPOUNDS
Carga Total (µg/kg)
ANALYSIS OF CROPS
2
COMPOUNDS
LEAVES
Ana Agüera
FRUIT
Maximum concentrations in zucchini
Compound
Concentration
(µg/kg)
Dosis max. Dipirona: 6 g/día
2 millions
Zucchini/day
4-AAA
1,17
Nicotine
0,38
Cigarrillo:
6500 zucchini
Ana Agüera
0.5 mg
Ana Agüera
THANK YOU !
-Field experiments are required
-The design of the treatments must be adjusted
to necessity in order to reduce cost
-Efficient control of the technologies applied
Ana Agüera

Degradación por Fotólisis Directa del Verde Malaquita. Análisis de

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