Organic Micropollutants in Treated Effluents from Textile Industries TOWEF0 Project Meeting Paris 2...

Organic Micropollutants in Treated Effluents from Textile Industries

TOWEF0 Project Meeting Paris 2 – 3 Sept. 2003

Robert Loos, Georg Hanke, Steven EisenreichJRC Ispra / Partner 6Inland and Marine Waters Unit

Effluent Characterisation

Workpackage 07

Evaluation of the Effect of the IPPC Directive on the Sustainable Waste Management in Textile Industries

Work Task - JRC Ispra

• WP07.01.6: Compendium of analytical methods for

organic micropollutants in textile industry (April 2002)

• WP07.02.6: Monitoring and physical-chemical

characterisation of textile industry effluents (05.2002 – 04.2003)

• WP07.04.4: Eco-toxicological characterisation of textile industry effluents

(Partner 4: Vito, Belgium)

• WP07.06.6: Effluent characterisation in the selected

textile finishing industries (06.2003 – 12.2003)

Policy background

• The objective of the IPPC Directive 96/61/EC is to prevent or reduce

industrial emissions into the environment. Article 14 demands the

monitoring of releases affecting the environment.

• In support of the IPPC Directive, analysis methods for organic

micropollutants in water samples were developed, optimized, and

validated, and many water samples analysed.

• Water Framework Directive 2000/60.

Demands the analysis of 33 priority compounds.

Multi-component analysis method for polar to medium-polar water

pollutants was developed (SSPE-LC-MS).

• New triple quad LC-MS-MS instrument.

Different Analytical Lines / Water Analysis

1. Polar water-soluble substances: SSPE – LC-MS

(Phenols, acids, sulfonates, dyes, drugs, amines, surfactants, pesticides)

2. Volatile compounds: Headspace GC-MS

(Benzene, toluene, chloroform, methylenechlorid, naphthalene, etc. …)

3. Unpolar contaminants: C18-SPE – GC-MS

(Unpolar pesticides (DDT), PAHs, phthalates, chlorobenzenes, hydro-

carbons, PCBs)

4. Physical and sum parameters

(pH, turbidity, DOC, TOC, color, etc. …)

Priority Organic Compounds measured by LC-MS

Column Superspher RP-18 (250 mm x 2 mm), flow 0.4 ml/min; aromatic amines: Synergi Polar-RP column (150 x 2 mm), flow 0.3 ml/min; italic ret. times: ion-pair chromatography with TBA/acetic acid, flow 0.3 ml/min.

Retention

Time Compounds m/z

(neg.) m/z (pos.)

Molecular Weight

Sensitivity [pg]

Alkylphenolic compounds (EDCs) 17.1 Bisphenol A 227 228 50 25.6 NPE1C, Nonylphenoxyacetic acid 277 278 20 25.6 NPE1C (d2) 279 280 20 26.8 OPE1C, Octylphenoxyacetic acid 263 264 30 28.3 Nonylphenol, technical mixture 219 220 50 31.6 4-n-Nonylphenol (d8) 227 228 50 29.4 Octylphenol 205 206 50 24.5 OPE1O, Octylphenolmonoethoxylate 268 250 100 23.8 OPE2O, Octylphenoldiethoxylate 312 294 5 29.0 NPE1O, Nonylphenolmonoethoxylate 282 264 300 29.0 NPE1O (d2) 284 266 300 28.0 NPE2O, Nonylphenoldiethoxylate 326 308 10 Phenols 7.8, 10.4 Phenol 93 94 1000 9.9 3-Chlorocatechol 143 144 50 11.5, 12.3 Nitrophenol 138 139 3 12.2, 15.2 2,4-Dinitrophenol 183 184 10 13.3, 16.1 2-Chlorophenol 127 128 5000 15.4 3,4-Dichlorocatechol 177/179 180 100 16.8 2-Methyl-4,6-dinitrophenol 197 198 1 16.9 4-Chloro-3-methylphenol 141 142 10 18.1 3-tert-Butylphenol 149 150 50 19.1 2,4-Dichlorophenol 161 162 500 20.6 2,4,6-Trichlorophenol 195 196 20 21.6 2,4,6-Tribromophenol 331, 333 330 30 24.3 PCP 265 264 5 2,4-Dimethylphenol n.d. 122 - Hydrochinone n.d. 110 - 2-Bromophenol n.d. 173 - Aromatic Sulfonates 6.6 Benzenesulfonate 157 157 30 9.2 1,5-Naphthalenedisulfonate 287 286 200 9.8 Anthraquinone-1,5-disulfonate 367 366 200 10.7 1-Amino-2-naphtholsulfonate 237 237 200 10.9 p-Toluenesulfonate 171 171 30 12.0 1,3,6-Naphthalenetrisulfonate 367 365 200 13.1 4-Chlorobenzenesulfonate 191 191 20 13.8 2-Amino-1-naphthalenesulfonate 222 222 30 14.3 2-Naphthalenesulfonate 207 207 10 16.1 Anthraquinone-2-sulfonate 287 287 20 17.2 Anthraquinone-2,6-disulfonate 367 366 200 16.3 Dodecylbenzenesulfonate (C12-LAS) 325 325 20 Dyes 15.8 Acid Red 1 464 466 40 16.1 Sulforhodamine G 529 531 531 35 10.1, 19.3 Acid Orange 8 341 343 20 11.6, 21.8 UniBlue A 483 485 30 13.0 Acid Orange 6 293 295 20 16.3 Disperse Blue 3 297 298 400 16.9 1,4-Diaminoanthraquinone 237 239 240 20(+) 400(-) 17.8 Sulforhodamine B 557 559 559 35 21.8 7-Diethylamino-4-methyl-coumarin 232, 254 256 2 23.9 Disperse Red 1 315 318 10 24.2 Disperse Blue 14 267 268 2

Pharmaceuticals 14.6 Carbamazepine 237 238 5 17.5 Benzafibrate 360, 274 361 5 21.3 Diclofenac 294, 250 296 296 5 21.8 Ibuprofen 205, 159 206 5 23.1 Gemfibrozil 249 250 5 Aromatic Amines 2.8 1,4-Diaminobenzene 109 108 50 3.9 2-Aminophenol 110 109 50 5.2 2,4-Diaminoanisole 139 138 20 5.4 2,4-Diaminotoluene 123 122 50 8.1 Aniline 94 93 2000 12.0 2-Amino-4-chlorophenol 144 143 500 14.4 4-Chloroaniline 128 127 15000 14.5 Benzidine 185 184 5 16.9 2-Aminonaphthalene 144 143 100 16.9 3,3’-Dimethylbenzidine 213 212 2 17.0 3,3'-Dimethoxybenzidine 245 244 3 17.4 N,N-Dimethylaniline 122 121 500 17.7 3,4-Dichloroaniline 162, 164 161 15000 19.2 4-Aminobiphenyl 170 169 100 20.5 3,3’-Dichlorobenzidine 254 253 100 20.1 4-Aminoazobenzene 198 197 5 Pesticides 8.9 Atrazine-desethyl 188 187 5 13.1 Bentazone 239 240 10 13.3 Simazine 202 206 5 15.0 2,4-D 221, 161 220/2 10 15.6 MCPA 199, 141 200 20 16.2 Carbaryl 145 202 5 16.3 Atrazine 216 215 3 17.1 Isoproturon 205 207 208 2 17.2 2,4,5-T 255, 195 254 10 17.2 Dichlorprop 233, 161 234/6 20 17.3 Diuron 231, 233 233 234 5 17.6 Mecoprop 213, 141 214 20 19.2 Terbutylazine 230 229 3 19.4 Propanil 216 218 218 5 20.3 Linuron 249 250 5 22.2 Alachlor 238, 162 270 5 23.3 Chlorfenvinphos 359 358 5 26.3 Trifluralin 336 338 50 28.4 Chlorpyrifos 352 350 50 NPEO (OPEO) Alkylphenolethoxylate Surfactants (+NH4) 27.8 (25.2) NPE3O (OPE3O) 370 (356) 352 (338) 500 (300) 27.7 (25.1) NPE4O (OPE4O) 414 (400) 396 (382) 200 (100) 27.6 (25.0) NPE5O (OPE5O) 458 (444) 440 (426) 100 (50) 27.5 (24.9) NPE6O (OPE6O) 502 (488) 484 (470) 100 (50) 27.4 (24.8) NPE7O (OPE7O) 546 (532) 528 (514) 100 (50) 27.3 (24.7) NPE8O (OPE8O) 590 (576) 572 (558) 100 (50) 27.3 (24.6) NPE9O (OPE9O) 634 (620) 616 (602) 200 (100) 27.2 (24.5) NPE10O (OPE10O) 678 (664) 660 (646) 300 (200) 27.1 (24.4) NPE11O (OPE11O) 722 (708) 704 (690) 400 (300) 27.0 (24.3) NPE12O (OPE12O) 766 (752) 748 (734) 500 (500) 26.9 (24.2) NPE13O (OPE13O) 810 (796) 792 (778) 800 (500) 26.9 (24.1) NPE14O (OPE14O) 854 (840) 836 (822) 800 (700) 26.8 (23.9) NPE15O (OPE15O) 898 (884) 880 (866) 800 (800)

Sequential SPE (SSPE)

400 mlwater atneutral pH

C18(500 mg)

10 mM TBA/HAc/-formic acid

1. Fraction:

2 x 3 mlHexane/DCM (3:1)

2. Fraction:

2 x 3 mlMeOH/Acetone/Ethylacetate (2:2:1), 0.1 % formic acid

Oasis HLB(200 mg)

Ion-pair SPE

3. Fraction:

2 x 3 mlMeOH/Acetone

Nonpolar Polar

R. Loos, G. Hanke, S.J. Eisenreich:Multi-Component Analysis of Polar Water Pollutants Using Sequential Solid-Phase Extraction Followed by LC-ESI-MS.J. Environ. Monit. 5 (2003) 384-394.

More simple SPE clean-up

Oasis HLB(200 mg)

Elution:

2 x 3 ml

MeOH/Acetone/ Ethylacetat

1 Fraction

Water at neutral pH

Sampling campaign in Belgium (17-18 June 2003)

Samples were taken three times at 3 different textile companies, the

corresponding WWTPs and the receiving waters (in total 30 samples).

• B04, Oudenaarde:

The effluent is treated in an own WWTP, and this effluent is discharged in the

sewer which is connected to the municipal WWTP of the city Oudenaarde.

This WWTP discharges into the River Schelde.• B05, Ronse:

The effluent is not treated and is discharged directly into a small creek

(Molenbeek).• B01, Waregem:

The effluent is discharged in the sewer, which is connected to the municipal

WWTP of the city Waregem. In this WWTP a lot of waste water from different

textile companies is treated. The WWTP discharges into a small creek

(Gaverbeek).

Samples were taken from the WWTP effluent and the creek.

Textile company B05 (Ronse)

Results from the multi-parameter in-situ

probe

Sample

Name

pH Conductivity

[S/m]

Turbidity

[NTU]

Dissolved

Oxygen [%]

Temp.

[ºC]

Color [m-1

]

436 nm

SAC [m-1

]

254 nm

BT05 5.20 0.29 357.00 sat 36.70 6.67 55.7

BT06 7.64 0.15 177.50 69.01 18.20 1.4 8.41

BT07 6.98 0.25 422.50 sat 22.00 6.35 57.1

BT18 12.03 1.94 106.85 sat 53.85 7.5 197.25

BT19 8.31 0.14 173.50 sat 17.70 1.7 12.8

BT20 9.37 0.19 570.00 sat 23.60 5.32 32.9

BT28 6.60 0.52 370.00 86.91 50.00 17.1 67.3

BT29 7.05 0.17 240.00 sat 18.50 1.85 11.3

BT30 6.76 0.21 375.00 sat 25.30 6.4 25.6

Measurements by Elisabetta Canuti

Normal SPE versus SSPE

And LC-MS versus LC-MS-MS

Normal SPE SSPE (C18 + Oasis)

(Oasis HLB) (3 fractions)

LC-MS LC-MS-MS LC-MS LC-MS-MS

30 Belgian Water Samples

LC Triple-quad MS-MS

1st Quad CollisionQuad

3rd Quad

• Very selective detection mode

• Sensitivity higher

(because no background noise)

( Atrazine 216 174, 132 ) MS-MS Transition

Example:

, extractor 8, cone 19,

80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250m/z0

100

%

0

100

%

IBUPROFEN-1 1 (0.517) Scan ES- 5.93e7204.97

158.87

96.35 140.63 156.86

160.82

161.89

206.04

IBUPROFEN-4 1 (0.517) Daughters of 205ES- 1.72e6161.21

122.76

205.20

scan, 1ppm

80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300m/z0

100

%

0

100

%

OPE1C-6 1 (0.517) Scan ES- 4.02e7263.14

96.68

88.73

97.12

97.24

141.04

105.75116.95 126.90

205.33171.09

253.24241.22227.19219.23

264.20

277.17

OPE1C-8 1 (0.517) Daughters of 263ES- 4.41e6205.31

106.00

scan, 1ppm

80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 310 320 330m/z0

100

%

0

100

%

NPE1C-6 1 (0.517) Scan ES- 7.15e7277.14

96.69

88.74

141.03

115.20219.19157.32143.26

171.26227.34

255.17

278.16

291.22304.98

NPE1C-7 1 (0.517) Daughters of 277ES- 1.97e6219.42

219.30

133.31

132.93

132.80

120.22

134.26148.38

190.41162.43

neg. , 1ppm, cone 40

80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300m/z0

100

%

0

100

%

PROPANIL-4 1 (0.517) Scan ES- 7.98e7216.04

96.74

88.54

97.12

141.04

105.81160.01

162.07

218.04

220.17

255.31253.18

PROPANIL-5 1 (0.517) Daughters of 216ES- 5.40e6160.08

123.94

216.07

Some examples for MS-MS fragmentations

Ibuprofen OPE1C

Propanil NPE1C

205 > 161 205 > 106

216 > 160 219 > 133

Compounds Cone

[V]

Cap.

[kV]

M. W. Transitions M fragments

(collision potential) Alkylphenolic compounds (EDCs) Bisphenol A 45 3.0 228 227 > 133 (30), 212 (20), 93 (30) NPE1C, Nonylphenoxyacetic acid 35 3.0 278 277 > 219 (18), 133 (40) NPE1C (d2) 35 3.0 280 279 > 219 (20), 133 (40) OPE1C, Octylphenoxyacetic acid 35 3.0 264 263 > 205 (20), 106 (30), 219 (15) Nonylphenol, technical mixture 45 3.0 220 219 > 133 (32), 119, 147 (30) 4-n-Nonylphenol (d8) 50 2.8 228 227 > 112 (24) Octylphenol 45 3.0 206 205 > 106 (20) OPE1O, Octylphenolmonoethoxylate 25 3.5 250 268 > 113 (10), 251 (7) OPE2O, Octylphenoldiethoxylate 25 3.5 294 312 > 183 (12), 121 (23) NPE1O, Nonylphenolmonoethoxylate 23 3.5 264 282 > 127 (10), 265 (7), 139 (9) NPE1O (d2) 25 3.5 266 284 > 127 (9), 85 (15) NPE2O, Nonylphenoldiethoxylate 23 3.5 308 326 > 183 (12), 121 (23), 127 (14) Phenols Phenol 94 93 no fragmentation 3-Chlorocatechol 34 3.0 144 143 > 107 (14), 79 (18) Nitrophenol 35 3.5 139 138 > 108 (14), 92 (18) 2,4-Dinitrophenol 37 2.8 184 183 > 109 (25), 153 (15), 137 (20), 123 (18) 2-Chlorophenol 35 3.4 128 127 no fragmentation, low sensitivity 3,4-Dichlorocatechol 30 3.0 180 177 > 105 (20), 77 (25) 2-Methyl-4,6-dinitrophenol 198 4-Chloro-3-methylphenol 142 3-tert-Butylphenol 150 2,4-Dichlorophenol 162 2,4,6-Trichlorophenol 196 2,4,6-Tribromophenol 45 3.0 330 328.4 > 78.8 (35), 80.8 (32) PCP 45 2.8 264 265 > 35 (23) Aromatic Sulfonates Benzenesulfonate 40 3.0 157 157 > 93 (20), 80 (25) 1,5-Naphthalenedisulfonate 40 3.2 286 287 > 207 (22), 143 (35), 80 (37) Anthraquinone-1,5-disulfonate 55 3.4 366 367 > 275 (27), 303 (20), 195 (38) 1-Amino-2-naphtholsulfonate 35 3.0 237 237 > 173 (17), 145 (27), 101 (37) p-Toluenesulfonate 40 2.8 171 171 > 107 (20), 80 (25) 1,3,6-Naphthalenetrisulfonate 365 366 low signal 4-Chlorobenzenesulfonate 40 2.8 191 191 > 127 (20), 80 (27) 2-Amino-1-naphthalenesulfonate 40 3.2 222 222 > 80 (25), 158 (22) 2-Naphthalenesulfonate 45 3.0 207 207 > 143 (22), 80 (27) Anthraquinone-2-sulfonate 45 2.8 287 287 > 223 (26), 195 (42), 80 (55) Anthraquinone-2,6-disulfonate 366 No signal Dodecylbenzenesulfonate (C12-LAS) 60 3.0 325 325 > 183 (40), 119 (55), 80 (60)

Optimisation of MS-MS parametersRed: pos.Blue: neg.

No single compounds available for this compounds

Optimisation of MS-MS parameters

Compounds Cone

[V]

Cap.

[kV]

M. W. Transitions M fragments

(collision potential) Pharmaceuticals Carbamazepine (+) 35 3.5 238 237 > 194 (18), 179 (35), 165 (40) Benzafibrate (-) 32 3.0 361 360 > 274 (17), 154 (30), 85 (20) Diclofenac (-) 25 3.0 296 294 > 250 (13) Ibuprofen (-) 25 3.0 206 205 > 161 (8) Gemfibrozil (-) 27 3.0 250 249 > 121 (15) Dyes Acid Red 1 50 3.5 466 464 > 359 (24) adduct 486 Sulforhodamine G (-) 75 3.0 531 529 > 485 (42), 405 (45) Acid Orange 8 45 2.8 343 341 > 185 (25), 170 (32), 121 (40), 106 (40) UniBlue A 65 3.0 485 483 > 328 (35), 392 (35), 419 (32) Acid Orange 6 37 3.0 295 293 > 171 (20), 213 (20), 156 (32) Disperse Blue 3 40 3.5 298 297 > 252 (20), 235 (32) 1,4-Diaminoanthraquinone (+) 45 3.4 240 293 > 166 (35), 139 (42) Sulforhodamine B (-) 70 3.0 559 557 > 513 (45), 433 (45) 7-Diethylamino-4-methyl-coumarin (+) 35 3.2 256 254 no fragments Disperse Red 1 (+) 45 3.5 318 315 > 134 (25), 255 (30), 209 (40) Disperse Blue 14 (+) (weak) 35 3.5 268 267 > 235 (18), 252 (30) Pesticides Atrazine-desethyl 35 3.5 187 188 > 146 (16), 104 (24), 110.2 (20) Bentazone (-) 3rd fr. 42 3.0 240 239 > 132 (27), 197 (22), 175 (20) Simazine 40 3.5 206 202 > 132 (18), 124 (18), 96 (23) 2,4-D 20 2.8 220/2 219 > 161 (13), 125 (27) MCPA 25 3.0 200 199 > 141 (15), 105 (25) Carbaryl (adduct 224) 38 3.5 202 205 > 164 (8), 182 (6), 120 (17), 123 (17) Atrazine 35 3.5 215 216 > 174 (17), 132 (25), 96 (25), 104 (30) Isoproturon (+) 229 adduct 30 3.5 208 207 > 72 (17), 165.2 (15) 2,4,5-T 20 3.0 254 253 > 195 (13), 159 (27) Dichlorprop 22 2.8 234/6 233 > 161 (13), 125 (25) Diuron (Na-adduct at 255) 30 3.5 234 233 > 72 (17) Mecoprop 25 2.8 214 213 > 141 (14), 105 (30) Terbutylazine 35 3.2 229 230 > 174 (17), 132 (25), 146 (24), 104 (32) Propanil (-) 40 3.0 218 216 > 160 (18), 124 (25) Linuron 33 3.5 250 249 > 160 (18), 182 (15), 88 (12) Alachlor 35 3.4 270 270 > 238.1 (11), 162 (18) (292 adduct) Chlorfenvinphos (Na-adduct) 30 3.5 358 359 > 155 (12), 127 (20), 205 (22) Trifluralin 40 3.5 338 337 no fragments Chlorpyrifos (3rd fraction) 32 3.5 350 352 > 200 (18), 324 (12), 153 (14), 115 (20)

Red: pos.Blue: neg.

19.50 20.00 20.50 21.00 21.50 22.00 22.50 23.00 23.50 24.00 24.50 25.00 25.50min0

100

%

F2:MRM of 16 channels,ES-294 > 250

3.051e+003

040803-025 Smooth(Mn,2x3) BT25

Diclofenac;20.75;1055.339;2627

19.33

24.12

22.87

19.50 20.00 20.50 21.00 21.50 22.00 22.50 23.00 23.50 24.00 24.50 25.00 25.50min0

100

%


3.141e+003

040803-023 Smooth(Mn,2x3) allmix/100

Diclofenac;20.75;1173.750;3030

19.50 20.00 20.50 21.00 21.50 22.00 22.50 23.00 23.50 24.00 24.50 25.00 25.50min0

100

%


1.686e+002

040803-027 Smooth(Mn,2x3) EA

19.50

20.0822.75

21.25 25.12

23.8724.58

Diclofenac

Blank

Standard

Sample

19.50 20.00 20.50 21.00 21.50 22.00 22.50 23.00 23.50 24.00 24.50 25.00 25.50min0

100

%


2.556e+002


PCP;22.83;68.027;164

20.9219.96

19.50 20.00 20.50 21.00 21.50 22.00 22.50 23.00 23.50 24.00 24.50 25.00 25.50min0

100

%


4.315e+002

040803-014 Smooth(Mn,2x3) BT19

PCP;22.79;135.900;336

19.04

24.58

19.50 20.00 20.50 21.00 21.50 22.00 22.50 23.00 23.50 24.00 24.50 25.00 25.50min0

100

%


1.058e+002

040803-011 Smooth(Mn,2x3) BT04

23.5422.8720.9620.58

19.46 21.75

24.83

25.79

PCP

8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0 18.5 19.0min0

100

%


1.099e+003

040803-010 Smooth(Mn,2x3) BT03

Sulforhodamine B11.91

367.654937

18.1413.13 16.34 17.44

8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0 18.5 19.0min0

100

%


2.299e+003


Sulforhodamine B11.91

848.0402196

8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0 18.5 19.0min0

100

%


1.319e+002

040803-009 Smooth(Mn,2x3) EA

11.37

9.218.049.88

15.0112.03 13.91 15.87 17.94

16.53 17.40

Sulforhodamine B

18.0 18.5 19.0 19.5 20.0 20.5 21.0 21.5 22.0 22.5 23.0 23.5 24.0 24.5 25.0 25.5 26.0 26.5 27.0 27.5min0

100

%

F2:MRM of 14 channels,ES+359 > 127

2.535e+002

120803-025 Smooth(Mn,2x3) BT26

Chlorvenfinvos;21.57;51.614;144

20.7517.91 19.3518.46

24.12

22.68

23.6423.04 24.67 25.8225.26 26.22 27.00

min0

100

%


2.785e+002

120803-025 Smooth(Mn,2x3) BT26


19.7217.76 18.2823.86

23.16 25.7824.71 26.59

18.0 18.5 19.0 19.5 20.0 20.5 21.0 21.5 22.0 22.5 23.0 23.5 24.0 24.5 25.0 25.5 26.0 26.5 27.0 27.5min0

100

%


7.164e+002



min0

100

%


1.292e+003



18.0 18.5 19.0 19.5 20.0 20.5 21.0 21.5 22.0 22.5 23.0 23.5 24.0 24.5 25.0 25.5 26.0 26.5 27.0 27.5min0

100

%


1.142e+002

120803-008 Smooth(Mn,2x3) EA

20.1618.9818.02

19.6521.4221.09

24.4523.7123.0422.64

25.26 25.78 26.96

min0

100

%


1.134e+002

120803-008 Smooth(Mn,2x3) EA

20.4618.43

17.9519.46

21.64 22.27 26.8925.1123.6022.90 25.56 26.15 27.70

Chlorvenfinphos

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0 17.0min0

100

%


1.053e+004

120803-013 Smooth(Mn,2x3) BT19

Simazine12.96

3309.42010394

min0

100

%


1.135e+004

120803-013 Smooth(Mn,2x3) BT19

Simazine12.96

3407.81211006

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0 17.0min0

100

%


1.257e+002

120803-008 Smooth(Mn,2x3) EA

4.654.03 6.155.00 7.26 7.67 9.858.738.35 10.55 15.9312.9311.49 11.96 13.43 14.61 16.43

min0

100

%


1.471e+002

120803-008 Smooth(Mn,2x3) EA

8.266.17

5.034.094.65 5.82

6.767.61

16.4315.8715.3411.149.52

10.2012.5511.90 14.7612.99 13.64 17.2816.99

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0 17.0min0

100

%


1.010e+003


Simazine;12.96;280.524;925

6.124.03

8.53 16.14

min0

100

%


1.045e+003


Simazine;12.93;291.789;952

10.207.59

Simazine

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0 17.0min0

100

%


1.084e+002

120803-008 Smooth(Mn,2x3) EA

12.7310.499.007.415.624.764.41 6.38

7.70 8.149.67 12.2611.49

16.7214.14

13.34

16.08

15.02

min0

100

%


1.897e+002

120803-008 Smooth(Mn,2x3) EA

Carbamazepin;14.11;26.999;88

7.734.65 6.005.29

6.327.29 12.2011.618.828.41 9.79 10.55

12.7616.8715.05 16.46

15.67

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0 17.0min0

100

%


6.742e+002


Carbamazepin14.11

167.346593

9.055.00 17.05

min0

100

%


4.418e+003


Carbamazepin;14.08;1241.308;4304

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0 17.0min0

100

%


2.997e+003

120803-011 Smooth(Mn,2x3) BT09

Carbamazepin;14.11;804.269;2706

9.47 13.2311.52 15.81

min0

100

%


2.247e+004

120803-011 Smooth(Mn,2x3) BT09

Carbamazepin14.11

6432.83322134

9.47

Carbamazepine

LC-MS-MS Chromatograms

Blank

Standard

Sample

LC-MS-MS Chromatograms

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0min0

100

%


4.739e+003

210803-035 Smooth(Mn,2x3) BT29

11.13

10.028.40

5.18

2-Amino-1-nasulfonate14.64

1570.1943576

min0

100

%


1.125e+004

210803-035 Smooth(Mn,2x3) BT29

10.02

8.405.15

11.06

12.28

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0min0

100

%


6.788e+002


11.694.81

min0

100

%


5.410e+003


2-Amino-1-nasulfonate14.46

1892.1355326

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0min0

100

%


6.867e+001

210803-031 Smooth(Mn,2x3) EA

4.22 7.626.925.40 6.03

14.499.328.06 11.2110.24 13.1312.24 15.45

min0

100

%


1.010e+002

210803-031 Smooth(Mn,2x3) EA

14.9014.53

11.219.919.394.70 5.965.26 7.18 8.51

12.7612.28 14.0513.31 15.49

2-Amino-1-naphthalenesulfonate

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0min0

100

%


2.625e+004

210803-005 Smooth(Mn,2x3) BT03

12.90

min0

100

%


7.356e+004

210803-005 Smooth(Mn,2x3) BT03

12.87

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0min0

100

%


3.951e+002

210803-004 Smooth(Mn,2x3) EA

7.10

5.59

min0

100

%


8.742e+002

210803-004 Smooth(Mn,2x3) EA

9.62 12.7211.21

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0min0

100

%


2.825e+003


Naphthalenesulfonate15.20

952.4102727

12.02

min0

100

%


7.672e+003


Naphthalenesulfonate15.20

2595.2867516

12.09

Naphthalenesulfonate

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0min0

100

%


5.900e+004

210803-014 Smooth(Mn,2x3) BT06

1,5-Naph-disulfonate;11.65;29773.740;5875414.31

min0

100

%


1.208e+005

210803-014 Smooth(Mn,2x3) BT06

1,5-Naph-disulfonate;11.61;60544.930;120190

14.31

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0min0

100

%


8.551e+001

210803-013 Smooth(Mn,2x3) EA

14.754.55 12.46

11.728.366.665.07 7.40 9.91 11.2410.32 13.4215.83

min0

100

%


9.235e+001

210803-013 Smooth(Mn,2x3) EA

14.498.104.30 6.556.14

5.774.817.25

13.649.959.39

10.8712.20

15.49

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0min0

100

%


3.320e+002



9.954.67 7.666.33 9.21 14.8613.39

min0

100

%


6.126e+002



8.14 13.50 14.12

1,5-Naphthalene-disulfonate

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0 17.0min0

100

%


1.306e+004

260803-007 Smooth(Mn,2x3) BT09

14.95

11.6612.79 13.41

min0

100

%


2.600e+004

260803-007 Smooth(Mn,2x3) BT09

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0 17.0min0

100

%


5.069e+003


min0

100

%


9.844e+003


5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0 17.0min0

100

%


1.046e+002

260803-013 Smooth(Mn,2x3) EA

4.3714.548.04

6.8713.37

9.588.91 10.6210.12 12.04

min0

100

%


1.551e+002

260803-013 Smooth(Mn,2x3) EA

14.916.505.624.08 13.8312.7010.047.677.17 9.25 11.12

17.66

Bentazone

BT04

12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.00 20.00 21.00 22.00Time0

100

%

0

100

%

210803-006 2: MRM of 18 Channels ES- 219 > 161

7.65e316.21

17.11


75416.21

17.6816.5517.53 21.6720.5917.96 20.2618.38

19.4620.97

21.91

16.00 16.50 17.00 17.50 18.00 18.50 19.00 19.50 20.00 20.50 21.00 21.50min0

100

%


9.461e+001

210803-004 Smooth(Mn,2x3) EA

18.15

17.6316.6921.4920.22

19.46

min0

100

%


1.040e+002

210803-004 Smooth(Mn,2x3) EA

16.3820.36

17.44 19.8419.13 21.20

allmix/100

12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.00 20.00 21.00 22.00Time0

100

%

0

100

%


1.06e416.29


1.08e316.29

18.9916.88 17.3518.66

21.2521.67

2,4-D

EA

12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.00 20.00 21.00 22.00 23.00 24.00Time0

100

%

0

100

%

0

100

%


2.69e417.95

17.45

18.24

20.24


1.20e418.04


29919.45

19.04

16.20

16.04

18.2018.04

16.45 16.9517.29

18.70

18.6220.95

20.2919.74 20.4921.03

21.6621.58 21.91

Acid Red 1

Simazine m/z 202

min5 10 15 20 25 30 35

0

5000

10000

15000

20000

25000

30000

MSD2 202, EIC=201.7:202.7 (C:\MYDOCU~1\LCMSDATA\AGI-1\0907-019.D) API-ES, Pos, SIM, Frag: 90

min5 10 15 20 25 30 35

0

2000

4000

6000

8000

10000

12000

14000

16000


min5 10 15 20 25 30 35

0

2000

4000

6000

8000

10000

12000

14000

16000


12.4

BT10

12.4

12.4

SPE-LC-MS

SSPE-LC-MS

BT10-2F

Standard

Some LC-MS Chromatograms

Acid Red 1 m/z 464

min5 10 15 20 25 30

0

2000

4000

6000

8000

10000

12000

14000

MSD1 464, EIC=463.7:464.7 (C:\MYDOCU~1\LCMSDATA\AGI-1\1107-020.D) API-ES, Neg, SIM, Frag: 90

min5 10 15 20 25 30

0

1000

2000

3000

4000

5000

6000

7000

8000


min5 10 15 20 25 30

0

1000

2000

3000

4000

5000

6000


17.8

BT25

17.7

17.7

BT26-3F

Standard

SPE-LC-MS

SSPE-LC-MS

Diclofenac m/z 250

min5 10 15 20 25 30 35

0

2000

4000

6000

8000

10000

12000


min5 10 15 20 25 30 35

0

20000

40000

60000

80000

100000

120000

140000

160000


min5 10 15 20 25 30 35

0

2000

4000

6000

8000

10000


19.7 BT06

Standard

SPE-LC-MS

SSPE-LC-MS

20.6

20.7

BT06-2F

2,4-D m/z 161

min5 10 15 20 25 30

0

1000

2000

3000

4000

5000

6000

7000

8000


min5 10 15 20 25 30

0

5000

10000

15000

20000

25000

30000

35000

40000


min5 10 15 20 25 300

500

1000

1500

2000

2500

3000


BT09

16.7

16.8

Standard

BT09-3F

SPE-LC-MS

SSPE-LC-MS

Some LC-MS Chromatograms

Double peak

Comparison between LC-MS and LC-MS-MS

• With MS-MS analysis is more selective (one can be much surer).Analysis is more simple, and faster.

• Many pollutants were only detected with MS-MS:2,4-Dinitrophenol, (Nonylphenol), (PCP), Uniblue A, Sulforhodamine B, Disperse Blue 14, Acid Red 1, Gemfibrozil, Propanil, Desethylatrazine, Linuron, Alachlor, Chlorvenfinphos, Carbaryl, 1,5-Naphthalenedisulfonate, 4-Chlorobenzene-sulfonate, (2-Amino-1-naphthalenesulfonate), Anthraquinone-2-sulfonate,Mecoprop, Bentazone, (Dichlorprop).

• However, the comparison shows that for other compoundsdetection was also possible with single MS:Nitrophenol, Diclofenac, Ibuprofen, Carbamazepine, (NPE1C), Simazine,

Atrazine, Terbutylazine, Diuron, NPE2O, MCPA.

• For some compounds SSPE is advantages over SPE.Bisphenol A, Isoproturon, Benzafibrate, Acid Red 1, Diclofenac.

• NPE1O only detected with MS.

Nitr

oph

enol

2,4-

Din

itro-

phen

ol

Pro

pan

il

BP

A

Un

iblu

e A

Sul

forh

od-

amin

e B

Ben

zafib

rate

Dic

lofe

nac

Ibu

prof

en

Gem

fibro

zil

NP

E1C

NP

PC

P

B04 BT01 0.0553 0.0674 - 0.0527 0.0393 0.0457 0.0092 0.0739 0.1876 - 2.7634 1.0702 0.0751

Plant effluent BT11 0.1245 0.0238 - - - 0.0777 0.0237 - - - 0.6895 1.1439 -

WWTP BT21 0.0870 0.0186 - - 1.4816 0.0653 0.0240 - - 0.0095 0.7137 1.2249 0.1229

WWTP BT12 0.0369 0.1386 - 0.0295 - 0.0310 0.0956 0.1964 0.0306 - 2.3632 5.2145 0.0197

Oudenaarde BT22 0.0235 0.1139 - - 0.0448 0.0270 0.0642 0.1714 0.0180 0.0010 2.4371 4.9258 0.0313

River Schelde BT03 0.0432 0.0597 - 0.0915 - 0.0255 0.0736 0.0137 0.0819 0.0124 1.2831 1.4870 -

after WWTP BT13 0.0422 0.0426 - 0.1085 - 0.0273 0.1010 0.0182 0.1004 0.0172 1.6773 2.2107 -

BT23 0.0465 0.0797 - 0.0872 - 0.0257 0.0906 0.0190 0.1293 0.0200 1.7180 2.2939 -

River Schelde BT04 0.0505 0.0575 - 0.0539 - 0.0316 0.0697 0.0118 0.0829 0.0159 2.0397 2.2591 -

before WWTP BT14 0.0490 0.0408 - 0.1291 - 0.0244 0.1244 0.0231 0.1293 0.0213 1.8163 2.3653 -

BT24 0.0430 0.0461 - 0.0899 - 0.0226 0.1107 0.0182 0.1175 0.0233 1.6353 2.1412 0.0074

BT24 0.0156 0.0586 - 0.1057 - 0.0370 0.0158 0.0663 0.0070 0.0030 0.5915 2.3557 0.0486

B05 effluent BT05 0.0518 0.0364 - - - 0.0941 0.0214 - 0.1826 - 0.3592 0.7437 -

BT18 0.0047 0.0107 - - - - 0.0021 - 0.0013 - 0.0052 0.0163 0.0203

BT28 0.3568 0.0508 - - - 0.0787 0.0427 - 0.0138 0.0106 0.1101 0.2562 -

Creek Molen- BT06 0.0313 0.0326 - 0.0594 - 0.0960 0.0038 0.1095 0.3247 - 2.8462 4.8591 0.0644

beek before BT19 0.0725 0.1487 - 0.0339 - 0.0807 0.0028 0.0562 0.1700 - 2.4442 3.9649 0.0743

Plant BT29 0.0450 0.0385 - 0.1059 - 0.0196 0.1053 0.0199 0.1448 0.0259 1.7676 4.4355 -

Creek Molen- BT07 0.0140 0.0040 - 0.0196 - 0.0282 0.0018 0.0355 0.0819 - 1.3881 2.1778 0.0414

beek after BT20 0.1195 0.1512 - - - 0.0608 0.0054 0.0275 0.1380 - 1.1463 3.1258 0.1160

Plant BT30 0.0432 0.0290 - - - 0.0373 0.0163 0.0221 0.0513 - 0.6759 1.6406 0.0417

WWTP BT08 - 0.0127 - 0.1073 - 0.0550 0.0112 0.0592 - 0.0007 0.2227 0.9311 0.0263

Waregem BT15 0.0444 0.0157 - - - 0.0212 0.0034 - - - 0.8495 2.1399 0.0244

BT25 - 0.0846 0.0022 0.1288 - 0.0355 0.0159 0.0617 - 0.0023 0.6411 2.2833 0.0252

Creek Gaver- BT09 0.0466 0.1296 - 0.0370 - 0.0084 0.0186 0.0163 0.0988 - 1.6312 2.1343 -

beek before BT16 0.0289 0.4545 0.0024 0.0912 - 0.0073 0.0319 0.0452 0.1072 0.0007 1.1139 1.5068 0.0239

Plant BT26 0.0392 0.4470 - 0.0808 - 0.0091 0.0193 0.0347 0.0688 - 0.9551 1.3016 0.0121

Creek Gaver- BT10 0.0263 0.0555 - 0.1099 - 0.0420 0.0149 0.0549 0.0276 - 0.5466 1.3823 0.0145

beek after BT17 0.0962 0.1617 - 0.1119 - 0.0410 0.0197 0.0634 0.0245 0.0029 0.8763 2.3803 0.0301

Plant BT27 0.1007 0.1379 - 0.1086 - 0.0356 0.0151 0.0559 0.0174 0.0022 0.7316 2.1081 0.0296

Polar water pollutants (SPE fraction)

LC-MS-MS resultsConcentrations in g/l

Sim

azin

e

Des

ethy

l-at

razi

ne

Atr

azin

e

Isop

rotu

ron

Car

bam

a-ze

pin

Diu

ron

Linu

ron

Ter

buty

l-az

ine

Ala

chlo

r

Dis

pers

e B

lue

14

Chl

orve

n-fin

phos

Chl

orpy

rifos

Car

bary

l

NP

E2O

B04 BT01 - - 0.0394 0.0088 0.0184 0.0042 - 0.0121 - - - - 0.0361 0.0137

Plant effluent BT11 - - 0.1667 0.0501 0.1050 0.0019 - 0.0785 - - 0.1000 - - 0.0610

WWTP BT21 - - 0.0636 - 0.0996 - - 0.0732 - - - - 0.0075 0.0678

WWTP BT12 2.7374 0.3057 1.9759 0.0143 0.3994 2.1799 0.0172 0.3977 - - - 0.0042 - 0.4230

Oudenaarde BT22 2.4015 0.2763 2.6598 0.0199 0.3076 2.4633 0.0185 0.2125 0.0121 - - - - 0.3354

River Schelde BT03 0.6200 0.2182 1.8385 0.1510 0.1108 0.9041 0.0217 0.0710 - - - - - 0.1283

after WWTP BT13 0.5246 0.2490 1.7576 0.0547 0.1215 0.4588 0.0140 0.0468 0.0155 - - - - 0.2462

BT23 0.4605 0.3024 2.0294 0.0896 0.1153 0.5712 0.0220 0.0495 - - 0.0094 - 0.0016 0.1356

River Schelde BT04 0.5707 0.2355 2.3029 0.1418 0.1177 0.8637 0.0190 0.1126 - - - - - 0.2275

before WWTP BT14 0.6091 0.3154 2.0977 0.1019 0.1471 0.6341 0.0124 0.0653 - - - 0.0030 - 0.1980

BT24 0.5103 0.2846 1.9624 0.1130 0.1260 0.5968 0.0121 0.0460 - - - - - 0.5297

BT24 0.4265 0.2615 1.7031 0.1067 0.1056 0.5993 0.0176 0.0475 - - 0.0093 - 0.0264 0.3354

B05 effluent BT05 - - 0.0969 - 0.2196 0.0041 - 0.0888 - - - - - 5.2764

BT18 - - 0.0061 - 0.0122 - - - - - - - - 0.0050

BT28 - - 0.1110 - 0.0998 - - 0.0748 - - 0.0928 - 0.0473 1.0858

Creek Molen- BT06 0.8767 0.1383 0.3058 - 0.1023 0.2076 0.0173 0.0233 - - - - - 1.0465

beek before BT19 0.9681 0.2735 0.7956 0.0021 0.1468 0.3115 0.0098 0.1796 0.0199 - - - - 1.7185

Plant BT29 0.6022 0.1934 0.4907 0.0079 0.1105 0.2712 0.0324 0.0616 - - - - 0.1328 0.8944

Creek Molen- BT07 0.4222 0.0477 0.1472 0.0054 0.0538 0.0985 0.0154 0.0154 - - - - 0.0638 0.5992

beek after BT20 0.8290 0.2970 0.5608 - 0.1576 0.1764 0.0155 0.1267 - - - - 0.0590 0.1626

Plant BT30 0.3158 0.1299 0.1889 - 0.0761 0.0710 0.0077 0.0406 - - 0.0090 - 0.0438 0.0691

WWTP BT08 1.6533 0.1740 0.4757 0.0001 0.3656 2.1662 0.0073 0.0092 - - - - - 0.0156

Waregem BT15 1.1173 0.1502 0.5520 0.0079 0.2754 1.7215 0.0098 0.0144 - - - - 0.0470 0.0308

BT25 1.7255 0.2148 0.8292 0.0003 0.3228 1.9427 0.0037 0.0101 0.0154 - - 0.0035 - 0.0219

Creek Gaver- BT09 1.3804 1.1023 8.4771 0.0435 0.0547 0.8719 0.0626 0.0141 - - 0.0046 0.0031 - 0.2646

beek before BT16 4.4066 0.7466 5.1309 0.0155 0.0941 1.5270 0.0331 0.0117 - 0.0119 0.0043 0.0050 - 0.3691

Plant BT26 5.5661 1.0849 5.9612 0.0134 0.1018 1.4228 0.0392 0.0149 - - 0.0045 0.0035 - 0.2644

Creek Gaver- BT10 2.6393 0.5546 5.4243 0.0315 0.3776 2.0980 0.0382 0.0140 - - - - - 0.0476

beek after BT17 1.9610 0.2855 1.9646 0.0038 0.2727 1.6211 0.0075 0.0062 0.0164 0.0128 0.0046 - - 0.0634

Plant BT27 2.0335 0.3342 2.2197 0.0108 0.2388 1.5761 0.0161 0.0133 - - - 0.0009 0.0204 0.0688



Nitr

ophe

nol

2,4-

Din

itro-

phen

ol

Ben

zene

-su

lfona

te

4-C

hlor

o-bz

sulfo

nate

p-T

olue

ne-

sulfo

nate

2-A

min

o-1-

nasu

lfona

te

NS

Ant

hra-

quin

on-1

,5-

disu

lfona

te

1,5-

Na-

disu

lfona

te

Ant

hra-

quin

on-2

-su

lfona

te

B04 BT01 - - 0.0645 0.0136 0.0572 0.0360 - - 0.5534 0.0086

Plant effluent BT11 - - 0.0067 - 0.5976 0.6379 39.146 - 10.102 0.0410

WWTP BT21 - 0.0096 - - - - 3.9051 - - 0.0036

WWTP BT12 0.0365 0.0510 0.1303 - 1.0448 0.1240 0.6764 - 8.5403 0.0082

Oudenaarde BT22 0.0232 0.0414 0.1500 - 1.5781 0.0731 0.1583 - 7.1472 0.0057

River Schelde BT03 0.0367 0.0203 0.0264 0.0086 0.9574 - 1.1168 - 1.0337 0.0038

after WWTP BT13 0.0325 0.0149 0.0337 - 0.6665 - - - 1.8213 0.0015

BT23 - - 0.0639 0.0157 0.1050 0.0415 0.1012 - 0.7680 0.0056

River Schelde BT04 0.0417 0.0160 0.0237 0.0086 0.5590 - 1.2231 - 0.8582 0.0024

before WWTP BT14 0.0631 0.0176 0.0566 - 0.3288 0.0919 0.5786 - 1.3750 0.0041

BT24 0.0334 0.0181 0.0826 0.0081 0.4848 - 2.9697 - 1.5852 0.0031

BT24 0.0438 0.0138 0.0978 0.0166 0.5988 - - - 1.5691 0.0048

B05 effluent BT05 - 0.0110 0.0959 - 2.2770 0.1513 82.813 - 122.41 0.0314

BT18 - - 0.0486 0.0081 0.1293 0.0995 5.7685 - 1.5829 0.0086

BT28 - 0.0058 - - 0.1975 - 70.589 - - -

Creek Molen- BT06 0.0274 0.0060 0.1314 0.0163 6.3051 0.5360 - - 20.613 0.0687

beek before BT19 0.0446 0.0262 0.2403 - 2.6414 0.3350 - - 18.476 0.0438

Plant BT29 0.0383 0.0195 0.1738 0.0227 7.3287 0.5880 - - 18.749 0.0654

Creek Molen- BT07 - 0.0008 - 0.0066 0.5914 0.7376 54.152 - 9.9139 0.0516

beek after BT20 0.1090 0.0253 0.8778 0.0227 26.707 0.1847 103.20 - 108.31 0.0415

Plant BT30 - 0.0299 0.1349 - 0.9110 - 0.5398 - 23.634 0.0039

WWTP BT08 - - 0.0296 - 0.2888 - - - 42.053 0.0021

Waregem BT15 - 0.0130 0.2652 - 0.8201 - - - 37.336 -

BT25 0.0678 0.1397 0.5994 0.0094 4.8254 - 5.0485 - 3.4690 0.0030

Creek Gaver- BT09 0.0154 0.0210 1.8119 0.0113 9.5037 - 0.4086 - 10.297 0.0044

beek before BT16 0.0626 0.1268 0.5160 - 3.7913 - 4.6292 0.0822 2.7781 -

Plant BT26 - 0.0146 0.1348 - 1.5386 - - - 39.975 0.0026

Creek Gaver- BT10 - 0.0082 0.4262 0.0168 10.389 - 0.1630 - 50.018 0.0035

beek after BT17 - 0.0328 0.3352 - 0.7140 - 0.5574 - 33.087 0.0027

Plant BT27 - 0.0282 - - 0.3893 - 0.7583 - 2.7111 0.0028

Polar water pollutants (3rd SSPE fraction)


MC

PA

2,4-

D

Mec

opro

p

Ben

tazo

ne

Dic

hlor

prop

2,4,

5-T

Aci

d R

ed 1

B04 BT01 0.0399 - - 0.0188 - - 0.0809

Plant effluent BT11 0.1276 - 0.1435 0.0443 - 0.0652 -

WWTP BT21 0.1015 - - 0.0397 - - -

WWTP BT12 0.3147 0.2327 0.1159 0.0914 - - 0.0234

Oudenaarde BT22 0.2737 0.2506 0.1251 0.0932 - - -

River Schelde BT03 0.2907 0.1686 0.0703 0.2196 0.1009 0.0024 -

after WWTP BT13 0.1900 0.0631 0.0438 0.1891 0.0744 0.0022 -

BT23 0.1635 0.0809 0.0499 0.1919 0.0864 0.0070 -

River Schelde BT04 0.2472 0.1458 0.0681 0.2864 0.0996 0.0022 -

before WWTP BT14 0.1867 0.0741 0.0821 0.2182 0.0983 0.0083 0.0291

BT24 0.1565 0.0618 0.0461 0.1485 0.0670 - 0.0127

BT24 0.1652 0.0708 0.0607 0.1772 0.0800 0.0078 0.0214

B05 effluent BT05 0.0823 0.0862 0.1412 0.0626 0.0555 0.0697 0.0954

BT18 - - - 0.0014 0.0047 - -

BT28 0.0832 0.0652 - 0.0169 - - -

Creek Molen- BT06 0.0965 0.0912 0.0676 0.0116 0.0071 0.2032 0.0434

beek before BT19 0.0751 0.0329 0.0639 0.0127 0.0218 0.1129 -

Plant BT29 0.0919 0.0428 0.0479 0.0127 0.0156 0.1489 -

Creek Molen- BT07 0.0339 0.0316 0.0329 0.0043 0.0053 0.0534 0.0476

beek after BT20 0.0741 0.0435 0.0820 0.0046 0.0212 0.0904 0.0364

Plant BT30 0.0384 0.0197 0.0299 0.0082 0.0095 0.0404 0.0543

WWTP BT08 0.0012 0.0056 0.0411 0.0523 - - 4.0302

Waregem BT15 0.0358 0.0434 0.0549 0.0484 0.0143 - 1.5082

BT25 0.0230 0.0342 0.0483 0.0561 0.0145 - 1.2574

Creek Gaver- BT09 4.3845 0.1661 0.0813 1.2174 0.1184 0.0021 -

beek before BT16 0.4013 0.0819 0.0633 0.2393 0.0328 - 0.0671

Plant BT26 1.0214 0.2738 0.0560 0.3285 0.0389 - -

Creek Gaver- BT10 1.3432 0.0489 0.0583 0.4122 0.0526 - 0.9382

beek after BT17 0.1007 0.0471 0.0516 0.0815 0.0145 - 1.5562

Plant BT27 0.1630 0.0802 0.0474 0.1023 0.0283 - 1.1931



Summary and Conclusion

• Sampling Campaign in Belgium (17-18 June)

• 30 samples analysed with two different SPE extraction

procedures and two different LC-MS principles.

(LC-single-quad-MS and LC-triple-quad-MS-MS)

• Results are quite good comparable.

• MS-MS is advantages, more pollutants were detected.

• MS-MS is more selective and sensitive.

• MS-MS faster, software advantages.

• For some compounds good results were also obtained

with MS (good comparability).

• Comparison of SPE and SSPE.

Summary and Conclusion

• Many polar water pollutants were detected.

• Also pollutants from the WFD priority list.

(Alachlor, Atrazine, Chlorfenvinphos, Chlorpyrifos, Diuron,

Isoproturon, Nonylphenol, Simazine, PCP).

• In Belgium especially high pesticide concentrations

(for some 2 – 8 g/l range).

(Not in Italy)

• Nonylphenol (0.01 – 5.2 g/l) and metabolites

(short-chain NPEOs, and NPECs)

Proposed Quality Standards (WFD)For Inland Waters

Compounds Proposals for Quality standards

Maximal Concentrations

Alachlor 0.035 µg/l 0.02 µg/l

Atrazine 0.34 µg/l 8.5 µg/l

Chlorfenvinphos 0.01 µg/l 0.1 µg/l

Chlorpyrifos 0.00046 µg/l 0.005 µg/l

Diuron 0.046 µg/l 2.4 µg/l

Isoproturon 0.32 µg/l 0.15 µg/l

Nonylphenols 0.33 µg/l 5.2 µg/l

Pentachlorophenol 0.1 µg/l 0.12 µg/l

Simazine < 1 µg/l 5.5 µg/l

Outlook / Workprogramme

• Comparison of chemical analysis results with

eco-toxicological data (estrogenic activity) from VITO.

EEQ calculations.

• Comparison of Italian and Belgian waters.

River Lambro (It) and River Schelde (Be)

• Results from different WWTPs.

- Fino Mornasco (Lariana): ozone treatment

- Waregem: sand filter treatment

- Oudenaarde: no sand filter (only biological)

• Effluent concentrations for most pollutants are significantly

higher in Oudenaarde compared with Waregem.

(Nitrophenols, Pharmaceuticals, NP, NPE1C, Atrazine, Terbutylazine, NPE2O)

Livescia Bulgarograsso Seveso

Compound TC2

before

TC1

Eff.

TC3

after

TC4

before

TC5

Eff.

TC6

after

TC8

before

TC7

Eff.

TC9

after

TC10

PCP 0.070 - 0.037 - - - - - - - Mononitrophenol - 0.030 0.026 0.025 0.145 0.121 0.031 0.164 0.134 0.145 2,4-Dinitrophenol - 0.028 0.022 0.041 - - - 0.022 - 0.088 Bisphenol A 0.043 - - - - - - - - - Nonylphenol 5.31 0.66 1.33 1.87 0.88 12.52 0.46 0.54 0.63 2.33 NPE1C 14.8 3.45 5.35 0.94 0.99 4.61 0.58 7.30 6.37 3.75 NPE2C 7.18 3.81 4.58 0.21 0.57 1.43 0.22 1.97 2.48 1.53 NPE3C 3.98 3.79 4.13 0.12 2.71 3.09 0.15 2.01 2.59 2.35 Atrazine - 0.041 0.033 - - - - - - - Diuron - - - 0.012 0.175 0.149 - - - - Benzenesulfonate 0.39 - - - - 0.42 - 0.37 - 0.13 2-Amino-1-naphthalenesulfonate 0.182 - 0.082 - - - 0.031 - p-Toluenesulfonate 0.17 - - 0.44 - 3.20 - 0.32 - - Naphthalenesulfonate 0.71 - 0.16 2.60 - 16.34 0.21 - 0.05 - Naphthalene-1,5-disulfonate 2.39 - 1.63 - 15.54 14.96 - - - 7.23 LAS (Dodecylbenzenesulfonate)

C10-LAS C11-LAS C12-LAS C13-LAS Σ LAS

80.1 42.5 24.7 24.5 171.8

0.59 0.46 0.42 0.80 2.3

9.71 4.63 1.66 1.56 17.6

46.9 34.3 31.3 42.9 155.4

0.16 0.18 0.23 0.60 1.2

210.2 165.6 164.4 268.7 808.9

10.1 5.14 3.31 4.29 22.8

0.16 0.12 0.19 0.31 0.8

1.98 1.11 0.82 1.02 4.9

37.2 26.4 24.3 34.7 122.6

NPE1O 0.65 - - 0.13 0.16 0.83 - - - - NPE2O 3.98 0.74 1.08 0.86 0.36 5.65 0.07 0.17 0.22 0.67 OPE2O - - - 0.08 - 0.35 - - - - NPE9O 5.51 - 1.35 16.1 - 69.5 1.47 - - 0.16 Disperse Blue 14 0.078 2.340 1.731 0.040 0.021 0.125 0.041 - - 0.072 Disperse Red 1 - - - 0.054 - 0.207 - - - - Acid Red 1 - 1.19 0.80 - - - - - - - Sulforhodamine B Pos. 8.21 0.71 1.57 0.31 0.60 0.76 0.09 1.67 0.62 0.71 IPC 4.74 0.81 1.32 0.13 0.91 1.45 - 0.71 0.66 0.87 Carbamazepine - 0.026 0.020 0.006 0.023 0.020 0.008 - - 0.020 3,3’-Dichlorobenzidine - - - 0.121 - - - - - -

Results from Italy

Sampling campaign to 3 different WWTPs, 12 June 2002

Results from ItalyCompound VC2 VC4 VC5 VC12 VC13 VC22

Mononitrophenol IPC (3.fr.) 0.199 0.148 0.098 0.028 0.165 0.040 PCP 2.fr 0.071 0.133 0.097 0.086 0.079 0.156 Bisphenol A 0.143 0.084 0.148 0.057 0.053 0.016 Nonylphenol 1.fr. 4.5 3.8 3.2 5.3 5.4 3.5 NPE1C 0.41 3.7 3.38 0.72 2.52 0.78 NPE2C 0.25 1.49 1.43 0.69 0.87 0.34 NPE3C 0.20 1.16 1.13 0.53 0.78 0.32 OPE1C 0.109 0.094 0.086 0.111 0.137 0.201 Atrazine 0.017 0.015 0.015 0.010 0.007 0.014 Atrazine-desethyl - - - - - 0.034 Propanil - - - - 0.033 0.010 Diuron - - - - - 0.007 Isoproturon 0.354 0.436 0.421 0.503 0.152 - Alachlor - - - - - 0.002 Trifluralin - 0.49 0.56 - 0.52 0.64 Chlorpyrifos 0.137 - - - - - Benzenesulfonate 0.135 - - - - - p-Toluenesulfonate 7.91 0.49 0.75 8.26 1.27 0.47 Naphthalenemonosulfonate 1.43 0.28 0.59 3.11 0.40 0.10 2-Amino-1-naphthalenesulfonate 0.112 0.047 0.065 - 0.066 - Anthraquinone-2,6-di-sulfonate - 0.91 - - 0.99 1.49

LAS

(Dodecylbenzenesulfonate)

C10-LAS C11-LAS C12-LAS C13-LAS Σ LAS

1195 1001 983 1135 4314

4.2 4.1 3.7 3.1 15.1

277 292 321 355 1245

1123 1135 1160 1211 4629

20.2 19.2 20.2 18.2 77.8

47.3 44.5 35.1 34.9 161.8

NPE1O 4.72 0.78 0.72 1.85 1.00 0.35 NPE2O 2.55 0.76 0.77 2.54 0.82 0.40 OPE2O 0.140 0.045 0.028 0.123 0.047 0.058 NPE9O 76.4 5.5 11.3 89.5 18.8 2.3 OPE9O 3.8 0.26 0.49 2.4 1.0 0.24 Benzafibrate 0.127 0.035 0.071 0.228 0.031 0.030 Gemfibrozil 0.340 0.111 0.167 0.603 0.089 0.030 Diclofenac 0.124 0.034 0.076 0.120 0.017 0.019 Ibuprofen 0.168 0.010 0.050 0.274 0.018 0.010 Carbamazepine 0.121 0.106 0.108 0.121 0.084 0.048 Acid Red 1 - - - 3.20 0.87 -

Sampling campaign in the area east of Milan at the River Lambro, 16 December 2002.

Organic Micropollutants in Treated Effluents from Textile Industries TOWEF0 Project Meeting Paris 2...

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