A New Multiresidue Method for the Determination of Multiclass Pesticides, Degradation Products and Pcbs in Water Using LC-MS/MS and GC-MS(N) Systems

SUPPLEMENTAL DATA

A new multiresidue method for the determination of multiclass pesticides, degradation products and PCBs in water using LC-MS/MS and GC-MS(n) systems

Angeliki C. Charalampousa,b*, George E. Miliadis, Michael A. Koupparisb aNational Reference Laboratory of Pesticides Residues, Benaki Phytopathological Institute, 14561 Kifissia, Greece

bLaboratory of Analytical Chemistry, Department of Chemistry, University of Athens, Panepistimiopolis, Athens 15771, Greece

Table 1S: Name, pesticide class, mode of action, negative logarithm to the base 10 of the octanol- water partition coefficient (pKow) and vapour pressure (Vp) of the studied analytes Vp Name Pesticide class Mode of action pKow (mPa) acetamiprid neonicotinoid insecticide 0.8 1.00E-03 acetochlor chloroacetamide herbicide 4.14 6.00E+00 aclonifen diphenyl ether herbicide 4.37 1.60E-02 acrinathrin pyrethrin insecticide 5.6 4.40E-05 alachlor chloroacetamide herbicide 3.09 2.00E+00 aldicarb sulfone carbamate insecticide -0.57 ametryn triazine herbicide 2.63 3.65E-01 atrazine triazine herbicide 2.5 1.50E-04 azimsulfuron sulfonylurea herbicide 4.43 4.00E-06 azinphos ethyl organophosphate insecticide 3.18 3.20E-01 azinphos methyl organophosphate insecticide 2.96 5.00E-04 azoxystrobin strobilurin fungicide 2.5 1.10E-07 benalaxyl acylalanine fungicide 3.54 6.60E-01 benfuracarb carbamate insecticide 4.22 1.00E-02 bensulfuron methyl sulfonylurea herbicide -0.99 2.80E-09 benzoximate other acaricide 2.4 4.50E-01 bifenthrin pyrethrin insecticide 6.6 2.40E-02 bitertanol triazole fungicide 4.1 2.20E-07 boscalid carboxamide fungicide 2.96 7.20E-04 bromophos ethyl organophosphate insecticide 6.13 - bromopropylate benzilate acaricide 5.4 6.80E-03 bromuconazole triazole fungicide 3.24 4.00E-03 bupirimate pyrimidinol fungicide 3.9 1.00E-01 buprofezin other insecticide 4.3 1.25E+00 cadusafos organophosphate insecticide 3.9 1.20E+02 carbofuran carbamate insecticide 1.52 3.10E-02 chlorbromuron urea herbicide 2.9 - chlordane alpha cyclodiene insecticide 5.57 1.30E+00 chlordane gamma cyclodiene insecticide 5.57 1.30E+00 chlorfenapyr arylpyrrole insecticide 4.83 1.20E-02 chlorfenvinfos organophosphate insecticide 3.85 1.00E+00 chlorobenzilate organochlorine acaricide 4.58 - chlorothalonil chloronitrile fungicide 2.92 7.60E-02 chlorotoluron urea herbicide 2.5 5.00E-03 chlorpropham carbamate herbicide 3.79 2.40E+01 chlorpyrifos organophosphate insecticide 4.7 2.70E+00 chlorpyrifos methyl organophosphate insecticide 4.24 3.00E+00 chlorsulfuron sulfonylurea herbicide -0.99 3.00E-06 clofentezine tetrazine acaricide 4.1 1.30E-04 clothianidin neonicotinoid insecticide 0.7 1.30E-04 cyfluthrin pyrethrin insecticide 6 9.60E-04 cypermethrin pyrethrin insecticide 6.6 2.00E-04 cyproconazole triazole fungicide 3.1 2.60E-02 cyprodinil anilinopyrimidine fungicide 3.9 5.10E-01 o, p' - DDD organochlorine metabolite 5.39 - p, p' - DDD organochlorine metabolite 5.39 - o, p' - DDE organochlorine metabolite 6.2 - p, p' - DDE organochlorine metabolite 6.2 - o, p' - DDT organochlorine insecticide 5.92 2.50E-02 p, p' - DDT organochlorine insecticide 5.92 2.50E-02 deltamethrin pyrethrin insecticide 4.6 1.24E-05 desethylterbuthylazine triazine metabolite 1.85 - desmetryn other herbicide 2.38 1.33E-01 diazinon organophosphate insecticide 3.3 1.20E+01 dicloran aromatic hydrocarbon fungicide 2.8 1.60E-01 dicofol other acaricide 4.3 5.30E-02 dieldrin cyclodiene insecticide 4.88 - difenoconazole triazole fungicide 4.4 3.30E-05 dimethenamide-P chloroacetamide herbicide 1.89 2.51E+00 dimethoate organophosphate insecticide 0.704 2.50E-01 dimethomorph cinnamic acid fungicide 2.63 9.70E-04 diniconazole triazole fungicide 4.3 2.93E+00 dinitramine dinitroaniline herbicide 4.3 4.79E-01 disulfoton sulfone organophosphate insecticide 3.95 - diuron urea herbicide 2.85 1.10E-03 dodemorph morpholine fungicide 4.14 4.80E-02 alpha - endosulfan cyclodiene insecticide 4.74 8.30E-01 beta - endosulfan cyclodiene insecticide 4.79 8.30E-01 endosulfan sulfate cyclodiene insecticide 3.18 - epoxiconazole triazole fungicide 3.44 1.00E-02 esfenvalerate pyrethrin insecticide 6.22 2.00E-04 ethalfluralin dinitroaniline herbicide 5.11 1.17E+01 ethion organophosphate insecticide 4.28 2.00E-01 ethofumesate benzofuran herbicide 2.7 1.00E-01 ethoprophos organophosphate insecticide 3.59 4.65E+01 etoxazole acaricide 5.59 2.18E-03 fenamidone imidazolinone fungicide 2.8 3.40E-04 fenamiphos organophosphate nematicide 3.3 1.20E-01 fenamiphos sulfone organophosphate nematicide fenarimol pyrimidine fungicide 3.69 6.50E-02 fenazaquin other acaricide 5.51 3.40E-03 fenbuconazole triazole fungicide 3.23 3.40E-01 fenhexamide hydroxyanilide fungicide 3.51 4.00E-04 fenitrothion organophosphate insecticide 3.43 1.80E+01 fenoxycarb carbamate insecticide 4.07 8.67E-04 fenpropathrin pyrethrin insecticide 6 7.30E-01 fensulfothion organophosphate insecticide 2.23 - fensulfothion oxon organophosphate metabolite 0.82 - fensulfothion oxon sulfone organophosphate metabolite - fensulfothion sulfone organophosphate metabolite 2.43 - fenthion organophosphate insecticide 4.84 7.40E-01 fenthion sulfone organophosphate metabolite 1.83 fenvalerate pyrethrin insecticide 5.01 1.92E-02 fluazifop aryloxyphenoxypropionic acid herbicide 3.18 8.00E-04 flucythrinate pyrethrin insecticide 4.7 1.20E-03 fluometuron urea herbicide 2.38 1.25E-01 fluquinconazole triazole fungicide 3.24 6.40E-06 flusilazole triazole fungicide 3.74 3.90E-02 flutriafol triazole fungicide 2.3 7.10E-06 foramsulfuron sulfonylurea herbicide 4.01 4.20E-08 fosthiazate organophosphate insecticide 1.68 5.60E-01 furathiocarb carbamate insecticide 4.6 3.90E-03 haloxyfop etotyl aryloxyphenoxypropionic ester herbicide 4.33 1.64E-05 haloxyfop methyl aryloxyphenoxypropionic ester herbicide 4 3.28E-01 alpha - HCH organochlorine insecticide 3.99 - beta - HCH organochlorine insecticide 3.99 - gamma - HCH organochlorine insecticide 3.5 4.40E+00 heptachlor organochlorine insecticide 4.95 5.30E+01 heptachlor-endo-epoxide organochlorine metabolite 4.24 - heptachlor-exo-epoxide organochlorine metabolite 4.24 - hexaconazole triazole fungicide 3.9 1.80E-02 hexythiazox other acaricide 2.53 3.40E-03 imazalil imidazole fungicide 3.82 1.58E-01 imidacloprid neonicotinoid insecticide 0.57 4.70E-07 indoxacarb oxadiazine insecticide 4.65 2.50E-05 iprodione dicarboximide fungicide 3 5.00E-04 iprovalicarb carbamate fungicide 3.2 4.40E-05 isophenphos methyl organophosphate insecticide 4 - isoproturon urea herbicide 2.5 3.15E-03 kresoxim methyl oximinoacetate fungicide 3.4 2.30E-03 lambda cyhalothrin pyrethrin insecticide 7 2.00E-04 malaoxon organophosphate metabolite 2.07 malathion organophosphate insecticide 2.75 5.30E+00 mecarbam organophosphate insecticide 2.31 neglible mepanipyrim anilinopyrimidine fungicide 3.28 2.32E-02 metalaxyl M acylalanine fungicide 1.71 3.30E+00 metamitron triazinone herbicide 0.83 8.60E-04 metconazole triazole fungicide 3.85 2.10E-05 methacrifos organophosphate insecticide 3 - methidathion organophosphate insecticide 2.2 2.50E-01 methiocarb carbamate insecticide 3.08 1.50E-02 methomyl carbamate insecticide 0.093 7.20E-01 methoxyfenozide diacylhydrazine insecticide 3.7 1.48E-03 metoxuron urea herbicide 1.6 4.30E+00 metribuzin triazinone herbicide 1.6 5.80E-02 metsulfuron methyl sulfonylurea herbicide 0.018 3.30E-07 monocrotophos organophosphate insecticide -0.22 2.90E-01 monolinuron urea herbicide 2.2 1.30E+00 myclobutanil triazole fungicide 2.94 2.13E-01 napropamaide alkanamide herbicide 3.3 5.30E-01 nicosulfuron sulfonylurea herbicide -0.36 8.00E-07 omethoate organophosphate insecticide -0.74 3.30E+00 oxadiazon oxadiazole herbicide 4.91 1.00E-01 oxadixyl oxazolidinone fungicide 0.65 3.30E-03 oxyfluorfen diphenyl ether herbicide 4.47 2.67E-02 plant growth paclobutazol triazole regulator 3.11 1.00E-03 parathion organophosphate insecticide 3.83 8.90E-01 parathion methyl organophosphate insecticide 3 2.00E-01 penconazole triazole fungicide 3.72 1.70E-01 pencycuron phenylurea fungicide 4.68 5.00E-07 pendimethalin dinitroaniline herbicide 5.2 1.94E+00 pentachloroaniline organochlorine metabolite 4.86 permethrin pyrethrin insecticide 6.1 2.00E-03 phenthoate organophosphate insecticide 3.69 5.30E+00 phosalone organophosphate insecticide 4.01 6.00E-02 phosmet organophosphate insecticide 2.95 6.50E-02 phoxim organophosphate insecticide 4.104 1.80E-01 pirimicarb carbamate insecticide 1.7 4.00E-01 pirimicarb desmethyl carbamate metabolite 0.42 - pirimiphos methyl organophosphate insecticide 4.2 2.00E+00 primisulfuron methyl sulfonylurea herbicide 0.2 5.00E-03 prochloraz imidazole fungicide 4.12 1.50E-01 profenofos organophosphate insecticide 4.44 1.24E-01 prometryn triazine herbicide 4.1 1.65E-01 propachlor chloroacetamide herbicide 1.85 1.00E+01 propamocarb carbamate fungicide 0.84 3.85E-02 propargite other acaricide 5.7 4.00E-02 propiconazole triazole fungicide 3.72 2.70E-02 propyzamide benzamide herbicide 3.1 5.80E-02 prothiofos organophosphate insecticide 5.67 3.00E-01 pyraclostrobin methoxycarbamate fungicide 3.99 2.60E-05 pyrazophos phosphorothiolate fungicide 3.8 2.20E-01 pyridaben other insecticide 6.37 1.00E-02 pyrifenox pyridine fungicide 3.4 1.70E+00 pyrimethanil anilinopyrimidine fungicide 2.84 2.20E+00 pyriproxyfen other insecticide 5.37 1.30E-02 quinoxyfen quinoline fungicide 4.66 1.20E-02 quizalofop aryloxyphenoxypropionate acid herbicide 4.28 - quizalofop-P-ethyl aryloxyphenoxypropionic ester herbicide 4.61 8.65E-04 resmethrin pyrethrin insecticide 5.43 - rimsulfuron sulfonylurea herbicide 0.288 1.50E-03 simazine triazine herbicide 2.1 2.94E-03 s-metolachlor chloroacetamide herbicide 3.05 3.70E+00 sulcotrione triketone herbicide -1.7 5.00E-03 tau-fluvalinate pyrethrin insecticide 4.26 9.00E-08 tebuconazole other fungicide - tebufenozide diacylhydrazine insecticide 4.25 1.56E-04 tebufenpyrad other acaricide 5.04 1.00E-02

tecnazene aromatic hydrocarbon fungicide 4 2.40E+02 tefluthrin pyrethrin insecticide 6.4 8.40E+00 terbuthylazine triazine herbicide 3.21 1.50E-01 tetraconazole triazole fungicide 3.56 1.80E-01 tetradifon other acaricide 4.61 9.40E-07 thiabentazole benzimidazole fungicide 2.39 4.60E-04 thiacloprid neonicotinoid insecticide 1.26 3.00E-07 thiamethoxam neonicotinoid insecticide -0.13 6.60E-06 thifensulfuron methyl sulfonylurea herbicide 1.06 1.70E-05 thiodicarb oxime carbamate insecticide 1.62 5.70E+00

tolclofos methyl aromatic hydrocarbon fungicide 4.56 5.70E+01 tolyfluanid sulfamide fungicide 3.9 2.00E-01 triadimefon triazole fungicide 3.11 2.00E-02 triadimenol triazole fungicide 3.08 6.00E-04 triazophos organophosphate insecticide 3.34 3.90E-01 trifloxystrobin oximinoacetate fungicide 4.5 3.40E-03 trifluralin dinitroaniline herbicide 4.83 6.10E+00 triticonazole triazole fungicide 3.29 1.00E-05 vinclozolin dicarboximide fungicide 3 1.30E-01 zoxamide benzamide fungicide 3.76 1.00E-02

Table 2S: PCB congener number, IUPAC name and pKow for the studied PCBs PCB Congener IUPAC name pKow PCB-1 2-Chlorobiphenyl 4.46 PCB-11 3,3'-Dichlorobiphenyl 5.28 PCB-28a 2,4,4'-Trichlorobiphenyl 5.67 PCB-47 2,2',4,4'-Tetrachlorobiphenyl 5.85 PCB-52a 2,2',5,5'-Tetrachlorobiphenyl 5.84 PCB-101a 2,2',4,5,5'-Pentachlorobiphenyl 6.64 PCB-117 2,3,4',5,6-Pentachlorobiphenyl 6.46 PCB-118b 2,3',4,4',5-Pentachlorobiphenyl 6.74 PCB-138a 2,2',3,4,4',5'-Hexachlorobiphenyl 6.83 PCB-153a 2,2',4,4',5,5'-Hexachlorobiphenyl 6.92 PCB-180a 2,2',3,4,4',5,5'-Heptachlorobiphenyl 7.36 PCB-185 2,2',3,4,5,5',6-Heptachlorobiphenyl 7.11 PCB-209 Decachlorobiphenyl 8.18 a Indicators PCBs b Dioxin like PCB

Table 3S: Retention time (tR), quantification and qualification ion transitions, capillary voltage (CV) and collision energy (CE) for pesticides analysed in LC-MS/MS and GC-MS/MS systems Quantification Qualification Analyte t (min) CV(V) CE(eV) CV(V) CE(eV) R Ion transitions Ion transitions LC-MS/MS acetamiprid 13.5 223.0 -> 126.0 36 27 223.0 -> 90.0 90 51 acetochlor 23.2 270-> 224 55 15 270-> 148 55 15 aclonifen 23.6 265.0 -> 248.0 135 15 265.0 -> 182.0 135 15 alachlor 22.7 270.0 -> 162.0 31 25 270.0 -> 238.0 31 25 aldicarb sulfone 7 240.0 -> 86.0 40 15 240.0 -> 148.0 25 25 ametryn 18.2 228.1 -> 186.2 36 25 228.1 -> 96.1 36 25 atrazine 18.1 216.1 -> 174.0 21 25 216.1 -> 103.9 21 27 azimsulfuron 20 425.1 -> 182.1 31 23 425.1 -> 156.1 31 43 azinphos ethyl 23.5 346.0 -> 132.2 135 15 346.0 -> 160.2 135 15 azinphos methyl 19.5 318.0 -> 132.2 16 23 318.0 -> 160.0 16 13 azoxystrobin 19.9 404.1 -> 371.9 36 19 404.1 -> 343.9 36 29 benalaxyl 24.3 326.2 -> 148.2 26 27 326.2 -> 208.2 26 21 benfuracarb 26.8 411.0 -> 252.0 135 25 411.0 -> 195.0 35 25 bensulfuron methyl 19.6 411.1 -> 148.9 51 27 411.1 -> 119.0 51 51 benzoxymate 25.1 364.0 -> 199.0 135 15 364.0 -> 105.0 135 15 boscalid 22.2 343.0 -> 140.0 27 44 343.0 -> 307.0 27 44 bromophos ethyl 30.4 395.0 -> 339.0 135 25 395.0 -> 367.0 135 25 bromuconazole 21.6 378.0 -> 159.0 46 30 378.0 -> 70.0 46 15 bupirimate 22.2 317.1 -> 166.1 95 35 317.1 -> 108.1 95 35 buprofezin 28.4 306.0 -> 201.0 40 21 306.0 -> 116.0 40 17 caduzafos 27 271.1 -> 97.0 35 15 271.1 -> 159.0 45 25 carbofuran 15.9 222.0 -> 123.0 21 15 222.0 -> 165.0 21 15 chlorfenvinfos 24.8 358.9 -> 99.2 65 35 358.9 -> 155.0 75 15 chlorobromuron 22 292.9 -> 182.1 51 23 292.9 -> 204.0 36 45 chlorpyriphos ethyl 28.4 350.0 -> 198.0 21 20 350.0 -> 125.0 21 20 chlorsulfuron 16.8 358.0 -> 167.0 135 25 358.0 -> 141.0 135 25 chlortoluron 17.8 213.1 -> 140.0 36 33 213.1 -> 72.0 36 33 clofentezine 26.5 303.0 -> 138.0 56 15.5 303.0 -> 102.0 56 47 clothianidin 9.87 250.0 -> 169.0 90 5 250.0 -> 132.0 90 15 cyproconazole 21.3 292.1 -> 70.2 16 35 292.1 -> 125.1 16 35 cyprodinil 23 226.0 -> 93.0 170 30 226.0 -> 77.0 170 70 desethylterbuthylazine 14.8 202.0 -> 146.0 135 25 202.0 -> 104.0 135 25 desmetryn 16.9 214.0 -> 82.0 135 15 214.0 -> 172.0 135 15 diazinon 24.3 305.1 -> 169.1 21 29 305.1 -> 96.6 21 41 difenoconazole 27.0 406.1 -> 250.9 41 37 406.1 -> 337.0 41 23 dimethenamide-P 20.1 276.0 -> 244.0 35 15 276.0 -> 168.0 35 15 dimethoate 12.0 230.0 -> 125.0 11 29 230.0 -> 199.0 11 13 dimethomorph 21.0 388.0 -> 165.0 60 17 388.0 -> 301.0 60 28 diniconazole 25.5 326.0 -> 70.0 135 15 326.0 -> 159.0 135 15 disulfoton sulfone 17.8 307.0 -> 97.0 65 15 307.0 -> 261.0 65 15 diuron 19.5 235.0 -> 72.0 120 40 235.0 -> 160.0 120 40 dodemorph 19 282.0 -> 98.0 72 16 282.0 -> 116.0 72 22 epoxiconazole 22.6 330.1 -> 121.0 36 27 330.1 -> 101.2 36 63 ethion 28.0 385.0 -> 199.0 135 15 385.0 -> 171.0 135 15 ethofumesate 20.1 304.0 -> 121.1 36 27 304.0 -> 161.2 36 31 ethoprophos 23.5 243.0 -> 97.0 45 25 243.0 -> 131.0 45 35 etoxazole 28.9 360.0 -> 141.0 66 37 360.0 -> 113.0 66 50 fenamidone 20.3 312.0 -> 92.0 41 33 312.0 -> 236.0 41 19 fenamiphos 24.5 304.1 -> 202.0 135 25 304.1 -> 217.1 135 25 fenamiphos sulfone 16.3 336.0 -> 266.0 135 25 336.0 -> 188.0 135 25 fenarimol 22.2 331.0 -> 268.0 46 31 331.0 -> 81.0 46 35 fenazaquin 31.5 307.0 -> 161.0 135 25 307.0 -> 147.0 135 25 fenbuconazole 22.9 337.0 -> 125.0 41 37 337.0 -> 70.0 41 33 fenhexamide 22.0 302.0 -> 97.0 35 25 302.0 -> 55.0 35 25 fenitrothion 21.6 278.1 -> 125.0 41 39 278.1 -> 108.9 41 35 fenoxycarb 24.0 302.0 -> 88.0 21 20 302.0 -> 116.0 21 12 fenpyroximate 31.0 422.0 -> 366.0 15 20 422.0 -> 135.0 15 41 fensulfothion 18.3 309.0 -> 253.0 150 25 309.0 -> 173.0 150 25 fensulfothion oxon 14.0 293.0 -> 237.0 65 35 293.0 -> 265.0 75 35 fensulfothion oxon sulfone 14.5 309.0 -> 253.0 65 25 309.0 -> 175.0 65 45 fensulfothion sulfone 18.8 325.0 -> 269.0 26 11 325.0 -> 297.0 26 16 fenthion 25.5 279.0 -> 247.0 41 10 279.0 -> 169.0 41 23 fenthion sulfone 11.8 311.0 -> 125.0 135 25 311.0 -> 109.0 135 25 fluazifop 27.0 328.0 -> 282.0 60 30 328.0 -> 328.0 60 30 flucythrinate 29.0 469.0 -> 199.0 135 25 469.0 -> 181.0 135 25 fluometuron 27.1 233.0->72.0 135 25 233.0->160.0 135 25 fluquinconazole 22.0 376.0 -> 349.0 130 30 376.0 -> 307.1 130 30 flusilazole 24.5 316.1 -> 165.0 85 25 316.1 -> 247.1 95 45 flutriafol 18.0 302.1 -> 122.9 41 39 302.1 -> 109.0 41 43 foramsulfuron 16.1 453.0->182.0 135 25 453.0->139.0 135 25 fosthiazate 17.3 284.0 -> 104.0 61 15 284.0 -> 228.0 61 27 furathiocarb 28.5 383.0 -> 195.0 51 23.5 383.0 -> 252.0 51 19 haloxyfop ethyl ester 28.0 434.0 -> 288.0 150 25 434.0 -> 288.0 150 25 haloxyfop methoxyethyl ester 25.8 376.0 -> 288.0 65 35 376.0 -> 316.0 75 45 hexaconazole 24 314.0 -> 70.0 30 20 314.0 -> 159.0 26 30 hexythiazox 29.5 353.0 -> 168.0 60 20 353.0 -> 228.0 60 30 imazalil 17.3 297.0 -> 159.0 135 30 297.0 -> 109.0 135 30 imidacloprid 12.5 256.0 -> 209.0 45 20 256.0 -> 175.0 45 25 indoxacarb 26.8 528.0 -> 293.0 76 15 528.0 -> 218.0 76 38 iprovalicarb 22.5 321.0 -> 119.0 51 23 321.0 -> 203.0 51 20 isophenphos methyl 23.8 332.0 -> 231.0 70 5 332.0 -> 199.0 70 30 isoproturon 17.9 207.0 -> 72.0 135 35 207.0 -> 165.0 135 35 kresoxim methyl 23.9 314.1 -> 115.9 16 21 314.1 -> 206.1 16 13 malaoxon 16.2 315.0 -> 99.2 31 17 315.0 -> 127.0 31 31 malathion 21.1 331.0 -> 99.0 26 29 331.0 -> 127.0 26 17 mecarbam 22.3 330.0 -> 97.0 135 25 330.0 -> 199.0 135 25 mepanipyrim 23.0 224.0 -> 77.0 40 49 224.0 -> 106.0 40 20 metalaxyl M 18.3 280.1 -> 159.9 46 19 280.1 -> 220.0 46 31 metamitron 11.7 203.1 -> 104.1 46 29 203.1 -> 175.0 46 29 metconazole 25.8 320.1 -> 125.0 48 23 320.1 -> 69.4 48 45 methacrifos 20.0 241.0 -> 125.0 135 15 241.0 -> 209.0 135 15 methidathion 19.0 303.0 -> 145.0 130 5 303.0 -> 85.0 130 5 methiocarb 20.3 243.0 -> 169.0 150 25 243.0 -> 169.0 150 25 methomyl 9.6 163.0 -> 88.0 15 10 163.0 -> 106.0 8 8 methoxyfenozide 21.2 369.0 -> 149.0 36 23 369.0 -> 133.0 36 41 metoxuron 14.1 229.0 -> 72.1 296 31 229.0 -> 156.1 26 35 metribuzin 15.2 215.0 -> 84.0 135 50 215.0 -> 74.0 135 50 metsulfuron methyl 16.1 382.1 -> 167.0 31 27 382.1 -> 198.9 31 21 monocrotophos 7.7 224.0 -> 98.0 40 20 224.0 -> 127.0 40 17 monolinuron 17 215.1 -> 148.0 61 25 215.1 -> 125.9 61 19 myclobutanil 21.4 289.0 -> 125.0 36 41 289.0 -> 70.0 36 33 napropamaide 22.1 272.0->171.0 135 25 272.0->129.0 135 25 nicosulfuron 16.2 411.1 -> 182.1 61 25 411.1 -> 213.0 61 23 omethoate 2.5 214.0 -> 109.0 50 30 214.0 -> 125.0 50 35 oxadiazon 29 362.0 -> 220.0 35 25 362.0 -> 177.0 35 25 oxadixyl 14.4 279.1 -> 133.3 46 17 279.1 -> 219.2 46 29 oxyfluorfen 27.1 379.0 -> 237.1 21 33 379.0 -> 316.0 21 29 paclobutazole 20.7 294.0 -> 70.0 150 25 294.0 -> 125.0 150 25 parathion ethyl 24.5 292.0 -> 236.1 51 21 292.0 -> 97.0 51 39 parathion methyl 14.4 264.0 -> 125.0 56 35 264.0 -> 232.1 56 33 penconazole 24.7 284.0 -> 158.9 41 39 284.0 -> 70.1 41 29 pencycuron 27 329.0 -> 125.0 135 25 329.0 -> 218.0 135 25 pendimethalin 29.5 282.0 -> 212.0 80 5 282.0 -> 194.0 80 10 permethrin 31.6 408.1 -> 183.1 31 25 408.1 -> 183.1 31 25 phosalone 25.4 367.9 -> 182.0 41 25 367.9 -> 110.9 41 25 phosmet 19.5 317.9 -> 133.1 31 29 317.9 -> 160.1 31 29 phoxim 25.8 299.0 -> 129.0 35 25 299.0 -> 77.0 35 25 pirimicarb 14.3 239.1 -> 72.1 16 21 239.1 -> 181.9 16 31 pirimicarb desmethyl 9.4 225.0 -> 168.0 135 25 225.0 -> 72.0 135 25 pirimiphos methyl 24.9 306.1 -> 164.1 26 39 306.1 -> 108.1 26 29 primisulfuron methyl 23 469.0 -> 199.0 71 25 469.0 -> 253.8 71 25 procloraz 24.6 376.0 -> 308.0 40 20 376.0 -> 266.0 30 30 profenofos 26.7 373.0 -> 303.0 40 20 373.0 -> 97.0 30 30 prometryn 20.4 242.1 -> 158.1 31 25 242.1 -> 200.2 31 25 propargite 29 368.0 -> 231.0 30 10 368.0 -> 175.0 1 21 propamocarb 2.8 189.0 -> 102.0 30 10 189.0 -> 144.0 30 21 propyconazole 25.5 342.1 -> 159.0 95 15 342.1 -> 69.1 95 15 pyraclostrobin 26 388.0 -> 163.0 11 29 388.0 -> 194.0 11 29 pyrazophos 26.5 374.0 -> 194.0 35 15 374.0 -> 222.0 35 15 pyridaben 30.3 365.0 -> 309.0 64 25 365.0 -> 148.0 64 33 pyrifenox 21.6 295.0 -> 93.1 16 41 295.0 -> 263.1 16 25 pyrimethanil 19.1 200.0 -> 107.0 30 30 200.0 -> 82.0 30 30 pyriproxyfen 29 322.0 -> 96.0 15 21 322.0 -> 185.0 11 29 quiazalofop 23 345.0->299.0 135 25 345.0->163.0 135 25 quizalofop-P-ethyl 27.0 373.0->299.0 135 25 373.0->271.0 135 25 quinoxyfen 28.2 308.0 -> 197.0 25 50 308.0 -> 162.0 25 50 rimsulfuron 16.1 432.0->182 135 25 432.0->325 135 25 s-metolachlor 22.4 284.1->176 135 25 284.1->251.9 135 25 simazine 15.7 202.1 -> 124.2 25 25 202.1 -> 132.2 25 25 sulcotrione 13.0 329.0->139.0 135 25 329.0->111.0 135 25 tebuconazole 24.0 308.0 -> 70.0 30 35 308.0 -> 125.0 30 20 tebufenozide 23.3 353.0 -> 133.0 40 20 353.0 -> 297.0 40 20 tebufenpyrad 28.0 334.0 -> 145.0 75 35 334.0 -> 117.0 75 35 terbuthylazine 21.0 230.1 -> 174.1 44 23 230.1 -> 103.9 44 23 tetraconazole 23.5 372.0 -> 159.0 40 10 372.0 -> 70.0 40 45 thiabentazole 7.5 202.0 -> 175.0 40 30 202.0 -> 131.0 40 30 thiacloprid 12.9 253.0 -> 126.0 81 29 253.0 -> 186.0 76 19 thiamethoxam 9.0 292.0 -> 211.0 51 17 292.0 -> 181.0 56 31 thifensulfuron methyl 15.7 388.0 -> 167.0 36 21 388.0 -> 204.9 36 21 thiodicarb 17.2 355.0 -> 88.0 30 25 355.0 -> 108.0 30 25 toclofos methyl 26.5 301.0 -> 269.0 135 15 301.0 -> 175.0 135 15 tolyfluanid 23.8 364.0 -> 137.1 6 25 364.0 -> 237.9 6 25 triadimefon 21.3 294.0 -> 197.0 28 21 294.0 -> 225.0 28 21 triadimenol 21.2 296.0 -> 70.0 11 9 296.0 -> 227.0 11 9 triazophos 23.3 314.0 -> 162.1 36 25 314.0 -> 119.1 36 25 trifloxystrobin 26.8 409.0 -> 186.0 6 21 409.0 -> 206.0 6 21 triticonazole 23.5 318.0 -> 70.0 135 25 318.0 -> 125.0 135 15 zoxamide 25.5 336.0 -> 187.0 135 35 336.0 -> 159.0 135 35 GC-MS/MS acrinathrin 34.8 181->152 - 20 208->181 - 10 bifenthrin 31.3 181->115 - 20 181->166 - 15 bromopropylate 31.5 185->157 - 15 341->183 - 25 chlorpyrifos methyl 13.3 286->93 - 15 286->63 - 20 chlordane alpha 20.7 373->301 - 15 373->263 - 15 chlordane gamma 23.6 373->301 - 15 373->263 - 15 chlorfenapyr 11.4 59->31 - 15 59->29 - 15 chlorobenzilate 23.5 139->111 - 15 251->139 - 15 chlorothalonil 14.9 266->231 - 15 266->170 - 35 chlorpropham 12.8 127->65 - 10 213->127 - 10 cyfluthrin 34.4 226->151 - 15 165->127 - 15 cypermethrin 37.3 181->127 - 15 181->152 - 15 o, p' - DDD 21.6 235->200 - 15 235->165 - 15 p, p' - DDD 24.3 235->200 - 15 235->165 - 15 o, p' - DDE 18.9 318->248 - 15 246->176 - 15 p, p' - DDE 21.2 318->248 - 15 246->176 - 15 o, p' - DDT 23.7 235->165 - 15 235->200 - 15 p, p' - DDT 24.4 235->200 - 15 235->165 - 15 deltamethrin 40.8 253->172 - 15 253->93 - 15 dicloran 10.2 206->176 - 15 206->148 - 15 p, p' - dicofol 23.7 139->75 - 15 139->111 - 15 dieldrin 21.3 279->243 - 15 344->263 - 25 dinitramine 13.2 305->216 - 15 305->232 - 15 alpha - endosulfan 19.5 170->99 - 25 194.9->124.9 - 20 beta - endosulfan 23.7 240.9->205.9 - 15 194.9->124.9 - 20 endosulfan sulfate 26.8 272->237 - 10 241->206 - 15 esfenvalerate 39.4 419.1->125 - 15 419.1->225.1 - 20 ethalfluralin 8.4 276->202 - 20 316->202 - 20 fenpropathrin 32.4 181->152 - 15 265->210 - 20 fenvalerate 38.9 181->152 - 15 167->125 - 15 alpha - HCH 10.2 219->183 - 15 219->145 - 10 beta - HCH 11.1 219->183 - 15 219->145 - 10 gamma - HCH 11.3 219->183 - 15 219->145 - 10 heptachlor-endo-epoxide 17.5 217->182 - 15 183->155 - 15 heptachlor-exo-epoxide 17.2 217->182 - 15 183->155 - 15 heptachlor 13.5 272->237 - 15 339->267 - 15 iprodione 31.2 314->56 - 35 314->245 - 15 lambda cyhalothrin 34.4 181->152 - 15 181->77 - 15 pentachloroaniline 12.4 263->192 - 15 247->227 - 15 permethrin 35.6+36 183->153 - 15 183->168 - 15 phenthoate 17.6 274->125 - 16 274->246 - 4 profenofos 16.2 337->267 - 15 139.2->97 - 10 propachlor 6 130->77 - 15 176->57 - 15 propyzamide 10.8 173->145 - 15 173->109 - 15 prothiofos 20.4 267->239 - 15 309->239 - 15 resmethrin 33.9 171->128 - 10 171->143 - 10 tau-fluvalinate 39+39.2 250->55 - 15 250->200 - 15 tecnazene 8.2 215->179 - 15 203->143 - 15 tefluthrin 11 177->127 - 15 197->141 - 15 tetradifon 33.5 227->199 - 15 356->159 - 15 trifluralin 8.6 306->264 - 15 306->160 - 15 vinclozolin 14.4 285->212 - 15 212->145 - 15

Table 4S: Retention time and selected ions for the studied PCBs a b b Analyte tR(min) I1 I2 I3

PCB-1 7.9 188 153 102 PCB-11 11.2 222 152 224 PCB-28 13.5 256 258 186 PCB-52 15 292 220 290 PCB-47 15.5 292 220 290 PCB-117 18.5 326 324 256 PCB-101 19.8 326 324 254 PCB-136 22.1 360 290 358 PCB-118 24.4 360 290 358 PCB-153 26 360 290 288 PCB-185 30.5 394 324 392 PCB-180 33.3 396 394 324 PCB-209 38.2 498 496 428 a: ion used for quantification purposes

b ions used for confirmation purposes