Analysis of Endocrine Disrupting Pesticides by Capillary GC with Mass Spectrometric Detection
Abstract
:1. Introduction
2. Definition and Characteristics of EDPs
Chemical group | Pesticide | CAS | Year | Exposure |
---|---|---|---|---|
Benzoic acid derivatives | Methyl p-Hydroxybenzoate | 99-76-3 | DHI 2006 | Medium |
Ethyl 4-hydroxybenzoate | 120-47-8 | DHI 2006 | Medium | |
n-Propyl p-hydroxybenzoate | 94-13-3 | DHI 2006 | Medium | |
Carbamates | Carbaryl | 63-25-2 | BKH 2002 | High |
DDT derivatives and metabolites | DDT (technical), (clofenotane) | 50-29-3 | EM 1999 | High |
o,p’-DDT | 789-02-6 | BKH 2002 | High | |
3-OH- o,p’-DDT | 43216-70-2 | BKH 2002 | High | |
4-MeO- o,p’-DDT | 65148-72-3 | BKH 2002 | High | |
5-OH- o,p’-DDT | 65148-73-4 | BKH 2002 | High | |
5-MeO- o,p’-DDT | 65148-74-5 | BKH 2002 | High | |
p,p’-DDT (clofenotane) | 50-29-3 | EM 1999 | High | |
o,p’-DDD | 53-19-0 | BKH 2002 | High | |
5-MeO- o,p’-DDD | 65148-75-6 | BKH 2002 | High | |
p,p’-DDD | 72-54-8 | BKH 2002 | High | |
m,p’-DDD | 4329-12-8 | BKH 2002 | High | |
o,p’-DDE | 3424-82-6 | BKH 2002 | High | |
3-MeO- o,p’-DDE | 65148-80-3 | BKH 2002 | High | |
4-MeO- o,p’-DDE | 65148-81-4 | BKH 2002 | High | |
5-MeO- o,p’-DDE | 65148-82-5 | BKH 2002 | High | |
p,p’-DDE | 72-55-9 | BKH 2002 | High | |
o,p’-DDA-glycinate | 65148-83-6 | BKH 2002 | High | |
o,p’-DDMU | 14835-94-0 | BKH 2002 | High | |
1,1,1,2-Tetrachloro-2,2-bis(4-chlorophenyl) ethane (tetrachloro DDT) | 3563-45-9 | EM 1999 | High | |
1,1,1-Trichloro-2,2-bis(4-chlorophenyl) ethane | 2971-22-4 | BKH 2002 | High | |
Dicarboximides | Procymidon | 32809-16-8 | BKH 2002 | High |
Vinclozolin | 50471-44-8 | EM 1999 | High | |
Dinitroanilines | Trifluralin | 1582-09-8 | DHI 2006 | High |
Diphenyl ether | Nitrofen | 1836-75-5 | EM 1999 | Medium |
Dithiocarbamates | Mancozeb | 8018-01-7 | BKH 2002 | High |
Maneb | 12427-38-2 | EM 1999 | High | |
Metam Natrium | 137-42-8 | EM 1999 | High | |
Dithiocarbamates | Metiram (Metiram-complex) | 9006-42-2 | BKH 2002 | High |
Thiram | 137-26-8 | EM 1999 | High | |
Zineb | 12122-67-7 | EM 1999 | High | |
Formamidine | Chlordimeform | 6164-98-3 | DHI 2006 | Low |
Chlorinated Phenol | Pentachlorophenol (PCP) | 87-86-5 | EM 2002 | High |
Chloroacetanilide | Acetochlor | 34256-82-1 | EM 1999 | High |
Alachlor | 15972-60-8 | EM 1999 | High | |
Chlorophenoxy acid | 2,4-dichlorophenoxybutyric acid (2,4-DB) | 94-82-6 | BKH 2002 | - |
Halogenated organic | Dibromoethane (EDB) | 106-93-4 | BKH 2002 | Medium |
Dibromochloropropane (DBCP) | 96-12-8 | DHI 2006 | - | |
HCH and isomers | Hexachlorocyclohexane | 608-73-1 | BKH 2002 | - |
Beta-HCH | 319-85-7 | BKH 2002 | High | |
Gamma-HCH (Lindane) | 58-89-9 | EM 1999 | High | |
Hydroxybenzonitrile | Ioxynil | 1689-83-4 | BKH 2002 | Medium |
Methoxychlor and derivatives | Methoxychlor | 72-43-5 | BKH 2002 | High |
p,p’-Methoxychlor | 72-43-5 | BKH 2002 | - | |
Bis-OH-Methoxychlor | 2971-36-0 | BKH 2002 | High | |
1,3-Dichloro-2,2-bis(4-methoxy-3-methylphenyl)propane | 30668-06-5 | BKH 2002 | - | |
Organochlorine | Chlordane | 12789-03-6 | EM 1999 | High |
Chlordane ( cis- and trans-) | 57-74-9 | EM 1999 | High | |
Cis-Nonachlor | 5103-73-1 | BKH 2002 | - | |
Hexachlorobenzene (HCB) | 118-74-1 | EM 1999 | High | |
Kepone (Chlordecone) | 143-50-0 | EM 1999 | High | |
Mirex | 2385-85-5 | EM 1999 | High | |
Toxaphene (Camphechlor) | 8001-35-2 | EM 1999 | High | |
Trans-Nonachlor | 39765-80-5 | BKH 2002 | - | |
Organotin | 2-propenoic acid, 2-methyl-, methyl ester (Stannane, tributylmeacrylate) | 26354-18-7 | EM 1999 | High |
Fentin acetate (triphenyltin acetate) | 900-95-8 | EM 1999 | High | |
Stannane, tributyl[(1-oxo-9,12-octadeca dienyl)oxy]-, (Z,Z)- | 24124-25-2 | EM 1999 | High | |
Stannane, tributyl[[[1,2,3,4,4a,4b,5,6,10,10a-decahydro-1,4a-dimethyl-7-(1-methylethyl)-1-phenanthrenyl]carbonyl]oxy]-,[1R-(1a,4ab,4ba,10aa)]- | 26239-64-5 | EM 1999 | High | |
Stannane, (benzoyloxy)tributyl- | 4342-36-3 | EM 1999 | High | |
Stannane, tributylfluoro- | 1983-10-4 | EM 1999 | High | |
Phenol, 2-[(tributylstannyl)oxy]carbony | 4342-30-7 | EM 1999 | High | |
Tributyl[(2-methyl-1-oxo-2-propenyl)oxy] stannane | 2155-70-6 | EM 1999 | High | |
Organophosphorous | Fenitrothion | 122-14-5 | EM 1999 | High |
Omethoate | 1113-02-6 | DHI 2006 | Low | |
Organothiophosphor | Quinalphos (Chinalphos) | 13593-03-8 | DHI 2006 | Medium |
Pyrethroids | Bifenthrin | 82657-04-3 | BKH 2002 | High |
Cyhalothrin | 91465-08-6 | BKH 2002 | High | |
Deltamethrin | 52918-63-5 | BKH 2002 | High | |
Resmethrin | 10453-86-8 | BKH 2002 | High | |
Pyrimidines and Pyridines | Fenarimol | 60168-88-9 | BKH 2002 | High |
Pyridinecarboxylic acid | Picloram | 1918-02-1 | BKH 2002 | Medium |
Triazines and Triazoles | Amitrol (Aminotriazole) | 61-82-5 | EM 1999 | Medium |
Atrazine | 1912-24-9 | EM 1999 | - | |
Metribuzin | 21087-64-9 | BKH 2002 | High | |
Ketoconazol | 65277-42-1 | BKH 2002 | High | |
Terbutryn | 886-50-0 | BKH 2002 | Medium | |
Urea | Linuron (Lorox) | 330-55-2 | EM 1999 | High |
Other pesticides | Ethylene Thiourea (ETU) | 96-45-7 | DHI 2006 | Low |
Chemical group | Pesticide | CAS | Year |
---|---|---|---|
Alkyl Phthalate | Diisobutylphthalate | 84-69-5 | DHI 2006 |
Anilide | Propanil | 709-98-8 | EM 1999 |
Azole | Etridiazole | 2593-15-9 | BKH 2002 |
Prochloraz | 67747-09-5 | EM 1999 | |
Triadimefon | 43121-43-3 | EM 1999 | |
Triadimenol | 123-88-6 | BKH 2002 | |
Benzimidazole | Carbendazim | 10605-21-7 | EM 1999 |
Carbamates | Aldicarb | 116-06-3 | BKH 2002 |
Carbofuran | 1563-66-2 | BKH 2002 | |
Fenoxycarb | 72490-01-8 | BKH 2002 | |
Methomyl | 16752-77-5 | BKH 2002 | |
DDT derivatives and metabolites | p,p’-DDA | 83-05-6 | DHI 2006 |
Dicarboximide | Iprodione | 36734-19-7 | EM 1999 |
Dithiocarbamate | Ziram | 137-30-4 | EM 1999 |
Halogenated organic | Methyl bromide (bromomethane) | 74-83-9 | EM 1999 |
HCH isomers | Delta-HCH | 319-86-8 | BKH 2002 |
Hydroxybenzonitrils | Bromoxynil | 1689-84-5 | BKH 2002 |
Chlorinated Phenol | 4-Chloro-3-methylphenol | 59-50-7 | EM 1999 |
4-Chloro-2-methylphenol | 1570-64-5 | EM 1999 | |
Chlorophenoxy acid | 2,4,5-Trichlorophenoxyacetic acid (2,4,5-T) | 93-76-5 | BKH 2002 |
2,4-Dichlorophenoxyacetic acid (2,4-D) | 94-75-7 | EM 1999 | |
Organochlorine | Aldrin | 309-00-2 | EM 1999 |
Dicofol (Kelthane) | 115-32-2 | EM 1999 | |
Dieldrin | 60-57-1 | EM 1999 | |
Endrin | 72-20-8 | EM 1999 | |
Endosulfan | 115-29-7 | EM 1999 | |
Endosulfan-alpha | 959-98-8 | EM 1999 | |
Endosulfan-beta | 33213-65-9 | EM 1999 | |
Heptachlor | 76-44-8 | EM 1999 | |
Oxychlordane | 27304-13-8 | EM 1999 | |
Organophosphorous | Acephate | 30560-19-1 | BKH 2002 |
Elsan (Dimephenthoate) | 2597-03-7 | DHI 2006 | |
Diazinon | 333-41-5 | EM 1999 | |
Dimethoate | 60-51-5 | EM 1999 | |
Chlorfenvinphos | 470-90-6 | BKH 2002 | |
Malathion | 121-75-5 | EM 1999 | |
Methylparathion | 298-00-0 | EM 1999 | |
Mevinphos (Phosdrin) | 7786-34-7 | BKH 2002 | |
Parathion (Parathion-ethyl) | 56-38-2 | EM 1999 | |
Phosophamidon | 13171-21-6 | BKH 2002 | |
Trichlorfon (Dipterex) | 52-68-6 | BKH 2002 | |
Phenol | p-Cresol | 106-44-5 | DHI 2006 |
4-Nitrophenol | 100-02-7 | DHI 2006 | |
o-Phenylphenol | 90-43-7 | EM 1999 | |
Pyrethrins | Pyrethrin | 121-29-9 | DHI 2006 |
Pyrethroids | Allethrin (d-trans-allethrin) | 584-79-2 | BKH 2002 |
Cypermethrin | 52315-07-8 | BKH 2002 | |
Fenothrin (sumithrin) | 26002-80-2 | BKH 2002 | |
Fenvalerate | 51630-58-1 | BKH 2002 | |
Fluvalinate | 69409-94-5 | BKH 2002 | |
Permethrin | 52645-53-1 | BKH 2002 | |
Triazines | Cyanazine | 21725-46-2 | BKH 2002 |
Prometryn | 7287-19-6 | BKH 2002 | |
Simazine | 122-34-9 | EM 1999 | |
Urea | Diuron | 330-54-1 | EM 1999 |
Other pesticides | Piperonyl butoxide | 51-03-6 | BKH 2002 |
Photomirex | 39801-14-4 | EM 1999 |
Chemical group | Category | Pesticide | CAS No. | Year |
---|---|---|---|---|
Azoles | 3b | Fenbuconazole | 114369-43-6 | DHI 2006 |
3a | Imazalil | 3554-44-0 | BKH 2002 | |
3a | Benomyl | 17804-35-2 | BKH 2002 | |
3b | Bitertanol | 55179-31-2 | BKH 2002 | |
3b | Cyproconazole | 94361-07-6 | BKH 2002 | |
Azoles | 3b | Difenoconazole | 119446-68-3 | BKH 2002 |
3b | Epiconazole | 121 | BKH 2002 | |
3b | Epoxiconazole | 135319-73-2 | BKH 2002 | |
3b | Flutriafol | 76674-21-0 | BKH 2002 | |
3b | Myclobutanil | 88671-89-0 | BKH 2002 | |
3b | Penconazole | 66246-88-6 | BKH 2002 | |
3b | Propiconazole | 60207-90-1 | BKH 2002 | |
3b | Fipronil | 120068-37-3 | BKH 2002 | |
3b | Tebuconazole | 107534-96-3 | BKH 2002 | |
2,6-Dinitroanilines | 3a | Oryzalin | 19044-88-3 | BKH 2002 |
3a | Pendimethalin | 40487-42-1 | BKH 2002 | |
3b | Prodiamine | 29091-21-2 | BKH 2002 | |
Formamidine | 3a | Amitraz | 33089-61-1 | BKH 2002 |
Organochlorine | 3a | Heptachlor-epoxide | 1024-57-3 | BKH 2002 |
Organophosphorus Phosphonoglycine Uracil | 3a | Demeton-s-methyl | 919-86-8 | BKH 2002 |
3a | Dichlorvos | 62-73-7 | BKH 2002 | |
3a | Chlorpyrifos | 2921-88-2 | BKH 2002 | |
3a | Oxydemeton-methyl | 301-12-2 | BKH 2002 | |
3a | Ronnel (fenchlorfos) | 299-84-3 | BKH 2002 | |
3a | Tetrachlorvinphos (Gardona) | 22248-79-9 | BKH 2002 | |
3b | Demefion | 682-80-4 | DHI 2006 | |
3b | Formothion | 2540-82-1 | DHI 2006 | |
Amide | 3a | Glyphosate | 1071-83-6 | BKH 2002 |
Aryloxyphenoxy propionic acid | 3a | Bromacil | 314-40-9 | DHI 2006 |
Bipyridylium | 3b | Pronamide | 23950-58-5 | BKH 2002 |
Dinitrophenol and derivatives | 3b | Fluazifop-butyl | 69806-50-4 | BKH 2002 |
3b | Paraquat | 4685-14-7 | BKH 2002 | |
Dithiocarbamate Organochlorine | 3b | Dinitrophenol | 25550-58-7 | DHI 2006 |
3b | Dinoseb | 88-85-7 | BKH 2002 | |
Organophosphorus | 3b | Nabam | 142-59-6 | BKH 2002 |
3b | Octachlorostyrene | 29082-74-4 | BKH 2002 | |
Phosphonoglycine | 3b | Glufosinate-ammonium | 70393-85-0 | DHI 2006 |
Pyridinecarboxylic acid | 3b | Thiazopyr | 117718-60-2 | BKH 2002 |
Pyrethroid | 3b | Esfenvalerate | 66230-04-4 | BKH 2002 |
Substituted Benzene | 3b | Pentachloronitrobenzene (Quintozene) | 82-68-8 | BKH 2002 |
Tetrazine | 3b | Clofentezine (chlorfentezine) | 74115-24-5 | BKH 2002 |
Thiocarbamate | 3b | Molinate | 2212-67-1 | BKH 2002 |
Other pesticides | 3a | Azadirachtin | 11141-17-6 | BKH 2002 |
3a | Abamectin | 71751-41-2 | BKH 2002 | |
3a | Diphenyl | 92-52-4 | BKH 2002 | |
3a | Glufosinate | 51276-47-2 | BKH 2002 | |
3a | Chlordene | 3734-48-3 | BKH 2002 | |
3b | Dimethylformamide (DMFA) | 68-12-2 | BKH 2002 | |
3b | Ethofenprox | 80844-07-1 | BKH 2002 |
3. Analysis of EDPs
3.1. Conventional Capillary GC with MS Detection
3.1.1. Sample Matrix and Sample Preparation
Analytes | Matrix | Sample preparation | Injection technique | LOD | Separation & detection | Ref. | |
---|---|---|---|---|---|---|---|
23 pesticides | apples | QuEChERS | PTV, SVV | EI: 0.09–3.12 µg/kg | GC-QMS (SIM) | [45] | |
NCI: 1.9–935 ng/kg | NCI, EI | ||||||
25 pesticides | apples | QuEChERS | PTV, SVV | EI: 0.02–6.32 µg/kg | fast GC-QMS (SIM) | [46] | |
NCI: 0.15–619.3 ng/kg | NCI, EI | ||||||
20 OCPs | 9 vegetable matrices | SBSE (PDMS 47 µL) | LVI-PTV, SVV | <10 µg/kg | GC-QMS (SIM) | [47] | |
EI | |||||||
29 pesticides | fruit and vegetables | QuEChERS | PTV, SVV | ≤5 µg/kg | fast GC-QMS (SIM) | [48][49] | |
EI | |||||||
35 pesticides | fruit and vegetables | QuEChERS | PTV, SVV | EI: ≤5 µg/kg, | fast GC-QMS (SIM) | [50] | |
NCI: ≤1 µg/kg | EI, NCI | ||||||
9 pesticides, phtalates, 1 PAH | water | on-line SPE | on-column, retaining precolumn, SVV | 0.1–20 ng/L | GC-QMS (FS) | [51] | |
EI | |||||||
11 pesticides, phthalates | water | on-line SPE | LVI-PTV, SVV | 1–36 ng/L | GC-QMS (FS) | [52] | |
EI | |||||||
HCB, atrazine, lindane, vinclozolin, malathion, aldrin, α-endosulfan, 4,4´-DDE, dieldrin, endrin, 4,4´-DDT | river water | SBSE (PDMS 63 µL) | split/splitless, LVI-PTV, SVV | 0.01–0.24 µg/L | GC-QMS (FS), EI | [53] | |
15 herbicides, 7 OPPs, 17 OCPs | water | SBSE (PDMS 47 µL) | PTV, SVV | 0.025–0.400 µg/L | GC-QMS (SIM)EI | [54] | |
32 EDCs and pesticides | water | SPE (LiChrolut EN/RP-18, Strata X) | splitless | 5.3–95.9 ng/L | GC-MS/MS (MRM), EI, quad., | [55] | |
58 potential EDCs and PPCPs (18 pesticides) | drinking water, surface, ground, waste water (raw and treated) | SPE (HLB), LLE | 1. splitless2. valve | 1–10 ng/L | 1. GC-MS/MS, EI, IT; 2. LC-MS/MS, ESI+, ESI–, APCI, triplequad. (MRM) | [56]] | |
6 EDC herbicides and 3 degrade. products | natural surface water | SPE (Bond Elut-ENV) | splitless | 2.3–115 ng/L | GC-QMS (SIM)EI | [57] | |
OPPs, OCPs, herbicides, PAHs, PCBs, phenols, organotins | estuarine and coastal water, sediments | SPE (Supelclean ENVI-18) | LVI-PTV, SVV | 10–250 µg/L | GC-QMS (SIM, FS) | [15] | |
EI | |||||||
1. 5 OCPs | wastewaters, surface and ground waters | SPE | 1. PTV, SVV;2. valve | 0.2 and 88.9 ng/L | 1. GC-QMS | [58] | |
2. 33 multi-class pollutants | 2. LC-MS/MS | ||||||
EDCs (1 pesticide), carbamazepine, pharmaceuticals | wastewater irrigated soil | ASE, isolation SPE (Oasis HLB) | splitless | 0.25–2.5 ng/g | GC-QMS (SIM, FS) | [59] | |
EI | |||||||
PBDEs, PCBs, insecticides, phthalates | indoor dust from vacuum cleaner | Soxhlet extraction, alumina cleaning | n. r. | 3–10 ng/g | GC-QMS (SIM) | [60] | |
EI | |||||||
18 OCPs | placenta samples from woman | SLE (Alumine), purification - preparative LC | n.r. | n.r. | GC-ECD | [61] | |
GC-MS, IT | |||||||
dicofol, DDTs | human milk | LLE, GPC | splitless | 0.1–0.2 ng/g | GC-MS (SIM) | [62] | |
EI | |||||||
OCPs, PCBs | Serum samples | SPE (C18), silica gel/florisil SPE cleaning | splitless | 0.4–12.0 ng/g | GC-HRMS (dual focusing sector field MS) | [63] | |
(SIM), EI | |||||||
PCBs, 6 DDT metabolites, HCHs, HCB, heptachlor, chlordanes, nanochlors, mirex | blood from delivering woman | SPE (Oasis HLB), florisil SPE cleaning | splitless | n.r. | GC-MS (SIM) | [64] | |
EI | |||||||
1. multiple class of pesticides | meconium | 1. SPE | splitless | 0.01–4.15 μg/g | GC-MS (SIM) | [65] | |
2. metabolites | 2. derivatization , LLE | EI |
3.1.2. GC Operating Conditions
3.1.3. Analytical Methods Overview—Analytes vs. Samples
3.2. Fast Capillary GC with MS Detection
Method/Results | GC-NCI-MS | GC-EI-MS |
---|---|---|
LCLs | 0.01, 0.05 µg/kg | 1 µg/kg |
R2 | 0.9936–1.0000 | 0.9882–0.9999 |
LODs | 0.15–88.82 ng/kg | 0.01–6.32 µg/kg |
LOQs | 0.52–291.35 ng/kg | 0.04–21.07 µg/kg |
4. Real-Life Samples Analysis
Matrix | Pesticide | NCI | EI | ||
---|---|---|---|---|---|
ci (µg/kg) | RSD (%) | ci (µg/kg) | RSD (%) | ||
orange | malathion | 50.1 | 0.52 | 52.5 | 3.5 |
lettuce | iprodione | 40.1 | 1.2 | 42.0 | 3.0 |
pear A | iprodione | 40.1 | 1.2 | 41.3 | 3.4 |
pear B | bifenthrin | 69.0 | 5.2 | 64.8 | 4.1 |
myclobutanil | 0.07 | 6.8 | n.d. | - | |
kohlrabi | metribuzin | 0.06 | 3.0 | n.d. | - |
vinclozolin | 0.15 | 2.1 | n.d | - | |
myclobutanil | 0.25 | 3.6 | n.d. | - | |
plum | iprodione | 234.3 | 0.31 | 241.1 | 2.8 |
strawberry | iprodione | 40.9 | 1.2 | 41.3 | 3.4 |
pepper | myclobutanil | 24.3 | 6.3 | 30.4 | 4.2 |
cypermethrin | 47.2 | 2.2 | 54.9 | 6.0 |
5. Conclusions
Acknowledgments
Conflict of Interest
References
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Matisová, E.; Hrouzková, S. Analysis of Endocrine Disrupting Pesticides by Capillary GC with Mass Spectrometric Detection. Int. J. Environ. Res. Public Health 2012, 9, 3166-3196. https://doi.org/10.3390/ijerph9093166
Matisová E, Hrouzková S. Analysis of Endocrine Disrupting Pesticides by Capillary GC with Mass Spectrometric Detection. International Journal of Environmental Research and Public Health. 2012; 9(9):3166-3196. https://doi.org/10.3390/ijerph9093166
Chicago/Turabian StyleMatisová, Eva, and Svetlana Hrouzková. 2012. "Analysis of Endocrine Disrupting Pesticides by Capillary GC with Mass Spectrometric Detection" International Journal of Environmental Research and Public Health 9, no. 9: 3166-3196. https://doi.org/10.3390/ijerph9093166