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Organophosphorus pesticide determination in biological specimens: bioanalytical and toxicological aspects

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Abstract

Organophosphorus insecticides, such as parathion-ethyl, quinalphos, chlorpyrifos, chlorfenvinphos or diazinon, are still widely used for pest control on crops. These compounds are extremely toxic to humans, and, even though specific legislation exists that controls the use of these substances, the frequency of toxic and/or fatal events and the existing data suggest that they are still easily accessed and the knowledge associated to the risks is not well-recognized. For these reasons, the determination of the exposure to these compounds, their detection (and of their metabolites as well) in biological samples, is of great importance in clinical and forensic toxicology, and, therefore, the development of techniques for this evaluation is an important task for laboratories. Most confirmatory analyses use blood, serum, plasma and urine as biological samples and are performed by either gas chromatographic-mass spectrometric or liquid chromatographic-mass spectrometric instrumentation, which represents the gold standard in what concerns high sensitivity. This paper will not only address the physical–chemical and toxicological aspects of this class of compounds but also perform a comprehensive and critical review on the analytical methods available for their determination in biological specimens, with special focus on the latest instrumental developments and sample preparation approaches.

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References

  1. Lock EA, Wilks MF (2001) Paraquat. In: Krieger R (ed) Handbook of pesticide toxicology, 2nd edn. Academic Press, San Diego, pp 1559–1603

    Chapter  Google Scholar 

  2. Holmstedt B (1963) Structure-activity relationships of the organophosphorus anticholinesterase agents. In: Koelle GB (ed) Cholinesterases and anticholinesterase agents, 1st edn. Springer-Verlag, Berlin, pp 428–485

    Chapter  Google Scholar 

  3. Martín Rubí JC, Yélamos Rodríguez F, Laynez Bretones F et al (1996) Poisoning caused by organophosphate insecticides. Study of 506 cases. Rev Clínica Española 196:145–149

    Google Scholar 

  4. Ballantyne B, Marrs TC (1992) Overview of the biological and clinical aspects of organophosphates and carbamates. In: Ballantyne B, Marrs TC (eds) Clinical and experimental toxicology of organophosphates and carbamates, 1st edn. Elsevier Ltd., London, pp 3–14

    Chapter  Google Scholar 

  5. Lange W, von Krueger G (1932) Über Ester der Monofluorphosphorsäure. Berichte der Dtsch Chem Gesellschaft 65:1598–1601. https://doi.org/10.1002/cber.19320650910

    Article  Google Scholar 

  6. Szinicz L (2005) History of chemical and biological warfare agents. Toxicology 214:167–181. https://doi.org/10.1016/j.tox.2005.06.011

    Article  CAS  PubMed  Google Scholar 

  7. Robinson JP, Leitenberg M (1971) Volume I: the rise of CB weapons. In: Almqvist, Wiksell (eds) The problem of chemical and biological warfare, Stockholm, pp 25–101

  8. Chai PR, Hayes BD, Erickson TB, Boyer EW (2018) Novichok agents: a historical, current, and toxicological perspective. Toxicol Commun 2:45–48. https://doi.org/10.1080/24734306.2018.1475151

    Article  PubMed  PubMed Central  Google Scholar 

  9. Eto M (1975) Organophosphorus pesticides: organic and biological chemistry. Press CRC, Cleveland

  10. Turner JA (2017) The pesticide manual, 17th edn. British Crop Protection Council, Surrey

    Google Scholar 

  11. Aprea C, Colosio C, Mammone T et al (2002) Biological monitoring of pesticide exposure: a review of analytical methods. J Chromatogr B 769:191–219. https://doi.org/10.1016/S1570-0232(02)00044-2

    Article  CAS  Google Scholar 

  12. Eddleston M, Karalliedde L, Buckley N et al (2002) Pesticide poisoning in the developing world—a minimum pesticides list. Lancet 360:1163–1167. https://doi.org/10.1016/S0140-6736(02)11204-9

    Article  PubMed  Google Scholar 

  13. Park M-J, In S, Lee S-K et al (2009) Postmortem blood concentrations of organophosphorus pesticides. Forensic Sci Int 184:28–31. https://doi.org/10.1016/j.forsciint.2008.11.008

    Article  CAS  PubMed  Google Scholar 

  14. Castillo-Sánchez J, Aguilera-del Real A, Rodriguez-Sánchez M, Valverde-García A (2000) Residue levels, decline curves, and plantation distribution of procymidone in green beans grown in greenhouse. J Agric Food Chem 48:2991–2994. https://doi.org/10.1021/jf990770y

    Article  CAS  PubMed  Google Scholar 

  15. Bossi R, Seiden P, Andersen SM et al (1999) Analysis of metsulfuron-methyl in soil by liquid chromatography/tandem mass spectrometry. Application to a field dissipation study. J Agric Food Chem 47:4462–4468. https://doi.org/10.1021/jf981280t

    Article  CAS  PubMed  Google Scholar 

  16. Ingerslev F, Nyholm N (2000) Shake-flask test for determination of biodegradation rates of (14)C-labeled chemicals at low concentrations in surface water systems. Ecotoxicol Environ Saf 45:274–283. https://doi.org/10.1006/eesa.1999.1877

    Article  CAS  PubMed  Google Scholar 

  17. Gunnell D, Eddleston M, Phillips MR, Konradsen F (2007) The global distribution of fatal pesticide self-poisoning: systematic review. BMC Public Health 7:1–15. https://doi.org/10.1186/1471-2458-7-357

    Article  Google Scholar 

  18. Hernández E, Pitarch E, Beltran J, López FJ (2002) Headspace solid-phase microextraction in combination with gas chromatography and tandem mass spectrometry for the determination of organochlorine and organophosphorus pesticides in whole human blood. J Chromatogr B 769:65–77. https://doi.org/10.1016/S1570-0232(01)00627-4

    Article  Google Scholar 

  19. Barr DB, Needham LL (2002) Analytical methods for biological monitoring of exposure to pesticides: a review. J Chromatogr B 778:5–29. https://doi.org/10.1016/S1570-0232(02)00035-1

    Article  CAS  Google Scholar 

  20. Multigner L (2005) Effets retardés des pesticides sur la santé humaine. Environ Risques Santé 4:187–194

    Google Scholar 

  21. Harshit D, Charmy K, Nrupesh P (2017) Organophosphorus pesticides determination by novel HPLC and spectrophotometric method. Food Chem 230:448–453. https://doi.org/10.1016/j.foodchem.2017.03.083

    Article  CAS  PubMed  Google Scholar 

  22. Sullivan JB, Blose J (1992) Organophosphate and carbamate insecticides. In: Sullivan JB, Krieger GR (eds) Hazardous materials toxicology: clinical principles of environmental health. Williams and Wilkins, Baltimore, pp 1015–1026

    Google Scholar 

  23. Kumar L, Agarwal SS, Chavali KH, Mestri SC (2009) Homicide by organophosphorus compound poisoning: a case report. Med Sci Law 49:136–138. https://doi.org/10.1258/rsmmsl.49.2.136

    Article  PubMed  Google Scholar 

  24. Jaga K, Dharmani C (2006) Ocular toxicity from pesticide exposure: a recent review. Environ Health Prev Med 11:102–107. https://doi.org/10.1265/ehpm.11.102

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  25. Wu M-L, Deng J-F (2009) Acute hemolysis caused by incidental trichlorfon exposure. J Chinese Med Assoc 72:214–218. https://doi.org/10.1016/S1726-4901(09)70058-9

    Article  CAS  Google Scholar 

  26. Wang C-L, Chuang H-Y, Chang C-Y et al (2000) An unusual case of organophosphate intoxication of a worker in a plastic bottle recycling plant: an important reminder. Environ Health Perspect 108:1103–1105. https://doi.org/10.2307/3434966

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  27. Tarbah FA, Shaheen AM, Benomran FA et al (2007) Distribution of dimethoate in the body after a fatal organphosphate intoxication. Forensic Sci Int 170:129–132. https://doi.org/10.1016/j.forsciint.2007.04.232

    Article  CAS  PubMed  Google Scholar 

  28. Pavlic M, Haidekker A, Grubwieser P, Rabl W (2002) Fatal intoxication with omethoate. Int J Legal Med 116:238–241. https://doi.org/10.1007/s00414-002-0299-6

    Article  CAS  PubMed  Google Scholar 

  29. Tarbah FA, Kardel B, Pier S et al (2004) Acute poisoning with phosphamidon: determination of dimethyl phosphate (DMP) as a stable metabolite in a case of organophosphate insecticide intoxication. J Anal Toxicol 28:198–203. https://doi.org/10.1093/jat/28.3.198

    Article  CAS  PubMed  Google Scholar 

  30. Office of Pesticide Programs (2002) Guidance on cumulative risk assessment of pesticide chemicals that have a common mechanism of toxicity. Washington, DC

    Google Scholar 

  31. Vapnek J, Pagotto I, Kwoka M (2007) Designing national pesticide legislation. Food and Agriculture Organization of the United Nations, Rome

    Google Scholar 

  32. Food and Drug Administration (1999) Pesticide analytical manual volume I: multiresidue methods, 3rd edn. Department of Health and Human Services, Washington, DC

    Google Scholar 

  33. World Health Organization (2002) The world health report 2002: reducing risks, promoting healthy life. https://www.who.int/whr/2002/en/. Accessed 27 Feb 2019

  34. Bertolote JM, Fleischmann A, Eddleston M, Gunnell D (2006) Deaths from pesticide poisoning: are we lacking a global response? Br J Psychiatry 189:201–203. https://doi.org/10.1192/bjp.bp.105.020834

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  35. World Health Organization (2019) Restricting access to the means for suicide. https://www.who.int/mental_health/prevention/suicide/pesticides/en/. Accessed 22 Feb 2019

  36. World Health Organization (2008) Acute pesticide poisoning: a proposed classification tool. https://www.who.int/bulletin/volumes/86/3/07-041814/en/. Accessed 22 Feb 2019

  37. Casey P, Vale JA (1994) Deaths from pesticide poisoning in England and Wales: 1945-1989. Hum Exp Toxicol 13:95–101. https://doi.org/10.1177/096032719401300206

    Article  CAS  PubMed  Google Scholar 

  38. Eddleston M, Mohamed F, Davies JOJ et al (2006) Respiratory failure in acute organophosphorus pesticide self-poisoning. An Int J Med 99:513–522. https://doi.org/10.1093/qjmed/hcl065

    Article  CAS  Google Scholar 

  39. Dhakne R, Mishra KK, Kumar V, Khairkar P (2016) Prolonged apnea during modified electroconvulsive therapy in a patient of suicidal attempt by organophosphorus poisoning—a case report. J ECT 32:136–138. https://doi.org/10.1097/YCT.0000000000000285

    Article  PubMed  Google Scholar 

  40. De Letter EA, Cordonnier JACM, Piette MHA (2002) An unusual case of homicide by use of repeated administration of organophosphate insecticides. J Clin Forensic Med 9:15–21. https://doi.org/10.1054/jcfm.2002.0532

    Article  PubMed  Google Scholar 

  41. Suzuki T, Morita H, Ono K et al (1995) Sarin poisoning in Tokyo subway. Lancet 345:980–981. https://doi.org/10.1016/j.jtcvs.2007.03.053

    Article  CAS  PubMed  Google Scholar 

  42. Kumar V (2004) Poisoning deaths in married women. J Clin Forensic Med 11:2–5. https://doi.org/10.1016/j.jcfm.2003.10.010

    Article  PubMed  Google Scholar 

  43. Ozdemir C, Kar H, Bilge Y et al (2009) Homicidal poisoning by injection of methidathion: the first ever report. Hum Exp Toxicol 28:521–524. https://doi.org/10.1177/0960327109348082

    Article  CAS  PubMed  Google Scholar 

  44. Hamad MH, Adeel AA, Alhaboob AAN et al (2016) Acute poisoning in a child following topical treatment of head lice (pediculosis capitis) with an organophosphate pesticide. Sudan J Paediatr 16:63–66

    PubMed  PubMed Central  Google Scholar 

  45. Chowdhary S, Bhattacharyya R, Banerjee D (2014) Acute organophosphorus poisoning. Clin Chim Acta 431:66–76. https://doi.org/10.1016/j.cca.2014.01.024

    Article  CAS  PubMed  Google Scholar 

  46. Poklis A, Kutz FW, Sperling JF, Morgan DP (1980) A fatal diazinon poisoning. Forensic Sci Int 15:135–140. https://doi.org/10.1016/0379-0738(80)90152-8

    Article  CAS  PubMed  Google Scholar 

  47. Vasilić Ž̌, Štengl B, Drevenkar V (1999) Dimethylphosphorus metabolites in serum and urine of persons poisoned by malathion or thiometon. Chem Biol Interact 119–120:479–487. https://doi.org/10.1016/S0009-2797(99)00061-7

    Article  PubMed  Google Scholar 

  48. Brunetto M del R, Burguera JL, Burguera M et al (1992) Observation on a human intentional poisoning case by the organophosphorus insecticide Fenthion. Investig Clin 33:89–94

    Google Scholar 

  49. Raposo R, Barroso M, Fonseca S et al (2010) Determination of eight selected organophosphorus insecticides in postmortem blood samples using solid-phase extraction and gas chromatography/mass spectrometry. Rapid Commun Mass Spectrom 24:3187–3194. https://doi.org/10.1002/rcm.4765

    Article  CAS  PubMed  Google Scholar 

  50. Casida JE, Durkin KA (2013) Anticholinesterase insecticide retrospective. Chem Biol Interact 203:221–225. https://doi.org/10.1016/j.cbi.2012.08.002

    Article  CAS  PubMed  Google Scholar 

  51. Worek F, Wille T, Koller M, Thiermann H (2016) Toxicology of organophosphorus compounds in view of an increasing terrorist threat. Arch Toxicol 90:2131–2145. https://doi.org/10.1007/s00204-016-1772-1

    Article  CAS  PubMed  Google Scholar 

  52. World Health Organization (1990) Public health impact of pesticides used in agriculture. https://apps.who.int/iris/handle/10665/61414. Accessed 27 Feb 2019

  53. Sharma VK, Jadhav RK, Rao GJ et al (1990) High performance liquid chromatographic method for the analysis of organophosphorus and carbamate pesticides. Forensic Sci Int 48:21–25. https://doi.org/10.1016/0379-0738(90)90268-4

    Article  CAS  PubMed  Google Scholar 

  54. Sogorb MA, Vilanova E, Carrera V (2004) Future applications of phosphotriesterases in the prophylaxis and treatment of organophosporus insecticide and nerve agent poisonings. Toxicol Lett 151:219–233. https://doi.org/10.1016/j.toxlet.2004.01.022

    Article  CAS  PubMed  Google Scholar 

  55. Nshimiyimana FX, Abdallah EA, Fekhaoui M et al (2014) Analysis method for pesticide residues in biological matrices: gas chromatography-mass spectrometry. J Life Sci 8:489–495

    CAS  Google Scholar 

  56. Konradsen F, Van Der Hoek W, Cole DC et al (2003) Reducing acute poisoning in developing countries—options for restricting the availability of pesticides. Toxicology 192:249–261. https://doi.org/10.1016/S0300-483X(03)00339-1

    Article  CAS  PubMed  Google Scholar 

  57. Freire C, Koifman S (2013) Pesticides, depression and suicide: a systematic review of the epidemiological evidence. Int J Hyg Environ Health 216:445–460. https://doi.org/10.1016/J.IJHEH.2012.12.003

    Article  CAS  PubMed  Google Scholar 

  58. Koh D, Jeyaratnam J (1996) Pesticides hazards in developing countries. Sci Total Environ 188:S78–S85. https://doi.org/10.1016/0048-9697(96)05279-5

    Article  CAS  PubMed  Google Scholar 

  59. Thompson TS, Treble RG, Magliocco A et al (1998) Case study: fatal poisoning by malathion. Forensic Sci Int 95:89–98. https://doi.org/10.1016/S0379-0738(98)00092-9

    Article  CAS  PubMed  Google Scholar 

  60. Miyazaki T, Yashiki M, Chikasue F et al (1988) A case of death from prothiophos poisoning. Forensic Sci Int 38:13–19. https://doi.org/10.1016/0379-0738(88)90004-7

    Article  CAS  PubMed  Google Scholar 

  61. Dulaurent S, Gaulier J-M, Blanc-Lapierre A et al (2013) Urinary determination of 2-isopropyl-4-methyl-6-hydroxypyrimidine in case of non fatal poisoning with diazinon. Forensic Sci Int 228:20–24. https://doi.org/10.1016/j.forsciint.2013.03.001

    Article  CAS  Google Scholar 

  62. Luzardo OP, Almeida-González M, Ruiz-Suárez N et al (2015) Validated analytical methodology for the simultaneous determination of a wide range of pesticides in human blood using GC-MS/MS and LC-ESI/MS/MS and its application in two poisoning cases. Sci Justice 55:307–315. https://doi.org/10.1016/j.scijus.2015.04.007

    Article  PubMed  Google Scholar 

  63. Inoue S, Saito T, Mase H et al (2007) Rapid simultaneous determination for organophosphorus pesticides in human serum by LC-MS. J Pharm Biomed Anal 44:258–264. https://doi.org/10.1016/j.jpba.2007.01.036

    Article  CAS  PubMed  Google Scholar 

  64. Takayasu T, Ishida Y, Nosaka M et al (2012) High concentration of methidathion detected in a fatal case of organophosphate-poisoning. Legal Med 14:263–266. https://doi.org/10.1016/j.legalmed.2012.04.007

    Article  CAS  PubMed  Google Scholar 

  65. Martínez MA, Ballesteros S (2012) Two suicidal fatalities due to the ingestion of chlorfenvinphos formulations: simultaneous determination of the pesticide and the petroleum distillates in tissues by gas chromatography-flame-ionization detection and gas chromatography-mass spectrometry. J Anal Toxicol 36:44–51. https://doi.org/10.1093/jat/bkr014

    Article  CAS  PubMed  Google Scholar 

  66. Abe E, Duverneuil C, De La Grandmaison G, Alvarez J-C (2008) A fatal dichlorvos poisoning: concentrations in biological specimens. J Forensic Sci 53:997–1000. https://doi.org/10.1111/j.1556-4029.2008.00774.x

    Article  CAS  PubMed  Google Scholar 

  67. Tsoukali H, Raikos N, Theodoridis G, Psaroulis D (2004) Headspace solid phase microextraction for the gas chromatographic analysis of methyl-parathion in post-mortem human samples: application in a suicide case by intravenous injection. Forensic Sci Int 143:127–132. https://doi.org/10.1016/j.forsciint.2004.02.032

    Article  CAS  PubMed  Google Scholar 

  68. Steinritz D, Eyer F, Worek F et al (2016) Repetitive obidoxime treatment induced increase of red blood cell acetylcholinesterase activity even in a late phase of a severe methamidophos poisoning: a case report. Toxicol Lett 244:121–123. https://doi.org/10.1016/j.toxlet.2015.07.010

    Article  CAS  PubMed  Google Scholar 

  69. Moffatt A, Mohammed F, Eddleston M et al (2010) Hypothermia and fever after organophosphorus poisoning in humans—a prospective case series. J Med Toxicol 6:379–385. https://doi.org/10.1007/s13181-010-0012-y

    Article  PubMed  PubMed Central  Google Scholar 

  70. Kamha AA, Al Omary IYM, Zalabany HA et al (2005) Organophosphate poisoning in pregnancy: a case report. Basic Clin Pharmacol Toxicol 96:397–398. https://doi.org/10.1111/j.1742-7843.2005.pto_09.x

    Article  CAS  PubMed  Google Scholar 

  71. Sungur M, Güven M (2001) Intensive care management of organophosphate insecticide poisoning. Crit Care 5:211–215

    Article  CAS  Google Scholar 

  72. United Nations (1992) 74th plenary meeting. Convention on the prohibition of the development, production, stockpiling and use of chemical weapons and on their destruction. In: A/RES/47/39. http://www.un.org/documents/ga/res/47/a47r039.htm. Accessed 25 Oct 2018

  73. John H, Worek F, Thiermann H (2008) LC-MS-based procedures for monitoring of toxic organophosphorus compounds and verification of pesticide and nerve agent poisoning. Anal Bioanal Chem 391:97–116. https://doi.org/10.1007/s00216-008-1925-z

    Article  CAS  PubMed  Google Scholar 

  74. Casida JE (1956) Metabolism of organophosphorus insecticides in relation to their antiesterase activity, stability, and residual properties. J Agric Food Chem 4:772–785. https://doi.org/10.1021/jf60067a001

    Article  CAS  Google Scholar 

  75. Mutch E, Williams FM (2006) Diazinon, chlorpyrifos and parathion are metabolised by multiple cytochromes P450 in human liver. Toxicology 224:22–32. https://doi.org/10.1016/j.tox.2006.04.024

    Article  CAS  PubMed  Google Scholar 

  76. Foxenberg RJ, McGarrigle BP, Knaak JB et al (2007) Human hepatic cytochrome P450-specific metabolism of parathion and chlorpyrifos. Drug Metab Dispos 35:189–193. https://doi.org/10.1124/dmd.106.012427

    Article  CAS  PubMed  Google Scholar 

  77. Moffat AC, Osselton MD, Widdop B (2011) Clarke’s analysis of drugs and poisons. Pharmaceutical Press, London

    Google Scholar 

  78. Taylor P (2006) Anticholinesterase agents. In: Brunton LL, Chabner BA, Knollmann BC (eds) Goodman & Gilman’s the pharmacological basis of therapeutics, 12th edn. McGraw-Hill Medical Pub. Division, New York, pp 239–254

    Google Scholar 

  79. De la Iglesia Huerta A, Cobos PD (2000) Plaguicidas: neurotoxicidad y vigilancia de la salud. Rev del Inst Nac Segur e Hig en el Trab 8:4–14

    Google Scholar 

  80. Saunders DS, Harper C (1994) Pesticides. In: Hayes AW (ed) Principles and methods of toxicology, 3rd edn. Raven Press, New York, pp 389–415

    Google Scholar 

  81. Cochran RC, Kishiyama J, Aldous C et al (1995) Chlorpyrifos: hazard assessment based on a review of the effects of short-term and long-term exposure in animals and humans. Food Chem Toxicol 33:165–172. https://doi.org/10.1016/0278-6915(94)00124-7

    Article  CAS  PubMed  Google Scholar 

  82. Ecobichon DJ (2001) Toxic effects of pesticides. In: Klaassen CD (ed) Cassarett and Doull’s toxicology, 6th edn. McGraw-Hill, New York, pp 763–810

    Google Scholar 

  83. Schenker MB, Albertson TE, Saiki CL (1992) Pesticides. In: Rom WN (ed) Environmental and occupational medicine, 2nd edn. Walters Kluver, Philadelphia, pp 887–920

    Google Scholar 

  84. Musshoff F, Junker H, Madea B (2002) Simple determination of 22 organophosphorous pesticides in human blood using headspace solid-phase microextraction and gas chromatography with mass spectrometric detection. J Chromatogr Sci 40:29–34. https://doi.org/10.1093/chromsci/40.1.29

    Article  CAS  PubMed  Google Scholar 

  85. Sidell FR (2008) A history of human studies with nerve agents by the UK and USA. In: Marrs T, Maynard R, Sidell F (eds) Chemical warfare agents: toxicology and treatment, 2nd edn. Wiley, West Sussex, pp 115–137

    Google Scholar 

  86. Okumura T, Takasu N, Ishimatsu S et al (1996) Report on 640 victims of the Tokyo subway sarin attack. Ann Emerg Med 28:129–135. https://doi.org/10.1016/S0196-0644(96)70052-5

    Article  CAS  PubMed  Google Scholar 

  87. Eddleston M, Street JM, Self I et al (2012) A role for solvents in the toxicity of agricultural organophosphorus pesticides. Toxicology 294:94–103. https://doi.org/10.1016/j.tox.2012.02.005

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  88. Peter JV, Sudarsan TI, Moran JL (2014) Clinical features of organophosphate poisoning: a review of different classification systems and approaches. Indian J Crit care Med 18:735–745. https://doi.org/10.4103/0972-5229.144017

    Article  PubMed  PubMed Central  Google Scholar 

  89. Sogorb MA, Vilanova E (2002) Enzymes involved in the detoxification of organophosphorus, carbamate and pyrethroid insecticides through hydrolysis. Toxicol Lett 128:215–228. https://doi.org/10.1016/S0378-4274(01)00543-4

    Article  CAS  PubMed  Google Scholar 

  90. Vilanova E, Sogorb MA (1999) The role of phosphotriesterases in the detoxication of organophosphorus compounds. Crit Rev Toxicol 29:21–57. https://doi.org/10.1080/10408449991349177

    Article  CAS  PubMed  Google Scholar 

  91. Aldridge WN, Reiner E (1974) Enzyme inhibitors as substrates. Interactions of esterases with esters of organophosphorus and carbamic acid. In: Aldridge WN (ed) The quarterly review of biology. North Holland, pp 253–254

  92. Kwong TC (2002) Organophosphate pesticides: biochemistry and clinical toxicology. Ther Drug Monit 24:144–149. https://doi.org/10.1097/00007691-200202000-00022

    Article  CAS  PubMed  Google Scholar 

  93. Holmstedt B (1959) Pharmacology of organophosphorus cholinesterase inhibitors. Pharmacol Rev 11:567–688

    CAS  PubMed  Google Scholar 

  94. Eaton DL, Daroff RB, Autrup H et al (2008) Review of the toxicology of chlorpyrifos with an emphasis on human exposure and neurodevelopment. Crit Rev Toxicol 38:1–125. https://doi.org/10.1080/10408440802272158

    Article  CAS  PubMed  Google Scholar 

  95. Yu-shan Z, Xiao-peng L, Hong-mei L et al (2013) Study on universal cleaning solution in removing blended pesticide residues in Chinese cabbage. J Environ Chem Ecotoxicol 5:202–207. https://doi.org/10.5897/JECE2013.0288

    Article  CAS  Google Scholar 

  96. Eddleston M, Eyer P, Worek F et al (2008) Predicting outcome using butyrylcholinesterase activity in organophosphorus pesticide self-poisoning. An Int J Med 101:467–474. https://doi.org/10.1093/qjmed/hcn026

    Article  CAS  Google Scholar 

  97. Masson P, Carletti E, Nachon F (2009) Structure, activities and biomedical applications of human butyrylcholinesterase. Protein Pept Lett 16:1215–1224. https://doi.org/10.2174/092986609789071207

    Article  CAS  PubMed  Google Scholar 

  98. Maxwell DM (1992) The specificity of carboxylesterase protection against the toxicity of organophosphorus compounds. Toxicol Appl Pharmacol 114:306–312. https://doi.org/10.1016/0041-008X(92)90082-4

    Article  CAS  PubMed  Google Scholar 

  99. Moralev SN, Rozengart EV (2007) Comparative enzymology of cholinesterases. International University Line, La Jolla

    Google Scholar 

  100. Maxwell DM, Brecht KM, O’Neill BL (1987) The effect of carboxylesterase inhibition on interspecies differences in soman toxicity. Toxicol Lett 39:35–42. https://doi.org/10.1016/0378-4274(87)90254-2

    Article  CAS  PubMed  Google Scholar 

  101. Lenz DE, Yeung D, Smith JR et al (2007) Stoichiometric and catalytic scavengers as protection against nerve agent toxicity: a mini review. Toxicology 233:31–39. https://doi.org/10.1016/j.tox.2006.11.066

    Article  CAS  PubMed  Google Scholar 

  102. Li H, Schopfer LM, Nachon F et al (2007) Aging pathways for organophosphate-inhibited human butyrylcholinesterase, including novel pathways for isomalathion, resolved by mass spectrometry. Toxicol Sci 100:136–145. https://doi.org/10.1093/toxsci/kfm215

    Article  CAS  PubMed  Google Scholar 

  103. Eddleston M, Szinicz L, Eyer P, Buckley N (2002) Oximes in acute organophosphorus pesticide poisoning: a systematic review of clinical trials. QJM 95:275–283. https://doi.org/10.1093/qjmed/95.5.275

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  104. Kumar GC, Bhuvana K, Venkatarathnamma PN, Sarala N (2015) Serum creatine phosphokinase as predictor of intermediate syndrome in organophosphorus poisoning. Indian J Crit Care Med 19:384–387. https://doi.org/10.4103/0972-5229.160274

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  105. Vale A, Lotti M (2015) Organophosphorus and carbamate insecticide poisoning. Handb Clin Neurol 131:149–168. https://doi.org/10.1016/B978-0-444-62627-1.00010-X

    Article  PubMed  Google Scholar 

  106. Benschop HP, de Jong LPA (2001) Toxicokinetics of nerve agents. In: Somani SM, Romano JA (eds) Chemical warfare agents: toxicity at low levels. CRC Press, Boca Raton, pp 25–81

    Google Scholar 

  107. McKeag D, Maini R, Taylor HR (2002) The ocular surface toxicity of paraquat. Br J Ophthalmol 86:350–351. https://doi.org/10.1136/bjo.86.3.350

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  108. Bradberry SM, Proudfoot AT, Vale JA (2004) Glyphosate poisoning. Toxicol Rev 23:159–167

    Article  CAS  Google Scholar 

  109. Van Wyk E, Bouwman H, Van der Bank H et al (2001) Persistent organochlorine pesticides detected in blood and tissue samples of vultures from different localities in South Africa. Comp Biochem Physiol Part C 129:243–264. https://doi.org/10.1016/S1532-0456(01)90201-7

    Article  Google Scholar 

  110. Furst P, Furst C, Wilmers K (1994) Human milk as a bioindicator for body burdens of PCDDs, PCDFs, organochlorine pesticides, and PCBs. Environ Heal Perspect Suppl 102:187–193. https://doi.org/10.1289/ehp.102-1566908

    Article  CAS  Google Scholar 

  111. Hamilton MG, Hill I, Conley J et al (2004) Clinical aspects of percutaneous poisoning by the chemical warfare agent VX: effects of application site and decontamination. Mil Med 169:856–862. https://doi.org/10.7205/MILMED.169.11.856

    Article  PubMed  Google Scholar 

  112. Lee EC (2003) Clinical manifestations of sarin nerve gas exposure. J Am Med Assoc 290:659–662. https://doi.org/10.1001/jama.290.5.659

    Article  Google Scholar 

  113. Thiermann H, Szinicz L, Eyer P et al (2007) Lessons to be learnt from organophosphorus pesticide poisoning for the treatment of nerve agent poisoning. Toxicology 233:145–154. https://doi.org/10.1016/j.tox.2006.11.056

    Article  CAS  PubMed  Google Scholar 

  114. Mumford H, Price ME, Wetherell JR (2008) A novel approach to assessing percutaneous VX poisoning in the conscious guinea-pig. J Appl Toxicol 28:694–702. https://doi.org/10.1002/jat.1324

    Article  CAS  PubMed  Google Scholar 

  115. Goel A, Aggarwal P (2007) Pesticide poisoning. Natl Med J India 20:182–191

    PubMed  Google Scholar 

  116. Reiter G, Mikler J, Hill I et al (2008) Chromatographic resolution, characterisation and quantification of VX enantiomers in hemolysed swine blood samples. J Chromatogr B 873:86–94. https://doi.org/10.1016/j.jchromb.2008.08.001

    Article  CAS  Google Scholar 

  117. Van Der Schans MJ, Lander BJ, Van Der Wiel H et al (2003) Toxicokinetics of the nerve agent (±)-VX in anesthetized and atropinized hairless guinea pigs and marmosets after intravenous and percutaneous administration. Toxicol Appl Pharmacol 191:48–62. https://doi.org/10.1016/S0041-008X(03)00216-3

    Article  CAS  PubMed  Google Scholar 

  118. Wester RC, Maibach HI, Bucks DAW, Guy RH (1983) Malathion percutaneous absorption after repeated administration to man. Toxicol Appl Pharmacol 68:116–119. https://doi.org/10.1016/0041-008X(83)90360-5

    Article  CAS  PubMed  Google Scholar 

  119. Sidell FR (1974) Soman and sarin: clinical manifestations and treatment of accident of accidental poisoning by organophosphates. Clin Toxicol 7:1–17. https://doi.org/10.3109/15563657408987971

    Article  CAS  PubMed  Google Scholar 

  120. Rengstorff RH (1994) Vision and ocular changes following accidental exposure to organophosphates. J Appl Toxicol 14:115–118. https://doi.org/10.1002/jat.2550140213

    Article  CAS  PubMed  Google Scholar 

  121. Feldmann RJ, Maibach HI (1974) Percutaneous penetration of some pesticides and herbicides in man. Toxicol Appl Pharmacol 28:126–132. https://doi.org/10.1016/0041-008X(74)90137-9

    Article  CAS  PubMed  Google Scholar 

  122. Alavanja MCR, Hoppin JA, Kamel F (2004) Health effects of chronic pesticide exposure: cancer and neurotoxicity. Annu Rev Public Health 25:155–197. https://doi.org/10.1146/annurev.publhealth.25.101802.123020

    Article  PubMed  Google Scholar 

  123. Rezg R, Mornagui B, Kamoun A et al (2007) Effect of subchronic exposure to malathion on metabolic parameters in the rat. Comptes Rendus - Biol 330:143–147. https://doi.org/10.1016/j.crvi.2006.11.002

    Article  CAS  Google Scholar 

  124. Masri W, Belwaer I, Brahmi N et al (2011) Incidence et caractéristiques des intoxications aux inhibiteurs de cholinestérases. Rev Francoph des Lab 429:41–46. https://doi.org/10.1016/S1773-035X(11)70766-3

    Article  Google Scholar 

  125. Dhanushka MAT, Peiris LDC (2017) Cytotoxic and genotoxic effects of acephate on human sperm. J Toxicol 2017:1–6. https://doi.org/10.1155/2017/3874817

    Article  CAS  Google Scholar 

  126. Perry MJ, Venners SA, Barr DB, Xu X (2007) Environmental pyrethroid and organophosphorus insecticide exposures and sperm concentration. Reprod Toxicol 23:113–118. https://doi.org/10.1016/j.reprotox.2006.08.005

    Article  CAS  PubMed  Google Scholar 

  127. Mostafalou S, Abdollahi M (2017) Pesticides: an update of human exposure and toxicity. Arch Toxicol 91:549–599. https://doi.org/10.1007/s00204-016-1849-x

    Article  CAS  PubMed  Google Scholar 

  128. Mostafalou S, Abdollahi M (2013) Pesticides and human chronic diseases: evidences, mechanisms, and perspectives. Toxicol Appl Pharmacol 268:157–177. https://doi.org/10.1016/j.taap.2013.01.025

    Article  CAS  PubMed  Google Scholar 

  129. Mikler J, Tenn C, Worek F et al (2011) Immobilization of Russian VX skin depots by localized cooling: implications for decontamination and medical countermeasures. Toxicol Lett 206:47–53. https://doi.org/10.1016/j.toxlet.2011.05.1047

    Article  CAS  PubMed  Google Scholar 

  130. Leikin JB, Thomas RG, Walter FG et al (2002) A review of nerve agent exposure for the critical care physician. Crit Care Med 30:2346–2354. https://doi.org/10.1097/01.CCM.0000029196.42315.83

    Article  PubMed  Google Scholar 

  131. World Health Organization (1986) Metabolism and mode of action. In: Organophosphorus insecticides: a general introduction. WHO, pp 39–48

  132. Ballesteros S, Torrecilla JM (2000) Plaguicidas. In: Mencías-Rodríguez E, Mayero-Franco LM (eds) Manual de Toxicología Básica, 1st edn. Ediciones Díaz de Santos, Madrid, pp 545–592

    Google Scholar 

  133. Barr DB, Barr JR, Driskell WJ et al (1999) Strategies for biological monitoring of exposure for contemporary-use pesticides. Toxicol Ind Health 15:168–179. https://doi.org/10.1177/074823379901500114

    Article  CAS  PubMed  Google Scholar 

  134. Salm P, Taylor PJ, Roberts D, de Silva J (2009) Liquid chromatography-tandem mass spectrometry method for the simultaneous quantitative determination of the organophosphorus pesticides dimethoate, fenthion, diazinon and chlorpyrifos in human blood. J Chromatogr B 877:568–574. https://doi.org/10.1016/j.jchromb.2008.12.066

    Article  CAS  Google Scholar 

  135. Jokanovic M (2001) Biotransformation of organophosphorus compounds. Toxicology 166:139–160. https://doi.org/10.1016/S0300-483X(01)00463-2

    Article  CAS  PubMed  Google Scholar 

  136. Bravo R, Driskell WJ, Whitehead RD et al (2002) Quantitation of dialkyl phosphate metabolites of organophosphate pesticides in human urine using GC-MS-MS with isotopic internal standards. J Anal Toxicol 26:245–252. https://doi.org/10.1093/jat/26.5.245

    Article  CAS  PubMed  Google Scholar 

  137. Bravo R, Caltabiano LM, Weerasekera G et al (2004) Measurement of dialkyl phosphate metabolites of organophosphorus pesticides in human urine using lyophilization with gas chromatography-tandem mass spectrometry and isotope dilution quantification. J Expo Anal Environ Epidemiol 14:249–259. https://doi.org/10.1038/sj.jea.7500322

    Article  CAS  PubMed  Google Scholar 

  138. Barr DB, Bravo R, Weerasekera G et al (2004) Concentrations of dialkyl phosphate metabolites of organophosphorus pesticides in the U.S. population. Environ Health Perspect 112:186–200. https://doi.org/10.1289/ehp.6503

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  139. Castorina R, Bradman A, McKone TE et al (2003) Cumulative organophosphate pesticide exposure and risk assessment among pregnant women living in an agricultural community: a case study from the CHAMACOS cohort. Environ Health Perspect 111:1640–1648. https://doi.org/10.1289/ehp.5887

    Article  PubMed  PubMed Central  Google Scholar 

  140. Wessels D, Barr DB, Mendola P (2003) Use of biomarkers to indicate exposure of children to organophosphate pesticides: implications for a longitudinal study of children’s environmental health. Environ Health Perspect 111:1939–1946. https://doi.org/10.1289/ehp.6179

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  141. Eskenazi B, Harley K, Bradman A et al (2004) Association of in utero organophosphate pesticide exposure and fetal growth and length of gestation in an agricultural population. Environ Health Perspect 112:1116–1124. https://doi.org/10.1289/EHP.6789

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  142. Hernández F, Sancho JV, Pozo OJ (2002) Direct determination of alkyl phosphates in human urine by liquid chromatography/electrospray tandem mass spectrometry. Rapid Commun Mass Spectrom 16:1766–1773. https://doi.org/10.1002/rcm.790

    Article  CAS  PubMed  Google Scholar 

  143. Van Welie RTH, Van Marrewijk CM, De Wolff FA, Vermeulen NPE (1991) Thioether excretion in urine of applicators exposed to 1,3-dichloropropene: a comparison with urinary mercapturic acid excretion. Br J Ind Med 48:492–498. https://doi.org/10.1136/oem.48.7.492

    Article  PubMed  PubMed Central  Google Scholar 

  144. Wester RC, Bucks DA, Maibach HI (1994) Human in vivo percutaneous absorption of pyrethrin and piperonyl butoxide. Food Chem Toxicol 32:51–53. https://doi.org/10.1016/0278-6915(84)90036-X

    Article  CAS  PubMed  Google Scholar 

  145. Griffin P, Mason H, Heywood K, Cocker J (1999) Oral and dermal absorption of chlorpyrifos: a human volunteer study. Occup Environ Med 56:10–13. https://doi.org/10.1136/oem.56.1.10

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  146. Driskell WJ, Hill RH (1997) Identification of a major human urinary metabolite of metolachlor by LC-MS/MS. Bull Environ Contam Toxicol 58:929–933. https://doi.org/10.1007/s001289900423

    Article  CAS  PubMed  Google Scholar 

  147. Kawabata S, Hayasaka M, Hayashi H et al (1994) Phenthoate metabolites in human poisoning. J Toxicol Clin Toxicol 32:49–60. https://doi.org/10.3109/15563659409000430

    Article  CAS  PubMed  Google Scholar 

  148. Nolan RJ, Rick DL, Freshour NL, Saunders JH (1984) Chlorpyrifos: pharmacokinetics in human volunteers. Toxicol Appl Pharmacol 73:8–15. https://doi.org/10.1016/0041-008X(84)90046-2

    Article  CAS  PubMed  Google Scholar 

  149. Vasilić Z, Drevenkar V, Rumenjak V et al (1992) Urinary excretion of diethylphosphorus metabolites in persons poisoned by quinalphos or chlorpyrifos. Arch Environ Contam Toxicol 22:351–357. https://doi.org/10.1007/BF00212552

    Article  PubMed  Google Scholar 

  150. Drevenkar V, Vasilić Ž, Štengl B et al (1993) Chlorpyrifos metabolites in serum and urine of poisoned persons. Chem Biol Interact 87:315–322. https://doi.org/10.1016/0009-2797(93)90059-8

    Article  CAS  PubMed  Google Scholar 

  151. Gul EE, Can I, Kusumoto FM (2012) Case report: an unusual heart rhythm associated with organophosphate poisoning. Cardiovasc Toxicol 12:263–265. https://doi.org/10.1007/s12012-012-9165-z

    Article  PubMed  Google Scholar 

  152. Rosado T, Soares S, Malaca S et al (2018) The role of liquid chromatography in toxicological analysis. In: Lucero I (ed) High-performance liquid chromatography: types, parameters and applications. Nova Science Publishers, New York, pp 1–120

    Google Scholar 

  153. Zhang W, Tang Y, Du D et al (2013) Direct analysis of trichloropyridinol in human saliva using an Au nanoparticles-based immunochromatographic test strip for biomonitoring of exposure to chlorpyrifos. Talanta 114:261–267. https://doi.org/10.1016/j.talanta.2013.06.012

    Article  CAS  PubMed  Google Scholar 

  154. Eskandari H, Naderi-Darehshori A (2012) Preparation of magnetite/poly(styrene-divinylbenzene) nanoparticles for selective enrichment-determination of fenitrothion in environmental and biological samples. Anal Chim Acta 743:137–144. https://doi.org/10.1016/j.aca.2012.07.012

    Article  CAS  PubMed  Google Scholar 

  155. Lu C, Rodríguez T, Funez A et al (2006) The assessment of occupational exposure to diazinon in Nicaraguan plantation workers using saliva biomonitoring. Ann N Y Acad Sci 1076:355–365. https://doi.org/10.1196/annals.1371.057

    Article  CAS  PubMed  Google Scholar 

  156. Curwin BD, Hein MJ, Barr DB, Striley C (2010) Comparison of immunoassay and HPLC-MS/MS used to measure urinary metabolites of atrazine, metolachlor, and chlorpyrifos from farmers and non-farmers in Iowa. J Expo Sci Environ Epidemiol 20:205–212. https://doi.org/10.1038/jes.2009.15

    Article  CAS  PubMed  Google Scholar 

  157. Yan X, Li H, Su X (2018) Review of optical sensors for pesticides. TrAC Trends Anal Chem 103:1–20. https://doi.org/10.1016/J.TRAC.2018.03.004

    Article  CAS  Google Scholar 

  158. Kumari R, Patel DK, Panchal S et al (2015) Fast agitated directly suspended droplet microextraction technique for the rapid analysis of eighteen organophosphorus pesticides in human blood. J Chromatogr A 1377:27–34. https://doi.org/10.1016/j.chroma.2014.12.006

    Article  CAS  PubMed  Google Scholar 

  159. Lacassie E, Dreyfuss M-F, Gaulier JM et al (2001) Multiresidue determination method for organophosphorus pesticides in serum and whole blood by gas chromatography—mass-selective detection. J Chromatogr B 759:109–116. https://doi.org/10.1016/S0378-4347(01)00211-0

    Article  CAS  Google Scholar 

  160. Kudo K, Nagamatsu K, Umehara T et al (2012) Rapid and reliable screening method for detection of 70 pesticides in whole blood by gas chromatography-mass spectrometry using a constructed calibration-locking database. Legal Med 14:93–100. https://doi.org/10.1016/j.legalmed.2012.01.002

    Article  CAS  PubMed  Google Scholar 

  161. Tarbah FA, Mahler H, Temme O, Daldrup T (2001) An analytical method for the rapid screening of organophosphate pesticides in human biological samples and foodstuffs. Forensic SciInt 121:126–133. https://doi.org/10.1016/S0379-0738(01)00462-5

    Article  CAS  Google Scholar 

  162. Russo MV, Campanella L, Avino P (2002) Determination of organophosphorus pesticide residues in human tissues by capillary gas chromatography-negative chemical ionization mass spectrometry analysis. J Chromatogr B 780:431–441. https://doi.org/10.1016/S1570-0232(02)00629-3

    Article  CAS  Google Scholar 

  163. Roca M, Leon N, Pastor A, Yusà V (2014) Comprehensive analytical strategy for biomonitoring of pesticides in urine by liquid chromatography-orbitrap high resolution mass spectrometry. J Chromatogr A 1374:66–76. https://doi.org/10.1016/j.chroma.2014.11.010

    Article  CAS  PubMed  Google Scholar 

  164. Duca RC, Salquebre G, Hardy E, Appenzeller BMR (2014) Comparison of solid phase- and liquid/liquid extraction for the purification of hair extract prior to multi-class pesticides analysis. J Chromatogr B Anal Technol Biomed Life Sci 955–956:98–107. https://doi.org/10.1016/j.jchromb.2014.02.035

    Article  CAS  Google Scholar 

  165. Araoud M, Gazzah N, Douki W et al (2012) Rapid multi-residue method for the determination of pesticide residues in human serum. African J Biotechnol 11:12579–12585. https://doi.org/10.5897/AJB11.3072

    Article  CAS  Google Scholar 

  166. Spaan S, Pronk A, Koch HM et al (2015) Reliability of concentrations of organophosphate pesticide metabolites in serial urine specimens from pregnancy in the generation R study. Pediatr Neurol 23:286–294. https://doi.org/10.1038/jes.2014.81

    Article  CAS  Google Scholar 

  167. Okamura A, Saito I, Ueyama J et al (2012) New analytical method for sensitive quantification of urinary 3-methyl-4-nitrophenol to assess fenitrothion exposure in general population and occupational sprayers. Toxicol Lett 210:220–224. https://doi.org/10.1016/j.toxlet.2011.10.008

    Article  CAS  PubMed  Google Scholar 

  168. Jayatilaka NK, Montesano MA, Whitehead RD et al (2011) High-throughput sample preparation for the quantitation of acephate, methamidophos, omethoate, dimethoate, ethylenethiourea, and propylenethiourea in human urine using 96-well-plate automated extraction and high-performance liquid chromatography-tandem mass spectrometry. Arch Environ Contam Toxicol 61:59–67. https://doi.org/10.1007/s00244-010-9593-3

    Article  CAS  PubMed  Google Scholar 

  169. Montesano MA, Olsson AO, Kuklenyik P et al (2007) Method for determination of acephate, methamidophos, omethoate, dimethoate, ethylenethiourea and propylenethiourea in human urine using high-performance liquid chromatography-atmospheric pressure chemical ionization tandem mass spectrometry. J Expo Sci Environ Epidemiol 17:321–330. https://doi.org/10.1038/sj.jes.7500550

    Article  CAS  PubMed  Google Scholar 

  170. Reemtsma T, Lingott J, Roegler S (2011) Determination of 14 monoalkyl phosphates, dialkyl phosphates and dialkyl thiophosphates by LC-MS/MS in human urinary samples. Sci Total Environ 409:1990–1993. https://doi.org/10.1016/j.scitotenv.2011.01.032

    Article  CAS  PubMed  Google Scholar 

  171. Wu C, Liu P, Zheng L et al (2010) GC-FPD measurement of urinary dialkylphosphate metabolites of organophosphorous pesticides as pentafluorobenzyl derivatives in occupationally exposed workers and in a general population in Shanghai (China). J Chromatogr B 878:2575–2581. https://doi.org/10.1016/j.jchromb.2010.07.021

    Article  CAS  Google Scholar 

  172. Davis MD, Wade EL, Restrepo PR et al (2013) Semi-automated solid phase extraction method for the mass spectrometric quantification of 12 specific metabolites of organophosphorus pesticides, synthetic pyrethroids, and select herbicides in human urine. J Chromatogr B 929:18–26. https://doi.org/10.1016/j.jchromb.2013.04.005

    Article  CAS  Google Scholar 

  173. Olsson AO, Baker SE, Nguyen JV et al (2004) A liquid chromatography-tandem mass spectrometry multiresidue method for quantification of specific metabolites of organophosphorus pesticides, synthetic pyrethroids, selected herbicides, and DEET in human urine. Anal Chem 76:2453–2461. https://doi.org/10.1021/ac0355404

    Article  CAS  PubMed  Google Scholar 

  174. Cequier E, Sakhi AK, Haug LS, Thomsen C (2016) Development of an ion-pair liquid chromatography–high resolution mass spectrometry method for determination of organophosphate pesticide metabolites in large-scale biomonitoring studies. J Chromatogr A 1454:32–41. https://doi.org/10.1016/j.chroma.2016.05.067

    Article  CAS  PubMed  Google Scholar 

  175. Odetokun MS, Montesano MA, Weerasekera G et al (2010) Quantification of dialkylphosphate metabolites of organophosphorus insecticides in human urine using 96-well plate sample preparation and high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry. J Chromatogr B 878:2567–2574. https://doi.org/10.1016/j.jchromb.2010.04.027

    Article  CAS  Google Scholar 

  176. Ueyama J, Saito I, Takaishi A et al (2014) A revised method for determination of dialkylphosphate levels in human urine by solid-phase extraction and liquid chromatography with tandem mass spectrometry: application to human urine samples from Japanese children. Environ Health Prev Med 19:405–413. https://doi.org/10.1007/s12199-014-0407-5

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  177. Pitarch E, Serrano R, López FJ, Hernández F (2003) Rapid multiresidue determination of organochlorine and organophosphorus compounds in human serum by solid-phase extraction and gas chromatography coupled to tandem mass spectrometry. Anal Bioanal Chem 376:189–197. https://doi.org/10.1007/s00216-003-1893-2

    Article  CAS  PubMed  Google Scholar 

  178. Barroso M, Gallardo E, Queiroz JA (2015) The role of liquid-phase microextraction techniques in bioanalysis. Bioanalysis 7:2195–2201. https://doi.org/10.4155/bio.15.136

    Article  CAS  PubMed  Google Scholar 

  179. Barroso M, Moreno I, da Fonseca B et al (2012) Role of microextraction sampling procedures in forensic toxicology. Bioanalysis 4:1805–1826. https://doi.org/10.4155/bio.12.139

    Article  CAS  PubMed  Google Scholar 

  180. Tsoukali H, Theodoridis G, Raikos N, Grigoratou I (2005) Solid phase microextraction gas chromatographic analysis of organophosphorus pesticides in biological samples. J Chromatogr B 822:194–200. https://doi.org/10.1016/j.jchromb.2005.05.035

    Article  CAS  Google Scholar 

  181. Ebrahimi M, Es’haghi Z, Samadi F et al (2012) Rational design of heteropolyacid-based nanosorbent for hollow fiber solid phase microextraction of organophosphorus residues in hair samples. J Chromatogr A 1225:37–44. https://doi.org/10.1016/j.chroma.2011.12.077

    Article  CAS  PubMed  Google Scholar 

  182. López FJ, Pitarch E, Egea S et al (2001) Gas chromatographic determination of organochlorine and organophosphorus pesticides in human fluids using solid phase microextraction. Anal Chim Acta 433:217–226. https://doi.org/10.1016/S0003-2670(01)00793-0

    Article  Google Scholar 

  183. Gallardo E, Barroso M, Margalho C et al (2006) Determination of parathion in biological fluids by means of direct solid-phase microextraction. Anal Bioanal Chem 386:1717–1726. https://doi.org/10.1007/s00216-006-0735-4

    Article  CAS  PubMed  Google Scholar 

  184. Gallardo E, Barroso M, Margalho C et al (2006) Solid-phase microextraction for gas chromatographic/mass spectrometric analysis of dimethoate in human biological samples. Rapid Commun Mass Spectrom 20:865–869. https://doi.org/10.1002/rcm.2388

    Article  CAS  PubMed  Google Scholar 

  185. Gallardo E, Barroso M, Margalho C et al (2006) Determination of quinalphos in blood and urine by direct solid-phase microextraction combined with gas chromatography-mass spectrometry. J Chromatogr B Anal Technol Biomed Life Sci 832:162–168. https://doi.org/10.1016/j.jchromb.2005.12.029

    Article  CAS  Google Scholar 

  186. Yang R, Xie W (2004) Preparation and usage of a new solid phase micro-extraction membrane. Forensic Sci Int 139:177–181. https://doi.org/10.1016/j.forsciint.2003.10.020

    Article  CAS  PubMed  Google Scholar 

  187. Santos C, Oppolzer D, Gonçalves A et al (2018) Determination of organophosphorous pesticides in blood using microextraction in packed sorbent and gas chromatography–tandem mass spectrometry. J Anal Toxicol 42:321–329. https://doi.org/10.1093/jat/bky004

    Article  CAS  PubMed  Google Scholar 

  188. Soares S, Castro T, Rosado T et al (2018) New analytical approach to determine organophosphorous insecticides in blood by dried matrix spots sampling and GC-MS/MS. Anal Bioanal Chem 410:7955–7964. https://doi.org/10.1007/s00216-018-1417-8

    Article  CAS  PubMed  Google Scholar 

  189. Srivastava A, Rai S, Sonker AK et al (2017) Simultaneous determination of multiclass pesticide residues in human plasma using a mini QuEChERS method. Anal Bioanal Chem 409:3757–3765. https://doi.org/10.1007/s00216-017-0317-7

    Article  CAS  PubMed  Google Scholar 

  190. Usui K, Hayashizaki Y, Minagawa T et al (2012) Rapid determination of disulfoton and its oxidative metabolites in human whole blood and urine using QuEChERS extraction and liquid chromatography-tandem mass spectrometry. Legal Med 14:309–316. https://doi.org/10.1016/j.legalmed.2012.06.005

    Article  CAS  PubMed  Google Scholar 

  191. Liao H-T, Hsieh C-J, Chiang S-Y et al (2011) Simultaneous analysis of chlorpyrifos and cypermethrin in cord blood plasma by online solid-phase extraction coupled with liquid chromatography-heated electrospray ionization tandem mass spectrometry. J Chromatogr B 879:1961–1966. https://doi.org/10.1016/j.jchromb.2011.05.028

    Article  CAS  Google Scholar 

  192. Saito T, Aoki H, Namera A et al (2011) Mix-mode TiO-C18 monolith spin column extraction and GC-MS for the simultaneous assay of organophosphorus compounds and glufosinate, and glyphosate in human serum and urine. Anal Sci 27:999–1005. https://doi.org/10.2116/analsci.27.999

    Article  CAS  PubMed  Google Scholar 

  193. Saito T, Fukushima T, Yui Y et al (2011) Monolithic spin column extraction and GC-MS for the simultaneous assay of diquat, paraquat, and fenitrothion in human serum and urine. Anal Bioanal Chem 400:25–31. https://doi.org/10.1007/s00216-010-4633-4

    Article  CAS  PubMed  Google Scholar 

  194. Jia G-F, Lv C-G, Zhu W-T et al (2008) Applicability of cloud point extraction coupled with microwave-assisted back-extraction to the determination of organophosphorous pesticides in human urine by gas chromatography with flame photometry detection. J Hazard Mater 159:300–305. https://doi.org/10.1016/j.jhazmat.2008.02.081

    Article  CAS  PubMed  Google Scholar 

  195. Aladaghlo Z, Fakhari A, Behbahani M (2016) Solvent-assisted dispersive solid-phase extraction: a sample preparation method for trace detection of diazinon in urine and environmental water samples. J Chromatogr A 1462:27–34. https://doi.org/10.1016/j.chroma.2016.07.084

    Article  CAS  PubMed  Google Scholar 

  196. Pelit FO, Yengin Ç (2014) Application of solidified floating organic drop microextraction method for biomonitoring of chlorpyrifos and its oxon metabolite in urine samples. J Chromatogr B 949–950:109–114. https://doi.org/10.1016/j.jchromb.2014.01.004

    Article  CAS  Google Scholar 

  197. Santos MG, Vitor RV, Andrade FL et al (2012) Molecularly imprinted solid phase extraction of urinary diethyl thiophosphate and diethyl dithiophosphate and their analysis by gas chromatography-mass spectrometry. J Chromatogr B 909:70–76. https://doi.org/10.1016/j.jchromb.2012.10.015

    Article  CAS  Google Scholar 

  198. Zhang S, Jiao Z, Yao W (2014) A simple solvothermal process for fabrication of a metal-organic framework with an iron oxide enclosure for the determination of organophosphorus pesticides in biological samples. J Chromatogr A 1371:74–81. https://doi.org/10.1016/j.chroma.2014.10.088

    Article  CAS  PubMed  Google Scholar 

  199. Pérez JJ, Williams MK, Weerasekera G et al (2010) Measurement of pyrethroid, organophosphorus, and carbamate insecticides in human plasma using isotope dilution gas chromatography-high resolution mass spectrometry. J Chromatogr B 878:2554–2562. https://doi.org/10.1016/j.jchromb.2010.03.015

    Article  CAS  Google Scholar 

  200. Barr DB, Barr JR, Maggio VL et al (2002) A multi-analyte method for the quantification of contemporary pesticides in human serum and plasma using high-resolution mass spectrometry. J Chromatogr B 778:99–111. https://doi.org/10.1016/S0378-4347(01)00444-3

    Article  CAS  Google Scholar 

  201. Hernández F, Sancho JV, Pozo OJ (2004) An estimation of the exposure to organophosphorus pesticides through the simultaneous determination of their main metabolites in urine by liquid chromatography-tandem mass spectrometry. J Chromatogr B 808:229–239. https://doi.org/10.1016/j.jchromb.2004.05.019

    Article  CAS  Google Scholar 

  202. Sancho JV, Pozo OJ, Hernández F (2000) Direct determination of chlorpyrifos and its main metabolite 3,5,6-trichloro-2-pyridinol in human serum and urine by coupled-column liquid chromatography/electrospray-tandem mass spectrometry. Rapid Commun Mass Spectrom 14:1485–1490. https://doi.org/10.1002/1097-0231(20000830)14:16<1485::AID-RCM51>3.0.CO;2-8

    Article  CAS  PubMed  Google Scholar 

  203. Oya N, Ito Y, Hioki K et al (2017) Quantitative analysis of organophosphate insecticide metabolites in urine extracted from disposable diapers of toddlers in Japan. Int J Hyg Environ Health 220:209–216. https://doi.org/10.1016/j.ijheh.2016.10.009

    Article  CAS  PubMed  Google Scholar 

  204. Tsatsakis AM, Barbounis MG, Kavalakis M et al (2010) Determination of dialkyl phosphates in human hair for the biomonitoring of exposure to organophosphate pesticides. J Chromatogr B Anal Technol Biomed Life Sci 878:1246–1252. https://doi.org/10.1016/j.jchromb.2010.02.021

    Article  CAS  Google Scholar 

  205. Kanavouras K, Tzatzarakis MN, Mastorodemos V et al (2011) A case report of motor neuron disease in a patient showing significant level of DDTs, HCHs and organophosphate metabolites in hair as well as levels of hexane and toluene in blood. Toxicol Appl Pharmacol 256:399–404. https://doi.org/10.1016/j.taap.2011.07.022

    Article  CAS  PubMed  Google Scholar 

  206. Knipe DW, Jayasumana C, Siribaddana S et al (2016) Feasibility of hair sampling to assess levels of organophosphate metabolites in rural areas of Sri Lanka. Environ Res 147:207–211. https://doi.org/10.1016/j.envres.2016.02.011

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  207. Whyatt RM, Barr DB (2001) Measurement of organophosphate metabolites in postpartum meconium as a potential biomarker of prenatal exposure: a validation study. Environ Health Perspect 109:417–420. https://doi.org/10.1289/ehp.01109417

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  208. Raina R (2011) Chemical analysis of pesticides using GC/MS, GC/MS/MS, and LC/MS/MS, pesticides—strategies for pesticides analysis. Biochem Trace Anal Facil:105–130. https://doi.org/10.5772/13242

    Google Scholar 

  209. Pitarch E, López FJ, Serrano R, Hernández F (2001) Multiresidue determination of organophosphorus and organochlorine pesticides in human biological fluids by capillary gas chromatography. Fresenius J Anal Chem 369:502–509. https://doi.org/10.1007/s002160100708

    Article  CAS  PubMed  Google Scholar 

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Funding

This work is supported by the FEDER funds through the POCI-COMPETE 2020—Operational Programme Competitiveness and Internationalisation in Axis I—strengthening research, technological development and innovation (project POCI-01-0145-FEDER-007491) and the National Funds by Fundação para a Ciência e a Tecnologia (FCT) (project UID/Multi /00709/2013). S. Soares acknowledges Programme Santander-Totta Universidades in the form of a fellowship (Bolsa BID/UBI-Santander Universidades/2018).

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Authors and Affiliations

  1. Centro de Investigação em Ciências da Saúde (CICS-UBI), Universidade da Beira Interior, Av. Infante D. Henrique, 6201-556, Covilhã, Portugal

    Sofia Soares, Tiago Rosado & Eugenia Gallardo

  2. Laboratório de Fármaco-Toxicologia—UBIMedical, Universidade da Beira Interior, Covilhã, Portugal

    Sofia Soares, Tiago Rosado & Eugenia Gallardo

  3. Serviço de Química e Toxicologia Forenses, Instituto Nacional de Medicina Legal e Ciências Forenses, Delegação do Sul, Lisboa, Portugal

    Mário Barroso

  4. Faculdade de Medicina, Universidade de Coimbra, Coimbra, Portugal

    Duarte Nuno Vieira

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  1. Sofia Soares
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Correspondence to Eugenia Gallardo.

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Soares, S., Rosado, T., Barroso, M. et al. Organophosphorus pesticide determination in biological specimens: bioanalytical and toxicological aspects. Int J Legal Med 133, 1763–1784 (2019). https://doi.org/10.1007/s00414-019-02119-9

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