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Published in: International Journal of Legal Medicine 3/2017

01-05-2017 | Original Article

The effect of sodium fluoride, formaldehyde, and storage temperature on the stability of methamidophos in post-mortem blood and liver

Authors: Zhiwen Wei, Qing Niu, Fan Zhang, Kun Xiao, Ling Liu, Yujin Wang, Juan Jia, Jie Cao, Shanlin Fu, Keming Yun

Published in: International Journal of Legal Medicine | Issue 3/2017

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Abstract

Poisoning by organophosphorus insecticides such as methamidophos makes up a significant portion of forensic identification cases in China. Stability of methamidophos during specimen storage remains largely unknown. This study aimed to examine the long-term stability of methamidophos in postmortem specimens. Three experimental dogs after oral administration of methamidophos were sacrificed, and blood and liver specimens were collected and stored at various conditions. Gas chromatography-mass spectrometry (GC/MS) was used to measure the methamidophos concentrations after 0, 4, 7, 12, 16, 60, and 180 days of storage. The results showed that methamidophos was not stable and followed first-order degradation kinetics at all storage conditions investigated. The degradation half-life in blood was 12.2, 16.9, 11.0, and 1.0 days when the samples were stored at room temperature (RT, 20 °C), 4 °C, −20 °C, and at RT with 1 % sodium fluoride (NaF), respectively. The degradation half-life in liver was 4.1, 9.8, 17.8, and 2.0 days when the samples were stored at RT, 4 °C, −20 °C, and at RT with liver fixed in 10 % formaldehyde solution, respectively. These findings are significant in guiding sample storage and data interpretation. Specimens containing methamidophos should be stored at −20 °C and analyzed as early as possible. Addition of NaF in blood and fixation of liver in formaldehyde should be avoided due to the accelerated degradation of methamidophos under these conditions. The preliminary study suggests that it might be possible to calculate methamidophos concentration at the time of death based on its first-order degradation kinetic under specific storage conditions.
Literature
1.
go back to reference Eddleston M (2000) Patterns and problems of deliberate self-poisoning in the developing world. QJM : monthly journal of the Association of Physicians 93(11):715–731CrossRefPubMed Eddleston M (2000) Patterns and problems of deliberate self-poisoning in the developing world. QJM : monthly journal of the Association of Physicians 93(11):715–731CrossRefPubMed
3.
go back to reference Gunnell D, Eddleston M, Phillips MR, Konradsen F (2007) The global distribution of fatal pesticide self-poisoning: systematic review. BMC Public Health 7(357). doi:10.1186/1471-2458-7-357 Gunnell D, Eddleston M, Phillips MR, Konradsen F (2007) The global distribution of fatal pesticide self-poisoning: systematic review. BMC Public Health 7(357). doi:10.​1186/​1471-2458-7-357
4.
go back to reference Eddleston M, Adhikari S, Egodage S, Ranganath H, Mohamed F, Manuweera G, Azher S, Jayamanne S, Juzczak E, Sheriff MR, Dawson AH, Buckley NA (2012) Effects of a provincial ban of two toxic organophosphorus insecticides on pesticide poisoning hospital admissions. Clinical toxicology (Philadelphia, Pa) 50 (3):202–209. doi:10.3109/15563650.2012.660573 Eddleston M, Adhikari S, Egodage S, Ranganath H, Mohamed F, Manuweera G, Azher S, Jayamanne S, Juzczak E, Sheriff MR, Dawson AH, Buckley NA (2012) Effects of a provincial ban of two toxic organophosphorus insecticides on pesticide poisoning hospital admissions. Clinical toxicology (Philadelphia, Pa) 50 (3):202–209. doi:10.​3109/​15563650.​2012.​660573
5.
go back to reference Meerdink GL (1989) Organophosphorus and carbamate insecticide poisoning in large animals. The Veterinary Clinics of North America. Food Animal Practice 5(2):375–389CrossRefPubMed Meerdink GL (1989) Organophosphorus and carbamate insecticide poisoning in large animals. The Veterinary Clinics of North America. Food Animal Practice 5(2):375–389CrossRefPubMed
6.
go back to reference Lima CS, Nunes-Freitas AL, Ribeiro-Carvalho A, Filgueiras CC, Manhaes AC, Meyer A, Abreu-Villaca Y (2011) Exposure to methamidophos at adulthood adversely affects serotonergic biomarkers in the mouse brain. Neurotoxicology 32(6):718–724. doi:10.1016/j.neuro.2011.08.002 CrossRefPubMed Lima CS, Nunes-Freitas AL, Ribeiro-Carvalho A, Filgueiras CC, Manhaes AC, Meyer A, Abreu-Villaca Y (2011) Exposure to methamidophos at adulthood adversely affects serotonergic biomarkers in the mouse brain. Neurotoxicology 32(6):718–724. doi:10.​1016/​j.​neuro.​2011.​08.​002 CrossRefPubMed
7.
go back to reference Emerick GL, Ehrich M, Jortner BS, Oliveira RV, Deoliveira GH (2012) Biochemical, histopathological and clinical evaluation of delayed effects caused by methamidophos isoforms and TOCP in hens: ameliorative effects using control of calcium homeostasis. Toxicology 302(1):88–95. doi:10.1016/j.tox.2012.08.002 CrossRefPubMed Emerick GL, Ehrich M, Jortner BS, Oliveira RV, Deoliveira GH (2012) Biochemical, histopathological and clinical evaluation of delayed effects caused by methamidophos isoforms and TOCP in hens: ameliorative effects using control of calcium homeostasis. Toxicology 302(1):88–95. doi:10.​1016/​j.​tox.​2012.​08.​002 CrossRefPubMed
8.
go back to reference Gubert P, Avila DS, Bridi JC, Saurin S, Lugokenski TH, Villarinho JG, Fachinetto R, Pereira ME, Ferreira J, da Rocha JB, Soares FA (2011) Low concentrations of methamidophos do not alter AChE activity but modulate neurotransmitters uptake in hippocampus and striatum in vitro. Life Sci 88(1–2):89–95. doi:10.1016/j.lfs.2010.10.031 CrossRefPubMed Gubert P, Avila DS, Bridi JC, Saurin S, Lugokenski TH, Villarinho JG, Fachinetto R, Pereira ME, Ferreira J, da Rocha JB, Soares FA (2011) Low concentrations of methamidophos do not alter AChE activity but modulate neurotransmitters uptake in hippocampus and striatum in vitro. Life Sci 88(1–2):89–95. doi:10.​1016/​j.​lfs.​2010.​10.​031 CrossRefPubMed
10.
go back to reference Chen ZL, Li SH, Wang Y, Yu L, Yi GL, Yan YL (2011) Analysis of 4713 cases of Wuhan pesticide poisoning reports of year 2002 to 2010. Chinese journal of industrial hygiene and occupational diseases 29(10):776–778PubMed Chen ZL, Li SH, Wang Y, Yu L, Yi GL, Yan YL (2011) Analysis of 4713 cases of Wuhan pesticide poisoning reports of year 2002 to 2010. Chinese journal of industrial hygiene and occupational diseases 29(10):776–778PubMed
11.
go back to reference Wang WJ, HQ L, Shao RD (2013) A case report of acute severe methamidophos poisoning associated with drowning. Chinese journal of industrial hygiene and occupational diseases 31(5):355PubMed Wang WJ, HQ L, Shao RD (2013) A case report of acute severe methamidophos poisoning associated with drowning. Chinese journal of industrial hygiene and occupational diseases 31(5):355PubMed
14.
go back to reference 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(16):1939–1946CrossRefPubMedPubMedCentral 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(16):1939–1946CrossRefPubMedPubMedCentral
15.
go back to reference Colak S, Erdogan MO, Baydin A, Afacan MA, Kati C, Duran L (2014) Epidemiology of organophosphate intoxication and predictors of intermediate syndrome. Turk J Med Sci 44(2):279–282CrossRefPubMed Colak S, Erdogan MO, Baydin A, Afacan MA, Kati C, Duran L (2014) Epidemiology of organophosphate intoxication and predictors of intermediate syndrome. Turk J Med Sci 44(2):279–282CrossRefPubMed
16.
go back to reference McConnell R, Delgado-Tellez E, Cuadra R, Torres E, Keifer M, Almendarez J, Miranda J, El-Fawal HA, Wolff M, Simpson D, Lundberg I (1999) Organophosphate neuropathy due to methamidophos: biochemical and neurophysiological markers. Arch Toxicol 73(6):296–300CrossRefPubMed McConnell R, Delgado-Tellez E, Cuadra R, Torres E, Keifer M, Almendarez J, Miranda J, El-Fawal HA, Wolff M, Simpson D, Lundberg I (1999) Organophosphate neuropathy due to methamidophos: biochemical and neurophysiological markers. Arch Toxicol 73(6):296–300CrossRefPubMed
17.
go back to reference Maretto GX, do Nascimento CP, Passamani LM, Schenberg LC, de Andrade TU, Figueiredo SG, Mauad H, Sampaio KN (2012) Acute exposure to the insecticide O,S-dimethyl phosphoramidothioate (methamidophos) leads to impairment of cardiovascular reflexes in rats. Ecotoxicol Environ Saf 80:203–207. doi:10.1016/j.ecoenv.2012.03.001 CrossRefPubMed Maretto GX, do Nascimento CP, Passamani LM, Schenberg LC, de Andrade TU, Figueiredo SG, Mauad H, Sampaio KN (2012) Acute exposure to the insecticide O,S-dimethyl phosphoramidothioate (methamidophos) leads to impairment of cardiovascular reflexes in rats. Ecotoxicol Environ Saf 80:203–207. doi:10.​1016/​j.​ecoenv.​2012.​03.​001 CrossRefPubMed
18.
go back to reference Garrido Frenich A, Martínez Vidal JL, Fernández Moreno JL, Romero-González R (2009) Compensation for matrix effects in gas chromatography–tandem mass spectrometry using a single point standard addition. J Chromatogr A 1216(23):4798–4808. doi:10.1016/j.chroma.2009.04.018 CrossRefPubMed Garrido Frenich A, Martínez Vidal JL, Fernández Moreno JL, Romero-González R (2009) Compensation for matrix effects in gas chromatography–tandem mass spectrometry using a single point standard addition. J Chromatogr A 1216(23):4798–4808. doi:10.​1016/​j.​chroma.​2009.​04.​018 CrossRefPubMed
19.
go back to reference Fernandez-Alba AR, Agüera A, Contreras M, Peñuela G, Ferrer I, Barceló D (1998) Comparison of various sample handling and analytical procedures for the monitoring of pesticides and metabolites in ground waters. J Chromatogr A 823(1–2):35–47. doi:10.1016/S0021-9673(98)00439-7 CrossRefPubMed Fernandez-Alba AR, Agüera A, Contreras M, Peñuela G, Ferrer I, Barceló D (1998) Comparison of various sample handling and analytical procedures for the monitoring of pesticides and metabolites in ground waters. J Chromatogr A 823(1–2):35–47. doi:10.​1016/​S0021-9673(98)00439-7 CrossRefPubMed
20.
go back to reference Ingelse BA, van Dam RCJ, Vreeken RJ, Mol HGJ, Steijger OM (2001) Determination of polar organophosphorus pesticides in aqueous samples by direct injection using liquid chromatography–tandem mass spectrometry. J Chromatogr A 918(1):67–78. doi:10.1016/S0021-9673(01)00660-4 CrossRefPubMed Ingelse BA, van Dam RCJ, Vreeken RJ, Mol HGJ, Steijger OM (2001) Determination of polar organophosphorus pesticides in aqueous samples by direct injection using liquid chromatography–tandem mass spectrometry. J Chromatogr A 918(1):67–78. doi:10.​1016/​S0021-9673(01)00660-4 CrossRefPubMed
21.
go back to reference Lehotay SJ, Son KA, Kwon H, Koesukwiwat U, Fu W, Mastovska K, Hoh E, Leepipatpiboon N (2010) Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in fruits and vegetables. J Chromatogr A 1217(16):2548–2560. doi:10.1016/j.chroma.2010.01.044 CrossRefPubMed Lehotay SJ, Son KA, Kwon H, Koesukwiwat U, Fu W, Mastovska K, Hoh E, Leepipatpiboon N (2010) Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in fruits and vegetables. J Chromatogr A 1217(16):2548–2560. doi:10.​1016/​j.​chroma.​2010.​01.​044 CrossRefPubMed
23.
go back to reference Jones JM, Raleigh MD, Pentel PR, Harmon TM, Keyler DE, Remmel RP, Birnbaum AK (2013) Stability of heroin, 6-monoacetylmorphine, and morphine in biological samples and validation of an LC-MS assay for delayed analyses of pharmacokinetic samples in rats. J Pharm Biomed Anal 74:291–297. doi:10.1016/j.jpba.2012.10.033 CrossRefPubMed Jones JM, Raleigh MD, Pentel PR, Harmon TM, Keyler DE, Remmel RP, Birnbaum AK (2013) Stability of heroin, 6-monoacetylmorphine, and morphine in biological samples and validation of an LC-MS assay for delayed analyses of pharmacokinetic samples in rats. J Pharm Biomed Anal 74:291–297. doi:10.​1016/​j.​jpba.​2012.​10.​033 CrossRefPubMed
24.
go back to reference Fucci N, De Giovanni N (2008) Stability of methadone and its main metabolite in oral fluid. Drug metabolism letters 2(2):125–129CrossRefPubMed Fucci N, De Giovanni N (2008) Stability of methadone and its main metabolite in oral fluid. Drug metabolism letters 2(2):125–129CrossRefPubMed
25.
go back to reference Clauwaert KM, Van Bocxlaer JF, De Leenheer AP (2001) Stability study of the designer drugs "MDA, MDMA and MDEA" in water, serum, whole blood, and urine under various storage temperatures. Forensic Sci Int 124 (1):36–42 Clauwaert KM, Van Bocxlaer JF, De Leenheer AP (2001) Stability study of the designer drugs "MDA, MDMA and MDEA" in water, serum, whole blood, and urine under various storage temperatures. Forensic Sci Int 124 (1):36–42
26.
go back to reference Maskell PD, Seetohul LN, Livingstone AC, Cockburn AK, Preece J, Pounder DJ (2013) Stability of 3,4-methylenedioxymethampetamine (MDMA), 4-methylmethcathinone (mephedrone) and 3-trifluromethylphenylpiperazine (3-TFMPP) in formalin solution. J Anal Toxicol 37(7):440–446. doi:10.1093/jat/bkt051 CrossRefPubMed Maskell PD, Seetohul LN, Livingstone AC, Cockburn AK, Preece J, Pounder DJ (2013) Stability of 3,4-methylenedioxymethampetamine (MDMA), 4-methylmethcathinone (mephedrone) and 3-trifluromethylphenylpiperazine (3-TFMPP) in formalin solution. J Anal Toxicol 37(7):440–446. doi:10.​1093/​jat/​bkt051 CrossRefPubMed
27.
go back to reference Anizan S, Bergamaschi MM, Barnes AJ, Milman G, Desrosiers N, Lee D, Gorelick DA, Huestis MA (2015) Impact of oral fluid collection device on cannabinoid stability following smoked cannabis. Drug testing and analysis 7(2):114–120. doi:10.1002/dta.1688 CrossRefPubMed Anizan S, Bergamaschi MM, Barnes AJ, Milman G, Desrosiers N, Lee D, Gorelick DA, Huestis MA (2015) Impact of oral fluid collection device on cannabinoid stability following smoked cannabis. Drug testing and analysis 7(2):114–120. doi:10.​1002/​dta.​1688 CrossRefPubMed
29.
go back to reference Skopp G, Klingmann A, Potsch L, Mattern R (2001) In vitro stability of cocaine in whole blood and plasma including ecgonine as a target analyte. Ther Drug Monit 23(2):174–181CrossRefPubMed Skopp G, Klingmann A, Potsch L, Mattern R (2001) In vitro stability of cocaine in whole blood and plasma including ecgonine as a target analyte. Ther Drug Monit 23(2):174–181CrossRefPubMed
30.
go back to reference Moriya F, Hashimoto Y (1996) Postmortem stability of cocaine and cocaethylene in blood and tissues of humans and rabbits. J Forensic Sci 41(4):612–616CrossRefPubMed Moriya F, Hashimoto Y (1996) Postmortem stability of cocaine and cocaethylene in blood and tissues of humans and rabbits. J Forensic Sci 41(4):612–616CrossRefPubMed
31.
go back to reference Heller S, Hiemke C, Stroba G, Rieger-Gies A, Daum-Kreysch E, Sachse J, Hartter S (2004) Assessment of storage and transport stability of new antidepressant and antipsychotic drugs for a nationwide TDM service. Ther Drug Monit 26(4):459–461CrossRefPubMed Heller S, Hiemke C, Stroba G, Rieger-Gies A, Daum-Kreysch E, Sachse J, Hartter S (2004) Assessment of storage and transport stability of new antidepressant and antipsychotic drugs for a nationwide TDM service. Ther Drug Monit 26(4):459–461CrossRefPubMed
32.
go back to reference Ali AM, Ali AA, Maghrabi IA (2015) Clozapine-carboxylic acid plasticized co-amorphous dispersions: preparation, characterization and solution stability evaluation. Acta Pharma 65(2):133–146. doi:10.1515/acph-2015-0014 CrossRef Ali AM, Ali AA, Maghrabi IA (2015) Clozapine-carboxylic acid plasticized co-amorphous dispersions: preparation, characterization and solution stability evaluation. Acta Pharma 65(2):133–146. doi:10.​1515/​acph-2015-0014 CrossRef
34.
go back to reference Diao X, Ma Z, Lei P, Zhong D, Zhang Y, Chen X (2013) Enantioselective determination of 3-n-butylphthalide (NBP) in human plasma by liquid chromatography on a teicoplanin-based chiral column coupled with tandem mass spectrometry. Journal of chromatography B, analytical technologies in the biomedical and Life Sci 939:67–72. doi:10.1016/j.jchromb.2013.09.014 CrossRef Diao X, Ma Z, Lei P, Zhong D, Zhang Y, Chen X (2013) Enantioselective determination of 3-n-butylphthalide (NBP) in human plasma by liquid chromatography on a teicoplanin-based chiral column coupled with tandem mass spectrometry. Journal of chromatography B, analytical technologies in the biomedical and Life Sci 939:67–72. doi:10.​1016/​j.​jchromb.​2013.​09.​014 CrossRef
35.
go back to reference Diao X, Ma Z, Wang H, Zhong D, Zhang Y, Jin J, Fan Y, Chen X (2013) Simultaneous quantitation of 3-n-butylphthalide (NBP) and its four major metabolites in human plasma by LC-MS/MS using deuterated internal standards. J Pharm Biomed Anal:78–79. doi:10.1016/j.jpba.2013.01.033 Diao X, Ma Z, Wang H, Zhong D, Zhang Y, Jin J, Fan Y, Chen X (2013) Simultaneous quantitation of 3-n-butylphthalide (NBP) and its four major metabolites in human plasma by LC-MS/MS using deuterated internal standards. J Pharm Biomed Anal:78–79. doi:10.​1016/​j.​jpba.​2013.​01.​033
38.
go back to reference Kocourek V, Hajšlová J, Holadová K, Poustka J (1998) Stability of pesticides in plant extracts used as calibrants in the gas chromatographic analysis of residues. J Chromatogr A 800(2):297–304CrossRef Kocourek V, Hajšlová J, Holadová K, Poustka J (1998) Stability of pesticides in plant extracts used as calibrants in the gas chromatographic analysis of residues. J Chromatogr A 800(2):297–304CrossRef
39.
go back to reference Moriya F, Hashimoto Y, Kuo T-L (1999) Pitfalls when determining tissue distributions of organophosphorus chemicals: sodium fluoride accelerates chemical degradation. J Anal Toxicol 23(3):210–215CrossRefPubMed Moriya F, Hashimoto Y, Kuo T-L (1999) Pitfalls when determining tissue distributions of organophosphorus chemicals: sodium fluoride accelerates chemical degradation. J Anal Toxicol 23(3):210–215CrossRefPubMed
40.
go back to reference Tracy TS, Rybeck BF, James DG, Knopp JB, Gannett PM (2001) Stability of benzodiazepines in formaldehyde solutions. J Anal Toxicol 25(3):166–173CrossRefPubMed Tracy TS, Rybeck BF, James DG, Knopp JB, Gannett PM (2001) Stability of benzodiazepines in formaldehyde solutions. J Anal Toxicol 25(3):166–173CrossRefPubMed
Metadata
Title
The effect of sodium fluoride, formaldehyde, and storage temperature on the stability of methamidophos in post-mortem blood and liver
Authors
Zhiwen Wei
Qing Niu
Fan Zhang
Kun Xiao
Ling Liu
Yujin Wang
Juan Jia
Jie Cao
Shanlin Fu
Keming Yun
Publication date
01-05-2017
Publisher
Springer Berlin Heidelberg
Published in
International Journal of Legal Medicine / Issue 3/2017
Print ISSN: 0937-9827
Electronic ISSN: 1437-1596
DOI
https://doi.org/10.1007/s00414-016-1518-x

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