@2024 Afarand., IRAN
ISSN: 1027-1457 Scientific Journal of Forensic Medicine 2019;25(3):121-129
ISSN: 1027-1457 Scientific Journal of Forensic Medicine 2019;25(3):121-129
Optimization of a Dispersive Liquid-Liquid Microextration Method for Analysis of Chlorpyrifos in Urine Using the Chemometrics Method
ARTICLE INFO
Article Type
Original ResearchAuthors
Mohammadzaheri R. (1)Ansari Dogaheh M. (2)
Kazemipour M. (1)
Soltaninejad K. (*3)
(*3) Forensic Toxicology Department, Legal Medicine Research Center, Legal Medicine Organization, Tehran, Iran
(1) Chemistry Department, Science Faculty, Kerman Branch, Islamic Azad University, Kerman, Iran
(2) Pharmaceutics Department, Pharmacy Faculty, Kerman University of Medical Sciences, Kerman, Iran
Correspondence
Address: Forensic Toxicology Department, Legal Medicine Research Center, Legal Medicine Organization, Behesht Street, Tehran, Iran. Postal Code: 1114795113Phone: +98 (21) 55613131
Fax: +98 (21) 55613131
kamsoltaninejad@gmail.com
Article History
Received: June 10, 2019Accepted: August 28, 2019
ePublished: September 21, 2019
ABSTRACT
Aims
The use of simple, low cost, high-efficiency microextraction methods are considered for sample preparation in forensic toxicology. Nowadays, the chemometrics technique can be used to determine the important and influencing factors on the response, to optimize the extraction methods. The aim of this study was to design and optimize a dispersive liquid-liquid microextraction (DLLME) method for the extraction of chlorpyrifos from the urine using a chemometrics method.
Materials & Methods In this experimental study, at first, a DLLME method for the extraction of chlorpyrifos in the urine sample was designed. Then, the Taguchi model was used for screening and investigating the role of effective factors on the extraction of chlorpyrifos from the urine and a central composite design was used to examine the interaction of these factors. After validation of the extracted data, chlorpyrifos was extracted from the urine using an optimized DLLME method and it detected and quantified using the high-performance liquid chromatography with photodiode array detector (HPLC-PDA).
Findings The optimized DLLME-HPLC-PDA method was linear in the range of 0.5 to 4μg/ml, and the R2 coefficient was 0.9996. The minimum rates of detection and quantification were calculated by 0.08 and 0.25μg/ml, respectively. The profitability of the method in the optimal condition was calculated by %95.6.
Conclusion The optimized DLLME-HPLC-PDA method can be used as a simple, fast, inexpensive, sensitive and precise method for chlorpyrifos analyzing in urine specimens in clinical and forensic toxicology laboratories.
Materials & Methods In this experimental study, at first, a DLLME method for the extraction of chlorpyrifos in the urine sample was designed. Then, the Taguchi model was used for screening and investigating the role of effective factors on the extraction of chlorpyrifos from the urine and a central composite design was used to examine the interaction of these factors. After validation of the extracted data, chlorpyrifos was extracted from the urine using an optimized DLLME method and it detected and quantified using the high-performance liquid chromatography with photodiode array detector (HPLC-PDA).
Findings The optimized DLLME-HPLC-PDA method was linear in the range of 0.5 to 4μg/ml, and the R2 coefficient was 0.9996. The minimum rates of detection and quantification were calculated by 0.08 and 0.25μg/ml, respectively. The profitability of the method in the optimal condition was calculated by %95.6.
Conclusion The optimized DLLME-HPLC-PDA method can be used as a simple, fast, inexpensive, sensitive and precise method for chlorpyrifos analyzing in urine specimens in clinical and forensic toxicology laboratories.
Keywords:
Chlorpyrifos ,
Chemometrics ,
Liquid-Liquid Microextraction ,
High Performance Liquid Chromatography ,
CITATION LINKS
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[16]Bicker W, Lämmerhofer M, Genser D, Kiss H, Lindner W. A case study of acute human chlorpyrifos poisoning: novel aspects on metabolism and toxicokinetics derived from liquid chromatography-tandem mass spectrometry analysis of urine samples. Toxicol Lett. 2005;159(3):235-51.
[17]Bicker W, Lämmerhofer M, Lindner W. Determination of chlorpyrifos metabolites in human urine by reversed-phase/weak anion exchange liquid chromatography-electrospray ionisation-tandem mass spectrometry. J Chromatogr B Analyt Technol Biomed Life Sci. 2005;822(1-2):160-9.
[18]Sancho JV, Pozo OJ, Hernández F. 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. 2000;14(16):1485-90.
[19]Shanker A, Sood C, Kumar V, Ravindranath SD. A modified extraction and clean-up procedure for the detection and determination of parathion-methyl and chlorpyrifos residues in tea. Pest Manag Sci. 2001;57(5):458-62.
[20]Wielgomas B, Czarnowski W. Headspace single-drop microextraction and GC-ECD determination of chlorpyrifos-ethyl in rat liver. Anal Bioanal Chem. 2008;390(7):1933-41.
[21]Li R, He L, Zhou T, Ji X, Qian M, Zhou Y, Wang Q. Simultaneous determination of chlorpyrifos and 3,5,6-trichloro-2-pyridinol in duck muscle by modified QuEChERS coupled to gas chromatography tandem mass spectrometry (GC-MS/MS). Anal Bioanal Chem. 2014;406(12):2899-907.
[22]Rahimi Moghadam M, Zargar B , Rastegarzadeh S . Novel magnetic hollow zein nanoparticles for preconcentration of chlorpyrifos from water and soil samples prior to analysis via high-performance liquid chromatography (HPLC). Analyst. 2018;143(9):2174-82.
[23]Ma JK, Huang XC, Wei SL. Preparation and application of chlorpyrifos molecularly imprinted solid-phase microextraction probes for the residual determination of organophosphorous pesticides in fresh and dry foods. J Sep Sci. 2018;41(15):3152-62.
[24]Rezaee M, Assadi Y, Hosseini MRM, Aghaee E, Ahmadia F, Berijani S. Determination of organic compounds in water using dispersive liquid–liquid microextraction. J Chromatogr A. 2006;1116(1-2):1-9.
[25]El-Gindy A, Hadad GM. Chemometrics in pharmaceutical analysis: an introduction, review, and future perspectives. J AOAC Int. 2012;95(3):609-23.
[26]Rasyid MFA, Salim MS, Akil HM, Ishak ZAM. Optimization of processing conditions via response surface methodology (RSM) of nonwoven flax fibre reinforced acrodur biocomposites. Procedia Chem. 2016;19:469-76.
[27]Sereshti, H, Karimi M, Samadi S. Application of response surface method for optimization of dispersive liquid–liquid microextraction of water-soluble components of Rosa damascena Mill. essential oil. J Chromatogr A. 2009;1216(2):198-204.
[28]Asghar A, Abdul Raman AA, Ashri Wan Daud WM. A comparison of central composite design and taguchi method for optimizing Fenton process. Sci World J. 2014;2014:1-14.
[29]Hu S, Xue J, Yang X, Chen X, Wang RQ, Bai XH. Sodium dodecyl sulfate sensitized switchable solvent liquid-phase microextractionfor the preconcentration of protoberberine alkaloids in Rhizoma coptidis. J Sep Sci. 2018;41(18):3614-21.
[30]Goudarzi N, Farsimadan S, Chamjangali MA, Bagherian GA. Optimization of modified dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography for the simultaneous preconcentration and determination of nitrazepam and midazolam drugs: An experimental design. J Sep Sci. 2015;38(10):1673-9.
[31]Park MJ, In SW, Lee SK, Choi WK, Park YS, Chung HS. Postmortem blood concentrations of organophosphorus pesticides. Forensic Sci Int. 2009;184(1-3):28-31.
[32]Abu-Qare AW, Abou-Donia MB. Quantification of nicotine, chlorpyrifos and their metabolites in rat plasma and urine using high-performance liquid chromatography. J Chromatogr B Biomed Sci Appl. 2001;757(2):295-300.
[33]Cho Y, Matsuoka N, Kamiya A. Determination of organophosphorus pesticides in biological samples of acute poisoning by HPLC with diode-array detector. Chem Pharm Bull. 1997;45(4):737-40.
[34]Kim HS, Kim J, Suh JH, Han SB. General unknown screening for pesticides in whole blood and Korean gastric contents by liquid chromatography-tandem mass spectrometry. Arch Pharm Res. 2014;37(10):1317-24.
[35]Santos C, Oppolzer D, Gonçalves A, Barroso M, Gallardo E. Determination of organophosphorous pesticides in blood using microextraction in packed sorbent and gas chromatography-tandem mass spectrometry. J Anal Toxicol. 2018;42(5):321-9.
[2]Christensen, K, Harper B, Luukinen, B, Buhl K, Stone D. Chlorpyrifos technical fact sheet [Internet]. Oregon: National Pesticide Information Center, Oregon State University Extension Services. 2009 [cited 2019 July 22]. Available from: http://npic.orst.edu/factsheets/archive/chlorptech.html.
[3]Rathod AL, Garg RK. Chlorpyrifos poisoning and its implications in human fatal cases: a forensic perspective with reference to Indian scenario. J Forensic Leg Med. 2017;47:29-34.
[4]Martínez MA, Ballesteros S, Sánchez de la Torre C, Sanchiz A, Almarza E, García-Aguilera A. Attempted suicide by ingestion of chlorpyrifos: identification in serum and gastric content by GC-FID/GC-MS. J Anal Toxicol. 2004;28(7):609-15.
[5]Lee JC, Lin KL, Lin JJ, Hsia SH, Wu CT. Non-accidental chlorpyrifos poisoning-an unusual cause of profound unconsciousness. Eur J Pediatr. 2010;169(4):509-11.
[6]Solomon GM, Moodley J. Acute chlorpyrifos poisoning in pregnancy: a case report. Clin Toxicol (Phila). 2007;45(4):416-9.
[7]Hadland SE, Levy S. Objective testing: urine and other drug tests. Child Adolesc Psychiatr Clin N Am. 2016;25(3): 549-65.
[8]Brun EM, Garcés-García M, Puchades R, Maquieira A. Highly sensitive enzyme-linked immunosorbent assay for chlorpyrifos. Application to olive oil analysis. J Agric Food Chem. 2005;53(24):9352-60.
[9]Otieno PO, Owuor PO, Lalah JO, Pfister G, Schramm KW. Comparative evaluation of ELISA kit and HPLC DAD for the determination of chlorpyrifos ethyl residues in water and sediments. Talanta. 2013;117:250-7.
[10]Rezk MR, Abd El-Aleem AEB, Khalile SM, El-Naggar OK. Selective determination of diazinon and chlorpyrifos in the presence of their degradation products: Application to environmental samples. J AOAC Int. 2018;101(4):1191-7.
[11]Rezk MR, Abd El-Aleem AEB, Khalile SM, El-Naggar OK. Determination of residues of diazinon and chlorpyrifos in lavender and rosemary leaves by gas chromatography. J AOAC Int. 2018;101(2):587-92.
[12]Dallegrave A, Pizzolato TM, Barreto F, Eljarrat E, Barceló D. Methodology for trace analysis of 17 pyrethroids and chlorpyrifos in foodstuff by gas chromatography-tandem mass spectrometry. Anal Bioanal Chem. 2016;408(27):7689-97.
[13]Płonka M, Walorczyk S, Miszczyk M, Kronenbach-Dylong D. Simultaneous gas chromatographic determination of chlorpyrifos and its impurity sulfotep in liquid pesticide formulations. J Environ Sci Health B. 2016;51(11):736-41.
[14]Tiwari MK, Guha S. Simultaneous analysis of endosulfan, chlorpyrifos, and their metabolites in natural soil and water samples using gas chromatography-tandem mass spectrometry. Environ Monit Assess. 2013;185(10):8451-63.
[15]Salm P, Taylor PJ, Roberts D, de Silva J. 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 Analyt Technol Biomed Life Sci. 2009;877(5-6):568-74.
[16]Bicker W, Lämmerhofer M, Genser D, Kiss H, Lindner W. A case study of acute human chlorpyrifos poisoning: novel aspects on metabolism and toxicokinetics derived from liquid chromatography-tandem mass spectrometry analysis of urine samples. Toxicol Lett. 2005;159(3):235-51.
[17]Bicker W, Lämmerhofer M, Lindner W. Determination of chlorpyrifos metabolites in human urine by reversed-phase/weak anion exchange liquid chromatography-electrospray ionisation-tandem mass spectrometry. J Chromatogr B Analyt Technol Biomed Life Sci. 2005;822(1-2):160-9.
[18]Sancho JV, Pozo OJ, Hernández F. 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. 2000;14(16):1485-90.
[19]Shanker A, Sood C, Kumar V, Ravindranath SD. A modified extraction and clean-up procedure for the detection and determination of parathion-methyl and chlorpyrifos residues in tea. Pest Manag Sci. 2001;57(5):458-62.
[20]Wielgomas B, Czarnowski W. Headspace single-drop microextraction and GC-ECD determination of chlorpyrifos-ethyl in rat liver. Anal Bioanal Chem. 2008;390(7):1933-41.
[21]Li R, He L, Zhou T, Ji X, Qian M, Zhou Y, Wang Q. Simultaneous determination of chlorpyrifos and 3,5,6-trichloro-2-pyridinol in duck muscle by modified QuEChERS coupled to gas chromatography tandem mass spectrometry (GC-MS/MS). Anal Bioanal Chem. 2014;406(12):2899-907.
[22]Rahimi Moghadam M, Zargar B , Rastegarzadeh S . Novel magnetic hollow zein nanoparticles for preconcentration of chlorpyrifos from water and soil samples prior to analysis via high-performance liquid chromatography (HPLC). Analyst. 2018;143(9):2174-82.
[23]Ma JK, Huang XC, Wei SL. Preparation and application of chlorpyrifos molecularly imprinted solid-phase microextraction probes for the residual determination of organophosphorous pesticides in fresh and dry foods. J Sep Sci. 2018;41(15):3152-62.
[24]Rezaee M, Assadi Y, Hosseini MRM, Aghaee E, Ahmadia F, Berijani S. Determination of organic compounds in water using dispersive liquid–liquid microextraction. J Chromatogr A. 2006;1116(1-2):1-9.
[25]El-Gindy A, Hadad GM. Chemometrics in pharmaceutical analysis: an introduction, review, and future perspectives. J AOAC Int. 2012;95(3):609-23.
[26]Rasyid MFA, Salim MS, Akil HM, Ishak ZAM. Optimization of processing conditions via response surface methodology (RSM) of nonwoven flax fibre reinforced acrodur biocomposites. Procedia Chem. 2016;19:469-76.
[27]Sereshti, H, Karimi M, Samadi S. Application of response surface method for optimization of dispersive liquid–liquid microextraction of water-soluble components of Rosa damascena Mill. essential oil. J Chromatogr A. 2009;1216(2):198-204.
[28]Asghar A, Abdul Raman AA, Ashri Wan Daud WM. A comparison of central composite design and taguchi method for optimizing Fenton process. Sci World J. 2014;2014:1-14.
[29]Hu S, Xue J, Yang X, Chen X, Wang RQ, Bai XH. Sodium dodecyl sulfate sensitized switchable solvent liquid-phase microextractionfor the preconcentration of protoberberine alkaloids in Rhizoma coptidis. J Sep Sci. 2018;41(18):3614-21.
[30]Goudarzi N, Farsimadan S, Chamjangali MA, Bagherian GA. Optimization of modified dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography for the simultaneous preconcentration and determination of nitrazepam and midazolam drugs: An experimental design. J Sep Sci. 2015;38(10):1673-9.
[31]Park MJ, In SW, Lee SK, Choi WK, Park YS, Chung HS. Postmortem blood concentrations of organophosphorus pesticides. Forensic Sci Int. 2009;184(1-3):28-31.
[32]Abu-Qare AW, Abou-Donia MB. Quantification of nicotine, chlorpyrifos and their metabolites in rat plasma and urine using high-performance liquid chromatography. J Chromatogr B Biomed Sci Appl. 2001;757(2):295-300.
[33]Cho Y, Matsuoka N, Kamiya A. Determination of organophosphorus pesticides in biological samples of acute poisoning by HPLC with diode-array detector. Chem Pharm Bull. 1997;45(4):737-40.
[34]Kim HS, Kim J, Suh JH, Han SB. General unknown screening for pesticides in whole blood and Korean gastric contents by liquid chromatography-tandem mass spectrometry. Arch Pharm Res. 2014;37(10):1317-24.
[35]Santos C, Oppolzer D, Gonçalves A, Barroso M, Gallardo E. Determination of organophosphorous pesticides in blood using microextraction in packed sorbent and gas chromatography-tandem mass spectrometry. J Anal Toxicol. 2018;42(5):321-9.