Skip to main content

19.12.2018 | Short Communication

A rapid screening color test for glyphosate using dabsyl derivatization

verfasst von: Daisuke Watanabe, Yuko Kazui, Hikoto Ohta

Erschienen in: Forensic Toxicology

Einloggen, um Zugang zu erhalten

Abstract

Purpose

Glyphosate is the most common herbicide in the world, and involved in many poisoning cases. However, the analysis of glyphosate has been difficult because of its high polarity and zwitterionic structure, and no simple screening tests for glyphosate have been known. The purpose of this study was to develop a rapid screening test for glyphosate.

Methods

Glyphosate was visualized through a color change induced by dabsyl derivatization, and the derivatized glyphosate was trapped on the surface of zirconia-coated silica particles by specific chemical interaction between a phosphonate group of glyphosate and the zirconia surface. The presence of glyphosate was indicated by the color change of zirconia surface, which was easily noticed by the naked eye.

Results

The developed method was applied to biological samples (urine and serum), beverage samples (green tea and cola drink), and soil samples. No false positive was observed and the detection limit was 100 μg/mL for the biological samples and 800 μg/mL for the beverage samples.

Conclusions

A simple screening method for glyphosate based on a color test was established. The method is rapid and requires less than 30 μL of samples. The sensitivity was sufficient for most cases of moderate to severe poisoning.
Literatur
2.
Zurück zum Zitat Stalikas CD, Konidari CN (2001) Analytical methods to determine phosphonic and amino acid group-containing pesticides. J Chromatogr A 907:1–19CrossRefPubMed Stalikas CD, Konidari CN (2001) Analytical methods to determine phosphonic and amino acid group-containing pesticides. J Chromatogr A 907:1–19CrossRefPubMed
3.
Zurück zum Zitat Kudzin ZH, Gralak DK, Andrijewski G, Drabowicz J, Łuczak J (2003) Simultaneous analysis of biologically active aminoalkanephosphonic acids. J Chromatogr A 998:183–199CrossRefPubMed Kudzin ZH, Gralak DK, Andrijewski G, Drabowicz J, Łuczak J (2003) Simultaneous analysis of biologically active aminoalkanephosphonic acids. J Chromatogr A 998:183–199CrossRefPubMed
4.
Zurück zum Zitat Moye HA, Deyrup CL (1984) A simple single-step derivatization method for the gas chromatographic analysis of the herbicide glyphosate and its metabolite. J Agric Food Chem 32:192–195CrossRef Moye HA, Deyrup CL (1984) A simple single-step derivatization method for the gas chromatographic analysis of the herbicide glyphosate and its metabolite. J Agric Food Chem 32:192–195CrossRef
5.
Zurück zum Zitat Hori Y, Fujisawa M, Shimada K, Hirose Y (2003) Determination of the herbicide glyphosate and its metabolite in biological specimens by gas chromatography-mass spectrometry. A case of poisoning by Roundup® herbicide. J Anal Toxicol 27:162–166CrossRefPubMed Hori Y, Fujisawa M, Shimada K, Hirose Y (2003) Determination of the herbicide glyphosate and its metabolite in biological specimens by gas chromatography-mass spectrometry. A case of poisoning by Roundup® herbicide. J Anal Toxicol 27:162–166CrossRefPubMed
6.
Zurück zum Zitat Tsunoda N (1993) Simultaneous determination of the herbicides glyphosate, glufosinate and bialaphos and their metabolites by capillary gas chromatography-ion-trap mass spectrometry. J Chromatogr A 637:167–173CrossRef Tsunoda N (1993) Simultaneous determination of the herbicides glyphosate, glufosinate and bialaphos and their metabolites by capillary gas chromatography-ion-trap mass spectrometry. J Chromatogr A 637:167–173CrossRef
7.
Zurück zum Zitat Motojyuku M, Saito T, Akieda K, Otsuka H, Yamamoto I, Inokuchi S (2008) Determination of glyphosate, glyphosate metabolites, and glufosinate in human serum by gas chromatography-mass spectrometry. J Chromatogr B 875:509–514CrossRef Motojyuku M, Saito T, Akieda K, Otsuka H, Yamamoto I, Inokuchi S (2008) Determination of glyphosate, glyphosate metabolites, and glufosinate in human serum by gas chromatography-mass spectrometry. J Chromatogr B 875:509–514CrossRef
8.
Zurück zum Zitat Stalikas CD, Pilidis GA (2000) Development of a method for the simultaneous determination of phosphoric and amino acid group containing pesticides by gas chromatography with mass-selective detection. Optimization of the derivatization procedure using an experimental design approach. J Chromatogr A 872:215–225CrossRefPubMed Stalikas CD, Pilidis GA (2000) Development of a method for the simultaneous determination of phosphoric and amino acid group containing pesticides by gas chromatography with mass-selective detection. Optimization of the derivatization procedure using an experimental design approach. J Chromatogr A 872:215–225CrossRefPubMed
9.
Zurück zum Zitat Tomita M, Okuyama T (1991) High-performance liquid chromatographic determination of glyphosate and (aminomethyl)phosphonic acid in human serum after conversion into p-toluenesulphonyl derivatives. J Chromatogr 566:239–243CrossRefPubMed Tomita M, Okuyama T (1991) High-performance liquid chromatographic determination of glyphosate and (aminomethyl)phosphonic acid in human serum after conversion into p-toluenesulphonyl derivatives. J Chromatogr 566:239–243CrossRefPubMed
10.
Zurück zum Zitat Nedelkoska TV, Low GK-C (2004) High-performance liquid chromatographic determination of glyphosate in water and plant material after pre-column derivatisation with 9-fluorenylmethyl chloroformate. Anal Chim Acta 511:145–153CrossRef Nedelkoska TV, Low GK-C (2004) High-performance liquid chromatographic determination of glyphosate in water and plant material after pre-column derivatisation with 9-fluorenylmethyl chloroformate. Anal Chim Acta 511:145–153CrossRef
11.
Zurück zum Zitat Patsias J, Papadopoulou A, Papadopoulou-Mourkidou E (2001) Automated trace level determination of glyphosate and aminomethyl phosphonic acid in water by on-line anion-exchange solid-phase extraction followed by cation-exchange liquid chromatography and post-column derivatization. J Chromatogr A 932:83–90CrossRefPubMed Patsias J, Papadopoulou A, Papadopoulou-Mourkidou E (2001) Automated trace level determination of glyphosate and aminomethyl phosphonic acid in water by on-line anion-exchange solid-phase extraction followed by cation-exchange liquid chromatography and post-column derivatization. J Chromatogr A 932:83–90CrossRefPubMed
12.
Zurück zum Zitat Bernal J, Bernal JL, Martin MT, Nozal MJ, Anadón A, Martínez-Larrañaga MR, Martínez MA (2010) Development and validation of a liquid chromatography-fluorescence-mass spectrometry method to measure glyphosate and aminomethylphosphonic acid in rat plasma. J Chromatogr B 878:3290–3296CrossRef Bernal J, Bernal JL, Martin MT, Nozal MJ, Anadón A, Martínez-Larrañaga MR, Martínez MA (2010) Development and validation of a liquid chromatography-fluorescence-mass spectrometry method to measure glyphosate and aminomethylphosphonic acid in rat plasma. J Chromatogr B 878:3290–3296CrossRef
13.
Zurück zum Zitat Yoshioka N, Asano M, Kuse A, Mitsuhashi T, Nagasaki Y, Ueno Y (2011) Rapid determination of glyphosate, glufosinate, bialaphos, and their major metabolites in serum by liquid chromatography-tandem mass spectrometry using hydrophilic interaction chromatography. J Chromatogr A 1218:3675–3680CrossRefPubMed Yoshioka N, Asano M, Kuse A, Mitsuhashi T, Nagasaki Y, Ueno Y (2011) Rapid determination of glyphosate, glufosinate, bialaphos, and their major metabolites in serum by liquid chromatography-tandem mass spectrometry using hydrophilic interaction chromatography. J Chromatogr A 1218:3675–3680CrossRefPubMed
14.
Zurück zum Zitat Guo H, Wang H, Zheng J, Liu W, Zhong J, Zhao Q (2018) Sensitive and rapid determination of glyphosate, glufosinate, bialaphos and metabolites by UPLC-MS/MS using a modified Quick Polar Pesticides Extraction method. Forensic Sci Int 283:111–117CrossRefPubMed Guo H, Wang H, Zheng J, Liu W, Zhong J, Zhao Q (2018) Sensitive and rapid determination of glyphosate, glufosinate, bialaphos and metabolites by UPLC-MS/MS using a modified Quick Polar Pesticides Extraction method. Forensic Sci Int 283:111–117CrossRefPubMed
15.
Zurück zum Zitat Watanabe D, Ohta H, Yamamuro T, Ohtsuru O, Miyazaki S, Ohira M (2014) Development of rapid cleanup method for phosphorous containing amino acid type herbicides by using monolithic silica spin column chemically modified by titanium dioxide, MonoSpin TiO. Rep Natl Res Inst Police Sci 63:1–7 (in Japanese) Watanabe D, Ohta H, Yamamuro T, Ohtsuru O, Miyazaki S, Ohira M (2014) Development of rapid cleanup method for phosphorous containing amino acid type herbicides by using monolithic silica spin column chemically modified by titanium dioxide, MonoSpin TiO. Rep Natl Res Inst Police Sci 63:1–7 (in Japanese)
16.
Zurück zum Zitat Watanabe D, Ohta H, Yamamuro T (2014) Solid-phase extraction of phosphorous-containing amino acid herbicides from biological specimens with a zirconia-coated silica cartridge. J Chromatogr B 969:69–76CrossRef Watanabe D, Ohta H, Yamamuro T (2014) Solid-phase extraction of phosphorous-containing amino acid herbicides from biological specimens with a zirconia-coated silica cartridge. J Chromatogr B 969:69–76CrossRef
17.
Zurück zum Zitat Nawrocki J, Rigney MP, McCormick A, Carr PW (1993) Chemistry of zirconia and its use in chromatography. J Chromatogr A 657:229–282CrossRefPubMed Nawrocki J, Rigney MP, McCormick A, Carr PW (1993) Chemistry of zirconia and its use in chromatography. J Chromatogr A 657:229–282CrossRefPubMed
18.
Zurück zum Zitat Romero R, Bagur MG, Sanchez-Vinas M, Gazquez D (2000) Optimization of experimental variables in the dabsyl chloride derivatization of biogenic amines for their determination by RP-HPLC. Chromatographia 51:404–410CrossRef Romero R, Bagur MG, Sanchez-Vinas M, Gazquez D (2000) Optimization of experimental variables in the dabsyl chloride derivatization of biogenic amines for their determination by RP-HPLC. Chromatographia 51:404–410CrossRef
19.
Zurück zum Zitat Chen Y-H, Shih L-L, Liou S-E, Chen C-C (2003) Analysis of dabsyl-Cl derivated amino acids by high performance liquid chromatography and tandem mass spectrometry. Food Sci Technol Res 9:276–282CrossRef Chen Y-H, Shih L-L, Liou S-E, Chen C-C (2003) Analysis of dabsyl-Cl derivated amino acids by high performance liquid chromatography and tandem mass spectrometry. Food Sci Technol Res 9:276–282CrossRef
20.
Zurück zum Zitat Zouaoui K, Dulaurent S, Gaulier JM, Moesch C, Lachâtre G (2013) Determination of glyphosate and AMPA in blood and urine from humans: About 13 cases of acute intoxication. Forensic Sci Int 226:e20–25CrossRefPubMed Zouaoui K, Dulaurent S, Gaulier JM, Moesch C, Lachâtre G (2013) Determination of glyphosate and AMPA in blood and urine from humans: About 13 cases of acute intoxication. Forensic Sci Int 226:e20–25CrossRefPubMed
21.
Zurück zum Zitat Roberts DM, Buckley NA, Mohamed FM, Eddleston M, Goldstein DA, Mehrsheikh A, Bleeke MS, Dawson AH (2010) A prospective observational study of the clinical toxicology of glyphosate-containing herbicides in adults with acute self-poisoning. Clin. Toxicol (Phila) 48(2):129–136CrossRef Roberts DM, Buckley NA, Mohamed FM, Eddleston M, Goldstein DA, Mehrsheikh A, Bleeke MS, Dawson AH (2010) A prospective observational study of the clinical toxicology of glyphosate-containing herbicides in adults with acute self-poisoning. Clin. Toxicol (Phila) 48(2):129–136CrossRef
22.
Zurück zum Zitat Suzuki O, Yashiki M (2002) Hand book of practical analysis of drugs and poisons in human specimens—chromatographic methods. Jiho, Tokyo, p 480 (in Japanese) Suzuki O, Yashiki M (2002) Hand book of practical analysis of drugs and poisons in human specimens—chromatographic methods. Jiho, Tokyo, p 480 (in Japanese)
Metadaten
Titel
A rapid screening color test for glyphosate using dabsyl derivatization
verfasst von
Daisuke Watanabe
Yuko Kazui
Hikoto Ohta
Publikationsdatum
19.12.2018
Verlag
Springer Singapore
Erschienen in
Forensic Toxicology
Print ISSN: 1860-8965
Elektronische ISSN: 1860-8973
DOI
https://doi.org/10.1007/s11419-018-00460-z

Neu im Fachgebiet Rechtsmedizin