Analysis of glyphosate, aminomethylphosphonic acid, and glufosinate from human urine by HRAM LC-MS
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RESEARCH PAPER
Analysis of glyphosate, aminomethylphosphonic acid, and glufosinate from human urine by HRAM LC-MS Adrian A. Franke 1 & Xingnan Li 1 & Jennifer F. Lai 1 Received: 4 June 2020 / Revised: 26 August 2020 / Accepted: 22 September 2020 # Springer-Verlag GmbH Germany, part of Springer Nature 2020
Abstract Aminomethylphosphonic acid (AMPA) is the main metabolite of glyphosate (GLYP) and phosphonic acids in detergents. GLYP is a synthetic herbicide frequently used worldwide alone or together with its analog glufosinate (GLUF). The general public can be exposed to these potentially harmful chemicals; thus, sensitive methods to monitor them in humans are urgently required to evaluate health risks. We attempted to simultaneously detect GLYP, AMPA, and GLUF in human urine by high-resolution accurate-mass liquid chromatography mass spectrometry (HRAM LC-MS) before and after derivatization with 9fluorenylmethoxycarbonyl chloride (Fmoc-Cl) or 1-methylimidazole-sulfonyl chloride (ImS-Cl) with several urine pretreatment and solid phase extraction (SPE) steps. Fmoc-Cl derivatization achieved the best combination of method sensitivity (limit of detection; LOD) and accuracy for all compounds compared to underivatized urine or ImS-Cl-derivatized urine. Before derivatization, the best steps for GLYP involved 0.4 mM ethylenediaminetetraacetic acid (EDTA) pre-treatment followed by SPE pre-cleanup (LOD 37 pg/mL), for AMPA involved no EDTA pre-treatment and no SPE pre-cleanup (LOD 20 pg/mL) or 0.2– 0.4 mM EDTA pre-treatment with no SPE pre-cleanup (LOD 19–21 pg/mL), and for GLUF involved 0.4 mM EDTA pretreatment and no SPE pre-cleanup (LOD 7 pg/mL). However, for these methods, accuracy was sufficient only for AMPA (101– 105%), while being modest for GLYP (61%) and GLUF (63%). Different EDTA and SPE treatments prior to Fmoc-Cl derivatization resulted in high sensitivity for all analytes but satisfactory accuracy only for AMPA. Thus, we conclude that our HRAM LC-MS method is suited for urinary AMPA analysis in cross-sectional studies. Keywords Glyphosate . Aminomethylphosphonic acid . Glufosinate . Urine . Humans . LC-MS
Introduction Glyphosate (GLYP; N-(phosphonomethyl)glycine) and glufosinate (GLUF; DL-homoalanin-4-yl-(methyl)phosphinate) are non-selective, synthetic post-emergence herbicides widely used in agricultural, forestry, and urban settings [1, 2]. Aminomethylphosphonic acid (AMPA) is the main (70%) GLYP degradation product of soil microbes [1, 3] and the key metabolite of phosphonate-containing household and industrial detergents [4, 5]. GLYP, AMPA, and GLUF have been detected in numerous foodstuffs and environmental water sources [1, 2, 5–10], indicating avenues by which these
* Adrian A. Franke [email protected] 1
University of Hawaii Cancer Center, Analytical Biochemistry Shared Resource, 701 Ilalo Street, Honolulu, HI 96813, USA
compounds may come into contact with humans who would otherwise not be exposed. Despite this, data on exposure to these compounds via urinary measurement among nonoccupationally
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