title: Solid-phase extraction of phosphorous-containing amino acid herbicides from biological specimens with a zirconia-coated silica cartridge.
abstract: We report a rapid solid-phase extraction method for glyphosate (Glyp), glufosinate (Gluf), and bialaphos (Bial) using a zirconia-coated silica cartridge, which interacts specifically with phosphorous-containing amino acid herbicides (PAAHs). We extracted PAAHs from serum and urine samples. The PAAHs were derivatized with trimethyl orthoacetate-acetic acid and analyzed by ultra-performance liquid chromatography/tandem mass spectrometry (UPLC-MS/MS). The intra-day and inter-day accuracy was within ±13% RE, the intra-day and inter-day precision was less than 12% RSD, and the total recovery was more than 60% for Glyp and more than 80% for Gluf and Bial. The linearity ranges of the calibration curves of the serum samples were 0.2-10,000μg/mL for Glyp, 0.1-1000μg/L for Gluf, and 0.5-1000μg/L for Bial; and those of the urine samples were 0.4-20,000μg/L for Glyp, 0.2-2000μg/L for Gluf, and 0.1-2000μg/L for Bial. This range covers almost all the reported poisoning cases involving these compounds, from very mild to fatal cases. The present paper offers a universal cleanup method for PAAHs in serum and urine samples for clinical and forensic analysis.
authors.affiliation: National Research Institute of Police Science, 6-3-1, Kashiwa-no-ha, Kashiwa, Chiba 277-0882, Japan. Electronic address: watanabe.daisuke@nrips.go.jp.
authors.forename: Daisuke
authors.initials: D
authors.lastname: Watanabe
authors.affiliation: National Research Institute of Police Science, 6-3-1, Kashiwa-no-ha, Kashiwa, Chiba 277-0882, Japan.
authors.forename: Hikoto
authors.initials: H
authors.lastname: Ohta
authors.affiliation: National Research Institute of Police Science, 6-3-1, Kashiwa-no-ha, Kashiwa, Chiba 277-0882, Japan.
authors.forename: Tadashi
authors.initials: T
authors.lastname: Yamamuro
mesh_terms: D000596:Amino Acids / Q000097:blood / Q000737:chemistry / Q000302:isolation & purification* / Q000652:urine; D002851:Chromatography, High Pressure Liquid / Q000379:methods; D006540:Herbicides / Q000097:blood / Q000737:chemistry / Q000302:isolation & purification* / Q000652:urine; D006801:Humans; D057230:Limit of Detection; D016014:Linear Models; D009943:Organophosphorus Compounds / Q000097:blood / Q000737:chemistry / Q000302:isolation & purification* / Q000652:urine; D015203:Reproducibility of Results; D012822:Silicon Dioxide / Q000737:chemistry; D052616:Solid Phase Extraction / Q000295:instrumentation / Q000379:methods*; D053719:Tandem Mass Spectrometry / Q000379:methods; D015040:Zirconium / Q000737:chemistry
chemical_list: D000596:Amino Acids; D006540:Herbicides; D009943:Organophosphorus Compounds; D012822:Silicon Dioxide; D015040:Zirconium; C028541:zirconium oxide
keywords: Glyphosate; Liquid chromatography–tandem mass spectrometry; Phosphorous containing amino acid herbicides; Zirconia-coated cartridge