title: Sequential extraction of inorganic arsenic compounds and methyl arsenate in human urine using mixed-mode monolithic silica spin column coupled with gas chromatography-mass spectrometry.
abstract: A sequential analytical method was developed for the detection of arsenite, arsenate, and methylarsenate in human urine by gas chromatography-mass spectrometry (GC-MS). The combination of a derivatization of trivalent arsenic compounds by 2,3-dithio-1-propanol (British antilewisite; BAL) and a reduction of pentavalent arsenic compounds (arsenate and methylarsenate) were accomplished to carry out the analysis of arsenic compounds in urine. The arsenic derivatives obtained using BAL were extracted in a stepwise manner using a monolithic spin column and analyzed by GC-MS. A linear curve was observed for concentrations of arsenic compounds of 2.0 to 200 ng/mL, where the correlation coefficients of calibration curves were greater than 0.996 (for a signal-to-noise (S/N) ratio >10). The detection limits were 1 ng/mL (S/N > 3). Recoveries of the targets in urine were in the range 91.9-106.5%, and RSDs of the intra- and interday assay for urine samples containing 5, 50, and 150 ng/mL of arsenic compounds varied between 2.95 and 13.4%. The results from real samples obtained from a patient suspected of having ingested As containing medications using this proposed method were in good agreement with those obtained using high-performance liquid chromatography with inductively coupled plasma mass spectrometry.
authors.affiliation: Department of Forensic Medicine, Institute of Biomedical & Heath Sciences, Hiroshima University, Hiroshima, Japan. namera@hiroshima-u.ac.jp
authors.forename: Akira
authors.initials: A
authors.lastname: Namera
authors.forename: Akito
authors.initials: A
authors.lastname: Takeuchi
authors.forename: Takeshi
authors.initials: T
authors.lastname: Saito
authors.forename: Shota
authors.initials: S
authors.lastname: Miyazaki
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Oikawa
authors.forename: Tatsuro
authors.initials: T
authors.lastname: Saruwatari
authors.forename: Masataka
authors.initials: M
authors.lastname: Nagao
mesh_terms: D001149:Arsenates / Q000652:urine*; D001152:Arsenicals / Q000652:urine*; D002851:Chromatography, High Pressure Liquid; D008401:Gas Chromatography-Mass Spectrometry; D006801:Humans; D012822:Silicon Dioxide / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D001149:Arsenates; D001152:Arsenicals; D012822:Silicon Dioxide