title: Rapid analysis of Lewisite metabolites in urine by high-performance liquid chromatography-inductively coupled plasma-mass spectrometry.
abstract: A high-throughput method has been developed for determining Lewisite [dichloro(2-chlorovinyl)arsine] exposure by measuring the urine metabolite 2-chlorovinylarsonous acid (CVAA) and the oxidized metabolite 2-chlorovinylarsonic acid (CVAOA). The rapid sample preparation included a simple dilution of 400 microL of urine with 40 microL of water and 1 mL of buffer containing an internal standard and brief centrifugation prior to analysis by high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (ICP-MS). CVAOA and CVAA were eluted isocratically with retention factors of approximately 3.0 and 4.2, respectively, from a reversed-phase polar embedded column with a cycle time of 5 min per sample. The dynamic reaction cell, typically used to remove polyatomic isobaric interferences, was not required for ICP-MS analysis because of the resolution of chloride from arsenical peaks of interest. This method was used to detect CVAA and CVAOA in the urine of a rat administered Lewisite up to 24 h after exposure. The method demonstrated linearity over at least three orders of magnitude and had a method detection limit of 1.3 microg/L as CVAA (1.4 microg/L CVAOA). The relative standard deviations for quality control samples ranged from 3 to 6%. The method was sensitive and selective with no false positives in 100 different urine samples collected from individuals with no known exposure to Lewisite. Ninety-six samples could be analyzed in an 8-h day.
authors.affiliation: Centers for Disease Control and Prevention, 4770 Buford Highway, Atlanta, GA 30341, USA. fmk9@cdc.gov
authors.forename: Rayman D
authors.initials: RD
authors.lastname: Stanelle
authors.forename: William J
authors.initials: WJ
authors.lastname: McShane
authors.forename: Elena N
authors.initials: EN
authors.lastname: Dodova
authors.forename: R Steven
authors.initials: RS
authors.lastname: Pappas
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Kobelski
mesh_terms: D000818:Animals; D001152:Arsenicals / Q000378:metabolism / Q000652:urine*; D002138:Calibration; D002851:Chromatography, High Pressure Liquid / Q000379:methods; D004781:Environmental Exposure / Q000032:analysis; D006801:Humans; D013058:Mass Spectrometry / Q000379:methods*; D010084:Oxidation-Reduction; D051381:Rats; D015203:Reproducibility of Results
chemical_list: C419383:2-chlorovinylarsonous acid; D001152:Arsenicals; C035965:lewisite