title: Arsenic speciation and identification of monomethylarsonous acid and monomethylthioarsonic acid in a complex matrix.
abstract: Anion-exchange chromatography was utilized for speciation of arsenite (As(III)), arsenate (As(V)), dimethylarsinic acid (DMA(V)), monomethylarsonic acid (MMA(V)), monomethylarsonous acid (MMA(III)), and the new As species monomethylthioarsonic acid (MMTA), using inductively coupled plasma mass spectrometric (ICPMS) detection. MMA(III) and MMTA were identified for the first time in freeze-dried carrot samples that were collected over 25 years ago as part of a joint U.S. EPA, U.S. FDA, and USDA study on trace elements in agricultural crops. The discovery of MMA(III) and MMTA in terrestrial foods necessitated the analytical characterization of synthetic standards of both species, which were used for standard addition in carrot extracts. The negative ion mode, high-resolution electrospray mass spectrometry (HR-ESI-MS) data produced molecular ions of m/z 122.9418 and 154.9152 for MMA(III) and MMTA, respectively. However, ESI-MS was not sensitive enough to directly identify MMA(III) and MMTA in the carrot extracts. Therefore, to further substantiate the identification of MMA(III) and MMTA, two additional separations using an Ion-120 column were developed using the more sensitive ICPMS detection. The first separation used 20 mM tetramethylammonium hydroxide at pH 12.2 with MMA(III) eluting in less than 7 min. In the second separation, MMTA eluted at 11.2 min by utilizing 40 mM ammonium carbonate at pH 9.0. Oxidation of MMA(III) and MMTA to MMA(V) with hydrogen peroxide was observed for standards and carrot extracts alike. Several samples of carrots collected from local markets in 2006 were also analyzed and found to contain low levels of inorganic arsenic species.
authors.affiliation: Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221, USA.
authors.forename: Santha Ketavarapu V
authors.initials: SK
authors.lastname: Yathavakilla
authors.forename: Michael
authors.initials: M
authors.lastname: Fricke
authors.forename: Patricia A
authors.initials: PA
authors.lastname: Creed
authors.forename: Douglas T
authors.initials: DT
authors.lastname: Heitkemper
authors.forename: Nohora V
authors.initials: NV
authors.lastname: Shockey
authors.forename: Carol
authors.initials: C
authors.lastname: Schwegel
authors.forename: Joseph A
authors.initials: JA
authors.lastname: Caruso
authors.forename: John T
authors.initials: JT
authors.lastname: Creed
mesh_terms: D020261:Arsenic Poisoning; D001152:Arsenicals / Q000032:analysis* / Q000378:metabolism; D018552:Daucus carota / Q000737:chemistry*; D004785:Environmental Pollutants / Q000032:analysis* / Q000737:chemistry / Q000378:metabolism; D006863:Hydrogen-Ion Concentration; D009942:Organometallic Compounds / Q000032:analysis* / Q000378:metabolism; D010936:Plant Extracts / Q000737:chemistry; D000644:Quaternary Ammonium Compounds / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods; D013997:Time Factors
chemical_list: D001152:Arsenicals; D004785:Environmental Pollutants; D009942:Organometallic Compounds; D010936:Plant Extracts; D000644:Quaternary Ammonium Compounds; C406082:monomethylarsonous acid; C027917:tetramethylammonium