Report on three aliphatic dimethylarsinoyl compounds as common minor constituents in marine samples. An investigation using high-performance liquid chromatography/inductively coupled plasma mass spectrometry and electrospray ionisation tandem mass spectrometry.

Three water-soluble aliphatic arsenicals, dimethylarsinoyl acetate (DMAA), dimethylarsinoyl ethanol (DMAE), and dimethylarsinoyl propionate (DMAP), were identified in marine biological samples. Sample extracts in methanol/water (1 + 1) were analysed by cation-exchange high-performance liquid chromatography/inductively coupled plasma mass spectrometry (HPLC/ICPMS). Eluate fractions from the HPLC/ICPMS analyses containing the compounds in question were collected and subjected to analysis by electrospray ionisation tandem mass spectrometry (ESI-MS/MS), which provided supportive evidence for the structures of the three compounds. The concentrations of the three arsenicals were determined in 37 marine organisms comprising algae, crustaceans, bivalves, fish and mammals by HPLC/ICPMS. The three arsenicals DMAA, DMAE and DMAP, which occurred at microg kg(-1) concentrations, were detected in 25, 23 and 17 of the 37 samples analysed, respectively. The limits of detection were 2-3 microg kg(-1) dry mass. The data illustrate that the three compounds are common minor constituents in marine samples. This is the first report on DMAE and DMAP as naturally occurring species in marine samples. The presence of DMAA and DMAE supports a proposed biosynthesis of arsenobetaine (AB) from dimethylarsinoylribosides. Alternative proposals, which explain the presence of the compounds in marine samples, are addressed briefly in the paper.

[1]  J. Edmonds,et al.  Transformations of arsenic in the marine environment , 1987, Experientia.

[2]  J. Edmonds,et al.  Dimethyloxarsylethanol from anaerobic decomposition of brown kelp (Ecklonia radiata): A likely precursor of arsenobetaine in marine fauna , 1982, Experientia.

[3]  E. Larsen,et al.  Selective arsenic speciation analysis of human urine reference materials using gradient elution ion-exchange HPLC-ICP-MS , 2004 .

[4]  W. Goessler,et al.  An origin for arsenobetaine involving bacterial formation of an arsenic-carbon bond. , 2004, FEMS microbiology letters.

[5]  Kevin A Francesconi,et al.  Determination of arsenic species: a critical review of methods and applications, 2000-2003. , 2004, The Analyst.

[6]  R. Vanholder,et al.  Identification of some arsenic species in human urine and blood after ingestion of Chinese seaweed Laminaria , 2004 .

[7]  W. Goessler,et al.  Organoarsenic Compounds in the Terrestrial Environment , 2003 .

[8]  J. Edmonds,et al.  Organoarsenic Compounds in the Marine Environment , 2003 .

[9]  E. Larsen,et al.  Determination of organoarsenic species in marine samples using gradient elution cation exchange HPLC-ICP-MS , 2003 .

[10]  J. Feldmann,et al.  New arsenosugar metabolite determined in urine by parallel use of HPLC-ICP-MS and HPLC-ESI-MS , 2003 .

[11]  Z. Mester,et al.  The speciation of natural tissues by electrospray-mass spectrometry. I: Biosynthesized species, As and Se , 2003 .

[12]  I. Feldmann,et al.  Metabolism of arsenic by sheep chronically exposed to arsenosugars as a normal part of their diet. 1. Quantitative intake, uptake, and excretion. , 2003, Environmental science & technology.

[13]  J. Szpunar,et al.  Characterization of arsenic species in kidney of the clam Tridacna derasa by multidimensional liquid chromatography-ICPMS and electrospray time-of-flight tandem mass spectrometry. , 2002, Analytical chemistry.

[14]  W. Goessler,et al.  Arsenic metabolites in human urine after ingestion of an arsenosugar. , 2002, Clinical chemistry.

[15]  K. Francesconi,et al.  Arsenic Compounds in the Environment , 2001 .

[16]  W. Goessler,et al.  Dimethylarsinoylacetate from microbial demethylation of arsenobetaine in seawater , 2001 .

[17]  K. Julshamn,et al.  Determination of arsenic in seafood by electrothermal atomic absorption spectrometry after microwave digestion: NMKL collaborative study. , 2000, Journal of AOAC International.

[18]  J. Edmonds Diastereoisomers of an 'arsenomethionine'-based structure from Sargassum lacerifolium: the formation of the arsenic-carbon bond in arsenic-containing natural products. , 2000, Bioorganic & medicinal chemistry letters.

[19]  I. Koch,et al.  Arsenic Species in Terrestrial Fungi and Lichens from Yellowknife, NWT, Canada , 2000 .

[20]  W. Goessler,et al.  Characterization of an algal extract by HPLC-ICP-MS and LC-electrospray MS for use in arsenosugar speciation studies , 2000 .

[21]  J. Edmonds,et al.  Arsenic metabolism in aquatic ecosystems , 1998 .

[22]  J. Neff Ecotoxicology of arsenic in the marine environment , 1997 .

[23]  E. Larsen Speciation of dimethylarsinyl-riboside derivatives (arsenosugars) in marine reference materials by HPLC-ICP-MS , 1995 .

[24]  C. Raston,et al.  Isolation, crystal structure and synthesis of arsenobetaine, the arsenical constituent of the western rock lobster panulirus longipes cygnus George , 1977 .