Clinical Chemistry
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Clinical Chemistry 48: 92-101, 2002;
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(Clinical Chemistry. 2002;48:92-101.)
© 2002 American Association for Clinical Chemistry, Inc.

Arsenic Metabolites in Human Urine after Ingestion of an Arsenosugar

Kevin A. Francesconi1a, René Tanggaar1,2, Christine J. McKenzie2 and Walter Goessler3

1 Institute of Biology and
2 Institute of Chemistry, University of Southern Denmark, 5230 Odense M, Denmark.

3 Institute of Chemistry, Analytical Chemistry, Karl-Franzens University, 8010 Graz, Austria.

aAddress correspondence to this author at: Institute of Biology, University of Southern Denmark, 5230 Odense M, Denmark. Fax 43-316-3809845; e-mail kaf{at}biology.sdu.dk.

Background: Arsenic-containing carbohydrates (arsenosugars) are common constituents of marine algae, including those species used as human food. The toxicology of these compounds has not been fully evaluated.

Methods: Arsenic metabolites in human urine were monitored over a 4-day period after ingestion of a synthetic specimen of arsenosugar. The metabolites were determined by HPLC-inductively coupled plasma mass spectrometry, and structural assignments were confirmed with liquid chromatography-electrospray ionization mass spectrometry.

Results: Approximately 80% of the total ingested arsenic was excreted in the urine during the 4 days of the experiment. There was a lag-period of ~13 h before substantial quantities of arsenic appeared in the urine, and the excretion rate peaked between 22 and 31 h. At least 12 arsenic metabolites were detected, only 3 of which could be positively identified. Dimethylarsinate (DMA) was the major metabolite, constituting 67% of the total arsenicals excreted. A new urinary arsenic metabolite, dimethylarsinoylethanol, represented 5% of the total arsenicals, whereas trimethylarsine oxide was present as a trace (0.5%) constituent. One other significant metabolite cochromatographed with a reduced DMA standard, and hence was possibly dimethylarsinous acid. The second most abundant metabolite in the urine (20% of the total arsenic) remained unidentified, whereas the rest of the excreted arsenic was made up of several trace metabolites and small amounts of unchanged arsenosugar.

Conclusions: Arsenosugars are biotransformed by humans to at least 12 arsenic metabolites, the toxicologies of which are currently unknown.




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