Arsenic Metabolites in Human Urine after Ingestion of an Arsenosugar

Abstract

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