Arsenic cycling in marine systems: degradation of arsenosugars to arsenate in decomposing algae, and preliminary evidence for the formation of recalcitrant arsenic
Jana Navratilova A , Georg Raber B , Steven J. Fisher C D and Kevin A. Francesconi B EA Faculty of Chemistry, Brno University of Technology, Institute of Food Science and Biotechnology, 61200 Brno, Czech Republic.
B Institute of Chemistry-Analytical Chemistry, Karl-Franzens University Graz, A-8010 Graz, Austria.
C Western Australian Fisheries and Marine Research Laboratories, PO Box 20 North Beach, Perth, WA 6920, Australia.
D Present address: Western Australian Department of Water, PO Box K822, Perth, WA 6842, Australia.
E Corresponding author. Email: kevin.francesconi@uni-graz.at
We dedicate this paper to the memory of the late Professor Kaise in recognition of his lifelong work on environmental arsenic chemistry.
Environmental Chemistry 8(1) 44-51 https://doi.org/10.1071/EN10107
Submitted: 1 October 2010 Accepted: 23 January 2011 Published: 28 February 2011
Environmental context. Despite high levels of complex organoarsenic compounds in marine organisms, arsenic in seawater is present almost entirely as inorganic species. We examine the arsenic products from a marine alga allowed to decompose under simulated natural coastal conditions, and demonstrate a multi-step conversion of organic arsenicals to inorganic arsenic. The results support the hypothesis that the arsenic marine cycle begins and ends with inorganic arsenic.
Abstract. Time series laboratory experiments were performed to follow the degradation of arsenic compounds naturally present in marine algae. Samples of the brown alga Ecklonia radiata, which contains three major arsenosugars, were packed into 12 tubes open to air at one end only, and allowed to naturally decompose under moist conditions. During the subsequent 25 days, single tubes were removed at intervals of 1–4 days; their contents were cut into four sections (from open to closed end) and analysed for arsenic species by HPLC/ICPMS following an aqueous methanol extraction. In the sections without direct contact with air, the original arsenosugars were degraded primarily to arsenate via two major intermediates, dimethylarsinoylethanol (DMAE) and dimethylarsinate (DMA). The section with direct contact with air degraded more slowly and significant amounts of arsenosugars remained after 25 days. We also report preliminary data suggesting that the amount of non-extractable or recalcitrant arsenic (i.e. insoluble after sequential extractions with water/methanol, acetone, and hexane) increased with time. Furthermore, we show that treatment of the pellet with 0.1-M trifluoroacetic acid at 95°C solubilises a significant amount of this recalcitrant arsenic, and that the arsenic is present mainly as a cationic species of currently unknown structure.
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