Arsenic speciation in plankton organisms from contaminated lakes: transformations at the base of the freshwater food chain.

The two complementary techniques high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) and X-ray absorption near edge structure (XANES) analysis were used to assess arsenic speciation in freshwater phytoplankton and zooplankton collected from arsenic-contaminated lakes in Yellowknife (Northwest Territories, Canada). Arsenic concentrations in lake water ranged from 7 μg L(-1) in a noncontaminated lake to 250 μg L(-1) in mine-contaminated lakes, which resulted in arsenic concentrations ranging from 7 to 340 mg kg(-1) d.w. in zooplankton organisms (Cyclops sp.) and from 154 to 894 mg kg(-1) d.w. in phytoplankton. The main arsenic compounds identified by HPLC-ICP-MS in all plankton were inorganic arsenic (from 38% to 98% of total arsenic). No other arsenic compounds were found in phytoplankton, but zooplankton organisms showed the presence of organoarsenic compounds, the most common being the sulfate arsenosugar, up to 47% of total arsenic, with traces of phosphate sugar, glycerol sugar, methylarsonate (MMA), and dimethylarsinate (DMA). In the uncontaminated Grace Lake, zooplankton also contained arsenobetaine (AB). XANES characterization of arsenic in the whole plankton samples showed As(V)-O as the only arsenic compound in phytoplankton, and As(III)-S and As(V)-O compounds as the two major inorganic arsenic species in zooplankton. The proportion of organoarsenicals and inorganic arsenic in zooplankton depends upon the arsenic concentration in lakes and shows the impact of arsenic contamination: zooplankton from uncontaminated lake has higher proportions of organoarsenic compounds and contains arsenobetaine, while zooplankton from contaminated area contains mostly inorganic arsenic.