John M. Gunn

Arsenic can accumulate in freshwater biota, sometimes reaching potentially harmful levels. However, the toxicity of arsenic strongly depends on which arsenic species are present. Although organic species are considered less harmful than inorganic ones, they have not been extensively studied in freshwater environments, and drivers of variation in arsenic speciation among sites and taxa remain unclear. We assessed concentrations of two organic arsenic species, arsenobetaine (AsB) and dimethylarsinic acid (DMA), in fish and invertebrates from three lakes near Sudbury, Ontario, Canada—a region with widespread mining impacts. Both AsB and DMA were detected in most samples ( n = 212), varying across a wide range of concentrations (<0.001–30.144 and <0.006–5.262 mg/kg dry wt, respectively). The lake with the most severe mining impacts typically had the highest concentrations (designated by square brackets []) of AsB and DMA. In contrast, the percentage of total arsenic made up by AsB (%AsB) and DMA (%DMA) did not vary significantly between lakes. Arsenic speciation in fish muscle varied with fish size, selenium concentrations, and trophic elevation (inferred from nitrogen stable isotope ratios δ 15 N), but relationships with dietary carbon source (inferred from carbon stable isotope ratios δ 13 C) were more varied. Within all three lake food webs, [AsB] and [DMA] typically underwent biodilution, decreasing with trophic elevation (i.e., δ 15 N). Although the aforementioned factors explained some variation in arsenic speciation, there remains considerable unexplained variation. Further studies on arsenic speciation in freshwater biota should target a wider diversity of taxa to better understand drivers of variation in arsenic speciation. In addition, research emphasizing the percentage of inorganic arsenic and other organic arsenic species is needed to improve environmental and human health risk assessments. Environ Toxicol Chem 2024;43:833–846. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.