Speciation and transport of arsenic in an acid sulfate soil-dominated catchment, eastern Australia.

Factors controlling the transport of geogenically-derived arsenic from a coastal acid sulfate soil into downstream sediments are identified in this study with both solid-phase associations and aqueous speciation clearly critical to the mobility and toxicity of arsenic. The data from both sequential extractions and X-ray adsorption spectroscopy indicate that arsenic in the unoxidised Holocene acid sulfate soils is essentially non-labile in the absence of prolonged oxidation, existing primarily as arsenopyrite or as an arsenopyrite-like species, likely arsenian pyrite. Anthropogenically-accelerated pedogenic processes, which have oxidised this material over time, have greatly enhanced the potential bioavailability of arsenic, with solid-phase arsenic almost solely present as As(V) associated with secondary Fe(III) minerals present. Analyses of downstream sediments reveal that a portion of the arsenic is retained as a mixed As(III)/As(V) solid-phase, though not at levels considered to be environmentally deleterious. Determination of arsenic speciation in pore waters using high performance liquid chromatography/Inductively Coupled Plasma-Mass Spectrometry shows a dominance of As(III) in upstream pore waters whilst an unidentified As species reaches comparative levels within the downstream, estuarine locations. Pore water As(V) was detected at trace concentrations only. The results demonstrate the importance of landscape processes to arsenic transport and availability within acid sulfate soil environments.