Trace element reactivity in FeS-rich estuarine sediments: Influence of formation environment and acid sulfate soil drainage

Iron monosulfides (FeS) precipitate during benthic mineralisation of organic C and are well known to have a strong influence on trace element bioavailability in sediments. In this study we investigate the reactivity of trace elements (As, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Zn) in sediments containing abundant and persistent FeS stores, collected from a south-western Australian estuarine system. Our objective was to explore the influence of sediment formation conditions on trace element reactivity by investigating sediments collected from different environments, including estuarine, riverine and acid sulfate soil influenced sites, within a single estuarine system. In general, we found a higher degree of reactivity (defined by 1mol/L HCl extractions) for Cd, Mn, Pb and Zn, compared with a lower reactivity of As, Co, Cr, Cu, Mo and Ni. Moderate to strong correlations (R2>0.4, P0.05). Based on their reactivity and correlations with AVS, it appears that interactions (sorption, co-precipitation) between FeS and Cd, Mn, Pb and Zn in many of the sediments from this study are probable. Our data also demonstrate that drainage from acid sulfate soils (ASS) can be a source of trace elements at specific sites. A principal components analysis of our reactive (1mol/L HCl extractable) trace element data clearly distinguished sites receiving ASS drainage from the other non-impacted sites, by a high contribution from Fe-Co-Mn-Ni along the first principal axis, and contributions from higher S-As/lower reactive Pb along the second axis. This demonstrates that trace element reactivity in sediments may provide a geochemical signature for sites receiving ASS drainage.