Determining metal origins and availability in fluvial deposits by analysis of geochemical baselines and solid-solution partitioning measurements and modelling

Metals in floodplain soils and sediments (deposits) can originate from lithogenic and anthropogenic sources, and their availability for uptake in biota is hypothesized to depend on both origin and local sediment conditions. In criteria-based environmental risk assessments, these issues are often neglected, implying local risks to be often over-estimated. Current problem definitions in river basin management tend to require a refined, site-specific focus, resulting in a need to address both aspects. This paper focuses on the determination of local environmental availabilities of metals in fluvial deposits by addressing both the origins of the metals and their partitioning over the solid and solution phases. The environmental availability of metals is assumed to be a key force influencing exposure levels in field soils and sediments. Anthropogenic enrichments of Cu, Zn and Pb in top layers could be distinguished from lithogenic background concentrations and described using an aluminium-proxy. Cd in top layers was attributed to anthropogenic enrichment almost fully. Anthropogenic enrichments for Cu and Zn appeared further to be also represented by cold 2 M HNO₃ extraction of site samples. For Pb the extractions over-estimated the enrichments. Metal partitioning was measured, and measurements were compared to predictions generated by an empirical regression model and by a mechanistic-kinetic model. The partitioning models predicted metal partitioning in floodplain deposits within about one order of magnitude, though a large inter-sample variability was found for Pb.