Spatial distribution of trace elements in the surface sediments of a major European estuary (Loire Estuary, France): Source identification and evaluation of anthropogenic contribution

- The first high-resolution mapping of metal contamination in the Loire Estuary
- The strongest EF values are obtained for Ag and Hg in the Loire surface sediments.
- Grain size and POC contents mainly control the spatial distribution of concentrations.
- Hg and Ag anomalies originated from the Loire watershed and intra-estuarine sources.
- The Loire Estuary is mainly characterized by slightly toxic or non-toxic sediments.

Assessing the extent of metal contamination in estuarine surface sediments is hampered by the high heterogeneity of sediment characteristics, the spatial variability of trace element sources, sedimentary dynamics and geochemical processes in addition to the need of accurate reference values for deciphering natural to anthropogenic contribution. Based on 285 surface sediment samples from the Loire Estuary, the first high-resolution spatial distributions are presented for grain-size, particulate organic carbon (POC) and the eight metals/metalloids identified as priority contaminants (Cd, Zn, Pb, Cu, As, Cr, Ni, Hg) plus Ag (an urban tracer). Grain-size and/or POC are major factors controlling the spatial distribution of trace element concentrations. The V-normalized trace metal concentrations divided by the V-normalized concentrations in the basin geochemical background showed the highest Enrichment Factors for Ag and Hg (EF; up to 34 and 140, respectively). These results suggest a severe contamination in the Loire Estuary for both elements. Intra-estuarine Ag and Hg anomalies were identified by comparison between respective normalized concentrations in the Loire Estuary surface sediments and those measured in the surface sediments at the outlet of the Loire River System (watershed-derived). Anthropogenic intra-estuarine Ag and Hg stocks in the uppermost centimetre of the sediment compared with rough annual fluvial flux estimates suggest that the overall strong Enrichment Factors for Ag (EFAg) and and Hg (EFHg) in the Loire Estuary sediments are mainly due to watershed-derived inputs, highlighting the need of high temporal hydro-geochemical monitoring to establish reliable incoming fluxes. Significant correlations obtained between EFCd and EFAg, EFCu and POC and EFHg and POC revealed common behavior and/or sources. Comparison of trace element concentrations with ecotoxicological indices (Sediment Quality Guidelines) provides first standardized information on the sediment quality in the Loire Estuary. The overall mean Effect Range Median quotients (m-ERM-q) results suggested that the Loire Estuary is mainly characterized by slightly toxic sediments even if ecotoxicological impacts have been previously reported on biota.