Zinc is one of the most widespread trace metals (TMs) in Earth surface environments and is the most concentrated TM in the downstream section of the Seine River (France) due to significant anthropogenic input from the Paris conurbation. In order to better identify the sources and cycling processes of Zn in this River basin, we investigated seasonal and spatial variations of Zn speciation in suspended particulate matter (SPM) in the oxic water column of the Seine River from upstream to downstream of Paris using synchrotron-based extend X-ray absorption fine structure (EXAFS) spectroscopy at the Zn K-edge. First-neighbor contributions to the EXAFS were analyzed in SPM samples, dried and stored under a dry nitrogen atmosphere or under an ambient oxygenated atmosphere. We found a sulfur first coordination environment around Zn (in the form of amorphous zinc sulfide) in the raw SPM samples stored under dry nitrogen vs an oxygen first coordination environment around Zn in the samples stored in an oxygenated atmosphere. These findings are supported by scanning electron microscopy and energy dispersive X-ray spectrometry observations. Linear combination fitting of the EXAFS data for SPM samples, using a large set of EXAFS spectra of Zn model compounds, indicates dramatic changes in the Zn speciation from upstream to downstream of Paris, with amorphous ZnS particles becoming dominant dowstream. In contrast, Zn species associated with calcite (either adsorbed or incorporated in the structure) are dominant upstream. Other Zn species representing about half of the Zn pool in the SPM consist of Zn-sorbed on iron oxyhydroxides (ferrihydrite and goethite) and, to a lesser extent, Zn-Al layered double hydroxides, Zn incorporated in dioctahedral layers of clay minerals and Zn sorbed to amorphous silica. Our results highlight the importance of preserving the oxidation state in TM speciation studies when sampling suspended matter, even in an oxic water column.

Four sediment cores collected in the Seine River basin and dated between 1916 and 2003 were analyzed for lead concentrations and isotopic composition. In all four cores, the measured Pb concentration (up to 460 mg kg(-1)) lies significantly above the natural background (27-40 mg kg(-1)), although a significant decrease (down to 75 mg kg(-1)) was observed during the second half of the 20th century which can be explained by the reduction of lead emissions. The (206)Pb/(207)Pb ratio measured in these samples indicates that the main source of Pb used in the Paris conurbation is characterized by a "Rio Tinto" signature (defined as (206)Pb/(207)Pb=1.1634 ± 0.0001). A high contribution, up to 25%, from the leaded gasoline (characterized by (206)Pb/(207)Pb=1.08 ± 0.02) is revealed in the Seine River downstream Paris, indicating that lead from the leaded gasoline is preferentially released to the river. The dominating Pb signature in the Paris conurbation that is currently sampled through incinerators fumes ((206)Pb/(207)Pb=1.1550 ± 0.0005) and waste water treatment plant ((206)Pb/(207)Pb=1.154 ± 0.002), represents a mixture of highly recycled lead from the Rio Tinto mine and lead from leaded gasoline (imprinted by the low (206)Pb/(207)Pb of the Broken Hill mine). This signature is called "urban" rather than "industrial", because it is clearly distinct from the Pb that is found in areas contaminated by heavy industry, i.e. the heavy industries located on the Oise River which used lead from European ores characterized by high (206)Pb/(207)Pb ratios (~1.18-1.19) and possibly a minor amount of North American lead ((206)Pb/(207)Pb ratios>1.20). The "urban" signature is also found in a rural area upstream of Paris in the 1970's. At the Seine River mouth in 2003, Pb with an urban signature represents 70% of the total Pb sediment content, with the 30% remaining corresponding to natural Pb.