Mercury Isotope Signatures in Contaminated Sediments as a Tracer for Local Industrial Pollution Sources

Mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) may cause characteristic isotope signatures of different mercury (Hg) sources and help understand transformation processes at contaminated sites. Here, we present Hg isotope data of sediments collected near industrial pollution sources in Sweden contaminated with elemental liquid Hg (mainly chlor-alkali industry) or phenyl-Hg (paper industry). The sediments exhibited a wide range of total Hg concentrations from 0.86 to 99 mu g g(-1)), consisting dominantly of organically-bound Hg and smaller amounts of sulfide-bound Hg. The three phenyl-Hg sites showed very similar Hg isotope signatures (MDF delta Hg-202: -0.2 parts per thousand to -0.5 parts per thousand; MIF Delta Hg-199: -0.05 parts per thousand to -0.10 parts per thousand). In contrast, the four sites contaminated with elemental Hg displayed much greater variations (delta Hg-202: -2.1 parts per thousand to 0.6 parts per thousand; Delta Hg-199: -0.19 parts per thousand to 0.03 parts per thousand) but with distinct ranges for the different sites. Sequential extractions revealed that sulfide-bound Hg was in some samples up to 1 parts per thousand heavier in delta Hg-202 than organically-bound Hg. The selectivity of the sequential extraction was tested on standard materials prepared with enriched Hg isotopes, which also allowed assessing isotope exchange between different Hg pools. Our results demonstrate that different industrial pollution sources can be distinguished on the basis of Hg isotope signatures, which may additionally record fractionation processes between different Hg pools in the sediments.