Mercury Isotope Fractionation in the Subsurface of a Hg(II) Chloride-Contaminated Industrial Legacy Site BroczaFlora M. BiesterHarald RichardJan-Helge KraemerStephan M. WiederholdJan G. 2019 To understand the transformations of mercury (Hg) species in the subsurface of a HgCl<sub>2</sub>-contaminated former industrial site in southwest Germany, Hg isotope analysis was combined with an investigation of Hg forms by a four-step sequential extraction protocol (SEP) and pyrolytic thermodesorption. Data from two soil cores revealed that the initial HgCl<sub>2</sub> was partly reduced to metallic Hg(0) and that Hg forms of different mobility and oxidation state coexist in the subsurface. The most contaminated sample (K2-8, 802 mg kg<sup>–1</sup> Hg) had a bulk δ<sup>202</sup>Hg value of around −0.43 ± 0.06‰ (2SD), similar to published average values for industrial Hg sources. Other sample signatures varied significantly with depth and between SEP pools. The most Hg-rich samples contained mixtures of Hg(0) and Hg­(II) phases, and the water-extractable, mobile Hg pool exhibited heavy δ<sup>202</sup>Hg values of up to +0.18‰. Sequential water extracts revealed slow dissolution kinetics of mobile Hg pools, continuously releasing isotopically heavy Hg into solution. This was further corroborated by heavy δ<sup>202</sup>Hg values of groundwater samples. Our results demonstrate that the Hg isotope signature of an industrial contamination source can be significantly altered during the transformations of Hg species in the subsurface, which complicates source tracing applications but offers the possibility of using Hg isotopes as process tracers in contaminated subsurface systems.