Trees predominantly take up mercury (Hg) from the atmosphere via stomatal assimilation of gaseous elemental Hg (GEM). Hg is oxidised in leaves/needles and transported to other tree anatomy including bole wood, where it can be stored long-term. Using Hg associated with growth rings facilitates archiving of historical GEM concentrations. Nonetheless, there are significant knowledge gaps on the cycling of Hg within trees. We investigate Hg archived in tree rings, internal tree Hg cycling, and differences in Hg uptake mechanisms in Norway spruce and European larch sampled within 1 km of a HgCl₂-contaminated site using total Hg (THg) and Hg stable isotope analyses. Tree ring samples are indicative of significant increases in THg concentrations (up to 521 µg kg⁻¹) from the background period (BGP; facility closed; 1992–present) to secondary industrial period (2ndIP; no HgCl₂ wood treatment; 1962–1992) to primary industrial period (1stIP; active HgCl₂ wood treatment; ≈ 1900–1962). Mass-dependent fractionation (MDF) Hg stable isotope data are shifted negative during industrial periods (δ²⁰²Hg of 1stIP: −4.32 ± 0.15 ‰, 2ndIP: −4.04 ± 0.32 ‰, BGP: −2.83 ± 0.74 ‰; 1 SD). Even accounting for a ≈ −2.6 ‰ MDF shift associated with stomatal uptake, these data are indicative of emissions derived from industrial activity being enriched in lighter isotopes associated with HgCl₂ reduction and Hg⁰ volatilisation. Similar MDF (δ²⁰²Hg: −3.90 ± 0.30 ‰; 1 SD) in bark Hg (137 ± 105 µg kg⁻¹) suggests that stomatal assimilation and downward transport is also the dominant uptake mechanism for bark Hg (reflective of negative stomatal-uptake MDF shift) rather than deposition to bark. THg was enriched in sapwood of all sampled trees across both tree species. This may indicate long-term storage of a fraction of Hg in sapwood or xylem solution. We also observed a small range of odd-isotope mass-independent fractionation (MIF). Differences in Δ¹⁹⁹Hg between periods of different industrial activities were significant (Δ¹⁹⁹Hg of 1stIP: 0.00 ± 0.03 ‰, 2ndIP: −0.06 ± 0.04 ‰, BGP: −0.13 ± 0.03 ‰; 1 SD), and we suggest MIF signatures are conserved during stomatal assimilation (reflect source MIF signatures). These data advance our understanding of the physiological processing of Hg within trees and provide critical direction to future research into the use of trees as archives for historical atmospheric Hg.

Stable mercury (Hg) isotope ratios are an emerging tracer for biogeochemical transformations in environmental systems, but their application requires knowledge of isotopic enrichment factors for individual processes. We investigated Hg isotope fractionation during dark, abiotic reduction of Hg(II) by dissolved iron(Fe)(II), magnetite, and Fe(II) sorbed to boehmite or goethite by analyzing both the reactants and products of laboratory experiments. For homogeneous reduction of Hg(II) by dissolved Fe(II) in continuously purged reactors, the results followed a Rayleigh distillation model with enrichment factors of -2.20 ± 0.16‰ (ε²⁰²Hg) and 0.21 ± 0.02‰ (E¹⁹⁹Hg). In closed system experiments, allowing reequilibration, the initial kinetic fractionation was overprinted by isotope exchange and followed a linear equilibrium model with -2.44 ± 0.17‰ (ε²⁰²Hg) and 0.34 ± 0.02‰ (E¹⁹⁹Hg). Heterogeneous Hg(II) reduction by magnetite caused a smaller isotopic fractionation (-1.38 ± 0.07 and 0.13 ± 0.01‰), whereas the extent of isotopic fractionation of the sorbed Fe(II) experiments was similar to the kinetic homogeneous case. Small mass-independent fractionation of even-mass Hg isotopes with 0.02 ± 0.003‰ (E²⁰⁰Hg) and ≈ -0.02 ± 0.01‰ (E²⁰⁴Hg) was consistent with theoretical predictions for the nuclear volume effect. This study contributes significantly to the database of Hg isotope enrichment factors for specific processes. Our findings show that Hg(II) reduction by dissolved Fe(II) in open systems results in a kinetic MDF with a larger ε compared to other abiotic reduction pathways, and combining MDF with the observed MIF allows the distinction from photochemical or microbial Hg(II) reduction pathways.

Interpretation of mercury (Hg) geochemistry in environmental systems remains a challenge. This is largely associated with the inability to identify specific Hg transformation processes and species using established analytical methods in Hg geochemistry (total Hg and Hg speciation). In this study, we demonstrate the improved Hg geochemical interpretation, particularly related to process tracing, that can be achieved when Hg stable isotope analyses are complemented by a suite of more established methods and applied to both solid- (soil) and liquid-phases (groundwater) across two Hg²⁺-chloride (HgCl₂) contaminated sites with distinct geological and physicochemical properties. This novel approach allowed us to identify processes such as Hg²⁺ (i.e., HgCl₂) sorption to the solid-phase, Hg²⁺ speciation changes associated with changes in groundwater level and redox conditions (particularly in the upper aquifer and capillary fringe), Hg²⁺ reduction to Hg⁰, and dark abiotic redox equilibration between Hg⁰ and Hg(II). Hg stable isotope analyses play a critical role in our ability to distinguish, or trace, these in situ processes. While we caution against the non-critical use of Hg isotope data for source tracing in environmental systems, due to potentially variable source signatures and overprinting by transformation processes, our study demonstrates the benefits of combining multiple analytical approaches, including Hg isotope ratios as a process tracer, to obtain an improved picture of the enigmatic geochemical behavior and fate of Hg at contaminated legacy sites.

Sorption of mercury (Hg) in soils is suggested to be predominantly associated with organic matter (OM). However, there is a growing collection of research that suggests that clay minerals and $\mathrm{Fe}/\mathrm{Mn}$ oxides are also important solid phases for the sorption of soluble Hg in soil–groundwater systems. We use a series of (60 mL syringe based) column experiments to examine sorption and subsequent desorption of HgCl₂ solutions (experiment 1 (EXP1): 46.1 ± 1.1 mg L⁻¹; experiment 2 (EXP2): 144 ± 6 mg L⁻¹) in low-OM (0.16 ± 0.02 %) solid-phase aquifer materials. Analyses of total Hg concentrations, Hg speciation (i.e. pyrolytic thermal desorption (PTD)), and Hg stable isotopes are performed on both solid- and liquid-phase samples across sorption and desorption phases of the experiments. The sorption breakthrough curve best fitted a Freundlich model. Despite the very low-OM content, the Hg equilibrium sorptive capacity in these columns is very high: 1510 ± 100 and 2320 ± 60 mg kg⁻¹ for EXP1 and EXP2, respectively, and it is similar to those determined for high-OM soils. Data from the experiments on mass-dependent Hg stable isotope fractionation data from these experiments (described by δ²⁰²Hg) support preferential sorption of lighter isotopes to the solid-phase materials with results indicating an isotopically heavier liquid phase and an isotopically lighter solid phase. Desorption fits exponential decay models, and 46 ± 6 % and 58 ± 10 % of the sorbed Hg is removed from the solid-phase materials at the termination of desorption in EXP1 and EXP2, respectively. The divergence of δ²⁰²Hg values between liquid and solid phases also continues into desorption. This desorption profile is linked to the initial release of easily exchangeable Hg(II) species physically sorbed to $\mathrm{Fe}/\mathrm{Mn}$ oxides and clay mineral surfaces (liquid phase enriched in heavy isotopes) and then slower release of Hg(II) species that have undergone secondary reaction to more stable/less-soluble Hg(II) species and/or diffusion/transport into the mineral matrices (processes favouring lighter isotopes; solid phase enriched in lighter isotopes). The secondary production of Hg(0) within the columns is confirmed by PTD analyses that indicate distinct Hg(0) release peaks in solid-phase samples at <175 ^∘C, which again agrees with field observations. Retardation (R_D) and distribution (K_D) coefficients are 77.9 ± 5.5 and 26.1 ± 3.0 mL g⁻¹ in EXP1, respectively, and 38.4 ± 2.7 and 12.4 ± 0.6 mL g⁻¹ in EXP2, respectively. These values are similar to values derived from column experiments on high-OM soil and provide the basis for future Hg fate and transport modelling in soil–groundwater systems.

Mercury (Hg) release from contaminated legacy sites is a large contributor to riverine ecosystems and can represent a significant local and regional environmental issue even long after the initial site contamination. Understanding processes of in-stream species transformation is therefore important to assess the fate and bioavailability of the released Hg. In this study, we investigated in-stream Hg transformation processes with analyses of Hg binding forms and Hg stable isotopes. Stream sediments were collected downstream of a former kyanization facility (Black Forest, SW Germany), where highly soluble Hg(II)-chloride (HgCl₂) was used as an anti-fouling agent to treat timber. Exfiltration of partly anoxic, contaminated groundwater with Hg concentrations of up to 700 μg L⁻¹ into the adjacent Gutach stream is the main source of Hg to sediments. Total Hg concentrations in the stream bottom sediments (<2 mm) ranged from background values of 6.3 µg kg⁻¹ upstream of the contaminated site to 77 mg kg⁻¹ near the location of exfiltration of contaminated groundwater. A five-step sequential extraction procedure and Hg pyrolytic thermal desorption (PTD) analyses indicated changes in Hg binding forms in the sediments along the flow path towards a higher proportion of organically bound Hg. A large shift towards negative δ²⁰²Hg values was observed downstream of the contaminated site (change of ≈2‰) along with a minor offset in mass-independent fractionation. Binary mixing models based on Hg isotope ratios using one industrial and different natural background endmembers were tested to estimate their respective contribution of Hg to the sediments but failed to produce plausible allocations. Based on the observed changes in isotopic composition, total Hg concentrations and Hg binding forms, we propose that the large extent of fractionation observed in downstream sediments is the result of a combination of kinetic isotope effects during sorption, redistribution of Hg within the sediment and the preferential transport of Hg associated with the sediment fine fraction. These results highlight the importance of transformation processes when assessing the sources and fate of Hg in environmental systems and show limitations of using simple mixing models based on Hg stable isotopes.