From Source Rock to Cinnabar – How the Giant Mercury Deposits in Earth’s Crust Formed

Mercury stable isotope compositions in magmatic-affected coal deposits: New insights to mercury sources, migration and enrichment

Mercury (Hg) stable isotope analysis is an emerging technique that has contributed to a better understanding of many aspects of the biogeochemical cycling of Hg in the environment. However, no study has yet evaluated its usefulness in elucidating the sources of methylmercury (MeHg) in songbird species, a common organism for biomonitoring of Hg in forested ecosystems. In the present pilot study, we examined stable mercury isotope ratios in blood of 4 species of songbirds and the invertebrates they are likely foraging on in multiple habitats in a small watershed of mixed forest and wetlands in Acadia National Park in Maine (USA). We found distinct isotopic signatures of MeHg in invertebrates (both mass-dependent fractionation [as δ202 Hg] and mass-independent fractionation [as Δ199 Hg]) among 3 interconnected aquatic habitats. It appears that the Hg isotopic compositions in bird blood cannot be fully accounted for by the isotopic compositions of MeHg in lower trophic levels in each of the habitats examined. Furthermore, the bird blood isotope results cannot be simply explained by an isotopic offset as a result of metabolic fractionation of δ202 Hg (e.g., internal demethylation). Our results suggest that many of the birds sampled obtain MeHg from sources outside the habitat they were captured in. Our findings also indicate that mass-independent fractionation is a more reliable and conservative tracer than mass-dependent fractionation for identifying sources of MeHg in bird blood. The results demonstrate the feasibility of Hg isotope studies of songbirds but suggest that larger numbers of samples and an expanded geographic area of study may be required for conclusive interpretation. Environ Toxicol Chem 2018;37:166-174. © 2017 SETAC.

The Hg isotopic composition of 1-year-old Norway spruce (Picea abies) shoots collected from Saarland cornurbation Warndt, Germany, since 1985 by the German Environmental Specimen Bank, were measured for a better understanding of the temporal trends of Hg sources. The isotopic data showed that Hg was mainly taken up as gaseous element mercury (GEM) and underwent oxidation in the spruce needles; this led to a significant decrease in the δ202Hg compared with the atmospheric Hg isotopic composition observed for deciduous leaves and epiphytic lichens. Observation of the odd mass-independent isotopic fractionation (MIF) indicated that Δ199Hg and Δ201Hg were close to but slightly lower than the actual values recorded from the atmospheric measurement of the GEM isotopic composition in non-contaminated sites in U.S. and Europe, whereas observation of the even-MIF indicated almost no differences for Δ200Hg. This confirmed that GEM is a major source of Hg accumulation in spruce shoots. Interestingly, the Hg isotopic composition in the spruce shoots did not change very significantly during the study period of >30 years, even as the Hg concentration decreased significantly. Even-MIF (Δ200Hg) and mass-dependent fractionation (MDF) (δ202Hg) of the Hg isotopes exhibited slight decrease with time, whereas odd-MIF did not show any clear trend. These results suggest a close link between the long-term evolution of GEM isotopic composition in the air and the isotopic composition of bioaccumulated Hg altered by mass-dependent fraction in the spruce shoots.

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 μg 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 δ(202)Hg: -0.2‰ to -0.5‰; MIF Δ(199)Hg: -0.05‰ to -0.10‰). In contrast, the four sites contaminated with elemental Hg displayed much greater variations (δ(202)Hg: -2.1‰ to 0.6‰; Δ(199)Hg: -0.19‰ to 0.03‰) but with distinct ranges for the different sites. Sequential extractions revealed that sulfide-bound Hg was in some samples up to 1‰ heavier in δ(202)Hg 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.

Mass-independent fractionation (MIF) of stable even mass number mercury (Hg) isotopes is observed in rainfall and gaseous elemental Hg0 globally and is used to quantify atmospheric Hg deposition pathways. The chemical reaction and underlying even-Hg MIF mechanism are unknown however and speculated to be caused by Hg photo-oxidation on aerosols at the tropopause. Here, we investigate the Hg isotope composition of free tropospheric Hg0 and oxidized HgII forms at the high-altitude Pic du Midi Observatory. We find that gaseous oxidized Hg has positive Δ199Hg, Δ201Hg, and Δ200Hg and negative Δ204Hg signatures, similar to rainfall Hg, and we document rainfall Hg Δ196Hg to be near zero. Cloud water and rainfall Hg show an enhanced odd-Hg MIF of 0.3‰ compared to gaseous oxidized HgII, potentially indicating the occurrence of in-cloud aqueous HgII photoreduction. Diurnal MIF observations of free tropospheric Hg0 show how net Hg0 oxidation in high-altitude air masses leads to opposite even- and odd-MIF in Hg0 and oxidized HgII. We speculate that even-Hg MIF takes place by a molecular magnetic isotope effect during HgII photoreduction on aerosols that involves magnetic halogen nuclei. A Δ200Hg mass balance suggests that global Hg deposition pathways in models are likely biased toward HgII deposition. We propose that Hg cycling models could accommodate the Hg-isotope constraints on emission and deposition fluxes.

Distribution of mercury isotope signatures in Yundang Lagoon, Xiamen, China, after long-term interventions

Mercury (Hg) stable isotopes have been broadly used to investigate the sources, transformation and deposition of atmospheric Hg during the industrial era thanks to the multiple isotope signatures deriving from mass-dependent (represented by δ202Hg) and mass-independent fractionation (represented by ΔxxxHg) in the environment. Less is known about the impact of past climate change on atmospheric Hg deposition and cycling, and whether Hg isotopes covary with past climate. Here, we investigate Hg concentration and Hg isotope signatures in a 6600-year-old ombrotrophic peat record from Amsterdam Island (AMS, 37.8oS), and in modern AMS rainfall and gaseous elemental Hg (Hg0) samples. Results show that Holocene atmospheric Hg deposition and plant Hg uptake covary with dust deposition, and are both lower under a high humidity regime associated with enhanced Southern Westerly Winds. Modern AMS gaseous Hg0 and rainfall HgII isotope signatures are similar to those in the Northern Hemisphere (NH). Holocene peat Δ199Hg and Δ200Hg are significantly correlated (R2 = 0.67, P < 0.001, n = 58), consistently oscillating between the modern Hg0 and rainfall HgII end-members. Peat Δ200Hg and Δ199Hg provide evidence of plant uptake of Hg0 as the dominant pathway of Hg deposition to AMS peatland, with some exceptions during humid periods. In contrast to NH archives generally documenting a modern increase in Δ199Hg, recent peat layers (post-1900CE) from AMS show the lowest Δ199Hg in the peat profile (−0.42 ± 0.27 ‰, 1σ, n = 8). This likely reflects a significant change in the post-depositional process on deposited anthropogenic Hg in 20th century (i.e. dark abiotic reduction), enabling more negative Δ199Hg to be observed in AMS peat. We further find that the oscillations of Hg isotopes are consistent with established Holocene climate variability from dust proxies. We suggest peat Hg isotope records might be a valid rainfall indicator.

Characteristics of Hg concentrations and isotopes in terrestrial and marine facies across the end-Permian mass extinction

Mass-dependent and mass-independent variations in the isotope composition of mercury in a sediment core from Lake Ontario as related to pollution history and biogeochemical processes

The mercury (Hg) isotopic composition was investigated in topsoils from two case studies in north of France. The Hg isotope composition was first determined in agricultural topsoils contaminated by a close by Pb-Zn smelter. The Hg isotopic composition was also measured in topsoils from an urban area in northeastern France (Metz). In both cases, no significant mass independent isotope fractionation could be found in the soils. However, the soil isotopic composition (δ(202)Hg) was enriched in the heavier isotopes as the Hg concentration increased in the soils. A linear relationship between the δ(202)Hg in soils and 1/[Hg] indicated a mixing between a contamination source and the Hg derived from the geogenic background soils. Such findings demonstrate that the contamination signature was preserved in the soils and that the deposition of anthropogenic Hg was predominant compared to reactions leading to isotope fractionation such as biotic and abiotic reduction of Hg(II) and resulting in Hg mobility or evasion from the soils. It was therefore possible, for the first time in the case of Hg, to evaluate the contribution of the contamination source relative to the background Hg source in urban topsoils using relative isotope abundances.

Photodegradation of monomethylmercury (MMHg) in surface waters induces mass-dependent and mass-independent fractionation (MIF) of mercury (Hg) isotopes, providing information on the fate of Hg. We aim to understand the mechanisms of MMHg photodegradation and Hg isotopic fractionation affected by physico-chemical factors in freshwater. We investigated the MMHg photodegradation under anoxic and oxic conditions. In addition, MMHg solution was exposed to simulated solar radiation wavelength including or not short UVB (280-305nm). Results for Hg species remaining in the solution showed lower εΔ199Hg in anoxic conditions within the range from -8.5 ± 0.6 ‰ to -16.9 ± 1.9 ‰ and -10.8 ± 0.7 ‰ to -29.3 ± 6.0 ‰ with and without short UVB, respectively, than oxic conditions from -16.8 ± 4.0 ‰ to -19.6 ± 4.1 ‰ and -29.1 ± 4.5 ‰ to -33.0 ± 7.7 ‰ regardless of purging mode. This is probably caused by slower spin interconversion in oxic conditions. In anoxic conditions, the average Δ199Hg/Δ201Hg slope increased from 1.42 ± 0.04 to 1.67 ± 0.08 with short UVB. Our study supports the finding that Δ199Hg/Δ201Hg generated by the photochemical magnetic isotope effect (MIE) varies significantly according to the UV spectral ranges. This highlights the importance of UV light interactions for Hg and other elements featuring photochemical MIE, providing a new basis for interpreting Hg odd-MIF signature.

Intracontinental and arc-related hydrothermal systems display distinct δ202Hg and Δ199Hg features: Implication for large-scale mercury recycling and isotopic fractionation in different tectonic settings

Effects of ultraviolet radiation on mercury isotope fractionation during photo-reduction for inorganic and organic mercury species

The geochemical cycle of mercury in Earth’s surface environment (atmosphere, hydrosphere, biosphere) has been extensively studied; however, the deep geological cycling of this element is less well known. Here we document distinct mass-independent mercury isotope fractionation (expressed as Δ199Hg) in island arc basalts and mid-ocean ridge basalts. Both rock groups show positive Δ199Hg values up to 0.34‰ and 0.22‰, respectively, which deviate from recent estimates of the primitive mantle (Δ199Hg: 0.00 ± 0.10‰, 2 SD)1. The positive Δ199Hg values indicate recycling of marine Hg into the asthenospheric mantle. Such a crustal Hg isotope signature was not observed in our samples of ocean island basalts and continental flood basalts, but has recently been identified in canonical end-member samples of the deep mantle1, therefore demonstrating that recycling of mercury can affect both the upper and lower mantle. Our study reveals large-scale translithospheric Hg recycling via plate tectonics.

The influence of topography on the biogeochemical cycle of mercury (Hg) has received relatively little attention. Here, we report the measurement of Hg species and their corresponding isotope composition in soil sampled along an elevational gradient transect on Mt. Leigong in subtropical southwestern China. The data are used to explain orography-related effects on the fate and behaviour of Hg species in montane environments. The total- and methyl-Hg concentrations in topsoil samples show a positive correlation with elevation. However, a negative elevation dependence was observed in the mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) signatures of Hg isotopes. Both a MIF (Δ199Hg) binary mixing approach and the traditional inert element method indicate that the content of Hg derived from the atmosphere distinctly increases with altitude.