Negative Mass-independent Fractionation Research Articles

Mercury evidence for combustion of organic-rich sediments during the end-Triassic crisis

The sources of isotopically light carbon released during the end-Triassic mass extinction remain in debate. Here, we use mercury (Hg) concentrations and isotopes from a pelagic Triassic–Jurassic boundary section (Katsuyama, Japan) to track changes in Hg cycling. Because of its location in the central Panthalassa, far from terrigenous runoff, Hg enrichments at Katsuyama record atmospheric Hg deposition. These enrichments are characterized by negative mass independent fractionation (MIF) of odd Hg isotopes, providing evidence of their derivation from terrestrial organic-rich sediments (Δ199Hg < 0‰) rather than from deep-Earth volcanic gases (Δ199Hg ~ 0‰). Our data thus provide evidence that combustion of sedimentary organic matter by igneous intrusions and/or wildfires played a significant role in the environmental perturbations accompanying the event. This process has a modern analog in anthropogenic combustion of fossil fuels from crustal reservoirs.

Intensified continental chemical weathering and carbon-cycle perturbations linked to volcanism during the Triassic\u2013Jurassic transition

Direct evidence of intense chemical weathering induced by volcanism is rare in sedimentary successions. Here, we undertake a multiproxy analysis (including organic carbon isotopes, mercury (Hg) concentrations and isotopes, chemical index of alteration (CIA), and clay minerals) of two well-dated Triassic–Jurassic (T–J) boundary sections representing high- and low/middle-paleolatitude sites. Both sections show increasing CIA in association with Hg peaks near the T–J boundary. We interpret these results as reflecting volcanism-induced intensification of continental chemical weathering, which is also supported by negative mass-independent fractionation (MIF) of odd Hg isotopes. The interval of enhanced chemical weathering persisted for ~2 million years, which is consistent with carbon-cycle model results of the time needed to drawdown excess atmospheric CO2 following a carbon release event. Lastly, these data also demonstrate that high-latitude continental settings are more sensitive than low/middle-latitude sites to shifts in weathering intensity during climatic warming events.

Mass-Independent Fractionation of Mercury Isotopes during Photoreduction of Soot Particle Bound Hg(II).

Soot and mercury (Hg) are two notorious air pollutants, and the fate and transport of Hg may be affected by soot at various scales in the environment as soot may be both a carrier and a reactant for active Hg species. This study was designed to quantify photoreduction of Hg(II) in the presence of soot and the associated Hg isotope fractionation under both atmospheric aerosol and aqueous conditions (water-saturated). Photoreduction experiments were conducted with diesel soot particulate matter under controlled temperature and relative humidity (RH) conditions using a flow-through semibatch reactor system. Mass-dependent fractionation resulted in the enrichment of heavier Hg isotopes in the remaining Hg(II) with enrichment factors (ε202Hg) of 1.48 ± 0.02‰ (±2 standard deviation) to 1.75 ± 0.05‰ for aerosol-phase reactions (RH 28-68%) and from 1.26 ± 0.11 to 1.50 ± 0.04‰ for aqueous-phase reactions. Positive odd mass-independent fractionation (MIF) was observed in aqueous-phase reactions, resulting in Δ199Hg values for reactant Hg(II) as high as 5.29‰, but negative odd-MIF occurred in aerosol-phase reactions, in which Δ199Hg values of reactant Hg(II) varied from -1.02 to 0‰. The average ratio of Δ199Hg/Δ201Hg (1.1) indicated that under all conditions, MIF was dominated by magnetic isotope effects during photoreduction of Hg(II). Increasing RH resulted in higher reduction rates but lower extents of negative MIF in the aerosol-phase experiments, suggesting that the reduction of soot particle-bound Hg(II) was responsible for the observed negative odd-MIF. Our results suggest that mass-independent Hg isotope fractionation during Hg(II) photoreduction varies with soot aerosol water content and that Hg-stable isotope ratios may be used to understand the transformational histories of aerosol-bound Hg(II) in the environment.

Mercury evidence of intense volcanic effects on land during the Permian-Triassic transition

Abstract The Siberian Traps large igneous province (STLIP) was the likely trigger for the ca. 252 Ma latest Permian mass extinction (LPME), but direct evidence for global volcanic effects on land remains rare. Here, we used mercury (Hg) enrichments, a proxy for ancient volcanic activity, to assess volcanic inputs to two terrestrial Permian-Triassic boundary (PTB) sections that were separated by thousands of kilometers and represent different latitudinal zones—the peri-equatorial Lubei section (South China craton) and the high-latitude (40–60°N) Dalongkou section (Junggar terrane). Both sections exhibit strong Hg enrichment within a discrete (≤40 m) stratigraphic window representing the LPME. At Lubei, this interval is also characterized by negative mass-independent fractionation (MIF) of odd Hg isotopes, consistent with massive volcanogenic and/or terrestrial Hg inputs. These findings are significant in documenting Hg spikes and negative MIF excursions near the PTB in terrestrial sections for the first time, providing evidence of the global influence of the STLIP, as well as in demonstrating at high stratigraphic resolution its synchronicity with the PTB negative carbon-isotope excursion (CIE), supporting a common global cause for these anomalies.

Photomicrobial Visible Light-Induced Magnetic Mass Independent Fractionation of Mercury in a Marine Microalga

Methylmercury (MeHg), a highly neurotoxic substance, accumulates in aquatic food webs, and is enriched in odd isotopes (i.e., 199Hg and 201Hg), purportedly as a result of abiotic photodegradation in surface waters. Here, we highlight the potential role of phytoplankton in the mass independent fractionation (MIF) of MeHg in marine food-webs by providing evidence of (1) degradation of intracellular MeHg and reduction of intracellular inorganic mercury (Hg(II)) in the marine microalga, Isochrysis galbana; (2) a large, positive MIF (Δ199Hgreactant – Δ199Hgproduct ∼ 5–10‰) during intracellular degradation of MeHg in cells exposed to visible light with no UVB, consistent with the accumulation of odd isotope-enriched MeHg in marine food-webs; and (3) a negative MIF (−1‰) during intracellular reduction of Hg(II) in the presence of UVB light. If representative of the photochemical reactivity of MeHg in marine phytoplankton, our results indicate that algal cell-mediated demethylation of MeHg by visible light could ...

Isotopic Composition of Atmospheric Mercury in China: New Evidence for Sources and Transformation Processes in Air and in Vegetation.

The isotopic composition of atmospheric total gaseous mercury (TGM) and particle-bound mercury (PBM) and mercury (Hg) in litterfall samples have been determined at urban/industrialized and rural sites distributed over mainland China for identifying Hg sources and transformation processes. TGM and PBM near anthropogenic emission sources display negative δ(202)Hg and near-zero Δ(199)Hg in contrast to relatively positive δ(202)Hg and negative Δ(199)Hg observed in remote regions, suggesting that different sources and atmospheric processes force the mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) in the air samples. Both MDF and MIF occur during the uptake of atmospheric Hg by plants, resulting in negative δ(202)Hg and Δ(199)Hg observed in litter-bound Hg. The linear regression resulting from the scatter plot relating the δ(202)Hg to Δ(199)Hg data in the TGM samples indicates distinct anthropogenic or natural influences at the three study sites. A similar trend was also observed for Hg accumulated in broadleaved deciduous forest foliage grown in areas influenced by anthropogenic emissions. The relatively negative MIF in litter-bound Hg compared to TGM is likely a result of the photochemical reactions of Hg(2+) in foliage. This study demonstrates the diagnostic stable Hg isotopic composition characteristics for separating atmospheric Hg of different source origins in China and provides the isotopic fractionation clues for the study of Hg bioaccumulation.

A hundred year record of industrial and urban development in French Alps combining Hg accumulation rates and isotope composition in sediment archives from Lake Luitel

This study reconstructs the history of multiple industrial and urban mercury (Hg) emissions recorded in the sediment archive of Lake Luitel (France) from AD ~1860 to AD 2011. For this purpose, we provide a well constrained short-lived radionuclides continuous age–depth relationship of the sediment sequence (mean accumulation rate of 5.18±0.28mm·yr−1) with Hg accumulation rates (Hg AR), Hg isotopic composition and extensive historical data. Hg AR were stable around 45μg·m−2·y−1 from 1860 to WWI and rose to reach their maximum at the end of WWII (250μgm−2y−1) followed by a gradual decreased to reach about 90μgm−2y−1 in the current period. Normalization to a terrigenous Hg proxy highlighted the dominance of atmospheric Hg inputs to the lake. The combination of Hg AR with isotopic signatures through the use of binary mixing (Δ199Hg vs 1/Hg AR) models and isotopic plots (and comparison to literature data) allowed us to identify the main industrial and urban historical inputs. The major outcome of this study is that the Hg mass independent fractionation (MIF) signature did not enable the identification of particular anthropogenic sources but reflected an integrated pool of industrial and urban emissions which tend to shift to less negative MIF values (mean: −0.15±0.04‰) during their period of maximum emissions. Temporal MIF and Hg AR variations depict the rising Hg emissions from the industrial revolution (1860–1910) to the modern industrial and urban development period (1950–1980). Mass dependent fractionation (MDF) signatures enabled the identification of major contributors in relation to their relative intensities lying between two endmember pools: (i) the combustion activities (smelters, cement factories and urban heating) with more negative δ202Hg values, and (ii) the chemical and electrometallurgical activities (electrochemistry, chlor-alkali) with higher δ202Hg values. Unconformities of MIF and MDF signatures were observed during WWI, WWII and interwar period, and were attributed to drastic and rapid changes in regional industrial activities. Finally, recent laws regarding Hg emissions (1998–2011) prove their efficiency as Hg AR decreased with a return to more negative MIF and MDF signatures such as during the industrial revolution period. Our study highlights that the combination of Hg isotopic data with Hg AR in sediment archives is a useful tool for reconstructing the history of anthropogenic Hg emissions, and has the potential to identifiy their relative contributions.

Mercury isotopes of atmospheric particle bound mercury for source apportionment study in urban Kolkata, India

Abstract The particle bound mercury (PBM) in urban-industrial areas is mainly of anthropogenic origin, and is derived from two principal sources: Hg bound to particulate matter directly emitted by industries and power generation plants, and adsorption of gaseous elemental mercury (GEM) and gaseous oxidized mercury (GOM) on air particulates from gas or aqueous phases. Here, we measured the Hg isotope composition of PBM in PM10 samples collected from three locations, a traffic junction, a waste incineration site and an industrial site in Kolkata, the largest metropolis in Eastern India. Sampling was carried out in winter and monsoon seasons between 2013–2015. The objective was to understand whether the isotope composition of the PBM represents source composition. The PBM collected from the waste burning site showed little mass independent fractionation (MIF) (Δ199Hg = +0.12 to -0.11‰), similar to the signature in liquid Hg and Hg ores around the world with no seasonal variations. Samples from the industrial site showed mostly negative MDF and MIF (δ202Hg = -1.34 to -3.48 ‰ and Δ199Hg = +0.01 to -0.31‰). The MDF is consistent with PBM generated by coal combustion however, the MIF is 0.15‰ more negative compared to the Hg isotope ratios in Indian coals. The traffic junction PBM is probably not produced in situ, but has travelled some distances from nearby industrial sources. The longer residence time of this PBM in the atmosphere has resulted in-aerosol aqueous photoreduction. Thus, the MIF displays a larger range (Δ199Hg = +0.33 to -0.30‰) compared to the signature from the other sites and with more positive values in the humid monsoon season. Different Hg isotopic signature of PBM in the three different sampling locations within the same city indicates that both source and post emission atmospheric transformations play important roles in determining isotopic signature of PBM.

Mercury Isotope Signatures as Tracers for Hg Cycling at the New Idria Hg Mine

Mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) of Hg isotopes provides a new tool for tracing Hg in contaminated environments such as mining sites, which represent major point sources of Hg pollution into surrounding ecosystems. Here, we present Hg isotope ratios of unroasted ore waste, calcine (roasted ore), and poplar leaves collected at a closed Hg mine (New Idria, CA, U.S.A.). Unroasted ore waste was isotopically uniform with δ(202)Hg values from -0.09 to 0.16‰ (± 0.10‰, 2 SD), close to the estimated initial composition of the HgS ore (-0.26‰). In contrast, calcine samples exhibited variable δ(202)Hg values ranging from -1.91‰ to +2.10‰. Small MIF signatures in the calcine were consistent with nuclear volume fractionation of Hg isotopes during or after the roasting process. The poplar leaves exhibited negative MDF (-3.18 to -1.22‰) and small positive MIF values (Δ(199)Hg of 0.02 to 0.21‰). Sequential extractions combined with Hg isotope analysis revealed higher δ(202)Hg values for the more soluble Hg pools in calcines compared with residual HgS phases. Our data provide novel insights into possible in situ transformations of Hg phases and suggest that isotopically heavy secondary Hg phases were formed in the calcine, which will influence the isotope composition of Hg leached from the site.

Isotopic composition of species-specific atmospheric Hg in a coastal environment

The isotopic composition of species-specific atmospheric mercury (Hg) was investigated in the coastal environment of Grand Bay, Mississippi, USA. Atmospheric mercury species (Hg0(g), HgII(g) and Hg(p)) were collected individually, and analyzed for isotopic composition. Gaseous elemental Hg (Hg0(g)) displayed δ202Hg ranging from −3.88‰ to −0.33‰. Aerosol Hg (Hg(p)) displayed intermediate δ202Hg ranging from −1.61‰ to −0.12‰, while reactive gaseous Hg (HgII(g)) displayed positive δ202Hg ranging from +0.51‰ to +1.61‰. Significant positive mass-independent fractionation (MIF) was observed in Hg(p) (∆199Hg=+0.36‰ to +1.36‰), while Hg0(g) displayed negative MIF (∆199Hg=−0.41‰ to −0.03‰) and HgII(g) displayed intermediate MIF (∆199Hg=−0.28‰ to 0.18‰). Positive MIF of 199Hg and 201Hg measured in Hg(p) is consistent with significant in-aerosol photoreduction. Significant MIF of 200Hg was observed in all Hg species with Hg0(g) displaying negative ∆200Hg values of −0.19‰ to −0.06‰ while HgII(g) and Hg(p) displayed positive ∆200Hg values of +0.06‰ to +0.28‰, which are similar to ∆200Hg values reported by Gratz et al. (2010). These results suggest that isotope tracing of each atmospheric Hg species may be feasible during important atmospheric processes such as wet and dry deposition.

A global model of mass independent mercury stable isotope fractionation

Mass independent fractionation (MIF) of stable isotopes associated with terrestrial geochemical processes was first observed in the 1980s for oxygen and in the 1990s for sulfur isotopes. Recently mercury (Hg) was added to this shortlist when positive odd Hg isotope anomalies were observed in biological tissues. Experimental work identified photoreduction of aquatic inorganic divalent Hg II and photodegradation of monomethylmercury species as plausible MIF inducing reactions. Observations of continental receptors of atmospheric Hg deposition such as peat, lichens, soils and, indirectly, coal have shown predominantly negative MIF. This has led to the suggestion that atmospheric Hg has negative MIF signatures and that these are the compliment of positive Hg MIF in the aquatic environment. Recent observations on atmospheric vapor phase Hg 0 and Hg II in wet precipitation reveal zero and positive Hg MIF respectively and are in contradiction with a simple aquatic Hg II photoreduction scenario as the origin for global Hg MIF observations. This study presents a synthesis of all terrestrial Hg MIF observations, and these are integrated in a one-dimensional coupled continent-ocean–atmosphere model of the global Hg cycle. The model illustrates how Hg MIF signatures propagate through the various Earth surface reservoirs. The scenario in which marine photoreduction is the main MIF inducing process results in negative atmospheric Δ 199Hg and positive ocean Δ 199Hg of −0.5‰ and +0.25‰, yet does not explain atmospheric Hg 0 and Hg II wet precipitation observations. Alternative model scenarios that presume in-cloud aerosol Hg II photoreduction and continental Hg II photoreduction at soil, snow and vegetation surfaces to display MIF are necessary to explain the ensemble of natural observations. The model based approach is a first step in understanding Hg MIF at a global scale and the eventual incorporation of Hg stable isotope information in detailed global mercury chemistry and transport models.