Mercury deposition and redox transformation processes in peatland constrained by mercury stable isotopes.

Peatland vegetation takes up mercury (Hg) from the atmosphere, typically contributing to net production and export of neurotoxic methyl-Hg to downstream ecosystems. Chemical reduction processes can slow down methyl-Hg production by releasing Hg from peat back to the atmosphere. The extent of these processes remains, however, unclear. Here we present results from a comprehensive study covering concentrations and isotopic signatures of Hg in an open boreal peatland system to identify post-depositional Hg redox transformation processes. Isotope mass balances suggest photoreduction of HgII is the predominant process by which 30% of annually deposited Hg is emitted back to the atmosphere. Isotopic analyses indicate that above the water table, dark abiotic oxidation decreases peat soil gaseous Hg0 concentrations. Below the water table, supersaturation of gaseous Hg is likely created more by direct photoreduction of rainfall rather than by reduction and release of Hg from the peat soil. Identification and quantification of these light-driven and dark redox processes advance our understanding of the fate of Hg in peatlands, including the potential for mobilization and methylation of HgII.

Isotopic Characterization of Mercury Atmosphere-Foliage and Atmosphere-Soil Exchange in a Swiss Subalpine Coniferous Forest.

To understand the role of vegetation and soil in regulating atmospheric Hg0, exchange fluxes and isotope signatures of Hg were characterized using a dynamic flux bag/chamber at the atmosphere-foliage/soil interfaces at the Davos-Seehornwald forest, Switzerland. The foliage was a net Hg0 sink and took up preferentially the light Hg isotopes, consequently resulting in large shifts (-3.27‰) in δ202Hg values. The soil served mostly as net sources of atmospheric Hg0 with higher Hg0 emission from the moss-covered soils than from bare soils. The negative shift of δ202Hg and Δ199Hg values of the efflux air relative to ambient air and the Δ199Hg/Δ201Hg ratio among ambient air, efflux air, and soil pore gas highlight that Hg0 re-emission was strongly constrained by soil pore gas evasion together with microbial reduction. The isotopic mass balance model indicates 8.4 times higher Hg0 emission caused by pore gas evasion than surface soil photoreduction. Deposition of atmospheric Hg0 to soil was noticeably 3.2 times higher than that to foliage, reflecting the high significance of the soil to influence atmospheric Hg0 isotope signatures. This study improves our understanding of Hg atmosphere-foliage/soil exchange in subalpine coniferous forests, which is indispensable in the model assessment of forest Hg biogeochemical cycling.

Predominant contributions through lichen and fine litter to litterfall mercury deposition in a subalpine forest.

Litterfall, typically referring to needles/leaves, may stand for >50% of the total mercury (Hg) deposition in forest ecosystems. By detailed categorisation, we reveal for the first time that the contributions through lichens and fine litter, together 9.98 µg Hg m-2 yr-1, could be as high as that in needle litter (9.96 µg m-2 yr-1) to the annual total Hg deposition (44.6 µg m-2 yr-1) in a subalpine forest in Switzerland. Noticeably, needle litter had the highest contribution (53%) to total Hg in the autumn litterfall but lichens and fine litter together predominated in other seasons (47-59%). Such a seasonal pattern is caused by the high ability of lichens and fine litter to accumulate Hg and the high needle litterfall in autumn, which is related to a good rainfall in summer followed by a dry period in autumn. The constantly higher Hg levels in lichens and fine litter than in needle litter together with similar seasonal patterns of litterfall during 2009-2019 and rainfall during 1980-2019 suggest that our finding can be generally valid. Here, we highlight not only the considerable role of non-needle litterfall in Hg deposition but also the association with weather for seasonal Hg dynamics in different litterfall components.

Mercury isotope evidence for Arctic summertime re-emission of mercury from the cryosphere.

During Arctic springtime, halogen radicals oxidize atmospheric elemental mercury (Hg0), which deposits to the cryosphere. This is followed by a summertime atmospheric Hg0 peak that is thought to result mostly from terrestrial Hg inputs to the Arctic Ocean, followed by photoreduction and emission to air. The large terrestrial Hg contribution to the Arctic Ocean and global atmosphere has raised concern over the potential release of permafrost Hg, via rivers and coastal erosion, with Arctic warming. Here we investigate Hg isotope variability of Arctic atmospheric, marine, and terrestrial Hg. We observe highly characteristic Hg isotope signatures during the summertime peak that reflect re-emission of Hg deposited to the cryosphere during spring. Air mass back trajectories support a cryospheric Hg emission source but no major terrestrial source. This implies that terrestrial Hg inputs to the Arctic Ocean remain in the marine ecosystem, without substantial loss to the global atmosphere, but with possible effects on food webs.

A spatial assessment of mercury content in the European Union topsoil.

Mapping of surface soil Hg concentrations, a priority pollutant, at continental scale is important in order to identify hotspots of soil Hg distribution (e.g. mining or industrial pollution) and identify factors that influence soil Hg concentrations (e.g. climate, soil properties, vegetation). Here we present soil Hg concentrations from the LUCAS topsoil (0-20 cm) survey including 21,591 samples from 26 European Union countries (one sample every ~200 km2). Deep Neural Network (DNN) learning models were used to map the European soil Hg distribution. DNN estimated a median Hg concentration of 38.3 µg kg-1 (2.6 to 84.7 µg kg-1) excluding contaminated sites. At continental scale, we found that soil Hg concentrations increased with latitude from south to north and with altitude. A GLMM revealed a correlation (R2 = 0.35) of soil Hg concentrations with vegetation activity, normalized difference vegetation index (NDVI), and soil organic carbon content. This observation corroborates the importance of atmospheric Hg0 uptake by plants and the build-up of the soil Hg pool by litterfall over continental scales. The correlation of Hg concentrations with NDVI was amplified by higher soil organic matter content, known to stabilize Hg in soils through thiol bonds. We find a statistically significant relation between soil Hg levels and coal use in large power plants, proving that emissions from power plants are associated with higher mercury deposition in their proximity. In total 209 hotspots were identified, defined as the top percentile in Hg concentration (>422 µg kg-1). 87 sites (42% of all hotspots) were associated with known mining areas. The sources of the other hotspots could not be identified and may relate to unmined geogenic Hg or industrial pollution. The mapping effort in the framework of LUCAS can serve as a starting point to guide local and regional authorities in identifying Hg contamination hotspots in soils.

Determination of (Bio)-available mercury in soils: A review.

Despite the mercury (Hg) control measures adopted by the international community, Hg still poses a significant risk to ecosystem and human health. This is primarily due to the ability of atmospheric Hg to travel intercontinentally and contaminating terrestrial and aquatic environments far from its natural and anthropogenic point sources. The issue of Hg pollution is further complicated by its unique physicochemical characteristics, most noticeably its multiple chemical forms that vary in their toxicity and environmental mobility. This meant that most of the risk evaluation protocols developed for other metal(loid)s are not suitable for Hg. Soil is a major reservoir of Hg and a key player in its global cycle. To fully assess the risks of soil Hg it is essential to estimate its bioavailability and/or availability which are closely linked to its toxicity. However, the accurate determination of the (bio)-available pools of Hg in soils is problematic, because the terms 'bioavailable' and 'available' are ill-defined. In particular, the term 'bioavailable pool', representing the fraction of Hg that is accessible to living organisms, has been consistently misused by interchanging with other intrinsically different terms e.g. mobile, labile, reactive and soluble pools. A wide array of physical, chemical, biological and isotopic exchange methods were developed to estimate the (bio)-available pools of Hg in soil in an attempt to offer a plausible assessment of its risks. Unfortunately, many of these methods do not mirror the (bio)-available pools of soil Hg and suffer from technical drawbacks. In this review, we discuss advantages and disadvantages of methods that are currently applied to quantify the (bio)-availability of Hg in soils. We recommended the most feasible methods and give suggestions how to improve the determination of (bio)-available Hg in soils.

Concurrently Measured Concentrations of Atmospheric Mercury in Indoor (household) and Outdoor Air of Basel, Switzerland.

Indoor air pollution can be a major health risk because urban populations spend up to 90% of their time in closed rooms. Gaseous elemental mercury (GEM) has not been measured as routinely as other indoor air pollutants due to the high costs and limited mobility of active Hg analyzers. However, household GEM concentrations may exceed Hg air quality guidelines as a result of potential indoor GEM sources like broken Hg thermometers. Here we deploy novel low-cost mercury passive air samplers (MerPAS) in 27 households (7 days) and at 14 outdoor locations (29-31 days) in Basel, Switzerland. Average Hg concentrations ranged from 2.0 to 10.8 ng m-3 indoors and from 1.8 to 2.5 ng m-3 outdoors. These results reveal that households are a net source of Hg to the urban atmosphere and exceed outdoor Hg levels by a factor of 2 on average. We estimated an average weekly intake rate of 0.01 µg of Hg/kg of body weight for adult residents in Basel, which is usually lower than Hg exposure of people with dental amalgam fillings. Our campaign demonstrates that air monitoring programs can easily be complemented by straightforward Hg measurements using MerPAS.

Recent advances in understanding and measurement of mercury in the environment: Terrestrial Hg cycling.

This review documents recent advances in terrestrial mercury cycling. Terrestrial mercury (Hg) research has matured in some areas, and is developing rapidly in others. We summarize the state of the science circa 2010 as a starting point, and then present the advances during the last decade in three areas: land use, sulfate deposition, and climate change. The advances are presented in the framework of three Hg "gateways" to the terrestrial environment: inputs from the atmosphere, uptake in food, and runoff with surface water. Among the most notable advances: These and other advances reported here are of value in evaluating the effectiveness of the Minamata Convention on reducing environmental Hg exposure to humans and wildlife.

Recent advances in understanding and measurement of Hg in the environment: Surface-atmosphere exchange of gaseous elemental mercury (Hg0).

The atmosphere is the major transport pathway for distribution of mercury (Hg) globally. Gaseous elemental mercury (GEM, hereafter Hg0) is the predominant form in both anthropogenic and natural emissions. Evaluation of the efficacy of reductions in emissions set by the UN's Minamata Convention (UN-MC) is critically dependent on the knowledge of the dynamics of the global Hg cycle. Of these dynamics including e.g. red-ox reactions, methylation-demethylation and dry-wet deposition, poorly constrained atmosphere-surface Hg0 fluxes especially limit predictability of the timescales of its global biogeochemical cycle. This review focuses on Hg0 flux field observational studies, namely the theory, applications, strengths, and limitations of the various experimental methodologies applied to gauge the exchange flux and decipher active sub-processes. We present an in-depth review, a comprehensive literature synthesis, and methodological and instrumentation advances for terrestrial and marine Hg0 flux studies in recent years. In particular, we outline the theory of a wide range of measurement techniques and detail the operational protocols. Today, the most frequently used measurement techniques to determine the net Hg0 flux (>95% of the published flux data) are dynamic flux chambers for small-scale and micrometeorological approaches for large-scale measurements. Furthermore, top-down approaches based on Hg0 concentration measurements have been applied as tools to better constrain Hg emissions as an independent way to e.g. challenge emission inventories. This review is an up-dated, thoroughly revised edition of Sommar et al. 2013 (DOI: 10.1080/10643389.2012.671733). To the tabulation of >100 cited flux studies 1988-2009 given in the former publication, we have here listed corresponding studies published during the last decade with a few exceptions (2008-2019). During that decade, Hg stable isotope ratios of samples involved in atmosphere-terrestrial interaction is at hand and provide in combination with concentration and/or flux measurements novel constraints to quantitatively and qualitatively assess the bi-directional Hg0 flux. Recent efforts in the development of relaxed eddy accumulation and eddy covariance Hg0 flux methods bear the potential to facilitate long-term, ecosystem-scale flux measurements to reduce the prevailing large uncertainties in Hg0 flux estimates. Standardization of methods for Hg0 flux measurements is crucial to investigate how land-use change and how climate warming impact ecosystem-specific Hg0 sink-source characteristics and to validate frequently applied model parameterizations describing the regional and global scale Hg cycle.

Vanadium-basidiomycete fungi interaction and its impact on vanadium biogeochemistry.

Fungi are well known to strongly interact with metals, thereby influencing metal biogeochemistry in the terrestrial environment. To assess and quantify potential fungi-vanadium (V) interactions, Amanita muscaria, Armillaria cepistipes, Xerocomus badius and Bjerkandera adusta were cultured in media containing soluble V (VOSO4 or NaVO3) or solid-phase V of different chemical forms and oxidation state (V2O3, VO2, V2O5, or V-Ti magnetite slag). All fungi underwent physiological and structural changes, as revealed by alterations in FT-IR peak positions and intensities relative to the control, and morphological changes of mycelia, as observed by scanning electron microscopy. The diametric growth size generally decreased with decreasing oxidation state of V and with increasing concentrations of VOSO4 and NaVO3, implying that V toxicity is dependent on V speciation. The tolerance index, the ratio of treated and control mycelium (dry weight), shows different tendencies, suggesting additional factors influencing fungi weight, such as the formation of extrahyphal crystals. Vanadium accumulation from VOSO4 and NaVO3 medium in all fungi (up to 51.3 mg g-1) shows the potential of fungi to immobilise soluble V, thereby reducing its impacts on environmental and human health. Uptake and accumulation of V in slag was insignificant, reflecting the association of slag V with insoluble crystalline materials. The fungal accumulation of V in medium amended with V-oxides demonstrates the ability of fungi to solubilise solid-phase V compounds, thereby introducing previously immobile V into the V biogeochemical cycle and into the food chain where it may impact ecological and human health. A.muscaria lowered the pH of the medium substantially during cultivation, indicating acidolysis and complexolysis via excretion of organic acids (e.g. oxalic acid). Oxidation of VOSO4 was observed by a colour change of the medium to yellow during B. adusta cultivation, revealing the role of fungally-mediated redox transformation in V (im)mobilisation. The calculated removal efficiencies of soluble V were 40-90% for A. cepistipes and X. badius, but a much lower recovery (0-20%) was observed from V oxides and slag (0-20%) by all fungi. This suggests the probable application of fungi for bio-remediation of mobile/soluble V in contaminated soils but not of V incorporated in the lattice of soil minerals.

Mercury emission from industrially contaminated soils in relation to chemical, microbial, and meteorological factors.

The Minamata Convention entered into force in 2017 with the aim to phase-out the use of mercury (Hg) in manufacturing processes such as the chlor-alkali or vinyl chloride monomer production. However, past industrial use of Hg had already resulted in extensive soil pollution, which poses a potential environmental threat. We investigated the emission of gaseous elemental mercury (Hg0) from Hg polluted soils in settlement areas in the canton of Valais, Switzerland, and its impact on local air Hg concentrations. Most soil Hg was found as soil matrix-bound divalent Hg (HgII). Elemental mercury (Hg0) was undetectable in soils, yet we observed substantial Hg0 emission (20-1392 ng m-2 h-1) from 27 soil plots contaminated with Hg (0.2-390 mg Hg kg-1). The emissions of Hg0 were calculated for 1274 parcels covering an area of 8.6 km2 of which 12% exceeded the Swiss soil remediation threshold of 2 mg Hg kg-1. The annual Hg0 emission from this area was approximately 6 kg a-1, which is almost 1% of the total atmospheric Hg emissions in Switzerland based on emission inventory estimates. Our results show a higher abundance of Hg resistance genes (merA) in soil microbial communities with increasing soil Hg concentrations, indicating that biotic reduction of HgII is likely an important pathway to form volatile Hg0 in these soils. The total soil Hg pool in the top 20 cm of the investigated area was 4288 kg; hence, if not remediated, these contaminated soils remain a long-term source of atmospheric Hg, which is prone to long-range atmospheric transport.

Sorption kinetics of isotopically labelled divalent mercury (196Hg2+) in soil.

Understanding the sorption kinetics of Hg2+ is the key to predicting its reactivity in soils which is indispensable for environmental risk assessment. The temporal change in the solubility of 196Hg2+ spikes (6 mg kg-1) added to a range of soils with different properties was investigated and modelled. The sorption of 196Hg2+ displayed a biphasic pattern with a rapid initial (short-term) phase followed by a slower (time-dependent) one. The overall reaction rate constants ranged from 0.003 to 4.9 h-1 and were significantly correlated (r = 0.94) to soil organic carbon (SOC). Elovich and Spherical Diffusion expressions compellingly fitted the observed 196Hg2+ sorption kinetics highlighting their flexibility to describe reactions occurring over multiple phases and wide timeframes. A parameterized Elovich model from soil variables indicated that the short-term sorption is solely controlled by SOC while the time-dependent sorption appeared independent of SOC and decreased at higher pH values and Al(OH)3 and MnO2 concentrations. This is consistent with a rapid chemical reaction of Hg2+ with soil organic matter (SOM) which is followed by a noticeably slower phase likely occurring through physical pathways e.g. pore diffusion of Hg2+ into spherical soil aggregates and progressive incorporation of soluble organic-Hg into solid phase. The model lines predicted that in soils with >4% SOC, Hg2+ is removed from soil solution over seconds to minutes; however, in soils with <2% SOC and higher pH values, Hg2+ may remain soluble for months and beyond with a considerable associated risk of re-emission or migration to the surrounding environments.

Mercury evasion from a boreal peatland shortens the timeline for recovery from legacy pollution.

Peatlands are a major source of methylmercury that contaminates downstream aquatic food webs. The large store of mercury (Hg) in peatlands could be a source of Hg for over a century even if deposition is dramatically reduced. However, the reliability of Hg mass balances can be questioned due to missing long-term land-atmosphere flux measurements. We used a novel micrometeorological system for continuous measurement of Hg peatland-atmosphere exchange to derive the first annual Hg budget for a peatland. The evasion of Hg (9.4 µg m-2 yr-1) over the course of a year was seven times greater than stream Hg export, and over two times greater than wet bulk deposition to the boreal peatland. Measurements of dissolved gaseous Hg in the peat pore water also indicate Hg evasion. The net efflux may result from recent declines in atmospheric Hg concentrations that have turned the peatland from a net sink into a source of atmospheric Hg. This net Hg loss suggests that open boreal peatlands and downstream ecosystems can recover more rapidly from past atmospheric Hg deposition than previously assumed. This has important implications for future levels of methylmercury in boreal freshwater fish and the estimation of historical Hg accumulation rates from peat profiles.