Mercury stable isotopes constrain atmospheric sources to the ocean.

Human exposure to toxic mercury (Hg) is dominated by the consumption of seafood1,2. Earth system models suggest that Hg in marine ecosystems is supplied by atmospheric wet and dry Hg(II) deposition, with a three times smaller contribution from gaseous Hg(0) uptake3,4. Observations of marine Hg(II) deposition and Hg(0) gas exchange are sparse, however5, leaving the suggested importance of Hg(II) deposition6 ill-constrained. Here we present the first Hg stable isotope measurements of total Hg (tHg) in surface and deep Atlantic and Mediterranean seawater and use them to quantify atmospheric Hg deposition pathways. We observe overall similar tHg isotope compositions, with median Δ200Hg signatures of 0.02‰, lying in between atmospheric Hg(0) and Hg(II) deposition end-members. We use a Δ200Hg isotope mass balance to estimate that seawater tHg can be explained by the mixing of 42% (median; interquartile range, 24-50%) atmospheric Hg(II) gross deposition and 58% (50-76%) Hg(0) gross uptake. We measure and compile additional, global marine Hg isotope data including particulate Hg, sediments and biota and observe a latitudinal Δ200Hg gradient that indicates larger ocean Hg(0) uptake at high latitudes. Our findings suggest that global atmospheric Hg(0) uptake by the oceans is equal to Hg(II) deposition, which has implications for our understanding of atmospheric Hg dispersal and marine ecosystem recovery.

Deforestation as an Anthropogenic Driver of Mercury Pollution.

Deforestation reduces the capacity of the terrestrial biosphere to take up toxic pollutant mercury (Hg) and enhances the release of secondary Hg from soils. The consequences of deforestation for Hg cycling are not currently considered by anthropogenic emission inventories or specifically addressed under the global Minamata Convention on Mercury. Using global Hg modeling constrained by field observations, we estimate that net Hg fluxes to the atmosphere due to deforestation are 217 Mg year-1 (95% confidence interval (CI): 134-1650 Mg year-1) for 2015, approximately 10% of global primary anthropogenic emissions. If deforestation of the Amazon rainforest continues at business-as-usual rates, net Hg emissions from the region will increase by 153 Mg year-1 by 2050 (CI: 97-418 Mg year-1), enhancing the transport and subsequent deposition of Hg to aquatic ecosystems. Substantial Hg emissions reductions are found for two potential cases of land use policies: conservation of the Amazon rainforest (92 Mg year-1, 95% CI: 59-234 Mg year-1) and global reforestation (98 Mg year-1, 95% CI: 64-449 Mg year-1). We conclude that deforestation-related emissions should be incorporated as an anthropogenic source in Hg inventories and that land use policy could be leveraged to address global Hg pollution.

Tundra uptake of atmospheric elemental mercury drives Arctic mercury pollution.

Anthropogenic activities have led to large-scale mercury (Hg) pollution in the Arctic. It has been suggested that sea-salt-induced chemical cycling of Hg (through 'atmospheric mercury depletion events', or AMDEs) and wet deposition via precipitation are sources of Hg to the Arctic in its oxidized form (Hg(ii)). However, there is little evidence for the occurrence of AMDEs outside of coastal regions, and their importance to net Hg deposition has been questioned. Furthermore, wet-deposition measurements in the Arctic showed some of the lowest levels of Hg deposition via precipitation worldwide, raising questions as to the sources of high Arctic Hg loading. Here we present a comprehensive Hg-deposition mass-balance study, and show that most of the Hg (about 70%) in the interior Arctic tundra is derived from gaseous elemental Hg (Hg(0)) deposition, with only minor contributions from the deposition of Hg(ii) via precipitation or AMDEs. We find that deposition of Hg(0)-the form ubiquitously present in the global atmosphere-occurs throughout the year, and that it is enhanced in summer through the uptake of Hg(0) by vegetation. Tundra uptake of gaseous Hg(0) leads to high soil Hg concentrations, with Hg masses greatly exceeding the levels found in temperate soils. Our concurrent Hg stable isotope measurements in the atmosphere, snowpack, vegetation and soils support our finding that Hg(0) dominates as a source to the tundra. Hg concentration and stable isotope data from an inland-to-coastal transect show high soil Hg concentrations consistently derived from Hg(0), suggesting that the Arctic tundra might be a globally important Hg sink. We suggest that the high tundra soil Hg concentrations might also explain why Arctic rivers annually transport large amounts of Hg to the Arctic Ocean.

Photochemistry of oxidized Hg(I) and Hg(II) species suggests missing mercury oxidation in the troposphere.

Mercury (Hg), a global contaminant, is emitted mainly in its elemental form Hg0 to the atmosphere where it is oxidized to reactive HgII compounds, which efficiently deposit to surface ecosystems. Therefore, the chemical cycling between the elemental and oxidized Hg forms in the atmosphere determines the scale and geographical pattern of global Hg deposition. Recent advances in the photochemistry of gas-phase oxidized HgI and HgII species postulate their photodissociation back to Hg0 as a crucial step in the atmospheric Hg redox cycle. However, the significance of these photodissociation mechanisms on atmospheric Hg chemistry, lifetime, and surface deposition remains uncertain. Here we implement a comprehensive and quantitative mechanism of the photochemical and thermal atmospheric reactions between Hg0, HgI, and HgII species in a global model and evaluate the results against atmospheric Hg observations. We find that the photochemistry of HgI and HgII leads to insufficient Hg oxidation globally. The combined efficient photoreduction of HgI and HgII to Hg0 competes with thermal oxidation of Hg0, resulting in a large model overestimation of 99% of measured Hg0 and underestimation of 51% of oxidized Hg and ∼66% of HgII wet deposition. This in turn leads to a significant increase in the calculated global atmospheric Hg lifetime of 20 mo, which is unrealistically longer than the 3-6-mo range based on observed atmospheric Hg variability. These results show that the HgI and HgII photoreduction processes largely offset the efficiency of bromine-initiated Hg0 oxidation and reveal missing Hg oxidation processes in the troposphere.

Mass-Independent Fractionation of Even and Odd Mercury Isotopes during Atmospheric Mercury Redox Reactions.

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.

Mercury in European topsoils: Anthropogenic sources, stocks and fluxes.

Mercury (Hg) is one of the most dangerous pollutants worldwide. In the European Union (EU), we recently estimated the Hg distribution in topsoil using 21,591 samples and a series of geo-physical inputs. In this manuscript, we investigate the impact of mining activities, chrol-alkali industries and other diffuse pollution sources as primary anthropogenic sources of Hg hotspots in the EU. Based on Hg measured soil samples, we modelled the Hg pool in EU topsoils, which totals about 44.8 Gg, with an average density of 103 g ha-1. As a following step, we coupled the estimated Hg stocks in topsoil with the pan-European assessment of soil loss due to water erosion and sediment distribution. In the European Union and UK, we estimated that about 43 Mg Hg yr-1 are displaced by water erosion and c. a. 6 Mg Hg yr-1 are transferred with sediments to river basins and eventually released to coastal Oceans. The Mediterranean Sea receives almost half (2.94 Mg yr-1) of the Hg fluxes to coastal oceans and it records the highest quantity of Hg sediments. This is the result of elevated soil Hg concentration and high erosion rates in the catchments draining into the Mediterranean Sea. This work contributes to new knowledge in support of the policy development in the EU on the Zero Pollution Action Plan and the Sustainable Development Goal (SDGs) 3.9 and 14.1, which both have as an objective to reduce soil pollution by 2030.

Automated Stable Isotope Sampling of Gaseous Elemental Mercury (ISO-GEM): Insights into GEM Emissions from Building Surfaces.

Atmospheric monitoring networks quantify gaseous elemental mercury (GEM) concentrations, but not isotopic compositions. Here, we present a new method for automated and quantitative stable isotope sampling of GEM (ISO-GEM) at the outlet of a commercial Hg analyzer. A programmable multivalve manifold selects Hg at the analyzer inlet and outlet based on specific criteria (location, time, GEM concentration, auxiliary threshold). Outlet Hg recovery was tested for gold traps, oxidizing acidic solution traps, and activated carbon traps. We illustrate the ISO-GEM method in an exploratory study on the effect of building walls on local GEM. We find that GEM concentrations directly at the building surface (wall inlet) are significantly enhanced (mean 3.8 ± 1.8 ng/m3) compared to 3 m from the building wall (free inlet) (mean 1.5 ± 0.4 ng/m3). GEM δ202Hg (-1.26‰ ± 0.41‰, 1 SD, n = 16) and Δ199Hg (-0.05‰ ± 0.10‰, 1 SD, n = 16) at the wall inlet were different from ambient GEM δ202Hg (0.76‰ ± 0.09‰, 1 SD, n = 16) and Δ199Hg (-0.21‰ ± 0.05‰, 1 SD, n = 16) at the free inlet. The isotopic fingerprint of GEM at the wall inlet suggests that GEM emission from the aluminum building surface affected local GEM concentration measurements. These results illustrate the versatility of the automated Hg isotope sampling.

Tropospheric GOM at the Pic du Midi Observatory-Correcting Bias in Denuder Based Observations.

Gaseous elemental mercury (GEM, Hg) emissions are transformed to divalent reactive Hg (RM) forms throughout the troposphere and stratosphere. RM is often operationally quantified as the sum of particle bound Hg (PBM) and gaseous oxidized Hg (GOM). The measurement of GOM and PBM is challenging and under mounting criticism. Here we intercompare six months of automated GOM and PBM measurements using a Tekran (TK) KCl-coated denuder and quartz regenerable particulate filter method (GOMTK, PBMTK, and RMTK) with RMCEM collected on cation exchange membranes (CEMs) at the high altitude Pic du Midi Observatory. We find that RMTK is systematically lower by a factor of 1.3 than RMCEM. We observe a significant relationship between GOMTK (but not PBMTK) and Tekran flushTK blanks suggesting significant loss (36%) of labile GOMTK from the denuder or inlet. Adding the flushTK blank to RMTK results in good agreement with RMCEM (slope = 1.01, r2 = 0.90) suggesting we can correct bias in RMTK and GOMTK. We provide a bias corrected (*) Pic du Midi data set for 2012-2014 that shows GOM* and RM* levels in dry free tropospheric air of 198 ± 57 and 229 ± 58 pg m-3 which agree well with in-flight observed RM and with model based GOM and RM estimates.

Methyl Mercury Formation in Hillslope Soils of Boreal Forests: The Role of Forest Harvest and Anaerobic Microbes.

Final harvest (clear-cutting) of coniferous boreal forests has been shown to increase streamwater concentrations and export of the neurotoxin methyl mercury (MeHg) to freshwater ecosystems. Here, the spatial distribution of inorganic Hg and MeHg in soil as a consequence of clear-cutting is reported. A comparison of soils at similar positions along hillslopes in four 80 years old Norway spruce (Picea abies) stands (REFs) with those in four similar stands subjected to clear-cutting (CCs) revealed significantly (p < 0.05) enhanced MeHg concentrations (ng g(-1)), MeHg areal masses (g ha(-1)), and percent MeHg of HgTOT in O horizons of CCs located between 1 and 41 m from streams. Inorganic Hg measures did not differ between REFs and CCs at any position. The O horizon thickness did not differ between CCs and REFs, but the groundwater table and soil water content were significantly higher at CCs than at REFs. The largest difference in percent MeHg of HgTOT (12 times higher at CCs compared to REFs, p = 0.003) was observed in concert with a significant enhancement in soil water content (p = 0.0003) at intermediate hillslope positions (20-38 m from stream), outside the stream riparian zone. Incubation experiments demonstrated that soils having significantly enhanced soil pools of MeHg after clear-cutting also showed significantly enhanced methylation potential as compared with similarly positioned soils in mature reference stands. The addition of inhibitors demonstrated that sulfate-reducing bacteria (SRB) and methanogens were key methylators. Rates of demethylation did not differ between CCs and REFs. Our results suggest that enhanced water saturation of organic soils providing readily available electron donors stimulate Hg-methylating microbes to net formation and buildup of MeHg in O horizons after forest harvest.

Mercury deposition and re-emission pathways in boreal forest soils investigated with Hg isotope signatures.

Soils comprise the largest terrestrial mercury (Hg) pool in exchange with the atmosphere. To predict how anthropogenic emissions affect global Hg cycling and eventually human Hg exposure, it is crucial to understand Hg deposition and re-emission of legacy Hg from soils. However, assessing Hg deposition and re-emission pathways remains difficult because of an insufficient understanding of the governing processes. We measured Hg stable isotope signatures of radiocarbon-dated boreal forest soils and modeled atmospheric Hg deposition and re-emission pathways and fluxes using a combined source and process tracing approach. Our results suggest that Hg in the soils was dominantly derived from deposition of litter (∼90% on average). The remaining fraction was attributed to precipitation-derived Hg, which showed increasing contributions in older, deeper soil horizons (up to 27%) indicative of an accumulation over decades. We provide evidence for significant Hg re-emission from organic soil horizons most likely caused by nonphotochemical abiotic reduction by natural organic matter, a process previously not observed unambiguously in nature. Our data suggest that Histosols (peat soils), which exhibit at least seasonally water-saturated conditions, have re-emitted up to one-third of previously deposited Hg back to the atmosphere. Re-emission of legacy Hg following reduction by natural organic matter may therefore be an important pathway to be considered in global models, further supporting the need for a process-based assessment of land/atmosphere Hg exchange.

Mercury isotope signatures in contaminated sediments as a tracer for local industrial pollution sources.

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.

Kinetics of Hg(II) exchange between organic ligands, goethite, and natural organic matter studied with an enriched stable isotope approach.

The mobility and bioavailability of toxic Hg(II) in the environment strongly depends on its interactions with natural organic matter (NOM) and mineral surfaces. Using an enriched stable isotope approach, we investigated the exchange of Hg(II) between dissolved species (inorganically complexed or cysteine-, EDTA-, or NOM-bound) and solid-bound Hg(II) (carboxyl-/thiol-resin or goethite) over 30 days under constant conditions (pH, Hg and ligand concentrations). The Hg(II)-exchange was initially fast, followed by a slower phase, and depended on the properties of the dissolved ligands and sorbents. The results were described by a kinetic model allowing the simultaneous determination of adsorption and desorption rate coefficients. The time scales required to reach equilibrium with the carboxyl-resin varied greatly from 1.2 days for Hg(OH)2 to 16 days for Hg(II)-cysteine complexes and approximately 250 days for EDTA-bound Hg(II). Other experiments could not be described by an equilibrium model, suggesting that a significant fraction of total-bound Hg was present in a non-exchangeable form (thiol-resin and NOM: 53-58%; goethite: 22-29%). Based on the slow and incomplete exchange of Hg(II) described in this study, we suggest that kinetic effects must be considered to a greater extent in the assessment of the fate of Hg in the environment and the design of experimental studies, for example, for stability constant determination or metal isotope fractionation during sorption.

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.

Solution speciation controls mercury isotope fractionation of Hg(II) sorption to goethite.

The application of Hg isotope signatures as tracers for environmental Hg cycling requires the determination of isotope fractionation factors and mechanisms for individual processes. Here, we investigated Hg isotope fractionation of Hg(II) sorption to goethite in batch systems under different experimental conditions. We observed a mass-dependent enrichment of light Hg isotopes on the goethite surface relative to dissolved Hg (ε(202)Hg of -0.30‰ to -0.44‰) which was independent of the pH, chloride and sulfate concentration, type of surface complex, and equilibration time. Based on previous theoretical equilibrium fractionation factors, we propose that Hg isotope fractionation of Hg(II) sorption to goethite is controlled by an equilibrium isotope effect between Hg(II) solution species, expressed on the mineral surface by the adsorption of the cationic solution species. In contrast, the formation of outer-sphere complexes and subsequent conformation changes to different inner-sphere complexes appeared to have insignificant effects on the observed isotope fractionation. Our findings emphasize the importance of solution speciation in metal isotope sorption studies and suggest that the dissolved Hg(II) pool in soils and sediments, which is the most mobile and bioavailable, should be isotopically heavy, as light Hg isotopes are preferentially sequestered during binding to both mineral phases and natural organic matter.

Evaluating atmospheric mercury (Hg) uptake by vegetation in a chemistry-transport model.

Mercury (Hg), a neurotoxic heavy metal, is transferred to marine and terrestrial ecosystems through atmospheric transport. Recent studies have highlighted the role of vegetation uptake as a sink for atmospheric elemental mercury (Hg0) and a source of Hg to soils. However, the global magnitude of the Hg0 vegetation uptake flux is highly uncertain, with estimates ranging 1000-4000 Mg per year. To constrain this sink, we compare simulations in the chemical transport model GEOS-Chem with a compiled database of litterfall, throughfall, and flux tower measurements from 93 forested sites. The prior version of GEOS-Chem predicts median Hg0 dry deposition velocities similar to litterfall measurements from Northern hemisphere temperate and boreal forests (∼0.03 cm s-1), yet it underestimates measurements from a flux tower study (0.04 cm s-1vs. 0.07 cm s-1) and Amazon litterfall (0.05 cm s-1vs. 0.17 cm s-1). After revising the Hg0 reactivity within the dry deposition parametrization to match flux tower and Amazon measurements, GEOS-Chem displays improved agreement with the seasonality of atmospheric Hg0 observations in the Northern midlatitudes. Additionally, the modelled bias in Hg0 concentrations in South America decreases from +0.21 ng m-3 to +0.05 ng m-3. We calculate a global flux of Hg0 dry deposition to land of 2276 Mg per year, approximately double previous model estimates. The Amazon rainforest contributes 29% of the total Hg0 land sink, yet continued deforestation and climate change threatens the rainforest's stability and thus its role as an important Hg sink. In an illustrative worst-case scenario where the Amazon is completely converted to savannah, GEOS-Chem predicts that an additional 283 Mg Hg per year would deposit to the ocean, where it can bioaccumulate in the marine food chain. Biosphere-atmosphere interactions thus play a crucial role in global Hg cycling and should be considered in assessments of future Hg pollution.

Using nitrogen isotope fractionation to assess the oxidation of substituted anilines by manganese oxide.

We explored the N isotope fractionation associated with the oxidation of substituted primary aromatic amines, which are often the position of initial attack in transformation processes of environmental contaminants. Apparent (15)N-kinetic isotope effects, AKIE(N), were determined for the oxidation of various substituted anilines in suspensions of manganese oxide (MnO(2)) and compared to reference experiments in homogeneous solutions and at electrode surfaces, as well as to density functional theory calculations of intrinsic KIE(N)for electron and hydrogen atom transfer reactions. Owing to the partial aromatic imine formation after one-electron oxidation and corresponding increase in C-N bond strength, AKIE(N)-values were inverse, substituent-dependent, and confined to the range between 0.992 and 0.999 in agreement with theory. However, AKIE(N)-values became normal once the fraction of cationic species prevailed owing to (15)N-equilibrium isotope effects, EIE(N), of 1.02 associated with N atom deprotonation. The observable AKIE(N)-values are substantially modulated by the acid/base pre-equilibria of the substituted anilines and isotope fractionation may even vanish under conditions where normal EIE(N) and inverse AKIE(N) cancel each other out. The pH-dependent trends of the AKIE(N)-values provide a new line of evidence for the identification of contaminant degradation processes via oxidation of primary aromatic amino groups.

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.

Experimental rainwater divalent mercury speciation and photoreduction rates in the presence of halides and organic carbon.

Mercury (Hg) photochemical redox reactions control atmospheric Hg lifetime and therefore play an important role in global Hg cycling. Oxidation of Hg(0) to Hg(II) is currently thought to be a Br-initiated two-stage reaction with end-products HgBr2, HgBrOH, HgBrONO, HgBrOHO. Atmospheric photoreduction of these Hg(II) compounds can take place in both the gas and aqueous phase. Here we present new experimental observations on aqueous Hg(II) photoreduction rates in the presence of dissolved organic carbon and halides and compare the findings to rainfall Hg(II) photoreduction rates. The pseudo first-order, gross photoreduction rate constant, kred, for 0.5 µM Hg(II) in the presence of 0.5 mg/ L of dissolved organic carbon (DOC) is 0.23 h-1, which is similar to the mean kred (0.15 ±â€¯0.01 h-1(σ, n = 3)) in high altitude rainfall and at the lower end of the median kred (0.41 h-1, n = 24) in continental and marine waters. Addition of bromide (Br-) to experimental Hg(II)-DOC solutions progressively inhibits Hg(II) photoreduction to reach 0.001 h-1 at total Br- of 10 mM. Halide substitution experiments give Hg(II)Xn(n-2) photoreduction rate constants of 0.016, 0.004 h-1, and < detection limit for X = Cl-, Br-, and I- respectively and reflect increasing stability of the Hg(II)-halide complex. We calculate equilibrium Hg(II) speciation in urban and high-altitude rainfall using Visual Minteq, which indicates Hg(II)-DOC to be the dominant Hg species. The ensemble of observations suggests that atmospheric gaseous HgBr2, HgCl2, HgBrNO2, HgBrHO2 forms, scavenged by aqueous aerosols and cloud droplets, are converted to Hg(II)-DOC forms in rainfall due to abundant organic carbon in aerosols and cloud water. Eventual photoreduction of Hg(II)-DOC in aqueous aerosols and clouds is, however, too slow to be relevant in global atmospheric Hg cycling.