Photoreduction Of Hg Research Articles

Distribution and Transformation of Mercury in Subtropical Wild-Caught Seafood from the Southern Taiwan Strait.

Wild-caught seafood contains significant amounts of mercury. Investigating the mercury accumulation levels in wild-caught seafood and analyzing its migration and transformation are of great value for assessing the health risks of mercury intake and for the tracking of mercury sources. We determined the concentrations and stable mercury isotopic compositions (δ202Hg, Δ199Hg, Δ200Hg, and Δ201Hg) of 104 muscle samples collected from 38 species of seafood typically harvested from the Taiwan Shallow Fishing Ground (TSFG), Southern Taiwan Strait. Overall, the concentrations of total mercury (THg) and methylmercury (MeHg) ranged from 11 to 479 ng/g (dry weight, dw) and 10 to 363 ng/g (dw), respectively, and were below the threshold value established by the USEPA and the Chinese government. Demersal and near-benthic species accumulated more mercury than pelagic or mesopelagic species. The characteristics of mercury isotopes in wild-caught marine species differed in terms of vertical and horizontal distribution. Considering the known peripheral land sources of mercury (Δ199Hg ≈ 0), the mercury in seafood from the TSFG (Δ199Hg > 0) did not originate from anthropogenic emissions. The ratio of Δ199Hg and Δ201Hg (1.18 ± 0.03) suggested that the photoreduction of Hg (II) and the photo-degradation of MeHg equally contributed to mass-independent fractionation. Based on the values of Δ199Hg/δ202Hg (1.18 ± 0.03), about 67% of the mercury in seawater had undergone microbial demethylation prior to methylation and entering the seafood. Additionally, the vertical distribution of Δ200Hg in seafood from different water depths implies that mercury input was in part caused by atmospheric deposition. Our results provide detailed information on the sources of mercury and its transfer in the food web in offshore fishing grounds.

Mesoporous α-Fe2O3/ZnO heterojunction with a synergistic effect for rapid and efficient reduction of mercury ions

Ease construction of mesoporous α-Fe2O3/ZnO heterostructures at diverse percentages of Fe2O3 was successfully achieved through the sol-gel method. The photoreduction of Hg(II) ions was conducted over newly synthesized mesoporous α-Fe2O3/ZnO heterostructures in the presence of formic acid as holes scavenger. 3%α-Fe2O3/ZnO heterojunction was exhibited remarkable improvement in the Hg(II) photoreduction through visible light exposure, with a photocatalytic efficiency ∼100% within 50 min, which was about 24 and 14 times higher than that of pristine ZnO NPs and commercial TiO2, respectively. The apparent rate constant of mesoporous 3% α-Fe2O3/ZnO photocatalyst was better 65 and 36 times than that of pristine ZnO NPs and commercial TiO2, respectively. The enhancement α-Fe2O3/ZnO heterojunction for Hg(II) photoreduction was ascribed by the synergistic effect, large surface/volume ratio with notably porous structure and the extended absorption capability with the improved separation of charge carriers efficiency due to fabrication of a heterojunction system. The results provide a favourable approach to fabricate mesoporous α-Fe2O3/ZnO heterojunction system with desirable potential photocatalysis applications.

A Laboratory Study on the Isotopic Composition of Hg(0) Emitted From Hg‐Enriched Soils in Wanshan Hg Mining Area

AbstractSoil Hg(0) emissions are an important source of atmospheric mercury (Hg), but the Hg isotopic signatures of this source remain poorly characterized. In this study, the fractionation of Hg isotopes during Hg (0) emissions from Hg‐enriched agricultural and forest soils in Wanshan Hg mining area were investigated through laboratory experiments. Significant mass‐dependent fractionation (MDF) of Hg isotopes and mass independent fractionation of odd Hg isotopes (odd‐MIF) were observed. Mean MDF enrichment factors (ε202HgHg(0)‐soil) of agricultural soil were in the range of −2.03‰ to −1.34‰ for agricultural soil in light‐, light moisture‐, and temperature‐controlled experiments, which were higher than those of forest soil in similar controls (means = −3.38‰ to −1.98‰). Temperature‐controlled experiments exhibited a larger MDF compared to light‐ and light moisture‐controlled experiments. Photoreduction of Hg in agricultural soil in the presence and absence of soil water generated a larger positive odd‐MIF (mean E199HgHg(0)­‐soil = 0.67‰ to 0.76‰, n = 2) than the temperature‐controlled experiments (mean E199HgHg(0)‐­soil = 0.18 ± 0.04‰, 1 SD), whereas the E199HgHg(0)‐­soil of forest soil in temperature controls (mean = 0.23 ± 0.03‰, 1 SD) were higher than that in light (mean = 0.18 ± 0.06‰, 1 SD) and light moisture‐controlled experiments (mean = −0.03 ± 0.06‰, 1 SD). It is speculated that photoreducible Hg (II) likely dominantly bound to S‐containing ligands in agricultural soil but to both S‐containing and sulfurless ligands in forest soil, resulting in significant positive odd‐MIF in Hg(0) product during photoreduction in the former case and a small magnitude of positive to some negative odd‐MIF in the latter case.

Dissolved Black Carbon Facilitates Photoreduction of Hg(II) to Hg(0) and Reduces Mercury Uptake by Lettuce (Lactuca sativa L.).

Here, we investigated the photoreduction of Hg(II) (Hg(NO3)2) mediated by dissolved black carbon (DBC, <0.45 μm size fraction) collected from water extracts of biochar derived by pyrolyzing crop residues (rice, soybean, and peanut). Under simulated sunlight conditions, the presence of 5 mg C/L DBC significantly facilitated the production of Hg(0) from Hg(II) (initially at 10 nmol/L) with a reduction ratio of 73 ± 4% in 5.3 h. Inhibition of photolysis-induced reactive oxygen species by a quencher or removal of dissolved oxygen indicated that Hg(II) was mainly reduced by superoxide anion (O2•-). Reduction by electrons transferred from photoexcited DBC components or by organic free radicals produced from photo-Fenton-like reactions was also proposed to play a role. Contrary to dissolved humic substances, the DBC-mediated photoreduction of Hg(II) led to unique positive mass-independent isotopic fractionation (MIF) of Hg(0) (Δ199Hg = 1.8 ± 0.3‰), which was attributed to the dominance of secondary Hg(II) reduction by O2•-. The leachate from soil amended with rice biochar at 1-5% mass ratios exhibited significantly higher photocatalytic efficiency than that from unamended soil (wherein the reduced Hg(0) increased from 27 ± 1 to 63 ± 2% in maximum), and the efficiency positively correlated with the percentage of amended biochar. Under natural illumination conditions, the total mercury and/or methylmercury uptake by roots, shoots, and leaves of lettuce (Lactuca sativa L.) grown in water extracts of rice biochar-amended soil was consistently lower (up to 70 ± 20%) than that without the biochar amendment. The findings highlight that DBC might play an important and previously unrecognized role in the biogeochemical cycle and the environmental impact of mercury.

Triblock copolymer-assisted synthesis of Z-scheme porous g-C3N4 based photocatalysts with promoted visible-light-driven performance

The challenge strategy for construction of the Z-scheme heterostructures including porous g-C3N4 based materials employing triblock copolymer and MCM-41 templates-assisted synthesis is to obtain stable photocatalysts with high charge-separation during photocatalysis application utilizing visible light. In this contribution, synthesis of mesoporous α-Fe2O3, CuO and CoFe2O4 nanoparticles (NPs) on porous g-C3N4 for promoted Hg(II) photoreduction efficiency have been evaluated compared with pristine g-C3N4. A Z-scheme system of mesoporous CuO, CoFe2O4 or Fe2O3-/g-C3N4 heterostructures provides an enhanced photocatalytic Hg(II) reduction, yielding a rate of 628.7, 472.2 and 424.1 μmolg−1h−1, respectively, which is ~7.77, 5.84 and 5.24 times greater than that pristine g-C3N4 (80.85 μmolg−1h−1). The photocatalytic efficiency was improved up ~100, 76.5, and 68.6% over mesoporous CuO, CoFe2O4 and Fe2O3-/g-C3N4, respectively, however, it was 12% over pristine g-C3N4 through 50 min illumination time. The enhanced photoreduction using Z-scheme CuO, CoFe2O4 and Fe2O3-/g-C3N4 heterostructures was attributed to its superb characteristics to expedite the photoreduction of Hg(II), involving: (i) 3D mesostructure and more suitable active sites which improves the Hg(II) adsorption, (ii) high surface area (188 m2 g-1) and narrow bandgap (1.93 eV) and (iii) the superior Z-scheme heterostructures characteristic efficiently enhances the electron-hole pairs separation. This research work creates new windows for mesoporous metal oxides and perovskites/g-C3N4 -based Z-scheme system for wastewater remediation, air purification and clean energy generation.

Rapid and Low Cost Determination of Total Mercury in Cat Foods by Photochemical Vapor Generation Coupled to Atomic Absorption Spectrometry.

A rapid and low-cost method for determination of total mercury (THg) in cat food was developed based on photochemical vapor generation (PVG) coupled to cold vapor atomic absorption spectrometry (CVAAS). Cat food samples with ingredients based on tuna fish and other seafood were investigated. Organic acid precursor and concentration for radical generation and Hg photoreduction, sample UV irradiation time, and carrier gas flow were optimized. Highest PVG efficiency was achieved using 10% v v-1 formic acid, 4-s UV irradiation time, and a carrier gas flow of 50mLmin-1. The calibration function presented a correlation coefficient of 0.99. Accuracy was confirmed by analysis of Certified Reference Materials with recoveries of 93-110% and relative standard deviation lower than 6%. Under optimized conditions, a procedural detection limit of 0.28μgkg-1 was obtained. Determination of THg in 10 samples of cat food purchased in local markets revealed a concentration range of 0.035-0.388mgkg-1. Highest concentrations were found in cat foods. Only one sample presented a concentration close to the regulatory limit of the European Commission Directive. Assuming the estimated daily food intake (EDI) calculated in a range of 0.0021 to 0.023mg of THg per day per kg body weight, it is concluded that it remains below that considered lethal for cats. The methodology is efficient, simple, low cost, and fit for purpose.

Permafrost Thaw Dominates Mercury Emission in Tibetan Thermokarst Ponds.

Increasing evidence shows that warming is driving Hg release from the cryosphere. However, Hg cycling in thawing permafrost is less understood to date. Here we show that permafrost thaw dominantly supplied no-run thermokarst ponds by permafrost melt waters (PMWs) with high concentration of photoreducible Hg (PRHg) and subsequently controlled Hg(0) emissions in the Tibetan Plateau. This study was motivated by field survey suggesting that thermokarst ponds as recipient aquatic systems of PMWs could be an active converter of PRHg to Hg(0). Annual Hg mass balance in three seasonally ice-covered thermokarst ponds suggests that PMWs were the dominant input (81.2% to 91.2%) of PRHg in all three thermokarst ponds, and PRHg input would be a constraint of Hg(0) emission owing to the fast photoreduction of PRHg to Hg(0) in the water column. Annual Hg(0) emission in the thermokarst ponds of study region was conservatively estimated to increase by 15% over the past half century. Our findings highlight that climate-induced landscape disturbances and changes in hydrogeochemical processes in climate-sensitive permafrost will quickly and in situ drive Hg stored in permafrost for a very long time into the modern day Hg cycle, which potentially offsets the anthropogenic Hg mitigation policies.

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 ± 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.

Gas-Phase Photolysis of Hg(I) Radical Species: A New Atmospheric Mercury Reduction Process.

The efficient gas-phase photoreduction of Hg(II) has recently been shown to change mercury cycling significantly in the atmosphere and its deposition to the Earth's surface. However, the photolysis of key Hg(I) species within that cycle is currently not considered. Here we present ultraviolet-visible absorption spectra and cross-sections of HgCl, HgBr, HgI, and HgOH radicals, computed by high-level quantum-chemical methods, and show for the first time that gas-phase Hg(I) photoreduction can occur at time scales that eventually would influence the mercury chemistry in the atmosphere. These results provide new fundamental understanding of the photobehavior of Hg(I) radicals and show that the photolysis of HgBr increases atmospheric mercury lifetime, contributing to its global distribution in a significant way.

Isotopic evidence for mercury photoreduction and retention on particles in surface waters of Central California, USA

Cache Creek (Coast Range, California) and the Yuba River (Sierra Nevada Foothills, California) are two river systems affected by extensive mercury (Hg) contamination due to legacy sources of Hg related to mining. Stable Hg isotope techniques have proven useful for elucidating the complex cycling of Hg within aquatic ecosystems, and we applied these techniques to improve understanding of Hg and methylmercury (MeHg) transformations in these watersheds. Total mercury (THg) concentrations and Hg stable isotope ratios were measured in filtered surface waters and suspended particulate matter collected from 14 sites within the Cache Cr. and Yuba R. watersheds. Filtered surface waters from both watersheds exhibited values of ∆199Hg (0.37‰ to 0.71‰), consistently elevated above those observed in sediments (∆199Hg average = 0.07‰). Associated suspended particulates from these surface water samples displayed a much greater range of values for ∆199Hg (−0.61‰ to 0.70‰), although suspended particulates from the Yuba R. exhibited mostly negative ∆199Hg values (−0.61‰ to 0.10‰). The relationship between ∆199Hg and ∆201Hg in the filtered surface waters and associated suspended particulates was calculated using a bivariate York regression, yielding a slope of 1.57 ± 0.49 (±2SE) for the Yuba R. and 1.40 ± 0.27 (±2SE) for Cache Cr., both within error of the previously reported experimentally-derived slopes for MeHg- and inorganic Hg(II)-photoreduction. This provides isotopic evidence that Hg photoreduction is occurring within these surface waters to a significant degree, and suspended particulate phases are retaining the reduced product of Hg photoreduction, particularly within the Yuba R. The isotopic compositions of filtered surface waters are consistent with the isotopic signatures recorded in biota at low trophic positions within these watersheds, suggesting that the reservoir of Hg incorporated within the biota of these systems is similar to the filter-passing Hg fraction in surface waters.

A model of mercury cycling and isotopic fractionation in the ocean

Abstract. Mercury speciation and isotopic fractionation processes have been incorporated into the HAMOCC offline ocean tracer advection code. The model is fast enough to allow a wide exploration of the sensitivity of the Hg cycle in the oceans, and of factors controlling human exposure to monomethyl-Hg through the consumption of fish. Vertical particle transport of Hg appears to play a discernable role in setting present-day Hg distributions, which we surmise by the fact that in simulations without particle transport, the high present-day Hg deposition rate leads to an Hg maximum at the sea surface, rather than a subsurface maximum as observed. Hg particle transport has a relatively small impact on anthropogenic Hg uptake, but it sequesters Hg deeper in the water column, so that excess Hg is retained in the model ocean for a longer period of time after anthropogenic Hg deposition is stopped. Among 10 rate constants in the model, steady-state Hg concentrations are most sensitive to reactions that are sources or sinks of Hg(0), the evasion of which to the atmosphere is the dominant sink term in the surface ocean. Isotopic fractionations in the interconversion reactions are most strongly expressed, in the isotopic signatures of dissolved Hg, in reactions that involve the dominant dissolved species, Hg(II), including mass independent fractionation during Hg photoreduction. The Δ199Hg of MMHg in the model, subject to photoreduction fractionation, reproduces the Δ199Hg of fish in the upper 1000 m of the ocean, while the impact of anthropogenic Hg deposition on Hg isotope ratios is essentially negligible.

Mercury isotope signatures record photic zone euxinia in the Mesoproterozoic ocean

Photic zone euxinia (PZE) is a condition where anoxic, H2S-rich waters occur in the photic zone (PZ). PZE has been invoked as an impediment to the evolution of complex life on early Earth and as a kill mechanism for Phanerozoic mass extinctions. Here, we investigate the potential application of mercury (Hg) stable isotopes in marine sedimentary rocks as a proxy for PZE by measuring Hg isotope compositions in late Mesoproterozoic (∼1.1 Ga) shales that have independent evidence of PZE during discrete intervals. Strikingly, a significantly negative shift of Hg mass-independent isotope fractionation (MIF) was observed during euxinic intervals, suggesting changes in Hg sources or transformations in oceans coincident with the development of PZE. We propose that the negative shift of Hg MIF was most likely caused by (i) photoreduction of Hg(II) complexed by reduced sulfur ligands in a sulfide-rich PZ, and (ii) enhanced sequestration of atmospheric Hg(0) to the sediments by thiols and sulfide that were enriched in the surface ocean as a result of PZE. This study thus demonstrates that Hg isotope compositions in ancient marine sedimentary rocks can be a promising proxy for PZE and therefore may provide valuable insights into changes in ocean chemistry and its impact on the evolution of life.

X-ray-Induced Photoreduction of Hg(II) in Aqueous Frozen Solution Yields Nearly Monatomic Hg(0).

We use X-ray-induced photochemistry, which is well known to cause changes in a number of systems, to reduce Hg(II) to Hg(0) in frozen aqueous solution with added glycerol maintained at 10 K. X-ray absorption spectroscopy was used to monitor the extent of the reaction and to characterize the species. An analysis of the extended X-ray absorption fine structure (EXAFS) of the photochemical product indicated a nearly monatomic Hg(0) species bound only by long, weak bonds to oxygens at ∼3.5 Å. The results of the EXAFS analysis agree quantitatively with the results of density functional theory calculations using the meta-GGA approximation with the M11-L functional. This is the first structural characterization of nearly monatomic Hg(0) bound by hard ligands similar to those expected in aqueousenvironmental systems. We conclude that Hg(0) is expected to exist in solution as a nearly monatomic entity.

Increasing chloride concentration causes retention of mercury in melted Arctic snow due to changes in photoreduction kinetics

Mercury (Hg) in the Arctic is a significant concern due to its bioaccumulative and neurotoxic properties, and the sensitivity of Arctic environments. Previous research has found high levels of Hg in snowpacks with high chloride (Cl−) concentrations. We hypothesised that Cl− would increase Hg retention by decreasing Hg photoreduction to Hg(0) in melted Arctic snow. To test this, changes in Hg photoreduction kinetics in melted Alert, NU snow were quantified with changing Cl− concentration and UV intensity. Snow was collected and melted in Teflon bottles in May 2014, spiked with 0–10μg/g Cl−, and irradiated with 3.52–5.78W·m−2 UV (280–400nm) radiation in a LuzChem photoreactor. Photoreduction rate constants (k) (0.14–0.59hr−1) had positive linear relationships with [Cl−], while photoreduced Hg amounts (Hg(II)red) had negative linear relationships with [Cl−] (1287–64pg in 200g melted snow). Varying UV and [Cl−] both altered Hg(II)red amounts, with more efficient Hg stabilisation by Cl− at higher UV intensity, while k can be predicted by Cl− concentration and/or UV intensity, depending on experimental parameters. Overall, with future projections for greater snowpack Cl− loading, our experimental results suggest that more Hg could be delivered to Arctic aquatic ecosystems by melted snow (smaller Hg(II)red expected), but the Hg in the melted snow that is photoreduced may do so more quickly (larger k expected).

Foliage/atmosphere exchange of mercury in a subtropical coniferous forest in south China

AbstractFoliage/atmosphere exchange is an important pathway of deposition and loss in the biogeochemical mercury (Hg) cycle of terrestrial ecosystems. The foliage/atmosphere fluxes of Hg0 were observed over four seasons in a Masson pine (Pinus massoniana) forest in south China. Hg0 exchange showed a bidirectional process but without clear compensation point. Hg0 emissions peaked midday in all four seasons, probably associated with Hg photoreduction on needle surface. Peaks in Hg0 adsorption/deposition often occurred in the morning, especially in spring and autumn. Although current‐year needles accumulated Hg at a rate of 19.4 µg m−2 yr−1, they were a net Hg0 source of 1.7 µg m−2 yr−1 to the atmosphere as their release of Hg exceeded inputs. In addition, previous‐year needles emitted Hg0 at an average rate of 9.2 µg m−2 yr−1. Based on the mass balance of Hg in the forest canopy, the dry deposition of Hg was estimated 52.5 µg m−2 yr−1, much higher than the wet deposition (to 14.4 µg m−2 yr−1). Although Hg in the atmosphere is considered the main source of Hg in folia, soil water may contribute to Hg0 emission by plant transpiration. These processes should be further studied in the future.

Photoreducible Mercury Loss from Arctic Snow Is Influenced by Temperature and Snow Age.

Mercury (Hg) is an important environmental contaminant, due to its neurotoxicity and ability to bioaccumulate. The Arctic is a mercury-sensitive region, where organisms can accumulate high Hg concentrations. Snowpack mercury photoredox reactions may control how much Hg is transported with melting Arctic snow. This work aimed to (1) determine the significance of temperature combined with UV irradiation intensity and snow age on Hg(0) flux from Arctic snow and (2) elucidate the effect of temperature on snowpack Hg photoreduction kinetics. Using a Teflon flux chamber, snow temperature, UV irradiation, and snow age were found to significantly influence Hg(0) flux from Arctic snow. Cross-correlation analysis results suggest that UV radiation has a direct effect on Hg(0)flux, while temperature may indirectly influence flux. Laboratory experiments determined that temperature influenced Hg photoreduction kinetics when snow approached the melting point (>-2 °C), where the pseudo-first-order reduction rate constant, k, decreased twofold, and the photoreduced Hg amount, Hg(II)red, increased 10-fold. This suggests that temperature influences Hg photoreduction kinetics indirectly, likely by altering the solid:liquid water ratio. These results imply that large mass transfers of Hg from snow to air may take place during the Arctic snowmelt period, altering photoreducible Hg retention and transport with snow meltwater.

Identifying the sources and processes of mercury in subtropical estuarine and ocean sediments using Hg isotopic composition.

The concentrations and isotopic compositions of mercury (Hg) in surface sediments of the Pearl River Estuary (PRE) and the South China Sea (SCS) were analyzed. The data revealed significant differences between the total Hg (THg) in fine-grained sediments collected from the PRE (8-251 μg kg(-1)) and those collected from the SCS (12-83 μg kg(-1)). Large spatial variations in Hg isotopic compositions were observed in the SCS (δ(202)Hg, from -2.82 to -2.10‰; Δ(199)Hg, from +0.21 to +0.45‰) and PRE (δ(202)Hg, from -2.80 to -0.68‰; Δ(199)Hg, from -0.15 to +0.16‰). The large positive Δ(199)Hg in the SCS indicated that a fraction of Hg has undergone Hg(2+) photoreduction processes prior to incorporation into the sediments. The relatively negative Δ(199)Hg values in the PRE indicated that photoreduction of Hg is not the primary route for the removal of Hg from the water column. The riverine input of fine particles played an important role in transporting Hg to the PRE sediments. In the deep ocean bed of the SCS, source-related signatures of Hg isotopes may have been altered by natural geochemical processes (e.g., Hg(2+) photoreduction and preferential adsorption processes). Using Hg isotope compositions, we estimate that river deliveries of Hg from industrial and urban sources and natural soils could be the main inputs of Hg to the PRE. However, the use of Hg isotopes as tracers in source attribution could be limited because of the isotope fractionation by natural processes in the SCS.

Photoreduction of Hg(ii) and photodemethylation of methylmercury: the key role of thiol sites on dissolved organic matter.

This study examined the kinetics of photoreduction of Hg(ii) and photodemethylation of methylmercury (MeHg(+)) attached to, or in the presence of, dissolved organic matter (DOM). Both Hg(ii) and MeHg(+) are principally bound to reduced sulfur groups associated with DOM in many freshwater systems. We propose that a direct photolysis mechanism is plausible for reduction of Hg(ii) bound to reduced sulfur groups on DOM while an indirect mechanism is supported for photodemethylation of MeHg(+) bound to DOM. UV spectra of Hg(ii) and MeHg(+) bound to thiol containing molecules demonstrate that the Hg(ii)-S bond is capable of absorbing UV-light in the solar spectrum to a much greater extent than MeHg(+)-S bonds. Experiments with chemically distinct DOM isolates suggest that concentration of DOM matters little in the photochemistry if there are enough reduced S sites present to strongly bind MeHg(+) and Hg(ii); DOM concentration does not play a prominent role in photodemethylation other than to screen light, which was demonstrated in a field experiment in the highly colored St. Louis River where photodemethylation was not observed at depths ≥ 10 cm. Experiments with thiol ligands yielded slower photodegradation rates for MeHg(+) than in experiments with DOM and thiols; rates in the presence of DOM alone were the fastest supporting an intra-DOM mechanism. Hg(ii) photoreduction rates, however, were similar in experiments with only DOM, thiols plus DOM, or only thiols suggesting a direct photolysis mechanism. Quenching experiments also support the existence of an intra-DOM photodemethylation mechanism for MeHg(+). Utilizing the difference in photodemethylation rates measured for MeHg(+) attached to DOM or thiol ligands, the binding constant for MeHg(+) attached to thiol groups on DOM was estimated to be 10(16.7).

Roles of chloride ion in photo-reduction/oxidation of mercury

Photo-reduction of divalent mercury (Hg(II)) in aquatic systems plays a key role in global biogeochemistry cycling of mercury (Hg) in the Earth’s surface environment. The mechanisms of this process with various Cl− concentrations ([Cl−]) under different pH values and irradiation wavelength ranges are still unclear. In this work, photo-reduction and photo-oxidation experiments of Hg with different [Cl−] and pH values under various light conditions were conducted. The results show that photo-reduction rate constants of Hg(II) decrease with the increasing of [Cl−] in neutral solution under full light spectrum. Photo-reduction rate constants of Hg(II) with Cl− is highly dependent on Hg(II) species, which is determined by [Cl−] and pH value. Irradiation wavelength ranges have significant effects on reaction processes of photo-reduction of Hg(II) and photo-oxidation of Hg(0) in the presence of Cl−. When cut off ultraviolet (UV) radiation (280–400 nm), the reduction rate constants decrease without Cl−, and increase with higher [Cl−], and the photo-oxidation rates of Hg(0) decrease with or without Cl−. Except Cl− complexation stabilize the reducible Hg ions in solutions, photo-oxidation is an important reason for Cl− lowering photo-reduction rate of Hg(II). The results are of great importance for understanding the photo-redox characters of Hg(II) with Cl−.

Air–snowpack exchange of bromine, ozone and mercury in the springtime Arctic simulated by the 1-D model PHANTAS – Part 2: Mercury and its speciation

Abstract. Atmospheric mercury depletion events (AMDEs) refer to a recurring depletion of mercury occurring in the springtime Arctic (and Antarctic) boundary layer, in general, concurrently with ozone depletion events (ODEs). To close some of the knowledge gaps in the physical and chemical mechanisms of AMDEs and ODEs, we have developed a one-dimensional model that simulates multiphase chemistry and transport of trace constituents throughout porous snowpack and in the overlying atmospheric boundary layer (ABL). This paper constitutes Part 2 of the study, describing the mercury component of the model and its application to the simulation of AMDEs. Building on model components reported in Part 1 ("In-snow bromine activation and its impact on ozone"), we have developed a chemical mechanism for the redox reactions of mercury in the gas and aqueous phases with temperature dependent reaction rates and equilibrium constants accounted for wherever possible. Thus the model allows us to study the chemical and physical processes taking place during ODEs and AMDEs within a single framework where two-way interactions between the snowpack and the atmosphere are simulated in a detailed, process-oriented manner. Model runs are conducted for meteorological and chemical conditions that represent the springtime Arctic ABL characterized by the presence of "haze" (sulfate aerosols) and the saline snowpack on sea ice. The oxidation of gaseous elemental mercury (GEM) is initiated via reaction with Br-atom to form HgBr, followed by competitions between its thermal decomposition and further reactions to give thermally stable Hg(II) products. To shed light on uncertain kinetics and mechanisms of this multi-step oxidation process, we have tested different combinations of their rate constants based on published laboratory and quantum mechanical studies. For some combinations of the rate constants, the model simulates roughly linear relationships between the gaseous mercury and ozone concentrations as observed during AMDEs/ODEs by including the reaction HgBr + BrO and assuming its rate constant to be the same as for the reaction HgBr + Br, while for other combinations the results are more realistic by neglecting the reaction HgBr + BrO. Speciation of gaseous oxidized mercury (GOM) changes significantly depending on whether or not BrO is assumed to react with HgBr to form Hg(OBr)Br. Similarly to ozone (reported in Part 1), GEM is depleted via bromine radical chemistry more vigorously in the snowpack interstitial air than in the ambient air. However, the impact of such in-snow sink of GEM is found to be often masked by the re-emissions of GEM from the snow following the photo-reduction of Hg(II) deposited from the atmosphere. GOM formed in the ambient air is found to undergo fast "dry deposition" to the snowpack by being trapped on the snow grains in the top ~1 mm layer. We hypothesize that liquid-like layers on the surface of snow grains are connected to create a network throughout the snowpack, thereby facilitating the vertical diffusion of trace constituents trapped on the snow grains at much greater rates than one would expect inside solid ice crystals. Nonetheless, on the timescale of a week simulated in this study, the signal of atmospheric deposition does not extend notably below the top 1 cm of the snowpack. We propose and show that particulate-bound mercury (PBM) is produced mainly as HgBr42− by taking up GOM into bromide-enriched aerosols after ozone is significantly depleted in the air mass. In the Arctic, "haze" aerosols may thus retain PBM in ozone-depleted air masses, allowing the airborne transport of oxidized mercury from the area of its production farther than in the form of GOM. Temperature dependence of thermodynamic constants calculated in this study for Henry's law and aqueous-phase halide complex formation of Hg(II) species is a critical factor for this proposition, calling for experimental verification. The proposed mechanism may explain observed changes in the GOM–PBM partitioning with seasons, air temperature and the concurrent progress of ozone depletion in the high Arctic. The net deposition of mercury to the surface snow is shown to increase with the thickness of the turbulent ABL and to correspond well with the column amount of BrO in the atmosphere.