MeHg Photodegradation Research Articles

Methylmercury photodegradation in paddy water: An overlooked process mitigating methylmercury risks

Photodegradation is critical to reduce the potent neurotoxic methylmercury (MeHg) in water and its subsequent accumulation along food chains. However, this process has been largely ignored in rice paddies, which are hotspots of MeHg production and receive about a quarter of the world's developed freshwater resources. Here, we reported that significant MeHg photodegradation, primarily mediated by hydroxyl radicals, occurs in the overlying water during rice growth. By incorporating field-measured light interception into a rice paddy biogeochemistry model, as well as photodegradation rates obtained from 42 paddy soils stretching ∼3500 km across China, we estimated that photodegradation reduced MeHg concentrations in paddy water and rice by 82 % and 11 %, respectively. Without photodegradation, paddy water could be a significant MeHg source for downstream ecosystems, with an annual export of 178 − 856 kg MeHg to downstream waters in China, the largest rice producer. These findings suggest that photodegradation in paddy water is critical for preventing greater quantities of MeHg entering human food webs.

Mechanism of methylmercury photodegradation in the yellow sea and East China Sea: Dominant pathways, and role of sunlight spectrum and dissolved organic matter

Mercury (Hg) is among the most concerned contaminants in the world due to its high toxicity, prevalent existence in the environments, and bioaccumulation via food chain. Methylmercury (MeHg) is the major form of Hg that accumulates along the food chain and poses threat to humans and wild life. Photodegradation is the dominant process that MeHg is eliminated from freshwater system and upper ocean. The formation of MeHg-dissolved organic matter (DOM) complexes and a variety of free radicals (FR)/reactive oxygen species (ROS) have been previously proposed to be involved in MeHg photodegradation. However, most of these studies were conducted in freshwater, and the mechanism of MeHg photodegradation in seawater remains unclear. In this study, the main pathways of MeHg photodegradation in the seawater of Yellow Sea (YS) and East China Sea (ECS) were investigated using FR/ ROS scavenger addition and DOM competing-ligand addition techniques. The results showed that direct photodegradation of MeHg-DOM complexes is the major pathway of MeHg photodegradation in the YS and ECS, while indirect photolysis of MeHg by hydroxyl radical (·OH) also plays a certain role at some sites. MeHg photodegradation was found to be mainly induced by ultraviolet (UV) light rather than visible light in YS and ECS seawater, and the contribution of UV-B was higher than UV-A which was opposite to that previously reported in freshwater. The energy for breaking the bond of CHg in MeHg-Cl complexes formed in seawater is higher than that in MeHg-DOM complexes and this may cause the relatively greater contribution of UV-B with higher energy to MeHg photodegradation in seawater. In addition, MeHg photodegradation in various fractions of natural DOM with different molecular weights, hydrophilicity/hydrophobicity and acid-base was tested. MeHg photodegradation rates (kd) varied in these fractions and kd in high molecular weight DOM and hydrophobic Acid (HOA) fractions were faster than that in the other fractions. A significantly positive correlation was observed between kd and thiol concentrations while there was no significant correlation between kd and other measured parameters representing the composition of DOM (specific UV absorbance at 254 nm (SUVA254), spectral slope (SR), chromophoric dissolved organic matter (CDOM), humification index (HIX), biological index (BIX) and fluorescent components). These results indicate that thiol may be the key functional group in DOM affecting the photodegradation of MeHg in the YS and ECS.

Mercury isotope compositions in seawater and marine fish revealed the sources and processes of mercury in the food web within differing marine compartments.

Anthropogenic activities and climate change have significantly increased mercury (Hg) levels in seawater. However, the processes and sources of Hg in differing marine compartments (e.g. estuary, marine continental shelf (MCS) or pelagic area) have not been well studied, which makes it difficult to understand Hg cycling in marine ecosystems. To address this issue, the total Hg (THg) concentration, methylmercury (MeHg) concentration and stable Hg isotopes were determined in seawater and fish samples collected from differing marine compartments of the South China Sea (SCS). The results showed that the estuarine seawater exhibited substantially higher THg and MeHg concentrations than those in the MCS and pelagic seawater. Significantly negative δ202Hg (-1.63‰ ± 0.42‰) in estuarine seawater compared with that in pelagic seawater (-0.58‰ ± 0.08‰) may suggest watershed input and domestic sewage discharge of Hg in the estuarine compartment. The Δ199Hg value in estuarine fish (0.39‰ ± 0.35‰) was obviously lower than that in MCS (1.10‰ ± 0.54‰) and pelagic fish (1.15‰ ± 0.46‰), which showed that relatively little MeHg photodegradation occurred in the estuarine compartment. The Hg isotope binary mixing model based on Δ200Hg revealed that approximately 74% MeHg in pelagic fish is derived from atmospheric Hg(II) deposition, and over 60% MeHg in MCS fish is derived from sediments. MeHg sources for estuarine fish may be highly complex (e.g. sediment or riverine/atmospheric input) and further investigations are warranted to clarify the contribution of each source. Our study showed that Hg stable isotopes in seawater and marine fish can be used to identify the processes and sources of Hg in different marine compartments. This finding is of great relevance to the development of marine Hg food web models and the management of Hg in fish.

Algal organic matter inhibits methylmercury photodegradation in eutrophic lake water: A dynamic study

Algal organic matter (AOM) is a major component of dissolved organic matter (DOM) in eutrophic lakes and could impact the photodegradation of neurotoxic methylmercury (MeHg) in water. Predicting these effects, however, is challenging, largely due to the dynamic changes of AOM during algal decomposition. Here, we investigated the effects of AOM on MeHg photodegradation throughout the algal decomposition process and elucidated these effects by characterizing dynamic changes of AOM and exploring the respective roles of various reactive oxygen species (ROS). Our results reveal that AOM derived from algal decomposition significantly inhibits MeHg photodegradation, and the extent of this inhibition varies depending on the specific lakes (8–21 %, p < 0.05) and their eutrophication states (16–28 %, p < 0.05). The inhibitory effect gradually weakened as the decomposition progressed, which may be attributed to the dynamic changes in the quantity and quality of AOM. Moreover, hydroxyl radical (·OH) was found to be the main contributor in driving MeHg photodegradation (15–23 %) during the early stages of decomposition (day 0–3), while in the later stage (day 12–24), the role of singlet oxygen (1O2, 15–20 %) and (3DOM*, 21–30 %) gradually strengthened and these three ROS jointly drove MeHg photodegradation. Based on our findings and recent studies, we propose that AOM derived from algal decomposition plays a vital role in increasing the risk of MeHg in eutrophic lakes. It promotes MeHg formation while simultaneously inhibiting its photodegradation. Integrating AOM-MeHg interactions into Hg biogeochemical cycling models would reduce uncertainties when predicting MeHg risks.

Declines of methylmercury along a salinity gradient in a low-lying coastal wetland ecosystem at South Carolina, USA

Wetlands are widely regarded as biogeochemical hotspots of highly toxic methylmercury (MeHg), mainly mediated by sulfate-reducing bacteria. In low-lying coastal wetlands, sea level rise, a phenomenon caused by global climate change, is slowly degrading numerous healthy freshwater forested wetlands into salt-degraded counterparts with a nickname “ghost forests”, and eventually converting them to saltmarshes. However, little is known about the changes of mercury (Hg) methylation, bioaccumulation, and biomagnification along the forest-to-saltmarsh gradient. Here, we conducted extensive field sampling in three wetland states (healthy forested wetlands, salt-degraded forested wetlands, and saltmarsh) along a salinity gradient (from 0 to 9.4 ppt) in Winyah Bay, South Carolina, USA. We found that in our study wetland systems the saltmarshes had the lowest levels of both total Hg and MeHg in sediments and biota, as compared to healthy forested wetlands and saltwater-degraded ghost forests. Our results suggest that the slow conversion of forested wetland to saltmarsh could reduce net MeHg production in our study wetland systems, which we hypothesized that could be attributed to increased sulfate reduction and excessive buildup of sulfide in sediment that inhibits microbial Hg methylation, and/or reduced canopy density and increased photodegradation of MeHg. However, it should be noted that biogeochemical MeHg responses to salinity changes may be site-specific and we urge more similar studies in other wetland systems along a salinity gradient. Therefore, long-term salinization of coastal wetlands and the slow conversion of forests to marshes could decrease long-term exposure of toxic MeHg levels in coastal food webs that are similar to our system, and ultimately reduce human exposure to this neurotoxin.

Role of light in methylmercury photodegradation: From irradiation to absorption in the presence of organic ligands

Photochemical degradation acts as the principal sink for methylmercury (MeHg) in surface water, which is regulated by light and solution matrix (especially the presence of dissolved organic matter, DOM). The spectral composition of light irradiation and the light absorption properties of reaction media (often exerted by DOM) are important in MeHg photodegradation, which has not yet been clearly resolved. Aiming to understand the role of light in MeHg photodegradation from the perspectives of both light irradiation and absorption, we investigated the photodegradation of MeHg under different simulated sunlight sources, with and without DOM model compounds of different molecular structures. The results show that the photodegradation of MeHg under different sunlight irradiation yields distinct first-order date constant, mainly due to the slight difference in UVB composition. The degradation of MeHg without DOM under a light source with high intensity in the UV region and no MeHg degradation under the UV-filtered light even in the presence of DOM showed the importance of UV lights in MeHg photodegradation. The use of ultrapure water as a reaction medium may be subject to MeHg loss through vessel adsorption, not just photolysis. Additionally, this work found that the type and position of coexisting substituents on aromatic thiols play a critical role in improving the photodegradation of MeHg, following amino > hydroxyl > carboxyl, para > meta > ortho. Based on the characterization of ultraviolet-visible absorption spectra and our previous work, it was concluded that the presence of DOM could induce red-shift in light absorption and reduce the electronic transition energy of the CHg bond, facilitating MeHg photodegradation. The structures of DOM affect the light absorption properties, which are related to MeHg photodegradation.

ENSO Climate Forcing of the Marine Mercury Cycle in the Peruvian Upwelling Zone Does Not Affect Methylmercury Levels of Marine Avian Top Predators.

Climate change is expected to affect marine mercury (Hg) biogeochemistry and biomagnification. Recent modeling work suggested that ocean warming increases methylmercury (MeHg) levels in fish. Here, we studied the influence of El Niño Southern Oscillations (ENSO) on Hg concentrations and stable isotopes in time series of seabird blood from the Peruvian upwelling and oxygen minimum zone. Between 2009 and 2016, La Niña (2011) and El Niño conditions (2015-2016) were accompanied by sea surface temperature anomalies up to 3 °C, oxycline depth change (20-100 m), and strong primary production gradients. Seabird Hg levels were stable and did not co-vary significantly with oceanographic parameters, nor with anchovy biomass, the primary dietary source to seabirds (90%). In contrast, seabird Δ199Hg, proxy for marine photochemical MeHg breakdown, and δ15N showed strong interannual variability (up to 0.8 and 3‰, respectively) and sharply decreased during El Niño. We suggest that lower Δ199Hg during El Niño represents reduced MeHg photodegradation due to the deepening of the oxycline. This process was balanced by equally reduced Hg methylation due to reduced productivity, carbon export, and remineralization. The non-dependence of seabird MeHg levels on strong ENSO variability suggests that marine predator MeHg levels may not be as sensitive to climate change as is currently thought.

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.

Mercury stable isotopes in flying fish as a monitor of photochemical degradation of methylmercury in the Atlantic and Pacific Oceans

The photochemical degradation of the neurotoxin methylmercury (MeHg) in marine surface waters is of great interest because it reduces the amount of MeHg available for uptake and bioaccumulation in marine aquatic food webs. Studies have shown that the dominant cause of odd isotope mass independent fractionation (odd-MIF) of Hg in marine foodwebs is the photo-degradation of MeHg. Residual MeHg is then incorporated into low trophic level organisms and bio-accumulated without additional mass independent fractionation. Based on this understanding of Hg isotope fractionation we sought to use Hg isotope measurements of fish tissues containing Hg mostly as MeHg to assess the relative degree of photochemical decomposition across the world's oceans. In 19 samples of flying fish, the magnitude of odd-MIF varies by a factor of ~2. We estimate that 56 to 80% of MeHg was photo-degraded prior to entering the food web depending on location. The proportion of MeHg degradation does not correlate with latitude, solar radiation or estimates of the concentration of DOC or chlorophyll at the collection sites, but it does correlate with proxies for water clarity. The ratio of odd-MIF for 199Hg compared to 201Hg is constant in all flying fish sampled (1.20 ± 0.03) suggesting that there is a common mechanism for photo-degradation of MeHg in surface waters across oceans and hemispheres. The ratio of odd-MIF to mass dependent fractionation (MDF) is generally consistent with photochemical degradation but is more variable (2.76 ± 0.33), suggesting that there is negligible internal demethylation of MeHg in flying fish and that variable amounts of MDF occur at different locations in the ocean, likely driven by variable rates of methylation and demethylation of Hg in the water column.

Different circulation history of mercury in aquatic biota from King George Island of the Antarctic

To trace the circulation history of aquatic bioavailable Hg in the Antarctic, the species and isotopic compositions of Hg in sediment, Archaeogastropoda (Agas), Neogastropoda (Ngas), and fish collected from King George Island were studied in detail. Positive mass independent fractionation (MIF) was observed and positively correlated with the percentages of methylmercury (MeHg%) in Agas and Ngas, suggesting an effect of MeHg accumulation during trophic transfer on MIF signatures. However, both the ratios of Δ199Hg/δ202Hg and Δ199Hg/Δ201Hg indicated different circulation histories of Hg in Agas, Ngas, and fish. The microbial methylation in sediment was the primary source of MeHg in Agas and Ngas (Δ199Hg/δ202Hg ∼0, Δ199Hg/Δ201Hg ∼1.00). In contrast, the MeHg in fish (Δ199Hg/δ202Hg = 0.55 ± 0.06, Δ199Hg/Δ201Hg = 1.19 ± 0.17) came from the combined sources of residual MeHg which had sunk from the surface water and microbial-methylated MeHg in sediments, and the bioavailable Hg in the sediments contributed to approximately 44% of the total Hg in fish. Subsequently, the Δ199Hg values of bioavailable MeHg and IHg in sediments were quantitatively calculated, which provided key end-member information for future source apportionment in the Antarctic and other pelagic regions. It was also found that the Hg accumulated in Agas and Ngas had no history of MeHg photo-degradation, indicating that the methylated Hg in benthic zones suffered little photo-degradation and thus presented high bioavailability and environmental risk.

A new pathway of monomethylmercury photodegradation mediated by singlet oxygen on the interface of sediment soil and water

Photodegradation is an important pathway for monomethylmercury (MeHg) degradation in aquatic ecosystems. In this process, dissolved organic matter (DOM) plays an essential role. However, little information is available regarding the photo-transformation of MeHg in shallow aquatic environments, where a significant portion of MeHg is associated with soil suspensions. In this study, 14 soils sampled from different sites in China were used to simulate these conditions. Our results clearly demonstrated that soil organic matter (SOM) was the most important factor controlling the MeHg photodegradation in suspension. Degradation in this heterogeneous aqueous system was shown to be mediated by the 1O2 produced by organic matter on the surface of the soil particles rather than by DOM. This was confirmed by the strong correlation between the kinetics rate constant of MeHg degradation and steady state concentrations of 1O2 (R2 = 0.81). Our results propose a new pathway of MeHg induced by sediment soils under sunlight irradiation. Identification of this pathway may improve the estimates of potential ecological risk of Hg in shallow field ecosystems.

Mechanisms of radical-initiated methylmercury degradation in soil with coexisting Fe and Cu

Methylmercury (MeHg) is a toxic compound. It forms mainly in reducing environments, and then degrades through biogeochemical processes. Photodegradation and microorganism degradation of MeHg are among the processes that have been reported. However, little attention has been focused on the abiotic degradation of MeHg in soil/sediment without light. In our study, the percent MeHg of total Hg in Guangzhou soil in southern China was found to be variable and exhibited a significant negative correlation with the content of Fe or Cu where annite (KFe2+3(AlSi3O10)(OH)2), a Fe-bearing mineral, was identified. To understand the mechanisms of radical-initiated MeHg degradation by Fe/Cu-containing components, batch experiments were done. Results showed that annite in the soils could activate O2 to generate OH and O2− and facilitate MeHg degradation under oxic conditions. Meanwhile, Cu components in the soil further enhanced the production of O2−, and was oxidized to Cu(III) promoting degradation of MeHg directly. These findings help us understand that the distribution of MeHg in soil depends on not only external pollution sources, but also on biogeochemical processes in subsurface environments.

Probing the DOM-mediated photodegradation of methylmercury by using organic ligands with different molecular structures as the DOM model

Photodegradation is the main depletion pathway for methylmercury (MeHg) in surface water. The formation of MeHg-dissolved organic matter (DOM) complexes has been found to be a key step in MeHg photodegradation. However, the major functional groups involved in the DOM-mediated process have yet to be clearly resolved. In this work, we systematically investigated the effects of DOM molecular structures on MeHg photodegradation by using a variety of organic ligands with different functional groups (e.g., thiosalicylate, thiophenol, and thioaniline). The results showed that thiol and phenyl groups may be the major functional groups governing DOM-mediated MeHg photodegradation, with photodegradation rates also dependent on the type (carboxyl, hydroxyl, and amino group) and position (ortho-, meta-, and para-) of other chemical substituents. The addition of “non-photochemically active” thiol ligands (e.g., mercaptoethanol and dithiothreitol) and high concentrations of Cl− can significantly inhibit the o-thiosalicylate-induced MeHg photodegradation, indicating that complexation of MeHg with these ligands is necessary for MeHg photodegradation. Sparging with O2 had a negligible effect on MeHg photodegradation, while sparging with N2 significantly enhanced MeHg photodegradation. This finding suggests that MeHg photodegradation may be a reductive process, which was further supported by identification of the degradation products of MeHg. A possible protonolysis mechanism of MeHg photodegradation in the presence of o-thiosalicylate was then proposed based on the findings of this study.

Role of Free Radicals/Reactive Oxygen Species in MeHg Photodegradation: Importance of Utilizing Appropriate Scavengers.

A variety of free radicals (FR)/reactive oxygen species (ROS) have been proposed to dominate methylmercury (MeHg) photodegradation, primarily based on the results of FR/ROS scavenger addition experiments. However, in addition to eliminating FR/ROS, the added scavengers may also affect the experimental results by altering some water chemical properties, resulting in a misleading assessment of the importance of FR/ROS. In this study, 20 common FR/ROS scavengers were evaluated in terms of their influence on light absorbance, pH, MeHg analysis, MeHg-dissolved organic matter (DOM) complexation, and the scavenger-induced degradation of MeHg. Only nine scavengers were identified to be appropriate for investigating MeHg photodegradation. By utilizing these appropriate scavengers, direct photodegradation of MeHg-DOM complexes was found to be the major pathway of MeHg photodegradation in Laoshan Reservoir water and Stone Old Beach seawater. In contrast, MeHg photodegradation in Ink River water primarily occurs through both ·OH and 3DOM* mediated indirect pathways and direct photodegradation of MeHg-DOM complexes. The diverse pathways of MeHg photodegradation in the tested water may be due to differences in water chemical properties. A severe overestimation of the role of FR/ROS was observed when several improper but commonly used scavengers were adopted, highlighting the necessity of utilizing appropriate scavengers.

Occurrence and photodegradation of methylmercury in surface water of Wen-Rui-Tang River network, Wenzhou, China

The spatial distribution and seasonal variations of methylmercury (MeHg) in Wen-Rui-Tang (WRT) River network were investigated by monitoring the MeHg concentrations in surface water samples collected from 30 sites across the river network over four seasons. Detection frequencies and concentrations of MeHg were generally higher in January, indicating that low sunlight irradiation, wind speed, and temperature conditions might enhance the persistence of MeHg in surface water. The MeHg levels varied with sampling locations, with the highest concentrations being observed in the industrial area especially around wastewater outfall, revealing that the mercury contamination in WRT River mainly comes from the industrial wastewater. Photodegradation of MeHg in WRT River surface water and the effects of natural constituents such as fulvic acid (FA), ferric ions (Fe3+), nitrate (NO3-), and dissolved oxygen on the MeHg photodegradation in aqueous solutions were studied under the simulated sunlight. The experimental data indicated that the indirect photodecomposition of MeHg occurred in WRT River surface water. Photodegradation of MeHg in FA solution was initiated by triplet 3FA* or MeHg-FA* via electron transfer interaction under light irradiations. The Fe3+ and NO3- can absorb light energy to produce ·OH and enhance the photochemical degradation of MeHg. The MeHg photodecompositions in FA, nitrate, and Fe3+ solutions were markedly accelerated after removing the dissolved oxygen.

Effects of molecular size fraction of DOM on photodegradation of aqueous methylmercury

This study investigated the photodegradation kinetics of MeHg in the presence of various size fractions of dissolved organic matter (DOM) with MW < 3.5 kDa, 3.5 < MW < 10 kDa, and MW > 10 kDa. The DOM fraction with MW < 3.5 kDa was most effective in MeHg photodegradation. Increasing UV intensity resulted in the increase of photodegradation rate of the MeHg in all size of DOM fractions. Higher rates of MeHg degradation was observed at higher pH. For the portion of MW < 3.5 kDa, the photodegradation rate of MeHg increased with increasing DOM concentration, indicating that radicals such as singlet oxygen (1O2) radicals can be effectively produced by DOM. At higher portion of MW > 3.5 kDa, the inhibition of MeHg degradation was observed due to the effect of DOM photo-attenuation. Our result indicates that radical mediated reaction is the main mechanism of photodegradation of MeHg especially in the presence of MW < 3.5 kDa. Our results imply that the smaller molecular weight fraction (MW < 3.5 kDa) of DOM mainly increased the photodegradation rate of MeHg.

Photodegradation mechanism of methyl mercury in environmental waters

Photodegradation is the major pathway of methyl mercury (MeHg) degradation in surface water. However, the mechanism underlying MeHg photodegradation is still not completely understood. Previous reports suggest four potential pathways are responsible for MeHg photodegradation, including direct photodegradation, hydroxyl radical dominant indirect photodegradation, singlet oxygen dominant indirect photodegradation, and comprehensive action of various free radicals/reactive oxygen species (ROS). Recently, we reported that dissolved organic matter (DOM)-MeHg complex play the dominant role in the photodegradation of MeHg in the Florida Everglades wetland water. Another very different pathway, involving direct photodegradation of MeHg- DOM complexes via intramolecular electron transfer, was proposed as the dominant mechanism for MeHg photodegradation in the Everglades water. Taking the differences in water chemistry in aquatic system into consideration, MeHg photodegradation in different waters should be investigated furtherly to inspect the dominant mechanism for MeHg photodegradation in normal aquatic system. In this study, based on our experimental results reported about the methyl mercury (MeHg) photodegradation in the Everglades wetland water, MeHg photodegradation in different other typical waters, including sea water, creek water and DOM contained solution were studied by the methods of N2/O2 purging and scavengers adding for further understanding of MeHg photodegradation mechanism. The influence of MeHg/DOM ratio and different MeHg ligands adding on MeHg photodegradation were also investigated. It was found that MeHg photodegradation rate constant in sea water ((17.95± 0.70)×10 - 3 E - 1 m2), creek water ((13.62±0.75)×10 - 3 E - 1 m2) and DOM contained solution ((6.08±0.33)× 10 - 3 E - 1 m2) differed greatly. However, the influences of N2/O2 purging and scavengers adding on MeHg photodegradation in three waters were very similar to that in the Everglades water previously reported. Firstly, MeHg photodegradation was promoted under the condition of purging N2 in all the studied waters. Secondly, the addition of scavengers of hydroxyl radical and hydrated electron had little influence on MeHg photodegradation, while addition of sodium azide inhibited MeHg photodegradation. As the production of reactive oxygen species is expected to increase under oxic conditions and decrease under anoxic conditions, the significant enhancement of MeHg photodegradation under anoxic conditions indicates that reactive species, especially singlet oxygen, may not play an important role in MeHg photodegradation in the studied waters. This was confirmed furtherly by the MeHg photodegradation in presence of scavengers of hydroxyl radical and hydrated electron. The inhibition of azide on MeHg photodegradation in studied waters was because the competition of N3 - with DOM for complexing MeHg rather than scavenging effect of N3 - on singlet oxygen. This was confirmed by the MeHg photodegradation in presence of cysteine (CYS) and N3 - , which showed that MeHg can be photo-degraded in presence of cysteine at a relatively high rate, while would be inhibited under dark or in presence of N3 - as competing ligand. It was also found that MeHg photodegradation rate constant was greatly influenced by MeHg/DOM ratio. With DOM concentration fixed as 2 mg L - 1, MeHg photodegradation rate constant remained almost unchanged with MeHg concentration increasing from 1 to 100 ng L - 1, then increased quickly when MeHg concentration was between 100 and 1000 ng L - 1, and then dropped sharped. This indicated that different of photodegradation pathways might play dominant role under the condition of different MeHg/DOM ratio. In the case of normal environ water with very low MeHg concentration and relatively high DOM concentration, MeHg mainly existed in the form of MeHg-DOM complex. Results above indicated that direct photodegradation of DOM-MeHg complexes via intra-molecular electron transfer was perhaps the dominant mechanism for MeHg photodegradation in normal environmental water.

Critical role of natural organic matter in photodegradation of methylmercury in water: Molecular weight and interactive effects with other environmental factors

Photodegradation is the main depletion pathway of methylmercury (MeHg) in surface water. However, the underlying mechanism of MeHg photodegradation is still not well understood. In this study, the critical role of natural organic matter (NOM) from Suwannee River natural organic matter of the International Humic Substance Society, especially its molecular weight, and the impacts of other related environmental factors in MeHg photodegradation were investigated. We observed that MeHg cannot photo-degrade in de-ionized water, excluding the direct photodegradation of MeHg. While either NOM or Fe3+ alone induced MeHg photodegradation, co-existing NOM significantly inhibited the Fe3+-induced degradation, highlighting the critical and complex role of NOM in MeHg photodegradation. Additionally, MeHg exhibited different photodegradation rates in the presence of molecular weight fractionated natural organic matter (Mf-NOM). More importantly, high concentration of NOM caused light attenuation significantly inhibited the photodegradation of MeHg, which was more significant for high molecular weight Mf-NOM. In the presence of Mf-NOM, MeHg photodegradation was also affected by light quality, pH and co-existing Cl− and NO3−. The study is helpful for a better understanding of the critical role of NOM and other environmental factors on MeHg photodegradation in surface water.

Diffusive gradients in thin films for predicting methylmercury bioavailability in freshwaters after photodegradation

Determination of the dissolved-bioavailable fraction of methylmercury (MeHg) and its degradation pathways in freshwaters deserve attention, to further our understanding of the potential risk and toxicity of MeHg. Since the photodegradation of MeHg is the most important known abiotic process able to demethylate MeHg, this study investigated the role of sunlight on MeHg bioavailability in freshwater environments. Experiments to calculate photodegradation rate constants of MeHg in different types of freshwater in combination with experiments to distinguish the labile fraction of MeHg after being exposed to sunlight were performed. The ability of diffusive gradients in thin films based on polyacrylamide (P-DGT) to assess DGT-labile MeHg during photodegradation was successfully tested. First order photodegradation rate constants (kpd) of bioavailable MeHg determined in five different types of waters with different amount of dissolved organic matter (DOM), were in the range 0.073–0.254h−1, confirming previous findings that once there is DOM in solution, which would favour the photodegradation process, the kpd is mainly affected by light attenuation. Simulated sunlight seems not to alter the lability of MeHg, although photodegradation processes may decrease the concentrations of MeHg, contributing to reduce the amount of bioavailable MeHg (i.e. MeHg uptake by DGT). However, the quality of DOM, rather than the quantity, plays an important role in the bioavailability of MeHg in freshwater.

The production of dissolved gaseous mercury from methylmercury photodegradation at different salinity

Photodegradation of methylmercury (MeHg) is an important process in mercury cycling that maintains low concentrations of MeHg in freshwater lakes; however, less is known about importance of this process in marine waters. The photo-induced formation of dissolved gaseous mercury (DGM, Hg0) from MeHg removal was investigated. This study examined the effect of various environmental factors (i.e. light wavelength and intensity, and MeHg concentration), and primary water constituents on the abiotic photodegradation of MeHg, especially under different salinity. MeHg photodegradation rates were positively correlated with the UV light intensity, implying that the attenuation of UV radiation had a significant effect on MeHg photodegradation. However, a high dissolved organic matters concentration and salinity inhibited MeHg photodegradation. DGM was always produced during the photodegradation of MeHg. Photodegradation rates of MeHg and DGM production decreased with increasing salinity, suggesting that the presence of chloride ions inhibited MeHg photodegradation. Therefore, this study implies that MeHg in freshwater could be more rapidly demethylated than that in seawater. In other words, MeHg flowing into the lake or river would be almost removed by photo demethylation. However, MeHg flowing to seawater would be hardly removed, which could have more chance for bioaccumulation in seawater.