MeHg Photodegradation Research Articles

Why Dissolved Organic Matter Enhances Photodegradation of Methylmercury

Methylmercury (MeHg) is known to degrade photochemically, but it remains unclear what roles naturally dissolved organic matter (DOM) and complexing organic ligands play in MeHg photodegradation. Here we investigate the rates and mechanisms of MeHg photodegradation using DOM with varying oxidation states and origins as well as organic ligands with known molecular structures. All DOM and organic ligands increased the rate of MeHg photodegradation under solar irradiation, but the first-order rate constants varied depending on the oxidation state of DOM and the type and concentration of the ligands. Reduced DOM photochemically degraded MeHg 3 times faster than oxidized DOM. Compounds containing both thiol and aromatic moieties within the same molecule (e.g., thiosalicylate and reduced DOM) increased MeHg photodegradation rates far more than those containing only aromatics or thiols (e.g., salicylate or glutathione, or their combinations). The mechanism is attributed in part to strong binding between MeHg and ...

Variation in terrestrial and aquatic sources of methylmercury in stream predators as revealed by stable mercury isotopes.

Mercury (Hg) is widely distributed in the environment, and its organic form, methylmercury (MeHg), can extensively bioaccumulate and biomagnify in aquatic and terrestrial food webs. Concentrations of MeHg in organisms are highly variable, and the sources in natural food webs are often not well understood. This study examined stable isotope ratios of MeHg (mass-dependent fractionation, as δ(202)HgMeHg; and mass-independent fractionation, as Δ(199)HgMeHg) in benthic invertebrates, juvenile steelhead trout (Oncorhynchus mykiss), and water striders (Gerris remigis) along a stream productivity gradient, as well as carnivorous terrestrial invertebrates, in a forested watershed at the headwater of South Fork Eel River in northern California. Throughout the sampling sites, δ(202)HgMeHg (after correction due to the effect of MeHg photodegradation) was significantly different between benthic (median = -1.40‰; range, -2.34 to -0.78‰; total number of samples = 29) and terrestrial invertebrates (median = +0.51‰; range, -0.37 to +1.40‰; total number of samples = 9), but no major difference between these two groups was found for Δ(199)HgMeHg. Steelhead trout (52 individual fishes) have MeHg of predominantly aquatic origins, with a few exceptions at the upstream locations (e.g., 1 fish collected in a tributary had a purely terrestrial MeHg source and 4 fishes had mixed aquatic and terrestrial MeHg sources). Water striders (seven pooled samples) derive MeHg largely from terrestrial sources throughout headwater sections. These data suggest that direct terrestrial subsidy (e.g., terrestrial invertebrates falling into water) can be important for some stream predators in headwater streams and could represent an important means of transfer of terrestrially derived MeHg (e.g., in situ methylation within forests, atmospheric sources) to aquatic ecosystems. Moreover, these findings show that terrestrial subsidies can enhance MeHg bioaccumulation of consumers in headwater streams where aqueous MeHg levels are very low.

Methylmercury photodegradation in surface water of the Florida Everglades: importance of dissolved organic matter-methylmercury complexation.

Photodegradation is the major pathway of methylmercury (MeHg) degradation in many surface waters. However, the mechanism of MeHg photodegradation is still not completely understood. Dissolved organic matter (DOM) is expected to play a critical role in MeHg photodegradation. By using several techniques, including N2/O2 purging and the addition of stable isotope (Me(201)Hg), scavengers, competing ligands, and a singlet oxygen ((1)O2) generator, the role played by MeHg-DOM complexation in MeHg photodegradation of Everglades surface water was investigated. DOM appeared to be involved in MeHg photodegradation via the formation MeHg-DOM complexes based on three findings: (1) MeHg was quickly photodegraded in solutions containing DOM extracts; (2) degradation of MeHg did not occur in deionized water; and (3) addition of competing complexation reagents (dithiothreitol-DTT) dramatically prohibited the photodegradation of MeHg in Everglades water. Further experiments indicated that free radicals/reactive oxygen species, including hydroxyl radical (·OH), (1)O2, triplet excited state of DOM ((3)DOM*), and hydrated electron (e(-)aq), played a minor role in MeHg photodegradation in Everglades water, based on the results of scavenger addition, (1)O2 generator addition and N2/O2 purging. A pathway, involving direct photodegradation of MeHg-DOM complexes via intramolecular electron transfer, is proposed as the dominant mechanism for MeHg photodegradation in Everglades water.

Towards Universal Wavelength-Specific Photodegradation Rate Constants for Methyl Mercury in Humic Waters, Exemplified by a Boreal Lake-Wetland Gradient

We report experimentally determined first-order rate constants of MeHg photolysis in three waters along a Boreal lake-wetland gradient covering a range of pH (3.8-6.6), concentrations of total organic carbon (TOC 17.5-81 mg L(-1)), total Fe (0.8-2.1 mg L(-1)), specific UV254 nm absorption (3.3-4.2 L mg(-1) m(-1)) and TOC/TON ratios (24-67 g g(-1)). Rate constants determined as a function of incident sunlight (measured as cumulative photon flux of photosynthetically active radiation, PAR) decreased in the order dystrophic lake > dystrophic lake/wetland > riparian wetland. After correction for light attenuation by dissolved natural organic matter (DOM), wavelength-specific (PAR: 400-700 nm, UVA: 320-400 nm and UVB: 280-320 nm) first-order photodegradation rate constants (kpd) determined at the three sites were indistinguishable, with average values (± SE) of 0.0023 ± 0.0002, 0.10 ± 0.024 and 7.2 ± 1.3 m(2) E(-1) for kpdPAR, kpdUVA, and kpdUVB, respectively. The relative ratio of kpdPAR, kpdUVA, and kpdUVB was 1:43:3100. Experiments conducted at varying MeHg/TOC ratios confirm previous suggestions that complex formation with organic thiol groups enhances the rate of MeHg photodegradation, as compared to when O and N functional groups are involved in the speciation of MeHg. We suggest that if the photon fluxes of PAR, UVA, and UVB radiation are separately determined and the wavelength-specific light attenuation is corrected for, the first-order rate constants kpdPAR, kpdUVA, and kpdUVB will be universal to waters in which DOM (possibly in concert with Fe) controls the formation of ROS, and the chemical speciation of MeHg is controlled by the complexation with DOM associated thiols.

Concurrent photolytic degradation of aqueous methylmercury and dissolved organic matter

Monomethyl mercury (MeHg) is a potent neurotoxin that threatens ecosystem viability and human health. In aquatic systems, the photolytic degradation of MeHg (photodemethylation) is an important component of the MeHg cycle. Dissolved organic matter (DOM) is also affected by exposure to solar radiation (light exposure) leading to changes in DOM composition that can affect its role in overall mercury (Hg) cycling. This study investigated changes in MeHg concentration, DOM concentration, and the optical signature of DOM caused by light exposure in a controlled field-based experiment using water samples collected from wetlands and rice fields. Filtered water from all sites showed a marked loss in MeHg concentration after light exposure. The rate of photodemethylation was 7.5×10−3m2mol−1 (s.d. 3.5×10−3) across all sites despite marked differences in DOM concentration and composition. Light exposure also caused changes in the optical signature of the DOM despite there being no change in DOM concentration, indicating specific structures within the DOM were affected by light exposure at different rates. MeHg concentrations were related to optical signatures of labile DOM whereas the percent loss of MeHg was related to optical signatures of less labile, humic DOM. Relationships between the loss of MeHg and specific areas of the DOM optical signature indicated that aromatic and quinoid structures within the DOM were the likely contributors to MeHg degradation, perhaps within the sphere of the Hg-DOM bond. Because MeHg photodegradation rates are relatively constant across freshwater habitats with natural Hg–DOM ratios, physical characteristics such as shading and hydrologic residence time largely determine the relative importance of photolytic processes on the MeHg budget in these mixed vegetated and open-water systems.

Photodegradation of methylmercury in stream ecosystems

Photodegradation is an important sink for highly toxic methylmercury (MeHg) in aquatic ecosystems. Lakes have been extensively studied for MeHg photodegradation, but much less is known about streams, mainly because of the heterogeneity in sunlight availability along stream reaches and because there has been a lack of tools with which to integrate this longitudinal variability. We utilize odd‐mass anomalies of stable Hg isotopes (i.e., Δ199Hg) as a proxy for estimating the relative extent of MeHg photodegradation in streams. In a northern California stream network, levels of MeHg in water and biota increased with increasing stream size in headwater and intermediate streams (drainage areas ranging from 0.6 to 150 km2), but MeHg levels decreased substantially in larger streams (drainage areas up to 1212 km2). In smaller streams, the increase of MeHg levels is attributed to increasing in situ MeHg production and is accompanied by only a small increase in Δ199Hg, indicating that the rate of MeHg photodegradation is low relative to the rate of in situ MeHg production. In larger streams, decreasing MeHg levels coincided with significant increases in Δ199Hg of MeHg (an average increase of 1.5‰ ± 0.5‰, n = 4), indicating that increasing MeHg photodegradation reduced MeHg levels in these wider, more open channels. Our findings clearly indicate that increasing sunlight availability in stream channels substantially increases MeHg photodegradation, which can reduce MeHg contamination in stream food webs.

Diurnal trends in methylmercury concentration in a wetland adjacent to Great Salt Lake, Utah, USA

A 24-h field experiment was conducted during July 2008 at a wetland on the eastern shore of Great Salt Lake (GSL) to assess the diurnal cycling of methylmercury (MeHg). Dissolved (< 0.45 μm) MeHg showed a strong diurnal variation with consistently decreasing concentrations during daylight periods and increasing concentrations during non-daylight periods. The proportion of MeHg relative to total Hg in the water column consistently decreased with increasing sunlight duration, indicative of photodegradation. During the field experiment, measured MeHg photodegradation rates ranged from 0.02 to 0.06 ng L − 1 h − 1 . Convective overturn of the water column driven by nighttime cooling of the water surface was hypothesized as the likely mechanism to replace the MeHg in the water column lost via photodegradation processes. A hydrodynamic model of the wetland successfully simulated convective overturn of the water column during the field experiment. Study results indicate that daytime monitoring of selected wetlands surrounding GSL may significantly underestimate the MeHg content in the water column. Wetland managers should consider practices that maximize the photodegradation of MeHg during daylight periods.

Mercury Isotopes Link Mercury in San Francisco Bay Forage Fish to Surface Sediments

Identification of sources of biologically accessible Hg is necessary to fully evaluate Hg exposure in aquatic ecosystems. This study assesses the relationship between Hg in forage fish and Hg in surface sediments throughout San Francisco Bay (SF Bay) and evaluates processes influencing the incorporation of Hg into the aquatic food web. We measured the Hg stable isotope compositions of two nearshore fish species and compared them with previously reported analyses of colocated intertidal surface sediments. Fish δ(202)Hg values (mass-dependent fractionation) demonstrated a distinct spatial gradient within SF Bay that ranged from 0.60‰ in the south to -0.25‰ in the north. Fish δ(202)Hg values were consistently higher than sediment δ(202)Hg values by 0.73‰ (±0.16‰, 1SD). Fish and sediment δ(202)Hg values in SF Bay proper were well correlated (r(2) = 0.83), suggesting that sediment is a primary source of Hg to the nearshore aquatic food web. Fish Δ(199)Hg values (mass-independent fractionation) ranged from 0.46‰ to 1.55‰, did not correlate with sediment values, and yielded a Δ(199)Hg/Δ(201)Hg ratio of 1.26 (±0.01, 1SD; r(2) = 0.99). This mass-independent fractionation is consistent with photodegradation of MeHg to varying degrees at each site prior to incorporation into the food web.

Degradation of Methylmercury and Its Effects on Mercury Distribution and Cycling in the Florida Everglades

Methylmercury (MeHg) is recognized as one of the major water quality concerns in the Florida Everglades. Degradation of MeHg in the water is thought to be one of the most important processes to the cycling of MeHg, but there is a lack of quantitative estimations of its effect on the distribution and cycling of MeHg in this ecosystem. Stable isotope (Me201Hg) addition method was implemented to investigate the degradation of MeHg in the Everglades. By combining these results with the field monitoring data, effects of photodegradation on MeHg distribution and its contribution to MeHg cycling were estimated. The results indicate that degradation of MeHg in Everglades water is mediated by sunlight and that UV-A and UV-B radiations are the principal driver. The spatial pattern of MeHg photodegradation potential (PPD) generally illustrated an increasing trend from north to south in the Everglades, which was opposite to the distribution of MeHg in water column. Correlation analysis shows that MeHg concentration in the water had a significant negative relation to PPD, suggesting that photodegradation could play an important role in controlling the distribution of MeHg in Everglades water. Furthermore, about 31.4% of MeHg input into the water body was removed by photodegradation, indicating its importance in the biogeochemical cycling of MeHg in the Everglades. This percent reduction is much lower than that reported for other ecosystems, which could be caused by the higher concentration of DOC in the Everglades. The relatively slower degradation of MeHg could be one of the main reasons for the high ratio of MeHg to total mercury (THg) in this ecosystem.

Production of methymercury by solar radiation

Methylmercury (MeHg) is photochemically degraded at the surface of freshwater lakes at around 18% day. Since MeHg is not thought to be formed in the water column, concentrations of MeHg at the lake surface should display a strong diurnal pattern due to the photodegradation of MeHg. However, previous investigators have found that MeHg concentrations peak at noon and microbial inhibitors do not prevent mercury methylation. These reports suggest that mercury methylation may mitigate the effect of photodegradation on surface MeHg concentrations. Lake water was fractionated by a tangential ultrafiltrator and exposed in Teflon bottles to sunlight for different periods of time. Concentrations of MeHg initially decreased by 50% but then increased once again. Since, this is a sealed system, we assume that dissolved organic carbon between 300 and 30 kDa was responsible for the abiotic photochemical production of MeHg. Using rate data collected on site, photomethylation rates are estimated at 20 pg/L.(kW/m 2 ) which corresponds to 35% of MeHg inputs in freshwater lakes. The observed dependence of photomethylation on dissolved organic carbon may provide a mechanistic explanation for why clear cutting which increases dissolved organic carbon, increases MeHg in biota.

Fluxes of methylmercury to the water column of a drainage lake: The relative importance of internal and external sources

We studied fluxes of methylmercury (MeHg) through a Precambrian Shield lake using a mass balance approach. The primary goal of the study was to determine the importance of various sources of MeHg to the water column of the lake. The relative importance of all sources was: in‐lake production &gt;&gt;&gt; inflow from a brown‐water lake with riparian wetlands &gt;&gt;&gt; wet deposition &gt; inflow from an upstream oligotrophic lake &gt; direct inflow from uplands surrounding the lake. MeHg accumulated in the hypolimnion of Lake 240 when oxygen was present. Water‐column sinks for MeHg included photodegradation of MeHg, which was about 3.5 times greater than the loss of MeHg through outflow. At present, there are few studies available on mass balance fluxes of MeHg in lakes, and this is the first study that includes losses of MeHg by photodegradation. The inclusion of photodegradation in this study results in a clear demonstration that in‐lake production of MeHg is very important. In drainage lakes, the relative importance of in‐lake production versus inflow of MeHg from wetlands will vary according to the extent of wetlands in the drainage basin, as well as the volume of precipitation, which produces runoff and transports MeHg from wetlands to downstream lakes.