Linking Mesoscale Spatial Variation in Methylmercury Production to Bioaccumulation in Tidal Marsh Food Webs.

Differences in sediment biogeochemistry among tidal marsh features with different hydrological and geomorphological characteristics, including marsh interiors, marsh edges, first-order channels, and third-order channels, can result in spatial variation in MeHg production and availability. To better understand the link between MeHg production in sediments and bioaccumulation in primary and secondary consumer invertebrates and fish, we characterized mesoscale spatial variation in sediment biogeochemistry and MeHg concentrations of sediments, water, and consumer tissues among marsh features. Our results indicated that marsh interiors had biogeochemical conditions, including greater concentrations of organic matter and sulfate reduction rates, that resulted in greater MeHg concentrations in sediments and surface water particulates from marsh interiors compared to other features. Tissue MeHg concentrations of consumers also differed among features, with greater concentrations from marsh edges and interiors compared to channels. This spatial mismatch of MeHg concentrations in sediments and water compared to those in consumers may have resulted from differences in behavior and physiology among consumers that influenced the spatial scale over which MeHg was integrated into tissues. Our results highlight the importance of sampling across a suite of marsh features and considering the behavioral and physiological traits of sentinel taxa for contaminant monitoring studies.

Resolving a paradox-high mercury deposition, but low bioaccumulation in northeastern Puerto Rico.

At a "clean air" trade winds site in northeastern Puerto Rico, we found an apparent paradox: atmospheric total mercury (THg) deposition was highest of any site in the USA Mercury Deposition Network, but assimilation into the local food web was quite low. Avian blood THg concentrations (n = 31, from eight species in five foraging guilds) ranged widely from 0.2 to 32 ng g-1 (median of 4.3 ng g-1). Within this population, THg was significantly greater at a low-elevation site near a wetland compared to an upland montane site, even when the comparison was limited to a single species. Overall, however, THg concentrations were approximately an order of magnitude lower than comparable populations in the continental U.S. In surface soil and sediment, potential rates of demethylation were 3 to 9-fold greater than those for Hg(II)-methylation (based on six radiotracer amendment incubations), but rates of change of ambient MeHg pools showed a slight net positive Hg(II)-methylation. Thus, the resolution of the paradox is that MeHg degradation approximately keeps pace with MeHg production in this landscape. Further, any net production of MeHg is subject to frequent flushing by high rainfall on chronically wet soils. The interplay of these microbial processes and hydrology appears to shield the local food web from adverse effects of high atmospheric mercury loading. This scenario may play out in other humid tropical ecosystems as well, but it is difficult to evaluate because coordinated studies of Hg deposition, methylation, and trophic uptake have not been conducted at other tropical sites.

Methylmercury Dynamics in Upper Sacramento Valley Rice Fields with Low Background Soil Mercury Levels.

Few studies have considered how methylmercury (MeHg, a toxic form of Hg produced in anaerobic soils) production in rice ( L.) fields can affect water quality, and little is known about MeHg dynamics in rice fields. Surface water MeHg and total Hg (THg) imports, exports, and storage were studied in two commercial rice fields in the Sacramento Valley, California, where soil THg was low (25 and 57 ng g). The median concentration of MeHg in drainage water exiting the fields was 0.17 ng g (range: <0.007-2.1 ng g). Compared with irrigation water, drainage water had similar MeHg concentrations, and lower THg concentrations during the growing season. Significantly elevated drainage water MeHg and THg concentrations were observed in the fallow season compared with the growing season. An analysis of surface water loads indicates that fields were net importers of both MeHg (76-110 ng m) and THg (1947-7224 ng m) during the growing season, and net exporters of MeHg (35-200 ng m) and THg (248-6496 ng m) during the fallow season. At harvest, 190 to 700 ng MeHg m and 1400 to 1700 ng THg m were removed from fields in rice grain. Rice straw, which contained 120 to 180 ng MeHg m and 7000-10,500 ng m THg was incorporated into the soil. These results indicate that efforts to reduce MeHg and THg exports in rice drainage water should focus on the fallow season. Substantial amounts of MeHg and THg were stored in plants, and these pools should be considered in future studies.

Isotopic Composition of Inorganic Mercury and Methylmercury Downstream of a Historical Gold Mining Region.

We measured total mercury (THg) and monomethyl mercury (MMHg) concentrations and mercury (Hg) isotopic compositions in sediment and aquatic organisms from the Yuba River (California, USA) to identify Hg sources and biogeochemical transformations downstream of a historical gold mining region. Sediment THg concentrations and δ(202)Hg decreased from the upper Yuba Fan to the lower Yuba Fan and the Feather River. These results are consistent with the release of Hg during gold mining followed by downstream mixing and dilution. The Hg isotopic composition of Yuba Fan sediment (δ(202)Hg = -0.38 ± 0.17‰ and Δ(199)Hg = 0.04 ± 0.03‰; mean ± 1 SD, n = 7) provides a fingerprint of inorganic Hg (IHg) that could be methylated locally or after transport downstream. The isotopic composition of MMHg in the Yuba River food web was estimated using biota with a range of %MMHg (the percent of THg present as MMHg) and compared to IHg in sediment, algae, and the food web. The estimated δ(202)Hg of MMHg prior to photodegradation (-1.29 to -1.07‰) was lower than that of IHg and we suggest this is due to mass-dependent fractionation (MDF) of up to -0.9‰ between IHg and MMHg. This result is in contrast to net positive MDF (+0.4 to +0.8‰) previously observed in lakes, estuaries, coastal oceans, and forests. We hypothesize that this unique relationship could be due to differences in the extent or pathway of biotic MMHg degradation in stream environments.

High-Resolution Remote Sensing of Water Quality in the San Francisco Bay-Delta Estuary.

The San Francisco Bay-Delta Estuary watershed is a major source of freshwater for California and a profoundly human-impacted environment. The water quality monitoring that is critical to the management of this important water resource and ecosystem relies primarily on a system of fixed water-quality monitoring stations, but the limited spatial coverage often hinders understanding. Here, we show how the latest technology in visible/near-infrared imaging spectroscopy can facilitate water quality monitoring in this highly dynamic and heterogeneous system by enabling simultaneous depictions of several water quality indicators at very high spatial resolution. The airborne portable remote imaging spectrometer (PRISM) was used to derive high-spatial-resolution (2.6 × 2.6 m) distributions of turbidity, and dissolved organic carbon (DOC) and chlorophyll-a concentrations in a wetland-influenced region of this estuary. A filter-passing methylmercury vs DOC relationship was also developed using in situ samples and enabled the high-spatial-resolution depiction of surface methylmercury concentrations in this area. The results illustrate how high-resolution imaging spectroscopy can inform management and policy development in important inland and estuarine water bodies by facilitating the detection of point- and nonpoint-source pollution, and by providing data to help assess the complex impacts of wetland restoration and climate change on water quality and ecosystem productivity.

Influence of irrigation water and soil on annual mercury dynamics in Sacramento Valley rice fields.

Methylmercury (MeHg) is a human and environmental toxin produced in flooded soils. Little is known about MeHg in rice (Oryza Sativa L.) fields in Sacramento Valley, California. The objectives of this study were to quantify mercury fractions in irrigation water and within rice fields and to determine their mercury pools in surface water, soil, and grain. Soil, grain, and surface water (dissolved and particulate) MeHg and total mercury (THg) were monitored in six commercial rice fields throughout a winter fallow season and subsequent growing season. Both dissolved and particulate mercury fractions were higher in fallow season rice field water. Total suspended solids and particulate mercury concentrations were positively correlated (r = 0.99 and 0.98 for THg and MeHg, respectively), suggesting that soil MeHg was suspended in the water column and potentially exported. Dissolved THg and MeHg concentrations were positively correlated with absorbance at 254 nm (r = 0.47 and 0.58, respectively) in fallow season field water. In the growing season, fields with higher irrigation water MeHg concentrations (due to recycled water use) had elevated field-water MeHg (r = 0.86) and grain MeHg concentrations (r = 0.96). Based on a mass balance analysis, soil mercury pools were orders of magnitude larger than surface water or grain mercury pools; however, fallow season drainage and grain harvest were the primary pathways for MeHg export. Based on these findings, reducing (1) discharge when water is turbid, (2) straw inputs, and (3) use of recycled irrigation water could help reduce mercury exports in rice field drainage water.

Kinetics of homogeneous and surface-catalyzed mercury(II) reduction by iron(II).

Production of elemental mercury, Hg(0), via Hg(II) reduction is an important pathway that should be considered when studying Hg fate in environment. We conducted a kinetic study of abiotic homogeneous and surface-catalyzed Hg(0) production by Fe(II) under dark anoxic conditions. Hg(0) production rate, from initial 50 pM Hg(II) concentration, increased with increasing pH (5.5-8.1) and aqueous Fe(II) concentration (0.1-1 mM). The homogeneous rate was best described by the expression, r(hom) = k(hom) [FeOH(+)] [Hg(OH)2]; k(hom) = 7.19 × 10(+3) L (mol min)(-1). Compared to the homogeneous case, goethite (α-FeOOH) and hematite (α-Fe2O3) increased and γ-alumina (γ-Al2O3) decreased the Hg(0) production rate. Heterogeneous Hg(0) production rates were well described by a model incorporating equilibrium Fe(II) adsorption, rate-limited Hg(II) reduction by dissolved and adsorbed Fe(II), and rate-limited Hg(II) adsorption. Equilibrium Fe(II) adsorption was described using a surface complexation model calibrated with previously published experimental data. The Hg(0) production rate was well described by the expression r(het) = k(het) [>SOFe((II))] [Hg(OH)2], where >SOFe((II)) is the total adsorbed Fe(II) concentration; k(het) values were 5.36 × 10(+3), 4.69 × 10(+3), and 1.08 × 10(+2) L (mol min)(-1) for hematite, goethite, and γ-alumina, respectively. Hg(0) production coupled to reduction by Fe(II) may be an important process to consider in ecosystem Hg studies.

Influence of dissolved organic matter character on mercury incorporation by planktonic organisms: an experimental study using oligotrophic water from Patagonian lakes.

Ligands present in dissolved organic matter (DOM) form complexes with inorganic divalent mercury (Hg2+) affecting its bioavailability in pelagic food webs. This investigation addresses the influence of a natural gradient of DOM present in Patagonian lakes on the bioaccumulation of Hg2+ (the prevailing mercury species in the water column of these lakes) by the algae Cryptomonas erosa and the zooplankters Brachionus calyciflorus and Boeckella antiqua. Hg2+ accumulation was studied through laboratory experiments using natural water of four oligotrophic Patagonian lakes amended witht'97Hg2+. The bioavailability of Hg2+ was affected by the concentration and character of DOM. The entrance of Hg2+ into pelagic food webs occurs mostly through passive and active accumulation. The incorporation of Hg2+ by Cryptomonas, up to 27% of the Hg2+ amended, was found to be rapid and dominated by passive adsorption, and was greatest when low molecular weight compounds with protein-like or small phenolic signatures prevailed in the DOM. Conversely, high molecular weight compounds with a humic or fulvic signature kept Hg2+ in the dissolved phase, resulting in the lowest Hg2+ accumulation in this algae. In Brachionus and Boeckella the direct incorporation of Hg from the aqueous phase was up to 3% of the Hg2+ amended. The dietary incorporation of Hg2+ by Boeckella exceeded the direct absorption of this metal in natural water, and was remarkably similar to the Hg2+ adsorbed in their prey. Overall, DOM concentration and character affected the adsorption of Hg2+ by algae through competitive binding, while the incorporation of Hg2+ into the zooplankton was dominated by trophic or dietary transfer.

How to overcome inter-electrode variability and instability to quantify dissolved oxygen, Fe(II), mn(II), and S(-II) in undisturbed soils and sediments using voltammetry.

BACKGROUND: Although uniquely capable of measuring multiple redox constituents nearly simultaneously with no or minimal sample pretreatment, voltammetry is currently underutilized in characterizing redox conditions in aquatic and terrestrial systems. Investigation of undisturbed media such as pore water requires a solid-state electrode, and such electrodes can be difficult to fabricate reproducibly. An approach to determine the concentrations of electroactive constituents using indirectly calibrated electrodes has been developed, but the protocol for and accuracy of this approach-the pilot ion method-has not been documented in detail. RESULTS: A detailed procedure for testing electrode quality is provided, and the application and limitations of the pilot ion method have been documented. To quantify Fe(II) and Mn(II), subtraction of non-linear baseline functions from voltammetric signals produced better calibration curves than did linear baselines, enabled lower detection limits and reliable deconvolution of overlapping signals, and was successfully applied to sediment pore water signals. We observed that electrode sensitivities often vary by tens of percent, and that the sensitivity declines over time. The ratio of calibration slopes of Mn(II) to Fe(II) varied by no more than 11% from one Hg/Au electrode to another and Fe(II) concentrations predicted by the Mn(II) pilot ion were, on average, 13% different from their actual values. However, concentration predictions by the pilot ion method were worse for less than 15 µM Fe(II) (46% different on average). The ratio of calibration slopes of Mn(II) to S(-II) varied by almost 20% from one Hg/Au electrode to another, and S(-II) predicted concentrations were as much as 58% different from their actual values. These predictions of Fe(II) and S(-II) concentrations indicate that the accuracy of the pilot ion method depends on how independent calibration slope ratios are from the electrode used. At medium-to-high concentration for the ocean, naturally derived dissolved organic carbon did not significantly affect the baseline-corrected electrode response of Mn(II) and Fe(II), but did significantly affect the response of S(-II). CONCLUSIONS: Despite their intrinsic variability, Hg/Au electrodes fabricated by hand can be used to quantify O2, S(-II), Fe(II), and Mn(II) without calibrating every electrode for every constituent of interest. The pilot ion method can achieve accuracies to within 20% or less, provided that the underlying principle-the independence of slope ratios-is demonstrated for all voltammetric techniques used, and effects of the physicochemical properties of the system on voltammetric signals are addressed through baseline subtraction.

Shallow groundwater mercury supply in a Coastal Plain stream.

Fluvial methylmercury (MeHg) is attributed to methylation in up-gradient wetland areas. This hypothesis depends on efficient wetland-to-stream hydraulic transport under nonflood and flood conditions. Fluxes of water and dissolved (filtered) mercury (Hg) species (FMeHg and total Hg (FTHg)) were quantified in April and July of 2009 in a reach at McTier Creek, South Carolina to determine the relative importance of tributary surface water and shallow groundwater Hg transport from wetland/floodplain areas to the stream under nonflood conditions. The reach represented less than 6% of upstream main-channel distance and 2% of upstream basin area. Surface-water discharge increased within the reach by approximately 10%. Mean FMeHg and FTHg fluxes increased within the reach by 23-27% and 9-15%, respectively. Mass balances indicated that, under nonflood conditions, the primary supply of water, FMeHg, and FTHg within the reach (excluding upstream surface water influx) was groundwater discharge, rather than tributary transport from wetlands, in-stream MeHg production, or atmospheric Hg deposition. These results illustrate the importance of riparian wetland/floodplain areas as sources of fluvial MeHg and of groundwater Hg transport as a fundamental control on Hg supply to Coastal Plain streams.

Spatial and seasonal variability of dissolved methylmercury in two stream basins in the eastern United States.

We assessed methylmercury (MeHg) concentrations across multiple ecological scales in the Edisto (South Carolina) and Upper Hudson (New York) River basins. Out-of-channel wetland/floodplain environments were primary sources of filtered MeHg (F-MeHg) to the stream habitat in both systems. Shallow, open-water areas in both basins exhibited low F-MeHg concentrations and decreasing F-MeHg mass flux. Downstream increases in out-of-channel wetlands/floodplains and the absence of impoundments result in high MeHg throughout the Edisto. Despite substantial wetlands coverage and elevated F-MeHg concentrations at the headwater margins, numerous impoundments on primary stream channels favor spatial variability and lower F-MeHg concentrations in the Upper Hudson. The results indicated that, even in geographically, climatically, and ecologically diverse streams, production in wetland/floodplain areas, hydrologic transport to the stream aquatic environment, and conservative/nonconservative attenuation processes in open water areas are fundamental controls on dissolved MeHg concentrations and, by extension, MeHg availability for potential biotic uptake.

Disentangling the effects of habitat biogeochemistry, food web structure, and diet composition on mercury bioaccumulation in a wetland bird.

Methylmercury (MeHg) is a globally pervasive contaminant with known toxicity to humans and wildlife. Several sources of variation can lead to spatial differences in MeHg bioaccumulation within a species including: biogeochemical processes that influence MeHg production and availability within an organism's home range; trophic positions of consumers and MeHg biomagnification efficiency in food webs; and individual prey preferences that influence diet composition. To better understand spatial variation in MeHg bioaccumulation within a species, we evaluated the effects of habitat biogeochemistry, food web structure, and diet composition in the wetland-obligate California black rail (Laterallus jamaicensis coturniculus) at three wetlands along the Petaluma River in northern San Francisco Bay, California, USA. The concentration of MeHg in sediments differed significantly among wetlands. We identified three sediment and porewater measurements that contributed significantly to a discriminant function explaining differences in habitat biogeochemistry among wetlands: the porewater concentration of ferrous iron, the percent organic matter, and the sediment MeHg concentration. Food web structure and biomagnification efficiency were similar among wetlands, with trophic magnification factors for MeHg ranging from 1.84 to 2.59. In addition, regurgitation samples indicated that black rails were dietary generalists with similar diets among wetlands (percent similarity indices > 70%). Given the similarities in diet composition, food web structure, and MeHg biomagnification efficiency among wetlands, we concluded that variation in habitat biogeochemistry and associated sediment MeHg production was the primary driver of differences in MeHg concentrations among black rails from different wetlands.

Human-induced and natural carbon storage in floodplains of the Central Valley of California.

Active floodplains can putatively store large amounts of organic carbon (SOC) in subsoils originating from catchment erosion processes with subsequent floodplain deposition. Our study focussed on the assessment of SOC pools associated with alluvial floodplain soils that are affected by human-induced changes in floodplain deposition and in situ SOC mineralisation due to land use change and drainage. We evaluated depth-dependent SOC contents based on 23 soil cores down to 3 m and 10 drillings down to 7 m in a floodplain area of the lower Cosumnes River. An estimate of 266 Mg C ha-1 or about 59% of the entire SOC stored within the 7 m profiles was found in the upper 2 m. Most profiles (n = 25) contained discrete buried A horizons at depths of approximately 0.8 m. These profiles had up to 130% higher SOC stocks. The mean δ13C of all deep soil profiles clearly indicated that arable land use has already altered the stable isotopic signature in the first meter of the profile. Radiocarbon dating showed that the 14C age in the buried horizon was younger than in overlaying soils indicating a substantial sedimentation phase for the overlaying soils. An additional analysis of total mercury contents in the soil profiles indicated that this sedimentation was associated with upstream hydraulic gold mining after the 1850s. In summary, deep alluvial soils in floodplains store large amounts of SOC not yet accounted for in global carbon models. Historic data give evidence that large amounts of sediment were transported into the floodplains of most rivers of the Central Valley and deposited over organically rich topsoil, which promoted the stabilization of SOC, and needs to be considered to improve our understanding of the human-induced interference with C cycling.

Wetland Management Strategy to Reduce Mercury in Water and Bioaccumulation in Fish.

Wetland environments provide numerous ecosystem services but also facilitate methylmercury (MeHg) production and bioaccumulation. We developed a wetland-management technique to reduce MeHg concentrations in wetland fish and water. We physically modified seasonal wetlands by constructing open- and deep-water treatment cells at the downstream end of seasonal wetlands to promote naturally occurring MeHg-removal processes. We assessed the effectiveness of reducing mercury (Hg) concentrations in surface water and western mosquitofish that were caged at specific locations within 4 control and 4 treatment wetlands. Methylmercury concentrations in wetland water were successfully decreased within treatment cells during only the third year of study; however, treatment cells were not effective for reducing total Hg concentrations. Furthermore, treatment cells were not effective for reducing total Hg concentrations in wetland fish. Mercury concentrations in fish were not correlated with total Hg concentrations in filtered, particulate, or whole water; and the slope of the correlation with water MeHg concentrations differed between months. Fish total Hg concentrations were weakly correlated with water MeHg concentrations in April when fish were introduced into cages but were not correlated in May when fish were retrieved from cages. Fish total Hg concentrations were greater in treatment wetlands than in control wetlands the year after the treatment wetlands' construction but declined by the second year. During the third year, fish total Hg concentrations increased in both control and treatment wetlands after an unexpected regional flooding event. Overall, we found limited support for the use of open- and deep-water treatment cells at the downstream end of wetlands to reduce MeHg concentrations in water but not fish. We suggest that additional evaluation over a longer period of time is necessary. Environ Toxicol Chem 2019;38:2178-2196. Published 2019 Wiley Periodicals, Inc. on behalf of SETAC. This article is a US government work, and as such, is in the public domain in the United States of America..

Comparison of total mercury and methylmercury cycling at five sites using the small watershed approach.

The small watershed approach is well-suited but underutilized in mercury research. We applied the small watershed approach to investigate total mercury (THg) and methylmercury (MeHg) dynamics in streamwater at the five diverse forested headwater catchments of the US Geological Survey Water, Energy, and Biogeochemical Budgets (WEBB) program. At all sites, baseflow THg was generally less than 1ng L(-1) and MeHg was less than 0.2ng L(-1). THg and MeHg concentrations increased with streamflow, so export was primarily episodic. At three sites, THg and MeHg concentration and export were dominated by the particulate fraction in association with POC at high flows, with maximum THg (MeHg) concentrations of 94 (2.56)ng L(-1) at Sleepers River, Vermont; 112 (0.75)ng L(-1) at Rio Icacos, Puerto Rico; and 55 (0.80)ng L(-1) at Panola Mt., Georgia. Filtered (<0.7microm) THg increased more modestly with flow in association with the hydrophobic acid fraction (HPOA) of DOC, with maximum filtered THg concentrations near 5ng L(-1) at both Sleepers and Icacos. At Andrews Creek, Colorado, THg export was also episodic but was dominated by filtered THg, as POC concentrations were low. MeHg typically tracked THg so that each site had a fairly constant MeHg/THg ratio, which ranged from near zero at Andrews to 15% at the low-relief, groundwater-dominated Allequash Creek, Wisconsin. Allequash was the only site with filtered MeHg consistently above detection, and the filtered fraction dominated both THg and MeHg. Relative to inputs in wet deposition, watershed retention of THg (minus any subsequent volatilization) was 96.6% at Allequash, 60% at Sleepers, and 83% at Andrews. Icacos had a net export of THg, possibly due to historic gold mining or frequent disturbance from landslides. Quantification and interpretation of Hg dynamics was facilitated by the small watershed approach with emphasis on event sampling.

Development of a mercury speciation, fate, and biotic uptake (BIOTRANSPEC) model: application to Lahontan Reservoir (Nevada, USA).

A mathematically linked mercury transport, speciation, kinetic, and simple biotic uptake (BIOTRANSPEC) model has been developed. An extension of the metal transport and speciation (TRANSPEC) model, BIOTRANSPEC estimates the fate and biotic uptake of inorganic (Hg(II)), elemental (Hg(0)) and organic (MeHg) forms of mercury and their species in the dissolved, colloidal (e.g., dissolved organic matter [DOM]), and particulate phases of surface aquatic systems. A pseudo-steady state version of the model was used to describe mercury dynamics in Lahontan Reservoir (near Carson City, NV, USA), where internal loading of the historically deposited mercury is remobilized, thereby maintaining elevated water concentrations. The Carson River is the main source of total mercury (THg), of which more than 90% is tightly bound in a gold-silver-mercury amalgam, to the system through loadings in the spring, with negligible input from the atmospheric deposition. The speciation results suggest that aqueous species are dominated by Hg-DOM, Hg(OH)(2), and HgClOH. Sediment-to-water diffusion of MeHg and Hg-DOM accounts for approximately 10% of total loadings to the water column. The water column acts as a net sink for MeHg by reducing its levels through two competitive processes: Uptake by fish, and net MeHg demethylation. Although reservoir sediments produce significant amounts of MeHg (4 g/d), its transport from sediment to water is limited (1.6 g/d), possibly because of its adsorption on metal oxides of iron and manganese at the sediment-water interface. Fish accumulate approximately 45% of the total MeHg mass in the water column, and 9% of total MeHg uptake by fish leaves the system because of fishing. Results from this new model reiterate the previous conclusion that more than 90% of THg input is retained in sediment, which perpetuates elevated water concentrations.

Methodological considerations regarding the use of inorganic 197Hg(II) radiotracer to assess mercury methylation potential rates in lake sediment.

Methodological considerations on the determination of benthic methyl-mercury (CH(3)Hg) production potentials were investigated on lake sediment, using (197)Hg radiotracer. Three methods to arrest bacterial activity were compared: flash freezing, thermal sterilization, and gamma-irradiation. Flash freezing showed similar CH(3)Hg recoveries as thermal sterilization, which was both 50% higher than the recoveries obtained with gamma-ray irradiation. No additional radiolabel was recovered in kill-control samples after an additional 24 or 65 h of incubation, suggesting that all treatments were effective at arresting Hg(II)-methylating bacterial activity, and that the initial recoveries are likely due to non-methylated (197)Hg(II) carry-over in the organic extraction and/or [(197)Hg]CH(3)Hg produced via abiotic reactions. Two CH(3)Hg extraction methods from sediment were compared: (a) direct extraction into toluene after sediment leaching with CuSO(4) and HCl and (b) the same extraction with an additional back-extraction step to thiosulphate. Similar information was obtained with both methods, but the low efficiency observed and the extra work associated with the back-extraction procedure represent significant disadvantages, even tough the direct extraction involves higher Hg(II) carry over.

Long-term trends of surface-water mercury and methylmercury concentrations downstream of historic mining within the Carson River watershed.

The Carson River is a vital water resource for local municipalities and migratory birds travelling the Pacific Flyway. Historic mining practices that used mercury (Hg) to extract gold from Comstock Lode ore has left much of the river system heavily contaminated with Hg, a practice that continues in many parts of the world today. Between 1998 and 2013, the United States Geological Survey (USGS) collected and analyzed Carson River water for Hg and methylmercury (MeHg) concentrations resulting in a sixteen year record of unfiltered total mercury (uf.THg), filtered (dissolved) Hg (f.THg), total methylmercury (uf.MeHg), filtered MeHg (f.MeHg), and particulate-bound THg (p.THg) and MeHg (p.MeHg) concentrations. This represents one of the longest continuous records of Hg speciation data for any riverine system, thereby providing a unique opportunity to evaluate long-term trends in concentrations and annual loads. During the period of analysis, uf.THg concentration and load trended downward at rates of -0.85% and -1.8% per year, respectively. Conversely, the f.THg concentration increased at a rate of 1.7% per year between 1998 and 2005, and 4.9% per year between 2005 and 2013. Trends in flow-normalized partition coefficients for both Hg and MeHg suggest a statistically significant shift from the particulate to the filtered phase. The upwardly accelerating f.THg concentration and observed shift from the solid phase to the aqueous phase among the pools of Hg and MeHg within the river water column signals an increased risk of deteriorating ecological conditions in the lower basin with respect to Hg contamination. More broadly, the 16-year trend analysis, completed 140 years after the commencement of major Hg releases to the Carson River, provides a poignant example of the ongoing legacy left behind by gold and silver mining techniques that relied on Hg amalgamation, and a cautionary tale for regions still pursuing the practice in other countries.

Effect of salinity on mercury methylating benthic microbes and their activities in Great Salt Lake, Utah.

Surface water and biota from Great Salt Lake (GSL) contain some of the highest documented concentrations of total mercury (THg) and methylmercury (MeHg) in the United States. In order to identify potential biological sources of MeHg and controls on its production in this ecosystem, THg and MeHg concentrations, rates of Hg(II)-methylation and MeHg degradation, and abundances and compositions of archaeal and bacterial 16 rRNA gene transcripts were determined in sediment along a salinity gradient in GSL. Rates of Hg(II)-methylation were inversely correlated with salinity and were at or below the limits of detection in sediment sampled from areas with hypersaline surface water. The highest rates of Hg(II)-methylation were measured in sediment with low porewater salinity, suggesting that benthic microbial communities inhabiting less saline environments are supplying the majority of MeHg in the GSL ecosystem. The abundance of 16S rRNA gene transcripts affiliated with the sulfate reducer Desulfobacterium sp. was positively correlated with MeHg concentrations and Hg(II)-methylation rates in sediment, indicating a potential role for this taxon in Hg(II)-methylation in low salinity areas of GSL. Reactive inorganic Hg(II) (a proxy used for Hg(II) available for methylation) and MeHg concentrations were inversely correlated with salinity. Thus, constraints imposed by salinity on Hg(II)-methylating populations and the availability of Hg(II) for methylation are inferred to result in higher MeHg production potentials in lower salinity environments. Benthic microbial MeHg degradation was also most active in lower salinity environments. Collectively, these results suggest an important role for sediment anoxia and microbial sulfate reducers in the production of MeHg in low salinity GSL sub-habitats and may indicate a role for salinity in constraining Hg(II)-methylation and MeHg degradation activities by influencing the availability of Hg(II) for methylation.

Mercury remediation in wetland sediment using zero-valent iron and granular activated carbon.

Wetlands are hotspots for production of toxic methylmercury (MeHg) that can bioaccumulate in the food web. The objective of this study was to determine whether the application of zero-valent iron (ZVI) or granular activated carbon (GAC) to wetland sediment could reduce MeHg production and bioavailability to benthic organisms. Field mesocosms were installed in a wetland fringing Hodgdon Pond (Maine, USA), and ZVI and GAC were applied. Pore-water MeHg concentrations were lower in treated compared with untreated mesocosms; however, sediment MeHg, as well as total Hg (THg), concentrations were not significantly different between treated and untreated mesocosms, suggesting that smaller pore-water MeHg concentrations in treated sediment were likely due to adsorption to ZVI and GAC, rather than inhibition of MeHg production. In laboratory experiments with intact vegetated sediment clumps, amendments did not significantly change sediment THg and MeHg concentrations; however, the mean pore-water MeHg and MeHg:THg ratios were lower in the amended sediment than the control. In the laboratory microcosms, snails (Lymnaea stagnalis) accumulated less MeHg in sediment treated with ZVI or GAC. The study results suggest that both GAC and ZVI have potential for reducing MeHg bioaccumulation in wetland sediment.