MeHg Export Research Articles

Landscape characteristics govern the impacts of beaver ponds on surface water methylmercury concentrations in boreal watersheds

Studies in boreal regions concerning the bioaccumulative neurotoxin methylmercury (MeHg) in natural wetlands and experimental reservoirs have shown that these waterbodies contribute to high MeHg levels in underlying sediments, inundated vegetation, and aquatic organisms. Beaver ponds are natural reservoirs that are ubiquitous in the Canadian boreal region and have been reported to increase downstream MeHg concentrations. However, the reported impacts of beaver ponds on stream MeHg vary widely across a limited number of studies, and factors influencing this variation are not well understood. To quantify the effect of beaver ponds on stream mercury concentrations, water samples were taken upstream and downstream of 10 in-channel beaver impoundments in northwestern Ontario, Canada. The downstream:upstream MeHg concentration ratios were related to pond and landscape characteristics to examine potential factors that play a role in determining the effect of beaver ponds on stream MeHg concentrations. Overall, MeHg concentrations were 1.6 times greater downstream of the beaver ponds, though this increase was not consistent; downstream concentrations up to 12 times greater and up to 5 times less were also observed. Landscape characteristics that can be readily obtained from existing spatial datasets or quantified using remote sensing techniques emerged as better predictors of downstream:upstream MeHg concentrations than site-specific stream chemistry parameters or pond characteristics that are more difficult to ascertain, with drier landscapes indicative of lower background MeHg export being more likely to exhibit greater increases in MeHg downstream of a beaver pond. These results suggest that the effects of beaver ponds on surface water MeHg concentrations are generally small but highly variable, and that the magnitude of the pond’s influence on stream MeHg are lessened in landscapes already conducive to higher MeHg concentrations.

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 254nm (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.

Methylmercury Export From a Headwater Peatland Catchment Decreased With Cleaner Emissions Despite Opposing Effect of Climate Warming

AbstractPeatlands are sources of bioaccumulating neurotoxin methylmercury (MeHg) that is linked to adverse health outcomes. Yet, the compounding impacts of climate change and reductions in atmospheric pollutants on mercury (Hg) export from peatlands are highly uncertain. We investigated the response in annual flow‐weighted concentrations (FWC) and yields of total‐Hg (THg) and MeHg to cleaner air and climate change using an unprecedented hydroclimatic (55‐year; streamflow, air temperature, precipitation, and peatland water tables), depositional chemistry (21‐year; Hg and major ions), and streamwater chemistry (∼17‐year; THg, MeHg, major ions, total organic carbon, and pH) data sets from a reference peatland catchment in Minnesota, USA. Over the hydroclimatic record, annual mean air temperature increased by ∼1.8°C, while baseflow and the efficiency that precipitation was converted to runoff (runoff ratio) decreased. Concurrently, precipitation‐based deposition of sulfate and Hg declined, where wet Hg deposition declined by ∼3–4 μg Hg m−2. Despite declines in wet Hg deposition over the study period, the catchment accumulated on average 0.04 ± 0.01 g Hg ha−1 yr−1 based on wet Hg deposition minus THg yield alone. Annual MeHg FWC was positively correlated with mean annual air temperatures (p = 0.03, r = 0.51), runoff ratio (p < 0.0001, r = 0.76), and wet Hg deposition concentration (p < 0.0001, r = 0.79). Decreasing wet Hg deposition and annual runoff ratios counterbalanced increased peatland MeHg production due to higher air temperatures, leading to an overall decline in streamwater MeHg FWC. Streamwater MeHg export may continue to decrease only as long as declines in runoff ratio and wet Hg deposition persistently outpace effects of increased air temperature.

Long-Term Experimental Manipulation of Atmospheric Sulfate Deposition to a Peatland: Response of Methylmercury and Related Solute Export in Streamwater.

Changes in sulfate (SO42-) deposition have been linked to changes in mercury (Hg) methylation in peatlands and water quality in freshwater catchments. There is little empirical evidence, however, of how quickly methyl-Hg (MeHg, a bioaccumulative neurotoxin) export from catchments might change with declining SO42- deposition. Here, we present responses in total Hg (THg), MeHg, total organic carbon, pH, and SO42- export from a peatland-dominated catchment as a function of changing SO42- deposition in a long-term (1998-2011), whole-ecosystem, control-impact experiment. Annual SO42- deposition to half of a 2-ha peatland was experimentally increased 6-fold over natural levels and then returned to ambient levels in two phases. Sulfate additions led to a 5-fold increase in monthly flow-weighted MeHg concentrations and yields relative to a reference catchment. Once SO42- additions ceased, MeHg concentrations in the outflow streamwater returned to pre-SO42- addition levels within 2 years. The decline in streamwater MeHg was proportional to the change in the peatland area no longer receiving experimental SO42- inputs. Importantly, net demethylation and increased sorption to peat hastened the return of MeHg to baseline levels beyond purely hydrological flushing. Overall, we present clear empirical evidence of rapid and proportionate declines in MeHg export from a peatland-dominated catchment when SO42- deposition declines.

In-Reservoir Physical Processes Modulate Aqueous and Biological Methylmercury Export from a Seasonally Anoxic Reservoir.

Anoxic conditions within reservoirs related to thermal stratification and oxygen depletion lead to methylmercury (MeHg) production, a key process governing the uptake of mercury in aquatic food webs. Once formed within a reservoir, the timing and magnitude of the biological uptake of MeHg and the relative importance of MeHg export in water versus biological compartments remain poorly understood. We examined the relations between the reservoir stratification state, anoxia, and the concentrations and export loads of MeHg in aqueous and biological compartments at the outflow locations of two reservoirs of the Hells Canyon Complex (Snake River, Idaho-Oregon). Results show that (1) MeHg concentrations in filter-passing water, zooplankton, suspended particles, and detritus increased in response to reservoir destratification; (2) zooplankton MeHg strongly correlated with MeHg in filter-passing water during destratification; (3) reservoir anoxia appeared to be a key control on MeHg export; and (4) biological MeHg, primarily in zooplankton, accounted for only 5% of total MeHg export from the reservoirs (the remainder being aqueous compartments). These results improve our understanding of the role of biological incorporation of MeHg and the subsequent downstream release from seasonally stratified reservoirs and demonstrate that in-reservoir physical processes strongly influence MeHg incorporation at the base of the aquatic food web.

Effect of exogenous and endogenous sulfide on the production and the export of methylmercury by sulfate-reducing bacteria.

Mercury (Hg) is a global pollutant of environmental and health concern; its methylated form, methylmercury (MeHg), is a potent neurotoxin. Sulfur-containing molecules play a role in MeHg production by microorganisms. While sulfides are considered to limit Hg methylation, sulfate and cysteine were shown to favor this process. However, these two forms can be endogenously converted by microorganisms into sulfide. Here, we explore the effect of sulfide (produced by the cell or supplied exogenously) on Hg methylation. For this purpose, Pseudodesulfovibrio hydrargyri BerOc1 was cultivated in non-sulfidogenic conditions with addition of cysteine and sulfide as well as in sulfidogenic conditions. We report that Hg methylation depends on sulfide concentration in the culture and the sulfides produced by cysteine degradation or sulfate reduction could affect the Hg methylation pattern. Hg methylation was independent of hgcA expression. Interestingly, MeHg production was maximal at 0.1-0.5mM of sulfides. Besides, a strong positive correlation between MeHg in the extracellular medium and the increase of sulfide concentrations was observed, suggesting a facilitated MeHg export with sulfide and/or higher desorption from the cell. We suggest that sulfides (exogenous or endogenous) play a key role in controlling mercury methylation and should be considered when investigating the impact of Hg in natural environments.

Export and bioaccumulation of methylmercury in streams draining distinct soils in the Central Brazilian Amazon, 2012-2013

BackgroundUpland forest streams of the Central Amazon are unique aquatic systems.These small streams have short, unpredictable and multimodal flood-pulses that are influenced by local rainfall. The biogeochemical cycles in these systems are almost unknown. This study investigated the role of soil type on the export and bioaccumulation of methylmercury (MeHg) in upland forest streams of the Central Amazon during a complete annual cycle. Basic ProceduresLimnological measurements and water samples for MeHg analyses were collected monthly from October 2012 to October 2013 in two headwater streams drained by different soil types, spodzol (Campina Stream) and oxisol (Barro Branco Stream), in natural forest reserves. Shrimp and fish were collected for total mercury (THg) in April 2013 in both streams. Main findingsMeHg in water varied from 0.04 to 0.50 ng/L in the Campina Stream and between <detection limit and 0.04 ng/L in Barro Branco Stream. Physical characteristics of soils and the interaction between mercury and organic matter influenced the methylation of mercury and its export to the streams. In both streams, MeHg export was highest during the rainy season, probably due to soil leaching, lateral flooding and soil hydromorphism during this period, processes conducive to mercury methylation and export. THg in shrimps (omnivores) and carnivorous fish, which fed on aquatic food items, reflected the MeHg differences between streams while those in insectivorous fish, feeding on allochthonous food items, did not. Principal ConclusionsMeHg dynamics in streams were influenced by the physical characteristics of basin soils and by local seasonal rainfall.

Methylmercury Transport and Fate Shows Strong Seasonal and Spatial Variability along a High Arctic Freshwater Hydrologic Continuum.

The presence of toxic methylmercury (MeHg) in Arctic freshwater ecosystems and foodwebs is a potential health concern for northern Indigenous people. Addressing this issue requires a better understanding of MeHg production, fate during transport, and uptake into foodwebs. We used methylation assays and spatiotemporal surveys of MeHg concentrations, during the ice-covered and open water seasons, across a hydrologic continuum (composed of thaw seeps, lake/ponds, and a wetland) to identify Hg methylation hotspots and seasonal differences in MeHg cycling unique to Arctic ecosystems. Ponds and saturated wetland soils support methylation hotspots during the open water season, but subsequent export of MeHg to downstream ecosystems is limited by particle settling, binding of MeHg on soil organic matter, and/or demethylation in drier wetland soils. During the ice-covered season, MeHg concentrations in lake waters were approximately ten-fold greater than in summer; however, zooplankton MeHg concentrations were paradoxically five times lower at this time. Despite limited evidence of snow-phase methylation, the snowpack is an important MeHg reservoir. Changes in ice-cover duration will alter MeHg production and bioaccumulation in lakes, while increased thaw and surface water flow will likely result in higher methylation rates at the aquatic-terrestrial interface and more efficient downstream transport of MeHg.

Mercury species export from the Arctic to the Atlantic Ocean

The Fram Strait is the only deep connection between the Arctic and Atlantic Oceans. The main water and mercury (Hg) fluxes between these oceans occur via the Fram Strait and Barents Sea Opening. Several Hg mass balance studies indicated a net Hg export from the Arctic to the Atlantic Ocean. However, in the absence of Hg measurements in the Fram Strait and Barents Sea Opening, these estimates were based on North Atlantic and central Arctic Ocean data alone. Here, we refine the Arctic total Hg (tHg) and methylated Hg (MeHg) mass budgets using new data acquired during the 2015 GEOTRACES (section GN04) TransArcII cruise in the Barents Sea Opening and the 2016 GEOTRACES (section GN05) GRIFF cruise, which covered the Fram Strait and Northeast Greenland Shelf. Total Hg increased westward along the Fram Strait transect, reaching the highest concentrations on the Northeast Greenland Shelf. Concentrations of tHg averaged 1.29 ± 0.43 pM in the East Greenland Current, while core waters of the West Spitsbergen Current had average values of 0.80 ± 0.26 pM. Using our new data, we estimate that 43 ± 9 Mg y−1 of tHg is transported to the Arctic Ocean in the core of the West Spitsbergen Current, while 54 ± 13 Mg y−1 of tHg is exported from the Arctic Ocean in the East Greenland Current and Recirculated Atlantic Water. This results in a net tHg export of 11 ± 8 Mg y−1via the Fram Strait. We find a shallow MeHg maximum (at 150 m depth) in the East Greenland Current, in agreement to what was reported for the central Arctic Ocean and Canadian Arctic Archipelago. The West Spitsbergen Current is characterized by lower MeHg concentrations and a deeper MeHg maximum, that is located at approximately 1000 m depth. We estimate a net MeHg export of 6 ± 2 Mg y−1 from the Arctic Ocean via the Fram Strait, which is nearly half of the exported tHg. Most of the exported MeHg is in the form of DMHg (2:1 ratio of dimethylmercury to monomethylmercury). Previous studies reported lower MeHg proportions. Our observations show that the Arctic Ocean is producing and exporting MeHg to the Atlantic Ocean. In total, the Arctic Ocean exports about 18 Mg y−1 of tHg to the Nordic Seas and North Atlantic via the Fram Strait and Davis Strait, of which 7.5 Mg y−1 is in the MeHg form.

Seasonal Dynamics and Interannual Variability in Mercury Concentrations and Loads through a Three-Reservoir Complex.

The Hells Canyon Complex (HCC) along the Snake River (Idaho-Oregon border, U.S.A.) encompasses three successive reservoirs that seasonally stratify, creating anoxic conditions in the hypolimnion that promote methylmercury (MeHg) production. This study quantified seasonal dynamics and interannual variability in mercury concentrations (inorganic divalent mercury (IHg) and MeHg) and loads at four reservoir inflow and outflow locations through the HCC (2014-2017). We observed (1) that the HCC is a net sink for both IHg and MeHg, (2) interannual variability in IHg and MeHg loads largely reflecting streamflow conditions, and (3) seasonal variability in particulate IHg loading at the inflow (greatest from February to April) and MeHg export from the outflow (greatest from September to December) of the HCC. Seasonal export of MeHg was evidenced by increases in monthly mean concentrations of unfiltered MeHg (approximately 2-fold) and the percentage of total mercury (THg) as MeHg (≥4-fold) coincident with reservoir destratification. Despite evidence of seasonal export of MeHg from the HCC, annual loads indicate a 42% decrease in unfiltered MeHg from HCC inflow to outflow. Results from this study improve the understanding of seasonal variability in mercury transport through and transformation within a reservoir complex.

Determination of picomolar levels of methylmercury complexes with low molecular mass thiols by liquid chromatography tandem mass spectrometry and online preconcentration

Methylmercury (MeHg) is one of the most potent neurotoxins. It is produced in nature through the methylation of inorganic divalent mercury (HgII) by phylogenetically diverse anaerobic microbes. The mechanistic understanding of the processes that govern the extent of bacterial export of MeHg, its bioaccumulation, and bio-toxicity depends on accurate quantification of its species, especially its complexation with low molecular mass thiols; organometallic complexes that are difficult to detect and measure in natural conditions. Here, we report the development of a novel analytical method based on liquid chromatography tandem mass spectrometry (LC-MS/MS) to determine 13 MeHg complexes with important thiol compounds which have been observed in the environment and in biological systems. By using online preconcentration via solid phase extraction (SPE), the method offers picomolar (12–530 pM) detection limits, the lowest reported so far for the determination of MeHg compounds. Among three different SPE materials, a weak cation exchange phase showed the best efficiency at a low pH of 2.5. We further report the presence of MeHg-cysteine, MeHg-cysteamine, MeHg-penicillamine, MeHg-cysteinylglycine, and MeHg-glutamylcysteine as the predominant MeHg–thiol complexes in the extracellular milieu of an important HgII methylating bacterium, Geobacter sulfurreducens PCA, exposed to 100 nM of HgII.

Methylmercury Modulation in Amazon Rivers Linked to Basin Characteristics and Seasonal Flood-Pulse.

We investigated the impact of the seasonal inundation of wetlands on methylmercury (MeHg) concentration dynamics in the Amazon river system. We sampled 38 sites along the Solimões/Amazon and Negro rivers and their tributaries during distinct phases of the annual flood-pulse. MeHg dynamics in both basins was contrasted to provide insight into the factors controlling export of MeHg to the Amazon system. The export of MeHg by rivers was substantially higher during high-water in both basins since elevated MeHg concentrations and discharge occurred during this time. MeHg concentration was positively correlated to %flooded area upstream of the sampling site in the Solimões/Amazon Basin with the best correlation obtained using 100 km buffers instead of whole basin areas. The lower correlations obtained with the whole basin apparently reflected variable losses of MeHg exported from upstream wetlands due to demethylation, absorption, deposition, and degradation before reaching the sampling site. A similar correlation between %flooded area and MeHg concentrations was not observed in the Negro Basin probably due to the variable export of MeHg from poorly drained soils that are abundant in this basin but not consistently flooded.

Forest harvest contribution to Boreal freshwater methyl mercury load

AbstractEffects of Boreal forest harvest on mercury (Hg) and methyl mercury (MeHg) soil pools and export by stream runoff were quantified by comparing 10 reference watersheds (REFs) covered by &gt;80 year old Norway spruce (Picea abies Karst.) forests with 10 similar watersheds subjected to clear‐cutting (CCs). While total Hg soil storage did not change, MeHg pools increased six times (p = 0.004) in the organic topsoil 2 years after clear‐cutting. In undulating terrain, situated above the postglacial marine limit (ML) of the ancient Baltic Sea, the mass ratio between flux‐weighted MeHg and dissolved organic carbon (MeHg/DOC) in stream runoff increased 1.8 times (p &lt; 0.004) as a consequence of forest harvest. When recalculated to 100% clear‐cutting of the watershed, the annual MeHg stream export increased 3.8 times (p = 0.047). Below the ML, where the terrain was flatter, neither the MeHg/DOC ratio nor the annual export of MeHg differed between REFs and CCs, likely because of the larger contribution of MeHg exported from peaty soils and small wetlands. The most robust measure, MeHg/DOC, was used to calculate MeHg loadings to Boreal headwaters. If the forest harvest effect lasts 10 years, clear‐cutting increases MeHg runoff by 12–20% in Sweden and 2% in the Boreal zone as a whole. In Sweden, having intensely managed forests, 37% and 56% of MeHg are exported from peatlands and forest soils, respectively, and forest clear‐cutting is adding another 6.6%. In the Boreal zone as a whole peatlands and forests soils contribute with 53% and 46%, respectively, and clear‐cutting is estimated to add another 1.0%. An expected rapid increase in Boreal forest harvest and disturbance urge for inclusion of land use effects in mercury biogeochemical cycling models at different scales.

Thiol-Facilitated Cell Export and Desorption of Methylmercury by Anaerobic Bacteria

Methylmercury (MeHg) toxin, formed by anaerobic bacteria, is rapidly excreted from cells, but the mechanism of this process is unclear. We studied the factors affecting MeHg export and its distribution in cells, on cell surfaces, and in solution by two known mercury methylators, Geobacter sulfurreducens PCA and Desulfovibrio desulfuricans ND132. Thiols, such as cysteine, were found to greatly facilitate desorption and export of MeHg, particularly by PCA cells. In cysteine-free assays (4 h), less than 10% of the synthesized MeHg was found in solution and greater than 90% was associated with PCA, of which about 73% was sorbed on the cell surface and 19% remained inside the cells. In comparison, 77% of MeHg was in solution, leaving about 13% of MeHg sorbed and about 10% inside the ND132 cells. Our results demonstrate that MeHg export is bacteria specific, time dependent, and influenced by thiols, implicating important roles of ligands, such as natural organic matter, in MeHg production and mobilization in th...

Identification and prioritization of management practices to reduce methylmercury exports from wetlands and irrigated agricultural lands.

The Sacramento-San Joaquin Delta's (Delta) beneficial uses for humans and wildlife are impaired by elevated methylmercury (MeHg) concentrations in fish. MeHg is a neurotoxin that bioaccumulates in aquatic food webs. The total maximum daily load (TMDL) implementation plan aimed at reducing MeHg in Delta fish obligates dischargers to conduct MeHg control studies. Over 150 stakeholders collaborated to identify 24 management practices (MPs) addressing MeHg nonpoint sources (NPS) in three categories: biogeochemistry (6), hydrology (14), and soil/vegetation (4). Land uses were divided into six categories: permanently and seasonally flooded wetlands, flooded and irrigated agricultural lands, floodplains, and brackish-fresh tidal marshes. Stakeholders scored MPs based on seven criteria: scientific certainty, costs, MeHg reduction potential, spatial applicability, technical capacity to implement, negative impacts to beneficial uses, and conflicting requirements. Semi-quantitative scoring for MPs applicable to each land use (totaling >400 individual scores) led to consensus-based prioritization. This process relied on practical experience from diverse and accomplished NPS stakeholders and synthesis of 17 previous studies. Results provide a comprehensive, stakeholder-driven prioritization of MPs for wetland and irrigated agricultural land managers. Final prioritization highlights the most promising MPs for practical application and control study, and a secondary set of MPs warranting further evaluation. MPs that address hydrology and soil/vegetation were prioritized because experiences were positive and implementation appeared more feasible. MeHg control studies will need to address the TMDL conundrum that MPs effective at reducing MeHg exports could both exacerbate MeHg exposure and contend with other management objectives on site.

Forest harvest effects on mercury in streams and biota in Norwegian boreal catchments

Forest harvesting practices can potentially increase mercury run-off from catchments. A paired catchment experiment was conducted in a boreal forest in southern Norway, to test effects of forest harvest operations on (i) concentrations and fluxes of methylmercury (MeHg), total mercury (HgT), nutrients and dissolved organic matter (TOC), and on (ii) MeHg bioaccumulation in stream foodwebs.Thirty percent of a catchment was harvested in winter time with snow cover but no soil frost, resulting in wheel tracks and soil compaction. Pre-harvest differences included higher streamwater MeHg, HgT and TOC, and lower pH in the treated catchment compared to the reference.No significant treatment effects on concentrations of MeHg, HgT and TOC were detected, whereas concentrations of nutrients (ammonium, nitrate, phosphorus (P)) increased significantly. Estimated catchment export of nitrate and ammonium increased fourfold, as a combined effect of changed discharge and concentrations. Export of MeHg and HgT increased weakly, primarily because of an increase in discharge.Levels of MeHg in stream invertebrates mirrored differences in aquatic MeHg between the two streams, resulting in higher MeHg in biota in the harvest catchment in pre-harvest conditions. After harvest, MeHg levels in primary consumers (herbivorous stoneflies) were no longer different between the two streams, despite continued exposure to higher aqueous MeHg in the harvested catchment. Simultaneously, dietary biomarkers (δ15N signature, lipid- and algal fatty acid content) in the stoneflies had changed significantly, consistent with higher nutrient loadings and associated higher diet availability in the harvested stream.The results of our experiment do not support that forest management has a strong impact on catchment MeHg production. Catchment disturbance through forest harvesting may decrease MeHg in aquatic biota, because of higher stream productivity and associated higher quality of dietary sources, at least in the short-term. Other studies on catchment MeHg production to disturbance have shown a range in responses, from strong to none. So far, no factor has emerged to explain such range in responses. Predictions of forest management effects on MeHg in streamwater and aquatic food webs are hampered by limited understanding of catchment controls on MeHg production.

Reprint of “Methylmercury production in and export from agricultural wetlands in California, USA: The need to account for physical transport processes into and out of the root zone”

Concentration and mass balance analyses were used to quantify methylmercury (MeHg) loads from conventional (white) rice, wild rice, and fallowed fields in northern California's Yolo Bypass. These analyses were standardized against chloride to distinguish transport pathways and net ecosystem production (NEP). During summer, chloride loads were both exported with surface water and moved into the root zone at a 2:1 ratio. MeHg and dissolved organic carbon (DOC) behaved similarly with surface water and root zone exports at ~3:1 ratio. These trends reversed in winter with DOC, MeHg, and chloride moving from the root zone to surface waters at rates opposite and exceeding summertime root zone fluxes. These trends suggest that summer transpiration advectively moves constituents from surface water into the root zone, and winter diffusion, driven by concentration gradients, subsequently releases those constituents into surface waters. The results challenge a number of paradigms regarding MeHg. Specifically, biogeochemical conditions favoring microbial MeHg production do not necessarily translate to synchronous surface water exports; MeHg may be preserved in the soils allowing for release at a later time; and plants play a role in both biogeochemistry and transport. Our calculations show that NEP of MeHg occurred during both summer irrigation and winter flooding. Wild rice wet harvesting and winter flooding of white rice fields were specific practices that increased MeHg export, both presumably related to increased labile organic carbon and disturbance. Outflow management during these times could reduce MeHg exports. Standardizing MeHg outflow:inflow concentration ratios against natural tracers (e.g. chloride, EC) provides a simple tool to identify NEP periods. Summer MeHg exports averaged 0.2 to 1μgm−2 for the different agricultural wetland fields, depending upon flood duration. Average winter MeHg exports were estimated at 0.3μgm−2. These exports are within the range reported for other shallow aquatic systems.

Mercury cycling in agricultural and managed wetlands: A synthesis of methylmercury production, hydrologic export, and bioaccumulation from an integrated field study

With seasonal wetting and drying, and high biological productivity, agricultural wetlands (rice paddies) may enhance the conversion of inorganic mercury (Hg(II)) to methylmercury (MeHg), the more toxic, organic form that biomagnifies through food webs. Yet, the net balance of MeHg sources and sinks in seasonal wetland environments is poorly understood because it requires an annual, integrated assessment across biota, sediment, and water components. We examined a suite of wetlands managed for rice crops or wildlife during 2007–2008 in California's Central Valley, in an area affected by Hg contamination from historic mining practices. Hydrologic management of agricultural wetlands for rice, wild rice, or fallowed — drying for field preparation and harvest, and flooding for crop growth and post-harvest rice straw decay — led to pronounced seasonality in sediment and aqueous MeHg concentrations that were up to 95-fold higher than those measured concurrently in adjacent, non-agricultural permanently-flooded and seasonally-flooded wetlands. Flooding promoted microbial MeHg production in surface sediment of all wetlands, but extended water residence time appeared to preferentially enhance MeHg degradation and storage. When incoming MeHg loads were elevated, individual fields often served as a MeHg sink, rather than a source. Slow, horizontal flow of shallow water in the agricultural wetlands led to increased importance of vertical hydrologic fluxes, including evapoconcentration of surface water MeHg and transpiration-driven advection into the root zone, promoting temporary soil storage of MeHg. Although this hydrology limited MeHg export from wetlands, it also increased MeHg exposure to resident fish via greater in situ aqueous MeHg concentrations. Our results suggest that the combined traits of agricultural wetlands — slow-moving shallow water, manipulated flooding and drying, abundant labile plant matter, and management for wildlife — may enhance microbial methylation of Hg(II) and MeHg exposure to local biota, as well as export to downstream habitats during uncontrolled winter-flow events.

Methylmercury production in and export from agricultural wetlands in California, USA: The need to account for physical transport processes into and out of the root zone

Concentration and mass balance analyses were used to quantify methylmercury (MeHg) loads from conventional (white) rice, wild rice, and fallowed fields in northern California's Yolo Bypass. These analyses were standardized against chloride to distinguish transport pathways and net ecosystem production (NEP). During summer, chloride loads were both exported with surface water and moved into the root zone at a 2:1 ratio. MeHg and dissolved organic carbon (DOC) behaved similarly with surface water and root zone exports at ~3:1 ratio. These trends reversed in winter with DOC, MeHg, and chloride moving from the root zone to surface waters at rates opposite and exceeding summertime root zone fluxes. These trends suggest that summer transpiration advectively moves constituents from surface water into the root zone, and winter diffusion, driven by concentration gradients, subsequently releases those constituents into surface waters. The results challenge a number of paradigms regarding MeHg. Specifically, biogeochemical conditions favoring microbial MeHg production do not necessarily translate to synchronous surface water exports; MeHg may be preserved in the soils allowing for release at a later time; and plants play a role in both biogeochemistry and transport. Our calculations show that NEP of MeHg occurred during both summer irrigation and winter flooding. Wild rice wet harvesting and winter flooding of white rice fields were specific practices that increased MeHg export, both presumably related to increased labile organic carbon and disturbance. Outflow management during these times could reduce MeHg exports. Standardizing MeHg outflow:inflow concentration ratios against natural tracers (e.g. chloride, EC) provides a simple tool to identify NEP periods. Summer MeHg exports averaged 0.2 to 1μgm−2 for the different agricultural wetland fields, depending upon flood duration. Average winter MeHg exports were estimated at 0.3μgm−2. These exports are within the range reported for other shallow aquatic systems.

Mercury cycling in agricultural and managed wetlands of California, USA: Seasonal influences of vegetation on mercury methylation, storage, and transport

Plants are a dominant biologic and physical component of many wetland capable of influencing the internal pools and fluxes of methylmercury (MeHg). To investigate their role with respect to the latter, we examined the changing seasonal roles of vegetation biomass and Hg, C and N composition from May 2007–February 2008 in 3 types of agricultural wetlands (domesticated or white rice, wild rice, and fallow fields), and in adjacent managed natural wetlands dominated by cattail and bulrush (tule). We also determined the impact of vegetation on seasonal microbial Hg methylation rates, and Hg and MeHg export via seasonal storage in vegetation, and biotic consumption of rice seed. Despite a compressed growing season of ~3months, annual net primary productivity (NPP) was greatest in white rice fields and carbon more labile (leaf median C:N ratio=27). Decay of senescent litter (residue) was correlated with microbial MeHg production in winter among all wetlands. As agricultural biomass accumulated from July to August, THg concentrations declined in leaves but MeHg concentrations remained consistent, such that MeHg pools generally increased with growth. Vegetation provided a small, temporary, but significant storage term for MeHg in agricultural fields when compared with hydrologic export. White rice and wild rice seeds reached mean MeHg concentrations of 4.1 and 6.2ng gdw−1, respectively. In white rice and wild rice fields, seed MeHg concentrations were correlated with root MeHg concentrations (r=0.90, p<0.001), suggesting transport of MeHg to seeds from belowground tissues. Given the proportionally elevated concentrations of MeHg in rice seeds, white and wild rice crops may act as a conduit of MeHg into biota, especially waterfowl which forage heavily on rice seeds within the Central Valley of California, USA. Thus, while plant tissues and rhizosphere soils provide temporary storage for MeHg during the growing season, export of MeHg is enhanced post-harvest through increased hydrologic and biotic export.