Sources of methylmercury to a wetland-dominated lake in northern Wisconsin

Several lines of evidence suggest that wetlands may be a major source of methylmercury (MeHg) to receiving waters, perhaps explaining the strong correlation between concentrations of waterborne MeHg and dissolved organic carbon (DOC) in regions such as northern Wisconsin. We evaluated the relative importance of wetland export in the MeHg budget of a wetland-dominated lake in northern Wisconsin using mass balance. Channelized runoff from a large headwater wetland was the major source of water and total mercury (HgT) to the lake during the study period. The wetland also exported MeHg in high concentrations (0.2-0.8 ng L(-1)), resulting in an export rate similar to those reported for other northern wetlands (ca. 0.3 microg MeHg m(-2) y(-1)). Yet, based on intensive sampling during 2002, the mass of MeHg that accumulated in the lake during summer was an order of magnitude greater than the export of MeHg from the wetland to the lake. Hence, a large in-lake source of MeHg is inferred from the mass balance. Most of the accumulated MeHg built-up in anoxic hypolimnetic waters; and the build-up was roughly balanced by losses of inorganic Hg (Hg(II)) implying a chemical transformation within the anoxic water column. An abundance of sulfate-reducing bacteria (SRB) in hypolimnetic waters, established by DNA analysis of the pelagic microbial community, along with a previous report documenting high methylation rates in the hypolimnion of this lake (ca. 10% d(-1)), suggest that this transformation was microbially mediated. These findings indicate that the direct effect of wetland runoff may be outweighed by indirect effects on the lacustrine MeHg cycle, enhancing the load of Hg(II), the activity of SRB, and the retention of MeHg, especially in northern lakes with flushing times longer than six months.     

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.     

Flood hydrology and methylmercury availability in coastal plain rivers

Mercury (Hg) burdens in top-predator fish differ substantially between adjacent South Carolina Coastal Plain river basins with similar wetlands coverage. In the Congaree River, floodwaters frequently originate in the Blue Ridge and Piedmont regions, where wetlands coverage and surface water dissolved methylmercury (MeHg) concentrations are low. Piedmont-driven flood events can lead to downward hydraulic gradients in the Coastal Plain riparian wetland margins, inhibiting MeHg transport from wetland sediments, and decreasing MeHg availability in the Congaree River habitat. In the adjacent Edisto River basin, floodwaters originate only within Coastal Plain sediments, maintaining upward hydraulic gradients even during flood events, promoting MeHg transport to the water column, and enhancing MeHg availability in the Edisto River habitat. These results indicate that flood hydrodynamics contribute to the variability in Hg vulnerability between Coastal Plain rivers and that comprehensive regional assessment of the relationship between flood hydrodynamics and Hg risk in Coastal Plain streams is warranted.     

Perfluoroalkyl contaminants in the Canadian Arctic: evidence of atmospheric transport and local contamination

Perfluorosulfonates (PFSAs) and perfluorocarboxylates (PFCAs) have been hypothesized to reach remote locations such as the Canadian Arctic either indirectly as volatile precursor chemicals that undergo atmospheric transport and subsequent degradation, or directly via oceanic and atmospheric transport of the PFSAs and PFCAs themselves. Water, sediment, and air samples were collected from three Arctic lakes (Amituk, Char, and Resolute) on Cornwallis Island, Nunavut, Canada. Samples were analyzed for PFSAs and PFCAs, precursor chemicals including the fluorotelomer alcohols (FTOHs) and polyfluorinated sulfonamides (FSAs), and precursor degradation products such as the fluorotelomer unsaturated carboxylates (FTUCAs). PFSAs and PFCAs were detected in water and sediment of all three Arctic lakes (concentrations ranged from nondetect to 69 ng/L and nondetect to 85 ng/g dry weight, respectively). FTOHs and FSAs were observed in air samples (mean concentrations ranged from 2.8 to 29 pg/m3), and confirm that volatile precursors are reaching Arctic latitudes. The observation of degradation products, including FTUCAs observed in sediment and atmospheric particles, and N-ethyl perfluorooctanesulfonamide (NEtFOSA) and perfluorooctanesulfonamide (PFOSA) in air samples, indicate that degradation of the FTOHs and FSAs is occurring in the Arctic environment. PFSAs and PFCAs were also observed on atmospheric particles (mean concentrations ranged from < 0.1 to 5.9 pg/m3). In addition, results of this study also indicate that local perfluoroalkyl contamination of Resolute Lake, which is located downstream of an airport wastewater input, has occurred.     

Distribution and fluxes of total and methylmercury in Lake Superior

Despite the importance and size of Lake Superior, little is known regarding the biogeochemical cycling or distribution of mercury within its waters. We present the results from two research cruises on total Hg (HgT) and methylmercury (MeHg) distributions in aqueous and particulate phases, and in offshore sediments. Open waters of Lake Superior are similar in HgT content to Lakes Michigan and Ontario (sub-ng L(-1)), whereas MeHg was only 1% of HgT. Seasonality in aqueous HgT distribution was observed, most likely from tributary inputs during Spring snowmelt. Suspended particles were enriched in MeHg relative to water and surficial sediments, suggesting enhanced particle partitioning followed by demethylation in the water column and in surface sediments. Distribution coefficients for mercury in surficial sediments were lower than those in suspended material, likely due to remineralization. Preliminary estimates of mass balance indicate that air-water exchange processes such as evasion and wet deposition dominate the HgT budget, due to the basin's relatively small watershed area relative to lake area. In contrast, methylmercury cycling within Lake Superior is influenced more strongly by watershed sources, as well as by sedimentary sources and photodemethylation. The Hg cycle in Lake Superior is unique in that it is more similar in many aspects to that in marine systems than in small lakes, where management data for freshwaters typically originates.     

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.     

Eight boreal wetlands as sources and sinks for methyl mercury in relation to soil acidity, c/n ratio, and small-scale flooding

Four years of catchment export and wetland input-output mass balances are reported for inorganic Hg (Hg(inorg)), methyl mercury (MeHg), dissolved organic carbon (DOC), and sulfate in eight Swedish boreal wetlands. All wetlands had a history of artificial drainage and seven were subjected to small-scale flooding during the complete study period (two sites) or the two last years (five sites). We used an approach in which specific runoff data determined at hydrological stations situated at a distance from the studied sites were used in the calculation of water and element budgets. All wetlands except one were significant sinks for Hg(inorg). Seven wetlands were consistent sources of MeHg and one (an Alnus glutinosa swamp) was a significant sink. The pattern of MeHg yields was in good agreement with previously determined methylation and demethylation rates in the wetland soils of this study, with a maximum MeHg yield obtained in wetlands with an intermediate soil acidity (pH ～5.0) and C/N ratio (～20). We hypothesize that an increased nutrient status from poor to intermediate conditions promotes methylation over demethylation, whereas a further increase in nutrient status and trophy to meso- and eutrophic conditions promotes demethylation over methylation. Small-scale flooding showed no or moderate changes in MeHg yield, maintaining differences among wetlands related to nutrient status.     

Importance of the forest canopy to fluxes of methyl mercury and total mercury to boreal ecosystems

The forest canopy was an important contributor to fluxes of methyl mercury (MeHg) and total mercury (THg) to the forest floor of boreal uplands and wetlands and potentially to downstream lakes, at the Experimental Lakes Area (ELA), northwestern Ontario. The estimated fluxes of MeHg and THg in throughfall plus litterfall below the forest canopy were 2 and 3 times greater than annual fluxes by direct wet deposition of MeHg (0.9 mg of MeHg ha(-1)) and THg (71 mg of THg ha(-1)). Almost all of the increased flux of MeHg and THg under the forest canopy occurred as litterfall (0.14-1.3 mg of MeHg ha(-1) yr(-1) and 110-220 mg of THg ha(-1) yr(-1)). Throughfall added no MeHg and approximately 9 mg of THg ha(-1) yr(-1) to wet deposition at ELA, unlike in other regions of the world where atmospheric deposition was more heavily contaminated. These data suggest that dry deposition of Hg on foliage as an aerosol or reactive gaseous Hg (RGM) species is low at ELA, a finding supported by preliminary measurements of RGM there. Annual total deposition from throughfall and litterfall under a fire-regenerated 19-yr-old jack pine/birch forest was 1.7 mg of MeHg ha(-1) and 200 mg of THg ha(-1). We found that average annual accumulation of MeHg and THg in the surficial litter/fungal layer of soils since the last forest fire varied between 0.6 and 1.6 mg of MeHg ha(-1) and between 130 and 590 mg of THg ha(-1) among sites differing in drainage and soil moisture. When soil Hg accumulation sites were matched with similar sites where litterfall and throughfall were collected, measured fluxes of THg to the forest floor (sources) were similar to our estimates of longterm soil accumulation rates (sinks), suggesting that the Hg in litterfall and throughfall is a new and not a recycled input of Hg to forested ecosystems. However, further research is required to determine the proportion of Hg in litterfall that is being biogeochemically recycled within forest and wetland ecosystems and, thus, does not represent new inputs to the forest ecosystem.     

The rise and fall of mercury methylation in an experimental reservoir

For the past 9 years, we experimentally flooded a wetland complex (peatland surrounding an open water pond) at the Experimental Lakes Area (ELA), northwestern Ontario, Canada, to examine the biogeochemical cycling of methyl mercury (MeHg) in reservoirs. Using input-output budgets, we found that prior to flooding, the wetland complex was a net source of approximately 1.7 mg MeHg ha(-1) yr(-1) to downstream ecosystems. In the first year of flooding, net yields of MeHg from the reservoir increased 40-fold to approximately 70 mg MeHg ha(-1) yr(-1). Subsequently, annual net yields of MeHg from the reservoir declined (10-50 mg MeHg ha(-1) yr(-1)) but have remained well above natural levels. The magnitude and timing of Hg methylation in the flooded peat portion of the wetland reservoir were very different than in the open water region of the reservoir. In terms of magnitude, net Hg methylation rates in the peat in the first 2 years of flooding were 2700 mg ha(-1) yr(-1), constituting over 97% of the MeHg produced at the whole-ecosystem level. But in the following 3 years, there was a large decrease in the mass of MeHg in the flooded peat due to microbial demethylation. In contrast, concentrations of MeHg in the open water region and in zooplankton, and body burdens of Hg in cyprinid fish, remained high for the full 9 years of this study. Microbial activity in the open water region also remained high, as evidenced by continued high concentrations of dissolved CO2 and CH4. Thus, the large short-term accumulation of MeHg mass in the peat appeared to have only a small influence on concentrations of MeHg in the biota; rather MeHg accumulation in biota was sustained by the comparatively small ongoing net methylation of Hg in the flooded pond where microbial activity remained high. In large reservoirs, where the effects of wind and fetch are greater than in the small experimental reservoir we constructed, differences can occur in the timing and extent of peat and soil erosion, effecting either transport of MeHg to the food chain or the fueling of microbial activity in open water sediments, both of which could have important long-term implications for MeHg concentrations in predatory fish.     

Mercury in soils, lakes, and fish in Voyageurs National Park (Minnesota): importance of atmospheric deposition and ecosystem factors

Concentrations of methylmercury in game fish from many interior lakes in Voyageurs National Park (MN, U.S.A.) substantially exceed criteria for the protection of human health. We assessed the importance of atmospheric and geologic sources of mercuryto interior lakes and watersheds within the Park and identified ecosystem factors associated with variation in methylmercury contamination of lacustrine food webs. Geologic sources of mercury were small, based on analyses of underlying bedrock and C-horizon soils, and nearly all mercury in the 0- and A-horizon soils was derived from atmospheric deposition. Analyses of dated sediment cores from five lakes showed that most (63% +/- 13%) of the mercury accumulated in lake sediments during the 1900s was from anthropogenic sources. Contamination of food webs was assessed by analysis of whole, 1-year-old yellow perch (Perca flavescens), a regionally important prey fish. The concentrations of total mercury in yellow perch and of methylmercury in lake water varied substantially among lakes, reflecting the influence of ecosystem processes and variables that affect the microbial production and abundance of methylmercury. Models developed with the information-theoretic approach (Akaike Information Criteria) identified lake water pH, dissolved sulfate, and total organic carbon (an indicator of wetland influence) as factors influencing methylmercury concentrations in lake water and fish. We conclude that nearly all of the mercury in fish in this seemingly pristine     

Influence of dissolved organic carbon on methylmercury bioavailability across Minnesota stream ecosystems

Stream ecosystems are widely contaminated by mercury (Hg) via atmospheric transport and deposition in watersheds. Dissolved organic carbon (DOC) is well-known to be the dominant ligand for aqueous methylmercury (MeHg), the bioaccumulative form of Hg in aquatic food webs. However, it is less clear if and how the concentration and character (e.g., aromaticity) of DOC influences the availability of dissolved MeHg to stream food webs. In this work, we analyzed total-Hg and/or MeHg concentrations in water, seston, and macroinvertebrates (filter-feeding hydropsychid caddisflies), and other physiochemical properties in 30 streams along a south-north geographic gradient in eastern Minnesota that corresponds to substantial changes in dominant land cover (i.e., agriculture, urban, wetland, and forest). In general, MeHg concentrations in seston and hydropsychids were higher in watersheds with more forest and wetland coverage, and increased with dissolved MeHg concentration. However, we found that the efficiency of MeHg incorporation into the stream food webs (i.e., bioconcentration factors of MeHg in both seston and hydropsychids, BCF(MeHg) = solid MeHg ÷ dissolved MeHg) decreased significantly with DOC concentration and aromaticity, suggesting that MeHg bioavailability to the base of food webs was attenuated at higher levels of terrestrial DOC. Therefore, our findings suggest that there is a dual role of DOC on MeHg cycling in streams: terrestrial DOC acts as the primary carrier ligand of dissolved MeHg for transport into surface waters, yet this aromatic DOC also attenuates dissolved MeHg uptake by aquatic food webs. Thus, consideration of MeHg bioavailability and its environmental regulation could help improve predictive models of MeHg bioaccumulation in stream ecosystems.     

Abiotic production of methylmercury by solar radiation

Methylmercury [MeHg(I) in the aerobic surface water of lakes is thought to be rapidly degraded, but contrary to expectations, we show that MeHg(I) concentrations often increase during sunlight hours or remain relatively constant. We hypothesized that there were water column processes that generated MeHg(I) and that these processes were linked to dissolved organic matter (DOM) and solar radiation. A 2-day diurnal pattern of MeHg(I) in surface water with corresponding bottled controls was assessed for two contrasting lakes in Kejimikujik, Nova Scotia, Canada. Following this study, a tangential ultrafiltrator was used to size-fractionate and generate a concentration gradient of DOM from four different lakes located near Lac Berthelot, Quebec, Canada. The watersheds of two of these lakes were not substantially logged whereas the other two had been extensively logged. Different size fractions of DOM as well as different concentrations of DOM were exposed to sunlight for varying periods of time. We observed that, in Keiimikujik, the concentration of MeHg(I) in surface waters peaked in the early afternoon. Furthermore, this also occurred in bottled water for one of the lakes, Puzzle, eliminating the possibility that in-lake mixing played a role in this pattern. The formation of MeHg(I) was found to be dependent on the size fraction and amount of DOM present in the water. Specifically, DOM less than 5 kDa or between 30 and 300 kDa generated MeHg(I) when exposed to sunlight, but larger fractions did not. Furthermore, although data are limited, we found that water from lakes with logged watersheds generated MeHg(I) when exposed to sunlight, whereas water from lakes with low levels of logging in the undisturbed watersheds did not. Our results demonstrate that MeHg(I) can be formed in freshwaters of certain lakes in response to solar radiation. This photoproduction of MeHg(I) is dependent on DOM concentrations and type, with the importance of water chemistry not yet clear. The significance of this process to freshwater lakes and the mechanism responsible for MeHg(I) photoproduction is still unclear, but a correction in the conventional wisdom that MeHg(I) is rapidly photodegraded is timely.     

Seabird guano is an efficient conveyer of persistent organic pollutants (POPs) to Arctic lake ecosystems

Migratory seabirds have been linked to localized "hotspots" of contamination in remote Arctic lakes. One of these lakes is Lake Ellasj?en on Bj?rn?ya in the Barents Sea. Here we provide quantitative evidence demonstrating that even relatively small populations of certain seabird species can lead to major impacts for ecosystems. In the present example, seabird guano accounts for approximately 14% of the contaminant inventory of the Lake Ellasj?en catchment area, approximately 80% of the contaminant inventory of the lake itself, and is approximately thirty times more efficient as a contaminant transport pathway compared to atmospheric long-range transport. We have further shown that this biological transport mechanism is an important contaminant exposure route for ecosystems, responsible for POPs levels in freshwater fish that are an order of magnitude higher than those in Arctic top predators. Given the worldwide presence of seabird colonies in coastal marine areas where resources are also harvested by humans, this biological transport pathway may be a greater source of dietary contamination than is currently recognized with consequent risks for human health.     

Sulfate addition increases methylmercury production in an experimental wetland

Atmospheric mercury is the dominant Hg source to fish in northern Minnesota and elsewhere. However, atmospherically derived Hg must be methylated prior to accumulating in fish. Sulfate-reducing bacteria are thought to be the primary methylators of Hg in the environment. Previous laboratory and field mesocosm studies have demonstrated an increase in methylmercury (MeHg) levels in sediment and peatland porewaters following additions of sulfate. In the current ecosystem-scale study, sulfate was added to half of an experimental wetland at the Marcell Experimental Forest located in northeastern Minnesota, increasing annual sulfate load by approximately four times relative to the control half of the wetland. Sulfate was added on four separate occasions during 2002 and delivered via a sprinkler system constructed on the southeast half (1.0 ha) of the S6 experimental wetland. MeHg levels were monitored in porewater and in outflow from the wetland. Prior to the first sulfate addition, MeHg concentrations (filtered, 0.7 microm) were not statistically different between the control (0.47 +/- 0.10 ng L(-1), n = 12; mean +/- one standard error) and experimental 0.52 +/- 0.05 ng L(-1), n = 18) halves. Following the first addition in May 2002, MeHg porewater concentrations increased to 1.63 +/- 0.27 ng L(-1) two weeks after the addition, a 3-fold increase. Subsequent additions in July and September 2002 did not raise porewater MeHg, but the applied sulfate was not observed in porewaters 24 h after addition. MeHg concentrations in outflow from the wetland also increased leading to an estimated 2.4x increase of MeHg flux from the wetland. Our results demonstrate enhanced methylation and increased MeHg concentrations within the wetland and in outflow from the wetland suggesting that decreasing sulfate deposition rates would lower MeHg export from wetlands.     

Review of methane mitigation technologies with application to rapid release of methane from the Arctic

Methane is the most important greenhouse gas after carbon dioxide, with particular influence on near-term climate change. It poses increasing risk in the future from both direct anthropogenic sources and potential rapid release from the Arctic. A range of mitigation (emissions control) technologies have been developed for anthropogenic sources that can be developed for further application, including to Arctic sources. Significant gaps in understanding remain of the mechanisms, magnitude, and likelihood of rapid methane release from the Arctic. Methane may be released by several pathways, including lakes, wetlands, and oceans, and may be either uniform over large areas or concentrated in patches. Across Arctic sources, bubbles originating in the sediment are the most important mechanism for methane to reach the atmosphere. Most known technologies operate on confined gas streams of 0.1% methane or more, and may be applicable to limited Arctic sources where methane is concentrated in pockets. However, some mitigation strategies developed for rice paddies and agricultural soils are promising for Arctic wetlands and thawing permafrost. Other mitigation strategies specific to the Arctic have been proposed but have yet to be studied. Overall, we identify four avenues of research and development that can serve the dual purposes of addressing current methane sources and potential Arctic sources: (1) methane release detection and quantification, (2) mitigation units for small and remote methane streams, (3) mitigation methods for dilute (<1000 ppm) methane streams, and (4) understanding methanotroph and methanogen ecology.     

Redox chemistry in Minnesota streams during episodes of increased methylmercury discharge

Mercury (Hg) and methylmercury (MeHg) are flushed from watersheds during hydrological events, contaminating downstream surface waters and resident fish populations. We monitored total mercury (THg), MeHg, and ancillary water chemistry parameters in two streams (Cedar Creek and Trott Brook) in east-central Minnesota on a weekly or semiweekly basis from April through October 2003. Heavy precipitation in late June resulted in discrete episodes of high concentrations (>1.2 ng/L) of MeHg in both streams in early July. The MeHg/THg ratio increased from 0.15 to 0.36 in Cedar Creek and from 0.13 to 0.46 in Trott Brook during the event. The high MeHg concentrations were accompanied by low dissolved oxygen concentrations and increased concentrations of dissolved organic carbon, Mn, Fe, and orthophosphate. A prolonged absence of precipitation during August and early September brought stream levels back to baseflow values, and MeHg concentrations decreased to less than 0.1 ng/L. These results suggest that warm-weather, high-discharge events are the primary route of export of MeHg from these watersheds, and baseflow contributes much less MeHg to downstream waters. The redox water chemistry during the,events sampled here suggests that MeHg in these streams is discharged from wetland areas where anoxic/anaerobic conditions prevail.     

Occurrence of organophosphorus flame retardant and plasticizers in three volcanic lakes of central Italy

The concentration levels, distribution, and seasonal fluctuations of 12 organophosphorus flame retardants and plasticizers (OPs), of which some are reported to be toxic to aquatic organisms, were investigated in lakes from June 2006 to June 2007. Three volcanic lakes located in the Lazio area (Central Italy) and characterized by a different anthropical impact were selected. Analysis of lake water samples showed that in closed ecosystems (hydrogeological systems), such as small volcanic lakes, OP contamination may occur even in the absence of industries and treated or untreated waste discharges. The selected substances were found at ng/L concentrations in all lakes. In the two more anthropized lakes tributyl phosphate and tripropyl phosphate were the most abundant OPs, with peaks of respectively 784 and 951 ng/L. Maximum pollution levels were reached in October-November, and concentrations decreased to a minimum value in March-April. Chlorinated OPs showed the same trend, but their concentrations were 1 order of magnitude lower and the level decreasing was shifted with respectto alkyl OPs. On the contrary, tris(2-butoxyethyl) phosphate concentrations were quite similar among all water samples analyzed, indicating that their sources were different in nature. One of the three lakes is an important source of drinkable water, so nine wells situated in its neighborhood were also examined. No correlation between lake water and groundwater contamination could be found.     

Spatial characteristics of net methylmercury production hot spots in peatlands

Many wetlands are sources of methylmercury (MeHg) to surface waters, yet little information exists about the distribution of MeHg within wetlands. Total mercury (THg) and MeHg in peat pore waters were studied in four peatlands in spring, summer, and fall 2005. Marked spatial variability in the distribution of MeHg, and %MeHg as a proxy for net MeHg production, was observed, with highest values occurring in discrete zones. We denote these zones "MeHg hot spots", defined as an area where the pore water %MeHg exceeded the 90th percentile of the data set (n=463) or >22% of THg as MeHg. MeHg hot spots occurred near the interface between peatland and the upland watershed with few exceptions. The %MeHg in pore water was significantly less in peatland interiors compared to upland-peatland interface zones, with the significance of these differences related to the delineation of the boundary between the two areas. Although further research is necessary, our data suggest that the occurrence of MeHg hot spots is related to the transport of solutes in upland runoff to the peatland perimeter and not to the accumulation of MeHg in this zone as a result of transport from either the peatland interior or the surrounding upland watershed. These findings augment the understanding of peatland MeHg production in upland-peatland watersheds, provide guidance for more accurate quantification of MeHg pool sizes in the landscape, and a spatial framework forthe further study of mercury methylation processes in peatlands.     

Absence of fractionation of mercury isotopes during trophic transfer of methylmercury to freshwater fish in captivity

We performed two controlled experiments to determine the amount of mass-dependent and mass-independent fractionation (MDF and MIF) of methylmercury (MeHg) during trophic transfer into fish. In experiment 1, juvenile yellow perch (Perca flavescens) were raised in captivity on commercial food pellets and then their diet was either maintained on unamended food pellets (0.1 μg/g MeHg) or was switched to food pellets with 1.0 μg/g or 4.0 μg/g of added MeHg, for a period of 2 months. The difference in δ(202)Hg (MDF) and Δ(199)Hg (MIF) between fish tissues and food pellets with added MeHg was within the analytical uncertainty (δ(202)Hg, 0.07 ‰; Δ(199)Hg, 0.06 ‰), indicating no isotope fractionation. In experiment 2, lake trout (Salvelinus namaycush) were raised in captivity on food pellets and then shifted to a diet of bloater (Coregonus hoyi) for 6 months. The δ(202)Hg and Δ(199)Hg of the lake trout equaled the isotopic composition of the bloater after 6 months, reflecting reequilibration of the Hg isotopic composition of the fish to new food sources and a lack of isotope fractionation during trophic transfer. We suggest that the stable Hg isotope ratios in fish can be used to trace environmental sources of Hg in aquatic ecosystems.     

Development of an ecosystem sensitivity model regarding mercury levels in fish using a preference modeling methodology: application to the Canadian boreal system

The objective of this study is to use a preference modeling methodology as a predictive tool to roughly assess the sensitivity of the ecosystems regarding mercury (Hg) concentrations in fish. We apply a preference modeling methodology to rank lakes within the boreal forest from highest to lowest Hg concentrations in fish using simple environmental factors. Among the numerous variables influencing Hg fate in the environment, we only retain simple key indicators that are expected to influence Hg concentrations in fish tissue such as watershed characteristics of the lake (percentage of the catchment area of the lake, ratio of drainage area versus lake area, percentage of the drainage area of the lake as wetlands, land use, and clear-cutting), lake characteristics (chlorophyll, dissolved organic carbon, pH, and fishing intensity), and atmospheric Hg inputs. Preliminary results of modeling that we carried out using a set of Canadian lakes of boreal forest data are promising. With only a minimum set of criteria, we are able to reproduce the trends of Hg contamination in fish caught in six regions of the Canadian boreal forest and classify the sensitivity of the ecosystems to Hg loadings in three categories: high, medium, and low.