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.

Role of Ester Sulfate and Organic Disulfide in Mercury Methylation in Peatland Soils.

We examined the composition and spatial correlation of sulfur and mercury pools in peatland soil profiles by measuring sulfur speciation by 1s X-ray absorption near-edge structure spectrocopy and mercury concentrations by cold vapor atomic fluorescence spectroscopy. Also investigated were the methylation/demethylation rate constants and the presence of hgcAB genes with depth. Methylmercury (MeHg) concentration and organic disulfide were spatially correlated and had a significant positive correlation (p < 0.05). This finding is consistent with these species being products of dissimilatory sulfate reduction. Conversely, a significant negative correlation between organic monosulfides and MeHg was observed, which is consistent with a reduction in Hg(II) bioavailability via complexation reactions. Finally, a significant positive correlation between ester sulfate and instantaneous methylation rate constants was observed, which is consistent with ester sulfate being a substrate for mercury methylation via dissimilatory sulfate reduction. Our findings point to the importance of organic sulfur species in mercury methylation processes, as substrates and products, as well as potential inhibitors of Hg(II) bioavailability. For a peatland system with sub-µmol L-1 porewater concentrations of sulfate and hydrogen sulfide, our findings indicate that the solid-phase sulfur pools, which have a much larger sulfur concentration range, may be accessible to microbial activity or exchanging with the porewater.

Mercury dynamics in the pore water of peat columns during experimental freezing and thawing.

Biogeochemical processes in northern peatland ecosystems are influenced by seasonal temperature fluctuations that are changing with the climate. Methylmercury (MeHg), commonly produced in peatlands, affects downstream waters; therefore, it is important to understand how temperature transitions affect mercury (Hg) dynamics. We investigated how the freeze-thaw cycle influences belowground peat pore water total Hg (THg), MeHg, and dissolved organic carbon (DOC). Four large, intact peat columns were removed from an ombrotrophic peat bog and experimentally frozen and thawed. Pore water was sampled across seven depths in the peat columns during the freeze-thaw cycle and analyzed for THg, MeHg, and DOC concentrations. Freezing results showed increased concentrations of THg below the ice layers and limited change in MeHg concentrations. During thawing, THg concentrations significantly increased, whereas MeHg concentrations decreased. Limited bromide movement and depth decreases in THg and DOC concentrations were associated with increased bulk density and degree of humification in the peat. The experiment demonstrates the effects of the freeze-thaw cycle on Hg concentrations in northern peatlands. Changes to freeze-thaw cycles with climate change may exacerbate Hg cycling and transport processes in peatland environments.

Temporal fluctuations in young-of-the-year yellow perch mercury bioaccumulation in lakes of northeastern Minnesota.

Identifying what determines fish mercury (Hg) bioaccumulation remains a key scientific challenge. While there has been substantial research on spatial variation in fish Hg bioaccumulation, the factors that influence temporal fluctuations in fish Hg have received less attention to date. In this study, we built upon a growing body of research investigating young-of-the-year (YOY) yellow perch Hg bioaccumulation and investigated annual fluctuations in YOY yellow perch Hg in six lakes in northeastern Minnesota over eight years. After accounting for spatial variation between the study lakes, we used model averaging to identify the lake physiochemical and climate factors that best explain temporal variation in fish biomass and fish Hg. Fish biomass of YOY yellow perch had a positive relationship with chlorophyll-α and total Kjeldahl nitrogen and a negative relationship with dissolved iron and dissolved oxygen. There was a positive relationship between annual variation in yellow perch Hg concentration and annual variation in lake total suspended solids, dissolved Fe and pH. Additionally, there was a negative relationship between fish Hg concentration and lake total Kjeldahl nitrogen and growing degree days. Together, our results suggest that annual variation in allochthonous inputs from the watershed, in-lake processes, and climate variables can explain temporal patterns in Hg bioaccumulation and growth biodilution is an important process controlling yellow perch Hg concentrations.

Response of pedogenic magnetite to changing vegetation in soils developed under uniform climate, topography, and parent material.

Pedogenesis produces fine-grained magnetic minerals that record important information about the ambient climatic conditions present during soil formation. Yet, differentiating the compounding effects of non-climate soil forming factors is a nontrivial challenge that must be overcome to establish soil magnetism as a trusted paleoenvironmental tool. Here, we isolate the influence of vegetation by investigating magnetic properties of soils developing under uniform climate, topography, and parent material but changing vegetation along the forest-prairie ecotone in NW Minnesota. Greater absolute magnetic enhancement in prairie soils is related to some combination of increased production of pedogenic magnetite in prairie soils, increased deposition of detrital magnetite in prairies from eolian processes, or increased dissolution of fine-grained magnetite in forest soils due to increased soil moisture and lower pH. Yet, grain-size specific magnetic properties associated with pedogenesis, for example relative frequency dependence of susceptibility and the ratio of anhysteretic to isothermal remanent magnetization, are insensitive to changing vegetation. Further, quantitative unmixing methods support a fraction of fine-grained pedogenic magnetite that is highly consistent. Together, our findings support climate as a primary control on magnetite production in soils, while demonstrating how careful decomposition of bulk magnetic properties is necessary for proper interpretation of environmental magnetic data.

Yellow Perch (Perca flavescens) Mercury Unaffected by Wildland Fires in Northern Minnesota.

Wildland fire can alter mercury (Hg) cycling on land and in adjacent aquatic environments. In addition to enhancing local atmospheric Hg redeposition, fire can influence terrestrial movement of Hg and other elements into lakes via runoff from burned upland soil. However, the impact of fire on water quality and the accumulation of Hg in fish remain equivocal. We investigated the effects of fire-specifically, a low-severity prescribed fire and moderate-severity wildfire-on young-of-the-year yellow perch () and lake chemistry in a small remote watershed in the Boundary Waters Canoe Area Wilderness in northeastern Minnesota. We used a paired watershed approach: the fire-affected watershed was compared with an adjacent, unimpacted (reference) watershed. Prior to fire, upland organic horizons in the two study watersheds contained 1549 µg Hg m on average. Despite a 19% decrease in upland organic horizon Hg stocks due to the moderate severity wildfire fire, fish Hg accumulation and lake productivity were not affected by fire in subsequent years. Instead, climate and lake water levels were the strongest predictors of lake chemistry and fish responses in our study lakes over 9 yr. Our results suggest that low- to moderate-severity wildland fire does not alter lake productivity or Hg accumulation in young-of-the-year yellow perch in these small, shallow lakes in the northern deciduous and boreal forest region.

Toward Bioremediation of Methylmercury Using Silica Encapsulated Escherichia coli Harboring the mer Operon.

Mercury is a highly toxic heavy metal and the ability of the neurotoxin methylmercury to biomagnify in the food chain is a serious concern for both public and environmental health globally. Because thousands of tons of mercury are released into the environment each year, remediation strategies are urgently needed and prompted this study. To facilitate remediation of both organic and inorganic forms of mercury, Escherichia coli was engineered to harbor a subset of genes (merRTPAB) from the mercury resistance operon. Protein products of the mer operon enable transport of mercury into the cell, cleavage of organic C-Hg bonds, and subsequent reduction of ionic mercury to the less toxic elemental form, Hg(0). E. coli containing merRTPAB was then encapsulated in silica beads resulting in a biological-based filtration material. Performing encapsulation in aerated mineral oil yielded silica beads that were smooth, spherical, and similar in diameter. Following encapsulation, E. coli containing merRTPAB retained the ability to degrade methylmercury and performed similarly to non-encapsulated cells. Due to the versatility of both the engineered mercury resistant strain and silica bead technology, this study provides a strong foundation for use of the resulting biological-based filtration material for methylmercury remediation.

Distribution and uptake dynamics of mercury in leaves of common deciduous tree species in Minnesota, U.S.A.

A sequential extraction technique for compartmentalizing mercury (Hg) in leaves was developed based on a water extraction of Hg from the leaf surface followed by a solvent extraction of the cuticle. The bulk of leaf Hg was found in the tissue compartment (90-96%) with lesser amounts in the surface and cuticle compartments. Total leaf concentrations of Hg varied among species and was most closely correlated with the number of stomates per sample, supporting the hypothesis that stomatal uptake of atmospheric Hg (most likely Hg(0)) is a potential uptake pathway. Mercury concentrations in leaves were monitored from emergence to senescence and showed a strong positive correlation with leaf age. Leaves accumulated Hg throughout the growing season; the highest uptake rates coincided with periods of high photosynthetic activity. Concentrations of Hg in leaf tissue increased steadily throughout the season, but no such trends were observed for surficial or cuticular accumulation. Factors affecting the variability of Hg in leaves were analyzed to improve protocols for the potential use of leaves as passive monitors of atmospheric Hg. Results show that total leaf Hg concentrations are affected by leaf age and leaf placement in the crown.

Mercury bioaccumulation in a stream network.

Mercury (Hg) contamination is common in stream and river ecosystems, but factors mediating Hg cycling in the flowing waters are much less understood than inthe lakes and wetlands. In this study, we examined the spatial patterns of methylmercury (MeHg) concentrations in the dominant groups of aquatic insect larvae across a network of streams (drainage area ranging from 0.5 to 150 km2) in northern California during summer baseflow conditions. We found that, with the exception of water striders, all invertebrate groups showed significant (p < 0.05) increases in MeHg concentrations with drainage area. The largest stream in our study watershed, the South Fork Eel River, had the highest aqueous MeHg concentration (unfiltered: 0.13-0.17 ng L(-1)) while most of the upstream tributaries had aqueous MeHg concentrations close to or below the established detection limits (0.02 ng L(-1)). A filamentous alga abundant in South Fork Eel River (Cladophora glomerata) had an exceptionally high fraction of total-Hg as MeHg (i.e., %MeHg from 50-100%). Since other potential hotspots of in-stream Hg methylation (e.g., surface sediment and deep pools) had %MeHg lower than or similar to surface water (approximately 14%), we hypothesize that Cladophora and possibly other autotrophs may serve as hotspots of in-stream MeHg production in this bedrock-dominated stream. Recent studies in other regions concluded that wetland abundance in the watershed is the predominant factor in governing Hg concentrations of stream biota. However, our results show that in the absence of wetlands, substantial spatial variation of Hg bioaccumulation can arise in stream networks due to the influence of in-stream processes.

Forest fire effects on mercury deposition in the boreal forest.

Particulate Hg (pHg) is a component of smoke from biomass burning and has the potential for local redeposition. Throughfall (precipitation collected beneath a conifer or deciduous canopy) and open precipitation samples were collected pre- and postfire in 2005 and 2006 using passive precipitation collectors across the Superior National Forest, located in northern Minnesota, USA. Samples were collected approximately every two weeks and analyzed for total Hg (THg) and methyl Hg (MeHg). THg concentrations increased significantly postfire in conifer throughfall (> 4x increase), open precipitation (2.5x), and when all canopy types were considered (2.9x). MeHg concentrations also increased after fire regardless of the covertype (conifer throughfall: 10x increase; open precipitation: 3.5x increase; deciduous throughfall: 1.7x increase; all canopy types analyzed together: 8x increase). Total Hg deposition increased significantly under conifer cover (3.8x). Methyl Hg deposition increased significantly after fire when all canopy types were analyzed together (4.6x) and in conifer throughfall (5.9x). Canopy type influenced the magnitude of postfire THg and MeHg increase and the duration of elevated MeHg levels. Particulate Hg present in forest fire smoke represents a short-term source of increased Hg in the atmosphere that is available for local redeposition during and following fire.

Effects of stream water chemistry and tree species on release and methylation of mercury during litter decomposition.

Foliage of terrestrial plants provides an important energy and nutrient source to aquatic ecosystems but also represents a potential source of contaminants, such as mercury (Hg). In this study, we examined how different stream water types and terrestrial tree species influenced the release of Hg from senesced litter to the water and its subsequent methylation during hypoxic litter decomposition. After laboratory incubations of maple leaf litter for 66 days, we observed 10-fold differences in dissolved Hg (DHg, < 0.45-microm) concentrations among different stream water types and more than 50-fold differences in dissolved methylmercury (DMeHg) concentrations. Percent MeHg (i.e., DMeHg x 100 / DHg on day 66) varied from 23-102% across seven natural stream water types. In general, stream waters with higher dissolved sulfate, suspended solid, and chlorophyll-a concentrations (e.g., eutrophic streams draining agricultural land) are associated with higher Hg release and methylation compared to more pristine sites (e.g., clear waters from coldwater trout stream). Across six tree species collected at the same site and incubated with the same source water, litter from slower decomposing species (e.g., cedar and pine) yielded higher DHg concentrations than those with more labile carbon (e.g., maple and birch). Percent MeHg, however, was relatively similar among different leaf species (i.e., 61-86%). Our study is the first to demonstrate that stream water chemistry and terrestrial plant litter characteristics are important factors determining Hg release and methylation during hypoxic litter decomposition. These results suggest that certain watershed and aquatic ecosystem properties can determine the levels of MeHg inputs during litterfall events.

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.