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.

Soil metabolome response to whole-ecosystem warming at the Spruce and Peatland Responses under Changing Environments experiment.

In this study, a suite of complementary environmental geochemical analyses, including NMR and gas chromatography-mass spectrometry (GC-MS) analyses of central metabolites, Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) of secondary metabolites, and lipidomics, was used to investigate the influence of organic matter (OM) quality on the heterotrophic microbial mechanisms controlling peatland CO2, CH4, and CO2:CH4 porewater production ratios in response to climate warming. Our investigations leverage the Spruce and Peatland Responses under Changing Environments (SPRUCE) experiment, where air and peat warming were combined in a whole-ecosystem warming treatment. We hypothesized that warming would enhance the production of plant-derived metabolites, resulting in increased labile OM inputs to the surface peat, thereby enhancing microbial activity and greenhouse gas production. Because shallow peat is most susceptible to enhanced warming, increases in labile OM inputs to the surface, in particular, are likely to result in significant changes to CO2 and CH4 dynamics and methanogenic pathways. In support of this hypothesis, significant correlations were observed between metabolites and temperature consistent with increased availability of labile substrates, which may stimulate more rapid turnover of microbial proteins. An increase in the abundance of methanogenic genes in response to the increase in the abundance of labile substrates was accompanied by a shift toward acetoclastic and methylotrophic methanogenesis. Our results suggest that as peatland vegetation trends toward increasing vascular plant cover with warming, we can expect a concomitant shift toward increasingly methanogenic conditions and amplified climate-peatland feedbacks.

Nitrogen and phosphorus cycling in an ombrotrophic peatland: a benchmark for assessing change.

Aims: Slow decomposition and isolation from groundwater mean that ombrotrophic peatlands store a large amount of soil carbon (C) but have low availability of nitrogen (N) and phosphorus (P). To better understand the role these limiting nutrients play in determining the C balance of peatland ecosystems, we compile comprehensive N and P budgets for a forested bog in northern Minnesota, USA. Methods: N and P within plants, soils, and water are quantified based on field measurements. The resulting empirical dataset are then compared to modern-day, site-level simulations from the peatland land surface version of the Energy Exascale Earth System Model (ELM-SPRUCE). Results: Our results reveal N is accumulating in the ecosystem at 0.2 ± 0.1 g N m-2 year-1 but annual P inputs to this ecosystem are balanced by losses. Biomass stoichiometry indicates that plant functional types differ in N versus P limitation, with trees exhibiting a stronger N limitation than ericaceous shrubs or Sphagnum moss. High biomass and productivity of Sphagnum results in the moss layer storing and cycling a large proportion of plant N and P. Comparing our empirically-derived nutrient budgets to ELM-SPRUCE shows the model captures N cycling within dominant plant functional types well. Conclusions: The nutrient budgets and stoichiometry presented serve as a baseline for quantifying the nutrient cycling response of peatland ecosystems to both observed and simulated climate change. Our analysis improves our understanding of N and P dynamics within nutrient-limited peatlands and represents a crucial step toward improving C-cycle projections into the twenty-first century.

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.

Climate Sensitivity of Peatland Methane Emissions Mediated by Seasonal Hydrologic Dynamics.

Peatlands are among the largest natural sources of atmospheric methane (CH4) worldwide. Peatland emissions are projected to increase under climate change, as rising temperatures and shifting precipitation accelerate microbial metabolic pathways favorable for CH4 production. However, how these changing environmental factors will impact peatland emissions over the long term remains unknown. Here, we investigate a novel data set spanning an exceptionally long 11 years to analyze the influence of soil temperature and water table elevation on peatland CH4 emissions. We show that higher water tables dampen the springtime increases in CH4 emissions as well as their subsequent decreases during late summer to fall. These results imply that any hydroclimatological changes in northern peatlands that shift seasonal water availability from winter to summer will increase annual CH4 emissions, even if temperature remains unchanged. Therefore, advancing hydrological understanding in peatland watersheds will be crucial for improving predictions of CH4 emissions.

Variation in peatland porewater chemistry over time and space along a bog to fen gradient.

Porewater chemistry is an integrative measure of the physical, chemical, and biological processes occurring within peatland ecosystems, and therefore some chemistry measures (e.g., pH, calcium concentrations) have been used to classify bog vs fen peatlands. However, porewater sampling is often limited in spatial and temporal resolution, highlighting the need for a more comprehensive analysis of spatiotemporal variation in porewater chemistry. We examined depth profiles of porewater chemistry in four nearby peatlands that fall along a bog to rich fen gradient in northcentral Minnesota, USA. Porewater was sampled ~monthly during one ice-free season from three replicate piezometer nests per peatland to quantify temporal and spatial variability of those depth profiles. Porewater depth profiles of pH, calcium and total organic carbon concentrations, and δ18O-H2O varied along the bog to fen gradient, but total nitrogen and total phosphorus concentrations did not. Porewater chemistry was similar in the bogs and poor fen which were all quite different from the rich fen. In contrast, temporal and spatial variation in porewater chemistry, quantified using coefficients of variation, did not differ between bogs and fens despite the hypothesis that variation in porewater chemistry would be lower in fens than bogs due to the perennial throughput of large volumes of discharging groundwater in the rich fen. Spatial and temporal variability in porewater chemistry across all peatland types highlights the importance of collecting porewater samples in multiples over time in both near-surface and deeper peats. This variation can be important when scaling findings to the peatland scale, assessing the representativeness of peatlands within a larger landscape, and understanding variability in solute export to downstream ecosystems.

Unprocessed Atmospheric Nitrate in Waters of the Northern Forest Region in the U.S. and Canada.

Little is known about the regional extent and variability of nitrate from atmospheric deposition that is transported to streams without biological processing in forests. We measured water chemistry and isotopic tracers (δ18O and δ15N) of nitrate sources across the Northern Forest Region of the U.S. and Canada and reanalyzed data from other studies to determine when, where, and how unprocessed atmospheric nitrate was transported in catchments. These inputs were more widespread and numerous than commonly recognized, but with high spatial and temporal variability. Only 6 of 32 streams had high fractions (>20%) of unprocessed atmospheric nitrate during baseflow. Seventeen had high fractions during stormflow or snowmelt, which corresponded to large fractions in near-surface soil waters or groundwaters, but not deep groundwater. The remaining 10 streams occasionally had some (<20%) unprocessed atmospheric nitrate during stormflow or baseflow. Large, sporadic events may continue to be cryptic due to atmospheric deposition variation among storms and a near complete lack of monitoring for these events. A general lack of observance may bias perceptions of occurrence; sustained monitoring of chronic nitrogen pollution effects on forests with nitrate source apportionments may offer insights needed to advance the science as well as assess regulatory and management schemes.

Contemporary Mobilization of Legacy Pb Stores by DOM in a Boreal Peatland.

We examined how different landscape areas in a catchment containing a northern ombrotrophic peatland and upland mineral soils responded to dramatic decreases in atmospheric deposition of lead (Pb). Pb concentrations in the outflow stream from the peatland measured from 2009-2015 indicated continued mobilization and export of Pb derived from historic inputs to the bog. In contrast, Pb concentrations in surface peat and runoff from upland mineral soils have declined in response to reductions in atmospheric deposition. Relative to the early 1980s, Pb concentrations in the streamflow decreased only ∼50%, while Pb in surface peat and upland subsurface runoff decreased by more than 90%. Water level fluctuations in the slow-accumulating peat have allowed dissolved organic matter (DOM) to continue mobilizing Pb deposited in the peatland decades earlier. Strong correlations between dissolved organic carbon (DOC) and Pb concentrations in outflow from the peatland and in bog porewaters demonstrate Pb mobility related to DOM production. Peat stores of Pb in 2016 were less than or equal to those reported in the early 1980s despite the dry mass inventory increasing by 60-80%. Much of the loss in Pb stored in peat can be accounted for by stream runoff from the peatland.

New Insights on Ecosystem Mercury Cycling Revealed by Stable Isotopes of Mercury in Water Flowing from a Headwater Peatland Catchment.

Stable isotope compositions of mercury (Hg) were measured in the outlet stream and in soil cores at different landscape positions in a 9.7-ha boreal upland-peatland catchment. An acidic permanganate/persulfate digestion procedure was validated for water samples with high dissolved organic matter (DOM) concentrations through Hg spike addition analysis. We report a relatively large variation in mass-dependent fractionation (δ202Hg; from -2.12 to -1.32‰) and a smaller, but significant, variation of mass-independent fractionation (Δ199Hg; from -0.35 to -0.12‰) during two years of sampling with streamflow varying from 0.003 to 7.8 L s-1. Large variations in δ202Hg occurred only during low streamflow (<0.6 L s-1), which suggest that under high streamflow conditions a peatland lagg zone between the bog (3.0 ha) and uplands (6.7 ha) becomes the dominant source of Hg in downstream waters. Further, a binary mixing model showed that except for the spring snowmelt period, Hg in streamwater from the catchment was mainly derived from dry deposition of gaseous elemental Hg (73-95%). This study demonstrates the usefulness of Hg isotopes for tracing sources of Hg deposition, which can lead to a better understanding of the biogeochemical cycling and hydrological transport of Hg in headwater catchments.

Comparisons of soil nitrogen mass balances for an ombrotrophic bog and a minerotrophic fen in northern Minnesota.

We compared nitrogen (N) storage and flux in soils from an ombrotrophic bog with that of a minerotrophic fen to quantify the differences in N cycling between these two peatlands types in northern Minnesota (USA). Precipitation, atmospheric deposition, and bog and fen outflows were analyzed for nitrogen species. Upland and peatland soil samples were analyzed for N content, and for ambient (DN) and potential (DEA) denitrification rates. Annual atmospheric deposition was: 0.88-3.07kg NH4(+)ha(-1)y(-1); 1.37-1.42kg NO3(-)ha(-1)y(-1); 2.79-4.69kg TNha(-1)y(-1). Annual N outflows were: bog-0.01-0.04kg NH4(+)ha(-1)y(-1), NO3(-) 0.01-0.06kgha(-1)y(-1), and TN 0.11-0.69kgha(-1)y(-1); fen-NH4(+) 0.01-0.16kgha(-1)y(-1), NO3(-) 0.29-0.48kgha(-1)y(-1), and TN 1.14-1.61kgha(-1)y(-1). Soil N content depended on location within the bog or fen, and on soil depth. DN and DEA rates were low throughout the uplands and peatlands, and were correlated with atmospheric N deposition, soil N storage, and N outflow. DEA was significantly greater than DN indicating C or N limitation of the denitrification process. We highlight differences between the bog and fen, between the upland mineral soils and peat, and the importance of biogeochemical hotspots within the peatlands. We point out the importance of organic N storage, as a source of N for denitrification, and propose a plausible link between organic N storage, denitrification and N export from peatlands. Finally, we considered the interactions of microbial metabolism with nutrient availability and stoichiometry, and how N dynamics might be affected by climate change in peatland ecosystems.