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.

Challenges in studying water fluxes within the soil-plant-atmosphere continuum: A tracer-based perspective on pathways to progress.

Tracing and quantifying water fluxes in the hydrological cycle is crucial for understanding the current state of ecohydrological systems and their vulnerability to environmental change. Especially the interface between ecosystems and the atmosphere that is strongly mediated by plants is important to meaningfully describe ecohydrological system functioning. Many of the dynamic interactions generated by water fluxes between soil, plant and the atmosphere are not well understood, which is partly due to a lack of interdisciplinary research. This opinion paper reflects the outcome of a discussion among hydrologists, plant ecophysiologists and soil scientists on open questions and new opportunities for collaborative research on the topic "water fluxes in the soil-plant-atmosphere continuum" especially focusing on environmental and artificial tracers. We emphasize the need for a multi-scale experimental approach, where a hypothesis is tested at multiple spatial scales and under diverse environmental conditions to better describe the small-scale processes (i.e., causes) that lead to large-scale patterns of ecosystem functioning (i.e., consequences). Novel in-situ, high-frequency measurement techniques offer the opportunity to sample data at a high spatial and temporal resolution needed to understand the underlying processes. We advocate for a combination of long-term natural abundance measurements and event-based approaches. Multiple environmental and artificial tracers, such as stable isotopes, and a suite of experimental and analytical approaches should be combined to complement information gained by different methods. Virtual experiments using process-based models should be used to inform sampling campaigns and field experiments, e.g., to improve experimental designs and to simulate experimental outcomes. On the other hand, experimental data are a pre-requisite to improve our currently incomplete models. Interdisciplinary collaboration will help to overcome research gaps that overlap across different earth system science fields and help to generate a more holistic view of water fluxes between soil, plant and atmosphere in diverse ecosystems.

Assessing leached TOC, nutrients and phenols from peatland soils after lab-simulated wildfires: Implications to source water protection.

Pollutant leaching from wildfire-impacted peatland soils (peat) is well-known, but often underestimated when considering boreal ecosystem source water protection and when treating source waters to provide clean drinking water. Burning peat impacts its physical properties and chemical composition, yet the consequences of these transformations to source water quality through pollutant leaching has not been studied in detail. We combusted near-surface boreal peat under simulated peat smoldering conditions at two temperatures (250 °C and 300 °C) and quantified the concentrations of the leached carbon, nutrients and phenols from 5 g peat L-1 reverse osmosis (RO) water suspensions over a 2-day leaching period. For the conditions studied, measured water quality parameters exceeded US surface water guidelines and even exceeded EU and Canadian wastewater/sewer discharge limits including chemical oxygen demand (COD) (125 mg/L), total nitrogen (TN) (15 mg/L), and total phosphorus (TP) (2 mg/L). Phenols were close to or higher than the suggested water supply standard established by US EPA (1 mg/L). Leached carbon, nitrogen and phosphorus mainly came from the organic fraction of peats. Heating peats to 250 °C promoted the leaching of carbon-related pollutants, whereas heating to 300 °C enhanced the leaching of nutrients. Post-heated peats leached higher loads of pollutants in water than pre-heated peats, suggesting that fire-damaged boreal peats may be a critical but underappreciated source of water pollution. A simplified Partial Least Squares (PLS) model based on other easily measured parameters provided a simple method for determining the extent of COD and phenolic pollution in bulk water, relevant for water and wastewater treatment plants. Conclusions from this lab study indicate the need for field measurements of aquatic pollutants downstream of peatland watersheds post-fire as well as increased monitoring and treatment of potable water sources for leachable micropollutants in fire-dominated forested peatlands.

Coupled hydrological and geochemical impacts of wildfire in peatland-dominated regions of discontinuous permafrost.

Naturally-ignited wildfires are increasing in frequency and severity in northern regions, contributing to rapid permafrost thaw-induced landscape change driven by climate warming. Low-severity wildfires typically result in minor organic matter loss. The impacts of such fires on the hydrological and geochemical dynamics of peat plateau-wetland complexes have not been examined. In 2014, a low-severity wildfire, with minimal ground surface damage, burned approximately one-half of a 5 ha permafrost plateau in the wetland-dominated landscape of the Scotty Creek watershed, Northwest Territories, Canada, in the discontinuous permafrost zone. In March 2016, hydrometeorological and permafrost conditions on the burned and unaffected plateaus were monitored including snowpack characteristics and surface energy dynamics. Pore water samples were collected from the saturated layer as thaw progressed throughout the growing season on the burned and unaffected plateaus. Repeated probing of the frost table depth was coupled with laboratory analyses of peat physical and hydraulic characteristics performed on peat cores collected from the top 20 cm of the ground surface in the burned and unaffected plots. The higher transmissivity of the burned forest canopy accelerated snowmelt promoting earlier onset of the thawing season and increased the ground heat flux to melt ground ice. Wildfire increased the thickness of the supra-permafrost layer, including the active layer and talik, resulting in a more uniform subsurface with limited depressional storage capacity and reduced preferential runoff flowpaths across the burned plateau. The incorporation of ash and char into the peat matrix reduced pore diameters, promoting greater subsurface soil moisture retention and longer pore water residence times ultimately providing greater opportunity for soil-water interaction and biogeochemical reactions. Consequently, pore water showed elevated dissolved solutes, dissolved organic matter and mercury concentrations in the burned site. Low-severity wildfires have the potential to trigger a series of complex, inter-related hydrological, thermal and biogeochemical processes and feedbacks.

Competitive transport processes of chloride, sodium, potassium, and ammonium in fen peat.

There is sparse information on reactive solute transport in peat; yet, with increasing development of peatland dominated landscapes, purposeful and accidental contaminant releases will occur, so it is important to assess their mobility. Previous experiments with peat have only evaluated single-component solutions, such that no information exists on solute transport of potentially competitively adsorbing ions to the peat matrix. Additionally, recent studies suggest chloride (Cl-) might not be conservative in peat, as assumed by many past peat solute transport studies. Based on measured and modelled adsorption isotherms, this study illustrates concentration dependent adsorption of Cl- to peat occurred in equilibrium adsorption batch (EAB) experiments, which could be described with a Sips isotherm. However, Cl- adsorption was insignificant for low concentrations (<500 mg L-1) as used in breakthrough curve experiments (BTC). We found that competitive adsorption of Na+, K+, and NH4+ transport could be observed in EAB and BTC, depending on the dissolved ion species present. Na+ followed a Langmuir isotherm, K+ a linear isotherm within the tested concentration range (~10 - 1500 mg L-1), while the results for NH4+ are inconclusive due to potential microbial degradation. Only Na+ showed clear evidence of competitive behaviour, with an order of magnitude decrease in maximum adsorption capacity in the presence of NH4+ (0.22 to 0.02 mol kg-1), which was confirmed by the BTC data where the Na+ retardation coefficient differed between the experiments with different cations. Thus, solute mobility in peatlands is affected by competitive adsorption.