Carl P. J. Mitchell

The effect of depositional history on contaminated bed sediment stability

Experiments were conducted in an annular flume using a commercially available kaolinite clay as well as contaminated bed sediment from Hamilton Harbour (Ontario) to assess their stability against erosion. Critical shear stress for erosion was measured under different conditions of bed formation (quiescently deposited beds and shear deposited beds) as well as with and without the presence of a biostabilized bed. Results suggest that a biostabilized bed and a bed formed under a flowing condition, similar to a river scenario, will be more resistant against erosion than will a non-biostabilized bed and a bed formed under quiescent conditions. Up to three cycles of erosion and flocculation/deposition were observed to occur within one experiment. These results suggest that the depositional history and biostabilization of river bed sediments need to be seriously considered within sediment and contaminant transport models if meaningful estimates of sediment and contaminant source, fate and effect are to be generated and used for the management of our aquatic ecosystems.

Hydrogeomorphic Controls on Reduction–Oxidation Conditions across Boreal Upland–Peatland Interfaces

The reduction–oxidation (redox) state of peatland pore waters plays an important role in many peatland biogeochemical processes. Recent research has also shown that the interface between ecosystems, or the ecotone, may be responsible for a disproportionate amount of biogeochemical activity when material and/or energy is hydrologically transported between ecosystems. The purpose of this research was to examine the spatiotemporal dynamics of redox conditions across two geomorphically distinct Boreal Precambrian Shield upland–peatland ecotones to determine the spatial and temporal scales at which these ecotones may be important. Pore water chemistry of iron and sulphur species was monitored across two upland–peatland ecotones in northwestern Ontario in conjunction with hydrological measurements under both stormflow and nonstormflow conditions. In addition, one upland–peatland ecotone was instrumented to make continuous measurements of in situ redox potential (Eh) over a 12-day period to determine whether measurements at a high temporal scale could provide additional insights into the transfer of nutrients across the upland–peatland interface. Results indicated that hydrology—specifically, groundwater flowpath and the strength of the hydrological connection between upland and peatland—determined the spatial extent of the ecotone as a biogeochemical hotspot. In situ Eh measurements showed that these ecotones may be most important over a scale of only several hours and are largely affected by lateral hydrological flows from the upland. The role of both hot spots and hot moments in biogeochemistry must be considered to accurately estimate the ability of a single ecosystem to process chemical inputs.

A preliminary assessment of water partitioning and ecohydrological coupling in northern headwaters using stable isotopes and conceptual runoff models.

Abstract We combined a conceptual rainfall‐runoff model and input–output relationships of stable isotopes to understand ecohydrological influences on hydrological partitioning in snow‐influenced northern catchments. Six sites in Sweden (Krycklan), Canada (Wolf Creek; Baker Creek; Dorset), Scotland (Girnock) and the USA (Dry Creek) span moisture and energy gradients found at high latitudes. A meta‐analysis was carried out using the Hydrologiska Byråns Vattenbalansavdelning (HBV) model to estimate the main storage changes characterizing annual water balances. Annual snowpack storage importance was ranked as Wolf Creek > Krycklan > Dorset > Baker Creek > Dry Creek > Girnock. The subsequent rate and longevity of melt were reflected in calibrated parameters that determine partitioning of waters between more rapid and slower flowpaths and associated variations in soil and groundwater storage. Variability of stream water isotopic composition depends on the following: (i) rate and duration of spring snowmelt; (ii) significance of summer/autumn rainfall; and (iii) relative importance of near‐surface and deeper flowpaths in routing water to the stream. Flowpath partitioning also regulates influences of summer evaporation on drainage waters. Deviations of isotope data from the Global Meteoric Water Line showed subtle effects of internal catchment processes on isotopic fractionation most likely through evaporation. Such effects are highly variable among sites and with seasonal differences at some sites. After accounting for climate, evaporative fractionation is strongest at sites where lakes and near‐surface runoff processes in wet riparian soils can mobilize isotopically enriched water during summer and autumn. Given close soil–vegetation coupling, this may result in spatial variability in soil water isotope pools available for plant uptake. We argue that stable isotope studies are crucial in addressing the many open questions on hydrological functioning of northern environments.

The effects of hydrologic fluctuation and sulfate regeneration on mercury cycling in an experimental peatland

A series of severe droughts during the course of a long-term, atmospheric sulfate-deposition experiment in a boreal peatland in northern Minnesota created a unique opportunity to study how methylmercury (MeHg) production responds to drying and rewetting events in peatlands under variable levels of sulfate loading. Peat oxidation during extended dry periods mobilized sulfate, MeHg, and total mercury (HgT) to peatland pore-waters during rewetting events. Pore-water sulfate concentrations were inversely related to antecedent moisture conditions and proportional to past and current levels of atmospheric sulfate deposition. Severe drying events caused oxidative release of MeHg to pore-waters and also resulted in increased net MeHg production likely because available sulfate stimulated the activity of sulfate-reducing bacteria, an important group of Hg-methylating bacteria in peatlands. Rewetting events led to increased MeHg concentrations across the peatland, but concentrations were highest in peat receiving elevated atmospheric sulfate deposition. Dissolved HgT concentrations also increased in peatland pore-waters following drought, but were not affected by sulfate loading and did not appear to be directly controlled by dissolved organic carbon mobilization to peatland pore-waters. Peatlands are often considered to be sinks for sulfate and HgT in the landscape and sources of MeHg. Hydrologic fluctuations not only serve to release previously sequestered sulfate and HgT from peatlands, but may also increase the strength of peatlands as sources of MeHg to downstream aquatic systems, particularly in regions that have experienced elevated levels of atmospheric sulfate deposition.A series of severe droughts during the course of a long-term, atmospheric sulfate-deposition experiment in a boreal peatland in northern Minnesota created a unique opportunity to study how methylmercury (MeHg) production responds to drying and rewetting events in peatlands under variable levels of sulfate loading. Peat oxidation during extended dry periods mobilized sulfate, MeHg, and total mercury (HgT) to peatland pore waters during rewetting events. Pore water sulfate concentrations were inversely related to antecedent moisture conditions and proportional to past and current levels of atmospheric sulfate deposition. Severe drying events caused oxidative release of MeHg to pore waters and resulted in increased net MeHg production likely because available sulfate stimulated the activity of sulfate-reducing bacteria, an important group of Hg-methylating bacteria in peatlands. Rewetting events led to increased MeHg concentrations across the peatland, but concentrations were highest in peat receiving elevated atmospheric sulfate deposition. Dissolved HgT concentrations also increased in peatland pore waters following drought but were not affected by sulfate loading and did not appear to be directly controlled by dissolved organic carbon mobilization to peatland pore waters. Peatlands are often considered to be sinks for sulfate and HgT in the landscape and sources of MeHg. Hydrologic fluctuations not only serve to release previously sequestered sulfate and HgT from peatlands but may also increase the strength of peatlands as sources of MeHg to downstream aquatic systems, particularly in regions that have experienced elevated levels of atmospheric sulfate deposition.

Analysis of airborne LiDAR surveys to quantify the characteristic morphologies of northern forested wetlands

A new technique for quantifying the geomorphic form of northern forested wetlands from airborne LiDAR surveys is introduced, demonstrating the unprecedented ability to characterize the geomorphic form of northern forested wetlands using high-resolution digital topography. Two quantitative indices are presented, including the lagg width index (LWI) which objectively quantifies the lagg width, and the lateral slope index (LSI) which is a proxy measurement for the dome shape or convexity of the wetland ground surface. For 14 forested wetlands in central Ontario, Canada, northwestern Ontario, Canada, and northern Minnesota, United States, these indices were systematically correlated to metrics of topographic setting computed from LiDAR digital elevation models. In particular, these indices were strongly correlated with a Peatland Topographic Index (PTI, r2 = 0.58 and r2 = 0.64, respectively, p < = 0.001) describing the relative influence of upslope contributing area on the hydrology and biogeochemistry of individual wetlands. The relationship between PTI and the LWI and LSI indices was interpreted as geomorphic evolution in response to the spatially varying influence of upslope runoff on subsurface hydrochemistry. Spatial patterns of near-surface pore water chemistry were consistent with this interpretation. Specifically, at four wetland sites sampled extensively for pore water chemistry, the mean and variance of near-surface pore water methylmercury (MeHg) concentrations were higher within the zone of enhanced upland-wetland interactions, as inferred from the LiDAR-derived LWI estimates. Use of LiDAR surveys to measure subtle topographic gradients within wetlands may therefore help quantify the influence of upland-wetland interactions on biogeochemical cycling and export in northern forested landscapes.

Accumulation and translocation of methylmercury and inorganic mercury in Oryza sativa: An enriched isotope tracer study.

Methylmercury (MeHg) accumulation in rice is an emerging human health issue, but uptake pathways and translocation into the grain remain poorly understood. We grew Oryza sativa plants in pots of wetland soil amended with an enriched mercury isotope (94.3% 200Hg) tracer, alongside unvegetated control pots, and assessed both ambient and tracer MeHg and inorganic Hg (IHg) concentrations in soil and plant tissues at three growth stages. Based on similar ratios of ambient:tracer MeHg concentrations in soil and plant tissues, we provide the first direct evidence that MeHg is first synthesized in saturated soil and subsequently translocated to rice grains. There is no evidence of in planta methylation of IHg, but significant losses of MeHg from plant tissues between flowering and maturity indicates likely in planta demethylation. In this greenhouse experiment, lower percent of tracer MeHg in vegetated soils at late growth stages suggests that rice plants reduce the net MeHg accumulation capacity of soils, although the mechanism remains unclear. For IHg, roots accumulated Hg from the soil, straw from the soil and the atmosphere, and grain almost entirely from the atmosphere. Management strategies that aim to reduce MeHg accumulation in rice should focus on mercury methylation in paddy soils, but IHg reductions will depend on regional controls of atmospheric Hg.

Gaseous mercury fluxes from forest soils in response to forest harvesting intensity: A field manipulation experiment

Forest harvesting leads to changes in soil moisture, temperature and incident solar radiation, all strong environmental drivers of soil-air mercury (Hg) fluxes. Whether different forest harvesting practices significantly alter Hg fluxes from forest soils is unknown. We conducted a field-scale experiment in a northern Minnesota deciduous forest wherein gaseous Hg emissions from the forest floor were monitored after two forest harvesting prescriptions, a traditional clear-cut and a clearcut followed by biomass harvest, and compared to an un-harvested reference plot. Gaseous Hg emissions were measured in quadruplicate at four different times between March and November 2012 using Teflon dynamic flux chambers. We also applied enriched Hg isotope tracers and separately monitored their emission in triplicate at the same times as ambient measurements. Clearcut followed by biomass harvesting increased ambient Hg emissions the most. While significant intra-site spatial variability was observed, Hg emissions from the biomass harvested plot (180 ± 170 ng m(-2)d(-1)) were significantly greater than both the traditional clearcut plot (-40 ± 60 ng m(-2)d(-1)) and the un-harvested reference plot (-180 ± 115 ng m(-2)d(-1)) during July. This difference was likely a result of enhanced Hg(2+) photoreduction due to canopy removal and less shading from downed woody debris in the biomass harvested plot. Gaseous Hg emissions from more recently deposited Hg, as presumably representative of isotope tracer measurements, were not significantly influenced by harvesting. Most of the Hg tracer applied to the forest floor became sequestered within the ground vegetation and debris, leaf litter, and soil. We observed a dramatic lessening of tracer Hg emissions to near detection levels within 6 months. As post-clearcutting residues are increasingly used as a fuel or fiber resource, our observations suggest that gaseous Hg emissions from forest soils will increase, although it is not yet clear for how long such an effect will persist.

Methylmercury in water, sediment, and invertebrates in created wetlands of Rouge Park, Toronto, Canada.

Thousands of hectares of wetlands are created annually because wetlands provide beneficial ecosystem services. Wetlands are also key sites for production of the bioaccumulative neurotoxin methylmercury (MeHg), but little is known about MeHg production in created systems. Here, we studied methylmercury in sediment, water, and invertebrates in created wetlands of various ages. Sediment MeHg reached 8 ng g(-1) in the newest wetland, which was significantly greater than in natural, control wetlands. This trend was mirrored in several invertebrate taxa, whose concentrations reached as high as 1.6 μg g(-1) in the newest wetland, above levels thought to affect reproduction in birds. The MeHg concentrations in created wetland invertebrate taxa generally decreased with increasing wetland age, possibly due to a combination of deeper anoxia and less organic matter accumulation in younger wetlands. A short-term management intervention and/or improved engineering design may be necessary to reduce the mercury-associated risk in newly created wetlands.

Mercury methylation in high and low-sulphate impacted wetland ponds within the prairie pothole region of North America

Using enriched stable (201)Hg injections into intact sediment cores, we provide the first reported Hg methylation potential rate constants (km) in prairie wetland ponds (0.016-0.17 d(-1)). Our km values were similar to other freshwater wetlands and did not differ in ponds categorized with high compared to low surface water concentrations of sulphate. Sites with high sulphate had higher proportions of methylmercury (MeHg) in sediment (2.9 ± 1.6% vs. 1.0 ± 0.3%) and higher surface water MeHg concentrations (1.96 ± 1.90 ng L(-1)vs. 0.56 ± 0.55 ng L(-1)). Sediment-porewater partitioning coefficients were small, and likely due to high ionic activity. Our work suggests while km measurements are useful for understanding mercury cycling processes, they are less important than surface water MeHg concentrations for assessing MeHg risks to biota. Significant differences in MeHg concentrations between sites with high and low sulphate concentrations may also inform management decisions concerning wetland remediation and creation.

Singular and Combined Effects of Blowdown, Salvage Logging, and Wildfire on Forest Floor and Soil Mercury Pools

A number of factors influence the amount of mercury (Hg) in forest floors and soils, including deposition, volatile emission, leaching, and disturbances such as fire. Currently the impact on soil Hg pools from other widespread forest disturbances such as blowdown and management practices like salvage logging are unknown. Moreover, ecological and biogeochemical responses to disturbances are generally investigated within a single-disturbance context, with little currently known about the impact of multiple disturbances occurring in rapid succession. In this study we capitalize on a combination of blowdown, salvage logging and fire events in the sub-boreal region of northern Minnesota to assess both the singular and combined effects of these disturbances on forest floor and soil total Hg concentrations and pools. Although none of the disturbance combinations affected Hg in mineral soil, we did observe significant effects on both Hg concentrations and pools in the forest floor. Blowdown increased the mean Hg pool in the forest floor by 0.76 mg Hg m(-2) (223%). Salvage logging following blowdown created conditions leading to a significantly more severe forest floor burn during wildfire, which significantly enhanced Hg emission. This sequence of combined events resulted in a mean loss of approximately 0.42 mg Hg m(-2) (68% of pool) from the forest floor, after conservatively accounting for potential losses via enhanced soil leaching and volatile emissions between the disturbance and sampling dates. Fire alone or blowdown followed by fire did not significantly affect the total Hg concentrations or pools in the forest floor. Overall, unexpected consequences for soil Hg accumulation and by extension, atmospheric Hg emission and risk to aquatic biota, may result when combined impacts are considered in addition to singular forest floor and soil disturbances.