Igor Lehnherr | University of Toronto (original) (raw)

Papers by Igor Lehnherr

Environmental science & technology, Jan 16, 2015

Caribou, which rely on lichens as forage, are the most important dietary source of neurotoxic mon... more Caribou, which rely on lichens as forage, are the most important dietary source of neurotoxic monomethylmercury (MMHg) to many of Canada's Arctic Aboriginal people. However, little is understood about the sources of MMHg to lichens in the High Arctic. We quantified MMHg, total mercury (THg) and other chemical parameters (e.g., marine and crustal elements, δ13C, δ15N, organic carbon, calcium carbonate) in lichen and soil samples collected along transects extending from the coast on Bathurst and Devon islands, Nunavut, to determine factors driving lichen MMHg and THg concentrations in the High Arctic. Lichen MMHg and THg concentrations ranged from 1.41 to 17.1 ng/g, and from 36.0 to 361 ng/g, respectively. Both were highly enriched over concentrations in underlying soils, indicating a predominately atmospheric source of Hg in lichens. However, MMHg and THg enrichment at coastal sites on Bathurst Island was far greater than on Devon Island. We suggest that this variability can be e...

Environmental science & technology, Jan 6, 2015

Our understanding of the biogeochemical cycling of monomethylmercury (MMHg) in the Arctic is inco... more Our understanding of the biogeochemical cycling of monomethylmercury (MMHg) in the Arctic is incomplete because atmospheric sources and sinks of MMHg are still unclear. We sampled air in the Canadian Arctic marine boundary layer to quantify, for the first time, atmospheric concentrations of methylated Hg species (both MMHg and dimethylmercury (DMHg)), and, estimate the importance of atmospheric deposition as a source of MMHg to Arctic land- and sea-scapes. Overall atmospheric MMHg and DMHg concentrations (mean ± SD) were 2.9 ± 3.6 and 3.8 ± 3.1 (n = 37) pg m(-3), respectively. Concentrations of methylated Hg species in the marine boundary layer varied significantly among our sites, with a predominance of MMHg over Hudson Bay (HB), and DMHg over Canadian Arctic Archipelago (CAA) waters. We concluded that DMHg is of marine origin and that primary production rate and sea-ice cover are major drivers of its concentration in the Canadian Arctic marine boundary layer. Summer wet deposition...

The Science of the total environment, Jan 15, 2015

This review summarizes data and information which have been generated on mercury (Hg) in the mari... more This review summarizes data and information which have been generated on mercury (Hg) in the marine environment of the Canadian Arctic since the previous Canadian Arctic Contaminants Assessment Report (CACAR) was released in 2003. Much new information has been collected on Hg concentrations in marine water, snow and ice in the Canadian Arctic. The first measurements of methylation rates in Arctic seawater indicate that the water column is an important site for Hg methylation. Arctic marine waters were also found to be a substantial source of gaseous Hg to the atmosphere during the ice-free season. High Hg concentrations have been found in marine snow as a result of deposition following atmospheric mercury depletion events, although much of this Hg is photoreduced and re-emitted back to the atmosphere. The most extensive sampling of marine sediments in the Canadian Arctic was carried out in Hudson Bay where sediment total Hg (THg) concentrations were low compared with other marine re...

Nature Geoscience, 2011

Monomethylmercury is a neurotoxin that accumulates in marine organisms, with serious implications... more Monomethylmercury is a neurotoxin that accumulates in marine organisms, with serious implications for human health. The toxin is of particular concern to northern Inuit peoples, for example, whose traditional diets are composed primarily of marine mammals and fish. The ultimate source of monomethylmercury to marine organisms has remained uncertain, although various potential sources have been proposed, including export from coastal

Environmental Science & Technology, 2007

We sampled seawater and snowpacks in the Canadian high Arctic for methylated species of mercury (... more We sampled seawater and snowpacks in the Canadian high Arctic for methylated species of mercury (Hg). We discovered that, although seawater sampled under the sea ice had very low concentrations of total Hg (THg, all forms of Hg in a sample; on average 0.14-0.24 ng L -1 ), 30-45% of the THg was in the monomethyl Hg (MMHg) form (on average 0.057-0.095 ng L -1 ), making seawater itself a direct source of MMHg for biomagnification through marine food webs. Seawater under the ice also contained high concentrations of gaseous elemental Hg (GEM; 129 ( 36 pg L -1 ), suggesting that open water regions such as polynyas and ice leads were a net source of ∼130 ( 30 ng Hg m -2 day -1 to the atmosphere. We also found 11.1 ( 4.1 pg L -1 of dimethyl Hg (DMHg) in seawater and calculated that there could be a significant flux of DMHg to the atmosphere from open water regions. This flux could then result in MMHg deposition into nearby snowpacks via oxidation of DMHg to MMHg in the atmosphere. In fact, we found high concentrations of MMHg in a few snowpacks near regions of open water. Interestingly, we discovered a significant log-log relationship between Clconcentrations in snowpacks and concentrations of THg. We hypothesize that as Clconcentrations in snowpacks increase, inorganic Hg(II) occurs principally as less reducible chloro complexes and, hence, remains in an oxidized state. As a result, snowpacks that receive both marine aerosol deposition of Cland deposition of Hg(II) via springtime atmospheric Hg depletion events, for example, may contain significant loads of Hg(II). Overall, though, the median wet/dry loads of Hg in the snowpacks we sampled in the high Arctic (5.2 mg THg ha -1 and 0.03 mg MMHg ha -1 ) were far below wet-only annual THg loadings throughout southern Canada and most of the U.S. (22-200 mg ha -1 ). Therefore, most Arctic snowpacks contribute relatively little to marine pools of both Hg(II) and MMHg at snowmelt.

The sources of methylmercury (MeHg; the toxic form of mercury that is biomagnified through foodwe... more The sources of methylmercury (MeHg; the toxic form of mercury that is biomagnified through foodwebs) to Arctic freshwater organisms have not been clearly identified. We used a mass balance approach to quantify MeHg production in two wetland ponds in the Lake Hazen region of northern Ellesmere Island, NU, in the Canadian High Arctic and to evaluate the importance of these systems as sources of MeHg to Arctic foodwebs. We show that internal production (1.8−40 ng MeHg m −2 d −1 ) is a much larger source of MeHg than external inputs from direct atmospheric deposition (0.029−0.051 ng MeHg m −2 d −1 ), as expected. Furthermore, MeHg cycling in these systems is dominated by Hg(II) methylation and MeHg photodemethylation (2.0−33 ng MeHg m −2 d −1 ), which is a sink for a large proportion of the MeHg produced by Hg(II) methylation in these ponds. We also show that MeHg production in the two study ponds is comparable to what has previously been measured in numerous more southerly systems known to be important MeHg sources, such as temperate wetlands and lakes, demonstrating that wetland ponds in the High Arctic are important sources of MeHg to local aquatic foodwebs.

The role of high arctic ecosystems in the global carbon budget has attracted scientific interest ... more The role of high arctic ecosystems in the global carbon budget has attracted scientific interest because a) arctic terrestrial ecosystems currently store significant amounts of organic carbon in permafrost and poorly drained tundra soils, and b) the arctic climate system is changing rapidly in response to global warming. The role of the high arctic terrestrial ecosystem as either a source or sink of atmospheric CO2 is unknown, although it is generally assumed that it will become a source of CO2 to the atmosphere as climate change continues to warm the region and previously sequestered organic matter in soils is mineralized as the active layer develops. We will present data on the net ecosystem exchange (NEE) of CO2 from high arctic tundra near Lake Hazen, Quittinirpaaq National Park (81°N) during the 2008 and 2009 growing seasons, collected using an eddy covariance flux tower. This is the first report of NEE from such a northerly latitude. We will also present data on the exchange of CH4 with tundra soils collected using static chambers. The tundra at Lake Hazen was a continuous CO2 sink during the growing season, and is carbon neutral during snow cover conditions in early spring. The CO2 flux correlated strongly with PAR and soil temperature. Despite active layer development at the site during our observation period (11 cm in 2008, 37 cm in 2009), no evidence of a corresponding CO2 pulse to the atmosphere was detected. Soil respiration rates, separately measured using a LiCOR 6400, indicated a correlation between soil respiration and plant cover corresponded. The strong correlation between NEE and vegetation parameters suggests that as vegetation cover increases in the high arctic in response to climate warming, the tundra at Lake Hazen may continue to function as a carbon sink despite continued active layer development. Dry tundra soils always consumed CH4 at our site, suggesting that parts of the high Arctic are actually sinks for this strong greenhouse gas.

Monomethyl mercury (MMHg), a vertebrate neurotoxin which bioaccumulates through foodwebs, is foun... more Monomethyl mercury (MMHg), a vertebrate neurotoxin which bioaccumulates through foodwebs, is found in some Arctic marine mammals at levels that may be harmful to northern peoples consuming them as food. Unfortunately, sources of MMHg to polar marine food webs remain unknown, in part due to the complex nature of Hg cycling in polar marine waters. Since 2005, we have been

High Arctic landscapes are essentially vast cold deserts interspersed with streams, ponds and wet... more High Arctic landscapes are essentially vast cold deserts interspersed with streams, ponds and wetlands. These landscapes may be important consumers and sources of the greenhouse gas methane (CH 4 ), though few measurements exist from this region. To quantify the flux of CH 4 (F CH 4 ) between the atmosphere and high Arctic landscapes on northern Ellesmere Island, Canada, we made static chamber measurements over five and three growing seasons at a desert and wetland, respectively, and eddy covariance (EC) measurements at a wetland in 2012. Chamber measurements revealed that, during the growing season, desert soils consumed CH 4 (−1.37 ± 0.06 mg-CH 4 m −2 d −1 ), whereas the wetland margin emitted CH 4 (+0.22 ± 0.14 mg-CH 4 m −2 d −1 ). Desert CH 4 consumption rates were positively associated with soil temperature among years, and were similar to temperate locations, likely because of suitable landscape conditions for soil gas diffusion. Wetland F CH 4 varied closely with stream discharge entering the wetland and hence extent of soil saturation. Landscape-scale F CH 4 measured by EC was +1.27 ± 0.18 mg-CH 4 m −2 d −1 and varied with soil temperature and carbon dioxide flux. F CH 4 measured using EC was higher than using chambers because EC measurements incorporated a larger, more saturated footprint of the wetland. Using EC F CH 4 and quantifying the mass of CH 4 entering and exiting the wetland in stream water, we determined that methanogenesis within wetland soils was the dominant source of F CH 4 . Low F CH 4 at the wetland was likely due to a shallow organic soil layer, and thus limited carbon resources for methanogens. Considering the prevalence of dry soils in the high Arctic, our results suggest that these landscapes cannot be overlooked as important consumers of atmospheric CH 4 .

The sources of methylmercury (MeHg; the toxic form of mercury that is biomagnified through foodwe... more The sources of methylmercury (MeHg; the toxic form of mercury that is biomagnified through foodwebs) to Arctic freshwater organisms have not been clearly identified. We used a mass balance approach to quantify MeHg production in two wetland ponds in the Lake Hazen region of northern Ellesmere Island, NU, in the Canadian High Arctic and to evaluate the importance of these systems as sources of MeHg to Arctic foodwebs. We show that internal production (1.8−40 ng MeHg m −2 d −1 ) is a much larger source of MeHg than external inputs from direct atmospheric deposition (0.029−0.051 ng MeHg m −2 d −1 ), as expected. Furthermore, MeHg cycling in these systems is dominated by Hg(II) methylation and MeHg photodemethylation (2.0−33 ng MeHg m −2 d −1 ), which is a sink for a large proportion of the MeHg produced by Hg(II) methylation in these ponds. We also show that MeHg production in the two study ponds is comparable to what has previously been measured in numerous more southerly systems known to be important MeHg sources, such as temperate wetlands and lakes, demonstrating that wetland ponds in the High Arctic are important sources of MeHg to local aquatic foodwebs.

Science of The Total Environment, 2014

This paper reviews progress made in the study of the transport, transformation, deposition and re... more This paper reviews progress made in the study of the transport, transformation, deposition and reemission of atmospheric Hg in the Canadian Arctic, focusing on field measurements. • Redox processes control the speciation of atmospheric Hg and bromine radicals are the primary oxidant of atmospheric Hg depletion in the spring • It is expected that a smaller fraction of deposited Hg will be reemitted from coastal snowpacks.

Atmospheric deposition of metals originating from a variety of sources, including bitumen upgradi... more Atmospheric deposition of metals originating from a variety of sources, including bitumen upgrading facilities and blowing dusts from landscape disturbances, is of concern in the Athabasca oil sands region of northern Alberta, Canada. Mercury (Hg) is of particular interest as methylmercury (MeHg), a neurotoxin which bioaccumulates through foodwebs, can reach levels in fish and wildlife that may pose health risks to human consumers. We used spring-time sampling of the accumulated snowpack at sites located varying distances from the major developments to estimate winter 2012 Hg loadings to a ∼20 000 km 2 area of the Athabasca oil sands region. Total Hg (THg; all forms of Hg in a sample) loads were predominantly particulate-bound (79 ± 12%) and increased with proximity to major developments, reaching up to 1000 ng m −2 . MeHg loads increased in a similar fashion, reaching up to 19 ng m −2 and suggesting that oil sands developments are a direct source of MeHg to local landscapes and water bodies. Deposition maps, created by interpolation of measured Hg loads using geostatistical software, demonstrated that deposition resembled a bullseye pattern on the landscape, with areas of maximum THg and MeHg loadings located primarily between the Muskeg and Steepbank rivers. Snowpack concentrations of THg and MeHg were significantly correlated (r = 0.45−0.88, p < 0.01) with numerous parameters, including total suspended solids (TSS), metals known to be emitted in high quantities from the upgraders (vanadium, nickel, and zinc), and crustal elements (aluminum, iron, and lanthanum), which were also elevated in this region. Our results suggest that at snowmelt, a complex mixture of chemicals enters aquatic ecosystems that could impact biological communities of the oil sands region.

Nature Geoscience, 2011

Monomethylmercury is a neurotoxin that accumulates in marine organisms, with serious implications... more Monomethylmercury is a neurotoxin that accumulates in marine organisms, with serious implications for human health 1 . The toxin is of particular concern to northern Inuit peoples, for example, whose traditional diets are composed primarily of marine mammals and fish 2 . The ultimate source of monomethylmercury to marine organisms has remained uncertain, although various potential sources have been proposed, including export from coastal 3 and deep-sea 4 sediments and major river systems 5,6 , atmospheric deposition 7 and watercolumn production 8,9 . Here, we report results from incubation experiments in which we added isotopically labelled inorganic mercury and monomethylmercury to seawater samples collected from a range of sites in the Canadian Arctic Archipelago. Monomethylmercury formed from the methylation of inorganic mercury in all samples. Demethylation of monomethylmercury was also observed in water from all sites. We determined steady-state concentrations of monomethylmercury in marine waters by incorporating the rate constants for monomethylmercury formation and degradation derived from these experiments into a numerical model. We estimate that the conversion of inorganic mercury to monomethylmercury in the water column accounts for around 47% (±62%, standard deviation) of the monomethylmercury present in polar marine waters, with site-to-site differences in inorganic mercury and monomethylmercury levels accounting for most of the variability. We suggest that water-column methylation of inorganic mercury is a significant source of monomethylmercury in pelagic marine food webs in the Arctic, and possibly in the world's oceans in general.

Environmental Science & Technology, 2009

Photodemethylation (PD) is thought to be the most important biogeochemical sink of methylmercury ... more Photodemethylation (PD) is thought to be the most important biogeochemical sink of methylmercury (MeHg) in freshwater lakes. However, we possess little mechanistic knowledge of this important biogeochemical process with regard to, for instance, the role of ultraviolet (UV) radiation versus visible light in mediating MeHg PD. This information is critical to correctly model MeHg PD at the whole-lake level, since wavelengths in the UV and visible regions of the solar spectrum are attenuated at very different rates in the water column of lakes. Furthermore, the established methodology for quantifying MeHg PD requires the addition of a MeHg spike, which often increases the concentration of ambient MeHg by 1 to 2 orders of magnitude; however, the assumption that the MeHg spike behaves like ambient MeHg has never been verified. We quantified MeHg PD rates using an isotopically enriched Me 199 Hg tracer added to lake waters already containing high concentrations of ambient MeHg, allowing us to simultaneously monitor the decomposition rate of the spike and ambient MeHg. Experiments were conducted at the Experimental Lakes Area to quantify the first-order rate constant (k pd ) of MeHg PD in samples exposed to (1) full solar radiation, (2) UV-A and visible light (i.e., with UV-B blocked), or (3) visible light only. We demonstrate for the first time that the use of a MeHg spike to quantify PD rates is appropriate since spike and ambient MeHgsboth in samples with and without a spike of Me 199 Hgsare photodemethylated at the same rate. We also show that rates of MeHg PD are reduced by an order of magnitude in the absence of UV radiation and that to correctly model MeHg PD at the whole-lake scale, both UV and visible light mediated MeHg PD rates must be independently calculated using the light-specific rate constants (k pd-UVB , k pd-UVA , k pd-VIS ). By examining modeled areal MeHg PD fluxes, we observed that UV radiation accounts for 58% and 79% of MeHg PD activity in a clear and colored lake, respectively. Finally, we demonstrate that correcting k pd-overall for the attenuation of solar radiation by Teflon bottles, which are normally used for MeHg PD experiments, increases the measured value of 3.69 × 10 -3 m 2 E -1 to 4.41 × 10 -3 m 2 E -1 .

Environmental science & technology, Jan 16, 2015

Caribou, which rely on lichens as forage, are the most important dietary source of neurotoxic mon... more Caribou, which rely on lichens as forage, are the most important dietary source of neurotoxic monomethylmercury (MMHg) to many of Canada's Arctic Aboriginal people. However, little is understood about the sources of MMHg to lichens in the High Arctic. We quantified MMHg, total mercury (THg) and other chemical parameters (e.g., marine and crustal elements, δ13C, δ15N, organic carbon, calcium carbonate) in lichen and soil samples collected along transects extending from the coast on Bathurst and Devon islands, Nunavut, to determine factors driving lichen MMHg and THg concentrations in the High Arctic. Lichen MMHg and THg concentrations ranged from 1.41 to 17.1 ng/g, and from 36.0 to 361 ng/g, respectively. Both were highly enriched over concentrations in underlying soils, indicating a predominately atmospheric source of Hg in lichens. However, MMHg and THg enrichment at coastal sites on Bathurst Island was far greater than on Devon Island. We suggest that this variability can be e...

Environmental science & technology, Jan 6, 2015

Our understanding of the biogeochemical cycling of monomethylmercury (MMHg) in the Arctic is inco... more Our understanding of the biogeochemical cycling of monomethylmercury (MMHg) in the Arctic is incomplete because atmospheric sources and sinks of MMHg are still unclear. We sampled air in the Canadian Arctic marine boundary layer to quantify, for the first time, atmospheric concentrations of methylated Hg species (both MMHg and dimethylmercury (DMHg)), and, estimate the importance of atmospheric deposition as a source of MMHg to Arctic land- and sea-scapes. Overall atmospheric MMHg and DMHg concentrations (mean ± SD) were 2.9 ± 3.6 and 3.8 ± 3.1 (n = 37) pg m(-3), respectively. Concentrations of methylated Hg species in the marine boundary layer varied significantly among our sites, with a predominance of MMHg over Hudson Bay (HB), and DMHg over Canadian Arctic Archipelago (CAA) waters. We concluded that DMHg is of marine origin and that primary production rate and sea-ice cover are major drivers of its concentration in the Canadian Arctic marine boundary layer. Summer wet deposition...

The Science of the total environment, Jan 15, 2015

This review summarizes data and information which have been generated on mercury (Hg) in the mari... more This review summarizes data and information which have been generated on mercury (Hg) in the marine environment of the Canadian Arctic since the previous Canadian Arctic Contaminants Assessment Report (CACAR) was released in 2003. Much new information has been collected on Hg concentrations in marine water, snow and ice in the Canadian Arctic. The first measurements of methylation rates in Arctic seawater indicate that the water column is an important site for Hg methylation. Arctic marine waters were also found to be a substantial source of gaseous Hg to the atmosphere during the ice-free season. High Hg concentrations have been found in marine snow as a result of deposition following atmospheric mercury depletion events, although much of this Hg is photoreduced and re-emitted back to the atmosphere. The most extensive sampling of marine sediments in the Canadian Arctic was carried out in Hudson Bay where sediment total Hg (THg) concentrations were low compared with other marine re...

Nature Geoscience, 2011

Monomethylmercury is a neurotoxin that accumulates in marine organisms, with serious implications... more Monomethylmercury is a neurotoxin that accumulates in marine organisms, with serious implications for human health. The toxin is of particular concern to northern Inuit peoples, for example, whose traditional diets are composed primarily of marine mammals and fish. The ultimate source of monomethylmercury to marine organisms has remained uncertain, although various potential sources have been proposed, including export from coastal

Environmental Science & Technology, 2007

We sampled seawater and snowpacks in the Canadian high Arctic for methylated species of mercury (... more We sampled seawater and snowpacks in the Canadian high Arctic for methylated species of mercury (Hg). We discovered that, although seawater sampled under the sea ice had very low concentrations of total Hg (THg, all forms of Hg in a sample; on average 0.14-0.24 ng L -1 ), 30-45% of the THg was in the monomethyl Hg (MMHg) form (on average 0.057-0.095 ng L -1 ), making seawater itself a direct source of MMHg for biomagnification through marine food webs. Seawater under the ice also contained high concentrations of gaseous elemental Hg (GEM; 129 ( 36 pg L -1 ), suggesting that open water regions such as polynyas and ice leads were a net source of ∼130 ( 30 ng Hg m -2 day -1 to the atmosphere. We also found 11.1 ( 4.1 pg L -1 of dimethyl Hg (DMHg) in seawater and calculated that there could be a significant flux of DMHg to the atmosphere from open water regions. This flux could then result in MMHg deposition into nearby snowpacks via oxidation of DMHg to MMHg in the atmosphere. In fact, we found high concentrations of MMHg in a few snowpacks near regions of open water. Interestingly, we discovered a significant log-log relationship between Clconcentrations in snowpacks and concentrations of THg. We hypothesize that as Clconcentrations in snowpacks increase, inorganic Hg(II) occurs principally as less reducible chloro complexes and, hence, remains in an oxidized state. As a result, snowpacks that receive both marine aerosol deposition of Cland deposition of Hg(II) via springtime atmospheric Hg depletion events, for example, may contain significant loads of Hg(II). Overall, though, the median wet/dry loads of Hg in the snowpacks we sampled in the high Arctic (5.2 mg THg ha -1 and 0.03 mg MMHg ha -1 ) were far below wet-only annual THg loadings throughout southern Canada and most of the U.S. (22-200 mg ha -1 ). Therefore, most Arctic snowpacks contribute relatively little to marine pools of both Hg(II) and MMHg at snowmelt.

The sources of methylmercury (MeHg; the toxic form of mercury that is biomagnified through foodwe... more The sources of methylmercury (MeHg; the toxic form of mercury that is biomagnified through foodwebs) to Arctic freshwater organisms have not been clearly identified. We used a mass balance approach to quantify MeHg production in two wetland ponds in the Lake Hazen region of northern Ellesmere Island, NU, in the Canadian High Arctic and to evaluate the importance of these systems as sources of MeHg to Arctic foodwebs. We show that internal production (1.8−40 ng MeHg m −2 d −1 ) is a much larger source of MeHg than external inputs from direct atmospheric deposition (0.029−0.051 ng MeHg m −2 d −1 ), as expected. Furthermore, MeHg cycling in these systems is dominated by Hg(II) methylation and MeHg photodemethylation (2.0−33 ng MeHg m −2 d −1 ), which is a sink for a large proportion of the MeHg produced by Hg(II) methylation in these ponds. We also show that MeHg production in the two study ponds is comparable to what has previously been measured in numerous more southerly systems known to be important MeHg sources, such as temperate wetlands and lakes, demonstrating that wetland ponds in the High Arctic are important sources of MeHg to local aquatic foodwebs.

The role of high arctic ecosystems in the global carbon budget has attracted scientific interest ... more The role of high arctic ecosystems in the global carbon budget has attracted scientific interest because a) arctic terrestrial ecosystems currently store significant amounts of organic carbon in permafrost and poorly drained tundra soils, and b) the arctic climate system is changing rapidly in response to global warming. The role of the high arctic terrestrial ecosystem as either a source or sink of atmospheric CO2 is unknown, although it is generally assumed that it will become a source of CO2 to the atmosphere as climate change continues to warm the region and previously sequestered organic matter in soils is mineralized as the active layer develops. We will present data on the net ecosystem exchange (NEE) of CO2 from high arctic tundra near Lake Hazen, Quittinirpaaq National Park (81°N) during the 2008 and 2009 growing seasons, collected using an eddy covariance flux tower. This is the first report of NEE from such a northerly latitude. We will also present data on the exchange of CH4 with tundra soils collected using static chambers. The tundra at Lake Hazen was a continuous CO2 sink during the growing season, and is carbon neutral during snow cover conditions in early spring. The CO2 flux correlated strongly with PAR and soil temperature. Despite active layer development at the site during our observation period (11 cm in 2008, 37 cm in 2009), no evidence of a corresponding CO2 pulse to the atmosphere was detected. Soil respiration rates, separately measured using a LiCOR 6400, indicated a correlation between soil respiration and plant cover corresponded. The strong correlation between NEE and vegetation parameters suggests that as vegetation cover increases in the high arctic in response to climate warming, the tundra at Lake Hazen may continue to function as a carbon sink despite continued active layer development. Dry tundra soils always consumed CH4 at our site, suggesting that parts of the high Arctic are actually sinks for this strong greenhouse gas.

Monomethyl mercury (MMHg), a vertebrate neurotoxin which bioaccumulates through foodwebs, is foun... more Monomethyl mercury (MMHg), a vertebrate neurotoxin which bioaccumulates through foodwebs, is found in some Arctic marine mammals at levels that may be harmful to northern peoples consuming them as food. Unfortunately, sources of MMHg to polar marine food webs remain unknown, in part due to the complex nature of Hg cycling in polar marine waters. Since 2005, we have been

High Arctic landscapes are essentially vast cold deserts interspersed with streams, ponds and wet... more High Arctic landscapes are essentially vast cold deserts interspersed with streams, ponds and wetlands. These landscapes may be important consumers and sources of the greenhouse gas methane (CH 4 ), though few measurements exist from this region. To quantify the flux of CH 4 (F CH 4 ) between the atmosphere and high Arctic landscapes on northern Ellesmere Island, Canada, we made static chamber measurements over five and three growing seasons at a desert and wetland, respectively, and eddy covariance (EC) measurements at a wetland in 2012. Chamber measurements revealed that, during the growing season, desert soils consumed CH 4 (−1.37 ± 0.06 mg-CH 4 m −2 d −1 ), whereas the wetland margin emitted CH 4 (+0.22 ± 0.14 mg-CH 4 m −2 d −1 ). Desert CH 4 consumption rates were positively associated with soil temperature among years, and were similar to temperate locations, likely because of suitable landscape conditions for soil gas diffusion. Wetland F CH 4 varied closely with stream discharge entering the wetland and hence extent of soil saturation. Landscape-scale F CH 4 measured by EC was +1.27 ± 0.18 mg-CH 4 m −2 d −1 and varied with soil temperature and carbon dioxide flux. F CH 4 measured using EC was higher than using chambers because EC measurements incorporated a larger, more saturated footprint of the wetland. Using EC F CH 4 and quantifying the mass of CH 4 entering and exiting the wetland in stream water, we determined that methanogenesis within wetland soils was the dominant source of F CH 4 . Low F CH 4 at the wetland was likely due to a shallow organic soil layer, and thus limited carbon resources for methanogens. Considering the prevalence of dry soils in the high Arctic, our results suggest that these landscapes cannot be overlooked as important consumers of atmospheric CH 4 .

The sources of methylmercury (MeHg; the toxic form of mercury that is biomagnified through foodwe... more The sources of methylmercury (MeHg; the toxic form of mercury that is biomagnified through foodwebs) to Arctic freshwater organisms have not been clearly identified. We used a mass balance approach to quantify MeHg production in two wetland ponds in the Lake Hazen region of northern Ellesmere Island, NU, in the Canadian High Arctic and to evaluate the importance of these systems as sources of MeHg to Arctic foodwebs. We show that internal production (1.8−40 ng MeHg m −2 d −1 ) is a much larger source of MeHg than external inputs from direct atmospheric deposition (0.029−0.051 ng MeHg m −2 d −1 ), as expected. Furthermore, MeHg cycling in these systems is dominated by Hg(II) methylation and MeHg photodemethylation (2.0−33 ng MeHg m −2 d −1 ), which is a sink for a large proportion of the MeHg produced by Hg(II) methylation in these ponds. We also show that MeHg production in the two study ponds is comparable to what has previously been measured in numerous more southerly systems known to be important MeHg sources, such as temperate wetlands and lakes, demonstrating that wetland ponds in the High Arctic are important sources of MeHg to local aquatic foodwebs.

Science of The Total Environment, 2014

This paper reviews progress made in the study of the transport, transformation, deposition and re... more This paper reviews progress made in the study of the transport, transformation, deposition and reemission of atmospheric Hg in the Canadian Arctic, focusing on field measurements. • Redox processes control the speciation of atmospheric Hg and bromine radicals are the primary oxidant of atmospheric Hg depletion in the spring • It is expected that a smaller fraction of deposited Hg will be reemitted from coastal snowpacks.

Atmospheric deposition of metals originating from a variety of sources, including bitumen upgradi... more Atmospheric deposition of metals originating from a variety of sources, including bitumen upgrading facilities and blowing dusts from landscape disturbances, is of concern in the Athabasca oil sands region of northern Alberta, Canada. Mercury (Hg) is of particular interest as methylmercury (MeHg), a neurotoxin which bioaccumulates through foodwebs, can reach levels in fish and wildlife that may pose health risks to human consumers. We used spring-time sampling of the accumulated snowpack at sites located varying distances from the major developments to estimate winter 2012 Hg loadings to a ∼20 000 km 2 area of the Athabasca oil sands region. Total Hg (THg; all forms of Hg in a sample) loads were predominantly particulate-bound (79 ± 12%) and increased with proximity to major developments, reaching up to 1000 ng m −2 . MeHg loads increased in a similar fashion, reaching up to 19 ng m −2 and suggesting that oil sands developments are a direct source of MeHg to local landscapes and water bodies. Deposition maps, created by interpolation of measured Hg loads using geostatistical software, demonstrated that deposition resembled a bullseye pattern on the landscape, with areas of maximum THg and MeHg loadings located primarily between the Muskeg and Steepbank rivers. Snowpack concentrations of THg and MeHg were significantly correlated (r = 0.45−0.88, p < 0.01) with numerous parameters, including total suspended solids (TSS), metals known to be emitted in high quantities from the upgraders (vanadium, nickel, and zinc), and crustal elements (aluminum, iron, and lanthanum), which were also elevated in this region. Our results suggest that at snowmelt, a complex mixture of chemicals enters aquatic ecosystems that could impact biological communities of the oil sands region.

Nature Geoscience, 2011

Monomethylmercury is a neurotoxin that accumulates in marine organisms, with serious implications... more Monomethylmercury is a neurotoxin that accumulates in marine organisms, with serious implications for human health 1 . The toxin is of particular concern to northern Inuit peoples, for example, whose traditional diets are composed primarily of marine mammals and fish 2 . The ultimate source of monomethylmercury to marine organisms has remained uncertain, although various potential sources have been proposed, including export from coastal 3 and deep-sea 4 sediments and major river systems 5,6 , atmospheric deposition 7 and watercolumn production 8,9 . Here, we report results from incubation experiments in which we added isotopically labelled inorganic mercury and monomethylmercury to seawater samples collected from a range of sites in the Canadian Arctic Archipelago. Monomethylmercury formed from the methylation of inorganic mercury in all samples. Demethylation of monomethylmercury was also observed in water from all sites. We determined steady-state concentrations of monomethylmercury in marine waters by incorporating the rate constants for monomethylmercury formation and degradation derived from these experiments into a numerical model. We estimate that the conversion of inorganic mercury to monomethylmercury in the water column accounts for around 47% (±62%, standard deviation) of the monomethylmercury present in polar marine waters, with site-to-site differences in inorganic mercury and monomethylmercury levels accounting for most of the variability. We suggest that water-column methylation of inorganic mercury is a significant source of monomethylmercury in pelagic marine food webs in the Arctic, and possibly in the world's oceans in general.

Environmental Science & Technology, 2009

Photodemethylation (PD) is thought to be the most important biogeochemical sink of methylmercury ... more Photodemethylation (PD) is thought to be the most important biogeochemical sink of methylmercury (MeHg) in freshwater lakes. However, we possess little mechanistic knowledge of this important biogeochemical process with regard to, for instance, the role of ultraviolet (UV) radiation versus visible light in mediating MeHg PD. This information is critical to correctly model MeHg PD at the whole-lake level, since wavelengths in the UV and visible regions of the solar spectrum are attenuated at very different rates in the water column of lakes. Furthermore, the established methodology for quantifying MeHg PD requires the addition of a MeHg spike, which often increases the concentration of ambient MeHg by 1 to 2 orders of magnitude; however, the assumption that the MeHg spike behaves like ambient MeHg has never been verified. We quantified MeHg PD rates using an isotopically enriched Me 199 Hg tracer added to lake waters already containing high concentrations of ambient MeHg, allowing us to simultaneously monitor the decomposition rate of the spike and ambient MeHg. Experiments were conducted at the Experimental Lakes Area to quantify the first-order rate constant (k pd ) of MeHg PD in samples exposed to (1) full solar radiation, (2) UV-A and visible light (i.e., with UV-B blocked), or (3) visible light only. We demonstrate for the first time that the use of a MeHg spike to quantify PD rates is appropriate since spike and ambient MeHgsboth in samples with and without a spike of Me 199 Hgsare photodemethylated at the same rate. We also show that rates of MeHg PD are reduced by an order of magnitude in the absence of UV radiation and that to correctly model MeHg PD at the whole-lake scale, both UV and visible light mediated MeHg PD rates must be independently calculated using the light-specific rate constants (k pd-UVB , k pd-UVA , k pd-VIS ). By examining modeled areal MeHg PD fluxes, we observed that UV radiation accounts for 58% and 79% of MeHg PD activity in a clear and colored lake, respectively. Finally, we demonstrate that correcting k pd-overall for the attenuation of solar radiation by Teflon bottles, which are normally used for MeHg PD experiments, increases the measured value of 3.69 × 10 -3 m 2 E -1 to 4.41 × 10 -3 m 2 E -1 .