Experimental evidence for recovery of mercury-contaminated fish populations.

Anthropogenic releases of mercury (Hg)1-3 are a human health issue4 because the potent toxicant methylmercury (MeHg), formed primarily by microbial methylation of inorganic Hg in aquatic ecosystems, bioaccumulates to high concentrations in fish consumed by humans5,6. Predicting the efficacy of Hg pollution controls on fish MeHg concentrations is complex because many factors influence the production and bioaccumulation of MeHg7-9. Here we conducted a 15-year whole-ecosystem, single-factor experiment to determine the magnitude and timing of reductions in fish MeHg concentrations following reductions in Hg additions to a boreal lake and its watershed. During the seven-year addition phase, we applied enriched Hg isotopes to increase local Hg wet deposition rates fivefold. The Hg isotopes became increasingly incorporated into the food web as MeHg, predominantly from additions to the lake because most of those in the watershed remained there. Thereafter, isotopic additions were stopped, resulting in an approximately 100% reduction in Hg loading to the lake. The concentration of labelled MeHg quickly decreased by up to 91% in lower trophic level organisms, initiating rapid decreases of 38-76% of MeHg concentration in large-bodied fish populations in eight years. Although Hg loading from watersheds may not decline in step with lowering deposition rates, this experiment clearly demonstrates that any reduction in Hg loadings to lakes, whether from direct deposition or runoff, will have immediate benefits to fish consumers.

Spatial analysis of a hydrocarbon waste-remediating landfarm demonstrates influence of management practices on bacterial and fungal community structure.

Cultivation of dedicated soil plots called 'landfarms' is an effective technology for bioremediation of hydrocarbon waste generated by various industrial practices. To understand the influence of soil conditions on landfarm microbial communities, analysis of bacterial and fungal community structure using next-generation sequencing at different sections and depths was performed across a hydrocarbon-waste landfarm in Regina, Saskatchewan, Canada. While a core set of hydrocarbon-associated bacterial and fungal taxa are present throughout the landfarm, unique bacterial and fungal operational taxonomic units are differentially abundant at sections within the landfarm, which correlate with differences in soil physiochemical properties and management practices. Increased frequency of waste application resulted in strong positive correlations between bacterial community assemblages and elevated amounts of oil, grease and F3 - F4 hydrocarbon fractions. In areas of standing water and lower application of hydrocarbon, microbial community structure correlated with soil pH, trace nutrients and metals. Overall, diversity and structure of bacterial communities remain relatively stable across the landfarm, while in contrast, fungal community structure appears more responsive to soil oxygen conditions. Results are consistent with the hypothesis that years of bioremediation activity have shaped microbial communities; however, several management practices can be undertaken to increase efficiency of remediation, including the removal of standing water and soil tilling across the landfarm.

Mercury and methylmercury in aquatic sediment across western North America.

Large-scale assessments are valuable in identifying primary factors controlling total mercury (THg) and monomethyl mercury (MeHg) concentrations, and distribution in aquatic ecosystems. Bed sediment THg and MeHg concentrations were compiled for >16,000 samples collected from aquatic habitats throughout the West between 1965 and 2013. The influence of aquatic feature type (canals, estuaries, lakes, and streams), and environmental setting (agriculture, forest, open-water, range, wetland, and urban) on THg and MeHg concentrations was examined. THg concentrations were highest in lake (29.3±6.5µgkg(-1)) and canal (28.6±6.9µgkg(-1)) sites, and lowest in stream (20.7±4.6µgkg(-1)) and estuarine (23.6±5.6µgkg(-1)) sites, which was partially a result of differences in grain size related to hydrologic gradients. By environmental setting, open-water (36.8±2.2µgkg(-1)) and forested (32.0±2.7µgkg(-1)) sites generally had the highest THg concentrations, followed by wetland sites (28.9±1.7µgkg(-1)), rangeland (25.5±1.5µgkg(-1)), agriculture (23.4±2.0µgkg(-1)), and urban (22.7±2.1µgkg(-1)) sites. MeHg concentrations also were highest in lakes (0.55±0.05µgkg(-1)) and canals (0.54±0.11µgkg(-1)), but, in contrast to THg, MeHg concentrations were lowest in open-water sites (0.22±0.03µgkg(-1)). The median percent MeHg (relative to THg) for the western region was 0.7%, indicating an overall low methylation efficiency; however, a significant subset of data (n>100) had percentages that represent elevated methylation efficiency (>6%). MeHg concentrations were weakly correlated with THg (r(2)=0.25) across western North America. Overall, these results highlight the large spatial variability in sediment THg and MeHg concentrations throughout western North America and underscore the important roles that landscape and land-use characteristics have on the MeHg cycle.

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.

Differential trends in mercury concentrations in double-crested cormorant populations of the Canadian Prairies.

Mercury and selenium concentrations were measured in double-crested cormorants (Phalacrocorax auritus), piscivorous fish, and common prey items in five lakes in two ecoregions in Saskatchewan, Canada. Hg and Se concentrations in cormorants were within the natural ranges of birds living in un-impacted sites. Site explained a significant proportion of the variation in total Hg (THg) and methylmercury (MeHg) concentrations in both cormorant breast muscle and livers. Birds nesting on more northern lakes in the Boreal Plain ecoregion (THg range 0.11-1.06 and 0.26-9.27 µg g(-1) wet weight, for breast and liver respectively) had lower THg concentrations compared to those from lakes in the Prairie ecoregion (THg range 0.60-4.26 µg g(-1) ww and 1.59-25.11 µg g(-1), for breast and liver respectively). Concentrations of MeHg in livers was also lower in birds from northern sites (0.06-1.15 µg g(-1) ww) compared to those from prairie sites (0.22-4.06 µg g(-1) ww). We documented a wide range of %MeHg in livers (4.5-52 %), indicative of detoxifying MeHg via demethylation to inorganic Hg. Our data suggest that the threshold value where demethylation rates increase substantially appears to be ~10 µg g(-1) ww MeHg, similar to thresholds in other wildlife. Molar ratios of Hg:Se suggests that some birds from highly saline Reed Lake in the prairie region had insufficient Se available to bind to Hg, thereby removing Se binding as a mitigative strategy for high Hg levels for these birds.

Environmental, geographic and trophic influences on methylmercury concentrations in macroinvertebrates from lakes and wetlands across Canada.

Macroinvertebrates are a key vector in the transfer of methylmercury (MeHg) to fish. However, the factors that affect MeHg concentrations and bioaccumulation in these organisms are not as well understood as for fish, and studies on a broad geographic scale are lacking. In this study, we gathered published and unpublished MeHg and carbon (δ(13)C) and nitrogen (δ(15)N) stable isotope data for freshwater macroinvertebrates from 119 lakes and wetlands across seven Canadian provinces, along with selected physical, chemical and biological characteristics of these systems. Overall, water pH was the most important determinant of MeHg concentrations in both predatory and non-predatory invertebrates [[Formula: see text] = 0.32, p < 0.001; multivariate canonical redundancy analysis (RDA)]. The location of lakes explained additional variation in invertebrate MeHg (partial R(2) = 0.08 and 0.06 for latitude and longitude, respectively; RDA), with higher concentrations in more easterly and southerly regions. Both invertebrate foraging behaviour and trophic position (indicated by functional feeding groups and δ(15)N values, respectively) also predicted MeHg concentrations in the organisms. Collectively, results indicate that in addition to their feeding ecology, invertebrates accumulate more MeHg in acidic systems where the supply of MeHg to the food web is typically high. MeHg concentrations in macroinvertebrates may also be influenced by larger-scale geographic differences in atmospheric mercury deposition among regions.

Concentrations of methylmercury in invertebrates from wetlands of the Prairie Pothole Region of North America.

Prairie wetlands may be important sites of mercury (Hg) methylation resulting in elevated methylmercury (MeHg) concentrations in water, sediments and biota. Invertebrates are an important food resource and may act as an indicator of MeHg exposure to higher organisms. In 2007-2008, invertebrates were collected from wetland ponds in central Saskatchewan, categorized into functional feeding groups (FFGs) and analyzed for total Hg (THg) and MeHg. Methylmercury and THg concentrations in four FFGs ranged from 0.2-393.5 ng · g(-1) and 9.7-507.1 ng · g(-1), respectively. Methylmercury concentrations generally increased from gastropods with significantly lower average MeHg concentrations compared to other invertebrate taxa. Surrounding land use (agricultural, grassland and organic agricultural) may influence MeHg concentrations in invertebrates, with invertebrate MeHg concentrations being higher from organic ponds (457.5 ± 156.7 ng · g(-1)) compared to those from grassland ponds (74.8 ± 14.6 ng · g(-1)) and ponds on agricultural lands (32.8 ± 6.2 ng · g(-1)).

Assessment of mercury bioaccumulation within the pelagic food web of lakes in the western Great Lakes region.

While mercury is a health hazard to humans and wildlife, the biogeochemical processes responsible for its bioaccumulation in pelagic food webs are still being examined. Previous studies have indicated both "bottom-up" control of piscivorous fish Hg content through methylmercury.(MeHg) supply, as well as site-specific trophic factors. We evaluated ten studies from the western Great Lakes region to examine the similarity of MeHg trophic transfer efficiency within the pelagic food web, and assessed regional-scale spatial variability. Analyses of bioaccumulation and biomagnification factors between water, seston, zooplankton, and preyfish indicated that the largest increases in MeHg occurred at the base of the food web, and that the relative extent of trophic transfer was similar between sites. Positive correlations were observed between aqueous unfiltered MeHg, total Hg, and dissolved organic carbon, and measures of the efficiency of MeHg trophic transfer were consistent across widely disparate systems (both natural and experimentally manipulated) throughout North America. Such similarity suggests that the aqueous supply of MeHg is largely controlling bioaccumulation in pelagic food webs, while local, lake-specific variability can result from an array of trophic (biological) factors.

Mercury concentrations in surface water and harvested waterfowl from the prairie pothole region of Saskatchewan.

Mercury cycling in prairie ecosystems is poorly understood. We examined methylmercury (MeHg) concentrations in whole water from 49 diverse prairie wetlands and lakes in Saskatchewan. We also determined total Hg (THg) concentrations in waterfowl harvested by hunters for consumption. Average whole water MeHg concentrations ranged from 0.02 to over 4 ng L(-1) and were higher in water from wetland ponds compared to those in lakes. High MeHg concentrations in prairie wetlands present the possibility of increased Hg concentrations in biota inhabiting these and other similar systems. We therefore measured THg in 72 birds representing 13 species of waterfowl that commonly use prairie aquatic habitats. A large range in THg concentrations was observed among individual birds, with values ranging from below the detection limit to over 435 ng g(-1). When waterfowl were classified according to diet, we observed clear evidence of THg biomagnification with increasing proportion of animal prey consumed. THg concentrations in waterfowl collected by hunters did not exceed consumption guidelines of 0.5 mg kg(-1) developed for fish. This is the first study that has reported MeHg concentrations in water from the prairie pothole region of southern Saskatchewan.

Mercury cycling in stream ecosystems. 2. Benthic methylmercury production and bed sediment-pore water partitioning.

Mercury speciation, controls on methylmercury (MeHg) production, and bed sediment-pore water partitioning of total Hg (THg) and MeHg were examined in bed sediment from eight geochemically diverse streams where atmospheric deposition was the predominant Hg input. Across all streams, sediment THg concentrations were best described as a combined function of sediment percent fines (%fines; particles < 63 microm) and organic content. MeHg concentrations were best described as a combined function of organic content and the activity of the Hg(II)-methylating microbial community and were comparable to MeHg concentrations in streams with Hg inputs from industrial and mining sources. Whole sediment tin-reducible inorganic reactive Hg (Hg(II)R) was used as a proxy measure for the Hg(II) pool available for microbial methylation. In conjunction with radiotracer-derived rate constants of 203Hg(II) methylation, Hg(II)R was used to calculate MeHg production potential rates and to explain the spatial variability in MeHg concentration. The %Hg(II)R (of THg) was low (2.1 +/- 5.7%) and was inversely related to both microbial sulfate reduction rates and sediment total reduced sulfur concentration. While sediment THg concentrations were higher in urban streams, %MeHg and %Hg(II)R were higher in nonurban streams. Sediment pore water distribution coefficients (log Kd's) for both THg and MeHg were inversely related to the log-transformed ratio of pore water dissolved organic carbon (DOC) to bed sediment %fines. The stream with the highest drainage basin wetland density also had the highest pore water DOC concentration and the lowest log Kd's for both THg and MeHg. No significant relationship existed between overlying water MeHg concentrations and those in bed sediment or pore water, suggesting upstream sources of MeHg production may be more important than local streambed production as a driver of water column MeHg concentration in drainage basins that receive Hg inputs primarily from atmospheric sources.

Long-term wet and dry deposition of total and methyl mercury in the remote boreal ecoregion of Canada.

Although a positive relationship between atmospheric loadings of inorganic mercury (Hg(II)) to watersheds and concentrations of methyl mercury (MeHg) in fish has now been established, net wet and dry deposition of Hg(II) and MeHg to watersheds remains challenging to quantify. In this study, concentrations and loadings of total mercury (THg; all forms of Hg in a sample) and MeHg in open area wet deposition, throughfall, and litterfall were quantified atthe remote Experimental Lakes Area in the boreal ecoregion, NW Ontario, Canada. Between 1992 and 2006, mean annual THg and MeHg loadings in the open were 36 +/- 17 and 0.5 +/- 0.2 mg ha(-1), respectively. Throughfall THg and MeHg loadings were generally 2-4 times and 0.8-2 times higher, respectively, than loadings in the open. Loadings of both THg and MeHg were highest under an old growth spruce/fir canopy and lowest under a deciduous maple canopy, whereas loadings under young jack pine and wetland spruce/pine/alder canopies were intermediate. Litterfall generally represented the largest input of THg (86-105 mg ha(-1)) and MeHg (0.7-0.8 mg ha(-1)) to the landscape on an annual basis. Using the "direct" method of estimating dry deposition (thoughfall + litterfall - open loadings), we calculated that annual dry deposition of THg and MeHg under forest canopies ranged from 105 to 201 mg ha(-1), whereas dry deposition of MeHg ranged from 0.7 to 1.2 mg ha(-1). Photoreduction and emission of wet-deposited Hg(ll) from canopy foliage were accounted for, resulting in 3-5% (5-6 mg ha(-1)) higher annual estimates of dry deposition than via the direct method alone. NetTHg and MeHg loadings to this remote landscape were lower than at any other previously studied forested site globally. This study shows that THg and MeHg loading can be extremely variable within a heterogeneous boreal landscape and that processes such as Hg photoreduction and emission from foliage should be considered when estimating dry deposition of Hg.

Methylmercury and total mercury in plant litter decomposing in upland forests and flooded landscapes.

The overall objectives of this study were to examine the effects of flooding on the decomposition and mercury (Hg) content of tissues from plants common to boreal upland forests at the Experimental Lakes Area in northwestern Ontario. We used litterbags to study changes in total Hg (THg), methyl Hg (MeHg), carbon (C), and nitrogen (N) in 12 different plant tissues (birch, alder, blueberry, and Labrador tea leaves, bunchberry plants, jack pine needles, Sphagnum spp., Polytrichum spp., and Pleurozium spp. bryophytes, lichen, and fresh and extensively decomposed wood) placed on unflooded boreal forest soils and in experimentally created reservoirs over an approximately 800 day period. Rates of decomposition (as indicated by differences in the percentage of C and N mass left in the tissues over time) were slower in plant tissues placed on unflooded soils compared to the same tissues that were inundated in reservoirs. Depending on tissue type and initial THg concentrations, decomposing litter on both unflooded and flooded soils was either a source or a sink for THg. Tissues where initial THg concentrations were greater than 30 ng g(-1) represented a source of THg to the surrounding environment, whereas tissues that had initial concentrations of less than 30 ng g(-1) gained THg mass. Initial rates of change in THg were more rapid in plant tissues placed in reservoirs compared to the same plant tissue placed on unflooded soils, but there were no differences in final THg masses after approximately 800 days. Plant tissues placed in reservoirs exhibited large increases in MeHg mass, whereas MeHg mass decreased in the same plants placed on unflooded soils. This is the first study examining THg and MeHg cycling in decomposing plants in upland boreal forests and reservoirs.