Environmental Drivers of Rare Earth Element Bioaccumulation in Freshwater Zooplankton.

Human activities have resulted in significant release of rare earth elements (REEs) into the environment. However, the pathways of REEs from waters and soils into freshwater food webs remain poorly understood. Recent studies suggest that aquatic invertebrates may be good biomonitors for REEs, yet there is little information on factors that control REE bioaccumulation in these organisms. Our goal was to study the environmental drivers of REE levels in zooplankton, a key component in plankton food webs, across lakes from geographic areas with different bedrock geology. From 2011 to 2014, bulk zooplankton samples were collected for REE analysis from 39 lakes in eastern Canada. We observed a more than 200 fold variation in surface water REE concentrations and a 10-fold variation in sediment REE concentrations. These concentration gradients were associated with a range of more than an order of magnitude in zooplankton REE concentrations (∑REEY 3.2-210 nmol g-1). We found higher REE bioaccumulation in zooplankton from lakes with lower pH and higher REE to dissolved organic carbon ratios. Bioaccumulation was also strongly linked to the free ion concentrations of REEs (REE3+) in surface waters. Our study suggests that zooplankton REE bioaccumulation is an excellent predictor of bioavailable REEs in freshwaters.

Ratio of Methylmercury to Dissolved Organic Carbon in Water Explains Methylmercury Bioaccumulation Across a Latitudinal Gradient from North-Temperate to Arctic Lakes.

We investigated monomethylmercury (MMHg) bioaccumulation in lakes across a 30° latitudinal gradient in eastern Canada to test the hypothesis that climate-related environmental conditions affect the sensitivity of Arctic lakes to atmospheric mercury contamination. Aquatic invertebrates (chironomid larvae, zooplankton) provided indicators of MMHg bioaccumulation near the base of benthic and planktonic food chains. In step with published data showing latitudinal declines in atmospheric mercury deposition in Canada, we observed lower total mercury concentrations in water and sediment of higher latitude lakes. Despite latitudinal declines of inorganic mercury exposure, MMHg bioaccumulation in aquatic invertebrates did not concomitantly decline. Arctic lakes with greater MMHg in aquatic invertebrates either had (1) higher water MMHg concentrations (reflecting ecosystem MMHg production) or (2) low water concentrations of MMHg, dissolved organic carbon (DOC), chlorophyll, and total nitrogen (reflecting lake sensitivity). The MMHg:DOC ratio of surface water was a strong predictor of lake sensitivity to mercury contamination. Bioaccumulation factors for biofilms and seston in Arctic lakes showed more efficient uptake of MMHg in low DOC systems. Environmental conditions associated with low biological production in Arctic lakes and their watersheds increased the sensitivity of lakes to MMHg.

Random forests as cumulative effects models: A case study of lakes and rivers in Muskoka, Canada.

Cumulative effects assessment (CEA) - a type of environmental appraisal - lacks effective methods for modeling cumulative effects, evaluating indicators of ecosystem condition, and exploring the likely outcomes of development scenarios. Random forests are an extension of classification and regression trees, which model response variables by recursive partitioning. Random forests were used to model a series of candidate ecological indicators that described lakes and rivers from a case study watershed (The Muskoka River Watershed, Canada). Suitability of the candidate indicators for use in cumulative effects assessment and watershed monitoring was assessed according to how well they could be predicted from natural habitat features and how sensitive they were to human land-use. The best models explained 75% of the variation in a multivariate descriptor of lake benthic-macroinvertebrate community structure, and 76% of the variation in the conductivity of river water. Similar results were obtained by cross-validation. Several candidate indicators detected a simulated doubling of urban land-use in their catchments, and a few were able to detect a simulated doubling of agricultural land-use. The paper demonstrates that random forests can be used to describe the combined and singular effects of multiple stressors and natural environmental factors, and furthermore, that random forests can be used to evaluate the performance of monitoring indicators. The numerical methods presented are applicable to any ecosystem and indicator type, and therefore represent a step forward for CEA.

Diet and landscape characteristics drive spatial patterns of mercury accumulation in a high-latitude terrestrial carnivore.

Limited information exists on mercury concentrations and environmental drivers of mercury bioaccumulation in high latitude terrestrial carnivores. Spatial patterns of mercury concentrations in wolverine (Gulo gulo, n = 419) were assessed across a 1,600,000 km2 study area in relation to landscape, climate, diet and biological factors in Arctic and boreal biomes of western Canada. Hydrogen stable isotope ratios were measured in wolverine hair from a subset of 80 animals to assess the spatial scale for characterizing environmental conditions of their habitat. Habitat characteristics were determined using GIS methods and raster datasets at two scales, the collection location point and a 150 km radius buffer, which was selected based on results of a correlation analysis between hydrogen stable isotopes in precipitation and wolverine hair. Total mercury concentrations in wolverine muscle ranged >2 orders of magnitude from 0.01 to 5.72 µg/g dry weight and varied geographically, with the highest concentrations in the Northwest Territories followed by Nunavut and Yukon. Regression models at both spatial scales indicated diet (based on nitrogen stable isotope ratios) was the strongest explanatory variable of mercury concentrations in wolverine, with smaller though statistically significant contributions from landscape variables (soil organic carbon, percent cover of wet area, percent cover of perennial snow-ice) and distance to the Arctic Ocean coast. The carbon and nitrogen stable isotope ratios of wolverine muscle suggested greater mercury bioaccumulation could be associated with feeding on marine biota in coastal habitats. Landscape variables identified in the modelling may reflect habitat conditions which support enhanced methylmercury transfer to terrestrial biota. Spatially-explicit estimates of wet atmospheric deposition were positively correlated with wolverine mercury concentrations but this variable was not selected in the final regression models. These landscape patterns provide a basis for further research on underlying processes enhancing methylmercury uptake in high latitude terrestrial food webs.

Mineralogical, geospatial, and statistical methods combined to estimate geochemical background of arsenic in soils for an area impacted by legacy mining pollution.

The estimation of geochemical background is complex in areas impacted by point sources of atmospheric emissions due to unknowns about pollutant dispersion, persistence of pollutants on the landscape, and natural concentrations of elements associated with parent material. This study combined mineralogical analysis with conventional statistical and geospatial methods to separate anthropogenically impacted soils from unimpacted soils in the Yellowknife area, Northwest Territories, Canada, a region that was exposed to 60 years of arsenic (As)-rich atmospheric mining emissions (1938-1999) and that hosts natural enrichments of As. High concentrations of As (up to 4700 mg kg-1) were measured in publicly accessible soils near decommissioned roaster stacks in the region and strong relationships between As and distance from the main emission sources persisted in surface soils and soils at depth in the soil profile more than 60 years after the bulk of mining emissions were released. Mineralogical analysis provided unambiguous evidence regarding the source of As minerals and highlighted that most As in surface soils within 15 km of Yellowknife is hosted as anthropogenic arsenic trioxide (As2O3), produced by roaster stack emissions. Statistical protocols for the estimation of geochemical background were applied to an existing database of till geochemistry (N = 1490) after removing samples from mining impacted areas. Results suggested geochemical background for the region is 0.25-15 mg kg-1 As, comparable to global averages, with upper thresholds elevated in volcanic units (30 mg kg-1 As) that often host sulfide mineralization in greenstone belts in the region.

Diet influences on growth and mercury concentrations of two salmonid species from lakes in the eastern Canadian Arctic.

Diet, age, and growth rate influences on fish mercury concentrations were investigated for Arctic char (Salvelinus alpinus) and brook trout (Salvelinus fontinalis) in lakes of the eastern Canadian Arctic. We hypothesized that faster-growing fish have lower mercury concentrations because of growth dilution, a process whereby more efficient growth dilutes a fish's mercury burden. Using datasets of 57 brook trout and 133 Arctic char, linear regression modelling showed fish age and diet indices were the dominant explanatory variables of muscle mercury concentrations for both species. Faster-growing fish (based on length-at-age) fed at a higher trophic position, and as a result, their mercury concentrations were not lower than slower-growing fish. Muscle RNA/DNA ratios were used as a physiological indicator of short-term growth rate (days to weeks). Slower growth of Arctic char, inferred from RNA/DNA ratios, was found in winter versus summer and in polar desert versus tundra lakes, but RNA/DNA ratio was (at best) a weak predictor of fish mercury concentration. Net effects of diet and age on mercury concentration were greater than any potential offset by biomass dilution in faster-growing fish. In these resource-poor Arctic lakes, faster growth was associated with feeding at a higher trophic position, likely due to greater caloric (and mercury) intake, rather than growth efficiency.

Seasonal variation of arsenic and antimony in surface waters of small subarctic lakes impacted by legacy mining pollution near Yellowknife, NT, Canada.

The seasonal variation in lake water arsenic (As) and antimony (Sb) concentrations was assessed in four small (<1.5km2) subarctic lakes impacted by As and Sb emissions from legacy mining activities near Yellowknife, Northwest Territories, Canada. Substantial variation in As concentrations were measured over the two-year period of study in all but the deepest lake (maximum depth 6.9m), including a four-fold difference in As in the shallowest lake ([As]: 172-846µgL-1; maximum depth 0.8m). Arsenic concentrations were enriched following ice cover development in the three shallowest lakes (50-110%) through a combination of physical and biogeochemical processes. Early winter increases in As were associated with the exclusion of solutes from the developing ice-cover; and large increases in As were measured once oxygen conditions were depleted to the point of anoxia by mid-winter. The onset of anoxic conditions within the water column was associated with large increases in the concentration of redox sensitive elements in lake waters (As, iron [Fe], and manganese [Mn]), suggesting coupling of As mobility with Fe and Mn cycling. In contrast, there was little difference in Sb concentrations under ice suggesting that Sb mobility was controlled by factors other than Fe and Mn associated redox processes. A survey of 30 lakes in the region during fall (open-water) and late-winter (under-ice) revealed large seasonal differences in surface water As were more common in lakes with a maximum depth <4m. This threshold highlights the importance of winter conditions and links between physical lake properties and biogeochemical processes in the chemical recovery of As-impacted subarctic landscapes. The findings indicate annual remobilization of As from contaminated lake sediments may be inhibiting recovery in small shallow lakes that undergo seasonal transitions in redox state.