Methylmercury Cycling in High Arctic Wetland Ponds: Controls on Sedimentary Production

Methylmercury (MeHg) is a potent neurotoxin that has been demonstrated to biomagnify in Arctic freshwater foodwebs to levels that may be of concern to Inuit peoples subsisting on freshwater fish, for example. The key process initiating the bioaccumulation and biomagnification of MeHg in foodwebs is the methylation of inorganic Hg­(II) to form MeHg, and ultimately how much MeHg enters foodwebs is controlled by the production and availability of MeHg in a particular water body. We used isotopically enriched Hg stable isotope tracers in sediment core incubations to measure potential rates of Hg­(II) methylation and investigate the controls on MeHg production in High Arctic wetland ponds in the Lake Hazen region of northern Ellesmere Island (Nunavut, Canada). We show here that MeHg concentrations in sediments are primarily controlled by the sediment methylation potential and the quantity of Hg­(II) available for methylation, but not by sediment demethylation potential. Furthermore, MeHg concentrations in pond waters are controlled by MeHg production in sediments, overall anaerobic microbial activity, and photodemethylation in the water column

Methylmercury Cycling in High Arctic Wetland Ponds: Sources and Sinks

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

Sources of Methylmercury to Snowpacks of the Alberta Oil Sands Region: A Study of In Situ Methylation and Particulates

Snowpacks in the Alberta Oil Sands Region (AOSR) of Canada contain elevated loadings of methylmercury (MeHg; a neurotoxin that biomagnifies through foodwebs) due to oil sands related activities. At sites ranging from 0 to 134 km from the major AOSR upgrading facilities, we examined sources of MeHg by quantifying potential rates of MeHg production in snowpacks and melted snow using mercury stable isotope tracer experiments, as well as quantifying concentrations of MeHg on particles in snowpacks (pMeHg). At four sites, methylation rate constants were low in snowpacks (<i>k</i>_m = 0.001–0.004 d^–1) and nondetectable in melted snow, except at one site (<i>k</i>_m = 0.0007 d^–1). The ratio of methylation to demethylation varied between 0.3 and 1.5, suggesting that the two processes are in balance and that in situ production is unlikely an important net source of MeHg to AOSR snowpacks. pMeHg concentrations increased linearly with distance from the upgraders (R² = 0.71, <i>p</i> < 0.0001); however, snowpack total particle and pMeHg loadings decreased exponentially over this same distance (R² = 0.49, <i>p</i> = 0.0002; R² = 0.56, <i>p</i> < 0.0001). Thus, at near-field sites, total MeHg loadings in snowpacks were high due to high particle loadings, even though particles originating from industrial activities were not MeHg rich compared to those at remote sites. More research is required to identify the industrial sources of snowpack particles in the AOSR

Mercury Biomagnification through Food Webs Is Affected by Physical and Chemical Characteristics of Lakes

Mercury (Hg) contamination in aquatic systems remains a global concern because the organic form, methyl Hg (MeHg), can biomagnify to harmful concentrations in fish, fish-eating wildlife, and humans. Food web transfer of MeHg has been explored using models of log MeHg versus relative trophic position (nitrogen isotopes, δ¹⁵N), but regression slopes vary across systems for unknown reasons. In this study, MeHg biomagnification was determined for 11 lake food webs in Kejimkujik National Park, Nova Scotia, Canada, and compared to physical and chemical lake characteristics using principal component and multiple regression analyses. MeHg biomagnification (regression slopes of log MeHg versus baseline-adjusted δ¹⁵N for fishes and invertebrates) varied significantly across lakes and was higher in systems with lower aqueous nutrient/MeHg/chloride scores. This is one of the largest, consistent data sets available on MeHg biomagnification through temperate lake food webs and the first study to use a principal component and multiple regression approach to understand how lake chemical and physical characteristics interact to affect biomagnification among systems. Overall, our results show that the magnitude of MeHg biomagnification through lake food webs is related to the chemical and physical characteristics of the systems, but the underlying mechanisms warrant further investigation

Widespread Atmospheric Tellurium Contamination in Industrial and Remote Regions of Canada

High tech applications, primarily photovoltaics, have greatly increased demand for the rare and versatile but toxic element tellurium (Te). Here we examine dated lake sediment Te concentration profiles collected near potential point sources (metal smelters, coal mining/combustion facilities, oil sands operations) and from rural regions and remote natural areas of Canada. Te contamination was most prevalent near a Cu/Zn smelter where observed deposition infers 21 g Te released per metric ton (t) of Cu processed. Globally, 9,500 t is predicted to have been atmospherically deposited near Cu smelters post-1900. In a remote area of central Canada (Experimental Lakes Area; ELA), preindustrial Te deposition rates were equivalent to the estimated average global mass flux supplied from natural sources; however more surprisingly, modern Te deposition rates were 6-fold higher and comparable with Te measurements in precipitation. We therefore suggest that sediment cores reliably record atmospheric Te deposition and that anthropogenic activities have significantly augmented atmospheric Te levels, making it an emerging contaminant of potential concern. Lake water residence time was found to influence lake sediment Te inventories among lakes within a region. The apparent settling rate for Te was comparable to macronutrients (C, N, P), likely indicative of significant biological processing of Te

Atmospheric Deposition of Mercury and Methylmercury to Landscapes and Waterbodies of the Athabasca Oil Sands Region

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 km² 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 (<i>r</i> = 0.45–0.88, <i>p</i> < 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

VRS-chlorophyll-a data from 23 sediment cores from study lakes in the Athabasca Oil Sands Region, Alberta, Canada

VRS-chlorophyll-a data from 23 sediment cores from study lakes in the Athabasca Oil Sands Region, Alberta, Canad

Nutrient (TN, DIN, TP, TDP, SRP) data from snowpack samples in the Athabasca Oil Sands Region, Alberta, Canada

Nutrient (TN, DIN, TP, TDP, SRP) data from snowpack samples in the Athabasca Oil Sands Region, Alberta, Canad

Alternative field curve modelling approach : regional models

In this thesis, we focus on thorough yield curve modelling. We build on extended classical Nelson-Siegel model, which we further develop to accommodate unobserved regional common factors and principal components. We centre our discussion on central European currencies' yield curves: CZK, HUF, PLN and SKK. We propose two novel models to capture regional dynamics; one based purely on state space formulation and the other relying also on principal components of the regional yield curves. Moreover, we supplement the models with two application examples in risk management and structural break detection. The main contribution of this thesis is a creation of a complete framework that enables us to analyse yield curves, to design risk scenarios and to detect structural breaks of various types

Deposition map of total dissolved phosphorus in 2014 snowpack.

<p>Interpolated loads of total dissolved phosphorus (TDP) (mg/m²) to the Athabasca Oil Sands Region in March 2014. Sedimentary VRS-chl<i>a</i> enrichment factors and DBT enrichment factors from each study lake are overlain.</p