[Show abstract][Hide abstract] ABSTRACT: Zooplankton play a central role in marine food webs, dictating the quantity and quality of energy available to upper trophic levels. They act as “keystone” species in transfer of mercury (Hg) up through the marine food chain. Here, we present the first pan-Arctic overview of total and monomethylmercury concentrations (THg and MMHg) and stable isotope ratios of carbon (δ13C) and nitrogen (δ15N) in selected zooplankton species by assembling data collected between 1998 and 2012 from six arctic regions (Laptev Sea, Chukchi Sea, southeastern Beaufort Sea, Canadian Arctic Archipelago, Hudson Bay and northern Baffin Bay). MMHg concentrations in Calanus spp., Themisto spp. and Paraeuchaeta spp. were found to increase with higher δ15N and lower δ13C. The southern Beaufort Sea exhibited both the highest THg and MMHg concentrations. Biomagnification of MMHg between Calanus spp. and two of its known predators, Themisto spp. and Paraeuchaeta spp., was greatest in the southern Beaufort Sea. Our results show large geographical variations in Hg concentrations and isotopic signatures for individual species related to regional ecosystem features, such as varying water masses and freshwater inputs, and highlight the increased exposure to Hg in the marine food chain of the southern Beaufort Sea.
Full-text · Article · May 2016 · Science of The Total Environment
[Show abstract][Hide abstract] ABSTRACT: The arctic has been contaminated by legacy organochlorine pesticides (OCPs) and currently used pesticides (CUPs) through atmospheric transport and oceanic currents. Here we report time trends and air-water exchange of OCPs and CUPs from research expeditions conducted between 1993-2013. Compounds determined in both air and water were trans- and cis-chlordanes (TC, CC), trans- and cis-nonachlors (TN, CN), heptachlor exo-epoxide (HEPX), dieldrin (DIEL), chlorobornanes (ΣCHBs, toxaphene), dacthal (DAC), endosulfans and metabolite endosulfan sulfate (ENDO-I, ENDO-II, ENDO SUL), chlorothalonil (CHT), chlorpyrifos (CPF) and trifluralin (TFN). Pentachloronitrobenzene (PCNB, quintozene) and its soil metabolite pentachlorothianisole (PCTA) were also found in air. Concentrations of most OCPs declined in surface water, whereas some CUPs increased (ENDO-I, CHT and TFN) or showed no significant change (CPF, DAC), while most compounds declined in air. Chlordane compound fractions TC/(TC+CC) and TC/(TC+CC+TN) decreased in water and air, while CC/(TC+CC+TN) and TN/(TC+CC+TN) increased, suggesting selective removal of more labile TC over time and/or a shift in chlordane sources. Water/air fugacity ratios indicated net volatilization (FR >1.0) or near equilibrium (FR not significantly different from 1.0) for most OCPs, but net deposition (FR <1.0) for ΣCHBs. Net deposition was shown for ENDO-I on all expeditions, while the net exchange direction of other CUPs varied. Understanding the processes and current state of air-surface exchange helps to interpret environmental exposure, evaluate the effectiveness of International Protocols and provides insights for the environmental fate of new and emerging chemicals.
[Show abstract][Hide abstract] ABSTRACT: Air samples collected during 1994-2000 at the Canadian Arctic air monitoring station Alert (82 degrees 30'N, 62 degrees 20'W) were analysed by enantiospecific gas chromatography-mass spectrometry for alpha-hexachlorocyclohexane (alpha-HCH), trans-chlordane (TC) and cis-chlordane (CC). Results were expressed as enantiomer fractions (EF = peak areas of (+)/[(+) + (-)] enantiomers), where EFs = 0.5, <0.5 and >0.5 indicate racemic composition, and preferential depletion of (+) and (-) enantiomers, respectively. Long-term average EFs were close to racemic values for alpha-HCH (0.504 +/- 0.004, n = 197) and CC (0.505 +/- 0.004, n = 162), and deviated farther from racemic for TC (0.470 +/- 0.013, n = 165). Digital filtration analysis revealed annual cycles of lower alpha-HCH EFs in summer-fall and higher EFs in winter-spring. These cycles suggest volatilization of partially degraded alpha-HCH with EF < 0.5 from open water and advection to Alert during the warm season, and background transport of alpha-HCH with EF > 0.5 during the cold season. The contribution of sea-volatilized alpha-HCH was only 11% at Alert, vs. 32% at Resolute Bay (74.68 degrees N, 94.90 degrees W) in 1999. EFs of TC also followed annual cycles of lower and higher values in the warm and cold seasons. These were in phase with low and high cycles of the TC / CC ratio (expressed as F-TC = TC/(TC + CC)), which suggests greater contribution of microbially "weathered" TC in summer-fall versus winter-spring. CC was closer to racemic than TC and displayed seasonal cycles only in 1997-1998. EF profiles are likely to change with rising contribution of secondary emission sources, weathering of residues in the environment, and loss of ice cover in the Arctic. Enantiomer-specific analysis could provide added forensic capability to air monitoring programs.
No preview · Article · Feb 2015 · Atmospheric Chemistry and Physics
[Show abstract][Hide abstract] ABSTRACT: For decades sea ice has been perceived as a physical barrier for the loading of contaminants to the Arctic Ocean. We show that sea ice, in fact, facilitates the delivery of organic contaminants to the Arctic marine food web through processes that: 1) are independent of contaminant physical-chemical properties (e.g. 2-3-fold increase in exposure to brine-associated biota), and 2) depend on physical-chemical properties and, therefore, differentiate between contaminants (e.g. atmospheric loading of contaminants to melt ponds over the summer, and their subsequent leakage to the ocean). We estimate the concentrations of legacy organochlorine pesticides (OCPs) and current-use pesticides (CUPS) in melt pond water in the Beaufort Sea, Canadian High Arctic, in 2008, at near-gas exchange equilibrium based on Henry's law constants (HLCs), air concentrations and exchange dynamics. CUPs currently present the highest risk of increased exposures through melt pond loading and drainage due to the high ratio of melt pond water to seawater concentration (Melt pond Enrichment Factor, MEF), which ranges from 2 for dacthal to 10 for endosulfan I. Melt pond contaminant enrichment can be perceived as a hypothetical 'pump' delivering contaminants from the atmosphere to the ocean under ice-covered conditions, with 2-10% of CUPs annually entering the Beaufort Sea via this input route compared to the standing stock in the Polar Mixed Layer of the ocean. The abovementioned processes are strongly favored in first-year ice compared to multi-year ice and, therefore, the dynamic balance between contaminant inventories and contaminant deposition to the surface ocean is being widely affected by the large-scale icescape transition taking place in the Arctic.
Full-text · Article · Jan 2015 · Science of The Total Environment
[Show abstract][Hide abstract] ABSTRACT: In 2012, Arctic cod (Boreogadus saida) were collected from offshore regions of the Beaufort Sea to determine the concentrations of CYP1A1 phase I metabolites of polycyclic aromatic hydrocarbons (OH-PAHs) in liver and to correlate measured concentrations with (i) morphometric measurements that are known to be indicative of fish health and, (ii) biochemical endpoints of health including vitamin A/E and metabolites and hepatic deiodinase activity (DI). Four ring OH-PAHs were detected in 90% of our samples with a mean liver concentration of 1829.2 ± 159.2 ng/g (ww). Total (∑) concentrations of 5/6-membered ring OH-PAHs in liver were smaller [mean of 931.6 ± 104.3 ng/g, (ww)] and detected less frequently (75%) than the 4-ring OH-PAHs. Fish length and liver weight were both negatively correlated to ∑concentrations of 4-ringed OH-PAHs (p<0.001). Liver somatic index was also negatively correlated to ∑4-OH-PAHs (p<0.05) but not for ∑5/6-OH-PAHs (p>0.1). There was a significant positive relationship between DI and 4-ring OH-PAHs (p<0.05) in liver suggesting an induction of this enzyme. No such correlation was observed for the 5/6-ring OH-PAHs. Retinyl palmitate (RP) was the only vitamin that could be measured in liver ranging from 0.230 to 26.3 ug/g (ww). No associations between RP and levels of the 4- or 5/6-ringed OH-PAHs were observed. Continued baseline studies are clearly warranted to further understand effects of OH-PAHs on fish health before planned exploration activities begin in this region.
[Show abstract][Hide abstract] ABSTRACT: The Canadian Arctic has vast freshwater resources, and fish are important in the diet of many Northerners. Mercury is a contaminant of concern because of its potential toxicity and elevated bioaccumulation in some fish populations. Over the last decade, significant advances have been made in characterizing the cycling and fate of mercury in these freshwater environments. Large amounts of new data on concentrations, speciation and fluxes of Hg are provided and summarized for water and sediment, which were virtually absent for the Canadian Arctic a decade ago. The biogeochemical processes that control the speciation of mercury remain poorly resolved, including the sites and controls of methylmercury production. Food web studies have examined the roles of Hg uptake, trophic transfer, and diet for Hg bioaccumulation in fish, and, in particular, advances have been made in identifying determinants of mercury levels in lake-dwelling and sea-run forms of Arctic char. In a comparison of common freshwater fish species that were sampled across the Canadian Arctic between 2002 and 2009, no geographic patterns or regional hotspots were evident. Over the last two to four decades, Hg concentrations have increased in some monitored populations of fish in the Mackenzie River Basin while other populations from the Yukon and Nunavut showed no change or a slight decline. The different Hg trends indicate that the drivers of temporal change may be regional or habitat-specific. The Canadian Arctic is undergoing profound environmental change, and preliminary evidence suggests that it may be impacting the cycling and bioaccumulation of mercury. Further research is needed to investigate climate change impacts on the Hg cycle as well as biogeochemical controls of methylmercury production and the processes leading to increasing Hg levels in some fish populations in the Canadian Arctic.
Full-text · Article · Jun 2014 · Science of The Total Environment
[Show abstract][Hide abstract] ABSTRACT: 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 regions in the circumpolar Arctic. Mass balance models have been developed to provide quantitative estimates of THg fluxes into and out of the Arctic Ocean and Hudson Bay. Several recent studies on Hg biomagnification have improved our understanding of trophic transfer of Hg through marine food webs. Over the past several decades, Hg concentrations have increased in some marine biota, while other populations showed no temporal change. Marine biota also exhibited considerable geographic variation in Hg concentrations with ringed seals, beluga and polar bears from the Beaufort Sea region having higher Hg concentrations compared with other parts of the Canadian Arctic. The drivers of these variable patterns of Hg bioaccumulation, both regionally and temporally, within the Canadian Arctic remain unclear. Further research is needed to identify the underlying processes including the interplay between biogeochemical and food web processes and climate change.
Full-text · Article · Jun 2014 · Science of The Total Environment
[Show abstract][Hide abstract] ABSTRACT: We show 2008 seasonal trends of total and mono-methyl mercury (THg and MeHg, respectively) in herbivorous (Calanus hyperboreus) and predatory (Chaetognaths, Paraeuchaeta glacialis and Themisto abyssorum) zooplankton species from the Canadian High Arctic (Amundsen Gulf and the Canadian Beaufort Sea) in relation to ambient seawater and diet. It has recently been postulated that the Arctic marine environment may be exceptionally vulnerable to toxic MeHg contamination through post-depositional processes leading to mercury transformation and methylation. Here, we show that C. hyperboreus plays a hitherto unrecognized central role in mercury transformation while, itself, not manifesting inordinately high levels of THg compared to its prey (pelagic particulate organic matter (POM)). Calanus hyperboreus shifts Hg from mainly inorganic forms in pelagic POM (> 99.5%) or ambient seawater (> 90%) to primarily organic forms (> 50%) in their tissue. We calculate that annual dietary intake of MeHg could supply only ~30% of the MeHg body burden in C. hyperboreus and, thus, transformation within the species, perhaps mediated by gut microbial communities, or bioconcentration from ambient seawater likely play overriding roles. Seasonal THg trends in C. hyperboreus are variable and directly controlled by species-specific physiology, e.g. egg laying and grazing. Zooplankton that prey on species such as C. hyperboreus provide a further biomagnification of MeHg and reflect seasonal trends observed in their prey.
Full-text · Article · Jun 2014 · Environmental Science and Technology
[Show abstract][Hide abstract] ABSTRACT: This paper synthesizes the sediment geochemistry data for 19 sediment cores from 16 lakes from various regions of Canada to describe general relationships between mercury (Hg) and the relative amount of labile organic matter (OM) as a proportion of total organic carbon. These relationships form the basis for proposing a general classification scheme of the capacity of a lake system to bind Hg to OM, which provides a first order screening of lakes to quickly assess them before further detailed analytical methods are employed. Mercury is known to have a strong affinity to OM before entering the lakes (binding with soil OM in the watershed) and also within the lakes (scavenging by autochthonous OM). Association of Hg with particulate OM, irrespective of the source, effectively captures available Hg (II) and ultimately sequesters it in bottom sediments. Relationships between total Hg concentration and the relative amount of labile OM in the sediments of a given system reveal important geochemical information; for example, the overall capacity of the system to effectively scavenge and fix available Hg, or its vulnerability to be overwhelmed by excess inputs of Hg in organic-poor or Hg contaminated systems.
No preview · Article · May 2014 · Chemical Geology
[Show abstract][Hide abstract] ABSTRACT: A combination of Rock-Eval pyrolysis and isotopic analyses is used to characterize the sources and distribution of organic matter in modern marine sediments from the subarctic Hudson Bay (including Hudson Strait and Foxe Basin), Canada. This approach reveals organic matter contributions from both marine and terrigenous sources, with spatial patterns and varying degrees of degradation that are consistent with inferences from traditional geochemical tracers for modern organic matter. Rock-Eval parameters characterize Hudson Bay organic matter with low hydrogen index, high oxygen index and a high degree of residual carbon that suggests heavily reworked materials. Locations of higher primary productivity in Hudson Strait, Foxe Basin, the northeast and far west of Hudson Bay, and the concentration of watershed runoff in the southern part of Hudson Bay can be delineated using the ratios between hydrogen and oxygen indices and from the distribution of labile organic carbon. Relatively high temperatures of peak hydrocarbon yield identify an advanced state of OM degradation or humic substances as important classes of organic carbon compounds in the majority of the sediment. Such highly degraded and oxygenated organic matter is unusual compared to that typically observed in other Arctic shelf seas and is consistent with a strong role for sediment and organic matter recycling in Hudson Bay. In the offshore region, the source of highly oxidized and labile organic matter identified by Rock-Eval parameters is resolved with δ13C and biomarker information that also permit examination of the sediment biogeochemical regime. This approach suggests that a distinct association with Mn enriched sediment contributes to the oxidization signal by abiotic or biological Mn related processes. These interpretations extend the limited information available on using Rock-Eval analyses to characterize organic matter in recently deposited marine sediments and describe an important consideration to using this method in Mn enriched environments.
Full-text · Article · Mar 2014 · Organic Geochemistry
[Show abstract][Hide abstract] ABSTRACT: Surface sediment samples from the Hudson Bay system were analysed in order to examine the role of key regulators of arctic marine productivity — light and nutrients as affected by freshwater stratification and sea-ice cover — on the spatial distribution and production of dinoflagellate cysts. Total cyst fluxes vary from 0.2 × 106 to 30.6 × 106 cysts m− 2 a− 1, with the highest values observed in eastern Hudson Bay. A total of 24 cyst taxa, representing 11 genera of five orders, were identified and distribution maps of the most common taxa have been produced. This is the first record of Echinidinium aculeatum, Echinidinium karaense, cf. Echinidinium delicatum, Islandinium brevispinosum, Selenopemphix quanta, cysts of Protoperidinium americanum, cysts of cf. Biecheleria sp. and Polarella glacialis in the Hudson Bay system. Dinoflagellate cyst assemblages show distinct spatial patterns revealing three compositional domains: eastern Hudson Bay, western-central Hudson Bay and Hudson Strait. The eastern domain is characterised by a dominance of autotrophic cysts of Pentapharsodinium dalei whereas the western-central domain is characterised by autotrophic Operculodinium centrocarpum with some contribution by heterotrophic Polykrikos sp. var. arctic morphotype and Polykrikos spp. Sites from Hudson Strait are distinguished by an overwhelming prevalence of heterotrophic Protoperidiniaceae cysts, mainly Islandinium minutum, and have the highest values of sedimentary biogenic silica, used as a proxy for diatom productivity.
Full-text · Article · Jan 2014 · Marine Micropaleontology
[Show abstract][Hide abstract] ABSTRACT: Elimination of persistent organic pollutants (POPs) under national and international regulations reduces "primary" emissions, but "secondary" emissions continue from residues deposited in soil, water, ice and vegetation during former years of usage. In a future, secondary source controlled world, POPs will follow the carbon cycle and biogeochemical processes will determine their transport, accumulation and fate. Climate change is likely to affect mobilisation of POPs through e.g., increased temperature, altered precipitation and wind patterns, flooding, loss of ice cover in polar regions, melting glaciers, and changes in soil and water microbiology which affect degradation and transformation. Chiral compounds offer advantages for following transport and fate pathways because of their ability to distinguish racemic (newly released or protected from microbial attack) and nonracemic (microbially degraded) sources. This paper discusses the rationale for this approach and suggests applications where chiral POPs could aid investigation of climate-mediated exchange and degradation processes. Multiyear measurements of two chiral POPs, trans-chlordane and α-HCH, at a Canadian Arctic air monitoring station show enantiomer compositions which cycle seasonally, suggesting varying source contributions which may be under climatic control. Large-scale shifts in the enantioselective metabolism of chiral POPs in soil and water might influence the enantiomer composition of atmospheric residues, and it would be advantageous to include enantiospecific analysis in POPs monitoring programs.
[Show abstract][Hide abstract] ABSTRACT: Water column concentrations of α-HCH were measured in the southern Beaufort Sea as part of the Canadian Arctic Shelf Exchange Study (CASES; 2003–04), the Circumpolar Flaw Lead System Study (CFL; 2007–08), and in the Mackenzie River during the 2008 NAHIDIK program. Atmospheric α-HCH concentrations were measured during CASES program. Inventories of α-HCH in the Polar Mixed Layer (PML) and the Pacific Mode Layer (PL) of the Beaufort Sea were calculated between 1986 and 2007 based on the available data. Between 1986 and 1993, there was a significant loading of α-HCH to the Beaufort Sea via the ocean currents. About 12% of the loading to the PML could be explained by the combined effect of the air–water gas exchange and the river runoff. After 1993, α-HCH inventories started decreasing, and could be well predicted exclusively by degradation. Ice formation was shown to be a solvent depleting process leading to a significant increase in the α-HCH concentration in the water just beneath the ice. Associated low α-HCH concentrations in the ice and relatively low ice export from the Beaufort Sea resulted in negligible influence of this output route on the inventories in the PML. The majority of α-HCH in the Beaufort Sea could be eliminated due to degradation by 2020, with concentrations in 2040 dropping to
Full-text · Article · Nov 2013 · Journal of Marine Systems
[Show abstract][Hide abstract] ABSTRACT: In this study, we examine mercury bioaccumulation by a first-year sea-ice (FYI) algal community in the western Canadian Arctic during the spring of 2008. Total mercury concentration in bottom sea-ice particulate ([PHg]T) ranged 0.004–0.022 mg/g dw and was limited by the amount of mercury available for uptake when the spring bloom commenced. Mercury in ice algae originated from a combination of brine and seawater as sources, while atmospheric mercury depletion events did not appear to significantly contribute as a source in a coupled manner. We show that the bottom sea-ice brine presents a chemically and biologically unique niche from which inorganic Hg makes its way into the food web. Once incorporated into algae, mercury can be transported spatially and trophically within the ecosystem by a range of processes including grazing, resuspension, remineralization, and sedimentation. Ice algae contribute 10–60% of the annual primary production in the Arctic and are thought to become even more productive and abundant under a mild climate change scenario. Replacement of multiyear ice with FYI in the Beaufort Sea alone could result in an additional influx of 48 kg/yr of particle bound Hg. Further studies are thus warranted to elucidate mechanisms by which mercury transformation processes and transfer into the Arctic marine food web are impacted by the interaction between sea ice, brine, and seawater.
Full-text · Article · Sep 2013 · Journal of Geophysical Research Atmospheres