Modeling historical budget for ß-Hexachlorocyclohexane (HCH) in the Arctic Ocean: A contrast to α-HCH.

The historical annual loading to, removal from, and cumulative burden in the Arctic Ocean for ß-hexachlorocyclohexane (ß-HCH), an isomer comprising 5-12% of technical HCH, is investigated using a mass balance box model from 1945 to 2020. Over the 76 years, loading occurred predominantly through ocean currents and river inflow (83%) and only a small portion via atmospheric transport (16%). ß-HCH started to accumulate in the Arctic Ocean in the late 1940s, reached a peak of 810 t in 1986, and decreased to 87 t in 2020, when its concentrations in the Arctic water and air were ∼30 ng m-3 and ∼0.02 pg m-3, respectively. Even though ß-HCH and α-HCH (60-70% of technical HCH) are both the isomers of HCHs with almost identical temporal and spatial emission patterns, these two chemicals have shown different major pathways entering the Arctic. Different from α-HCH with the long-range atmospheric transport (LRAT) as its major transport pathway, ß-HCH reached the Arctic mainly through long-range oceanic transport (LROT). The much higher tendency of ß-HCH to partition into the water, mainly due to its much lower Henry's Law Constant than α-HCH, produced an exceptionally strong pathway divergence with ß-HCH favoring slow transport in water and α-HCH favoring rapid transport in air. The concentration and burden of ß-HCH in the Arctic Ocean are also predicted for the year 2050 when only 4.4-5.3 t will remain in the Arctic Ocean under the influence of climate change.

Steady-State Based Model of Airborne Particle/Gas and Settled Dust/Gas Partitioning for Semivolatile Organic Compounds in the Indoor Environment.

Indoor semivolatile organic compounds (SVOCs), present in the air, airborne particles, settled dust, and other indoor surfaces, can enter the human body through several pathways. Knowing the partitioning between gaseous and particulate phases is important in identifying specific pathway contributions and thereby accurately assessing human exposure. Numerous studies have developed equilibrium equations to predict airborne particle/gas (P/G) partitioning in air (KP) and dust/gas (D/G) partitioning in settled dust (KD). The assumption that P/G and D/G equilibria are instantaneous for airborne and settled dust phases, commonly adopted by current indoor fate models, is not likely valid for compounds with high octanol-air partition coefficients (KOA). Here, we develop steady-state based equations to predict KP and KD in the indoor environment. Results show that these equations perform well and are verified by worldwide monitoring data. It is suggested that instantaneous steady state could work for P/G and D/G partitioning of SVOCs in indoor environments, and the equilibrium is just a special case of the steady state when log KOA < 11.38 for P/G partitioning and log KOA < 10.38 for D/G partitioning. These newly developed equations and methods provide a tool for more accurate assessment for human exposure to SVOCs in the indoor environment.

Approach to Predicting the Size-Dependent Inhalation Intake of Particulate Novel Brominated Flame Retardants.

The risk of human exposure to particulate novel brominated flame retardants (NBFRs) in the atmosphere has received increasing attention from scientists and the public, but currently, there is no reliable approach to predict the intake of these compounds on the basis of their size distribution. Here, we develop a reliable approach to predict the size-dependent inhalation intake of particulate NBFRs, based on the gas/particle (G/P) partitioning behavior of the NBFRs. We analyzed the concentrations of eight NBFRs in 363 size-segregated particulate samples and 99 paired samples of gaseous and bulk particles. Using these data, we developed an equation to predict the G/P partitioning quotients of NBFRs in particles in different size ranges (KPi) based on particle size. This equation was then successfully applied to predict the size-dependent inhalation intake of particulate NBFRs in combination with an inhalation exposure model. This new approach provides the first demonstration of the effects of the temperature-dependent octanol-air partitioning coefficient (KOA) and total suspended particle concentration (TSP) on the intake of particulate NBFRs by inhalation. In an illustrative case where TSP = 100 µg m-3, inhalation intake of particulate NBFRs exceeded the intake of gaseous NBFRs when log KOA > 11.4.

Particle/gas partitioning for semi-volatile organic compounds (SVOCs) in Level III multimedia fugacity models: Gaseous emissions.

Atmospheric transport is a global-scale process that moves semi-volatile organic compounds (SVOCs) rapidly from source regions to remote locations, where these chemicals have never been produced or used. Particle/gas (P/G) partitioning of SVOCs during atmospheric transport governs wet and dry deposition, and thereby controls the efficiency and scope of long-range atmospheric transport and fate for these sorts of compounds. Previous work has shown that the assumption of steady state between particulate and gaseous phases in the atmosphere leads to model results that more closely match observations especially for compounds that strongly favor the particulate phase. Here, the practical application of steady-state P/G partitioning in the atmosphere in multimedia fugacity models is presented in greater detail. A method is developed whereby the fugacity of a chemical in the particle-phase is set equal to that in the gaseous phase (a pseudo equilibrium) but still maintains steady state of the chemical between air and aerosols in the atmosphere. This procedure greatly simplifies the application of multimedia fugacity models. Using this approach, a condition of steady state between air and aerosols is developed and applied in a Level III six-compartment six-fugacity model, which becomes a much simpler Level III six-compartment four-fugacity model. This newly-developed model is then applied to data observed during a monitoring program.

Particle/gas partitioning for semi-volatile organic compounds (SVOCs) in level III multimedia fugacity models: Both gaseous and particulate emissions.

Multimedia fugacity models have long been used to address the fate of toxic organic chemical emissions by providing a quantitative account of the sources, transport processes, and sinks. Recently, we have examined three level-III fugacity models (E4F (equilibrium six-compartment four-fugacity), S6F (steady-state six-compartment six-fugacity) and S4F (steady-state six-compartment four-fugacity) Models), in the context of their performance set against real-world data, and their practicality of application. Here, we discuss how the balance between gaseous and aerosol phases of emissions assumed for initial conditions affects the different model outcomes. Our results show that the S6F Model predictions closely match those of the S4F Model when chemical emissions are entirely in the gas-phase. As the particulate proportion of the emission increases, the S6F Model predictions diverge from those of the S4F Model and approach those of the E4F Model. Once the particulate portion reaches 100%, the S6F and E4F Models produce identical results: an internally inconsistent system where chemicals are not in a steady state between air and aerosols, and mass balance for both air and aerosols is not achieved. Thus, in terms of practicality, internal consistency, chemical mass balance and agreement with observations, the S4F Model is clearly the best choice.

Slopes and intercepts from log-log correlations of gas/particle quotient and octanol-air partition coefficient (vapor-pressure) for semi-volatile organic compounds: I. Theoretical analysis.

Gas/particle partitioning governs the transport and fate of semi-volatile organic compounds (SVOCs) released to the atmosphere. The partition quotient of SVOCs, KP, is related to their subcooled liquid vapor pressure (logKP = mp logPL + bp) and to their octanol-air partition coefficient (logKP = mo logKOA + bo). Previous theory predicts that -mp and mo should be close to, or equal to 1 based on the assumption that gas- and particle-phases are at equilibrium in the atmosphere. Here, we develop analytical equations to calculate mo and bo as functions of logKOA and mp and bp as functions of logPL. We find that experimental, analytical, or statistical artifacts and other reported factors are not the leading causes for deviations of the slopes, mp and mo, from -1 and 1, respectively. Rather, it is the inherent parameter, KOA, that determines mo and bo, and equivalently, PL is the major parameter determining mp and bp, and such deviations are evidence that equilibrium is an inappropriate assumption. In contrast, the actual steady-state between gas and particle phases of SVOCs leads that their -mp and mo should range from 0 to 1, implying that equilibrium is a reasonable assumption only when -mp and mo are larger than 0.49. To illustrate these points, we provide a detailed discussion of the global atmospheric transport of polybrominated diphenyl ethers (PBDEs) with emphasis on Polar Regions where low air temperatures favor a special steady-state, where their slopes mp and mo can reach 0, indicating a constant value of logKP (-1.53).

Slopes and intercepts from log-log correlations of gas/particle quotient and octanol-air partition coefficient (vapor-pressure) for semi-volatile organic compounds: II. Theoretical predictions vs. monitoring.

The logarithm of gas/particle (G/P) partition quotient (logKP) has been found to have a linear relationship with logKOA (octanol-air partition coefficient) with slope mo and intercept bo and logPL (subcooled liquid vapor pressure) with slope mp and intercept bp. In the sister paper of the present work, analytical equations to predict the slope mo and intercept bo based on logKOA and predict the slope mp and intercept bp based on logPL are developed using steady state theory. In this work, the equations are evaluated using world-wide monitoring data (262 pairs for mo and bo values and 292 pairs for mp and bp values produced from more than 10,000 monitiring data worldwide) for selected seven groups of semi-volatile organic compounds (SVOCs), including polybrominated diphenyl ethers (PBDEs), polychlorinated dibenzo-p-dioxins and polychorinated dibenzofurans (PCDD/Fs), polyclorinated biphenyl (PCBs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated naphthalenes (PCNs), organochlorinated pesticides (OCPs), novel brominated flame retardants (NBFRs), and other selected halogenated flame retardants. The slopes and intercepts predicted by the steady state equations reproduce the trends observed in monitoring regression results for the seven SVOC groups, with 44.4% of the variation of monitoring mo values accounted for by logKOA and 48.2% of the variation of monitoring mp values accounted for by logPL. Theoretically, the values of mo can be any value between 0 and 1 dependent on the values of KOA, and are not constrained to 1 as in equilibrium theory. Likewise, the values of mp can be any value between 0 and -1 dependent on the values of PL, and not constrained to -1 predicted by the equilibrium theory. The influence of sampling artifacts on the G/P partitioning of SVOCs has most likely been overemphasized by the equilibrium theory. Thus, the equilibrium approach should be abandoned in favor of the steady state approach for calculating the G/P partition quotients for SVOCs with high KOA values (>1011.38) or low PL values (<10-4.92).

New equation to predict size-resolved gas-particle partitioning quotients for polybrominated diphenyl ethers.

Gas/particle (G/P) partition quotients of semi-volatile organic compounds (SVOCs) for bulk air have been widely discussed in experimental and theoretical contexts, but research on size-resolved G/P partition quotients (KPi) are scarce and limited in scope. To investigate G/P partition behavior of polybrominated diphenyl ethers (PBDEs) for size-segregated particles in the atmosphere, 396 individual size-segregated particulate samples (36 batches × 11 size-ranges), and 108 pairs of concurrent gaseous and bulk particulate samples were collected in Harbin, China. A steady-state equation based on bulk particles is derived to determine G/P partition quotients of PBDEs for size-segregated particles, which depends on the organic matter contents of size-segregated particles (fOMi). This equation can well predict KPi with knowledge of bulk partition quotient (KPS), ambient temperature, and fOMi, the results of which match well with monitoring data in Harbin and other published data collected in Shanghai and Guangzhou of China and Thessaloniki of Greece, and remedies a defect of over-estimate KPi for high-brominated PBDEs by the previous equation. In particular, the new equation contributes to obtaining the PBDEs concentrations in all atmospheric phase from partial phase, then provides a credible path to evaluate healthy exposure dose from the airborne PBDEs, by co-utilization with exposure models.

Polycyclic aromatic compounds (PACs) in the Canadian environment: A review of sampling techniques, strategies and instrumentation.

A wide variety of sampling techniques and strategies are needed to analyze polycyclic aromatic compounds (PACs) and interpret their distributions in various environmental media (i.e., air, water, snow, soils, sediments, peat and biological material). In this review, we provide a summary of commonly employed sampling methods and strategies, as well as a discussion of routine and innovative approaches used to quantify and characterize PACs in frequently targeted environmental samples, with specific examples and applications in Canadian investigations. The pros and cons of different analytical techniques, including gas chromatography - flame ionization detection (GC-FID), GC low-resolution mass spectrometry (GC-LRMS), high performance liquid chromatography (HPLC) with ultraviolet, fluorescence or MS detection, GC high-resolution MS (GC-HRMS) and compound-specific stable (δ13C, δ2H) and radiocarbon (Δ14C) isotope analysis are considered. Using as an example research carried out in Canada's Athabasca oil sands region (AOSR), where alkylated polycyclic aromatic hydrocarbons and sulfur-containing dibenzothiophenes are frequently targeted, the need to move beyond the standard list of sixteen EPA priority PAHs and for adoption of an AOSR bitumen PAC reference standard are highlighted.

Gas/particle partitioning of semi-volatile organic compounds in the atmosphere: Transition from unsteady to steady state.

We derive differential equations to determine the kinetics of gas/particle partitioning of semi-volatile organic compounds (SVOCs). These equations model the transient states from initiation of sorption to particles (non-steady state) through the establishment of steady state. Two hypothetical scenarios are examined: (1) exchange of SVOCs between gas- and particle-phases alone; and (2) both gas/particle partitioning and wet and dry deposition of particles. The differential equations show that, under Scenario 1, a steady state is reached as an equilibrium between gas- and particle-phases, whereas under Scenario 2, the attained steady state is not in equilibrium. Our model shows that SVOCs in atmosphere where particle deposition is occurring reach a steady non-equilibrium state sooner than they would reach equilibrium under Scenario 1. We infer that SVOCs in the atmosphere will reach steady state instead of equilibrium between gaseous and particulate phases in circumstances where wet and dry deposition of particles cannot be neglected. In addition, our study indicates that the time for SVOCs to reach steady state in the atmosphere is fast, most likely within minutes or hours, suggesting that SVOCs are in steady or quasi-steady state in the atmosphere. Our analysis also reveals that gas/particle partitioning and particle deposition of SVOCs are dependent on each other.

Subsurface seawater methylmercury maximum explains biotic mercury concentrations in the Canadian Arctic.

Mercury (Hg) is a contaminant of major concern in Arctic marine ecosystems. Decades of Hg observations in marine biota from across the Canadian Arctic show generally higher concentrations in the west than in the east. Various hypotheses have attributed this longitudinal biotic Hg gradient to regional differences in atmospheric or terrestrial inputs of inorganic Hg, but it is methylmercury (MeHg) that accumulates and biomagnifies in marine biota. Here, we present high-resolution vertical profiles of total Hg and MeHg in seawater along a transect from the Canada Basin, across the Canadian Arctic Archipelago (CAA) and Baffin Bay, and into the Labrador Sea. Total Hg concentrations are lower in the western Arctic, opposing the biotic Hg distributions. In contrast, MeHg exhibits a distinctive subsurface maximum at shallow depths of 100-300 m, with its peak concentration decreasing eastwards. As this subsurface MeHg maximum lies within the habitat of zooplankton and other lower trophic-level biota, biological uptake of subsurface MeHg and subsequent biomagnification readily explains the biotic Hg concentration gradient. Understanding the risk of MeHg to the Arctic marine ecosystem and Indigenous Peoples will thus require an elucidation of the processes that generate and maintain this subsurface MeHg maximum.

The distribution and trends of persistent organic pollutants and mercury in marine mammals from Canada's Eastern Arctic.

Arctic contaminant research in the marine environment has focused on organohalogen compounds and mercury mainly because they are bioaccumulative, persistent and toxic. This review summarizes and discusses the patterns and trends of persistent organic pollutants (POPs) and mercury in ringed seals (Pusa hispida) and polar bears (Ursus maritimus) in the Eastern Canadian Arctic relative to the rest of the Canadian Arctic. The review provides explanations for these trends and looks at the implications of climate-related changes on contaminants in these marine mammals in a region that has been reviewed little. Presently, the highest levels of total mercury (THg) and the legacy pesticide HCH in ringed seals and polar bears are found in the Western Canadian Arctic relative to other locations. Whereas, highest levels of some legacy contaminants, including ∑PCBs, PCB 153, ∑DDTs, p,p'-DDE, ∑CHLs, ClBz are found in the east (i.e., Ungava Bay and Labrador) and in the Beaufort Sea relative to other locations. The highest levels of recent contaminants, including PBDEs and PFOS are found at lower latitudes. Feeding ecology (e.g., feeding at a higher trophic position) is shaping the elevated levels of THg and some legacy contaminants in the west compared to the east. Spatial and temporal trends for POPs and THg are underpinned by historical loadings of surface ocean reservoirs including the Western Arctic Ocean and the North Atlantic Ocean. Trends set up by the distribution of water masses across the Canadian Arctic Archipelago are then acted upon locally by on-going atmospheric deposition, which is the dominant contributor for more recent contaminants. Warming and continued decline in sea ice are likely to result in further shifts in food web structure, which are likely to increase contaminant burdens in marine mammals. Monitoring of seawater and a range of trophic levels would provide a better basis to inform communities about contaminants in traditionally harvested foods, allow us to understand the causes of contaminant trends in marine ecosystems, and to track environmental response to source controls instituted under international conventions.

Current use pesticide and legacy organochlorine pesticide dynamics at the ocean-sea ice-atmosphere interface in resolute passage, Canadian Arctic, during winter-summer transition.

Here, we present the first detailed analysis of processes by which various current use pesticides (CUPs) and legacy organochlorine pesticides (OCPs) are concentrated in melt ponds that form on Arctic sea ice in the summer, when surface snow is melting and ice eventually breaks up. Four current use pesticides (dacthal, chlorpyrifos, trifluralin, and pentachloronitrobenzene) and one legacy organochlorine pesticide (α-hexachlorocyclohexane) were detected in ponds in Resolute Passage, Canadian Arctic, in 2012. Melt-pond concentrations changed over time as a function of gas exchange, precipitation, and dilution with melting sea ice. Observed increases in melt-pond concentrations for all detected pesticides were associated with precipitation events. Dacthal reached the highest concentration of all current use pesticides in ponds (95±71pgL-1), a value exceeding measured concentrations in the under-ice (0m) and 5m seawater by >10 and >16 times, respectively. Drainage of dacthal-enriched pond water to the ocean during ice break-up provides an important ice-mediated annual delivery route, adding ~30% of inventory in the summer Mixed Layer (ML; 10m) in the Resolute Passage, and a concentrating mechanism with potential implications for exposures to organisms such as ice algae, and phytoplankton.

Decabrominated Diphenyl Ethers (BDE-209) in Chinese and Global Air: Levels, Gas/Particle Partitioning, and Long-Range Transport: Is Long-Range Transport of BDE-209 Really Governed by the Movement of Particles?

In this paper, we report air concentrations of BDE-209 in both gas- and particle-phases across China. The annual mean concentrations of BDE-209 were from below detection limit (BDL) to 77.0 pg·m-3 in the gas-phase and 1.06-728 pg·m-3 in the particle-phase. Among the nine PBDEs measured, BDE-209 is the dominant congener in Chinese atmosphere in both gas and particle phases. We predicted the partitioning behavior of BDE-209 in air using our newly developed steady state equation, and the results matched the monitoring data worldwide very well. It was found that the logarithm of the partition quotient of BDE-209 is a constant, and equal to -1.53 under the global ambient temperature range (from -50 to +50 °C). The gaseous fractions of BDE-209 in air depends on the concentration of total suspended particle (TSP). The most important conclusion derived from this study is that, BDE-209, like other semivolatile organic compounds (SVOCs), cannot be sorbed entirely to atmospheric particles; and there is a significant amount of gaseous BDE-209 in global atmosphere, which is subject to long-range atmospheric transport (LRAT). Therefore, it is not surprising that BDE-209 can enter the Arctic through LRAT mainly by air transport rather than by particle movement. This is a significant advancement in understanding the global transport process and the pathways entering the Arctic for chemicals with low volatility and high octanol-air partition coefficients, such as BDE-209.

Spatiotemporal patterns of mercury accumulation in lake sediments of western North America.

For the Western North America Mercury Synthesis, we compiled mercury records from 165 dated sediment cores from 138 natural lakes across western North America. Lake sediments are accepted as faithful recorders of historical mercury accumulation rates, and regional and sub-regional temporal and spatial trends were analyzed with descriptive and inferential statistics. Mercury accumulation rates in sediments have increased, on average, four times (4×) from 1850 to 2000 and continue to increase by approximately 0.2µg/m(2) per year. Lakes with the greatest increases were influenced by the Flin Flon smelter, followed by lakes directly affected by mining and wastewater discharges. Of lakes not directly affected by point sources, there is a clear separation in mercury accumulation rates between lakes with no/little watershed development and lakes with extensive watershed development for agricultural and/or residential purposes. Lakes in the latter group exhibited a sharp increase in mercury accumulation rates with human settlement, stabilizing after 1950 at five times (5×) 1850 rates. Mercury accumulation rates in lakes with no/little watershed development were controlled primarily by relative watershed size prior to 1850, and since have exhibited modest increases (in absolute terms and compared to that described above) associated with (regional and global) industrialization. A sub-regional analysis highlighted that in the ecoregion Northwestern Forest Mountains, <1% of mercury deposited to watersheds is delivered to lakes. Research is warranted to understand whether mountainous watersheds act as permanent sinks for mercury or if export of "legacy" mercury (deposited in years past) will delay recovery when/if emissions reductions are achieved.

Pan-Arctic concentrations of mercury and stable isotope ratios of carbon (δ(13)C) and nitrogen (δ(15)N) in marine zooplankton.

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 (δ(13)C) and nitrogen (δ(15)N) 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 δ(15)N and lower δ(13)C. 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.

Local contamination, and not feeding preferences, explains elevated PCB concentrations in Labrador ringed seals (Pusa hispida).

Polychlorinated biphenyls (PCBs) in high trophic level species typically reflect the contributions of myriad sources, such that source apportionment is rarely possible. The release of PCBs by a military radar station into Saglek Bay, Labrador contaminated the local marine food web. For instance, while heavier (higher chlorinated) PCB profiles in some ringed seals (Pusa hispida) were previously attributed to this local source, differences in feeding preferences among seals could not be ruled out as a contributing factor. Herein, similar fatty acid profiles between those seals with 'local' PCB profiles and those with 'long-range' or background profiles indicate little support for the possibility that differential feeding ecologies underlay the divergent PCB profiles. Ringed seals appeared to feed predominantly on zooplankton (Mysis oculata and Themisto libellula), followed by the dusky snailfish (Liparis gibbus), arctic cod (Boreogadus saida), and shorthorn sculpin (Myoxocephalus scorpius). Principal components analysis (PCA) and PCB homolog profiles illustrated the extent of contamination of the Saglek food web, which had very different (and much heavier) PCB profiles than those food web members contaminated by 'long-range' sources. Locally contaminated prey had PCB levels that were higher (2- to 544-fold) than prey contaminated by 'long-range' sources and exceeded wildlife consumption guidelines for PCBs. The application of multivariate analyses to two distinct datasets, including PCB congeners (n=50) and fatty acids (n=65), afforded the opportunity to clearly distinguish the contribution of locally-released PCBs to a ringed seal food web from those delivered via long-ranged transport. Results from the present study strongly suggest that habitat use rather than differences in prey selection is the primary mechanism explaining the divergent PCB patterns in Labrador ringed seals.

The delivery of organic contaminants to the Arctic food web: why sea ice matters.

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.

Spatial, temporal, and source variations of hydrocarbons in marine sediments from Baffin Bay, Eastern Canadian Arctic.

With declining sea ice conditions in Arctic regions owing to changing climate, the large prospective reservoirs of oil and gas in Baffin Bay and Davis Strait are increasingly accessible, and the interest in offshore exploration and shipping through these regions has increased. Both of these activities are associated with the risk of hydrocarbon releases into the marine ecosystem. However, hydrocarbons are also present naturally in marine environments, in some cases deriving from oil seeps. We have analyzed hydrocarbon concentrations in eleven sediment cores collected from northern Baffin Bay during 2008 and 2009 Amundsen expeditions and have examined the hydrocarbon compositions in both pre- and post-industrial periods (i.e., before and after 1900) to assess the sources of hydrocarbons, and their temporal and spatial variabilities. Concentrations of ΣPAHs ranged from 341 to 2693 ng g(-1) dw, with concentrations in cores from sites within the North Water (NOW) Polynya generally higher. Individual PAH concentrations did not exceed concentrations of concern for marine aquatic life, with one exception found in a core collected within the NOW (one of the seven sediment core samples). Hydrocarbon biomarkers, including alkane profiles, OEP (odd-to-even preference), and TAR (terrigenous/aquatic ratios) values indicated that organic carbon at all sites is derived from both terrigenous higher plants and marine algae, the former being of greater significance at coastal sites, and the latter at the deepest sites at the southern boundary of the NOW. Biomarker ratios and chemical profiles indicate that petrogenic sources dominate over combustion sources, and thus long-range atmospheric transport is less significant than inputs from weathering. Present-day and historic pre-1900 hydrocarbon concentrations exhibited less than an order of magnitude difference for most compounds at all sites. The dataset presented here provides a baseline record of hydrocarbon concentrations in Baffin Bay sediments in advance of offshore exploration and increased shipping activities.

Local environmental conditions determine the footprint of municipal effluent in coastal waters: a case study in the Strait of Georgia, British Columbia.

To predict the likely effects of management action on any point source discharge into the coastal ocean, it is essential to understand both the composition of the effluent and the environmental conditions in the receiving waters. We illustrate a broadly-applicable approach to evaluating the comprehensive environmental footprint of a discharge, using regional geochemical budgets and nearfield monitoring. We take as a case study municipal effluent discharged into the Strait of Georgia (west coast of Canada), where there has been public controversy over the discharge of screened or primary-treated effluent directly into the ocean. Wastewater contributes ≤ 1% of the nitrogen, organic carbon and oxygen demand in the Strait and is unlikely to cause eutrophication, harmful algal blooms or hypoxia in this region. Metals (Hg, Pb, Cd) are controlled by natural cycles augmented by past mining and urbanization, with 0.3-5% of the flux contributed by wastewater. Wastewater contributes ~5% of PCBs but ≤ 60% of PBDEs and is likely also important for pharmaceuticals and personal care products. Effects of high organic flux on benthos are measurable in the immediate receiving environment. The availability of particle-active contaminants to enter the food chain depends on how long those contaminants remain in the sediment surface mixed layer before burial. Secondary treatment, slated for completion in Vancouver in 2030, will reduce fluxes of some contaminants, but will have negligible effect on regional budgets for organic carbon, nitrogen, oxygen, metals and PCBs. Removal of PBDEs from wastewater will affect regional budgets, depending on how the sludge is sequestered.