Phycotoxins in bivalves from the western Canadian Arctic: The first evidence of toxigenicity.

This study presents the first evidence that a diverse suite of phycotoxins is not only being actively produced by the toxigenic algal communities in the Canadian Arctic waters, but is also entering the marine food web. We detected measurable amounts of Amnesic Shellfish Toxins (ASTs) and Paralytic Shellfish Toxins (PSTs), as well as trace amounts of other lipophilic toxin groups including pectenotoxins, yessotoxins, and cyclic imines, in bivalves collected from the Canadian Beaufort Sea in 2014 and 2018. There appear to be species-specific differences in accumulation and retention of AST by Arctic bivalves, with significantly higher concentrations recorded in Nuculanidae than Propeamussiidae, likely reflecting physiological and allometric differences. We further confirm the omnipresence of potentially toxic taxonomically-versatile phytoplankton communities in the western Canadian Arctic comprising Pseudo-nitzschia delicatissima group, P. obtusa, Dinophysis acuminata, Prorocentrum minimum, Alexandrium tamarense, and Gymnodinium spp. Although measurements of actual toxicity levels and profiles of these species at the time of sampling fall outside of the scope of this study, we show that high abundance and competitive success of known AST-producers, Pseudo-nitzschia spp., are possible in Canadian Arctic waters. In 2014, a strong dominance of Pseudo-nitzschia spp. was observed at a few shallow coastal stations, representing nearly 40% of the total phytoplankton cell abundances with > 106 cells/L at the depth of maximum chlorophyll a. We further describe oceanographic conditions conducive to high abundances of toxin-producing algae, indicating that temperature is likely a key factor. Even though measured AST and PST concentrations in bivalve tissue remained well below the Health Canada's levels at which monitored fisheries would close, i.e., 5% and 4%, respectively, their presence demonstrate that phycotoxin accumulation is occurring in food webs of the Canadian Beaufort Sea. Yet, the phycotoxin production controls and trophic transfer mechanisms remain unknown. Canadian Arctic marine ecosystems are rapidly changing and temperatures are expected to continue to increase. Given that these changes simultaneously affect multiple, and often co-occurring, species of primary producers, adaptive capacity is likely to play an important role in the structure of phytoplankton communities in the Canadian Arctic.

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.

Organophosphate Esters in Canadian Arctic Air: Occurrence, Levels and Trends.

Fourteen organophosphate esters (OPEs) were measured in the filter fraction of 117 active air samples from yearly ship-based sampling campaigns (2007-2013) and two land-based stations in the Canadian Arctic, to assess trends and long-range transport potential of OPEs. Four OPEs were detected in up to 97% of the samples, seven in 50% or less of the samples, and three were not detected. Median concentrations of ∑OPEs were 237 and 50 pg m(-3) for ship- and land-based samples, respectively. Individual median concentrations ranged from below detection to 119 pg m(-3) for ethanol, 2-chloro-, phosphate (3:1) (TCEP). High concentrations of up to 2340 pg m(-3) were observed for Tri-n-butyl phosphate (TnBP) at a land-based sampling location in Resolute Bay from 2012, whereas it was only detected in one ship-based sample at a concentration below 100 pg m(-3). Concentrations of halogenated OPEs seemed to be driven by river discharge from the Nelson and Churchill Rivers (Manitoba) and Churchill River and Lake Melville (Newfoundland and Labrador). In contrast, nonhalogenated OPE concentrations appeared to have diffuse sources or local sources close to the land-based sampling stations. Triphenyl phosphate (TPhP) showed an apparent temporal trend with a doubling-time of 11 months (p = 0.044). The results emphasize the increasing relevance of halogenated and nonhalogenated OPEs as contaminants in the Arctic.

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.

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.

Transformation of mercury at the bottom of the Arctic food web: an overlooked puzzle in the mercury exposure narrative.

We show 2008 seasonal trends of total and monomethyl 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 postdepositional 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.

Importance of Arctic zooplankton seasonal migrations for α-hexachlorocyclohexane bioaccumulation dynamics.

Like most zooplankton, Calanus hyperboreus undergoes seasonal migration spending late spring and summer grazing at the surface and the rest of the year in diapause at depth. As a result, in the Arctic Ocean this copepod resides for part of the year in the hexachlorocyclohexane (HCH) enriched surface water and for part of the year at depth where HCH undergoes significant microbial degradation resulting in far lower concentrations (~3 times for α-HCH). We collected C. hyperboreus from summer and winter from the Amundsen Gulf and measured their α-HCH concentrations, enantiomeric compositions, and bioaccumulation factors (BAFs) to investigate how this copepod responds to the change in exposure to α-HCH. C. hyperboreus collected in winter were also cultured for 5 weeks under surface water conditions without feeding to investigate bioconcentration dynamics following spring ascent. Concentration of α-HCH was 2-3 times higher in individuals from the summer than those from the winter. Log BAF from the summer (feeding period) does not exceed log BCF (bioconcentration factor) from the culturing experiment (no feeding) suggesting that α-HCH concentration in C. hyperboreus is maintained through equilibration rather than feeding. After the spring ascent from deep waters, C. hyperboreus approach equilibrium partitioning with the higher surface water concentrations of α-HCH within 3-4 weeks with about 60% of bioconcentration taking place in the first week. The C. hyperboreus α-HCH chiral signature also reflects ambient seawater and can therefore be used as a determinant of residence depth. Even though a single cycle of seasonal migration does not result in a significant redistribution of α-HCH in the water column, this process could have a significant cumulative effect over longer time scales with particular local importance where the zooplankton biomass is high and the ocean depth is great enough to provide substantial vertical concentration gradients.

Air-water exchange of anthropogenic and natural organohalogens on International Polar Year (IPY) expeditions in the Canadian Arctic.

Shipboard measurements of organohalogen compounds in air and surface seawater were conducted in the Canadian Arctic in 2007-2008. Study areas included the Labrador Sea, Hudson Bay, and the southern Beaufort Sea. High volume air samples were collected at deck level (6 m), while low volume samples were taken at 1 and 15 m above the water or ice surface. Water samples were taken within 7 m. Water concentration ranges (pg L(-1)) were as follows: α-hexachlorocyclohexane (α-HCH) 465-1013, γ-HCH 150-254, hexachlorobenzene (HCB) 4.0-6.4, 2,4-dibromoanisole (DBA) 8.5-38, and 2,4,6-tribromoanisole (TBA) 4.7-163. Air concentration ranges (pg m(-3)) were as follows: α-HCH 7.5-48, γ-HCH 2.1-7.7, HCB 48-71, DBA 4.8-25, and TBA 6.4 - 39. Fugacity gradients predicted net deposition of HCB in all areas, while exchange directions varied for the other chemicals by season and locations. Net evasion of α-HCH from Hudson Bay and the Beaufort Sea during open water conditions was shown by air concentrations that averaged 14% higher at 1 m than 15 m. No significant difference between the two heights was found over ice cover. The α-HCH in air over the Beaufort Sea was racemic in winter (mean enantiomer fraction, EF = 0.504 ± 0.008) and nonracemic in late spring-early summer (mean EF = 0.476 ± 0.010). This decrease in EF was accompanied by a rise in air concentrations due to volatilization of nonracemic α-HCH from surface water (EF = 0.457 ± 0.019). Fluxes of chemicals during the southern Beaufort Sea open water season (i.e., Leg 9) were estimated using the Whitman two-film model, where volatilization fluxes are positive and deposition fluxes are negative. The means ± SD (and ranges) of net fluxes (ng m(-2) d(-1)) were as follows: α-HCH 6.8 ± 3.2 (2.7-13), γ-HCH 0.76 ± 0.40 (0.26-1.4), HCB -9.6 ± 2.7 (-6.1 to -15), DBA 1.2 ± 0.69 (0.04-2.0), and TBA 0.46 ± 1.1 ng m(-2) d(-1) (-1.6 to 2.0).