In situ microcosms deployed at the coast of British Columbia (Canada) to study dilbit weathering and associated microbial communities under marine conditions.

Douglas Channel and the adjacent Hecate Strait (British Columbia, Canada) are part of a proposed route to ship diluted bitumen (dilbit). This study presents how two types of dilbit naturally degrade in this environment by using an in situ microcosm design based on dilbit-coated beads. We show that dilbit-associated n-alkanes were microbially biodegraded with estimated half-lives of 57-69 days. n-Alkanes appeared to be primarily degraded using the aerobic alkB, ladA and CYP153 pathways. The loss of dilbit polycyclic aromatic hydrocarbons (PAHs) was slower than of n-alkanes, with half-lives of 89-439 days. A biodegradation of PAHs could not be conclusively determined, although a significant enrichment of the phnAc gene (a marker for aerobic PAH biodegradation) was observed. PAH degradation appeared to be slower in Hecate Strait than in Douglas Channel. Microcosm-associated microbial communities were shaped by the presence of dilbit, deployment location and incubation time but not by dilbit type. Metagenome-assembled genomes of putative dilbit-degraders were obtained and could be divided into populations of early, late and continuous degraders. The majority of the identified MAGs could be assigned to the orders Flavobacteriales, Methylococcales, Pseudomonadales and Rhodobacterales. A high proportion of the MAGs represent currently unknown lineages or lineages with currently no cultured representative.

Fate of diluted bitumen spilled in the coastal waters of British Columbia, Canada.

There is public concern about the behaviour of spilled diluted bitumen (dilbit) in marine and estuarine waters. We provide a preliminary assessment of the results of laboratory experiments and models, in the context of environmental conditions in the coastal waters of British Columbia. Most dilbit spilled within this region would likely float at the surface and be transported to shore by winds and currents. Fresh dilbit is too light to sink in coastal waters. Highly weathered dilbit could sink where salinity is less than 14, typically only near river mouths and in the top 1-3 m of fjords after heavy rainfall. Subsurface plumes of weathered dilbit could re-emerge at the surface. Sinking oil-particle aggregates are unlikely to form in coastal waters. However, dilbit could be entrained below the surface by wave mixing during storms and to depths of 150 m by coherent mixing in the Haro Strait tidal convergence zone.

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.

PBDE and PCB accumulation in benthos near marine wastewater outfalls: the role of sediment organic carbon.

Polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) were measured in sediments and benthic invertebrates near submarine municipal outfalls in Victoria and Vancouver, B.C., Canada, two areas with contrasting receiving environments. PBDE concentrations in wastewater exceeded those of the legacy PCBs by eight times at Vancouver and 35 times at Victoria. Total PBDE concentrations in benthic invertebrates were higher near Vancouver than Victoria, despite lower concentrations in sediments, and correlated with organic carbon-normalized concentrations in sediment. Principal Components Analysis indicated uptake of individual PBDE congeners was determined by sediment properties (organic carbon, grain size), while PCB congener uptake was governed by physico-chemical properties (octanol-water partitioning coefficient). Results suggest the utility of sediment quality guidelines for PBDEs and likely PCBs benefit if based on organic carbon-normalized concentrations. Also, where enhanced wastewater treatment increases the PBDEs to particulate organic carbon ratio in effluent, nearfield benthic invertebrates may face increased PBDE accumulation.

Effect of receiving environment on the transport and fate of polybrominated diphenyl ethers near two submarine municipal outfalls.

The fate of contaminants entering the marine environment through wastewater outfalls depends on the contaminant's persistence and affinity for particles. However, the physical characteristics of the receiving environment, for example, current velocity and sedimentary processes, may be even more important. Because of the complexity of natural settings and the lack of appropriate comparative settings, this is not frequently evaluated quantitatively. The authors investigated the near-field accumulation of particle-reactive polybrominated diphenyl ethers (PBDEs) entering coastal waters by way of two municipal outfalls: one discharging into a high-energy, low-sedimentation environment near Victoria, BC, Canada; the other into a low-energy, high-sedimentation environment, near Vancouver, BC. The authors used ²¹°Pb profiles in box cores together with an advection-diffusion model to determine surface mixing and sedimentation rates, and to model the depositional history of PBDEs at these sites. Surprisingly, 88 to 99% of PBDEs were dispersed beyond the near-field at both sites, but a greater proportion of PBDEs was captured in the sediment near the Vancouver outfall where rapid burial was facilitated by inorganic sediment supplied from the nearby Fraser River. Although the discharge of PBDEs was much lower from the Victoria outfall than from Vancouver, some sediment PBDE concentrations were higher near Victoria.

Environmental fractionation of PCBs and PBDEs during particle transport as recorded by sediments in coastal waters.

The Strait of Georgia (British Columbia, Canada) is a hydrologically complex inland sea with a rich abundance and diversity of species of aquatic life. Marine sediments, as both a sink for hydrophobic contaminants and a potential source for aquatic food webs, were collected from 41 sites throughout the 6,900-km(2) Strait of Georgia. The congener-specific concentrations of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), including BDE-209, were measured. Urban harbors represented hotspots for both PCBs and PBDEs, whereas PBDEs were also found at high concentrations near municipal outfalls. Patterns of PCB distribution were consistent with historical point source emissions in urban areas and environmental distillation toward lighter profiles in remote sites over time. The single congener BDE-209 dominated the PBDEs, accounting for 52% of the average total concentration. However, nonurban deep-water sediment PBDE profiles were both heavier and had higher concentration-weighted average log K(OW) (octanol-water partition coefficient) values compared to shallow samples (percent BDE-209 of total PBDE, 66 versus 32%; log K(OW) , 9.5 versus 8.2, respectively). Collectively, our results suggest that although source signals largely explain PCB and PBDE hotspots in the Strait of Georgia, the combination of physicochemical properties and environmental processes drive divergent compositional fates for the PCBs and the heavier PBDEs in the sediments of the Strait of Georgia.

Coupling laser ablation and atomic fluorescence spectrophotometry: an example using mercury analysis of small sections of fish scales.

Mercury is a toxic element that exchanges among air, water, and sediments and biomagnifies into high trophic level organisms. Here, we present a novel combination of laser ablation with relatively low-cost cold vapor atomic fluorescence spectrophotometry to analyze Hg vaporized from targeted patches of fish scale 300-500 µm square. This method permits the analysis of multiple samples from the same scale, which is useful, because fish scale growth rings may provide an archive from which spatial and temporal trends in environmental Hg can be inferred at fine resolution. The detection limit of the method is 1.5 pg Hg, with a precision of 0.1 pg/µL. Developed using fish scales, the method could be adapted to other media, such as baleen, shells, nails, hair, teeth, wood and, possibly, varved sediments.

Natural and anthropogenic mercury distribution in marine sediments from Hudson Bay, Canada.

Twelve marine sediment cores from Hudson Bay, Canada, were collected to investigate the response of sub-Arctic marine sediments to atmospherically transported anthropogenic mercury (Hg). Modeling by a two-layer sediment mixing model suggests that the historical Hg deposition to most of the sediment cores reflects the known history of atmospheric Hg deposition in North America, with an onset of increasing anthropogenic Hg emissions in the late 1800s and early 1900s and a reduction of Hg deposition in the mid- to late-1900s. However, although anthropogenic Hg has contributed to a ubiquitous increase in Hg concentrations in sediments over the industrial era, the most elevated industrial-era sedimentary Hg concentrations only marginally exceed the upper preindustrial sedimentary Hg concentrations. Analysis of delta13C and relationship between Hg and organic matter capture suggests that the response of Hudson Bay sediments to changes in atmospheric Hg emissions is largely controlled by the particle flux in the system and that natural changes in organic matter composition and dynamics can cause variation in sedimentary Hg concentrations at least to the same extent as those caused by increasing anthropogenic Hg emissions.

Biogeochemical controls on PCB deposition in Hudson Bay.

PCB concentrations, congener patterns, and fluxes were examined in 13 dated and organically characterized (C, N, delta(13)C, delta(15)N) marine sediment cores from Hudson Bay, Canada, to investigate the importance of organic matter (OM) supply and transport to PCB sequestration. Drawdown of PCBs, supported by marine primary production, is reflected in elevated summation operatorPCB concentrations and more highly chlorinated PCB signatures in surface sediments underlying eutrophic regions. Sediments in oligotrophic regions, which are dominated by "old" marine OM, have lower PCB concentrations and weathered signatures. For the surface of Hudson Bay, average atmospheric deposition appears to be very low (ca. 1.4 pg summation operatorPCBs cm(-2) a(-1)) compared to fluxes reported for nearby lakes (ca. 44 pg summation operatorPCBs cm(-2) a(-1)). (210)Pb fails to provide a means to normalize the fluxes, highlighting important differences in the biocycling of (210)Pb and PCBs. Unlike (210)Pb, atmospheric PCB exchange with the water's surface is partially forced by the aquatic organic carbon cycle. The extremely low atmospheric deposition of PCBs to the surface of Hudson Bay is likely a reflection of the Bay's exceptionally low productivity and vertical carbon fluxes. If future marine production and vertical flux of carbon increase due to loss of ice cover or change in river input as consequences of global warming, PCB deposition would also increase.

Large and growing environmental reservoirs of Deca-BDE present an emerging health risk for fish and marine mammals.

Polybrominated diphenyl ethers (PBDEs) have been the subject of intense scientific and regulatory scrutiny during recent years. Of the three commercial forms (Penta, Octa and Deca) of PBDEs that have been widely used as flame retardants in textiles, furniture upholstery, plastics, and electronics, only Deca-BDE remains on the general market in North America, while a recent ruling of the European Court spells an impending end to its use in Europe. We review here highlights of aquatic research documenting the rapid emergence of PBDEs as a high priority environmental concern in Canada. PBDEs are being introduced in large quantities to the aquatic environment through sewage discharge and atmospheric deposition. In certain environmental compartments, the single congener BDE-209, the main ingredient in the Deca-BDE formulation, has surpassed the legacy PCBs and DDT as the top contaminant by concentration. Limited biomagnification of BDE-209 in aquatic food webs reflects its high log K(ow) and preferential partitioning into the particle phase. As a result, large environmental reservoirs of BDE-209 are being created in sediments, and these may present a long-term threat to biota: BDE-209 breaks down into more persistent, more bioaccumulative, more toxic, and more mobile PBDE congeners in the environment.

Historical trends in mercury sedimentation and mixing in the Strait of Georgia, Canada.

Seventeen sediment cores collected in the Strait of Georgia reveal a history of mercury contamination that began in the 1860s and include episodic contamination during World War II and in the late 1960s. Surface sediment mercury concentrations ranged from 60 to 420 ng/g dry weight and the current fluxes to sediments are estimated at 5-181 ng cm(-2) a(-1). In one location in Port Moody Arm, a Hg spill seems to have sufficiently poisoned the sediments to eliminate biomixing for about 20 years. Although the surface concentration of Hg is likely to decrease at all stations in coming years, sites in the industrialized Vancouver Harbor and Port Moody Arm will continue to be sufficiently contaminated to endanger benthic organisms. Variations in sedimentation and mixing rates among sites result in surface sediment Hg concentration patterns that do not reflect accurately the distribution of Hg flux. In particular, the concentration of Hg in sediments near the mouth of the Fraser River is low, despite the high Hg load of that river, because of dilution by other particles. A preliminary Hg budget indicates that most of the Hg enters the Strait of Georgia via the Fraser River (2090 kg a(-1)), and that, while burial in Strait of Georgia sediments is a major sink (1800 kg a(-1)), there may be a significant outflow of Hg through Juan de Fuca Strait (approximately 3400 kg a(-1)).