Informing the Exposure Landscape: The Fate of Microplastics in a Large Pelagic In-Lake Mesocosm Experiment.

Understanding microplastic exposure and effects is critical to understanding risk. Here, we used large, in-lake closed-bottom mesocosms to investigate exposure and effects on pelagic freshwater ecosystems. This article provides details about the experimental design and results on the transport of microplastics and exposure to pelagic organisms. Our experiment included three polymers of microplastics (PE, PS, and PET) ranging in density and size. Nominal concentrations ranged from 0 to 29,240 microplastics per liter on a log scale. Mesocosms enclosed natural microbial, phytoplankton, and zooplankton communities and yellow perch (Perca flavescens). We quantified and characterized microplastics in the water column and in components of the food web (biofilm on the walls, zooplankton, and fish). The microplastics in the water stratified vertically according to size and density. After 10 weeks, about 1% of the microplastics added were in the water column, 0.4% attached to biofilm on the walls, 0.01% within zooplankton, and 0.0001% in fish. Visual observations suggest the remaining >98% were in a surface slick and on the bottom. Our study suggests organisms that feed at the surface and in the benthos are likely most at risk, and demonstrates the value of measuring exposure and transport to inform experimental designs and achieve target concentrations in different matrices within toxicity tests.

A Multicompartment Assessment of Microplastic Contamination in Semi-remote Boreal Lakes.

Microplastic contamination is ubiquitous across the globe, even in remote locations. Still, the sources and pathways of microplastics to such locations are largely unknown. To investigate microplastic contamination in a semi-remote location, we measured microplastic concentrations in nine oligotrophic lakes within and around the International Institute for Sustainable Development-Experimental Lakes Area in northwestern Ontario, Canada. Our first objective was to establish ambient concentrations of microplastics in bottom sediments, surface water, and atmospheric deposition in semi-remote boreal lakes. Across all lakes, mean shallow and deep sediment microplastic concentrations, near-surface water microplastic concentrations from in situ filtering, and dry atmospheric microplastic deposition rates were 551 ± 354 particles kg-1, 177 ± 103 particles kg-1, 0.2 ± 0.3 particles L-1, and 0.4 ± 0.2 particles m-2 day-1, respectively. Our second objective was to investigate whether microplastic contamination of these lakes is driven by point sources including local runoff and direct anthropogenic inputs or nonpoint sources such as atmospheric deposition. Lakes were selected based on three levels of anthropogenic activity-low, medium, and high-though activity levels were minimal across all study lakes compared with highly populated areas. Whereas a positive correlation would indicate that point sources were a likely pathway, we observed no relationship between the level of anthropogenic activity and microplastic contamination of surface water. Moreover, the composition of microplastics in surface water and atmospheric deposition were similar, comprising mostly polyester and acrylic fibers. Together, these results suggest that atmospheric deposition may be the main pathway of microplastics to these remote boreal lakes. Environ Toxicol Chem 2024;43:999-1011. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Chemical Weathering Patterns of Diluted Bitumen Spilled into Freshwater Limnocorrals.

Due to the sudden nature of oil spills, few controlled studies have documented how oil weathers immediately following accidental release into a natural lake environment. Here, we evaluated the weathering patterns of Cold Lake Winter Blend, a diluted bitumen (dilbit) product, by performing a series of controlled spills into limnocorrals installed in a freshwater lake in Northern Ontario, Canada. Using a regression-based design, we added seven different dilbit volumes, ranging from 1.5 to 180 L, resulting in oil-to-water ratios between 1:71,000 (v/v) and 1:500 (v/v). We monitored changes in the composition of various petroleum hydrocarbons (PHCs), including n-alkanes, polycyclic aromatic hydrocarbons (PAHs), and oil biomarkers in dilbit over time, as it naturally weathered for 70 days. Depletion rate constants (kD) of n-alkanes and PAHs ranged from 0.0009 to 0.41 d-1 and 0.0008 to 0.38 d-1, respectively. There was no significant relationship between kD and spill volume, suggesting that spill size did not influence the depletion of petroleum hydrocarbons from the slick. Diagnostic ratios calculated from concentrations of n-alkanes, isoprenoids, and PAHs indicated that evaporation and photooxidation were major processes contributing to dilbit weathering, whereas dissolution and biodegradation were less important. These results demonstrate the usefulness of large scale field studies carried out under realistic environmental conditions to elucidate the role of different weathering processes following a dilbit spill.

Radio- and stable carbon isotope analysis reveals minimal assimilation of petrogenic carbon into an oligotrophic freshwater food web after experimental spills of diluted bitumen.

Following an oil spill into water, bacteria can biodegrade petroleum hydrocarbons which could lead to petrogenic carbon assimilation by aquatic biota. We used changes in the isotope ratios of radio- (Δ14C) and stable (δ13C) carbon to examine the potential for assimilation of petrogenic carbon into a freshwater food web following experimental spills of diluted bitumen (dilbit) into a boreal lake in northwestern Ontario, Canada. Different volumes (1.5, 2.9, 5.5, 18, 42, 82, and 180 L) of Cold Lake Winter Blend (a heavy crude blend of bitumen and condensate) dilbit were applied to seven 10-m diameter littoral limnocorrals (approximate volume of 100 m3), and two additional limnocorrals had no added dilbit to serve as controls. Particulate organic matter (POM) and periphyton from oil-treated limnocorrals had lower δ13C (up to 3.2‰ and 2.1‰ for POM and periphyton, respectively) than the control at every sampled interval (3, 6 and 10 weeks for POM and 6, 8 and 10 weeks for periphyton). Dissolved organic and inorganic carbon (DOC and DIC, respectively) had lower Δ14C in the oil-treated limnocorrals relative to the control (up to 122‰ and 440‰ lower, respectively). Giant floater mussel (Pyganodon grandis) housed for 25 days in aquaria containing oil-contaminated water from the limnocorrals did not show significant changes in δ13C values of muscle tissue compared to mussels housed in control water. Overall, the changes in δ13C and Δ14C observed indicated small amounts (up to 11% in DIC) of oil carbon incorporation into the food web. The combined δ13C and Δ14C data provide evidence for minimal incorporation of dilbit into the food web of this oligotrophic lake, suggesting that microbial degradation and subsequent incorporation of oil C into the food web may play a relatively small role in the ultimate fate of oil in this type of ecosystem.

Chemical communication in wood frog (Rana sylvatica) tadpoles is influenced by early-life exposure to naphthenic acid fraction compounds.

Environmental pollutants can disrupt chemical communication between aquatic organisms by interfering with the production, transmission, and/or detection of, as well as responses to, chemical cues. Here, we test the hypothesis that early-life exposure to naphthenic acid fraction compounds (NAFCs) from oil sands tailings disrupts antipredator-associated chemical communication in larval amphibians. Wild adult wood frogs (Rana sylvatica) captured during their natural breeding period were combined (1 female:2 males) in six replicate mesocosms filled with either uncontaminated lakewater or with NAFCs isolated from an active tailings pond in Alberta, Canada, at nominal 5 mg/L concentrations. Egg clutches were incubated and tadpoles maintained in their respective mesocosms for ∼40 days post-hatch. Tadpoles (Gosner stage 25-31) were then transferred individually to trial arenas filled with uncontaminated water and exposed to one of six chemical alarm cue (AC) stimuli solutions following a 3 × 2 × 2 design (3 AC types × 2 stimulus carriers × 2 rearing exposure groups). Relative to control tadpoles, NAFC-exposed tadpoles demonstrated higher baseline activity levels (line crosses and direction changes) when introduced to uncontaminated water. Antipredator responses differed in graded fashion with AC type, with control ACs eliciting the greatest latency to resume activity, water the least, and NAFC-exposed ACs intermediate. Pre- to post-stimulus difference scores were non-significant in control tadpoles, while NAFC-exposed tadpoles demonstrated significantly greater variation. While this suggests that exposure to NAFCs from fertilization through hatching may have interfered with AC production, it is unclear whether the quality or quantity of cues was affected. There was also no clear evidence that NAFC carrier water interfered with ACs or the alarm response in unexposed control tadpoles. These results emphasize the importance of understanding how behavioral and physiological effects of early-life NAFC exposure on critical antipredator responses may persist across life history stages.

Bioaccumulation and toxicokinetics of polycyclic aromatic compounds and metals in giant floater mussels (Pyganodon grandis) exposed to a simulated diluted bitumen spill.

Oil spills constitute a major risk to the environment and the bioaccumulation potential of the derived oil constituents will influence their impact on aquatic biota. Here we determined the bioaccumulation potential and toxicokinetic parameters of polycyclic aromatic compounds (PACs) and various selected metals in the giant floater mussels (Pyganodon grandis) following experimental oil spills in a freshwater lake. Specifically, these mussels were exposed ex situ for 25 days to water contaminated with naturally weathered diluted bitumen (dilbit), a form of oil commonly transported through pipelines. We detected greater concentrations of total PAC in mussels (∑PAC44) exposed to dilbit-contaminated water (25.92-27.79 µg g-1 lipid, n = 9, at day 25 of the uptake phase) compared to mussels from a control with no exposure to dilbit (average of 2.62 ± 1.95 µg g-1 lipid; ±SD, n = 17). This study demonstrates the importance of including alkylated PACs when assessing the impacts of an oil spill as the concentration of alkylated PACs in mussel tissue were an order of magnitude higher than their parent counterparts. However, metal accumulation in dilbit-exposed mussels did not exceed the unexposed controls, suggesting no excess metal accumulation by mussels from a 25-day dilbit exposure. From first-order one-compartment models, mean uptake rate constants (0.78-18.11 L g-1 day-1, n = 29) and bioconcentration factors (log values from 4.02 to 5.92 L kg-1, n = 87) for the 29 individual PACs that accumulated in mussels demonstrated that some alkylated PACs had greater bioaccumulation potential compared to their parent PAC counterpart but for the most part, alkylated and parent PACs had comparable BCF values. Results from this study also demonstrated that giant floater mussels could be used to biomonitor PAC contamination following oil spills as PACs accumulated in mussel tissue and some were still detectable following the 16-day depuration phase. This study provides the largest, most comprehensive set of toxicokinetic and bioaccumulation parameters for PACs and their alkylated counterparts (44 analytes) in freshwater mussels obtained to date.

Experimental Evidence from the Field that Naturally Weathered Microplastics Accumulate Cyanobacterial Toxins in Eutrophic Lakes.

Freshwater ecosystems with recurring harmful algal blooms can also be polluted with plastics. Thus the two environmental problems may interact. To test whether microplastics influence the partitioning of microcystins in freshwater lakes, we examined the sorption of four microcystin congeners to different polymers of commercially available plastics (low-density polyethylene, polyethylene terephthalate, polyvinyl chloride, and polypropylene). We conducted three experiments: a batch sorption experiment in the laboratory with pristine microplastics of four different polymers, a second batch sorption experiment in the laboratory to compare pristine and naturally weathered microplastics of a single polymer, and a 2-month sorption experiment in the field with three different polymers experiencing natural weathering in a eutrophic lake. This series of experiments led to a surprising result: microcystins sorbed poorly to all polymers tested under laboratory conditions (<0.01% of the initial amount added), irrespective of weathering, yet in the field experiment, all polymers accumulated microcystins under ambient conditions in a eutrophic lake (range: 0-84.1 ng/g). Furthermore, we found that the sorption capacity for microcystins differed among polymers in the laboratory experiment yet were largely the same in the field. We also found that the affinity for plastic varied among microcystin congeners, namely, more polar congeners demonstrated a greater affinity for plastic than less polar congeners. Our study improves our understanding of the role of polymer and congener type in microplastic-microcystin sorption and provides novel evidence from the field, showing that naturally weathered microplastics in freshwater lakes can accumulate microcystins. Consequently, we caution that microplastics may alter the persistence, transport, and bioavailability of microcystins in freshwaters, which could have implications for human and wildlife health. Environ Toxicol Chem 2022;41:3017-3028. © 2022 SETAC.

Responses of Wild Finescale Dace (Phoxinus neogaeus) to Experimental Spills of Cold Lake Blend Diluted Bitumen at the International Institute for Sustainable Development-Experimental Lakes Area, Northwestern Ontario.

Pipelines carrying diluted bitumen (dilbit) traverse North America and may result in dilbit release into sensitive freshwater ecosystems. To better understand the potential effects of a freshwater oil release, the Boreal-lake Oil Release Experiment by Additions to Limnocorrals project at the International Institute for Sustainable Development-Experimental Lakes Area (Ontario, Canada) modeled seven dilbit spills contained within a 10-m diameter of littoral limnocorrals in a boreal lake. Wild finescale dace (Phoxinus neogaeus) were released in the limnocorrals 21 days after oil addition and remained there for 70 days. Dilbit volumes covered a large range representing a regression of real spill sizes and total polycyclic aromatic compounds (TPAC) between 167 ng L-1 day-1 and 1989 ng L-1 day-1 . We report the effects of chronic exposure on reproductive potential as well as physiological responses in the gallbladder and liver. In exposures >1000 ng L-1 day-1 , there was a significant decrease in fish retrieval, culminating in zero recapture from the three highest treatments. Among the fish from the limnocorrals with lower levels of TPAC (<500 ng L-1 day-1 ), effects were inconsistent. Gallbladder bile fluorescence for a naphthalene metabolite was significantly different in fish from the oil-exposed limnocorrals when compared to the lake and reference corral, indicating that fish in these lower exposures were interacting with dilbit-derived polycyclic aromatic compounds. There were no significant differences in condition factor, somatic indices, or hepatocyte volume indices. There were also no significant changes in the development of testes or ovaries of exposed dace. The results from the present study may serve to orient policymakers and emergency responders to the range of TPAC exposures that may not significantly affect wild fish. Environ Toxicol Chem 2022;41:2745-2757. © 2022 SETAC.

Resilience of larval wood frogs (Rana sylvatica) to hydrocarbons and other compounds released from naturally weathered diluted bitumen in a boreal lake.

The risks to aquatic wildlife from spills of diluted bitumen (dilbit) into inland waters are poorly understood. In this paper, we describe the response of larval wood frogs (Rana sylvatica) to hydrocarbons and other compounds released from experimental spills of dilbit in a temperate boreal lake. To simulate a wide range of environmentally relevant oil spill scenarios, different volumes of Cold Lake Winter Blend dilbit (0, 1.5, 2.9, 5.5, 18, 42, 82, and 180 L) were added to 10 m diameter in-lake limnocorrals. Larvae (n = 360) were reared (from Gosner Stage (GS) 25 to ∼42) in land-based aquatic microcosms, where they were first exposed to clean water during a 2-week baseline phase, and then (at GS ∼30), to contaminated water withdrawn from the limnocorrals for 3 weeks. We observed no statistically significant trends in survival, growth, or development of larvae as a consequence of exposure to the chemical compounds released from naturally weathered dilbit. Likewise, neither cytochrome P450 1A biomarkers nor levels of thyroid hormones in wood frogs near metamorphic climax were significantly related to volume of the oil spills. However, there was a modest statistically significant decrease in larval activity (up to 8.7% relative to the control), but no change in other behavioral metrics (i.e., sociality or space use). Our work adds to the limited body of literature on the effects of unconventional oils on aquatic wildlife and helps to inform risk assessments regarding pipeline projects.

Fathead Minnows Exposed to Organic Compounds from Oil Sands Tailings as Embryos Have Reduced Survival, Impaired Development, and Altered Behaviors That Persist into Larval Stages.

Our study evaluated whether exposure to naphthenic acid fraction compounds (NAFCs) extracted from oil sands process-affected waters (OSPW) has adverse effects on fish embryos that persist into later life. We exposed fathead minnow (Pimephales promelas) embryos to concentrations of NAFCs found in OSPW (2.5-54 mg/L) for 7 days (1 day postfertilization to hatch), then raised surviving larvae in outdoor mesocosms of uncontaminated lake water for 1 month. Embryos exposed to NAFCs were more likely to exhibit malformations (by up to 8-fold) and had slower heart rates (by up to 24%) compared to controls. Fish raised in uncontaminated lake water following exposure to NAFCs as embryos, were 2.5-fold less likely to survive during the larval stage than control fish. These fish also showed up to a 45% decrease in swim activity and a 36% increase in swim burst events during behavioral tests relative to controls. We conclude that exposure to NAFCs during the embryonic stage can have lasting effects on fish survival, physiology, and behavior that persist at least through the larval stage. These findings of delayed mortalities and persistent sublethal effects of embryonic NAFC exposure are relevant to informing the development of regulations on treated OSPW releases from mining operations. Environ Toxicol Chem 2022;41:1319-1332. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Effect of spilled diluted bitumen on chemical air-water exchange in boreal lake limnocorrals.

Following spills into water, petroleum oils can spread widely and produce surface slicks. Resulting slicks may impede volatilization and possibly increase chemical persistence in water. While the influence of oil films on chemical air-water exchange has been examined through theoretical and laboratory studies, field studies have not been conducted to assess the relevance of these effects following actual oil spill events. Here we evaluated the effect of diluted bitumen (dilbit) experimentally spilled in limnocorrals installed in a boreal lake on the volatilization of sulfur hexafluoride (SF6), a non-reactive volatile tracer gas. Dilbit spills were monitored over 70 days and SF6 was introduced twice (after 7 and 48 days) to evaluate the influence of spilled dilbit on the loss of SF6 from water. Volatilization rate constants of SF6 (kVOL) significantly decreased by up to 80% with increasing total dilbit spill cover. Using a theoretical equation, decreases in kVOL were largely explained by a reduction in open water area where chemical exchange across the air-water interface occurs. Apparent effects of the slick on SF6 mass transfer were estimated to be smaller by comparison (20%).To account for this reduction in volatilization, oil spill fate models should include a correction to consider the impact of spill cover on the air-water exchange of organic chemicals.

Simulating diluted bitumen spills in boreal lake limnocorrals - Part 1: Experimental design and responses of hydrocarbons, metals, and water quality parameters.

Large-scale, in-lake enclosures (limnocorrals) were used to simulate spills of diluted bitumen (dilbit) in a boreal lake. In this study we use these simulated spills, which covered a range of sizes (oil:water ratio) representative of the upper 25% of onshore crude oil spills in North America (2008-2019), to assess the fate of dilbit-derived hydrocarbons and metals as well as the impacts of the spills on standard water quality parameters. The systems were monitored over 70 days following the application of dilbit amounts ranging between 1.5 and 179.8 L into 10-m diameter, ~100 m3 limnocorrals. The concentration of total petroleum hydrocarbons (TPH) in the water column increased rapidly over the first two weeks reaching a plateau that ranged between 200 µg/L and 2200 µg/L for the lowest and highest treatment respectively. The concentration of total polycyclic aromatic compounds (PACs) also increased over the first two weeks, prior to a slow decrease until day 70. The maximum measured concentrations in the highest treatment were 2858 ng/L for the sum of all 46 quantified PACs, 2716 ng/L for alkylated PACs and 154 ng/L for the 16 EPA priority PAHs. The concentrations of PACs in the sediment increased continuously over the study in the three highest treatments with maximum observed concentrations of 189 ng/g for ΣPAC46, 169 ng/g for ΣPACalk. No significant treatment-related changes in the 16 EPA priority PAHs were observed in the sediment. Of the 25 metals quantified in the water column, only manganese, molybdenum, and vanadium displayed a significant treatment effect with increases of 280, 76 and 25% respectively in the total fraction. These results can help us understand and predict the fate of oil-derived contaminants following a spill and characterize the exposure of freshwater organisms living within them. These results should help inform the risk assessment of future dilbit transportation projects.

Chemical identification of microplastics ingested by Red Phalaropes (Phalaropus fulicarius) using Fourier Transform Infrared spectroscopy.

Chemical characterization of plastics ingested by wildlife helps identify sources of plastic pollution in nature and informs assessments of exposure risk to contaminants. In 2016, Red Phalaropes (Phalaropus fulicarius) were found dead on the north coast of British Columbia, Canada, during their southward migration. Previously, ingested particles suspected to be plastics were reported upon gut examination in all carcasses collected, which likely contributed to mortality. Here, we provide chemical identification of the ingested particles using Fourier Transform Infrared (FTIR) spectroscopy. Polymer identification was successful for 41 of the 52 analysed particles (79%): 41 (79%) were confirmed as plastics, 6 (11%) were not plastics, and 5 (10%) could not be identified. The most commonly ingested plastics were polyethylene (42%) and polypropylene (23%), both of which are known to float in the marine environment. Our study highlights the vulnerability of surface foraging seabirds to plastic pollution in the marine environment.

David W. Schindler (1940-2021).

A world-renowned scientist who combined his formidable intellect with passionate advocacy to address problems affecting global freshwaters and the people who rely on them, while empowering generations of diverse peoples to action.

Simulating a Spill of Diluted Bitumen: Environmental Weathering and Submergence in a Model Freshwater System.

The main petroleum product transported through pipelines in Canada is diluted bitumen (dilbit), a semiliquid form of heavy crude oil mixed with natural gas condensates to facilitate transport. The weathering, fate, behavior, and environmental effects of dilbit are crucial to consider when responding to a spill; however, few environmental studies on dilbit have been completed. We report on 11-d-long experimental spills of dilbit (Cold Lake Winter Blend) in outdoor microcosms meant to simulate a low-energy aquatic system containing natural lake water and sediments treated with low (1:8000 oil:water) and high (1:800 oil:water) volumes of dilbit. In the first 24 h of the experiment, volatile hydrocarbons quickly evaporated from the dilbit, resulting in increased dilbit density and viscosity. These changes in dilbit's physical and chemical properties ultimately led to its submergence after 8 d. We also detected rapid accumulation of polycyclic aromatic compounds in the water column of the treated microcosms following the spills. The present study provides new information on the environmental fate and behavior of dilbit in a freshwater environment that will be critical to environmental risk assessments of proposed pipeline projects. In particular, the study demonstrates the propensity for dilbit to sink under ambient environmental conditions in freshwaters typical of many boreal lakes. Environ Toxicol Chem 2019;38:2621-2628. © 2019 SETAC.

Experimental iron amendment suppresses toxic cyanobacteria in a hypereutrophic lake.

The effects of reducing nutrient inputs to lakes and reservoirs are often delayed by hysteresis resulting from internal phosphorus (P) loading from sediments. Consequently, controlling harmful algal blooms (HABs) in many eutrophic ecosystems requires additional management to improve water quality. We manipulated iron (Fe) concentrations in a hypereutrophic lake to determine if Fe amendment would suppress HABs by inhibiting P release from sediments. Our experiment consisted of 15 in situ mesocosms, 12 of which each received a different dose of Fe (ranging from 2 to 225 g/m2 ); the remaining three were unmanipulated to serve as controls. Iron amendment decreased P accumulation in porewaters and the flux of P from sediments, which significantly lowered P concentrations in the water column. Iron exerted significant dose-dependent negative effects on the biomass of phytoplankton and periphyton, and reduced the dominance of cyanobacteria. Even at the lowest doses, Fe appeared to reduce the toxicity of cyanobacterial blooms, as measured by concentrations of hepatotoxic microcystins. Overall, our findings highlight the potential for Fe treatment as an effective strategy for minimizing HABs in eutrophic lakes and reservoirs. More broadly, our study reinforces the importance of Fe in regulating the trophic state of freshwaters, and the sensitivity of certain ecosystems to changes in Fe supply. Finally, we hypothesize that decreases in natural Fe supplies to lakes associated with anthropogenic activities may worsen outbreaks of toxic cyanobacteria.

Reducing Phosphorus to Curb Lake Eutrophication is a Success.

As human populations increase and land-use intensifies, toxic and unsightly nuisance blooms of algae are becoming larger and more frequent in freshwater lakes. In most cases, the blooms are predominantly blue-green algae (Cyanobacteria), which are favored by low ratios of nitrogen to phosphorus. In the past half century, aquatic scientists have devoted much effort to understanding the causes of such blooms and how they can be prevented or reduced. Here we review the evidence, finding that numerous long-term studies of lake ecosystems in Europe and North America show that controlling algal blooms and other symptoms of eutrophication depends on reducing inputs of a single nutrient: phosphorus. In contrast, small-scale experiments of short duration, where nutrients are added rather than removed, often give spurious and confusing results that bear little relevance to solving the problem of cyanobacteria blooms in lakes.

Probing the debromination of the flame retardant decabromodiphenyl ether in sediments of a boreal lake.

After decades of use of polybrominated diphenyl ethers (PBDEs) as flame retardants, a large reservoir of these toxins has accumulated in ecosystems worldwide. The present study used an innovative approach to examine whether the fully brominated PBDE decabromodiphenyl ether (decaBDE) degrades to more toxic congeners in aquatic environments. The authors incubated intact sediment microcosms with high-purity [(13)C]decaBDE in a remote boreal lake to assess its debromination under ambient conditions. Although the addition of [(13)C]decaBDE increased total PBDE concentrations in sediment more than 10-fold, the relative amount of [(13)C]decaBDE in sediment did not change significantly over a 1-mo incubation. However, observation of small quantities of lower-brominated [(13)C]BDEs lent support to the hypothesis that decaBDE is slowly debrominated. The authors observed a significant increase in octaBDEs and nonaBDEs in profundal, but not littoral, sediment over 30 d. A second experiment in which sediment was incubated under different light and oxygen regimes yielded a surprising result-oxygen significantly stimulated the formation of octaBDEs and nonaBDEs. The authors also conducted a large-scale in situ enclosure experiment in which they followed the fate of experimentally added decaBDE in sediment over 26 mo, but that study yielded little evidence of decaBDE debromination. Overall, the authors suggest that the debromination of decaBDE occurs very slowly, if at all, in natural sediment of boreal lakes, in contrast to the rapid degradation kinetics reported by most laboratory-based studies, which are usually conducted by dissolving decaBDE in organic solvents. The findings reinforce the need for field studies on contaminant fate to inform environmental policy decisions.

Temporal changes in the distribution, methylation, and bioaccumulation of newly deposited mercury in an aquatic ecosystem.

Our objective was to examine how the behavior of atmospheric mercury (Hg) deposited to boreal lake mesocosms changed over time. We added inorganic Hg enriched in a different stable isotope in each of two years, which allowed us to differentiate between Hg added in the first and second year. Although inorganic Hg and methylmercury (MeHg) continued to accumulate in sediments throughout the experiment, the availability of MeHg to the food web declined within one year. This decrease was detected in periphyton, zooplankton, and water mites, but not in gomphid larvae, amphipods, or fish. We suggest that reductions in atmospheric Hg deposition should lead to decreases in MeHg concentrations in biota, but that changes will be more easily detected in short-lived pelagic species than long-lived species associated with benthic food webs.

Experimental evidence of a linear relationship between inorganic mercury loading and methylmercury accumulation by aquatic biota.

Developing effective regulations on mercury (Hg) emissions requires a better understanding of how atmospheric Hg deposition affects methylmercury (MeHg) levels in aquatic biota. This study tested the hypothesis that MeHg accumulation in aquatic food webs is related to atmospheric Hg deposition. We simulated a range of inorganic Hg deposition rates by adding isotopically enriched Hg(II) (90.9% 202Hg) to 10-m diameter mesocosms in a boreal lake. Concentrations of experimentally added ("spike") Hg were monitored in zooplankton, benthic invertebrates, and fish. Some Hg(II) added to the mesocosms was methylated and incorporated into the food web within weeks, demonstrating that Hg(II) deposited directly to aquatic ecosystems can become quickly available to biota. Relationships between Hg(II) loading rates and spike MeHg concentrations in zooplankton, benthic invertebrates, and fish were linear and significant. Furthermore, spike MeHg concentrations in the food web were directly proportional to Hg(II) loading rates (i.e., a percent change in Hg(II) loading rate resulted in, statistically, the same percent change in MeHg concentration). This is the first experimental determination of the relationship between Hg(II) loading and MeHg bioaccumulation in aquatic biota. We conclude that changes in atmospheric Hg deposition caused by increases or decreases in Hg emissions will ultimately affect MeHg levels in aquatic food webs.