Experimental evidence for recovery of mercury-contaminated fish populations.

Anthropogenic releases of mercury (Hg)1-3 are a human health issue4 because the potent toxicant methylmercury (MeHg), formed primarily by microbial methylation of inorganic Hg in aquatic ecosystems, bioaccumulates to high concentrations in fish consumed by humans5,6. Predicting the efficacy of Hg pollution controls on fish MeHg concentrations is complex because many factors influence the production and bioaccumulation of MeHg7-9. Here we conducted a 15-year whole-ecosystem, single-factor experiment to determine the magnitude and timing of reductions in fish MeHg concentrations following reductions in Hg additions to a boreal lake and its watershed. During the seven-year addition phase, we applied enriched Hg isotopes to increase local Hg wet deposition rates fivefold. The Hg isotopes became increasingly incorporated into the food web as MeHg, predominantly from additions to the lake because most of those in the watershed remained there. Thereafter, isotopic additions were stopped, resulting in an approximately 100% reduction in Hg loading to the lake. The concentration of labelled MeHg quickly decreased by up to 91% in lower trophic level organisms, initiating rapid decreases of 38-76% of MeHg concentration in large-bodied fish populations in eight years. Although Hg loading from watersheds may not decline in step with lowering deposition rates, this experiment clearly demonstrates that any reduction in Hg loadings to lakes, whether from direct deposition or runoff, will have immediate benefits to fish consumers.

A genome catalogue of mercury-methylating bacteria and archaea from sediments of a boreal river facing human disturbances.

Methyl mercury, a toxic compound, is produced by anaerobic microbes and magnifies in aquatic food webs, affecting the health of animals and humans. The exploration of mercury methylators based on genomes is still limited, especially in the context of river ecosystems. To address this knowledge gap, we developed a genome catalogue of potential mercury-methylating microorganisms. This was based on the presence of hgcAB from the sediments of a river affected by two run-of-river hydroelectric dams, logging activities and a wildfire. Through the use of genome-resolved metagenomics, we discovered a unique and diverse group of mercury methylators. These were dominated by members of the metabolically versatile Bacteroidota and were particularly rich in microbes that ferment butyrate. By comparing the diversity and abundance of mercury methylators between sites subjected to different disturbances, we found that ongoing disturbances, such as the input of organic matter related to logging activities, were particularly conducive to the establishment of a mercury-methylating niche. Finally, to gain a deeper understanding of the environmental factors that shape the diversity of mercury methylators, we compared the mercury-methylating genome catalogue with the broader microbial community. The results suggest that mercury methylators respond to environmental conditions in a manner similar to the overall microbial community. Therefore, it is crucial to interpret the diversity and abundance of mercury methylators within their specific ecological context.

Enhanced Bioaccumulation and Transfer of Monomethylmercury through Periphytic Biofilms in Benthic Food Webs of a River Affected by Run-of-River Dams.

Run-of-river (ROR) power plants impound limited terrestrial areas compared to traditional hydropower plants with large reservoirs and are assumed to have reduced impacts on mercury cycling. We conducted a study on periphyton and benthic communities from different habitats of the St. Maurice River (Québec, Canada) affected by two ROR power plants and their effect on the bioaccumulation and biomagnification of monomethylmercury (MMHg). Proportion of total mercury as MMHg reached maximum values about 2.9 times higher in flooded sites compared to unflooded sites. Impoundment by ROR would therefore provide favorable environments for the growth of periphyton, which can produce and accumulate MMHg. Periphyton MMHg concentrations significantly explained concentrations in some benthic macroinvertebrates, reflecting a local transfer. Through the analysis of δ13C and δ15N signatures, we found that flooding, creating scattered lenthic habitats, led to modifications in trophic structures by the introduction of new organic matter sources. The computed trophic magnification slopes did not show significant differences in the transfer efficiency of MMHg between sectors, while intercepts of flooded sectors were higher. Increases in MMHg concentrations in flooded areas are likely due to the impoundment, combined with watershed disturbances, and the creation of small habitats favorable to periphyton should be included in future predictive models.

Effect of cooking temperature on metal concentrations and speciation in fish muscle and seal liver.

Fish and marine mammals constitute a significant part of the country food diet of many Indigenous communities in Canada. These animals sometimes accumulate essential elements as well as elevated levels of toxic metals. We experimentally assessed how changes in cooking temperature (23-99 °C by boiling) modified elemental concentrations in whitefish muscle and grey seal liver (two organs commonly consumed in some northern communities). Wet and dry elemental concentrations changed linearly as a function of temperature, and two patterns were observed: methylmercury, selenium, and rare earth elements tended to remain associated with the food during cooking, whereas alkali, alkaline-earth metals, and arsenic were significantly transferred to cooking juices. Mass balances indicated that speciation of mercury was stable during cooking. Because elements generally behaved similarly as those of their periodic table group or their ecotoxicological classes (A, B, intermediate), we propose that elemental behavior during cooking is partly a function of chemical affinity, and this relationship can be used to predict the behavior of data-poor elements of emerging concern, such as technology-critical elements. Furthermore, the marked increases and decreases in elemental concentrations during cooking (e.g., -14% As and +39% Se in whitefish; -22% Cd and +55% Hg in seal liver, on a wet weight basis) should be considered when assessing risk because current exposure models usually only consider elemental concentrations in raw food.

Understanding Food Web Mercury Accumulation Through Trophic Transfer and Carbon Processing along a River Affected by Recent Run-of-river Dams.

Unlike large dams which favor methylation of Hg in flooded soils over long periods, run-of-river dams are designed to flood a limited area of soils and are therefore not expected to significantly affect mercury (Hg) cycling or carbon processing. We studied the Hg and carbon cycles within food webs from several sectors along the Saint-Maurice River, Quebec, Canada, that differ in how they are influenced by two run-of-river dams and other watershed disturbances. We observed peak Hg concentrations in fish five-year postimpoundment, but these levels were reduced three years after this peak. Methylmercury concentrations in low trophic level fish and invertebrates were related to their carbon source (δ13C) rather than their trophic positions (δ15N). Biomagnification, measured by trophic magnification slopes, was driven mainly by methylmercury concentrations in low-trophic level organisms and environmental factors related to organic matter degradation and Hg-methylation. River sectors, δ13C and δ15N, predicted up to 80% of the variability in food web methylmercury concentrations. The installation of run-of-river dams and the related pondages, in association with other watershed disturbances, altered carbon processing, promoted Hg-methylation and its accumulation at the base of the food web, and led to a temporary increase in Hg levels in fish.

Environmental Drivers of Rare Earth Element Bioaccumulation in Freshwater Zooplankton.

Human activities have resulted in significant release of rare earth elements (REEs) into the environment. However, the pathways of REEs from waters and soils into freshwater food webs remain poorly understood. Recent studies suggest that aquatic invertebrates may be good biomonitors for REEs, yet there is little information on factors that control REE bioaccumulation in these organisms. Our goal was to study the environmental drivers of REE levels in zooplankton, a key component in plankton food webs, across lakes from geographic areas with different bedrock geology. From 2011 to 2014, bulk zooplankton samples were collected for REE analysis from 39 lakes in eastern Canada. We observed a more than 200 fold variation in surface water REE concentrations and a 10-fold variation in sediment REE concentrations. These concentration gradients were associated with a range of more than an order of magnitude in zooplankton REE concentrations (∑REEY 3.2-210 nmol g-1). We found higher REE bioaccumulation in zooplankton from lakes with lower pH and higher REE to dissolved organic carbon ratios. Bioaccumulation was also strongly linked to the free ion concentrations of REEs (REE3+) in surface waters. Our study suggests that zooplankton REE bioaccumulation is an excellent predictor of bioavailable REEs in freshwaters.

Ratio of Methylmercury to Dissolved Organic Carbon in Water Explains Methylmercury Bioaccumulation Across a Latitudinal Gradient from North-Temperate to Arctic Lakes.

We investigated monomethylmercury (MMHg) bioaccumulation in lakes across a 30° latitudinal gradient in eastern Canada to test the hypothesis that climate-related environmental conditions affect the sensitivity of Arctic lakes to atmospheric mercury contamination. Aquatic invertebrates (chironomid larvae, zooplankton) provided indicators of MMHg bioaccumulation near the base of benthic and planktonic food chains. In step with published data showing latitudinal declines in atmospheric mercury deposition in Canada, we observed lower total mercury concentrations in water and sediment of higher latitude lakes. Despite latitudinal declines of inorganic mercury exposure, MMHg bioaccumulation in aquatic invertebrates did not concomitantly decline. Arctic lakes with greater MMHg in aquatic invertebrates either had (1) higher water MMHg concentrations (reflecting ecosystem MMHg production) or (2) low water concentrations of MMHg, dissolved organic carbon (DOC), chlorophyll, and total nitrogen (reflecting lake sensitivity). The MMHg:DOC ratio of surface water was a strong predictor of lake sensitivity to mercury contamination. Bioaccumulation factors for biofilms and seston in Arctic lakes showed more efficient uptake of MMHg in low DOC systems. Environmental conditions associated with low biological production in Arctic lakes and their watersheds increased the sensitivity of lakes to MMHg.

Evaluation of on-line concentration coupled to liquid chromatography tandem mass spectrometry for the quantification of neonicotinoids and fipronil in surface water and tap water.

A study was initiated to investigate a fast and reliable method for the determination of selected systemic insecticides in water matrixes and to evaluate potential sources of bias in their analysis. Acetamiprid, clothianidin, desnitro-imidacloprid, dinotefuran, fipronil, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam were amenable to analysis via on-line sample enrichment hyphenated to ultra-high-performance liquid chromatography tandem mass spectrometry. The selection of on-line solid-phase extraction parameters was dictated by a multicriterion desirability approach. A 2-mL on-line injection volume with a 1500 µL min-1 loading flow rate met the objectives sought in terms of chromatographic requirements, extraction efficiency, sensitivity, and precision. A total analysis time of 8 min per sample was obtained with method limits of detection in the range of 0.1-5 ng L-1 for the scope of targeted analytes. Automation at the sample concentration step yielded intraday and interday precisions in the range of 1-23 and 2-26%, respectively. Factors that could affect the whole method accuracy were further evaluated in matrix-specific experiments. The impact of the initial filtration step on analyte recovery was evaluated in ultra-pure water, tap water, and surface water. Out of the nine membranes tested, glass fiber filters and polyester filters appeared as the most appropriate materials. Sample storage stability was also investigated across the three matrix types; the targeted analytes displayed suitable stability during 28 days at either 4 °C or - 20 °C, with little deviations (± 10%) with respect to the initial T0 concentration. Method applicability was demonstrated in a range of tap water and surface water samples from the province of Québec, Canada. Results from the present survey indicated a predominance of thiamethoxam (< 0.5-10 and 3-61 ng L-1 in tap water and river water, respectively), clothianidin (< 0.5-6 and 2-88 ng L-1 in tap water and river water, respectively), and imidacloprid (< 0.1-1 and 0.8-38 ng L-1 in tap water and river water, respectively) among the targeted analytes. Graphical abstract ᅟ Development of solid-phase extraction coupled on-line to UHPLC-MS/MS for the rapid screening of systemic insecticides in water.

Fate and Trophic Transfer of Rare Earth Elements in Temperate Lake Food Webs.

Many mining projects targeting rare earth elements (REE) are in development in North America, but the background concentrations and trophic transfer of these elements in natural environments have not been well characterized. We sampled abiotic and food web components in 14 Canadian temperate lakes unaffected by mines to assess the natural ecosystem fate of REE. Individual REE and total REE concentrations (sum of individual element concentrations, ΣREE) were strongly related with each other throughout different components of lake food webs. Dissolved organic carbon and dissolved oxygen in the water column, as well as ΣREE in sediments, were identified as potential drivers of aqueous ΣREE. Log10 of median bioaccumulation factors ranged from 1.3, 3.7, 4.0, and 4.4 L/kg (wet weight) for fish muscle, zooplankton, predatory invertebrates, and nonpredatory invertebrates, respectively. [ΣREE] in fish, benthic macroinvertebrates, and zooplankton declined as a function of their trophic position, as determined by functional feeding groups and isotopic signatures of nitrogen (δ15N), indicating that REE were subject to trophic dilution. Low concentrations of REE in freshwater fish muscle compared to their potential invertebrate prey suggest that fish fillet consumption is unlikely to be a significant source of REE to humans in areas unperturbed by mining activities. However, other fish predators (e.g., piscivorous birds and mammals) may accumulate REE from whole fish as they are more concentrated than muscle. Overall, this study provides key information on the baseline concentrations and trophic patterns for REE in freshwater temperate lakes in Quebec, Canada.

Receptors rather than signals change in expression in four physiological regulatory networks during evolutionary divergence in threespine stickleback.

The molecular mechanisms underlying behavioural evolution following colonization of novel environments are largely unknown. Molecules that interact to control equilibrium within an organism form physiological regulatory networks. It is essential to determine whether particular components of physiological regulatory networks evolve or if the network as a whole is affected in populations diverging in behavioural responses, as this may affect the nature, amplitude and number of impacted traits. We studied the regulation of four physiological regulatory networks in freshwater and marine populations of threespine stickleback raised in a common environment, which were previously characterized as showing evolutionary divergence in behaviour and stress reactivity. We measured nineteen components of these networks (ligands and receptors) using mRNA and monoamine levels in the brain, pituitary and interrenal gland, as well as hormone levels. Freshwater fish showed higher expression in the brain of adrenergic (adrb2a), serotonergic (htr2a) and dopaminergic (DRD2) receptors, but lower expression of the htr2b receptor. Freshwater fish also showed higher expression of the mc2r receptor of the glucocorticoid axis in the interrenals. Collectively, our results suggest that the inheritance of the regulation of these networks may be implicated in the evolution of behaviour and stress reactivity in association with population divergence. Our results also suggest that evolutionary change in freshwater threespine stickleback may be more associated with the expression of specific receptors rather than with global changes of all the measured constituents of the physiological regulatory networks.

Photodemethylation of Methylmercury in Eastern Canadian Arctic Thaw Pond and Lake Ecosystems.

Permafrost thaw ponds of the warming Eastern Canadian Arctic are major landscape constituents and often display high levels of methylmercury (MeHg). We examined photodegradation potentials in high-dissolved organic matter (DOC) thaw ponds on Bylot Island (BYL) and a low-DOC oligotrophic lake on Cornwallis Island (Char Lake). In BYL, the ambient MeHg photodemethylation (PD) rate over 48 h of solar exposure was 6.1 × 10(-3) m(2) E(-1), and the rate in MeHg amended samples was 9.3 × 10(-3) m(2) E(-1). In contrast, in low-DOC Char Lake, PD was only observed in the first 12 h, which suggests that PD may not be an important loss process in polar desert lakes. Thioglycolic acid addition slowed PD, while glutathione and chlorides did not impact northern PD rates. During an ecosystem-wide experiment conducted in a covered BYL pond, there was neither net MeHg increase in the dark nor loss attributable to PD following re-exposure to sunlight. We propose that high-DOC Arctic thaw ponds are more prone to MeHg PD than nearby oligotrophic lakes, likely through photoproduction of reactive species rather than via thiol complexation. However, at the ecosystem level, these ponds, which are widespread through the Arctic, remain likely sources of MeHg for neighboring systems.

Mercury, hydroquinone and clobetasol propionate in skin lightening products in West Africa and Canada.

Skin lightening products are types of cosmetics (creams, gels, lotions and soaps) applied voluntarily on skin. Several of these products contain a variety of active ingredients that are highly toxic. Among those toxic agents, the present study focuses on mercury, hydroquinone, and clobetasol propionate. Out of the 93 lightening soaps and 98 creams purchased in large city markets in sub-Saharan West Africa and in small ethnic shops in Canada, 68-84% of all creams and 7.5-65% of all soaps exceeded regulatory guidelines for at least one active ingredient when considering different regulations. Mercury was found in high concentrations mainly in soaps, while hydroquinone and clobetasol propionate concentrations exceeded US FDA standards in some creams for all countries included in our study. Concentrations of the three compounds declared on labels of soaps and creams usually did not correspond to concentrations actually measured, particularly for mercury and hydroquinone. Overall, our results indicate that most studied skin-lightening products are potentially toxic and that product labels are frequently inaccurate with respect to the presence of toxic agents.

Relationship between Extracellular Low-Molecular-Weight Thiols and Mercury Species in Natural Lake Periphytic Biofilms.

The uptake of mercury by microorganisms is a key step in the production of methylmercury, a biomagnifiable toxin. Mercury complexation by low-molecular-weight (LMW) thiols can affect its bioavailability and thus the production of methylmercury. Freshwater biofilms were sampled in the summer using artificial Teflon substrates submerged for over a year to allow natural community colonization in the littoral zone of a Boreal Shield lake. Inside biofilms, concentrations of different extracellular thiol species (thioglycolic acid, l-cysteine-l-glycine, cysteine, and glutathione) were up to 3 orders of magnitude greater than in the surrounding water column, potentially more readily controlling mercury speciation than in the water column. All biofilm thiols except thioglycolic acid were highly correlated to chlorophyll a, likely indicating an algal origin. Extracellular total mercury represented 3 ± 1% of all biofilm mercury and was preferentially found in the capsular fraction. Levels of LMW thiols of presumed algal origins were highly correlated with total mercury in the mobile colloidal fraction of biofilms. We propose that periphytic phototrophic microorganisms such as algae likely affect the bioavailability of mercury through the exudation of LMW thiols, and thus they may play a key role in the production of methylmercury in biofilms.

High Methylmercury in Arctic and Subarctic Ponds is Related to Nutrient Levels in the Warming Eastern Canadian Arctic.

Permafrost thaw ponds are ubiquitous in the eastern Canadian Arctic, yet little information exists on their potential as sources of methylmercury (MeHg) to freshwaters. They are microbially active and conducive to methylation of inorganic mercury, and are also affected by Arctic warming. This multiyear study investigated thaw ponds in a discontinuous permafrost region in the Subarctic taiga (Kuujjuarapik-Whapmagoostui, QC) and a continuous permafrost region in the Arctic tundra (Bylot Island, NU). MeHg concentrations in thaw ponds were well above levels measured in most freshwater ecosystems in the Canadian Arctic (>0.1 ng L(-1)). On Bylot, ice-wedge trough ponds showed significantly higher MeHg (0.3-2.2 ng L(-1)) than polygonal ponds (0.1-0.3 ng L(-1)) or lakes (<0.1 ng L(-1)). High MeHg was measured in the bottom waters of Subarctic thaw ponds near Kuujjuarapik (0.1-3.1 ng L(-1)). High water MeHg concentrations in thaw ponds were strongly correlated with variables associated with high inputs of organic matter (DOC, a320, Fe), nutrients (TP, TN), and microbial activity (dissolved CO2 and CH4). Thawing permafrost due to Arctic warming will continue to release nutrients and organic carbon into these systems and increase ponding in some regions, likely stimulating higher water concentrations of MeHg. Greater hydrological connectivity from permafrost thawing may potentially increase transport of MeHg from thaw ponds to neighboring aquatic ecosystems.

Effects of experimental thermocline and oxycline deepening on methylmercury bioaccumulation in a Canadian shield lake.

Environmental disturbances like deforestation or climate change may influence lake thermal and oxic stratification, thereby modifying cycles of contaminants such as mercury (Hg). In a lake naturally separated into three basins, the thermocline and oxycline of an experimental basin were deepened by 4 and 3 m, respectively, to study the effect on the methylmercury (MeHg) accumulation. This treatment decreased hypolimnetic MeHg concentration by approximately 90%, zooplankton concentrations by 30 to 50%, and in some fish by 45%. A multiple linear regression indicated that oxycline depth significantly influenced hypolimnetic MeHg concentrations, with no significant effect of thermocline depth, anoxic water volume, interface area of oxic-anoxic water, and sediment area in contact with anoxic water. Fish MeHg decline varied, with a greater response by low oxygen-tolerant bullhead. Increased pelagic primary and secondary production likely caused zooplankton and fish MeHg decreases via algal and growth dilution. Environmental changes leading to oxycline deepening are therefore predicted to cause a decrease in MeHg bioaccumulation in similar Canadian Shield lakes. If associated ecosystem impacts related to the deepening treatment are deemed acceptable, then this experiment provides a potential remediation method for small lakes confronted with MeHg accumulation.

Methylmercury in northern pike (Esox lucius) liver and hepatic mitochondria is linked to lipid peroxidation.

Methylmercury (MeHg) readily bioaccumulates and biomagnifies in aquatic food webs leading to elevated concentrations in fish and may thus induce toxicity. Oxidative stress is a suggested effect of MeHg bioaccumulation in fish. However, studies on how MeHg triggers oxidative stress in wild fish are scarce. The purpose of this study was to link the subcellular distribution of MeHg in the liver of northern pike from the St. Maurice River (Québec, Canada), affected by two run-of-river (RoR) dams, artificial wetlands, forest fires, and logging activity, to lipid peroxidation as an indicator of oxidative stress. We also evaluated the protective effects of the glutathione (GSH) system and selenium (Se), as they are known to alleviate MeHg toxicity. A customized subcellular partitioning protocol was used to separate the liver into metal-sensitive (mitochondria, microsome/lysosome and HDP - heat-denatured proteins) and metal-detoxified fractions (metal-rich granules and HSP - heat-stable proteins). We examined the relation among THg, MeHg, and Se concentration in livers and subcellular fractions, and the hepatic ratio of total GSH (GSHt) to oxidized glutathione (GSSG) on lipid peroxidation levels, using the concentrations of malondialdehyde (MDA), a product of lipid peroxidation. Results showed that hepatic MDA concentration was positively correlated with the combined MeHg and Se concentrations in northern pike liver (r2 = 0.88, p < 0.001) and that MDA concentrations were best predicted by MeHg associated with the mitochondria (r2 = 0.71, p < 0.001). This highlights the need for additional research on the MeHg influence on fish health and the interactions between Hg and Se in northern pike.

An investigation of enhanced mercury bioaccumulation in fish from offshore feeding.

We investigated the dietary pathways of mercury transfer in the food web of Morency Lake (Canada) to determine the influence of carbon source and habitat use on mercury bioaccumulation in fish. Whole-body concentrations of methylmercury (MeHg) were significantly different in four fish species (white sucker, brown bullhead, pumpkinseed and smallmouth bass) and increased with both trophic position and greater feeding on offshore (versus littoral) carbon. An examination of fish gut contents and the depth distribution of invertebrates in Morency Lake showed that smallmouth bass and brown bullhead were supplementing their littoral diet with the consumption of either opossum shrimp (Mysis diluviana) or profundal amphipods in offshore waters. The zooplanktivore Mysis had significantly higher MeHg concentrations than zooplankton and benthic invertebrates, and it was an elevated source of MeHg to smallmouth bass. In contrast, profundal amphipods consumed by brown bullhead did not have higher MeHg concentrations than littoral amphipods. Instead, partitioning of benthic invertebrate resources likely explains the greater MeHg bioaccumulation in brown bullhead, associated with offshore feeding of amphipods. White sucker and brown bullhead had a similar trophic position but white sucker consumed more chironomids, which had one-third the MeHg concentration of amphipods. Our findings suggest that offshore feeding in a lake can affect fish MeHg bioaccumulation via two different processes: (1) the consumption of MeHg-enriched pelagic prey, or (2) resource partitioning of benthic primary consumers with different MeHg concentrations. These observations on the mechanisms of habitat-specific bioaccumulation highlight the complexity of MeHg transfer through lake food webs.

The relationship between zooplankton vertical distribution and the concentration of aqueous Hg in boreal lakes: A comparative field study.

The production of the highly toxic monomethylmercury (MeHg) is heterogenous throughout the water column. Multiple factors have been identified to significantly affect this process, such as an extended anoxic water layer and a deep-water phytoplankton maximum. However, the role of water column heterogeneity on mercury (Hg) cycling is still poorly known, especially concerning the role of zooplankton grazers. Here, four boreal lakes with contrasting characteristics were sampled (i.e., transparency and the presence/absence of fish) at both day and night in order to maximize the heterogeneity in zooplankton abundance both among and within lakes, and to investigate their potential links with Hg vertical heterogeneity. Diel variation of the concentrations of both dissolved total Hg (DTHg) and total Hg (THg) were observed, with night samples significantly higher than day samples. Although this pattern was not related to diel changes in the vertical distribution of zooplankton, results showed that the presence of large copepods (>1.2 mm) and medium-sized (0.6 to 1.2 mm) cladocerans was significantly associated with lower concentrations of DTHg in the water at a given depth, whereas the presence of medium-sized copepods was significantly associated with the concentration of THg. The presence of cladocerans was significantly associated with the ratio between the dissolved MeHg and DTHg (conventionally used as a proxy of methylation potential). Phytoplankton biomass was directly correlated with the concentration of both dissolved and total MeHg and the methylation potential. At the same time, phytoplankton biomass was inversely related to the fraction of DTHg. These results suggest a potential key role of the heterogeneity of biotic factors in the water column, especially of phytoplankton and zooplankton, in the cycling of total Hg and MeHg in boreal lakes.

How do metals interact with periphytic biofilms?

Extracellular matrix of periphyton has complex structural and chemical composition regulating metal transfer within biofilms with consequences for metal transfer to aquatic food webs. We investigated which metal species were retained in the loosely (LB) and the tightly bound (TB) fractions of the periphyton matrix from three pristine lakes at different growth stages. We measured the fluorescent dissolved organic matter (FDOM) composition with parallel factor analysis (PARAFAC) and the co-occurrence of essential and non-essential metals with FDOM in the two matrix fractions. The LB and TB fractions of periphyton had distinct fluorescence composition from the water column. The PARAFAC model identified five components, including two (C2 and C4) appearing to be of periphytic origin. The humic-like C2 was almost exclusive to periphyton and the tryptophan-like C4, associated to biofilm phototrophy, represented up to 47.0 ± 7.3 % of total fluorescence in the LB fraction. Most metals had significant positive relationships with four FDOM components in the LB fraction while C2 was the only component in the TB fraction to show such significant relationships. Components in the LB fraction seemed to act as scavengers for metals, preventing them from reaching the cellular fraction, while C2 from the TB fraction was likely promoting the bioavailability of essential metals for microorganisms inside periphyton. This study highlights the contrasting roles of the extracellular matrix on metal mobility beyond the usually proposed protection mechanisms. We suggest an experimental model for the study of metal regulation processes of the periphytic extracellular polymeric substances with a focus on the components produced by microorganisms within periphyton and their distribution in the different matrix fractions.

Rare earth element bioaccumulation and cerium anomalies in biota from the Eastern Canadian subarctic (Nunavik).

Recent increases in the demand for rare earth elements (REE) have contributed to various countries' interest in exploration of their REE deposits, including within Canada. Current limited knowledge of REE distribution in undisturbed subarctic environments and their bioaccumulation within northern species is addressed through a collaborative community-based environmental monitoring program in Nunavik (Quebec, Canada). This study provides background REE values (lanthanides + yttrium) and investigates REE anomalies (i.e., deviations from standard pattern) across terrestrial, freshwater, and marine ecosystems in an area where a REE mining project is in development. Results are characteristic of a biodilution of REE, with the highest mean total REE concentrations (ΣREE) reported in sediments (102 nmol/g) and low trophic level organisms (i.e., biofilm, macroalgae, macroinvertebrates, common mussels, and reindeer lichens; 101-102 nmol/g), and the lowest mean concentrations in higher-level consumers (i.e., goose, ptarmigan, char, whitefish, cod, sculpin and seal; 10-2 - 101 nmol/g). The animal tissues are of importance to northern villages and analyses demonstrate a species-specific bioaccumulation of REE, with mean concentrations up to 40 times greater in liver compared to muscle, with bones and kidneys presenting intermediate concentrations and the lowest in blubber. Further, a tissue-specific fractionation was presented, with significant light REE (LREE) enrichment compared to heavy REE (HREE) in consumer livers (LREE/HREE ≅ 101) and the most pronounced negative cerium (Ce) anomalies (<0.80) in liver and bones of fish species. These fractionation patterns, along with novel negative relationships presented between fish size (length, mass) and Ce anomalies suggest metabolic, ecological, and/or environmental influences on REE bioaccumulation and distribution within biota. Background concentration data will be useful in the establishment of REE guidelines; and the trends discussed support the use of Ce anomalies as biomarkers for REE processing in animal species, which requires further investigation to better understand their controlling factors.