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.

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.

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.

Spatial distribution and speciation of mercury in a recovering deepwater redfish (Sebastes mentella) population from St. Lawrence Estuary and Gulf, Canada.

Mercury (Hg) pollution poses a significant threat to the environment, particularly in the form of methylmercury (MeHg). However, little is known about the distribution and influencing factors of Hg in deep-sea (>200m) fish, which is crucial for assessing potential health risks to fish and humans. In Canada, the deepwater redfish (Sebastes mentella) has been designated as an endangered species. After a 25-year fishing moratorium, the redfish population in the St. Lawrence Estuary and Gulf is recovering, and resuming of commercial fishing and human consumption are expected. This study aimed to investigate the distribution of MeHg and total Hg (THg) in the muscle of redfish, as well as the factors influencing its distribution, and to assess the potential human health risks associated with redfish consumption. The redfish samples (n = 123) were collected by Fisheries and Oceans Canada in 2019. The concentrations of THg and MeHg in redfish muscle were determined to be 93.3 ± 183 ng/g (mean ± SD, wet weight) and 78.2 ± 149 ng/g, respectively. Large redfish (>30 cm) accumulated 20 to 30 times more Hg than small redfish (17-30 cm). Small redfish from the Estuary-Western Gulf had higher levels of MeHg and THg than those from the Laurentian Channel and the Northeast Gulf, but the Hg availability to redfish among the three areas were similar. Significant predictors of MeHg concentrations in redfish muscle were determined to be fish length, muscle moisture, δ15N, and N%. MeHg consumption by the general population with an average fish consumption rate is not anticipated to have adverse effects. This study establishes a baseline for future Hg monitoring in the deep water environments in this region. Further research is required to elucidate the cause-effect relationships between various environmental/biological parameters and Hg accumulation in deep-sea biota.

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.

Significance of chemical affinity on metal subcellular distribution in yellow perch (Perca flavescens) livers from Lake Saint-Pierre (QUEBEC, Canada).

The subcellular partitioning approach provides useful information on the location of metals within cells and is often used on organisms with high levels of bioaccumulation to establish relationships between the internal concentration and the potential toxicity of metals. Relatively little is known about the subcellular partitioning of metals in wild fish with low bioaccumulation levels in comparison with those from higher contaminated areas. This study aims to examine the subcellular partitioning of various metals considering their chemical affinity and essentiality at relatively low contamination levels. Class A (Y, Sr), class B (Cu, Cd, MeHg), and borderline (Fe, Mn) metal concentrations were measured in livers and subcellular fractions of yellow perch (n = 21) collected in Lake Saint-Pierre, QC, Canada. The results showed that all metals, apart from MeHg, were distributed among subcellular fractions according to their chemical affinity. More than 60% of Y, Sr, Fe, and Mn were found in the metal-sensitive fractions. Cd and Cu were largely associated with the metallothionein-like proteins and peptides (60% and 67% respectively) whereas MeHg was found mainly in the metal-sensitive fractions (86%). In addition, the difference between the subcellular distribution of Cu and other essential metals like Fe and Mn denotes that, although the essentiality of some metals is a determinant of their subcellular distribution, the chemical affinity of metals is also a key driver. The similarity of the subcellular partitioning results with previous studies on yellow perch and other fish species from higher contaminated areas supports the idea that metals are distributed in the cellular environment according to their chemical properties regardless of the bioaccumulation gradient.

The speciation of arsenic in the muscle tissue of inland and coastal freshwater fish from a remote boreal region.

Elevated concentrations of total arsenic (As) have been reported in boreal freshwater fish in both human-impacted and relatively pristine areas. We assessed the arsenic speciation profiles in muscle tissue of six fish species (n = 300) sampled from nine locations across a remote freshwater watershed in northern Ontario, Canada, extending from inland headwater lakes to the coastal marine confluence. Of the five arsenic species measured, only arsenobetaine (AsB) and dimethylarsinic acid (DMA) were detected in these fish. Riverine fish had up to 10-fold higher total [As] when compared to lacustrine fish. On average, these riverine fish also had higher percentages of AsB (%AsB, 60 ± 26%) and lower percentages of unmeasured arsenic (%UNM, 20 ± 21%), compared to lacustrine fish (28 ± 18% and 52 ± 21% %AsB and %UNM, respectively). DMA percentages (%DMA) were relatively consistent across the watershed, averaging 20 ± 21% across all fish. We examined ecological drivers of As speciation and found that %AsB increased slightly with fish weight in large-body predatory fish, but not in forage fish or insectivores. Furthermore, %AsB was positively related to trophic elevation (inferred from δ15N) in lacustrine fish across 3 out of 4 communities and within some populations. Lastly, riverine fish with a more marine-based diet had markedly higher %AsB when compared to fish with more freshwater-based diets, indicating an effect of anadromy on arsenic speciation. Overall, knowledge on arsenic speciation in freshwater fish has been limited and these results indicate potential drivers that can be considered in future studies. Furthermore, the absence of toxic inorganic As species in these boreal fish is an important consideration for future environmental monitoring practices and risk assessments, some of which assume 10-20% of total [As] in fish is present as toxic inorganic As. Additional studies on As bioaccumulation and biotransformation are needed in freshwater systems, particularly at the base of aquatic food webs.

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.

Selenium Interactions with Algae: Chemical Processes at Biological Uptake Sites, Bioaccumulation, and Intracellular Metabolism.

Selenium (Se) uptake by primary producers is the most variable and important step in determining Se concentrations at higher trophic levels in aquatic food webs. We gathered data available about the Se bioaccumulation at the base of aquatic food webs and analyzed its relationship with Se concentrations in water. This important dataset was separated into lotic and lentic systems to provide a reliable model to estimate Se in primary producers from aqueous exposure. We observed that lentic systems had higher organic selenium and selenite concentrations than in lotic systems and selenate concentrations were higher in lotic environments. Selenium uptake by algae is mostly driven by Se concentrations, speciation and competition with other anions, and is as well influenced by pH. Based on Se species uptake by algae in the laboratory, we proposed an accurate mechanistic model of competition between sulfate and inorganic Se species at algal uptake sites. Intracellular Se transformations and incorporation into selenoproteins as well as the mechanisms through which Se can induce toxicity in algae has also been reviewed. We provided a new tool for risk assessment strategies to better predict accumulation in primary consumers and consequently to higher trophic levels, and we identified some research needs that could fill knowledge gaps.

Three-layered silver nanoparticles to trace dissolution and association to a green alga.

Core-shell silver nanoparticles (NPs) consisting of an inner Ag core and successive layers of Au and Ag (Ag@Au@Ag) were used to measure the simultaneous association of Ag NPs and ionic Ag by the green alga Chlamydomonas (C.) reinhardtii. Dissolution of the inner Ag core was prevented by a gold (Au) layer, while the outer Ag layer was free to dissolve. In short-term experiments, we exposed C. reinhardtii to a range of environmentally realistic Ag concentrations added as AgNO3 or as NPs. Results provide three lines of evidence for the greater cell-association of NPs compared to dissolved Ag over the concentration range tested, assuming that cell-association comprises both uptake and adsorption. First, the cell-association rate constants (kuw) for total Ag (AgNP+D), NPs (AgNP) and AuNP were similar and 2.2-fold higher than the one from AgD exposure, suggesting predominant association of the particles over the dissolved form. Second, model calculations based on Ag fluxes suggested that only 6-33% of algal burden was from AgD. Third, the significantly lower AgNP/Au ratio measured with the algae after exposure (2.1 ± 0.1) compared to the AgNP/Au ratio of the NPs in the media (2.47 ± 0.05) suggests cell-association of NPs depleted in Ag. Core-shell NPs provide an innovative tool to understand NP behavior and to directly delineate Ag accumulation from ion and NPs in aquatic systems.

The fish or the egg: Maternal transfer and subcellular partitioning of mercury and selenium in Yellow Perch (Perca flavescens).

Mercury (Hg) is a trace element of particular concern since it is ubiquitous in the environment and because its methylated form (MeHg) readily bioaccumulates and biomagnifies in food webs. This latter process leads to elevated Hg concentrations in fish and may thus induce toxicity. Maternal transfer of bioaccumulated contaminants to offspring is a suggested mechanism of impaired reproductive success in fish. The purpose of this study was to assess the toxicity potential of Hg during maternal transfer in Yellow Perch from Lake Saint-Pierre (Quebec, Canada) using a subcellular partitioning approach. We also evaluated potential protective effects of selenium, as this element has been shown to alleviate Hg toxicity through sequestration. A customized subcellular partitioning protocol was used to separate liver and gonad of Yellow Perch into various subcellular fractions. Results show that, in the liver, MeHg was primarily (51%) associated to the subcellular fraction containing cytosolic enzymes. Furthermore, 23% and 15% of MeHg was found in hepatic and gonadal mitochondria, respectively, suggesting that Yellow Perch is not effectively detoxifying this metal. There was also a strong relationship (R2 = 0.73) between MeHg bioaccumulation in the liver and MeHg concentrations in gonadal mitochondria, which corroborates the potential risk linked to MeHg maternal transfer. On the other hand, we also found that selenium might have a protective effect on Hg toxicity at a subcellular level. In fact, Se:Hg molar ratios in subcellular fractions were systematically above 1 in all tissues and fractions examined, which corresponds to the suggested protective threshold. This study provides the first assessment of subcellular Se:Hg molar ratios in fish. Since early developmental stages in aquatic biota are particularly sensitive to Hg, this study represents a step forward in understanding the likelihood for toxic effects in wild fish through maternal transfer.

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.

Organic selenium, selenate, and selenite accumulation by lake plankton and the alga Chlamydomonas reinhardtii at different pH and sulfate concentrations.

Selenium (Se) concentrations measured in lake planktonic food chains (microplankton <64 µm, copepods, and Chaoborus larvae) were strongly correlated with the concentrations of dissolved organic Se. These correlations were strengthened slightly by adding the concentrations of dissolved selenate to those of organic Se. To better understand the role of Se species and the influence of water chemistry on Se uptake, we exposed the green alga Chlamydomonas reinhardtii to selenite, selenate, or selenomethionine at various H+ ion and sulfate concentrations under controlled laboratory conditions. At low sulfate concentrations, inorganic Se species (selenate >> selenite) were more readily accumulated by this alga than was selenomethionine. However, at higher sulfate concentrations the uptake of selenite was higher than that of selenate, whereas the uptake of selenomethionine remained unchanged. Although the pH of the exposure water did not influence the uptake of selenate by this alga, the accumulation of selenomethionine and selenite increased with pH because of their relative pH-related speciation. The Se concentrations that we measured in C. reinhardtii exposed to selenomethionine were 30 times lower than those that we measured in field-collected microplankton exposed in the same laboratory conditions. This difference is explained by the taxa present in the microplankton samples. Using the present laboratory measurements of Se uptake in microplankton and of natural Se concentrations in lake water allowed us to model Se concentrations in a lake pelagic food chain. Environ Toxicol Chem 2018;37:2112-2122. © 2018 SETAC.

Hepatic oxidative stress and metal subcellular partitioning are affected by selenium exposure in wild yellow perch (Perca flavescens).

Yellow perch (Perca flavescens) collected from 11 lakes in the Canadian mining regions of Sudbury (Ontario) and Rouyn-Noranda (Quebec) display wide ranges in the concentrations of cadmium (Cd), nickel (Ni), selenium (Se), and thallium (Tl) in their livers. To determine if these trace elements, as well as copper (Cu) and zinc (Zn), are causing oxidative stress in these fish, we measured three biochemical indicators (glutathione (GSH), glutathione disulfide (GSSG) and thiobarbituric acid-reactive substances (TBARS)) in their livers. We observed that 44% of the yellow perch that we collected were at risk of cellular oxidative stress and lipid peroxidation. Considering all fish from all lakes, higher liver Se concentrations were coincident with both lower proportions of GSSG compared to GSH and lower concentrations of TBARS, suggesting that the essential trace-element Se acts as an antioxidant. Furthermore, fish suffering oxidative stress had higher proportions of Cd, Cu and Zn in potentially sensitive subcellular fractions (organelles and heat-denatured proteins) than did fish not suffering from stress. This result suggests that reactive oxygen species may oxidize metal-binding proteins and thereby reduce the capacity of fish to safely bind trace metals. High Cd concentrations in metal-sensitive subcellular fractions likely further exacerbate the negative effects of lower Se exposure.

Using Sulfur Stable Isotopes to Understand Feeding Behavior and Selenium Concentrations in Yellow Perch (Perca flavescens).

We measured selenium (Se) concentrations in yellow perch (Perca flavescens) muscle and their prey collected from four Se-contaminated lakes located near metal smelters in the eastern Canadian cities of Sudbury and Rouyn-Noranda. Yellow perch Se concentrations were related to their weight in two of the four lakes. Measurements of sulfur stable isotopes (δ(34)S) in yellow perch muscle and stomach contents showed that larger fish tended to feed less on zooplankton and more on benthic invertebrates than did smaller fish. Because Se concentrations are lower and δ(34)S signatures are higher in zooplankton than in sediment-feeding invertebrates, there was an inverse relationship between animal Se concentrations and δ(34)S signatures in all of our study lakes. δ(34)S signatures were highly effective in characterizing these food web relationships. Selenium concentrations in yellow perch were 1.6 times those of its prey, which indicates that Se is biomagnified by this fish in our study lakes. Estimated Se concentrations in yellow perch gonads suggest that in two of our study lakes one-third of fish are at risk of reproductive toxicity.

Uptake and subcellular distributions of cadmium and selenium in transplanted aquatic insect larvae.

We transplanted larvae of the phantom midge Chaoborus punctipennis from a lake having lower concentrations of Cd and Se (Lake Dasserat) to a more contaminated lake (Lake Dufault) located near a metal smelter in Rouyn-Noranda, Quebec. Transplanted individuals were held in mesh mesocosms for up to 16 days where they were fed with indigenous contaminated zooplankton. Larval Cd and Se burdens increased over time, and came to equal those measured in indigenous C. punctipennis from contaminated Lake Dufault. Larval Se burdens increased steadily, whereas those of Cd showed an initial lag phase that we explain by a change in the efficiency with which this insect assimilated Cd from its prey. We measured Cd and Se in subcellular fractions and found that larvae sequestered the majority (60%) of the incoming Cd in a detoxified fraction containing metal-binding proteins, whereas a minority of this nonessential metal was in sensitive fractions (20%). In contrast, a much higher proportion of the essential element Se (40%) was apportioned to metabolically active sensitive fractions. Larvae took up equimolar quantities of these elements over the course of the experiment. Likewise, Cd and Se concentrations in wild larvae were equimolar, which suggests that they are exposed to equimolar bioavailable concentrations of these elements in our study lakes.

Relating selenium concentrations in a planktivore to selenium speciation in lakewater.

We measured selenium (Se) speciation in the waters of 16 lakes located near two major metal smelters and compared it to Se concentrations in a potential biomonitor, the planktivorous insect Chaoborus. We used this sentinel because planktonic algae and crustaceans, which are lower in the trophic chain leading to Chaoborus, are more difficult to separate and identify to species, whereas many fish species are not obligate planktivores. Percentages of selenate and organo-Se were generally higher in acidic lakes, whereas those of selenite were usually greater in alkaline waters. Chaoborus Se concentrations varied widely among lakes and, with the exception of a single high-sulfate lake, were significantly and highly correlated with those of dissolved organo-Se plus selenate (Se(VI)). We suggest that Chaoborus larvae would be highly effective for monitoring the Se-exposure of planktonic food webs in lakes.

Nickel dynamics in the lakewater metal biomonitor Chaoborus.

Nickel (Ni) is a widespread contaminant present at toxic concentrations in aquatic systems in the vicinity of some mining and smelting operations. However, its accumulation by aquatic animals has been little studied and there are few biomonitors for this metal. Recently, larvae of the aquatic insect Chaoborus were shown to be effective as biomonitors for Ni concentrations in lakewater. Since animals are more effective as biomonitors when we understand how they take up their contaminants (from water or from food) and the rate at which they exchange contaminants with their surroundings, we set out to measure these parameters for Chaoborus. To achieve these goals, we exposed the components of a laboratory food chain (green alga, cladoceran, Chaoborus) to realistic Ni concentrations. We found that the majority ( approximately 65%) of the Ni taken up by Chaoborus flavicans comes from lakewater, with the remainder coming from its planktonic prey (Daphnia magna). This result is consistent with the low mean efficiency (14%) with which C. flavicans assimilated Ni from its prey. To explain the low efficiency of Ni uptake from food we measured the subcellular distribution of Ni in prey, which predicted that the majority of the Ni in prey ( approximately 55%) was available for assimilation by the predator. This potential Ni uptake efficiency was only reached in animals that ingested few prey, likely because their gut passage time was longer than those ingesting many prey. We also measured Ni uptake and loss by C. flavicans exposed to Ni in water then used these data to parameterize a mechanistic bioaccumulation model that allowed us to describe Ni exchange between this insect and water. Lastly, we used these model constants, along with field measurements of Ni in 10 Canadian lakes, to predict Ni concentrations in field populations of Chaoborus. Model predictions overestimated Ni concentrations in field populations by a factor of 4. We suggest that uncertainties in the rate constant for Ni uptake from water and a lack of measured Ni concentrations in the prey eaten by Chaoborus larvae in the field could explain this difference.

Influence of prey type on nickel and thallium assimilation, subcellular distribution and effects in juvenile fathead minnows (Pimephales promelas).

Because fish take up metals from prey, it is important to measure factors controlling metal transfer between these trophic levels so as to explain metal bioaccumulation and effects in fish. To achieve this, we exposed two types of invertebrates, an oligochaete (Tubifex tubifex) and a crustacean (Daphnia magna), to environmentally relevant concentrations of two important contaminants, nickel (Ni) and thallium (Tl), and fed these prey to juvenile fathead minnows (Pimephales promelas). We then measured the assimilation efficiency (AE), subcellular distribution and effects of these metals in fish. Fish assimilated dietary Tl more efficiently from D. magna than from T. tubifex, and more efficiently than Ni, regardless of prey type. However, the proportion of metal bound to prey subcellular fractions that are likely to be trophically available (TAM) had no significant influence on the efficiency with which fish assimilated Ni or Tl. In fish, the majority of their Ni and Tl was bound to subcellular fractions that are purportedly detoxified, and prey type had a significant influence on the proportion of detoxified Ni and Tl in fish. We measured higher activities of cytochrome C oxidase and glutathione S-transferase in fish fed D. magna compared to fish fed T. tubifex, regardless of the presence or absence of Ni or Tl in prey. However, we measured decreased activities of glutathione S-transferase and nucleoside diphosphate kinase in fish fed Tl-contaminated D. magna compared to fish from the three other treatment levels.

Assessment of nickel contamination in lakes using the phantom midge Chaoborus as a biomonitor.

Nickel (Ni) can be present in concentrations of concern in waters near mining and industrial sites. We tested species of the phantom midge Chaoborus as a biomonitor for this trace metal by collecting water and Chaoborus larvae from 15 lakes located along a Ni gradient mainly in the vicinity of smelters located in Sudbury, ON, Canada. We measured pH, trace metals, major ions, as well as inorganic and organic carbon concentrations in lakewater for use in calculating ambient metal speciation using the Windermere Humic Aqueous Model (WHAM). Nickel concentrations in Chaoborus species varied widely among our study lakes and could be related to concentrations of the free Ni2+ ion in lakewater if competitive interactions with hydrogen ions (H+) were taken into account We verified this inhibitory effect in the laboratory by exposing Chaoborus punctipennis to constantfree Ni2+ ion concentrations at various H+ ion concentrations. As expected, larvae exposed to high concentrations of H+ ions accumulated less Ni. Overall, our results suggest that Chaoborus larvae would be an excellent biomonitor for Ni in lakewater and as such would be a useful component of risk assessment strategies designed to evaluate Ni exposure to aquatic organisms in lakes.