Papers by Bernard Vigneault

Environ Toxicol Chem, 2007
Sulfate-reducing passive bioreactors treat acid mine drainage (AMD) by increasing its pH and alka... more Sulfate-reducing passive bioreactors treat acid mine drainage (AMD) by increasing its pH and alkalinity and by removing metals as metal sulfide precipitates. In addition to discharge limits based on physicochemical parameters, however, treated effluent is required to be nontoxic. Acute and sublethal toxicity was assessed for effluent from 3.5-L column bioreactors filled with mixtures of natural organic carbon sources and operated at different hydraulic retention times (HRTs) for the treatment of a highly contaminated AMD. Effluent was first tested for acute (Daphnia magna and Oncorhynchus mykiss) and sublethal (Pseudokirchneriella subcapitata, Ceriodaphnia dubia, and Lemna minor) toxicity. Acute toxicity was observed for D. magna, and a toxicity identification evaluation (TIE) procedure was then performed to identify potential toxicants. Finally, metal speciation in the effluent was determined using ultrafiltration and geochemical modeling for the interpretation of the toxicity results. The 10-d HRT effluent was nonacutely lethal for O. mykiss but acutely lethal for D. magna. The toxicity to D. magna, however, was removed by 2 h of aeration, and the TIE procedure suggested iron as a cause of toxicity. Sublethal toxicity of the 10-d HRT effluent was observed for all test species, but it was reduced compared to the raw AMD and to a 7.3-d HRT effluent. Data regarding metal speciation indicated instability of both effluents during aeration and were consistent with the toxicity being caused by iron. Column bioreactors in operation for more than nine months efficiently improved the physicochemical quality of highly contaminated AMD at different HRTs. The present study, however, indicated that design of passive treatment should include sufficient HRT and posttreatment aeration to meet acute toxicity requirements.

Water Research, 2001
The objective of this study was to assess the effectiveness of an engineered shallow water cover ... more The objective of this study was to assess the effectiveness of an engineered shallow water cover in reducing the oxidation of sulfidic mine tailings and thus preventing the development of acid rock drainage. Fresh tailings were submerged under a 0.3-m water cover in experimental field cells. From 1996 to 1998, we followed the chemistry of the interstitial water near the tailings-overlying water interface using in situ dialysis, and determined pH and dissolved oxygen (DO) profiles across the tailing water interface using micro-electrodes. Penetration of DO into the tailings was limited to <7 mm, even in the presence of DO produced by benthic periphyton. Anoxia in the tailings was further demonstrated by the appearance of dissolved sigmaH2S, Fe and Mn in pore water at depths -1.5 cm below the interface. However, there was clear evidence of surface oxidation of the mine tailings at the mm scale (i.e., DO depletion, coupled with localized increases in [H+] and [SO4(2-)]). Mobilization of Cd and Zn from this surface layer was indicated by the presence of sub-surface peaks in the concentrations of these two metals in the tailings interstitial water and by a change in their solid phase partitioning from refractory to more labile fractions. In contrast, mobilization of Cu from tailings was less evident. Unlike previous reports, which suggested that submerged tailings were effectively inert, our results show alteration of the superficial layer over time.

Integrated Environmental Assessment and Management, 2014
Lemna minor, a free-floating macrophyte, is used for biomonitoring of mine effluent quality under... more Lemna minor, a free-floating macrophyte, is used for biomonitoring of mine effluent quality under the Metal Mining Effluent Regulations (MMER) of the Environmental Effects Monitoring (EEM) program in Canada and is known to be sensitive to trace metals commonly discharged in mine effluents such as Ni. Environment Canada's standard toxicity testing protocol recommends frond count (FC) and dry weight (DW) as the 2 required toxicity endpoints-this is similar to other major protocols such as those by the US Environmental Protection Agency (USEPA) and the Organisation for Economic Co-operation and Development (OECD)-that both require frond growth or biomass endpoints. However, we suggest that similar to terrestrial plants, average root length (RL) of aquatic plants will be an optimal and relevant endpoint. As expected, results demonstrate that RL is the ideal endpoint based on the 3 criteria: accuracy (i.e., toxicological sensitivity to contaminant), precision (i.e., lowest variance), and ecological relevance (metal mining effluents). Roots are known to play a major role in nutrient uptake in conditions of low nutrient conditions-thus having ecological relevance to freshwater from mining regions. Root length was the most sensitive and precise endpoint in this study where water chemistry varied greatly (pH and varying concentrations of Ca, Mg, Na, K, dissolved organic carbon, and an anthropogenic organic contaminant, sodium isopropyl xanthates) to match mining effluent ranges. Although frond count was a close second, dry weight proved to be an unreliable endpoint. We conclude that toxicity testing for the floating macrophyte should require average RL measurement as a primary endpoint.
Encyclopedia of Aquatic Ecotoxicology, 2013

Journal of Phycology, 2005
The effects of humic substances and low pH on short-term Cd uptake by Pseudokirchneriella subcapi... more The effects of humic substances and low pH on short-term Cd uptake by Pseudokirchneriella subcapitata (Korshikov) Hindak and Chlamydomonas reinhardtii Dang were investigated under defined exposure conditions. The uptake experiments were run in the presence of either a synthetic organic ligand (nitrilotriacetate) or natural organic ligands (Suwannee River fulvic or humic acid). An ion-exchange method was used to measure the free Cd 2 þ concentrations in the exposure solutions. At pH 5, measured free Cd 2 þ concentrations agreed with estimations made using the geochemical equilibrium model WHAM, but at pH 7 the model overestimated complexation by both Suwannee River fulvic and humic acids compared with the ion-exchange measurements. Consistent with the metal internalization step being rate limiting for overall short-term uptake, intracellular Cd uptake was linear for exposure times less than 20 min at pH 5 or pH 7 for both algal species. After taking into account complexation of Cd in solution, Suwannee River humic substances had no additional effects on cadmium uptake at pH 7, as would be predicted by the free ion model. This absence of effects other than complexation persisted at pH 5, where the tendency of humic substances to adsorb to the algal cell surface is favored. Changes in pH strongly influenced Cd uptake, with the intracellular flux of Cd being at least 20 times lower at pH 5 than at pH 7 for P. subcapitata. Our results support models such as the free ion model or the biotic ligand model, in which humic substances act indirectly on Cd uptake by reducing the bioavailability of Cd by complexation in solution.

Journal of Phycology, 2005
In the St. Lawrence Estuary, annual recurrent blooms of the toxic dinoflagellate Alexandrium tama... more In the St. Lawrence Estuary, annual recurrent blooms of the toxic dinoflagellate Alexandrium tamarense L. Balech are associated with brackish waters. Riverine inputs are suspected to favor bloom development by increasing water column stability and/or by providing growth stimulants such as humic substances (HS). A 17-day culture experiment was conducted to evaluate the importance of HS as growth factors for A. tamarense. Nonaxenic cultures were exposed to four HS extracts from three different sources: humic and fulvic acids isolated from the Manicouagan River, Quebec, Canada; humic acids from the Suwannee River, Georgia, United States; and a desalted alkaline soil extract. For each extract, four concentrations were tested as supplements to the artificial Keller medium, a nitrate-rich algal culture medium. Additions of HS from all sources significantly enhanced the overall growth rates relative to the controls. Concentrations of HS, estimated by UV spectrophotometry, remained constant throughout the exponential growth phase, suggesting that the HS were acting mainly as growth promoters during our experiment. Dose-response curves indicated that HS could increase the growth rate of A. tamarense even at low concentrations, such as those encountered in the St. Lawrence Estuary. Our results support the hypothesis that HS from the Manicouagan River plume can stimulate the development of toxic dinoflagellate blooms.

Environmental Toxicology and Chemistry, 2013
The effect of major cation activity (Ca 2þ , Mg 2þ , Na þ , K þ ) on Ni toxicity, with dose expre... more The effect of major cation activity (Ca 2þ , Mg 2þ , Na þ , K þ ) on Ni toxicity, with dose expressed as exposure (total dissolved Ni concentration Ni Tot ) or free Ni ion activity (in solution Ni 2þ ), or as tissue residue (Ni concentration in plant tissue Ni Tiss ) to the aquatic plant Lemna minor L. was examined. In addition, Ni accumulation kinetics was explored to provide mechanistic insight into current approaches of toxicity modeling, such as the tissue residue approach and the biotic ligand model (BLM), and the implications for plant Ni risk assessment. Major cations did not inhibit Ni accumulation via competitive inhibition as expected by the BLM framework. For example, Ca 2þ and Mg 2þ (sulfate as counter-anion) had an anticompetitive effect on Ni accumulation, suggesting that Ca or Mg forms a ternary complex with Ni-biotic ligand. The counter-anion of the added Ca (sulfate, chloride, or nitrate) affected plant response (percentage of root growth inhibition) to Ni. Generally, sulfate and chloride influenced plant response while nitrate did not, even when compared within the same range of Ca 2þ , which suggests that the anion dominated the observed plant response. Overall, although an effect of major cations on Ni toxicity to L. minor L. was observed at a physiological level, Ni 2þ or Ni Tot alone modeled plant response, generally within a span of twofold, over a wide range of water chemistry. Thus, consideration of major cation competition for improving Ni toxicity predictions in risk assessment for aquatic plants may not be necessary. Environ. Toxicol. Chem. 2013;32:810-821. # 2013 SETAC

Environmental Toxicology and Chemistry, 2008
Sulfate-reducing passive bioreactors treat acid mine drainage (AMD) by increasing its pH and alka... more Sulfate-reducing passive bioreactors treat acid mine drainage (AMD) by increasing its pH and alkalinity and by removing metals as metal sulfide precipitates. In addition to discharge limits based on physicochemical parameters, however, treated effluent is required to be nontoxic. Acute and sublethal toxicity was assessed for effluent from 3.5-L column bioreactors filled with mixtures of natural organic carbon sources and operated at different hydraulic retention times (HRTs) for the treatment of a highly contaminated AMD. Effluent was first tested for acute (Daphnia magna and Oncorhynchus mykiss) and sublethal (Pseudokirchneriella subcapitata, Ceriodaphnia dubia, and Lemna minor) toxicity. Acute toxicity was observed for D. magna, and a toxicity identification evaluation (TIE) procedure was then performed to identify potential toxicants. Finally, metal speciation in the effluent was determined using ultrafiltration and geochemical modeling for the interpretation of the toxicity results. The 10-d HRT effluent was nonacutely lethal for O. mykiss but acutely lethal for D. magna. The toxicity to D. magna, however, was removed by 2 h of aeration, and the TIE procedure suggested iron as a cause of toxicity. Sublethal toxicity of the 10-d HRT effluent was observed for all test species, but it was reduced compared to the raw AMD and to a 7.3-d HRT effluent. Data regarding metal speciation indicated instability of both effluents during aeration and were consistent with the toxicity being caused by iron. Column bioreactors in operation for more than nine months efficiently improved the physicochemical quality of highly contaminated AMD at different HRTs. The present study, however, indicated that design of passive treatment should include sufficient HRT and posttreatment aeration to meet acute toxicity requirements.

Environmental Geochemistry and Health, 2009
The fate, bioavailability and environmental impacts of metals discharged in municipal and mining ... more The fate, bioavailability and environmental impacts of metals discharged in municipal and mining wastewater discharge will depend to a large extent on chemical speciation and distribution. Previous studies on metal bioaccumulation have shown that total metal concentrations are not a good predictor of bioavailability in the dispersion plumes of municipal effluents. The objective of this study was to determine the solid phase speciation of metals in surface waters receiving urban and mining effluents in order to assess their fate and relative mobility in the receiving environment. Suspended particulate matter was sampled using sediment traps at several sites downstream of effluent outfall plumes as well as at reference upstream sites. Particulate metal in operationally defined fractions-exchangeable/carbonates, reducible, oxidisable and residual-were determined in suspended particulate matter with a series of selective chemical extractions. Metal enrichment in suspended particles was generally observed in both mining and urban effluent discharges. When compared to its receiving environment, the mining effluent appeared to release more particulate metals (Cu, Fe, Zn) in the most reactive fractions (i.e. exchangeable/carbonates ? reducible forms, 23-43%), while other released metals, such as Cd and Mn, were predominantly in the least reactive forms (i.e., oxidisable ? residual, 73-97%). In contrast, the reactivity of all particulate metals, with the exception of Mn, from the urban effluent was much higher, with up to 65, 42, 30 and 43% for Cd, Cu, Fe and Zn, respectively, in the two most reactive fractions. As expected in effluent dispersion plumes, parameters such as the organic carbon, Fe oxide and carbonate contents have specific effects on the partitioning of several trace metals, particularly Cd, Cu and Zn. Our results indicated that the relative distributions of metals among geochemical fractions varied in the effluent receiving waters where organic carbon and Fe oxides appeared as the most important parameters. This could therefore decrease the exposure for aquatic organisms that are exposed to those contaminated sediments as well as the risk to human health.
Environmental Chemistry, 2012
Environmental context. Predicting metal toxicity is an important tool for effective and efficient... more Environmental context. Predicting metal toxicity is an important tool for effective and efficient risk assessment and regulation of metal pollution in the environment. The present study aims to provide scientific support for the development of a predictive Ni toxicity model for aquatic plants that is particularly applicable to miningaffected natural waters. We show that the effects of pH and natural organic ligands on Ni accumulation and toxicity can be modelled, but further research is required to understand the effects of flotation ligands used in the mining industry.

Comparative Biochemistry and Physiology Part C: Toxicology & Pharmacology, 2002
To elicit a biological response from a target organism andyor to accumulate within this organism,... more To elicit a biological response from a target organism andyor to accumulate within this organism, a metal must first interact with a cell membrane. For hydrophilic metal species, this interaction with the cell surface can be represented in terms of the formation of M-X-cell surface complexes, e.g. M q X-celllM-X-cell, where X-cell is a cellular zq y y ligand present at the cell surface. According to the free-ion model, or its derivative the biotic ligand model (BLM), the biological response elicited by the metal will be proportional to {M-X-cell}. In this paper, using freshwater algae as our test species, we examine some of the key assumptions that underlie the BLM, namely that metal internalization is slow relative to the other steps involved in metal uptake (i.e. the M-X-cell complex is in equilibrium with metal species in solution), that internalization occurs via cation transport, and that internalization must occur for toxicity to appear. Recent experiments with freshwater algae are described, demonstrating anomalously high metal accumulation andyor toxicity in the presence of a common low molecular weight metabolite (alanine), or in the presence of an assimilable inorganic anion (thiosulfate). The possible implications of these findings for the application of the BLM to higher organisms are discussed. ᮊ
Australian Journal of Chemistry, 2004
ABSTRACT

Aquatic Toxicology, 2007
We tested the predictive ability of the dynamic multipathway bioaccumulation model (DYMBAM) to ch... more We tested the predictive ability of the dynamic multipathway bioaccumulation model (DYMBAM) to characterize Cd accumulation in Daphnia magna, a species commonly used in toxicity tests and because of its sensitivity, particularly to metals, a species that is relied upon in ecological risk assessments. We conducted chronic exposure experiments in which D. magna were exposed to either dietborne Cd alone or to both dietborne and waterborne Cd. In the food-only treatments, the algae Chlamydomonas reinhardtii or Pseudokirchneriella subcapitata were pre-exposed to free Cd ion concentrations, [Cd 2+ ], from 0.001 to 100 nM (0.001-11 g L −1 ) then, on a daily feeding renewal basis, fed to D. magna over 21 days. In the water plus food treatment, D. magna were exposed for 21 days to the same range of [Cd 2+ ] and fed with the same algal species that had been exposed to Cd at various concentrations. In the algal exposure media, Cd concentrations in algae were directly related to those in water and were characterized by a linear regression model using the log transformed concentration of the WHAM predicted Cd 2+ concentration. The DYMBAM was used with estimated values of the model constants for ingestion rate (0.08-0.34 g g −1 day −1 ) and growth rate (0.085-0.131 day −1 ) based on our experimental data and with literature values for rate constants of Cd influx and efflux as well as Cd assimilation efficiency. Measured Cd concentrations in D. magna agreed with model predictions within a factor of 3. Using the model, we predict that food is an important contributor of Cd burden to D. magna, particularly at lower Cd exposure concentrations over an environmentally realistic gradient of free Cd in water. However, this cladoceran also takes up Cd from water and this exposure route becomes increasingly important at very high concentrations of free Cd (>10 nM or 1.1 g L −1 ). Nevertheless, Cd produced lethal effects in D. magna that were exposed to this metal in water and diet, but exposure to Cd in food only did not result in toxic effects (as measured by survival and reproduction). explains its increasing use in establishing acute water-quality guidelines. In contrast, most ecological risk assessments focus on longterm exposures. During chronic exposures, animals take up metals from both water and food, both of which can potentially contribute to toxic effects. Waterborne metals usually cause respiratory impairment in fish . The mechanism of toxicity of many cationic metals is mainly related to specific inhibitory effects on ion transport functions in fish gills . This mechanistic information helped guide the development of the biotic ligand model (BLM) framework, which resulted in the development of chronic BLMs for risk 0166-445X/$ -see front matter

Aquatic Toxicology, 2007
A biotic ligand model (BLM) to predict chronic Cu toxicity to Ceriodaphnia dubia was developed an... more A biotic ligand model (BLM) to predict chronic Cu toxicity to Ceriodaphnia dubia was developed and tested. The effect of cationic competition, pH and natural organic matter complexation of Cu was examined to develop the model. There was no effect of cationic competition using increasing Ca and Na concentrations in our exposures. However, we did see a significant regression of decreasing toxicity (measured as the IC25; concentration at which there was a 25% inhibition of reproduction) as Mg concentration increased. However, taking into account the actual variability of the IC25 and since the relative increase in IC25 due to additional Mg was small (1.5-fold) Mg competition was not included in the model. Changes in pH had a significant effect on Cu IC25, which is consistent with proton competition as often suggested for acute BLMs. Finally, natural organic matter (NOM) was added to exposures resulting in significant decreases in toxicity. Therefore, our predictive model for chronic Cu toxicity to C. dubia includes the effect of pH and NOM complexation. The model was validated with Cu IC25 data generated in six natural surface waters collected from across Canada. Using WHAM VI, we calculated Cu speciation in each natural water and using our model, we generated "predicted" IC25 data. We successfully predicted all Cu IC25 within a factor of 3 for the six waters used for validation. Crown

Aquatic Geochemistry, 2010
Combining in situ diffusion and column ion-exchange equilibration, we measured free metal ion con... more Combining in situ diffusion and column ion-exchange equilibration, we measured free metal ion concentrations (Cd, Cu and Zn) in water samples collected from the epilimnion of 14 lakes in the Rouyn-Noranda area (600 km north-west of Montreal, QC, Canada). Lakes were selected to represent a wide range of physico-chemical characteristics (hardness, pH, dissolved organic matter-DOM, degree of metal contamination), to determine the influence of these parameters on metal speciation. Total dissolved metal concentrations, as determined within the diffusion cells, varied over one to two orders of magnitude: [Cd] 0.19-2.9 nM; [Cu] 36-190 nM; [Zn] 7-2,800 nM. The proportion of total dissolved metal present as free Cd 2? and Zn 2? was relatively constant for the 14 selected lakes, despite the wide pH (4.5-8) and DOM (3-23 mg C/L) ranges, probably reflecting the inverse relationship observed between pH and DOM; this proportion did, however, vary with DOM and pH for Cu. Our experimental free metal ion concentrations were compared with those calculated with the thermodynamic models WHAM (Windermere Humic Aqueous Model VI) and ECOSAT 4.7 (incorporating the NICA-Donnan model). Measured and calculated values were in reasonable agreement for both Cd and Zn although measured values were generally slightly higher, i.e. less than one order of magnitude. For several lakes, measured free Cu concentrations were, however, much higher than the calculated values, suggesting that these models overestimate Cu complexation. The gap between measured and calculated free metal ion concentration becomes more important as the total metal concentration decreases and as pH increases.
Environmental Science & Technology, 2000
... Cells were grown axenically in Fraquil media (18), buffered at pH 7 with 0.01 M HEPES (N-(2-h... more ... Cells were grown axenically in Fraquil media (18), buffered at pH 7 with 0.01 M HEPES (N-(2-hydroxyethyl)piperazine-N'-2-ethanesulfonic acid, HEPES). ... Exposure media consisted of fresh culture medium, without added trace metals and vitamins. ...
Uploads
Papers by Bernard Vigneault