Integrative assessment of selenium speciation, biogeochemistry, and distribution in a northern coldwater ecosystem.

For the past decade, considerable research has been conducted at a series of small lakes receiving treated liquid effluent containing elevated selenium (Se) from the Key Lake uranium (U) milling operation in northern Saskatchewan, Canada. Several studies related to this site, including field collections of water, sediment, and biota (biofilm and/or periphyton, invertebrates, fish, and birds), semicontrolled mesocosm and in situ caging studies, and controlled laboratory experiments have recently been published. The aim of the present investigation was to compile the site-specific information obtained from this multidisciplinary research into an integrative perspective regarding the influence of Se speciation on biogeochemical cycling and food web transfer of Se in coldwater ecosystems. Within lakes, approximately 50% of sediment Se was in the form of elemental Se, although this ranged from 0% to 81% among samples. This spatial variation in elemental Se was positively correlated with finer particles (less sand) and percent total organic C content in sediments. Other Se species detected in sediments included selenosulfides, selenite, and inorganic metal selenides. In contrast, the major Se form in sediment-associated biofilm and/or periphyton was an organoselenium species modeled as selenomethionine (SeMet), illustrating the critical importance of this matrix in biotransformation of inorganic Se to organoselenium compounds and subsequent trophic transfer to benthic invertebrates at the base of the food web. Detritus displayed a Se speciation profile intermediate between sediment and biofilm, with both elemental Se and SeMet present. In benthic detritivore (chironomid) larvae and emergent adults, and in foraging and predatory fishes, SeMet was the dominant Se species. The proportion of total Se present as a SeMet-like species displayed a direct nonlinear relationship with increasing whole-body Se in invertebrates and fishes, plateauing at approximately 70% to 80% of total Se as a SeMet-like species. In fish collected from reference lakes, a selenocystine-like species was the major Se species detected. Similar Se speciation profiles were observed using 21-day mesocosm and in situ caging studies with native small-bodied fishes, illustrating the efficient bioaccumulation of Se and use of these semicontrolled approaches for future research. A simplified conceptual model illustrating changes in Se speciation through abiotic and biotic components of lakes was developed, which is likely applicable to a wide range of northern industrial sites receiving elevated Se loading into aquatic ecosystems.

Species sensitivity distribution evaluation for selenium in fish eggs: considerations for development of a Canadian tissue-based guideline.

A freshwater Se guideline was developed for consideration based on concentrations in fish eggs or ovaries, with a focus on Canadian species, following the Canadian Council of Ministers of the Environment protocol for developing guideline values. When sufficient toxicity data are available, the protocol recommends deriving guidelines as the 5th percentile of the species sensitivity distribution (SSD). When toxicity data are limited, the protocol recommends a lowest value approach, where the lowest toxicity threshold is divided by a safety factor (e.g., 10). On the basis of a comprehensive review of the current literature and an assessment of the data therein, there are sufficient egg and ovary Se data available for freshwater fish to develop an SSD. For most fish species, Se EC10 values (10% effect concentrations) could be derived, but for some species, only no-observed-effect concentrations and/or lowest-observed-effect concentrations could be identified. The 5th percentile egg and ovary Se concentrations from the SSD were consistently 20 µg/g dry weight (dw) for the best-fitting distributions. In contrast, the lowest value approach using a safety factor of 10 would result in a Se egg and ovary guideline of 2 µg/g dw, which is unrealistically conservative, as this falls within the range of egg and ovary Se concentrations in laboratory control fish and fish collected from reference sites. An egg and ovary Se guideline of 20 µg/g dw should be considered a conservative, broadly applicable guideline, as no species mean toxicity thresholds lower than this value have been identified to date. When concentrations exceed this guideline, site-specific studies with local fish species, conducted using a risk-based approach, may result in higher egg and ovary Se toxicity thresholds.

Effect of sampling method on contaminant measurement in pore-water and surface water at two uranium operations: can method affect conclusions?

This paper describes a comparison of two methods of sediment pore-water sampling and two methods of surface water sampling that were used in a broader investigation of cause(s) of adverse effects on benthic invertebrate communities at two Saskatchewan uranium operations (Key Lake and Rabbit Lake). Variables measured and compared included pH, ammonia, DOC, and trace metals. The two types of sediment pore-water samples that were compared are centrifuged and 0.45-microm filtered sediment core samples vs. 0.2-microm dialysis (peeper) samples. The two types of surface water samples that were compared are 53-microm filtered Van Dorn horizontal beta samples vs. 0.2-microm dialysis (peeper) samples. Results showed that 62% of the sediment core pore water values were higher than the corresponding peeper pore-water measurements, and that 63% of the Van Dorn surface water measurements were lower than corresponding peeper surface water measurements. Furthermore, only 24% and 14% of surface water and pore-water measurements, respectively, fell within +/-10% range of one another; 73% and 50%, respectively, fell within +/-50%. Although somewhat confounded by differences in filtering method, the observed differences are believed to primarily be related to small, vertical differences in the environment sampled. Despite observed differences in concentrations of toxicologically relevant variables generated by the different sampling methods, the weight of evidence (WOE) conclusions drawn from each set of exposure data on the possible cause(s) of in situ toxicity to Hyalella azteca from a related study were the same at each uranium operation. However, this concurrence was largely due to other dominant lines of evidence. The WOE conclusions at Key Lake were dominated by the toxicity response of H. azteca in relation to exposure chemistry, where as the WOE conclusions at Rabbit Lake were informed by exposure chemistry, the toxicological response of H. azteca, and whole-body contaminant concentrations in the test organisms. Had these multiple lines of evidence not been available, differences in exposure chemistry generated by the different sampling methods could have substantially influenced the identification of potential causes of in situ toxicity.

Bioassays with caged hyalella azteca to determine in situ toxicity downstream of two Saskatchewan, Canada, uranium operations.

The main objectives of this in situ study were to evaluate the usefulness of an in situ bioassay to determine if downstream water bodies at the Key Lake and Rabbit Lake uranium operations (Saskatchewan, Canada) were toxic to Hyalella azteca and, if toxicity was observed, to differentiate between the contribution of surface water and sediment contamination to in situ toxicity. These objectives were achieved by performing 4-d in situ bioassays with laboratory-reared H. azteca confined in specially designed, paired, surface water and sediment exposure chambers. Results from the in situ bioassays revealed significant mortality, relative to the respective reference site, at the exposure sites at both Key Lake (p