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.

Larval deformities associated with selenium accumulation in northern pike (Esox lucius) exposed to metal mining effluent.

The objective of this study was to investigate selenium toxicosis in larval northern pike (Esox lucius) originating from reproductively mature pike collected downstream of a uranium milling operation in northern Saskatchewan, Canada. Eggs were obtained from female pike collected from a reference site and three sites representing an exposure gradient (approximately 2, 10, and 15 km downstream of effluent discharge). Embryos were incubated following a two-way (crossover) analysis of variance experimental design that allowed discrimination between effects due to maternal transfer to eggs and effects due to site water exposure in the developing embryos. The major finding of this study was a significant increase in the frequencies of individual deformities (skeletal curvatures, craniofacial deformities, and fin deformities) and edema in fry originating from high and medium exposure site females (mean selenium concentrations of 48.23 and 31.28 microg/g egg dry weight and 38.27 and 16.58 microg/g muscle dry weight, respectively) compared to reference site females. Selenium concentrations resulting in a 20% increase in total deformities above background levels (EC20S) were 33.55 and 21.54 micro/g dry weight in eggs and muscle, respectively. Mathematical conversion of the egg- and muscle-derived relationships to whole body selenium levels resulted in similar EC20S of 15.56 and 17.72 microg/g dry weight, respectively. These relationships between tissue selenium levels and larval deformities suggest that northern pike are within the same range of sensitivity to selenium as the majority of warm water (e.g., centrarchids and cyprinids) and cold water (e.g., salmonids) fish species studied to date.