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.
To determine whether Hg from geologic/mining-related sources at Pinchi Lake (BC, Canada) was causing elevated Hg exposure and/or adversely affecting reproduction in fish-eating birds, breeding bald eagles (Haliaeetus leucocephalus) on Pinchi Lake and four nearby reference lakes were sampled for blood and feather Hg concentrations and monitored for reproductive success during the summers of 2000, 2001, and 2002. Eggs of red-necked grebes (Podiceps grisgena) also were collected and analyzed. Mercury levels in species at various trophic levels from Pinchi Lake averaged approximately twice those in the same species from nearby lakes combined, even in the absence of substantial new inputs of Hg to Pinchi Lake over several decades. In Pinchi Lake, Hg concentrations in blood and feathers of eagles and eggs of grebes were significantly higher than those in corresponding samples from reference lakes. However, the mean Hg concentration (0.25 microg/g wet wt) in grebe eggs from Pinchi Lake was substantially lower than accepted threshold levels for reproductive toxicity in most avian species (0.5-1.0 microg/g wet wt). Mercury concentrations in the blood of adult eagles and their chicks were highly correlated (r = 0.91, p = 0.004). Despite elevated Hg exposure in adult eagles nesting on Pinchi Lake (blood Hg concentration, 4.3-9.4 microg/ml), birds appeared to be in good body condition, did not differ significantly in terms of weight from eagles nesting on reference lakes, and exhibited no evidence of obvious abnormal behavior or lack of coordination. Eagle reproductive success and productivity on Pinchi Lake were not significantly different from those on all reference lakes combined (p = 0.483).
Postmortem examinations were conducted on 82 bald eagles (Haliaeetus leucocephalus) found dead or dying in British Columbia, Canada, from 1987 to 1994. As part of the examination, livers were analyzed for total mercury (Hg) content, as well as methylmercury (meHg) and selenium (Se) in selected individuals. In total, 67 eagles were classed as having low Hg exposure [total Hg liver residues ranging from 0.5 to 17.2 mg/kg dry weight (dw)]. Fourteen eagles were moderately exposed (liver residues ranging from 19.2 to 36.8 mg/kg Hg dw). One eagle was judged to have died of Hg poisoning, with a total liver Hg content of 130.3 mg/kg dw, of which approximately 77% was meHg. The poisoned eagle and most of the exposed eagles were found in locations where effluent from pulp and paper processing plants is discharged along the British Columbia coast. In total, 6% of eagles examined died as a result of acute metal toxicosis (one from Hg poisoning, four from lead poisoning), in comparison to 72% dying from trauma (electrocution, vehicle/power line collision, eagle attack, trap, gunshot, drowning, and asphyxiation) and 11% from disease. The cause of death was undetermined in the remaining 11% of eagles.
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