The essential toxin: the changing perception of selenium in environmental sciences.

Subsurface agricultural drainage waters from western San Joaquin Valley, California, were found to contain elevated concentrations of the element selenium in the form of selenate. In 1978, these drainage waters began to replace previous input to Kesterson Reservoir, a pond system within Kesterson National Wildlife Refuge; this substitution was completed by 1982. In the 1983 nesting season, unusual rates of deformity and death in embryos and hatchlings of wild aquatic birds (up to 64% of eared grebe and American coot nests) occurred at the refuge and were attributed to selenium toxicosis. Features necessary for contamination to have taken place included geologic setting, climate, soil type, availability of imported irrigation water, type of irrigation, and the unique chemical properties of selenium. The mechanisms of biogeochemical cycling raise questions about other ecosystems and human exposure.

Biogeochemical cycling of selenium in the San Joaquin Valley, California, USA

Most studies on the microbial transformations of elements have emphasized nutrient cycling within the biosphere or the economics of agricultural or industrial processes. Cyclic transformations within the biosphere between soluble, insoluble, and gaseous forms of carbon, nitrogen, hydrogen, oxygen, and sulfur are well known. Recently, attention has been focused on the role of microorganisms in the production and degradation of chemicals containing toxic elements (Alexander, 1973; Wood, 1974). Measures to increase animal and food crop production or disposal of waste materials can result in the introduction of elements in amounts harmful to terrestrial and aquatic ecosystems. Many elements and their compounds vary widely in both toxicity and mobility. Consequently, their safe disposal or effective recycling requires an understanding of their potential toxicities and possible transformations in the environment.

Microorganisms and the Biological Cycling of Selenium

Ecological impacts of water-quality problems have developed in the western United States resulting from the disposal of seleniferous agricultural wastewater in wetland areas. Overt effects of selenium toxicosis occurred at five areas where deformities of wild aquatic birds were similar to those first observed at Kesterson National Wildlife Refuge in the west-central San Joaquin Valley of California. These areas are: Tulare Lake Bed Area, California, Middle Green River Basin, Utah, Kendrick Reclamation Project Area, Wyoming, Sun River Basin, Montana, and Stillwater Wildlife Management Area, Nevada. Potential for ecological damage is indicated at six more sites in Oregon, Colorado, the Colorado/Kansas border, and South Dakota out of 16 areas in 11 states where biological tissue data were collected. This conclusion is based on the fact that selenium bioaccumulated in bird livers to median levels that had exceeded or were in the range associated with adverse reproductive effects. Selenium concentrations in samples of fish and bird eggs support these conclusions at a majority of these areas. Reason for concern is also given for the lower Colorado River Valley, although this is not exclusively a conclusion from these reconnaissance data. Biogeochemical conditions and the extent of selenium contamination of water, bottom sediment, and biota from which this assessment was made are given here. In a companion paper, the biogeochemical pathway postulated for selenium contamination to take place from natural geologic sources to aquatic wildlife is defined.

Bioaccumulation of selenium from natural geologic sources in western states and its potential consequences

Selenium species, particularly the oxyanions selenite (SeO3 (2-)) and selenate (SeO4 (2-)), are significant pollutants in the environment that leach from rocks and are released by anthropogenic activities. Selenium is also an essential micronutrient for organisms across the tree of life, including microorganisms and human beings, particularly because of its presence in the 21st genetically encoded amino acid, selenocysteine. Environmental microorganisms are known to be capable of a range of transformations of selenium species, including reduction, methylation, oxidation, and demethylation. Assimilatory reduction of selenium species is necessary for the synthesis of selenoproteins. Dissimilatory reduction of selenate is known to support the anaerobic respiration of a number of microorganisms, and the dissimilatory reduction of soluble selenate and selenite to nanoparticulate elemental selenium greatly reduces the toxicity and bioavailability of selenium and has a major role in bioremediation and potentially in the production of selenium nanospheres for technological applications. Also, microbial methylation after reduction of Se oxyanions is another potentially effective detoxification process if limitations with low reaction rates and capture of the volatile methylated selenium species can be overcome. This review discusses microbial transformations of different forms of Se in an environmental context, with special emphasis on bioremediation of Se pollution.

Microbial transformations of selenium species of relevance to bioremediation

Thiobacillus ferrooxidans can derive its energy from the oxidation of copper selenide. In this metabolic oxidation process, copper goes into solution and elemental selenium is deposited.

Fathi Habashi

Papers

Oxidation of copper (II) selenide by Thiobacillus ferrooxidans