An evaluation of selenium concentrations in water, sediment, invertebrates, and fish from the Republican River Basin: 1997-1999.

The Republican River Basin of Colorado, Nebraska, and Kansas lies in a valley which contains Pierre Shale as part of its geological substrata. Selenium is an indigenous constituent in the shale and is readily leached into surrounding groundwater. The Basin is heavily irrigated through the pumping of groundwater, some of which is selenium-contaminated, onto fields in agricultural production. Water, sediment, benthic invertebrates, and/or fish were collected from 46 sites in the Basin and were analyzed for selenium to determine the potential for food-chain bioaccumulation, dietary toxicity, and reproductive effects of selenium in biota. Resulting selenium concentrations were compared to published guidelines or biological effects thresholds. Water from 38% of the sites (n = 18) contained selenium concentrations exceeding 5 microg L(-1), which is reported to be a high hazard for selenium accumulation into the planktonic food chain. An additional 12 sites (26% of the sites) contained selenium in water between 3-5 microg L(-1), constituting a moderate hazard. Selenium concentrations in sediment indicated little to no hazard for selenium accumulation from sediments into the benthic food chain. Ninety-five percent of benthic invertebrates collected exhibited selenium concentrations exceeding 3 microg g(-1), a level reported as potentially lethal to fish and birds that consume them. Seventy-five percent of fish collected in 1997, 90% in 1998, and 64% in 1999 exceeded 4 microg g(-1) selenium, indicating a high potential for toxicity and reproductive effects. However, examination of weight profiles of various species of collected individual fish suggested successful recruitment in spite of selenium concentrations that exceeded published biological effects thresholds for health and reproductive success. This finding suggested that universal application of published guidelines for selenium may be inappropriate or at least may need refinement for systems similar to the Republican River Basin. Additional research is needed to determine the true impact of selenium on fish and wildlife resources in the Basin.

Improved selenium recovery from tissue with modified sample decomposition.

The present paper describes a simple modification of a recently reported decomposition method for determination of selenium in biological tissue by hydride generation atomic absorption. The modified method yielded slightly higher selenium recoveries (3-4%) for selected reference tissues and fish tissue spiked with selenomethionine. Radiotracer experiments indicated that the addition of a small volume of hydrochloric acid to the wet digestate mixture reduced slight losses of selenium as the sample initially went to dryness before ashing. With the modified method, selenium spiked as selenomethionine behaved more like the selenium in reference tissues than did the inorganic spike forms when this digestion modification was used.

Determination of arsenic and selenium in whole fish by continuous-flow hydride generation atomic absorption spectrophotometry.

A combined wet chemical and dry ash digestion and use of a continuous-flow hydride generator coupled with a flame-heated quartz cell enabled the simple, precise, and highly automated atomic absorption determination of arsenic and selenium in tissues of whole fish. Percent relative standard deviation averaged 4% for each element; method detection limits (micrograms/g dry wt) were about 0.06 for arsenic and 0.04 for selenium. Digestion of samples proceeded with little operator attention and without perchloric acid. Analysis for arsenic as As(V) simplified sample preparation but care had to be exercised to avoid interferences from high concentrations of selenium.