Advances in Fluidized Bed Reactor Treatment of Selenium in Mining Waters

Selenium (Se) in effluent waters has become a significant challenge for a number of industries. Toxicity studies and new reports of occurrence have certainly caused increased scrutiny and actions in the mining industry today (Sandy, DiSante, 2010). While initial activity in addressing selenium-laden waters were conducted in the coal mining industry, today a much broader range of mine types are beginning to search for solutions to selenium treatment of their mining waters, including both hard rock mining operations (gold, nickel, zinc, etc.) and soft rock mining (phosphate, uranium, etc.) Throughout North America, new regulations covering selenium discharge are either in place or being developed. While a number of physical/chemical approaches show promise in selenium treatment, when considering optimal cost and treatment efficacy issues, biological treatment ? particularly fixed-film biological treatment - is reported to be one of the most promising approaches to managing selenium-containing waters. Among biological treatment options, the fluidized bed reactor (FBR) has undergone extensive pilot testing for Se treatment in the last three years, including eight pilot programs, and the first FBR system is now operating at a coal mining site. In all tests, the FBR has been shown to be a highly cost-effective approach to selenium treatment based on its physical and performance characteristics. This is consistent with its history for reaching low levels of treatment in similar service for other oxyanions including perchlorate, nitrate and various metals. With the results from the most recent testing, the technology has been shown to be adaptable to an ever-broadening range of influent water conditions and flow rates, in varying terrains and weather conditions. Selenium occurs in various valence states from -2 to +6 (Sobolewski, 2005). The speciation of selenium plays a critical role in understanding the effectiveness of any approach for removal, especially to low levels. Elemental selenium is insoluble and has little effect on living organisms. Colloidal fractions are known to occur. In aqueous environments such as coal mining runoff, selenium is most often found as the oxygenated anions of selenite (SeO32-, Se4+) and selenate, (SeO42-, Se6+). Selenium is commonly found in mining waters in concentrations ranging from 3 to >12,000 µg/L. The U.S. National Primary Drinking Water Standard MCL is 50 µg/L for selenium (EU 10 µg/L; WHO 40 µg/L). The National Fresh Water Quality Standard is 5 µg/L for selenium. The U.S. Fish and Wildlife Service has recommended that the National Fresh Water Quality Standard be lowered to 2 µg/L to protect fish, waterfowl, and endangered aquatic species. Several states have followed with enforcement actions at these same low levels. In Canada, permits may require stakeholders to monitor levels in water or biota, or to comply with guidelines, at either the National or Provincial levels, which can be as low as 1 or 2 µg/L in surface waters. Treatment of selenium in all mining waters presents a series of challenges. It can be present in relatively dilute concentrations and in streams with variable and often high flow rates. It can be present in many soluble and particulate forms, which may affect process design and treatability. The conditions of influent selenium-containing waters can vary, with issues such as temperature, pH, total dissolved solids and other contaminants affecting the ability to remove selenium selectively and economically. Treatment of selenium often results in the generation of a concentrated by-product requiring disposal, and re-release from residuals can occur. Beyond these issues, the physical environment of a mining operation can offer challenges such as remoteness and harsh and/or cold weather. Currently available selenium treatment technology (Table 1) includes biological treatment and a number of physical-chemical processes ? such as ion exchange, membrane filtration and adsorption ? that vary widely in efficiency and cost. Most treatment options remain either too costly and/or unproven for selenium-containing streams for reasons that include poor removal efficiency, variability in volume and composition of influents, system sizing and logistics considerations, as well as operating requirements.