Selenium (Se) is both beneficial and toxic to animals, plants, and humans. Consequently, it is imperative to know its concentration in the environment and to understand the processes controlling its distribution. Determinations of Se concentrations in a variety of materials indicate that Se is widely distributed throughout the environment. The processes responsible for its distribution include volcanic activity, the burning of fossil fuels, the weathering of rocks and soils, groundwater transport, precipitation of minerals, adsorption, chemical or bacterial reduction and oxidation, and metabolic uptake and release by plants and animals. The importance of a particular process in controlling the distribution of Se is intimately linked to the speciation of Se, which is controlled by the pH and redox conditions of the environment. Selenium can exist as selenide (Se²⁻), elemental Se (Se⁰), selenite (SeO²⁻₃), and selenate (SeO²⁻₄). Each oxidation state exhibits different chemical behavior. Selenide and elemental Se occur in acidic, reducing, and organic-rich environments. Metal selenides, Se-sulfides, and elemental Se are insoluble, and therefore biologically unavailable. For the pH and redox conditions of most soil and aquatic environments, SeO²⁻₃ and SeO²⁻₄; should be the dominant forms of Se. Selenite is immobilized by adsorption onto particles, particularly Fe oxyhydroxides. Selenate is highly mobile and biologically available because of the solubility of its salts and its weak adsorption by particles. Microbial action can change the speciation of Se through oxidation or reduction, or through the formation of organic Se compounds.