Selenium Speciation in Waste Materials From an Exhausted Iberian Pyrite Belt Mine

Selenium is an essential nutrient for humans, animals and microorganisms, but it becomes toxic at concentrations slightly above the nutritional levels. This naturally occurring trace element can be released to the environment from various anthropogenic sources such as mining, agricultural, petrochemical and industrial processes and its toxicity is developed along a complex cycle involving adsorption by soil components and subsequent accumulation by plants. In the environment, selenium can occur in several oxidation states ranging from selenide (Se=) to elemental selenium (Se0), selenite (Se4+) and selenate (Se6+). Selenium contents above 900 ppm were recently assigned in mine wastes from the sulphur factory at the São Domingos exhausted pyrite mine exploited in the Iberian Pyrite Belt (south Portugal) since Roman times until 1966. Aiming at a sustainable remediation of this mining site, an X-ray absorption spectroscopy study using synchrotron radiation, combined with X-ray diffraction, was undertaken to clarify the speciation state of selenium and the nature of Se-carrier phase(s). The results show that selenium does not significantly replace sulphur under the form of selenate in the dominant sulphate phases and occasionally remains as a substituting selenide anion in debris of the original sulphides present in the mine waste materials