Thermodynamics of Environmentally Important Natural and Synthetic Phases Containing Selenium

Abstract

Understanding and deciphering the processes proceeding near the surface are the urgent tasks of contemporary mineralogy and geochemistry, which are especially important for resolving ecological challenges and developing principles of rational environmental management. The paper presents our systematized data published about the thermodynamics of selenites, which are formed in the weathering zone of the sulfide ores, and determines approaches to quantitative physicochemical modeling of their formation conditions. The activities of components in natural waters beyond the zones of natural (oxidation zones) and man-made contamination with selenium (a _ΣSe = 10⁻⁹, a _ΣFe = 10⁻⁵, a _ΣCu = 10⁻⁷, a _ΣZn = 5 × 10⁻⁷, a _ΣCo = 10⁻⁸, a _ΣNi = 6 × 10⁻⁸, and a _ΣPb = 10⁻⁸) and in waters formed in the oxidation zone (a _ΣSe = 10⁻⁵–10⁻⁴, a _ΣFe = 10⁻², a _ΣCu = 10⁻², a _ΣZn = 10⁻², a _ΣCo = 10⁻³, a _ΣNi = 10⁻², a _ΣPb = 10⁻⁴) have been estimated. Eh–pH diagrams were calculated and plotted using the Geochemist’s Workbench (GMB 7.0) software package. The database comprises the thermodynamic parameters of 46 elements, 47 main particles, 48 redox pairs, 551 particles in solution, 624 solid phases, and 10 gases. The Eh–pH diagrams of the Me–Se–H₂O systems (Me = Cu, Pb, Co, Ni, Fe, Zn) were plotted for the average contents of these elements in underground water and for their contents in oxidation zones of sulfide deposits. The formation of Co, Ni, Fe, Cu, Zn, and Pb selenites and selenates at the surface is discussed.