A calorimetric and thermodynamic investigation of three hydrous selenites, ZnSeO3 center dot 2H(2)O, ZnSeO3 center dot H2O and CdSeO3 center dot H2O, was undertaken. All three phases were synthesized by mixing of aqueous solutions of zinc and cadmium nitrates, accordingly, and sodium selenite and characterized by XRD powder diffraction, energy dispersive X-ray microanalysis, inductively coupled plasma mass spectrometry and thermal analisys methods. The low-temperature heat capacity of ZnSeO3 center dot 2H(2)O, ZnSeO3 center dot H2O and CdSeO3 center dot H2O were measured using adiabatic calorimetry between 5 and 324 K, and the third-law entropies were determined. Values of molar third law entropy S-m degrees(298 K, ZnSeO3 center dot 2H(2)O, cr.) = 179 +/- 1 J.K-1.mol(-1), S-m degrees(298 K, ZnSeO3 center dot H2O, cr.) = 150 +/- 1 J.K-1.mol(-1), S-m degrees(298 K, CdSeO3 center dot H2O, cr.) = 171 +/- 1 J.K-1.mol(-1) were calculated. The expanded uncertainties for S-m degrees are given at the 0.95 confidence level (k approximate to 2). The enthalpies of formation for ZnSeO3 center dot H2O, ZnSeO3 center dot 2H(2)O and CdSeO3 center dot H2O were determined using H2SO4-solution calorimetry giving Delta H-f(m)degrees(298 K, ZnSeO3 center dot 2H(2)O, cr) = -1238 +/- 2 kJ.mol(-1), Delta H-f(m)degrees(298 K, ZnSeO3 center dot H2O, cr) = -931 +/- 2 kJ.mol(-1), Delta H-f(m)degrees(298 K, CdSeO3 center dot H2O, cr) = -906 +/- 2 kJ.mol(-1). The expanded uncertainties for Delta H-f(m)degrees are given at the 0.95 confidence level (k approximate to 2). The Gibbs energy of formation for ZnSeO3 center dot 2H(2)O, ZnSeO3 center dot H2O and CdSeO3 center dot H2O at T = 298 K, 1 atm have been calculated on the basis on Delta H-f(m)degrees and Delta S-f(m)degrees : Delta(f)G(m)degrees(298 K, ZnSeO3 center dot 2H(2)O, cr.) = -1035 +/- 2 kJ.mol(-1), Delta(f)G(m)degrees(298 K, ZnSeO3 center dot H2O, cr.) = -790 +/- 2 kJ.mol(-1) and Delta(f)G(m)degrees(298 K, CdSeO3 center dot 2H(2)O, cr.) = -768 +/- 2 kJ.mol(-1). The expanded uncertainties for Delta(f)G(m)degrees are given at the 0.95 confidence level (k approximate to 2). Smoothed C-p,C-m degrees(T) values between T = 0 K and T = 320 K for ZnSeO3 center dot 2H(2)O(cr.), ZnSeO3 center dot H2O(cr.) and CdSeO3 center dot H2O(cr.) are presented along with values for S-m degrees and the functions [H-m degrees(T) - H-m degrees(0)] and [G(m)degrees(T) - H-m degrees(0)]. These results motivate a reevaluation of the natural conditions under which selenites, and selenates replace selenides, and sulfides in the oxidation zones of sulfide ore deposits or upon weathering of technologic waste. The values of Delta(f)G degrees for ZnSeO3 center dot 2H(2)O, ZnSeO3 center dot H2O and CdSeO3 center dot H2O were used to calculate the Eh-pH diagrams of the Zn-SeH2O and Cd-Se-H2O, systems. These diagrams have been constructed for the average contents of these elements in acidic waters of the oxidation zones of sulfide deposits. The behavior of selenium, zinc, and cadmium in the surface environment have been quantitatively explained by variations of the redox potential and the acidity-basicity of the mineral-forming medium. Precisely these parameters determine the migration ability of selenium compounds and its precipitation in the form of various solid phases. (C) 2017 Elsevier Ltd.