Polyhalite is an important coexisting mineral with halite in salt repositories for nuclear waste disposal, such as Waste Isolation Pilot Plant (WIPP) in Carlsbad, New Mexico. The thermal stability of this mineral is a key knowledge in evaluating the integrity of a salt repository in the long term, as water may release due to thermal decomposition of polyhalite. Previous studies on structural evolution of polyhalite at elevated temperatures laid the basis for detailed calorimetric measurements. Using high-temperature oxide-melt drop-solution calorimetry at 975 K with sodium molybdate as the solvent, we have determined the standard enthalpies of formation from constituent sulfates (Delta H degrees(f,sul)), oxides (Delta H degrees(f,ox)) and elements (Delta H degrees(f,ele)) of a polyhalite sample with the composition of K2Ca2Mg(SO4)(4) center dot 1.95H(2)O from the Salado formation at the WIPP site. The obtained results are: Delta H degrees(f,sul) = -152.5 +/- 5.3 kJ/mol, Delta H degrees(f,ox) = -1926.1 +/- 10.5 kJ/mol, and Delta H degrees(f,ele) = -6301.2 +/- 9.9 kJ/mol. Furthermore, based on the estimated formation entropies of polyhalite, its standard Gibbs free energy of formation has been derived to be in the range of -5715.3 +/- 9.9 kJ/mol to -5739.3 +/- 9.9 kJ/mol. These determined thermodynamic properties provide fundamental parameters for modeling the stability behavior of polyhalite in salt repositories. (C) 2017 Elsevier Ltd.