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Twenty frescoes from "The Assumption" Cathedral located in the island town of Sviyazhsk (Tatarstan Republic, Russian Federation)—dated back to the times of Tsar Ivan IV "the Terrible"—were chemically analyzed in situ with a portable X-ray fluorescence (pXRF) spectrometer. The investigation focused on identifying the pigments and their combinations in the paint recipes. One hundred ninety-three micropoints randomly chosen from the white, yellow, orange, pink, brown, red, grey, black, green, and blue areas were measured for major and minor elements. The compositional types separated within each color indicate different recipes. The statistical processing of the data unveiled the most important oxides (CaO, MgO, Fe2O3, PbO, SO3, Sb2O3, Al2O3, SiO2, and P2O5) and their relationships. The results allowed to infer the mineral composition of the paints, and, hence, the recipes used by the Russian artisans. Slaked lime and slaked dolomitic lime mixed with variable amounts of "antimony white" and "bone white" were used for white, pink, yellow, and orange paints and for preparing a basic batch for all other colors. Mostly yellow ochre, red ochre, and lead minerals, and occasionally blue ochre, green earth, realgar, orpiment, bone black, galena, stibnite, and magnetite were the pigments involved in various amounts in preparing the paints. [ABSTRACT FROM AUTHOR]