In this work, we performed a comprehensive spectroscopic analysis of the “Portrait of a Young Man in a Wide-Brimmed Hat with a Feather” authored by an unknown artist and housed in the National Art Museum of the Republic of Belarus. Previously this portrait was a part of the Myatlev collection (St. Petersburg, Russia). Extensive analysis, including microscopic examination, X-ray radiography, luminescent studies, and complex multi-analytical studies of the chemical composition of art materials allowed us to suggest the dating and attribution of the painting. Laser-induced breakdown spectrometry (LIBS), Fourier transform Infrared spectrometry (FTIR) and Surface-enhanced Raman scattering (SERS) were also used. Gold nanoparticles in toluene were used to enhance the signal of Raman scattering, enabling the unambiguous identification of pigments within the painting layers of the historical object.Moreover, we discovered the portrait of another person on the same canvas under the top layer of paint. A comparative analysis of grounds and painting materials did not reveal significant differences in the technological features of both images. Therefore, we can assume that both portraits were created in the same historical period and followed the traditions of the same art school. Lead white, bone black, red, yellow and brown ochres as well as lapis lazuli were identified as the pigments.The results obtained do not contradict to art critics hypothesis that the underlying painting is the portrait of King of Polish-Lithuanian Commonwealth11The Polish–Lithuanian Commonwealth formally known as the Kingdom of Poland and the Grand Duchy of Lithuania was established as a single entity by the Union of Lublin in 1569. It existed until 1795. Wladislaw IV Vasa created in the first half of XVII century. Then, it became the base for a new painting, which might be a self-portrait of the king’s illegitimate son Count Vasenau and was created in the middle of XVII century.
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