Tracing the Alteration of Verdigris Pigment through Combined Raman Spectroscopy and X-ray Diffraction, Part II: Natural Ageing

Abstract This study explores the natural alteration of verdigris, both in the form of neutral verdigris (Cu(II) (CH3COO)2⋅H2O) and basic verdigris (Cu(II)x(CH3COO)y(OH)z ⋅nH2O), through combined Raman spectroscopy and X-ray diffraction investigation of samples created seven to eleven years prior to analysis. The naturally aged paint films of neutral or basic verdigris in gum arabic on paper and parchment provide insight into the pigment’s well-known instability relevant to historical works in aqueous media on maps, prints, books and manuscript materials. The latter historical application is an area that has received far less attention than alteration of verdigris in oil-based paint films. Findings shed new light on alternate pathways for conversion of neutral verdigris to basic verdigris, including the formation of a previously unknown form of verdigris and amorphous material on alkaline paper substrates. Additionally, we demonstrate for the first time that copper hydroxyl chlorides can form in situ from neutral verdigris, in this case on parchment that has a chlorine-rich surface. These results advance our understanding of neutral verdigris alteration, and complement results from our prior artificial ageing study. Both studies point to neutral verdigris as the historically more important form throughout its heyday. Improved understanding of neutral verdigris instability and its alteration pathways are critical for confident identification of the pigment in historical works, leading to better risk assessment of collections of verdigris-containing heritage, such as maps.