Plumbonacrite identified by X-ray powder diffraction tomography as a missing link during degradation of red lead in a Van Gogh painting.

Red lead, a semiconductor pigment used by artists since antiquity, is known to undergo several discoloration phenomena. These transformations are either described as darkening of the pigment caused by the formation of either plattnerite (β-PbO2) or galena (PbS) or as whitening by which red lead is converted into anglesite (PbSO4) or (hydro)cerussite (2 PbCO3⋅Pb(OH)2; PbCO3). X-ray powder diffraction tomography, a powerful analytical method that allows visualization of the internal distribution of different crystalline compounds in complex samples, was used to investigate a microscopic paint sample from a Van Gogh painting. A very rare lead mineral, plumbonacrite (3 PbCO3⋅Pb(OH)2⋅PbO), was revealed to be present. This is the first reported occurrence of this compound in a painting dating from before the mid 20th century. It constitutes the missing link between on the one hand the photoinduced reduction of red lead and on the other hand (hydro)cerussite, and thus sheds new light on the whitening of red lead.

[1]  V. Lopata,et al.  Stability and solubility relationships between some solids in the system PbO–CO2–H2O , 1984 .

[2]  Jaap J. Boon,et al.  Analytical Imaging Studies of Cross-Sections of Paintings Affected by Lead Soap Aggregate Formation , 2007 .

[3]  K. Janssens,et al.  XRDUA: crystalline phase distribution maps by two‐dimensional scanning and tomographic (micro) X‐ray powder diffraction , 2014 .

[4]  P. Bleuet,et al.  Classification of lead white pigments using synchrotron radiation micro X-ray diffraction , 2007 .

[5]  P. Williams,et al.  Stability of plumbonacrite , 1981 .

[6]  T. Grygar,et al.  Degradation of lead-based pigments by salt solutions , 2009 .

[7]  Koen Janssens,et al.  High energy X-ray powder diffraction for the imaging of (hidden) paintings , 2011 .

[8]  N. Tamura,et al.  Micro scanning X-ray diffraction study of Gallo-Roman Terra Sigillata ceramics , 2006 .

[9]  P. P. Lottici,et al.  Spectroscopic study of the degradation products in the holy water fonts in Santa Maria della Steccata Church in Parma (Italy). , 2008, Analytica chimica acta.

[10]  J. Vallet,et al.  Chromatic alterations of red lead pigments in artworks: a review , 2008 .

[11]  V. A. Solé,et al.  A multiplatform code for the analysis of energy-dispersive X-ray fluorescence spectra , 2007 .

[12]  J. Tétreault,et al.  Corrosion of Copper and Lead by Formaldehyde, Formic and Acetic Acid Vapours , 2003 .

[13]  Koen Janssens,et al.  Combined use of synchrotron radiation based micro-X-ray fluorescence, micro-X-ray diffraction, micro-X-ray absorption near-edge, and micro-fourier transform infrared spectroscopies for revealing an alternative degradation pathway of the pigment cadmium yellow in a painting by Van Gogh. , 2012, Analytical chemistry.

[14]  Danica Srećković-Batoćanin,et al.  Interaction between binding materials—the cause of damage to gabbro stone on the monument to the unknown soldier (Serbia) , 2010 .

[15]  A Note on a Modern Lead White, also Known as 'Synthetic Plumbonacrite' , 2007 .

[16]  Yangen Zhou,et al.  Visible light-induced highly efficient organic pollutant degradation and concomitant CO2 fixation using red lead , 2012 .

[17]  P. Bleuet,et al.  Diffraction/scattering computed tomography for three-dimensional characterization of multi-phase crystalline and amorphous materials , 2012 .

[18]  C. Hogan,et al.  Casting light on the darkening of colors in historical paintings. , 2013, Physical review letters.

[19]  N. Eastaugh.  Pigment compendium : a dictionary and optical microscopy of historical pigments , 2008 .

[20]  P. Bleuet,et al.  Probing the structure of heterogeneous diluted materials by diffraction tomography. , 2008, Nature materials.

[21]  Koen Janssens,et al.  Micro X‐ray diffraction and fluorescence tomography for the study of multilayered automotive paints , 2010 .

[22]  D. Bersani,et al.  Micro-Raman study of copper hydroxychlorides and other corrosion products of bronze samples mimicking archaeological coins , 2012, Analytical and Bioanalytical Chemistry.

[23]  E. Dooryhée,et al.  Non-destructive synchrotron X-ray diffraction mapping of a Roman painting , 2005 .