Abstract
Efforts to read medieval manuscript waste recycled as bookbinding material in the sixteenth and seventeenth centuries have resulted in the chemical analysis of four books housed at the University Library of Southern Denmark and the Smithsonian Libraries in Washington DC. Four green coloured book bindings have been investigated by optical microscopy, micro X-ray fluorescence, X-ray diffraction, Raman spectroscopy, mass spectroscopy, and laser ablation inductively coupled plasma mass spectrometry. The results show that the green pigments used to obscure the manuscript waste in all four cases contain orpiment (As2S3) and indigo (C16H11N2O2). Although the books were printed in diverse places in Europe—Basel, Bologna, and Lübeck—the styles of their bindings indicate that they were likely bound in the same region in the same period. It is further likely that they acquired their arsenic-rich paint as part of the bookbinding process. Issues concerning the toxicity, health issues for library staff, conservators and researchers handling the books are also addressed.
Highlights
Three sixteenth and seventeenth century books were identified in the Herlufsholm Special Collection of the University Library of Southern Denmark, the bindings of which were partly decorated with green paint found to contain arsenic
Microscopic observations The four microscope pictures taken in polarized light (Fig. 2) show that the four samples are different in appearance and in thickness of the applied green paint layer
The four volumes dating from the sixteenth to early seventeenth century with original book bindings investigated here all have similar chemical composition; it is likely that the binders of these books referenced the same recipe for the colour pigment
Summary
Three sixteenth and seventeenth century books were identified in the Herlufsholm Special Collection of the University Library of Southern Denmark, the bindings of which were partly decorated with green paint found to contain arsenic. This was reported in Denmark [1] and projected to the public, internationally, via The Conversation [2]. Relying only on μ-XRF in Denmark it was speculated that the paint could perhaps be Emerald Green (Cu(CH3COO)2·3Cu(AsO2)2), which the present work shows is not the case This seems to be the first report on poisonous green book bindings in the scientific literature. The question of the nature of the green colour, its original purpose, its chemistry, the particular history of the physical objects, as well as issues related to the handling and keeping of the particular books—and of similar painted works—is of potential importance to academic and national libraries, archives, museums, collectors, as well as to historical chemistry and physics
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