Thank you for your interest in contributing data about bookbindings colored with arsenic-containing green pigment to the Poison Book Project. In order to maintain the integrity of our arsenical bindings database, we ask that you submit corroborating evidence along with the bibliographic information for each emerald green book.
To submit data to the Arsenical Books Database:
- Fill out this form with the information on your book.
- When submitting data, please be prepared to provide the following information for each binding: title, author, publisher, location, date, type of corroborating evidence, type of emerald green material (e.g. bookcloth, paper, onlay, endpaper, textblock edges, etc.)
- Under “Collection Name,” please tell us the name of your institution; alternatively, let us know if the book belongs to a private collection. If you do not give us permission to use the name of the collection publicly, then we will list the contribution to the database as “undisclosed institution” or “private owner.”
- In addition to the information you provide in the form, please be prepared to submit corroborating evidence, as detailed below, for the presence of arsenic.
Identification Methods for Emerald Green Bookcloth
X-ray Fluorescence Spectroscopy (XRF)
Portable XRF using a zero background plate has proven efficient and accurate as the primary method for identification of emerald green bookcloth in this study. According to the data collected thus far, emerald green pigment was rarely, if ever, mixed with additional pigments when used as a bookcloth colorant. The qualitative XRF spectra consistently indicate strong peaks for copper and arsenic. We strongly recommend collecting qualitative data (counts/spectra), not quantitative data (ppm or %). XRF analysis, we strongly recommend collecting qualitative data (counts/spectra), not quantitative data (ppm or %). We also recommend using a zero background plate placed just inside the book cover to avoid interference from elements in the text block.
Please submit XRF spectra as a PDF or JPG.
Technical specifications: At Winterthur, we use the following instrument and settings: Bruker Tracer III-SD XRF spectrometer using a rhodium tube (40kV high voltage, 9.6μA anode current, 25μm Ti/305μm Al filter) for 60 seconds live time irradiation.
Raman Spectroscopy
When possible, Raman spectroscopy has been used to confirm copper acetoarsenite (emerald green) as the specific molecular compound present in arsenical green bookcloth. At Winterthur, over a dozen books found to contain copper and arsenic (with XRF) have been confirmed with Raman to contain emerald green.
Please submit Raman spectra as a PDF or JPG.
Technical specifications: At Winterthur, we have had success with the following Raman parameters on bookcloth: Renishaw Invia Raman spectrometer extended scan from 150-1200cm-1; 60 accumulations of 25s each at 5% laser power with a 785nm diode laser.
Polarized Light Microscopy (PLM)
In an effort to explore additional techniques for the reliable identification of emerald green, small, destructive samples of seven green bookcloths were analyzed by polarized light microscopy. Examination in plane- and cross-polarized light conclusively and correctly identified emerald green as the colorant in three of the samples, and found a mixture of Prussian blue and chrome yellow in the other four.
Please submit a PLM photomicrograph as a PDF or JPG.
Tips and recommendations for sampling, sample preparation, and analysis by PLM have been compiled into a document available here.
vis-NIR
A publication by researchers at the University of St Andrews describes the use of vis-NIR to detect emerald green (copper acetoarsenite) in 19th-century bookbindings. While the Poison Book Project team has not personally confirmed this method of identification, the use of vis-NIR offers a promising alternative to the established methods listed above. Arsenical books identified with vis-NIR – some of which were further confirmed with Raman spectroscopy– by the University of St Andrews research team have been included in the Arsenical Books Database. (M. P. Gil, E. Henderson, J. Burdge, E. Kotze and W. McCarthy, Detecting Emerald Green in 19thC book bindings using vis-NIR spectroscopy, Analytical Methods, 2023, DOI: 10.1039/D3AY01329D).
Microchemical Test Kits
The Winterthur research team has tested two microchemical test kits for the detection of arsenic, Millipore and Industrial Test Systems. Both accurately confirmed the presence of arsenic in emerald green bookcloth. However, these tests rely on the creation and measurement of arsine gas, arsenic’s most deadly form, and the amount of arsine gas produced when testing emerald green bookcloth proved higher than the test kit’s measurement scale. The test strips also contain other toxic components such as mercury, and each test produces a significant amount (100 mL) of contaminated solvent that must be disposed of properly. Arsenic spot tests should be performed only by persons trained in chemical safety, wearing appropriate PPE, under a certified chemical fume hood, with access to safe disposal for hazardous waste according to state law. Arsenic test kits should never be used in the home or general library environment.