It’s Only a Part of the Story: Analytical Investigation of the Inks and Dyes Used in the Privilegium Maius

Abstract

The Privilegium maius is one of the most famous and spectacular forgeries in medieval Europe. It is a set of charters made in the 14th century upon commitment by Duke Rudolf IV, a member of the Habsburg family, to elevate the rank and the prestige of his family. These five charters, now kept at the Österreichisches Staatsarchiv in Vienna, have been subjected to a thorough interdisciplinary study in order to shed light on its controversial story. The charters are composed of pergamenaceous documents bound to wax seals with coloured textile threads. The present contribution concerns the characterisation of the inks used for writing and of the dyes used to colour to the threads: Are they compatible with the presumed age of the charters? Though showing only a part of the whole story of the charters, dyes analysis could contribute in assessing their complex history from manufacturing to nowadays. The dyes were characterised with non-invasive in situ measurements by means of fibre optic (FORS) and with micro-invasive measurements by means of Surface Enhanced Raman Spectroscopy (SERS) and High-Performance Liquid Chromatography with Mass Spectrometry (HPLC-MS) analysis. The results showed that the threads of four of the charters (three dyed with madder, one with orchil) were apparently coloured at different dyeing stages, then re-dyed in the 19–20th century.

Interpol questioned documents review 2019–2022

“…including any other technology used to prepare the document. The following 64 articles [ [548] , [549] , [550] , [551] , [552] , [553] , [554] , [555] , [556] , [557] , [558] , [559] , [560] , [561] , [562] , [563] , [564] , [565] , [566] , [567] , [568] , [569] , [570] , [571] , [572] , [573] , [574] , [575] , [576] , [577] , [578] , [579] , [580] ] [ [581] , [582] , [583] , [584] , [585] , [586] , [587] , [588] , [589] , [590] , [591] , [592] , [593] , [594] , [595] , [596] , [597] , [598] , [599] , [600] , [601] , [602] , [603] , [604] , [605] , [606] , [607] , [608] , [609] , [610] , [611] ], combined with 17 presentations [...…”

“…Calà et al [ 594 ] identified possible forgeries in historical documents using non-destructive and micro-destructive methods. Studying mainly the ink and dyed threads on the Privilegium maius, the team used Fiber Optics Diffuse Reflectance Spectroscopy (FORS) analysis to distinguish the types of black ink present.…”

Identification of aloe and other dyes by means of SERS and HPLC-DAD-MS in the embroidery of a 15th century English folded almanac

“…It is also worth noting the absence of the two anthraquinones anthrapurpurin and flavopurpurin which, according to recent works by Liu [33,34], provides evidence of the natural provenance of madder used to dye the embroidery: in fact these two compounds can be used as the markers for distinguishing between synthetic alizarin and natural alizarin from madder.…”

Characterizing different types of black fountain pen ink using the chemical approach

“…Paper chromatography and thin layer chromatography (TLC) [5] have the advantage of simple and direct operation for routine analysis. Analytical methods, including high-performance liquid chromatography (HPLC), [6,7] capillary electrophoresis (CE), [8,9] laser desorption ionization (LDI), [10,11] and matrixassisted laser desorption/ionization (MALDI), [12,13] secondary ion mass spectrometry (SIMS), [14,15] and electrospray ionization mass spectrometry (ESI-MS), [16] have also been used to identify the dyes and pigments in ink samples.…”