Shades of red: A chemical exploration of pigments and dyes in 19th century postage stamps by a multi-analytical methodology.

A total of 57 European, Canadian and North American postage stamps, all in red shades, were analyzed with the main goal of unraveling which pigments or dyes were used to produce the red color in the period dated from 1841 to 1899. Both non-destructive techniques, including X-Ray Fluorescence (XRF), Fiber Optics Reflectance Spectra (FORS), and Steady State Fluorescence Spectroscopy, and destructive methods such as High-Performance Liquid Chromatography coupled with Diode-Array Detection (HPLC-DAD) and Electrospray Ionization High-Resolution Mass Spectrometry (ESI-HRMS), were utilized for a comprehensive analysis. The examined red shades were identified as originating from either a single pigment or dye, or a combination of both. XRF analysis detected red lead/litharge in 14 postage stamps, vermilion in 8 and iron oxide in 4. The mapping results obtained by this technique were shown to be very important in the determination of inorganic pigments. Most specimens contained a natural organic dye, with carminic acid being the most prevalent, appearing in 30 samples. In contrast, alizarin was identified in only 3 of the examined postage stamps. A synthetic dye, eosin Y, first synthesised by Heinrich Caro in 1871, was detected in 11 stamps and suggested by FORS and steady-state fluorescence in 6 others printed from 1879 onwards. HPLC-HRMS provided more detailed information on the natural colorant. In 19 samples both organic and inorganic dyes or pigments were found to coexist. It has been shown that spectroscopic techniques, when used with an appropriate database, can play a role in suggesting the presence of certain compounds that are subsequently detected by other techniques.