Investigation of red paint sample From an Egyptian artifact Sample investigated Title: painted mummy shroud Artist: Unknown Accession No.: 1973.4.503 Material: Paint Date/Provenance: 1st century AD Egypt Plate 1 Experimental LCMS analysis of the red pigment A small sample of the red paint was hydrolysed in methanol with amberlite-15 acidic resin beads as an acid catalyst for 2 hours. The mixture was filtered and subjected to LC-MS analysis using dilute formic acid in methanol as one solvent and water as the other in a gradient elution. Analysis was performed using a ThermoFinnegan Surveyor attached to a ThermoFinnegan LCQ Advantage ion trap instrument operating in negative electrospray ionization mode. The parameters were optimized by tuning the detector to the deprotonated quasimolecular ions of carminic Acid, Kermesic acid, Laccaic acid A, Alizarin and purpurin. Results Total ion count Purpurin Alizarin Kermisic acid Relative Abundance Carminic acid Lacchaic acid A RT: 0.00 - 12.06 0.45 100 NL: 7.45E5 TIC MS Egyptian Sample Carminic acid 95 90 85 80 75 70 alizarin 65 purpurin 60 4.41 55 50 5.45 45 40 35 0.37 3.32 30 3.19 25 10.15 3.72 3.85 1.70 20 8.56 4.12 0.56 0.85 15 6.56 0.91 10 1.57 4.92 2.87 1.83 1.17 5.05 5.63 8.48 7.63 6.96 7.36 7.68 9.09 9.14 9.54 9.89 9.01 10.20 10.60 11.74 11.13 11.48 8.16 6.30 2.10 2.37 5 0 0 1 2 3 4 5 6 Time (min) 7 8 9 10 11 Figure 1 Whole chromatogram (bottom) and individual detections for each compound by selected ion monitoring above 12 LCMS In the LC MS investigation Alizarin, purpurin and carminic acid were found,(Figure 1) which indicates that the pigment is a mixture of madder lake and cochineal carmine. Madder lake has been used as a pigment for a very long time There are two varieties of cochineal which yield carminic acid as the main colourant and these are: American cochineal which was not available in Europe and the middle East until the late 15th century. Armenian Cochinial which may have been used at much earlier times. It has been used as a textile dye, (see for example Cardon, D., 2007, , Judith Hofenk de Graff,2009) but little is known of its use in pigments. This may have been confused with Kermes by historians who do report that kermes lake was used in ancient Egypt (see for example Helmut Scheppe and Heinz Roosen-runge , 1986) References Cardon, D., 2007, Natural Dyes-Sources, Tradition, Technology, Science, Archetype, London. Hofenk de Graaf, J.H., 2009 The colourful past: The origins, chemistry and identification of na tural dyestuffs, Archetype, London Scheppe, Helmut and Roosen-Runge , Heinz, 1986, ‘Cochinial Carmine and kermes carmine in Robert Feller (Ed.) Artists’ Pigments – A handbook of their History and Characteristics.Cambridge.
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