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      The significance of petroleum bitumen in ancient Egyptian mummies

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          Abstract

          Mummification was practised in ancient Egypt for more than 3000 years, emerging from initial observations of buried bodies preserved by natural desiccation. The use of organic balms (and other funerary practices) was a later introduction necessitated by more humid burial environments, especially tombs. The dark colour of many mummies led to the assumption that petroleum bitumen (or natural asphalt) was ubiquitous in mummification; however, this has been questioned for more than 100 years. We test this by investigating 91 materials comprising balms, tissues and textiles from 39 mummies dating from ca 3200 BC to AD 395. Targeted petroleum bitumen biomarker (steranes and hopanes) analyses by gas chromatography-mass spectrometry selected ion monitoring (GC-MS SIM, m/z 217 and 191) showed no detectable bitumen use before the New Kingdom ( ca 1550–1070 BC). However, bitumen was used in 50% of New Kingdom to Late Period mummies, rising to 87% of Ptolemaic/Roman Period mummies. Quantitative determinations using 14C analyses reveal that even at peak use balms were never more than 45% w/w bitumen. Critically, the dark colour of balms can be simulated by heating/ageing mixtures of fats, resins and beeswax known to be used in balms. The application of black/dark brown balms to bodies was deliberate after the New Kingdom reflecting changing funerary beliefs and shifts in religious ideology.

          This article is part of the themed issue ‘Quantitative mass spectrometry’.

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          Organic chemistry of embalming agents in Pharaonic and Graeco-Roman mummies.

          Chemical treatments were an essential element of ancient Egyptian mummification. Although the inorganic salt natron is recognized as having a central role as a desiccant, without the application of organic preservatives the bodies would have decomposed in the humid environment of the tombs. The nature of the organic treatments remains obscure, because the ancient Egyptians left no written record of the process. Secondary textual evidence for mummification is provided by Herodotus, Diodorus Siculus, Strabo and Pliny. The most important account is that of Herodotus (about 450 yr bc), although archaeological evidence shows that by this time the process had declined significantly and the best results had been achieved centuries before. His account mentions myrrh, cassia, palm wine, 'cedar oil' (still widely disputed) and 'gum'; however, it is vague with respect to the specific natural products used. Here we report the results of chemical investigations of a substantial collection of samples of tissues, wrappings and 'resinous/bituminous' materials from provenanced and dated Egyptian mummies. We focused on examples of the 'classic' mummy-making culture of the Pharaonic or dynastic period, from which we can begin to track the development of mummification chronologically.
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            Studies of organic residues from ancient Egyptian mummies using high temperature-gas chromatography-mass spectrometry and sequential thermal desorption-gas chromatography-mass spectrometry and pyrolysis-gas chromatography-mass spectrometry.

            The techniques of gas chromatography-mass spectrometry (GC-MS) and sequential thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) have been utilised to characterise the constituents of tissue-derived or applied organic material from two Pharaonic Egyptian mummies with a view to identifying embalming practices/substances. The results obtained using TD-GC-MS revealed a series of monocarboxylic acids with the C16:0, C18:1 and C18:0 components dominating in both mummies. The thermal desorption products related to cholesterol, i.e., cholesta-3,5,7-triene and cholesta-3,5-diene (only in Khnum Nakht), were detected in both mummies. Khnum Nakht also contained a number of straight chain alkyl amides (C16-C18) and an alkyl nitrile (C18). Other products included the 2,5-diketopiperazine derivative (DKP) of proline-glycine (pro-gly) which was a major component (7.9%) in Khnum Nakht but only a very minor component in Horemkenesi. Py-GC-MS of samples of both specimens yielded a series of alkene/alkane doublets (Horemkenesi C6-C18, Khnum Nakht C6-C24) which dominated their chromatograms. Series of methyl ketones in the C9-C19 chain length range were also present, with C5-C7 cyclic ketones occurring in Horemkenesi only. These ketones are indicative of covalent bond cleavage, probably of polymerised acyl lipids. Nitrogenous products included nitriles (C9-C18) which were significant in both samples, and amides which were only detected in Khnum Nakht. Also present amongst the pyrolysis products were three steroidal hydrocarbons, cholest-(?)-ene, cholesta-3,5,7-triene and cholesta-3,5-diene. High temperature-GC-MS of trimethylsilylated lipid extracts yielded similar monocarboxylic acids to that obtained using TD-GC-MS, while a series of alpha, omega-dicarboxylic acids and a number of mono- and di-hydroxy carboxylic acids not seen in the thermal desorption or pyrolysis GC-MS analyses were significant constituents in both mummy samples. Overall, the use of GC-MS and sequential TD-GC-MS and Py-GC-MS has demonstrated in both mummies the presence of a complex suite of lipids and proteinaceous components whose compositions indicates extensive alteration via oxidative and hydrolytic processes during long-term interment. None of the classical embalming resins was detected but an exogenous origin for at least a proportion of these components cannot be discounted since fats, oils and gelatin have been proposed as embalming agents in mummification. The combined approach of sequential TD- and Py-GC-MS has potential for application to the characterisation of embalming materials in mummies. Most importantly these techniques virtually eliminate any destruction of the mummified bodies thereby allowing the scope of investigations of ancient Egyptian funerary practices to be significantly extended.
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              Characterisation of embalming materials of a mummy of the Ptolemaic era. Comparison with balms from mummies of different eras.

              Gas chromatography-mass spectrometry has been used to determine the nature of organic materials used in mummification balms. A comparative analysis of samples taken from Egyptian mummies is developed. The results are given in two parts. First, it is shown that the chemical composition of the balm is practically independent of the part of the mummy from which it is taken. This study was done on a Ptolemaic mummy (circa 100 BC from the Guimet Museum in Lyon). Fats, beeswax, and diterpenic resins were the main components: they were found everywhere. Castor oil was also very often detected (in half of the samples). This particular fat is present in the balm inside the thorax but not in the skull. Moreover it is shown that a vegetable tannin was employed. Components indicative of vegetable tannin input (gallic acid and inositols) were found in seven samples out of eighteen, particularly close to the body and on the canopic pack of the heart. Secondly, some conclusions from a comparative study of the composition of balms from mummies of various social levels as well as of different Egyptian periods are reported. It is shown that beeswax was used as from very early times (XVIIIth dynasty). The mixture of beeswax, fats, and diterpenoid resins would appear to be more recent. The balms of three mummies dating from more recent Egyptian periods (XIXth to XXVth dynasty) were analysed. No evidence of a resin, gum-resin, or plant gum could be found. Some mummies would appear to have been embalmed with fats or beeswax. Finally, the entrails canopic pack said to belong to Ramses II undoubtedly shows an embalming process with a triterpenic resin of the mastic type. The adopted analytical methodology enabled us to achieve simultaneous detection of four components of the balm of the Ptolemaic mummy. Analysis of the other five mummies revealed far less complex chemical compositions for the balms. This may be an indication of different embalming processes, although we should bear in mind the question of organic matter preservation through the ages.
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                Author and article information

                Journal
                Philos Trans A Math Phys Eng Sci
                Philos Trans A Math Phys Eng Sci
                RSTA
                roypta
                Philosophical transactions. Series A, Mathematical, physical, and engineering sciences
                The Royal Society
                1364-503X
                1471-2962
                28 October 2016
                28 October 2016
                : 374
                : 2079 , Theme issue ‘Quantitative mass spectrometry’ compiled and edited by Pawel Urban
                : 20160229
                Affiliations
                [1 ]Organic Geochemistry Unit, School of Chemistry, University of Bristol , Cantock's Close, Bristol BS8 1TS, UK
                [2 ]Department of Egyptology, The American University in Cairo , AUC Avenue, PO Box 74, Tagammu 5, New Cairo 11835, Egypt
                Author notes

                One contribution of 19 to a theme issue ‘ Quantitative mass spectrometry’.

                Author information
                http://orcid.org/0000-0002-9483-2750
                Article
                rsta20160229
                10.1098/rsta.2016.0229
                5031647
                27644983
                4bd4ad83-bd8f-4897-818a-c6213afff697
                © 2016 The Authors.

                Published by the Royal Society under the terms of the Creative Commons Attribution License http://creativecommons.org/licenses/by/4.0/, which permits unrestricted use, provided the original author and source are credited.

                History
                : 28 July 2016
                Funding
                Funded by: MS facilities;
                Categories
                1002
                5
                78
                67
                Articles
                Research Article
                Custom metadata
                October 28, 2016

                mummification,asphalt,quantification,biomarkers,radiocarbon analysis

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