Analysis of Red Paint and Filling Material from the Sarcophagus of Queen Hatshepsut andKing Thutmose IAuthor(s): Richard NewmanSource: Journal of the Museum of Fine Arts, Boston, Vol. 5 (1993), pp. 62-65Published by: Museum of Fine Arts, BostonStable URL: http://www.jstor.org/stable/20519754 .

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RICHARD NEWMAN

Analysis of Red Paint and Filling Material from the Sarcophagus of Queen Hatshepsut and King Thutmose I

Red Paint

The reddish color of the sarcophagus exterior is due to red-colored paint; thick deposits can be seen in hieroglyphs and other recessed areas, while only thin washes occur on polished stone surfaces. Six samples from the left (east) side were analyzed by electron microprobe,' Fourier transform infrared microscopy (FTIR),2 and gas chromatog raphy/mass spectrometry (GC/MS),3 to identify the pigments and binder(s). The analyses indicate that the red paint, which is of similar if not identical composition in all of the samples, contains red earth (or ochre), the only red pigment that has been found to date in ancient Egyptian paints. Kaolinite (a clay mineral) and quartz are components of this earth pigment, as indicated by the FTIR spectra (fig. i). The spectra also suggest that the pigment was bound with a plant gum, a type of binder that was common in ancient Egypt.4

Plant gums can be hydrolyzed to yield simple sugars, the types and relative amounts of which vary somewhat from one gum to another.5 Two samples of paint were analyzed for simple sugars by GC/MS. The samples gave virtually identical results, showing the presence of large amounts of xylose and glucose, and smaller amounts of fucose, rham nose, galactose, and possibly arabinose (fig. 2). These results suggest that more than one sugar-containing material is present in the paint.

One component may be gum tragacanth, a gum that could have been available in ancient Egypt (xylose and fucose are important sugars in this gum). Glucose is not usually found in plant gums, although it is present in honey, plant juices, sugar, and some seeds; perhaps some sugar (in the form of plant juice or honey) was added to make the paint a little stickier.

Exactly why this red paint is present on the surface is not certain. As speculated in the preceding article,6 it may simply have been brushed or smeared over the surface as a guide for the stoneworkers polishing the stone. Thus the thicker deposits found in the hieroglyphs and other recessed areas of the design may be fortuitous rather than indicating intentional filling of these design elements with red paint. There are no indications of other colors anywhere on the exterior of the sar cophagus, although paint does remain on the figures on the inside ends (these figures were added during alteration of the sarcophagus).7

Filling Material in Altered Inscriptions

During alteration of the sarcophagus, portions of many inscriptions were filled with a brownish-black material. One sample from a charac ter on the top edge of the left (east) side was analyzed by a combination

RICHARD NEWMAN is Research Scientist, Research Laboratory, Museum of Fine Arts, Boston.

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NEWMAN: Analysis of Red Paint

Fig. i. Fourier transform infrared absorption Kao spectra of two red paint samples from the Qtz 1

sarcophagus exterior. Peaks marked "Kao" are due to kaolinite, those marked "Qtz" to quartz, both of which are components of the red pigment. Peaks due to the paint binder are also marked. Qtz

Binder

Kao Binder - XKao

Kao

Kao Binder Qtz 44 ~~~~~~~~~~~~~~~~Binder

Kao I I I 'I I T

4000 3500 3000 2500 2000 1500 1000 600.0

WAVENUMBERS

Fig. 2. Portion of total ion chromatogram Abundance from hydrolyzed sample of red paint from a 40000 recessed area of the design on the sarcoph- Glucose agus exterior. Simple sugars, analyzed as 35000 Xylose oxime-trimethylsilyl derivatives, are labeled (most give rise to two separate peaks, as indi- 300000 cated).

25000 Arabinose

20000 GaadseGal+Glu Fucose

15000- Rhamnose Rh

10000 F

500

Time - 11.50 12.00 12.50 13.00 13.50 14.00 14.50 15.00 15.50

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JOURNAL of the Museum of Fine Arts, Boston VOL. 5, I993

Abundance Palmitate Fig. 3. Portions of total ion chromatogram 60000- / from methylated methylene chloride extract

i of a sample of fill from an altered inscription. 50000 Upper trace shows major peaks, all due to

fatty acids as indicated. Lower trace is an ex 40000- panded portion of the chromatogram, show

ing some of the less abundant compounds 30000 Stearate detected, which mainly consist of straight 20000 A l lIr| chain hydrocarbons (labeled "H," preceded 20000

- Myristate C-15 acid C-17 acid by number of carbon atoms) and fatty acids

(labeled "A," again preceded by number of 10000 4, carbon atoms).

0 I ,,, ., . , I' Time 9.60

. 0.0. 0 11.00 12.00 13.00 14.00 15.00 16.00 17.00

Abundance 1 8A

35000 22A24

30000

2500027 29

20000 19A 2A 23AH25

15000 - 24H

10000

5000

23H 0 ' 'Il. . . . Il. . . . . ..l lIl l.

Time . 15.00 16.00 17.00 18.00 19.00 20.00 21.00 22.00 23.00

of the same techniques used with the red paint. The sample is mostly organic in nature, and contains little or no inorganic filler (a very small amount of calcium carbonate was detected). The principal compounds detected by GC/MS were fatty acids (fig. 3, top). These are present as free fatty acids in the sample, rather than in the form of triglycerides (the form in which they occur in vegetable oils).8 The source of these fatty acids may be an animal source, given the relative abundance of

myristic acid. Among the minor peaks in the chromatogram is a series due to hy

drocarbons (fig. 3, bottom); the source of these is not clear, but does not appear to a plant wax or beeswax, nor does the pattern resemble that of the hydrocarbons found in bitumen or asphaltum. GC/MS analysis detected traces of two compounds indicative of mastic resin, a type of resin that would have been available in ancient Egypt.9 No sugars were detected by GC/MS in a different portion of the sample, so no gum is apparently present. The FTIR spectrum suggested that a protein-con taining material, such as animal glue, could also be present. Thus the fill was made from a mixture of materials, which included mastic resin and a fatty substance, perhaps animal fat.

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NEWMAN: Analysis of Red Paint

Notes

i. The elemental compositions of small por tions of the samples were analyzed by qual itative energy-dispersive X-ray fluorescence

in a Cameca MBX microprobe (Dept. of Earth

and Planetary Sciences, Harvard University).

2. Samples were pressed in a diamond anvil

cell and analyzed on a Nicolet 5 ioP FT-IR

spectrometer with an attached Nic-Plan in

frared microscope at a resolution of 8

wavenumbers; 300 scans were co-added.

3. Samples were hydrolyzed and derivatized

following the procedure described by D.

Erhardt, W. Hopwood, M. Baker, and D. von

Endt ("A Systematic Approach to the Instru

mental Analysis of Natural Finishes and

Binding Media," American Institute for Con

servation Preprints of Papers Presented at

the Sixteenth Annual Meeting, New Or

leans, Louisiana, June 1-5,1988 [Washing

ton, D.C., 1988], pp. 67-84), except derivati

zation was carried out with 30 microliters of

a lab-prepared oxime reagent (8.5 mg hydro

xylamine hydrochloride/ml in pyridine) and

10 microliters of trimethylsilylimidazole.

Analyses were carried out on a Hewlett Pack

ard 5890 capillary gas Chromatograph with

an HP 5 971A mass selective detector. Split

sampling was utilized, with a non-polar col

umn. The mass spectrometer was operated in selected ion monitoring mode, using a

program that included the five major ions of

each of eight common simple sugars. Iden

tifications were made on the basis of renten

tion time and mass spectra with reference to

simple sugar and gum standards prepared and analyzed by the same procedures.

4. A. Lucas and J. R. Harris, Ancient Egyp tian Materials and Industries (London, 1962,

1989 reprint), pp. 5-6; and Catherine Vieil

lescazes and Daniel Lefur, "Identification du

liant dans la peinture murale ?gyptienne

(temple de Karnak), Bulletin del? Soci?t?

d'Egyptologie Gen?ve 15 (1991), pp. 95-100.

5. See, for example, J. Twilley, "The Analysis of Ex?date Plant Gums and Their Artistic

Applications: an Interim Report," in Ar

chaeological Chemistry III, ACS Advances

in Chemistry Series, No. 205 (Washington,

D.C., 1984), pp. 357-394

6. See preceding article, p. 37.

7. Ibid., p. 49.

8. A crushed sample was saponified and ex

tracted following a procedure described by D. Erhardt et al. (note 3). Methylation was

carried out with 10 microliters of dimethyl formamide dimethyl acetal. GC/MS analysis

was carried out both with the mass spec trometer in scan mode (50-500 amu) and

selected ion monitoring mode, utilizing a

program that includes characteristic ions for

fatty acids, wax hydrocarbons, hopanes of

asphaltum and bitumen, and some of the

compounds found in pine and mastic resins.

A second portion of the sample was ex

tracted by heating in m?thyl?ne chloride and

then methylated before analysis by GC/MS.

The profiles of fatty acids in the saponified

sample and m?thyl?ne chloride solution

were essentially identical, indicating that

the fatty acids are not present in the form of

esters (as in triglyc?rides), which the FTIR

spectrum also indicated.

9. The compounds, detected by selected ion

monitoring in the methylated m?thyl?ne chloride extract, were methyl moronate (base

peak, m/z 189; molecular ion, m/z 468) and

methyl oleanonate (base peak, m/z 203; molecular ion, m/z 468). For a discussion of

the source(s) of this resin in antiquity, see J. Mills and R. White, "The Identity of the Res

ins from the Late Bronze Age Shipwreck at

Ulu Burun (Kas)," Archaeometry 31 (1989),

pp. 37-44

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