Green Fluorescence from the Hair of Lindow Man
Smith, Gerald J., Antiquity
'Lindow Man II' was discovered in a peat bog in Cheshire, England and his well preserved body has been carbon-dated at |approximately~ 2000 years BP (Stead et al. 1986). Bright green fluorescence has been observed from the hair of Lindow Man II and also from the animal fur arm-band he was wearing (Priston 1986). Trace elemental analysis of skin from Lindow Man III recovered from the same peat bog as that in which Lindow Man II was found revealed the presence of very high levels of copper (Pyatt et al. 1991). This observation, together with contemporary Roman records of Celtic customs, prompted Pyatt et al. (1991) to propose that the copper found in the skin of Lindow Man III was associated with pigments used by the Celts to paint their bodies. Further, it was suggested that the copper in such pigments may have been responsible for the green fluorescence observed from the fur arm-band of Lindow Man II. However, X-ray energy dispersive analysis of the elements contained in the hair of Lindow Man II shows no signs of copper (Connelly et al. 1986), and despite this the hair exhibits green fluorescence, which therefore must originate from some other species. From the work reported here, it is concluded that the green fluorescence observed from the hair of Lindow Man II probably originates from species derived from the hair keratin by an anaerobic, chemical reaction with acid present in the peat bog.
Fluorescence is the emission of light which follows and results from absorption of radiation by some molecules. The intensity of fluorescence depends on the amount of light absorbed by the fluorescing molecule. This in turn depends on the wavelength of the light in a way which is characteristic of the molecule. Fluorescence is always at somewhat longer wavelengths than the light which is absorbed, and thereby excites the fluorescence. The spectrum of the fluorescence is characteristic of the molecule from which it originates. Because of this and its dependence on the wavelength of the exciting light, fluorescence provides a useful, non-destructive analytical probe for some materials. For example, fluorescence spectroscopy has already helped to identify fluorescent component species in wool and hair including various protein degradation products (Leaver 1978; Smith & Melhuish 1985; Collins et al. 1988).
Animal fibres such as fur, hair and wool are largely composed of the protein, keratin. Indeed, in scoured wool the fibre is almost entirely protein or protein degradation products. Proteins are composed of a variety of amino acids. As such, the species responsible for the fluorescence observed from keratin are most likely to be the aromatic amino acids, viz. tryptophan, tyrosine and phenylalanine or their degradation products. Tryptophan is responsible for the fluorescence from keratin excited at short wavelengths (|is less than~300 nanometre). The spectrum of this fluorescence peaks at a wavelength of 340 nm and extends to about 450 nm (Smith et al. 1980). In addition to the fluorescence from tryptophan, Smith and Melhuish (1985) reported observing blue fluorescence when keratin is exposed to light at wavelengths between 320 nm and 400 nm and green fluorescence when excited in the region of 450 nm. Collins et al. (1988) have also observed fluorescence from wool in the visible region of the spectrum and noted that the green fluorescence is most intense at the weathered tip region of the fibre. While the blue fluorescence could originate from oxidation products of tryptophan and tyrosine (Smith & Melhuish 1985; Collins et al. 1988), these materials do not produce strong green fluorescence.
In the absence of oxygen, proteinaceous materials have been found to undergo chemical reactions with acid to produce chemicals known as beta-carbolines (Tschesche et al. 1958; Dillon et al. 1976; Dillon 1981). Some members of the beta-carboline chemical family exhibit blue fluorescence while other beta-carbolines display green/yellow fluorescence (Dillon et al. …