Investigations of the physical and chemical structure of archaeological fibresArchaeological fibres can be defined as natural fibres that belong to different time periods, which found in cemeteries or excavation sites. The preservation conditions cause degradation, mineralisation and sometimes a complete deterioration of these fibres, because the chemical and physical structure of the fibres changed over time in response to the specific burial environments. The ancient fibres from different archaeological sites were analysed by several non destructive analytical techniques such as optical Microscopy, Environmental Scanning Electron Microscopy, Attenuated Total Reflectance FTIR and Wide Angle X-Ray Scattering Analysis as well as destructive analytical techniques such as Scanning Electron Microscopy, Transmission Fourier Transform Infrared Spectroscopy, Energy Dispersive X-Ray Spectroscopy and Differential Scanning Calorimetry. These analytical techniques showed that keratin fibres from a central European climate have a larger damage at the fibre surface compared with frozen conditions. While bog conditions were the best in preserving the surface. FTIR analysis provides information about cystine oxidation changes in keratin fibres. For all ancient keratin fibres showed a silica peak at 1030 cm-1 which affected the symmetric cysteic acid peak at 1040 cm-1. For this reason the asymmetrical cysteic acid peak 1175 cm-1 was used for identification of cystine oxidation changes. Transmission FTIR gives a better view of the overall chemical changes in both cortex and cuticle compared to ATR analysis. All ancient wools and highly medullated Iceman deer hairs showed the highest concentration of cysteic acid compared with human hair and goat hair. Also it was shown that warm conditions have bigger effect on both the degree of oxidation of cystine and the ions uptake from the environment. The modulated DSC analysis gives a better view on the degree of degradation of hair proteins compared to WAXS analysis. To get a reliable result it is important to correct the DSC data according to the protein content of the fibre.

Human hair profiling is an integral part of a forensic investigation but it is one of the most technically difficult subjects in forensic science. This thesis describes the research and development of a novel approach for the rapid identification of unknown human and other related keratin fibres found at a crime scene. The work presented here is developed systematically and considers sample collection, sample preparation, analysis and interpretation of spectral data for the profiling of hair fibres encountered in criminal cases. Spectral comparison of fibres was facilitated with the use of chemometrics methods such as PCA, SIMCA and Fuzzy Clustering, and the less common approach of multi-criteria decision making methodology (MCDM). The aim of the thesis was to investigate the potential of some vibrational spectroscopy techniques for matching and discrimination of single keratin hair fibres in the context of forensic evidence. The first objective (chapter 3) of the thesis was to evaluate the use of Raman and FT-IR micro-spectroscopy techniques for the forensic sampling of hair fibres and to propose the preferred technique for future forensic hair comparisons. The selection of the preferred technique was based on criteria such as spectral quality, ease of use, rapid analysis and universal application to different hair samples. FT-IR micro-spectroscopy was found to be the most appropriate technique for hair analysis because it enabled the rapid collection of spectra from a wide variety of hair fibres. Raman micro-spectroscopy, on the other hand, was hindered with fluorescence problems and did not allow the collection of spectra from pigmented fibres. This objective has therefore shown that FT-IR micro-spectroscopy is the preferable spectroscopic technique for forensic analysis of hair fibres, whilst Raman spectroscopy is the least preferred. The second objective (chapter 3) was to investigate, through a series of experiments, the effect of chemical treatment on the micro-environment of human hair fibres. The effect of bleaching agents on the hair fibres was studied with some detail at different treatment times and the results indicate a significant change in the chemical environment of the secondary structure of the hair fibre along with changes in the C-C backbone structure. One of the most important outcomes of this research was the behaviour of the fÑ-helix during chemical treatment. The hydrogen bonding in the fÑ-helix provides for the stable structure of the fibre and therefore any disruption to the fÑ-helix will inevitably damage the molecular structure of the fibre. The results highlighted the behaviour of the fÑ-helix, which undergoes a significant decrease in content during oxidation, and is partly converted to a random-coil structure, whilst the fÒ-sheet component of the secondary structure remains unaffected. The reported investigations show that the combination of FT-IR and Raman micro-spectroscopy can provide an insight and understanding into the complex chemical properties and reactions within a treated hair fibre. Importantly, this work demonstrates that with the aid of chemometrics, it is possible to investigate simultaneously FT-IR and Raman micro-spectroscopic information from oxidised hair fibres collected from one subject and treated at different times. The discrimination and matching of hair fibres on the basis of treatment has potential forensic applications. The third objective (chapter 4) attempted to expand the forensic application of FT-IR micro-spectroscopy to other keratin fibres. Animal fibres are commonly encountered in crime scenes and it thus becomes important to establish the origin of those fibres. The aim of this work was to establish the forensic applications of FT-IR micro-spectroscopy to animal fibres and to investigate any fundamental molecular differences between these fibres. The results established a discrimination between fibres consisting predominantly of fÑ-helix and those containing mainly a fÒ-sheet structure. More importantly, it was demonstrated through curve-fitting and chemometrics, that each keratin fibre contains a characteristic secondary structure arrangement. The work presented here is the first detailed FT-IR micro-spectroscopic study, utilising chemometrics as well as MCDM methods, for a wide range of keratin fibres, which are commonly, found as forensic evidence. Furthermore, it was demonstrated with the aid of the rank ordering MCDM methods PROMETHEE and GAIA, that it is possible to rank and discriminate keratin fibres according to their molecular characteristics obtained from direct measurements together with information sourced from the literature. The final objective (chapter 5) of the thesis was to propose an alternative method for the discrimination and matching of single scalp human hair fibres through the use of FT-IR micro-spectroscopy and chemometrics. The work successfully demonstrated, through a number of case scenarios, the application of the technique for the identification of variables such as gender and race for an unknown single hair fibre. In addition, it was also illustrated that known hair fibres (from the suspect or victim) can be readily matched to the unknown hair fibres found at the crime scene. This is the first time that a substantial, systematic FT-IR study of forensic hair identification has been presented. The research has shown that it is possible to model and correlate individual¡¦s characteristics with hair properties at molecular level with the use of chemometrics methods. A number of different, important forensic variables of immediate use to police in a crime scene investigation such as gender, race, treatment, black and white hair fibres were investigated. Blind samples were successfully applied both to validate available experimental data and extend the current database of experimental determinations. Protocols were posed for the application of this methodology in the future. The proposed FT-IR methodology presented in this thesis has provided an alternative approach to the characterisation of single scalp human hair fibres. The technique enables the rapid collection of spectra, followed by the objective analytical capabilities of chemometrics to successfully discriminate animal fibres, human hair fibres from different sources, treated from untreated hair fibres, as well as black and white hair fibres, on the basis of their molecular structure. The results can be readily produced and explained in the courts of law. Although the proposed relatively fast FT-IR technique is not aimed at displacing the two slower existing methods of hair analysis, namely comparative optical microscopy and DNA analysis, it has given a new dimension to the characterisation of hair fibres at a molecular level, providing a powerful tool for forensic investigations.