• A Comparative Study on the Physicochemical Parameters and Trace Elements in Raw Milk Samples Collected from Misurata- Libya

      Elbagerma, Mohamed A.; Edwards, Howell G.M.; Alajtal, Adel I. (2014)
      This research work was carried out to compare the physicochemical parameters of milk samples from four different animal species namely cow, goat, camel and sheep. Milk samples were collected from different areas of Misurata, Libya and analyzed for the key physiochemical parameters, pH, titratable acidity, total solids, ash, fat, protein and lactose. Furthermore in this study the concentrations of Zinc (Zn), Cadmium (Cd), Chromium (Cr), Magnesium (Mg), Manganese (Mn), Potassium (K), Calcium (Ca) Copper (Cu), Iron (Fe) and Lead (Pb) in similar commercial milk specimens from the same area were determined using microwave plasma- atomic emission spectrometry In fresh cow’s milk, the mean concentrations of Pb, Cd, Cr, Cu, Fe, Zn, Mg, Mn, Ca and K were 0.13± 0.19 (mg/l), 0.004± 0.001 (mg/l), 0.04± 0.01 (mg/l), 0.17± 0.11 (mg/l), 0.72± 0.02 (mg/l), 1.98± 0.04 (mg/l), 214.00± 0.20 (mg/l), 0.080± 0.05 (mg/l), 423.0± 3.5 (mg/l) and 427.0± 2.5 (mg/l), respectively. While the mean concentration of Pb, Cd, Cr, Cu, Fe, Zn, Mg, Mn, Ca and K, in the goat’s milk were 0.761 ± 0.78 (mg/l), 0.085 ± 0.02 (mg/l), 1.253 ± 0.18 (mg/l), 0.400± 0.08 (mg/l), 1.23± 0.21 (mg/l), 3.110± 0.15 (mg/l), 140.0± 0.31 (mg/l), 0.097± 0.07 (mg/l), 473± 5.12 (mg/l) and 510± 6.05 (mg/l), respectively. The concentration of Pb, Cd, Cr, Cu, Fe, Zn, Mg, Mn, Ca and K, in the camel’s milk were 0.025 ± 0.019 (mg/l), 0.091± 0.05 (mg/l), 0.069± 0.07 (mg/l), 0.080 ± 0.05 (mg/l), 1.680 ± 0.43 (mg/l), 5.380 ± 1.17 (mg/l), 120.0 ± 0.11 (mg/l), 0.094 ± 0.04 (mg/l), 520.0 ± 0.32 (mg/l) and 571.0± 0.81 (mg/l), respectively. The concentration of Pb, Cd, Cr, Cu, Fe, Zn, Mg, Mn, Ca and K, in the sheep’s milk were 0.062± 0.03, 0.106± 0.11, 0.040± 0.01, 0.201± 0.10, 0.880± 0.31, 5.350± 0.50, 180± 1.20, 0.072± 0.01, 478± 3.10, and 593.96± 1.87, respectively.
    • An analytical Raman spectroscopic study of an important english oil painting of the 18th Century

      Edwards, Howell G.M.; Vandenabeele, P.; Jehlička, J.; Benoy, T.J. (2014-01)
      An opportunity was afforded to analyse pigment specimens from an unrestored oil painting in the style of the English School of the mid-18th Century prior to conservation being undertaken. Raman spectroscopy was adopted to characterise the pigments and indicated the presence of a novel red pigment which was assigned to the complex chromium mineral, hemihedrite, in addition to other interesting materials found in combination. This is the first recorded identification of hemihedrite spectral signals in an art context in a range of mineral pigments that are otherwise typical of this period and some hypotheses are presented to explain its presence based on its occurrence with associated mineral pigments. It is suggested that the presence of powdered glass identified in certain areas of the painting enhanced the reflectivity of the pigment matrix.
    • Analysis of yellow "fat" deposits on Inuit boots

      Edwards, Howell G.M.; Stern, Ben; Burgio, L.; Kite, M. (2009)
      Irregular residues of a yellow deposit that was assumed to be seal fat used for waterproofing were observed in the creases of the outer surface of a pair of Inuit boots from Arctic Canada. A sample of this deposit detached from one of these areas on these boots was examined initially by FT-Raman microscopy, from which interesting and rather surprising results demanded further analysis using FT-IR and GC-MS. The non-destructive Raman spectroscopic analysis yielded spectra which indicated the presence of a tree resin from the Pinaceae sp. The Raman spectra were also characteristic of a well-preserved keratotic protein and indicative of adherent skin. Subsequent FT-IR spectroscopic analysis supported the attribution of a Pinaceae resin to the yellow deposit. GC-MS analysis of the same deposits identified the presence of pimaric, sandaracopimaric, dehydroabietic and abietic acids, all indicative of an aged Pinaceae resin. These results confirmed that the Inuit people had access to tree resins which they probably used as a waterproofing agent.
    • Analytical Raman spectroscopy in a forensic art context: the non-destructive discrimination of genuine and fake lapis lazuli

      Ali, Esam M.A.; Edwards, Howell G.M. (2014)
      The differentiation between genuine and fake lapis lazuli specimens using Raman spectroscopy is assessed using laboratory and portable instrumentation operating at two longer wavelengths of excitation in the near-infrared, namely 1064 and 785 nm. In spite of the differences between the spectra excited here in the near infrared and those reported in the literature using visible excitation, it is clear that Raman spectroscopy at longer wavelengths can provide a means of differentiating between the fakes studied here and genuine lapis lazuli. The Raman spectra obtained from portable instrumentation can also achieve this result, which will be relevant for the verification of specimens which cannot be removed from collections and for the identification of genuine lapis lazuli inlays in, for example, complex jewellery and furniture. The non-destructive and non-contact character of the technique offers a special role for portable Raman spectroscopy in forensic art analysis.
    • Biomarkers and their Raman spectroscopic signatures: a spectral challenge for analytical astrobiology

      Edwards, Howell G.M.; Hutchinson, I.B.; Ingley, R.; Jehlička, J. (2014)
      The remote robotic exploration of extraterrestrial scenarios for evidence of biological colonization in 'search for life' missions using Raman spectroscopy is critically dependent on two major factors: firstly, the Raman spectral recognition of characteristic biochemical spectral signatures in the presence of mineral matrix features; and secondly, the positive unambiguous identification of molecular biomaterials which are indicative of extinct or extant life. Both of these factors are considered here: the most important criterion is the clear definition of which biochemicals truly represent biomarkers, whose presence in the planetary geological record from an analytical astrobiological standpoint will unambiguously be indicative of life as recognized from its remote instrumental interrogation. Also discussed in this paper are chemical compounds which are associated with living systems, including biominerals, which may not in themselves be definitive signatures of life processes and origins but whose presence provides an indicator of potential life-bearing matrices.
    • Calculation and Measurement of Terahertz Active Normal Modes in Crystalline PETN

      Burnett, A.; Kendrick, John; Cunningham, J.E.; Hargreaves, Michael D.; Munshi, Tasnim; Edwards, Howell G.M.; Linfield, E.H.; Davies, G.A. (2010)
      The terahertz frequency spectrum of pentaerythritol tetranitrate (PETN) is calculated using Discover[1] with the COMPASS[2] force field, CASTEP[3] and PWscf.[4] The calculations are compared to each other and to terahertz spectra (0.3-3 THz) of crystalline PETN recorded at 4 K. A number of analysis methods are used to characterise the calculated normal modes.
    • Characterization of paint and varnish on a medieval Coptic-Byzantine icon: Novel usage of dammar resin?

      Abdel-Ghani, Mona H.; Edwards, Howell G.M.; Stern, Ben; Janaway, Robert C. (Elsevier, 2009)
      A comprehensive study has been undertaken into a 13th century Coptic-Byzantine icon from the St. Mercurius Church, St. Mercurius monastery, Old Cairo, Egypt. The layered structure, pigment composition and varnish identification were revealed by means of optical and Raman microscopy and gas chromatography¿mass spectrometry (GC¿MS). The structure of the icon comprised six layers; wooden panel, canvas, white ground, two bole layers and a single paint layer. Azurite (2CuCO3·Cu(OH)2), cinnabar (mercuric (II) sulfide ¿-HgS), yellow ochre (Fe2O3·H2O), hydromagnesite Mg5(CO3)4(OH)2·4H2O and lamp black (carbon, C) are the pigments identified in the icon. The green paint area is of interest as it is applied neither with a green pigment nor with a mixture of a blue and yellow pigment. Instead, a yellow layer of dammar resin was applied on top of blue azurite to obtain the green colour. Pinaceae sp. resin mixed with drying oil was used as a protective varnish.
    • The Degradation of Human Hair Studied by FT-Raman Spectroscopy

      Edwards, Howell G.M.; Farwell, Dennis W.; Wilson, Andrew S. (1998)
    • The degradation of lignocellulosics under conditions applicable to wetlands in northern Greece

      Petrou, M.; Edwards, Howell G.M.; Janaway, Robert C.; Kavvouras, P.; Thompson, Gill B.; Wilson, Andrew S. (2008)
    • Detection of pigments of halophilic endoliths from gypsum: Raman portable instrument and European Space Agency's prototype analysis

      Culka, A.; Osterrothova, K.; Hutchinson, I.B.; Ingley, R.; McHugh, M.; Oren, A.; Edwards, Howell G.M.; Jehlička, J. (2014)
      A prototype instrument, under development at the University of Leicester, for the future European Space Agency (ESA) ExoMars mission, was used for the analysis of microbial pigments within a stratified gypsum crust from a hypersaline saltern evaporation pond at Eilat (Israel). Additionally, the same samples were analysed using a miniaturized Raman spectrometer, featuring the same 532 nm excitation. The differences in the position of the specific bands, attributed to carotenoid pigments from different coloured layers, were minor when analysed by the ESA prototype instrument; therefore, making it difficult to distinguish among the different pigments. The portable Delta Nu Advantage instrument allowed for the discrimination of microbial carotenoids from the orange/green and purple layers. The purpose of this study was to complement previous laboratory results with new data and experience with portable or handheld Raman systems, even with a dedicated prototype Raman system for the exploration of Mars. The latter is equipped with an excitation wavelength falling within the carotenoid polyene resonance region. The ESA prototype Raman instrument detected the carotenoid pigments (biomarkers) with ease, although further detailed distinctions among them were not achieved.
    • Diagnostic Raman Spectroscopy for the Forensic Detection of Biomaterials and the Preservation of Cultural Heritage

      Munshi, Tasnim; Edwards, Howell G.M. (2005)
      This paper reviews the contributions of analytical Raman spectroscopy to the non-destructive characterisation of biological materials of relevance to forensic science investigations, including the sourcing of resins and the identification of the biodegradation of art and archaeological artefacts. The advantages of Raman spectroscopy for non-destructive analysis are well-appreciated; however, the ability to record molecular information about organic and inorganic species present in a heterogeneous specimen at the same time, the insensitivity of the Raman scattering process to water and hydroxyl groups, which removes the necessity for sample desiccation, and the ease of illumination for samples of very small and very large sizes and unusual shapes are also apparent. Several examples are used to illustrate the application of Raman spectroscopic techniques to the characterisation of forensic biomaterials and for the preservation of cultural heritage through case studies in the following areas: wall-paintings and rock art, human and animal tissues and skeletal remains, fabrics, resins and ivories.
    • Exceptional preservation of a prehistoric human brain from Heslington, Yorkshire, UK

      O'Connor, Sonia A.; Ali, Esam M.A.; Al-Sabah, S.; Anwar, D.; Bergström, E.; Brown, K.A.; Buckberry, Jo; Collins, M.; Denton, J.; Dorling, K.; et al. (2011)
      Archaeological work in advance of construction at a site on the edge of York, UK, yielded human remains of prehistoric to Romano-British date. Amongst these was a mandible and cranium, the intra-cranial space of which contained shrunken but macroscopically recognizable remains of a brain. Although the distinctive surface morphology of the organ is preserved, little recognizable brain histology survives. Though rare, the survival of brain tissue in otherwise skeletalised human remains from wet burial environments is not unique. A survey of the literature shows that similar brain masses have been previously reported in diverse circumstances. We argue for a greater awareness of these brain masses and for more attention to be paid to their detection and identification in order to improve the reporting rate and to allow a more comprehensive study of this rare archaeological survival.
    • An experimental and computational study on the epimeric contribution to the infrared spectrum of budesonide

      Ali, H.R.H.; Edwards, Howell G.M.; Kendrick, John; Munshi, Tasnim; Scowen, Ian J. (2010)
      Budesonide is a mixture of 22R and 22S epimers. The epimeric content of budesonide was reported in both British and European pharmacopoeias to be within the range of 60-49/40-51 for R and S epimers, respectively. In this work, contribution of the two epimers to the overall infrared spectrum of budesonide has been investigated by quantum chemical calculations.
    • Forensic and security applications of a long-wavelength dispersive Raman system

      Ali, Esam M.A.; Edwards, Howell G.M.; Cox, R. (2015)
      A novel dispersive system operating at 1064-nm excitation and coupled with transfer electron InGaAs photocathode and electron bombardment CCD technology has been evaluated for the analysis of drugs of abuse and explosives. By employing near-IR excitation at 1064-nm excitation wavelength has resulted in a significant damping of the fluorescence emission compared to 785-nm wavelength excitation. Spectra of street samples of drugs of abuse and plastic explosives, which usually fluoresce with 785-nm excitation, are readily obtained in situ within seconds through plastic packaging and glass containers using highly innovative detector architecture based upon a transfer electron (TE) photocathode and electron bombarded gain (EB) technology that allowed the detection of NIR radiation at 1064nm without fluorescence interference. This dispersive near-IR Raman system has the potential to be an integral part in the armoury of the forensic analyst as a non-destructive tool for the in-situ analysis of drugs of abuse and explosives. Copyright (c) 2015 John Wiley & Sons, Ltd.
    • Fourier transform Raman spectroscopy: Evaluation as a non- destructive technique for studying the degradation of human hair from archaeological and forensic environments

      Wilson, Andrew S.; Edwards, Howell G.M.; Farwell, Dennis W.; Janaway, Robert C. (1999)
      Fourier transform (FT) Raman spectroscopy was evaluated as a non-destructive analytical tool for assessing the degradative state of archaeological and forensic hair samples. This work follows the successful application of FT-Raman spectroscopy to studies of both modern hair and ancient keratotic biopolymers, such as mummified skin. Fourteen samples of terminal scalp hair from 13 disparate depositional environments were analysed for evidence of structural alteration. Degradative change was evidenced by alteration to the amide I and III modes near 1651 and 1128 cm−1, respectively, and loss of definition to the (CC) skeletal backbone and the impact of environmental contaminants was noted.
    • Fourier-transform Raman spectroscopic study of a Neolithic waterlogged wood assemblage

      Petrou, M.; Edwards, Howell G.M.; Janaway, Robert C.; Thompson, Gill B.; Wilson, Andrew S. (2009)
      The use of Fourier-transform Raman spectroscopy for characterising lignocellulosics has increased significantly over the last twenty years. Here, an FT-Raman spectroscopic study of changes in the chemistry of waterlogged archaeological wood of Pinus sp. and Quercus sp. from a prehistoric assemblage recovered from northern Greece is presented. FT-Raman spectral features of biodeteriorated wood were associated with the depletion of lignin and/or carbohydrate polymers at various stages of deterioration. Spectra from the archaeological wood are presented alongside spectra of sound wood of the same taxa. A comparison of the relative changes in intensities of spectral bands associated with lignin and carbohydrates resulting from decay clearly indicated extensive deterioration of both the softwood and hardwood samples and the carbohydrates appear to be more deteriorated than the lignin. The biodeterioration of the archaeological timbers followed a pattern of initial preferential loss of carbohydrates causing significant loss of cellulose and hemicellulose, followed by the degradation of lignin.
    • FT-Raman Spectroscopic Study of Calcium-Rich and Magnesium-Rich Carbonate Minerals

      Munshi, Tasnim; Edwards, Howell G.M.; Jenlicka, J.; Jorge Villar, Susana E. (2005)
      Calcium and magnesium carbonates are important minerals found in sedimentary environments. Although sandstones are the most common rock colonized by endolith organisms, the production of calcium and magnesium carbonates is important in survival strategies of organisms and as a source for the removal of oxalate ions. Extremophile organisms in some situations may convert or destroy carbonates of calcium and magnesium, which gives important information about the conditions under which these organisms can survive. The identification on the surface of Mars of 'White Rock' formations, in Juventae Chasma or Sabaea Terra, as possibly carbonate rocks makes the study of these minerals a prerequisite of remote Martian exploration. Here, we show the protocol for the identification by Raman spectroscopy of different calcium and magnesium carbonates and we present a database of relevance in the search for life, extinct or extant, on Mars; this will be useful for the assessment of data obtained from remote, miniaturized Raman spectrometers now proposed for Mars exploration.
    • FT-Raman spectroscopy of the Candelaria and Pyxine lichen species: A new molecular structural study

      Fernandes, R.F.; Ferreira, G.R.; Spielmann, A.A.; Edwards, Howell G.M.; de Oliveira, L.F.C. (2015-12)
      In this work the chemistry of the lichens Candelaria fibrosa and Pyxine coccifera have been investigated for the first time using FT-Raman spectroscopy with the help of quantum mechanical DFT calculations to support spectral band assignments. The non-destructive spectral vibrational analysis provided evidence for the presence of pulvinic acid derivatives and conjugated polyenes, which probably belong to a carotenoid with characteristic signatures at ca. 1003, 1158 and 1525 cm−1 assigned respectively to δ(C–CH3), ν(C–C) and ν(Cdouble bond; length as m-dashC) modes. The identification of features arising from chiodectonic acid in the Pyxine species and calycin and pulvinic dilactone pigments in C. fibrosa were assisted by the quantum mechanical DFT calculations. Raman spectroscopy can provide important spectroscopic data for the identification of the biomarker spectral signatures nondestructively for these lichen pigments without the need for chemical extraction processes.
    • Gristhorpe Man: a Raman spectroscopic study of 'mistletoe berries' in a Bronze Age log coffin burial

      Edwards, Howell G.M.; Montgomery, Janet; Melton, Nigel D.; Hargreaves, Michael D.; Wilson, Andrew S.; Carter, E.A. (2010-02-10)
      In 1834 in a tumulus at Gristhorpe, North Yorkshire, UK, an intact coffin fashioned from the hollowed-out trunk of an oak tree was found to contain a well-preserved skeleton stained black from the oak tannins, wrapped in an animal skin and buried with a range of grave artefacts, including a bronze dagger, flints and a bark vessel. The remains were deposited in the Rotunda Museum at Scarborough, where closure due to refurbishment in 2005–2008 provided an opportunity for the scientific investigation of the skeletal remains and artefacts using a wide range of techniques. Dendrochronological and radiocarbon dating has established the age of the skeleton as 2140–1940 BC at 95% confidence, in the Early Bronze Age. As part of this project, Raman spectra of several mysterious small spherical objects discovered in the coffin underneath the skeleton and initially believed to be ‘mistletoe berries’ associated with ancient burial customs have been recorded non-destructively. The interpretation of the Raman spectral data, microscopic analysis and comparison with modern specimens has led to the conclusion that the small spheres are phosphatic urinary stones, which reflect the archaeological dietary evidence and stable isotope analysis of bone collagen of Gristhorpe Man.