• Gristhorpe man: an early bronze age log-coffin burial scientifically defined

      Melton, Nigel D.; Montgomery, Janet; Knüsel, Christopher J.; Batt, Catherine M.; Needham, S.; Parker Pearson, M.; Sheridan, A.; Heron, Carl P.; Horsley, T.; Schmidt, Armin R.; et al. (2010)
      A log-coffin excavated in the early nineteenth century proved to be well enough preserved in the early twenty-first century for the full armoury of modern scientific investigation to give its occupants and contents new identity, new origins and a new date. In many ways the interpretation is much the same as before: a local big man buried looking out to sea. Modern analytical techniques can create a person more real, more human and more securely anchored in history. This research team shows how.
    • Historical Pigments: a survey of analytical chemical archaeometric usage and terminology for forensic art analysis

      Edwards, Howell G.M. (2015)
      The adoption of mineral pigments for artistic expression can be traced back to the paintings of the Magdalenian and Cro-Magnon cultures of about 25 000 years BCE, wherein a limited range of oxides such as pyrolusite, goethite, and hematite were utilized along with the first synthetic pigment, carbon, to decorate cave dwellings with surprisingly lifelike images. The growth of chemistry created a new palette of colors, culminating in the preparation of organic dyes and pigments in the mid-nineteenth century. The historical usage of mineral pigments largely based on metal sulfides, oxides, carbonates, sulfates, and nitrates followed by early natural organic extracts from botanical and insect species such as dragon's blood, indigo, gamboge, and cochineal that were later partially superseded by a wide range of synthetic azo dyes is described, where possible alongside their accepted date of first adoption in artworks; while this is relatively easy to define in the case of synthetic materials, it is rather more conjectural for the establishment of an historical timeline for naturally occurring minerals. The characterization of pigments using analytical chemical techniques applied to artworks and artifacts can therefore be used to identify an out-of-context material in an otherwise perfectly acceptable work of art sufficient to render an appellation of ‘fake’ being applied to the object. However, unrecorded later restoration whereby an artwork has been retouched using modern, more stable pigments replacing their more fugitive analogues can cause problems in this respect. In this article, the mineral pigments used are tabulated along with their synthetic counterparts that frequently have precise dates for their appearance in the chemical literature giving rise to a contextual and chronological aspect to analytical science applied to artworks – a forensic art theme. Much work has recently been discussed in the analytical discrimination between natural mineral pigments used historically and their more recent synthetic counterparts: here, terminological differences are critically important and often lacking – hence, the confused usage of terms such as cinnabar and vermilion, lapis lazuli and ultramarine, which are to be found in artists' manuals and contemporary texts.
    • Hydrothermal modification of the Sikhote-Alin iron meteorite under low pH geothermal environments. A plausibly prebiotic route to activated phosphorus on the early Earth

      Bryant, D.E.; Greenfield, D.; Walshaw, R.D.; Johnson, B.R.G.; Herschy, B.; Smith, C.; Pasek, M.A.; Telford, Richard; Scowen, Ian J.; Munshi, Tasnim; et al. (2013)
      The Sikhote-Alin (SA) meteorite is an example of a type IIAB octahedrite iron meteorite with ca. 0.5 wt% phosphorus (P) content principally in the form of the siderophilic mineral schreibersite (Fe,Ni)(3)P. Meteoritic in-fall to the early Earth would have added significantly to the inventory of such siderophilic P. Subsequent anaerobic corrosion in the presence of a suitable electrolyte would produce P in a form different to that normally found within endogenous geochemistry which could then be released into the environment. One environment of specific interest includes the low pH conditions found in fumaroles or volcanically heated geothermal waters in which anodic oxidation of Fe metal to ferrous (Fe2+) and ferric (Fe3+) would be coupled with cathodic reduction of a suitable electron acceptor. In the absence of aerobic dioxygen (E-o = +1.229 V), the proton would provide an effective final electron acceptor, being converted to dihydrogen gas (E-o = 0 V). Here we explore the hydrothermal modification of sectioned samples of the Sikhote-Alin meteorite in which siderophilic P-phases are exposed. We report on both, (i) simulated volcanic conditions using low pH distilled water and (ii) geothermally heated sub-glacial fluids from the northern Kverkfjoll volcanic region of the Icelandic Vatnajokull glacier. A combination of X-ray photoelectron spectroscopy (XPS) and electrochemical measurements using the scanning Kelvin probe (SKP) method reveals that schreibersite inclusions are significantly less susceptible to anodic oxidation than their surrounding Fe-Ni matrix, being some 550 mV nobler than matrix material. This results in preferential corrosion of the matrix at the matrix-inclusion boundary as confirmed using topological mapping via infinite focus microscopy and chemical mapping through Raman spectroscopy. The significance of these observations from a chemical perspective is that electrochemically noble inclusions such as schreibersite are likely to have been released into the geological environment through an undermining corrosion of the surrounding matrix, thus affording localised sources of available water-soluble, chemically reactive P in the form of H-phosphite [H2PO3-, Pi(III) as determined by P-31 NMR spectroscopy]. This compound has been shown to have considerable prebiotic chemical potential as a source of condensed P-oxyacids. Here we demonstrate that Pi(III) resulting from the hydrothermal modification of Sikhote- Alin by sub-glacial geothermal fluids can be readily dehydrated into the condensed P-oxyacid pyrophosphite [H2P2O52-, PPi(III)] by dry-heating under mild (85 degrees C) conditions. The potential significance of this latter condensed P-compound for prebiotic chemistry is discussed in the light of its modified chemical properties compared to pyrophosphate [H2P2O72-, PPi(V)].
    • Impact shocked rocks as protective habitats on an anoxic early Earth

      Bryce, C.C.; Horneck, G.; Rabbow, E.; Edwards, Howell G.M.; Cockell, C.S. (2015)
      On Earth, microorganisms living under intense ultraviolet (UV) radiation stress can adopt endolithic lifestyles, growing within cracks and pore spaces in rocks. Intense UV irradiation encountered by microbes leads to death and significant damage to biomolecules, which also severely diminishes the likelihood of detecting signatures of life. Here we show that porous rocks shocked by asteroid or comet impacts provide protection for phototrophs and their biomolecules during 22 months of UV radiation exposure outside the International Space Station. The UV spectrum used approximated the high-UV flux on the surface of planets lacking ozone shields such as the early Earth. These data provide a demonstration that endolithic habitats can provide a refugium from the worst-case UV radiation environments on young planets and an empirical refutation of the idea that early intense UV radiation fluxes would have prevented phototrophs without the ability to form microbial mats or produce UV protective pigments from colonizing the surface of early landmasses.
    • Life in the Sabkha: Raman Spectroscopy of Halotrophic Extremophiles of Relevance to Planetary Exploration

      Edwards, Howell G.M.; Mohsin, M.A.; Sadhooni, F.N.; Hassan, N.K.N.; Munshi, Tasnim (2006)
      The Raman spectroscopic biosignatures of halotrophic cyanobacterial extremophiles from sabkha evaporitic saltpans are reported for the first time and ideas about the possible survival strategies in operation have been forthcoming. The biochemicals produced by the cyanobacteria which colonise the interfaces between large plates of clear selenitic gypsum, halite, and dolomitized calcium carbonates in the centre of the salt pans are identifiably different from those which are produced by benthic cyanobacterial mats colonising the surface of the salt pan edges in the intertidal zone. The prediction that similar geological formations would have been present on early Mars and which could now be underlying the highly peroxidised regolith on the surface of the planet has been confirmed by recent satellite observations from Mars orbit and by localised traverses by robotic surface rovers. The successful adoption of miniaturised Raman spectroscopic instrumentation as part of a scientific package for detection of extant life or biomolecular traces of extinct life on proposed future Mars missions will depend critically on interpretation of data from terrestrial Mars analogues such as sabkhas, of which the current study is an example.
    • Miniaturized Raman instrumentation detects carotenoids in Mars-analogue rocks from the Mojave and Atacama deserts

      Vítek, P.; Jehlička, J.; Edwards, Howell G.M.; Hutchinson, I.B.; Ascaso, C.; Wierzchos, J. (2014)
      This study is primarily focused on proving the potential of miniaturized Raman systems to detect any biomolecular and mineral signal in natural geobiological samples that are relevant for future application of the technique within astrobiologically aimed missions on Mars. A series of evaporites of varying composition and origin from two extremely dry deserts were studied, namely Atacama and Mojave. The samples represent both dry evaporitic deposits and recent evaporitic efflorescences from hypersaline brines. The samples comprise halite and different types of sulfates and carbonates. The samples were analysed in two different ways: (i) directly as untreated rocks and (ii) as homogenized powders. Two excitation wavelengths of miniaturized Raman spectrometers were compared: 532 and 785 nm. The potential to detect carotenoids as biomarkers on Mars compared with the potential detection of carbonaceous matter using miniaturized instrumentation is discussed.
    • Monitoring of Heavy Metal Content in Tawargah Pond in Libya

      Alajtal, Adel I.; Edwards, Howell G.M.; Elbagerma, Mohamed A. (2013)
      The current study investigated the distribution of inorganic metals in the biggest reservoir in the neighbourhood of Misurata City, Tawargah Pond. The investigation was carried out during the topical periods of dry and wet season between August 2010 and January 2011. Levels of trace metals lead (Pb), copper (Cu), iron (Fe) and zinc (Zn)) were determined in the water samples taken. An atomic absorption spectrophotometer, Model 180-30 Hitachi, was used to determine heavy metal concentrations. The instrument was calibrated and standardized with different working standards. After making sure that the instrument was properly calibrated and results of the standard measurements were in the confidence limit, the concentration of metals in each sample was measured individually. High levels of lead and iron were found in water which indicates a possible contribution from the industrial activities and air pollution.
    • Morphological biosignatures from relict fossilised sedimentary geological specimens: a Raman spectroscopic study

      Edwards, Howell G.M.; Jorge Villar, Susana E.; Pullan, D.; Hargreaves, Michael D.; Hofmann, B.A.; Westall, F. (2007)
      Morphological biosignatures (features related to life) and associated terrestrial sedimentary structures that provide possible sampling targets for the remote astrobiological exploration of planets have been analysed using Raman spectroscopic techniques. The spectral data from a suite of samples comprising crypto-chasmoendoliths, preserved microbial filaments and relict sedimentary structures comprise a preliminary database for the establishment of key Raman biosignatures. This will form the basis for the evaluation of prototype miniaturised instrumentation for the proposed ESA ExoMars mission scheduled for 2013. The Raman spectral biosignatures of carotenoids and scytonemin, organic biomolecules characteristic of the cyanobacterial colonisation of geological matrices and biogeologically modified minerals are also identifiable in the sedimentary specimen materials. The results of this study demonstrate the basis of the molecular recognition of extinct and extant exobiology that will feed into the elemental structural analyses of morphological structures provided by associated SEM, XRD and laser-induced breakdown spectroscopy (LIBS) techniques on robotic analytical landers.
    • Potential and limits of Raman spectroscopy for carotenoid detection in microorganisms: implications for astrobiology

      Jehlička, J.; Edwards, Howell G.M.; Osterrothova, K.; Novotna, J.; Nedbalova, L.; Kopecky, J.; Nemec, I.; Oren, A. (2014-12-13)
      In this paper, it is demonstrated how Raman spectroscopy can be used to detect different carotenoids as possible biomarkers in various groups of microorganisms. The question which arose from previous studies concerns the level of unambiguity of discriminating carotenoids using common Raman microspectrometers. A series of laboratory-grown microorganisms of different taxonomic affiliation was investigated, such as halophilic heterotrophic bacteria, cyanobacteria, the anoxygenic phototrophs, the non-halophilic heterotrophs as well as eukaryotes (Ochrophyta, Rhodophyta and Chlorophyta). The data presented show that Raman spectroscopy is a suitable tool to assess the presence of carotenoids of these organisms in cultures. Comparison is made with the high-performance liquid chromatography approach of analysing pigments in extracts. Direct measurements on cultures provide fast and reliable identification of the pigments. Some of the carotenoids studied are proposed as tracers for halophiles, in contrast with others which can be considered as biomarkers of other genera. The limits of application of Raman spectroscopy are discussed for a few cases where the current Raman spectroscopic approach does not allow discriminating structurally very similar carotenoids. The database reported can be used for applications in geobiology and exobiology for the detection of pigment signals in natural settings.
    • Potential for analysis of carbonaceous matter on Mars using Raman spectroscopy

      Hutchinson, I.B.; Parnell, J.; Edwards, Howell G.M.; Jehlička, J.; Marshall, C.P.; Harris, L.V.; Ingley, R. (2014)
      The ESA/Roscosmos ExoMars rover will be launched in 2018. The primary aim of the mission will be to find evidence of extinct or extant life by extracting samples from the subsurface of Mars. The rover will incorporate a drill that is capable of extracting cores from depths of up to 2 m, a Sample Preparation and Distribution System (SPDS) that will crush the core into small grains and a suite of analytical instruments. A key component of the analytical suite will be the Raman Laser Spectrometer (RLS) that will be used to probe the molecular and mineralogical composition of the samples. In this work we consider the capability of the proposed Raman spectrometer to detect reduced carbon (possibly associated with evidence for extinct life) and to identify the level of thermal alteration/maturity. The Raman analysis of 21 natural samples of shale (originating from regions exhibiting different levels of thermal maturity) is described and it is shown that reduced carbon levels as low as 0.08% can be readily detected. It is also demonstrated that the Raman spectra obtained with the instrument can be used to distinguish between samples exhibiting high and low levels of thermal maturity and that reduced carbon can be detected in samples exposed to significant levels of oxidation (as expected on the surface of Mars). (C) 2014 Published by Elsevier Ltd.
    • Raman and SEM analysis of a biocolonised hot spring travertine terrace in Svalbard, Norway

      Jorge Villar, Susana E.; Benning, L.G.; Edwards, Howell G.M.; AMASE team (2007)
      A profile across 8 layers from a fossil travertine terrace from a low temperature geothermal spring located in Svalbard, Norway has been studied using both Raman spectroscopy and SEM (Scanning Electron Microscopy) techniques to identify minerals and organic life signals. Calcite, anatase, quartz, haematite, magnetite and graphite as well as scytonemin, three different carotenoids, chlorophyll and a chlorophyll-like compound were identified as geo- and biosignatures respectively, using 785 and/or 514 nm Raman laser excitation wavelengths. No morphological biosignatures representing remnant microbial signals were detected by high-resolution imaging, although spectral analyses indicated the presence of organics. In contrast, in all layers, Raman spectra identified a series of different organic pigments indicating little to no degradation or change of the organic signatures and thus indicating the preservation of fossil biomarker compounds throughout the life time of the springs despite the lack of remnant morphological indicators. With a view towards planetary exploration we discuss the implications of the differences in Raman band intensities observed when spectra were collected with the different laser excitations. We show that these differences, as well as the different detection capability of the 785 and 514 nm laser, could lead to ambiguous compound identification. We show that the identification of bio and geosignatures, as well as fossil organic pigments, using Raman spectroscopy is possible. These results are relevant since both lasers have been considered for miniaturized Raman spectrometers for planetary exploration.
    • Raman spectroscopic analyses of preserved historical specimens of human hair attributed to Robert Stephenson and Sir Isaac Newton

      Edwards, Howell G.M.; Hassan, N.F.; Wilson, Andrew S. (2004)
      The Raman spectra of two historical specimens of human hair attributed to the engineer Robert Stephenson and scientist Sir Isaac Newton, preserved in private collections are reported. Comparisons are made with the Raman spectra of modern hair specimens and with hair from archaeological excavations. The hair spectra collected with a laser excitation of 785 nm are of a better quality than those collected using 1064 nm. The historical hair specimens are remarkably well-defined spectroscopically in terms of the amide I vibrational mode and the ν(SS), ascribed to a predominantly gauche–gauche–gauche CSSC conformation. The contrast with degraded hair specimens recovered from archaeological excavations is striking. The presence of a weak feature near 2590 cm−1 in the hair samples attributed to a ν(SH) vibration could be indicative of a reduction process operative on the CSSC cystine keratotic linkages and a possible origin of this is bacterial biodegradation identified histologically. This study demonstrates the molecular information available from non-destructive Raman spectroscopic analysis from single hair shafts or small bundles of fibres which complements information available from histological and destructive analytical techniques for rare biological specimens subjected to conservation or curation procedures in museums or private collections.
    • Raman spectroscopic analysis of human remains from a seventh century cist burial on Anglesey, UK

      Edwards, Howell G.M.; Wilson, Andrew S.; Nik Hassan, N.F.; Davidson, A.; Burnett, A. (2006-02)
      Specimens from human remains exhibiting unusual preservation excavated from a seventh century stone cist burial at Towyn y Capel in Anglesey, UK, have been analysed using Raman spectroscopy with near-infrared laser excitation at 1,064 and 785 nm. Specimens of hair and bone provided evidence for severe degradation and microbial colonisation. The deposits within the stone cist showed that some microbially mediated compounds had been formed. Analysis of crystals found at the interface between the hair and the skeletal neck vertebrae revealed a mixture of newberyite and haematite, associated with decomposition products of the hair and bone. An interesting differential degradation was noted in the specimens analysed which could be related to the air-void and the presence of plant root inclusions into the stone cist. This is the first time that Raman spectroscopy has been used in the forensic archaeological evaluation of burial remains in complex and dynamic environments.
    • Raman spectroscopic analysis of the effect of the lichenicolous fungus Xanthoriicola physciae on its lichen host

      Edwards, Howell G.M.; Seaward, Mark R.D.; Preece, T.F.; Jorge Villar, Susana E.; Hawksworth, D.L. (2016)
      Lichenicolous (lichen-dwelling) fungi have been extensively researched taxonomically over many years, and phylogenetically in recent years, but the biology of the relationship between the invading fungus and the lichen host has received limited attention, as has the effects on the chemistry of the host, being difficult to examine in situ. Raman spectroscopy is an established method for the characterization of chemicals in situ, and this technique is applied to a lichenicolous fungus here for the first time. Xanthoriicola physciae occurs in the apothecia of Xanthoria parietina, producing conidia at the hymenium surface. Raman spectroscopy of apothecial sections revealed that parietin and carotenoids were destroyed in infected apothecia. Those compounds protect healthy tissues of the lichen from extreme insolation and their removal may contribute to the deterioration of the apothecia. Scytonemin was also detected, but was most probably derived from associated cyanobacteria. This work shows that Raman spectroscopy has potential for investigating changes in the chemistry of a lichen by an invading lichenicolous fungus.
    • Raman spectroscopic and structural investigation of 1,4-diphenylbuta-1,3-diene and selected monomethyl and dimethyl substituted homologues

      Bowen, Richard D.; Edwards, Howell G.M.; Waller, Zoe A.E. (2006)
      The Raman and mass spectra of 1,4-diphenylbuta-1,3-diene and several of its monomethyl and dimethyl homologues are reported and discussed, with a view to developing a spectroscopic protocol for detecting the presence and position of a methyl group in these compounds. Raman spectroscopy and mass spectrometry are shown to provide complementary information, by which the four available monomethyl homologues may be readily distinguished from each other and 1,4-diphenylbuta-1,3-diene itself. The utility of these 1,4-diarylbutadienes as model compounds for carotenoids and related materials, which may serve as indicators of extinct or extant extraterrestrial life, is considered.
    • Raman Spectroscopic and structural studies of indigo and its four 6,6'-Dihalogeno analogues

      Bowen, Richard D.; Edwards, Howell G.M.; Jorge Villar, Susana E.; Karapanayiotis, Thanassis (2004)
      The Raman and electron impact mass spectra of synthetic indigo and its four 6,6'-dihalogeno analogues are reported and discussed. The influence of varying the halogen on these Raman spectra is considered. Particular emphasis is laid on distinguishing indigo from 6,6'-dibromoindigo and differentiating between the dihalogenocompounds, so as to develop protocols for determining whether artefacts are coloured with dyes of marine or terrestrial origin and whether such artefacts are dyed with genuine Tyrian Purple or with dihalogenoindigo substitutes that do not contain bromine. The value of even low resolution electron impact mass spectrometry in a forensic context as a means of identifying authentic 6,6'-dibromoindigo and distinguishing it from its dihalogenoanalogues is emphasised.
    • Raman spectroscopic characterisations and analytical discrimination between caffeine and demethylated analogues of pharmaceutical relevance

      Edwards, Howell G.M.; Munshi, Tasnim; Anstis, M. (2005)
      The FT Raman spectrum of caffeine was analysed along with that of its demethylated analogues, theobromine and theophylline. The similar but not identical structures of these three compounds allowed a more detailed assignment of the Raman bands. Noticeable differences in the Raman spectra of these compounds were apparent and key marker bands have been identified for the spectroscopic identification of these three compounds.
    • Raman spectroscopic fingerprints of scytonemin-imine: density functional theory calculations of a novel potential biomarker

      Varnali, T.; Edwards, Howell G.M. (2014-12-13)
      Scytonemin-imine, a novel derivative of scytonemin, has been isolated and identified very recently and proposed to serve as a photoprotective biomarker for certain bacteria growing under intense photon flux density. This study predicts theoretically the Raman spectrum of scytonemin-imine by density functional theory calculations and provides comparison of major bands to those of scytonemin, the parent compound for which both the experimentally characterized and theoretically predicted spectra exist in the literature. It is proposed to be an addendum to the collection of our previous work on scytonamin and its derivatives to facilitate recognition of the diagnostic Raman spectral signatures for scytonemin-imine.
    • Raman spectroscopic identification of scytonemin and its derivatives as key biomarkers in stressed environments

      Varnali, T.; Edwards, Howell G.M. (2014-12-13)
      Raman spectroscopy has been identified as an important first-pass analytical technique for deployment on planetary surfaces as part of a suite of instrumentation in projected remote space exploration missions to detect extant or extinct extraterrestrial life signatures. Aside from the demonstrable advantages of a non-destructive sampling procedure and an ability to record simultaneously the molecular signatures of biological, geobiological and geological components in admixture in the geological record, the interrogation and subsequent interpretation of spectroscopic data from these experiments will be critically dependent upon the recognition of key biomolecular markers indicative of life existing or having once existed in extreme habitats. A comparison made with the characteristic Raman spectral wavenumbers obtained from standards is not acceptable because of shifts that can occur in the presence of other biomolecules and their host mineral matrices. In this paper, we identify the major sources of difficulty experienced in the interpretation of spectroscopic data centring on a key family of biomarker molecules, namely scytonemin and its derivatives; the parent scytonemin has been characterized spectroscopically in cyanobacterial colonies inhabiting some of the most extreme terrestrial environments and, with the support of theoretical calculations, spectra have been predicted for the characterization of several of its derivatives which could occur in novel extraterrestrial environments. This work will form the foundation for the identification of novel biomarkers and for their Raman spectroscopic discrimination, an essential step in the interpretation of potentially complex and hitherto unknown biological radiation protectants based on the scytoneman and scytonin molecular skeletons which may exist in niche geological scenarios in the surface and subsurface of planets and their satellites in our Solar System.
    • Raman spectroscopic study of "The Malatesta": a Renaissance painting?

      Edwards, Howell G.M.; Vandenabeele, P.; Benoy, T.J. (2015-02-25)
      Raman spectroscopic analysis of the pigments on an Italian painting described as a “Full Length Portrait of a Gentleman”, known also as the “Malatesta”, and attributed to the Renaissance period has established that these are consistent with the historical research provenance undertaken earlier. Evidence is found for the early 19th Century addition of chrome yellow to highlighted yellow ochre areas in comparison with a similar painting executed in 1801 by Sir Thomas Lawrence of John Kemble in the role of Hamlet, Prince of Denmark. The Raman data are novel in that no analytical studies have previously been made on this painting and reinforces the procedure whereby scientific analyses are accompanied by parallel historical research.