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Journal articleSephton MA, 2010,
Drilling in Extreme Environments: Penetration and Sampling on Earth and other Planets, Yoseph Bar-Cohen, Kris Zacny (Eds.), Wiley-VCH, 2010. (Book Review)
, International Journal of Rock Mechanics and Mining Science, Vol: 47, Pages: 1405-1405, ISSN: 1365-1609 -
Journal articleGrant J, Westall F, Beaty D, et al., 2010,
Two Rovers to the Same Site on Mars, 2010: Possibilities for Cooperative Science
, Astrobiology, Vol: 10, Pages: 663-685, ISSN: 1531-1074 -
Journal articleJolley D, Gilmour I, Gurov E, et al., 2010,
Two large meteorite impacts at the Cretaceous-Paleogene boundary
, Geology, Vol: 38, Pages: 835-838The end-Cretaceous mass extinction has been attributed by most to a single asteroid impact at Chicxulub on the Yucatán Peninsula, Mexico. The discovery of a second smaller crater with a similar age at Boltysh in the Ukraine has raised the possibility that a shower of asteroids or comets impacted Earth close to the Cretaceous-Paleogene (K-Pg) boundary. Here we present palynological and δ13C evidence from crater-fi ll sediments in the Boltysh impact crater. Our analyses demonstrate that a post-impact fl ora, formed on the ejecta layer, was in turn devastated by the K-Pg event. The sequence of fl oral recovery from the K-Pg event is directly comparable with that in middle North America. We conclude that the Boltysh crater predated Chicxulub by ~2–5 k.y., a time scale that constrains the likely origin of the bodies that formed the two known K-Pg craters.
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Journal articleBlyth AJ, Watson JS, Woodhead J, et al., 2010,
Organic compounds preserved in a 2.9 million year old stalagmite from the Nullarbor Plain, Australia
, Chemical Geology, Vol: 279, Pages: 101-105 -
Journal articleCourt RW, Baki AO, Sims MA, et al., 2010,
Novel solvent systems for in situ extraterrestrial sample analysis
, PLANET SPACE SCI, Vol: 58, Pages: 1470-1474, ISSN: 0032-0633The life marker chip (LMC) is being designed to test for the chemical signature of life in the soil and rocks of Mars. It will use an antibody array as part of its detection and characterisation system and aims to detect both polar and non-polar molecules at the sub-ppm to tens of ppb level. It is necessary to use a solvent to transfer organic compounds from the Martian samples to the LMC itself, but organic solvents such as dichloromethane or hexane, commonly used to dissolve non-polar molecules, are incompatible with the LMC antibodies. Hence, an aqueous-based solvent capable of dissolving the biomarkers that might exist in the soil or rocks of Mars is required. Solvent extractions of a Martian soil analogue, JSC Mars-1, spiked with a range of standards show that a 20:80 (vol:vol) mixture of methanol and water is incapable of extracting compounds insoluble in water. However, addition of 1.5 mg ml−1 of the surfactant polysorbate 80 produces extraction efficiencies of the aliphatic standards, hexadecane and phytane, equal to 25–30% of those produced by the common organic solvent mixture 93:7 (vol:vol) dichloromethane:methanol. Extraction of squalene and stigmasterol using the polysorbate solution is less efficient but still successful, at 5–10% of the efficiency of 93:7 dichloromethane:methanol. Such aliphatic compounds with occasional functional groups represent the compound classes to which most fossil organic biomarkers belong. The polysorbate solution did not extract the aromatic compounds pyrene and anthracene with great efficiency. A solvent of 20:80 methanol:water with 1.5 mg ml−1 polysorbate 80 is therefore capable of selectively extracting aliphatic biomarkers from Martian samples and transferring them to the antibody sites on the life marker chip.
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Journal articleSephton MA, 2010,
Organic Geochemistry and the Exploration of Mars
, J COSMOLOGY, Vol: 5, Pages: 1141-1149The Red Planet provides a relatively accessible world on which theories of life’s diversity and origin can be tested. Such examinations are imminent with a number of missions to Mars forthcoming. These missions contain several life detection instruments that will sample the surface and subsurface. Organic geochemical knowledge from terrestrial studies can inform our search for organic matter in Mars rocks. Recent data on Mars minerals and atmospheric gases suggest which methods may be most useful to access any organic records present. A mineralogically-diverse Mars provides varying opportunities for the preservation of past and present life. Extinct or extant life will occupy specific size fractions that must be targeted. Studies suggest that methane is most likely derived from the subsurface. Even if abiotic in origin, the combination of reduced gases and oxidised minerals provides opportunities for life. In the near subsurface methane may be polymerised by cosmic radiation to form abiotic organic matter. This paper considers terrestrial approaches that may be useful in a Martian context.
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Journal articleMeredith W, Gomes RL, Cooper M, et al., 2010,
Hydropyrolysis over a platinum catalyst as a preparative technique for the compound-specific carbon isotope ratio measurement of C27 steroids
, RAPID COMMUN MASS SP, Vol: 24, Pages: 501-505, ISSN: 1097-0231Compound-specific stable carbon isotope analysis by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) is an important method for the determination of the 13C/12C ratios of biomolecules such as steroids, for a wide range of applications. However, steroids in their natural form exhibit poor chromatographic resolution, while derivatisation adds carbon thereby corrupting the stable isotopic composition. Hydropyrolysis with a sulphided molybdenum catalyst has been shown to defunctionalise the steroids, while leaving their carbon skeleton intact, allowing for the accurate measurement of carbon isotope ratios. The presence of double bonds in unsaturated steroids such as cholesterol resulted in significant rearrangement of the products, but replacing the original catalyst system with one of platinum results in higher conversions and far greater selectivity. The improved chromatographic performance of the products should allow GC/C/IRMS to be applied to more structurally complex steroid hormones and their metabolites.
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Journal articleCockell CS, Osinski GR, Banerjee NR, et al., 2010,
Microbe–mineral environment and gypsum neogenesis in a weathered polar evaporite
, Geobiology, Vol: 8, Pages: 293-308Evaporitic deposits are a globally widespread habitat for micro-organisms. The microbe–mineral environment in weathered and remobilized gypsum from exposed mid-Ordovician marine evaporite beds in the polar desert of Devon Island, Nunavut, Canadian High Arctic was examined. The gypsum is characterized by internal green zones of cyanobacterial colonization (dominated by Gloeocapsa/Aphanothece and Chroococcidiopsis spp. morphotypes) and abundant black zones, visible from the surface, that contain pigmented cyanobacteria and fungi. Bioessential elements in the gypsum are primarily provided by allochthonous material from the present-day polar desert. The disruption, uplift and rotation of the evaporite beds by the Haughton meteorite impact 39 Ma have facilitated gypsum weathering and its accessibility as a habitat. No cultured cyanobacteria, bacteria and fungi were halophilic consistent with the expectation that halophily is not required to persist in gypsum habitats. Heterotrophic bacteria from the evaporite were slightly or moderately halotolerant, as were heterotrophs isolated from soil near the gypsum outcrop showing that halotolerance is common in arctic bacteria in this location. Psychrotolerant Arthrobacter species were isolated. No psychrophilic organisms were isolated. Two Arthrobacter isolates from the evaporite were used to mediate gypsum neogenesis in the laboratory, demonstrating a potential role for microbial biomineralization processes in polar environments.
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Journal articleWatson JS, Sephton MA, Gilmour I, 2010,
Thermochemolysis of the Murchison meteorite: identification of oxygen bound and occluded units in the organic macromolecule
, INT J ASTROBIOL, Vol: 9, Pages: 201-208, ISSN: 1473-5504An organic macromolecular residue, prepared from the Murchison meteorite by treatment with hydrofluoric and hydrochloric acids, was subjected to online thermochemolysis with tetramethylammonium hydroxide (TMAH). The most abundant compound released by thermochemolysis was benzoic acid. Other abundant compounds include methyl and dimethyl benzoic acids as well as methoxy benzoic acids. Short chain dicarboxylic acids (C4–8) were also released from the organic macromolecule. Within the C1 and C2 benzoic acids all possible structural isomers are present reflecting the abiotic origin of these units. The most abundant isomers include 3,4-dimethylbenzoic acid (DMBA), 3,5-DMBA, 2,6-DMBA and phenylacetic acid. Thermochemolysis also liberates hydrocarbons that are not observed during thermal desorption; these compounds include naphthalene, methylnaphthalenes, biphenyl, methylbiphenyls, acenaphthylene, acenaphthene, phenanthrene, anthracene, fluoranthene and pyrene. The lack of oxygen containing functional groups in these hydrocarbons indicates that they represent non-covalently bound, occluded molecules within the organic framework. This data provides a valuable insight into oxygen bound and physically occluded moieties in the Murchison organic macromolecule and implies a relative order of synthesis or agglomeration for the detected organic constituents.
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Conference paperNeedham AW, Smith CL, Howard KT, et al., 2009,
GAMMA IRRADIATION EFFECTS IN MARS ANALOGUES
, 72nd Annual Meeting of the Meteoritical-Society, Publisher: METEORITICAL SOC, Pages: A155-A155, ISSN: 1086-9379 -
Journal articleNicoara S, Tonidandel L, Traldi P, et al., 2009,
Determining the levels of volatile organic pollutants in urban air using a gas chromatography-mass spectrometry method
, Journal of Environmental and Public HealthThe paper presents the application of a method based on coupled gas chromatography-mass spectrometry, using an isotopically labelled internal standard for the quantitative analysis of benzene (B), toluene (T), ethyl benzene (E), and o-, m-, p-xylenes (X). Their atmospheric concentrations were determined based on short-term sampling, in different sites of Cluj-Napoca, a highly populated urban centre in N-W Romania, with numerous and diversified road vehicles with internal combustion engines. The method is relatively inexpensive and simple and shows good precision and linearity in the ranges of 7–60 μg/m3 (B), 13–90 μg/m3 (T), 7–50 μg/m3 (E), 10–70 μg/m3 (X-m,p), and 20–130 μg/m3 (X-o). The limits of quantitation/detection of the method LOQ/LOD are of 10/5 μg/m3 (Xo), 5/3 μg/m3 (B, E, X-m,p), and of 3/1 μg/m3 (T), respectively.
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Journal articleGomes RL, Meredith W, Snape CE, et al., 2009,
Conjugated steroids: analytical approaches and applications
, ANAL BIOANAL CHEM, Vol: 393, Pages: 453-458, ISSN: 1618-2642An introduction to conjugated steroids and the justification for their analysis is provided covering both environmental and biological samples. Determining conjugated steroids or indeed any organic chemical which is conjugated upon excretion from the body has relevance in diagnostic monitoring, forensic screening and environmental analysis (from the endocrine disrupter perspective). The various analytical approaches and the accompanying issues are application-dependent. There are numerous options at each stage of analysis, from extraction, hydrolysis, derivatisation, and detection, and advances can be confined to the specific application for which it was developed. Emphasis is placed on the choice of separation and how gas or liquid chromatography necessitates different preparative stages to enable conjugated steroid determination. Possible future directions and research for conjugated steroid analysis are discussed.
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Journal articleSephton MA, Visscher H, Looy CV, et al., 2009,
Chemical constitution of a Permian-Triassic disaster species
, GEOLOGY, Vol: 37, Pages: 875-878, ISSN: 0091-7613One of the most controversial biological proxies of environmental crisis at the close of the Permian is the organic microfossil Reduviasporonites. The proliferation of this disaster species coincides with the mass extinction and numerous geochemical disturbances. Originally Reduviasporonites was assigned to fungi, opportunistically exploiting dying end-Permian forests, but subsequentgeochemical data have been used to suggest an algal origin. We have used high-sensitivity equipment, partly designed to detect interstellar grains in meteorites, to reexamine the geochemical signature of Reduviasporonites. Organic chemistry, carbon and nitrogen isotopes, and carbon/nitrogen ratios are consistent with a fungal origin. The use of this microfossil as a marker of terrestrial ecosystem collapse should not be merely discounted. Unequivocally diagnostic data, however, may have been precluded by post-burial replacement of its organic constituents.
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Journal articleGomes RL, Meredith W, Snape CE, et al., 2009,
Analysis of conjugated steroid androgens: Deconjugation, derivatisation and associated issues
, Journal of Pharmaceutical and Biomedical Analysis, Vol: 49, Pages: 1133-1140, ISSN: 0731-7085Gas chromatography/mass spectrometry (GC/MS) is the preferred technique for the detection of urinary steroid androgens for drug testing in athletics. Excreted in either the glucuronide or sulfated conjugated form, steroids must first undergo deconjugation followed by derivatisation to render them suitable for GC analysis. Discussed herein are the deconjugation and the derivatisation preparative options. The analytical challenges surrounding these preparatory approaches, in particular the inability to cleave the sulfate moiety have led to a focus on testing protocols that reply on glucuronide conjugates. Other approaches which alleviate the need for deconjugation and derivatisation are also highlighted.
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Journal articleCourt RW, Sephton MA, 2009,
Quantitative flash pyrolysis Fourier transform infrared spectroscopy of organic materials
, Analytica Chimica Acta, Vol: 639, Pages: 62-66, ISSN: 0003-2670Thermal degradation is a common technique used to investigate the nature of organic materials. However, existing methods for the Fourier transform infrared (FTIR) identification and quantification of volatile products from the thermal degradation of organic materials are limited to the technique of thermogravimetric analysis (TGA)–FTIR, which utilizes relatively low heating rates. However, the thermal degradation products of organic materials are known to vary depending on the rate of heating, with lower heating rates of biomass associated with increased yields of solid char and decreased yields of volatiles, as well as a greater opportunity for secondary reactions between the residue and the pyrolysis products. Hence, it is difficult to relate the products of organic matter thermally degraded at <100 °C min−1 in TGA to the products of flash pyrolysis at up to 20,000 °C s−1. We have developed and applied a novel methodology for quantitative flash pyrolysis–FTIR analysis of the volatile pyrolysis products of organic-rich materials. Calibration curves of water, carbon dioxide and methane have been constructed and used to determine absolute volatile release from wood (ash, Lat. Fraxinus). This technique is quicker and simpler than comparable pyrolysis–gas chromatography–mass spectrometry techniques, and avoids errors associated with the lower rates of temperature increase associated with techniques such as thermogravimetric analysis.
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Journal articleCourt RW, Sephton MA, 2009,
Investigating the contribution of methane produced by ablating micrometeorites to the atmosphere of Mars
, EARTH PLAN SCI LETT, Vol: 288, Pages: 382-385, ISSN: 0012-821XThe presence of methane in the atmosphere of Mars has been suggested as evidence of life, as methane has a short lifetime in the atmosphere of Mars of just a few hundred years, requiring replacement by mechanisms, continuous or episodic, such as biology, volcanism, serpentinization of ultramafic crust or large cometary or asteroidal impacts. The potential of meteoritic infall to deliver significant quantities of methane is restricted by the low abundance of free methane in carbonaceous meteorites. However, the delivery of meteoritic material to the surface of a planet is an energetic process, and the ability of carbonaceous meteorites to generate methane upon ablation during atmospheric entry has not been previously considered. Here, we use analytical pyrolysis to simulate the ablation and pyrolysis of carbonaceous micrometeorites upon atmospheric entry, and Fourier-transform infrared spectroscopy to quantify the subsequent yield of methane. We show that ablation produces a yield of methane that is approximately two orders of magnitude greater than the measured free methane present in the CM2 carbonaceous chondrite, Murchison, but that this previously overlooked source of methane can only account for less than 10 kg of methane annually, a mass far below that required to maintain the abundance of methane observed in the atmosphere of Mars. Our data support attempts to search for life and explore subsurface chemical processes on the Red Planet.
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Journal articlePeeters Z, Quinn R, Martins Z, et al., 2009,
Habitability on planetary surfaces: interdisciplinary preparation phase for future Mars missions
, INT J ASTROBIOL, Vol: 8, Pages: 301-315, ISSN: 1473-5504Life on Earth is one of the outcomes of the formation and evolution of our solar system and has adapted to every explored environment on planet Earth. Recent discoveries have shown that life can exist in extreme environments, such as hydrothermal vents, in deserts and in ice lakes in Antarctica. These findings challenge the definition of the ‘planetary habitable zone’. The objective of future international planetary exploration programmes is to implement a long-term plan for the robotic and human exploration of solar system bodies. Mars has been a central object of interest in the context of extraterrestrial life. The search for extinct or extant life on Mars is one of the main goals of space missions to the Red Planet during the next decade. In this paper we describe the investigation of the physical and chemical properties of Mars soil analogues collected in arid deserts. We measure the pH, redox potential and ion concentrations, as well as carbon and amino acid abundances of soils collected from the Atacama desert (Chile and Peru) and the Salten Skov sediment from Denmark. The samples show large differences in their measured properties, even when taken only several meters apart. A desert sample and the Salten Skov sediment were exposed to a simulated Mars environment to test the stability of amino acids in the soils. The presented laboratory and field studies provide limits to exobiological models, evidence on the effects of subsurface mineral matrices, support current and planned space missions and address planetary protection issues.
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Journal articlePerry RS, Sephton MA, 2009,
Reply to comments on defining biominerals and organominerals: Direct and indirect indicators of life [Perry et al., Sedimentary Geology, 201, 157-179]
, SED GEOL, Vol: 213, Pages: 156-156, ISSN: 0037-0738 -
Book chapterMartins Z, Sephton MA, 2009,
Extraterrestrial amino acids
, Origins and Synthesis of Amino Acids., Editors: Hughes, Hughes, Weinheim, Publisher: Wiley-VCH, Pages: 3-42, ISBN: 9789783527324 -
Journal articleBlyth AJ, Watson JS, 2009,
Thermochemolysis of organic matter preserved in stalagmites: a preliminary study
, Organic Geochemistry, Vol: 40, Pages: 1029-1031The analysis of organic matter (OM) preserved in stalagmites is a growing field, but there have been few studies of biomarker compounds such as lignin phenols that are widely used in other palaeoenvironmental contexts. Here we present a preliminary qualitative study of the OM in six stalagmite samples from contrasting environments, using thermochemolysis in the presence of tetramethylammonium hydroxide (TMAH). The results indicate that a wide variety of products is preserved, including several potential lignin-derived compounds, but also that further research is needed to maximise compound recovery and allow the analysis of dissolved OM preserved in stalagmites to reach its full potential.
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