Orbital pacing of the Early Jurassic carbon cycle, black-shale formation and seabed methane seepage

The Early Jurassic (ca 201 to 174 Ma) was marked by a series of rapid perturbations in climate, the environment and global geochemical cycles, which have been linked to volcanic outgassing and the release of biogenic or thermogenic methane into the ocean–atmosphere system. The state of the global carbon cycle and prevailing climatic and environmental conditions that existed at this time are, however, poorly constrained. Here, mudrocks of the Lower Sinemurian Arietites bucklandi ammonite Biozone at coastal exposures at Kilve, Somerset, UK, have been studied. This succession includes laminated organic-rich black shales, which are present throughout the Bristol Channel Basin, and coincides with a 2 to 3‰ negative carbon-isotope excursion, distinct changes in inferred land vegetation and abundant marine prasinophytes (green algae). The event itself does not represent a single perturbation of the regional environment, but follows in a sequence of eccentricity-modulated, precession-paced perturbations that occur throughout the preceding Hettangian stage, with the periodic formation of organic-rich laminated black shales in the Bristol Channel Basin. However, the Early Sinemurian event studied herein is more extreme in nature, with sedimentary total organic carbon values of 5 to 11% persisting over about 2 m, representing ca 100 kyr, possibly in phase with short (ca 100 kyr) and long (ca 405 kyr) eccentricity forcing. The formation of methane-seep carbonate-cemented mounds took place relatively soon after the deposition of laminated black shales. Biogenic methane probably formed in response to microbial methanogenesis in the organic-rich black shale, which was subsequently channelled to the sediment–water interface approximately 5 m above the source bed, and ca 200 kyr after cessation of formation of the black shale

Medical encounters (including injury and illness) at mass community-based endurance sports events: an international consensus statement on definitions and methods of data recording and reporting

Mass participation endurance sports events are popular but a large number of participants are older and may be at risk of medical complications during events. Medical encounters (defined fully in the statement) include those traditionally considered 'musculoskeletal' (eg, strains) and those due to 'illness' (eg, cardiac, respiratory, endocrine). The rate of sudden death during mass endurance events (running, cycling and triathlon) is between 0.4 and 3.3 per 100 000 entrants. The rate of other serious medical encounters (eg, exertional heat stroke, hyponatraemia) is rarely reported; in runners it can be up to 100 times higher than that of sudden death, that is, between 16 and 155 per 100 000 race entrants. This consensus statement has two goals. It (1) defines terms for injury and illness-related medical encounters, severity and timing of medical encounters, and diagnostic categories of medical encounters, and (2) describes the methods for recording data at mass participation endurance sports events and reporting results to authorities and for publication. This unifying consensus statement will allow data from various events to be compared and aggregated. This will inform athlete/patient management, and thus make endurance events safer

Organic residue analysis of Egyptian votive mummies and their research potential

YesVast numbers of votive mummies were produced in Egypt during the Late Pharaonic, Ptolemaic, and Roman periods. Although millions remain in situ, many were removed and have ultimately entered museum collections around the world. There they have often languished as uncomfortable reminders of antiquarian practices with little information available to enhance their value as artefacts worthy of conservation or display. A multi-disciplinary research project, based at the University of Manchester, is currently redressing these issues. One recent aspect of this work has been the characterization of natural products employed in the mummification of votive bundles. Using gas chromatography–mass spectrometry and the well-established biomarker approach, analysis of 24 samples from 17 mummy bundles has demonstrated the presence of oils/fats, natural waxes, petroleum products, resinous exudates, and essential oils. These results confirm the range of organic materials employed in embalming and augment our understanding of the treatment of votives. In this first systematic initiative of its kind, initial findings point to possible trends in body treatment practices in relation to chronology, geography, and changes in ideology which will be investigated as the study progresses. Detailed knowledge of the substances used on individual bundles has also served to enhance their value as display items and aid in their conservation.RCB is supported by a PhD studentship from the Art and Humanities Research Council (43019R00209). L.M. and S.A.W. are supported by a Leverhulme Trust Research Project Award (RPG-2013-143)

Analysis of unresolved complex mixtures of hydrocarbons extracted from Late Archean sediments by comprehensive two-dimensional gas chromatography (GC×GC)

Author Posting. © Elsevier B.V., 2008. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Organic Geochemistry 39 (2008): 846-867, doi:10.1016/j.orggeochem.2008.03.006.Hydrocarbon mixtures too complex to resolve by traditional capillary gas chromatrography display gas chromatograms with dramatically rising baselines or “humps” of coeluting compounds that are termed unresolved complex mixtures (UCMs). Because the constituents of UCMs are not ordinarily identified, a large amount of geochemical information is never explored. Gas chromatograms of saturated/unsaturated hydrocarbons extracted from Late Archean argillites and greywackes of the southern Abitibi Province of Ontario, Canada contain UCMs with different appearances or “topologies” relating to the intensity and retention time of the compounds comprising the UCMs. These topologies appear to have some level of stratigraphic organization, such that samples collected at any stratigraphic formation collectively are dominated by UCMs that either elute early- (within a window of C15-C20 of n-alkanes), early- to mid- (C15-C30 of n-alkanes), or have a broad UCM that extends through the entire retention time of the sample (from C15-C42 of n-alkanes). Comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC×GC-MS) was used to resolve the constituents forming these various UCMs. Early- to mid- eluting UCMs are dominated by configurational isomers of alkyl-substituted and non substituted polycyclic compounds that contain up to six rings. Late eluting UCMs are composed of C36-C40 mono-, bi-, and tricyclic archaeal isoprenoid diastereomers. Broad UCMs spanning the retention time of compound elution contain nearly the same compounds observed in the early-, mid-, and late retention time UCMs. Although the origin of the polycyclic compounds is unclear, the variations in the UCM topology appear to depend on the concentration of initial compound classes that have the potential to become isomerized. Isomerization of these constituents may have resulted from hydrothermal alteration of organic matter.This project was supported by NASA Exobiology grant #NAG5-13446 to Fabien Kenig. GC×GC analysis was supported by NSF grant IIS-0430835 and the Seaver Foundation to Christopher M. Reddy. Preparation of the archaeal biphytane standard was supported by NSF grant ARC-0520226 to Benjamin Van Mooy

Facile Preparation of Organic Nanoparticles by Interfacial Cross-Linking of Reverse Micelles and Template Synthesis of Subnanometer Au−Pt Nanoparticles

A single- and a double-tailed cationic surfactant with the triallylammonium headgroup formed reverse micelles (RMs) in heptane/chloroform containing a small amount of water. The reverse micelles were cross-linked at the interface upon UV irradiation in the presence of a water-soluble dithiol cross-linker and a photoinitiator. The resulting interfacially cross-linked reverse micelles (ICRMs) of the single-tailed surfactant aggregated in a solvent-dependent fashion, whereas those of the double-tailed were identical in size as the corresponding RMs. The ICRMs could extract anionic metal salts, such as AuCl4− and PtCl62−, from water into the organic phase. Au and Pt metal nanoparticles were produced upon reduction of metal salts. The covalent nature of the ICRMs made the template synthesis highly predictable, with the size of the metal particles controlled by the amount of the metal salt and the method of reduction. Nanoalloys were obtained by combining two metal precursors in the same reaction. Reduction of the ICRM-entrapped aurate also occurred without any external reducing agents, and the gold nanoparticles differed dramatically from those obtained through sodium borohydride reduction. The same template allowed the preparation of luminescent Au4, Au8, and Au13−Au23 clusters, as well as gold nanoparticles several nanometers in size, simply by using different amounts of gold precursor and reducing conditions

A comparison between faecal sterols and coliform counts in the investigation of sewage contamination in sediments

In September 2002, nine sediment samples (0-2 cm) were collected from Botafogo Cove (southwestern part of Guanabara Bay) in order to compare the use of chemical (coprostanol) and biological markers (E. coli and total coliforms) in identifying faecal contamination. The values found (organic carbon - 6.0 to 64.8 mg g-1; coprostanol - 1.4 to 105 µg g-1; E. coli - Em setembro de 2002, foram coletadas nove amostras de sedimento superficial (0-2 cm) na Enseada de Botafogo (sudoeste da Baía de Guanabara/RJ), a fim de comparar o uso de marcadores químicos (coprostanol) e biológicos (E. coli e coliformes totais) na identificação da contaminação fecal da região. Os resultados obtidos (carbono orgânico - 6,0 to 64,8 mg g-1; coprostanol - 1,4 to 105 µg g-1; E. coli - < 30 to 2400 NMP/10g e coliformes totais - 40 to 9300 NMP/10g) foram iguais ou maiores aos observados em outras áreas contaminadas da Baía de Guanabara. Nas estações próximas à linha de costa, as concentrações de coprostanol e as contagens das bactérias confirmaram que o esgoto doméstico se acumulou no sedimento da enseada. As concentrações de coprostanol se mantiveram altas nas estações distantes das fontes de contaminação, porém o material fecal representou uma menor fração do carbono orgânico. Nessas mesmas estações, redução na contagem de colimetria foi proporcionalmente mais alta, provavelmente pela baixa sobrevivência das bactérias devido ao efeito de luz, salinidade e temperatura. durante o transporte e deposição das partículas de esgoto. Portanto, baseando-se nos resultados obtidos, o coprostanol foi um indicador mais adequado da contaminação fecal nos sedimentos da Enseada de Botafogo