Hydrogen isotope exchange between n-alkanes and water under hydrothermal conditions

Author Posting. © The Author(s), 2011. 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 Geochimica et Cosmochimica Acta 77 (2012): 582–599, doi:10.1016/j.gca.2011.10.008.To investigate the extent of hydrogen isotope (2H and 1H) exchange between hydrocarbons and water under hydrothermal conditions, we performed experiments heating C1–C5 n-alkanes in aqueous solutions of varying initial 2H/1H ratios in the presence of a pyrite-pyrrhotite-magnetite redox buffer at 323ºC and 35–36MPa. Extensive and reversible incorporation of water-derived hydrogen into C2–C5 n-alkanes was observed on timescales of months. In contrast, comparatively minor exchange was observed for CH4. Isotopic exchange is facilitated by reversible equilibration of n-alkanes and their corresponding n-alkenes with H2 derived from the disproportionation of water. Rates of δ2H variation in C3+ n-alkanes decreased with time, a trend that is consistent with an asymptotic approach to steady-state isotopic compositions regulated by alkane-water isotopic equilibrium. Substantially slower δ2H variation was observed for ethane relative to C3–C5 n-alkanes, suggesting that the greater stability of C3+ alkenes and isomerization reactions may dramatically enhance rates of 2H/1H exchange in C3+ n-alkanes. Thus, in reducing aqueous environments, reversible reaction of alkenes and their corresponding alkanes facilitates rapid 2H/1H exchange between alkyl- and water-bound hydrogen on relatively short geological timescales at elevated temperatures and pressures. The proximity of some thermogenic and purported abiogenic alkane δ2H values to those predicted for equilibrium 2H/1H fractionation with ambient water suggests that this process may regulate the δ2H signatures of some naturally occurring hydrocarbons.This research received financial support from the Department of Energy (grant DE-FG02-97ER14746), the National Science Foundation (grant OCE-0549829) and the WHOI Deep Ocean Exploration Institute Graduate Fellowship (to E.P. Reeves)

Thermoanaerosceptrum fracticalcis gen. nov. sp. nov., a novel fumarate-fermenting microorganism from a deep fractured carbonate aquifer of the US Great Basin

Deep fractured rock ecosystems across most of North America have not been studied extensively. However, the US Great Basin, in particular the Nevada National Security Site (NNSS, formerly the Nevada Test Site), has hosted a number of influential subsurface investigations over the years. This investigation focuses on resident microbiota recovered from a hydrogeologically confined aquifer in fractured Paleozoic carbonate rocks at 863 – 923 m meters below land surface. Analysis of the microorganisms living in this oligotrophic environment provides a perspective into microbial metabolic strategies required to endure prolonged hydrogeological isolation deep underground. Here we present a microbiological and physicochemical characterization of a deep continental carbonate ecosystem and describe a bacterial genus isolated from the ecosystem. Strain DRI-13T is a strictly anaerobic, moderately thermophilic, fumarate-respiring member of the phylum Firmicutes. This bacterium grows optimally at 55°C and pH 8.0, can tolerate a concentration of 100 mM NaCl, and appears to obligately metabolize fumarate to acetate and succinate. Culture-independent 16S rRNA gene sequencing indicates a global subsurface distribution, while the closest cultured relatives of DRI-13T are Pelotomaculum thermopropionicum (90.0% similarity) and Desulfotomaculum gibsoniae (88.0% similarity). The predominant fatty acid profile is iso-C15:0, C15:0, C16:0 and C14:0. The percentage of the straight-chain fatty acid C15:0 is a defining characteristic not present in the other closely related species. The genome is estimated to be 3,649,665 bp, composed of 87.3% coding regions with an overall average of 45.1% G+C content. Strain DRI-13T represents a novel genus of subsurface bacterium isolated from a previously uncharacterized rock-hosted geothermal habitat. The characterization of the bacterium combined with the sequenced genome provides insights into metabolism strategies of the deep subsurface biosphere. Based on our characterization analysis we propose the name Thermoanaerosceptrum fracticalcis (DRI-13T = DSM 100382T = ATCC TSD-12T)

Long term geological record of a global deep subsurface microbial habitat in sand injection complexes

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Characterization and Solution Structure of the Factor VIII C2 Domain in a Ternary Complex with Classical and Non-classical Inhibitor Antibodies

The most significant complication for patients with severe cases of congenital or acquired hemophilia A is the development of inhibitor antibodies against coagulation factor VIII (fVIII). The C2 domain of fVIII is a significant antigenic target of anti-fVIII antibodies. Here, we have utilized small angle x-ray scattering (SAXS) and biochemical techniques to characterize interactions between two different classes of anti-C2 domain inhibitor antibodies and the isolated C2 domain. Multiple assays indicated that antibodies 3E6 and G99 bind independently to the fVIII C2 domain and can form a stable ternary complex. SAXS-derived numerical estimates of dimensional parameters for all studied complexes agree with the proportions of the constituent proteins. Ab initio modeling of the SAXS data results in a long kinked structure of the ternary complex, showing an angle centered at the C2 domain of ∼130°. Guided by biochemical data, rigid body modeling of subunits into the molecular envelope of the ternary complex suggests that antibody 3E6 recognizes a C2 domain epitope consisting of the Arg2209–Ser2216 and Leu2178–Asp2187 loops. In contrast, antibody G99 recognizes the C2 domain primarily through the Pro2221–Trp2229 loop. These two epitopes are on opposing sides of the fVIII C2 domain, are consistent with the solvent accessibility in the context of the entire fVIII molecule, and provide further structural detail regarding the pathogenic immune response to fVIII

Structure of Blood Coagulation Factor VIII in Complex With an Anti-C2 Domain Non-Classical, Pathogenic Antibody Inhibitor

Factor VIII (fVIII) is a procoagulant protein that binds to activated factor IX (fIXa) on platelet surfaces to form the intrinsic tenase complex. Due to the high immunogenicity of fVIII, generation of antibody inhibitors is a common occurrence in patients during hemophilia A treatment and spontaneously occurs in acquired hemophilia A patients. Non-classical antibody inhibitors, which block fVIII activation by thrombin and formation of the tenase complex, are the most common anti-C2 domain pathogenic inhibitors in hemophilia A murine models and have been identified in patient plasmas. In this study, we report on the X-ray crystal structure of a B domain-deleted bioengineered fVIII bound to the non-classical antibody inhibitor, G99. While binding to G99 does not disrupt the overall domain architecture of fVIII, the C2 domain undergoes an ~8 Å translocation that is concomitant with breaking multiple domain-domain interactions. Analysis of normalized B-factor values revealed several solvent-exposed loops in the C1 and C2 domains which experience a decrease in thermal motion in the presence of inhibitory antibodies. These results enhance our understanding on the structural nature of binding non-classical inhibitors and provide a structural dynamics-based rationale for cooperativity between anti-C1 and anti-C2 domain inhibitors

Structure of Blood Coagulation Factor VIII in Complex with Anti-C2 Domain Inhibitory Antibody

Factor VIII (fVIII) is a procoagulant protein that binds to activated factor IX (fIXa) on platelet surfaces to form the intrinsic tenase complex. Due to the high immunogenicity of fVIII, generation of antibody inhibitors is a common occurrence in patients during hemophilia A treatment and spontaneously occurs in acquired hemophilia A patients. Non-classical antibody inhibitors, which block fVIII activation by thrombin and formation of the tenase complex, are the most common anti-C2 domain pathogenic inhibitors in hemophilia A murine models and have been identified in patient plasmas. In this study, we report on the X-ray crystal structure of a B domain-deleted bioengineered fVIII bound to the non classical antibody inhibitor, G99. While binding to G99 does not disrupt the overall domain architecture of fVIII, the C2 domain undergoes an ~8 Å translocation that is concomitant with breaking multiple domain-domain interactions. Analysis of normalized B-factor values revealed several solvent-exposed loops in the C1 and C2 domains which experience a decrease in thermal motion in the presence of inhibitory antibodies. Our results enhance our understanding on the structural nature of binding non-classical inhibitors and provide a structural dynamics-based rationale for cooperativity between anti-C domain inhibitors

Summarizing activity limitations in children with chronic illnesses living in the community: a measurement study of scales using supplemented interRAI items

<p>Abstract</p> <p>Background</p> <p>To test the validity and reliability of scales intended to measure activity limitations faced by children with chronic illnesses living in the community. The scales were based on information provided by caregivers to service program personnel almost exclusively trained as social workers. The items used to measure activity limitations were interRAI items supplemented so that they were more applicable to activity limitations in children with chronic illnesses. In addition, these analyses may shed light on the possibility of gathering functional information that can span the life course as well as spanning different care settings.</p> <p>Methods</p> <p>Analyses included testing the internal consistency, predictive, concurrent, discriminant and construct validity of two activity limitation scales. The scales were developed using assessment data gathered in the United States of America (USA) from over 2,700 assessments of children aged 4 to 20 receiving Medicaid Early and Periodic Screening, Diagnostic and Treatment (EPSDT) services, specifically Personal Care Services to assist children in overcoming activity limitations. The Medicaid program in the USA pays for health care services provided to children in low-income households. Data were collected in a single, large state in the southwestern USA in late 2008 and early 2009. A similar sample of children was assessed in 2010, and the analyses were replicated using this sample.</p> <p>Results</p> <p>The two scales exhibited excellent internal consistency. Evidence on the concurrent, predictive, discriminant, and construct validity of the proposed scales was strong. Quite importantly, scale scores were not correlated with (confounded with) a child's developmental stage or age. The results for these scales and items were consistent across the two independent samples.</p> <p>Conclusions</p> <p>Unpaid caregivers, usually parents, can provide assessors lacking either medical or nursing training with reliable and valid information on the activity limitations of children. One can summarize these data in scales that are both internally consistent and valid. Researchers and clinicians can use supplemented interRAI items to provide guidance for professionals and programs serving children, as well as older persons. This research emphasizes the importance of developing medical information systems that allow one to integrate information not only across care settings but also across an individual's life course.</p

Versatility and Stereotypy of Free-Tailed Bat Songs

In mammals, complex songs are uncommon and few studies have examined song composition or the order of elements in songs, particularly with respect to regional and individual variation. In this study we examine how syllables and phrases are ordered and combined, ie “syntax”, of the song of Tadarida brasiliensis, the Brazilian free-tailed bat. Specifically, we test whether phrase and song composition differ among individuals and between two regions, we determine variability across renditions within individuals, and test whether phrases are randomly ordered and combined. We report three major findings. First, song phrases were highly stereotyped across two regions, so much so that some songs from the two colonies were almost indistinguishable. All males produced songs with the same four types of syllables and the same three types of phrases. Second, we found that although song construction was similar across regions, the number of syllables within phrases, and the number and order of phrases in songs varied greatly within and among individuals. Last, we determined that phrase order, although diverse, deviated from random models. We found broad scale phrase-order rules and certain higher order combinations that were highly preferred. We conclude that free-tailed bat songs are composed of highly stereotyped phrases hierarchically organized by a common set of syntactical rules. However, within global species-specific patterns, songs male free-tailed bats dynamically vary syllable number, phrase order, and phrase repetitions across song renditions

Planetary mass spectrometry for agnostic life detection in the Solar system

For the past fifty years of space exploration, mass spectrometry has provided unique chemical and physical insights on the characteristics of other planetary bodies in the Solar System. A variety of mass spectrometer types, including magnetic sector, quadrupole, time-of-flight, and ion trap, have and will continue to deepen our understanding of the formation and evolution of exploration targets like the surfaces and atmospheres of planets and their moons. An important impetus for the continuing exploration of Mars, Europa, Enceladus, Titan, and Venus involves assessing the habitability of solar system bodies and, ultimately, the search for life—a monumental effort that can be advanced by mass spectrometry. Modern flight-capable mass spectrometers, in combination with various sample processing, separation, and ionization techniques enable sensitive detection of chemical biosignatures. While our canonical knowledge of biosignatures is rooted in Terran-based examples, agnostic approaches in astrobiology can cast a wider net, to search for signs of life that may not be based on Terran-like biochemistry. Here, we delve into the search for extraterrestrial chemical and morphological biosignatures and examine several possible approaches to agnostic life detection using mass spectrometry. We discuss how future missions can help ensure that our search strategies are inclusive of unfamiliar life forms.https://www.frontiersin.org/articles/10.3389/fspas.2021.755100/ful

Causes of unrest at silicic calderas in the East African Rift: new constraints from InSAR and soil-gas chemistry at Aluto volcano, Ethiopia

This work is a contribution to the Natural Environment Research Council (NERC) funded RiftVolc project (NE/L013932/1, Rift volcanism: past, present, and future). W.H., J.B., T.A.M., and D.M.P. are supported by and contribute to the NERC Centre for the Observation and Modelling of Earthquakes, Volcanoes, and Tectonics (COMET). Envisat data were provided by ESA. ALOS data were provided through ESA third party mission. W.H. funded by NERC studentship, NE/J5000045/1. Additional funding for fieldwork was provided by University College (University of Oxford), the Geological Remote Sensing Group, the Edinburgh Geological Society, and the Leverhulme Trust. Analytical work at the University of New Mexico was supported by the Volcanic and Geothermal Volatiles Lab at the Center for Stable Isotopes and an NSF grant EAR-1113066 to T.P.F.Restless silicic calderas present major geological hazards, and yet many also host significant untapped geothermal resources. In East Africa this poses a major challenge, although the calderas are largely unmonitored their geothermal resources could provide substantial economic benefits to the region. Understanding what causes unrest at these volcanoes is vital for weighing up the opportunities against the potential risks. Here we bring together new field and remote sensing observations to evaluate causes of ground deformation at Aluto, a restless silicic volcano located in the Main Ethiopian Rift (MER). Interferometric Synthetic Aperture Radar (InSAR) data reveal the temporal and spatial characteristics of a ground deformation episode that took place between 2008 and 2010. Deformation time-series reveal pulses of accelerating uplift that transition to gradual long-term subsidence, and analytical models support inflation source depths of ∼5 km. Gases escaping along the major fault zone of Aluto show high CO2 flux, and a clear magmatic carbon signature (CO2–δ13C of −4.2 to −4.5 ‰). This provides compelling evidence that the magmatic and hydrothermal reservoirs of the complex are physically connected. We suggest that a coupled magmatic-hydrothermal system can explain the uplift-subsidence signals. We hypothesize that magmatic fluid injection and/or intrusion in the cap of the magmatic reservoir drives edifice wide inflation while subsequent deflation is related to magmatic degassing and depressurization of the hydrothermal system. These new constraints on the plumbing of Aluto yield important insights into the behaviour of rift volcanic systems and will be crucial for interpreting future patterns of unrest.Publisher PDFPeer reviewe