Hydrogen and Oxygen Isotope Fractionation Between Brucite and Aqueous NaCl Solutions from 250 to 450°C

Hydrogen and oxygen isotope fractionation factors between brucite and aqueous NaCl solutions (1000lnαbr-sw) have been calibrated by experiment from 250 to 450°C at 0.5 Kb. For D/H fractionation, 1000lnα br-sw values are as follows: −32 ± 6‰ (250°C, 3.2 wt% NaCl), −21 ± 2‰ (350°C, 10.0 wt% NaCl), and −22 ± 2‰ (450°C, 3.2 wt% NaCl), indicating that brucite is depleted in D relative to coexisting aqueous NaCl solutions. These results are in good agreement with previous D/H fractionation factors determined in the brucite-water system, indicating that any effects of dissolved salt on D/H fractionation are relatively small, particularly in solutions with near seawater salinity. The maximum salt effect (+4‰) was observed in 10.0 wt% NaCl solutions at 350°C, suggesting that the addition of dissolved NaCl increases the amount of deuterium fractionated into mineral structures. For 18O/16O fractionation, 1000lnαbr-sw values in 3.0 wt% NaCl solutions are −6.0 ± 1.3‰, −5.6 ± 0.7‰ and −4.1 ± 0.2‰, at 250, 350, and 450°C, respectively, and −5.8 ± 0.6‰ in 10.0 wt % NaCl at 350°C. These data indicate that brucite is depleted in 18O relative to coexisting aqueous NaCl solutions and that the degree of depletion decreases slightly with increasing temperature and is not strongly dependent on salinity. We calculated 18O/16O brucite-water fractionation factors from available calibrations of the salt-effect on 18O/16O fractionation between coexisting phases. The resulting values were fit to the following equation that is valid from 250 to 450°C 1000ln αbr-w = 9.54 × 106T−2 − 3.53 × 104T−1 + 26.58 where T is temperature in Kelvins. These new data have been used to improve the prediction of 18O/16O fractionation factors in the talc-water and serpentine-water systems by modifying existing empirical bond-water models. The results of this analysis indicate that the δ18O composition of talc-brucite and serpentine-brucite pairs could be used as a geothermometer and that these coexisting phases should display the following order of 18O enrichment: talc \u3e serpentine \u3e brucite

Genus-Specific Carbon Fixation Activity Measurements Reveal Distinct Responses to Oxygen among Hydrothermal Vent Campylobacteria

Molecular surveys of low temperature deep-sea hydrothermal vent fluids have shown that Campylobacteria (previously Epsilonproteobacteria) often dominate the microbial community and that three genera, Arcobacter, Sulfurimonas, and Sulfurovum, frequently coexist. In this study, we used replicated radiocarbon incubations of deep-sea hydrothermal fluids to investigate activity of each genus under three experimental conditions. To quantify genus-specific radiocarbon incorporation, we used newly designed oligonucleotide probes for Arcobacter, Sulfurimonas, and Sulfurovum to quantify their activity using catalyzed-reporter deposition fluorescence in situ hybridization (CARD-FISH) combined with fluorescence-activated cell sorting. All three genera actively fixed CO2 in short-term (similar to 20 h) incubations, but responded differently to the additions of nitrate and oxygen. Oxygen additions had the largest effect on community composition, and caused a pronounced shift in community composition at the amplicon sequence variant (ASV) level after only 20 h of incubation. The effect of oxygen on carbon fixation rates appeared to depend on the initial starting community. The presented results support the hypothesis that these chemoautotrophic genera possess functionally redundant core metabolic capabilities, but also reveal finer-scale differences in growth likely reflecting adaptation of physiologically-distinct phylotypes to varying oxygen concentrations in situ. Overall, our study provides new insights into how oxygen controls community composition and total chemoautotrophic activity, and underscores how quickly deep-sea vent microbial communities respond to disturbances. IMPORTANCE Sulfidic environments worldwide are often dominated by sulfur-oxidizing, carbon-fixing Campylobacteria. Environmental factors associated with this group's dominance are now understood, but far less is known about the ecology and physiology of members of subgroups of chemoautotrophic Campylobacteria. In this study, we used a novel method to differentiate the genus-specific chemoautotrophic activity of three subtypes of Campylobacteria. In combination with evidence from microscopic counts, chemical consumption/production during incubations, and DNA-based measurements, our data show that oxygen concentration affects both community composition and chemoautotrophic function in situ. These results help us better understand factors controlling microbial diversity at deep-sea hydrothermal vents, and provide first-order insights into the ecophysiological differences between these distinct microbial taxa

Oxygen and hydrogen isotope fractionation in serpentine–water and talc–water systems from 250 to 450°C MPa

Oxygen and hydrogen isotope fractionation factors in the talc–water and serpentine–water systems have been determined by laboratory experiment from 250 to 450 °C at 50 MPa using the partial exchange technique. Talc was synthesized from brucite + quartz, resulting in nearly 100% exchange during reaction at 350 and 450 °C. For serpentine, D–H exchange was much more rapid than 18O–16O exchange when natural chrysotile fibers were employed in the initial charge. In experiments with lizardite as the starting charge, recrystallization to chrysotile enhanced the rate of 18O–16O exchange with the coexisting aqueous phase. Oxygen isotope fractionation factors in both the talc–water and serpentine–water systems decrease with increasing temperature and can be described from 250 to 450 °C by the relationships: 1000 ln = 11.70 × 106/T2 − 25.49 × 103/T + 12.48 and 1000 ln = 3.49 × 106/T2 − 9.48 where T is temperature in Kelvin. Over the same temperature interval at 50 MPa, talc–water D–H fractionation is only weakly dependent on temperature, similar to brucite and chlorite, and can be described by the equation: 1000 ln = 10.88 × 106/T2 − 41.52 × 103/T + 5.61 where T is temperature in Kelvin. Our D–H serpentine–water fractionation factors calibrated by experiment decrease with temperature and form a consistent trend with fractionation factors derived from lower temperature field calibrations. By regression of these data, we have refined and extended the D–H fractionation curve from 25 to 450 °C, 50 MPa as follows: 1000 ln = 3.436 × 106/T2 − 34.736 × 103/T + 21.67 where T is temperature in Kelvin. These new data should improve the application of D–H and 18O–16O isotopes to constrain the temperature and origin of hydrothermal fluids responsible for serpentine formation in a variety of geologic settings

Cloud condensation nucleus activity comparison of dry- and wet-generated mineral dust aerosol: the significance of soluble material

This study examines the interaction of clay mineral particles and water vapor for determining the conditions required for cloud droplet formation. Droplet formation conditions are investigated for two common clay minerals, illite and sodium-rich montmorillonite, and an industrially derived sample, Arizona Test Dust. Using wet and dry particle generation coupled to a differential mobility analyzer (DMA) and cloud condensation nuclei counter, the critical activation of the clay mineral particles as cloud condensation nuclei is characterized. Electron microscopy (EM) is used in order to determine non-sphericity in particle shape. It is also used in order to determine particle surface area and account for transmission of multiply charged particles by the DMA. Single particle mass spectrometry and ion chromatography are used to investigate soluble material in wet-generated samples and demonstrate that wet and dry generation yield compositionally different particles. Activation results are analyzed in the context of both κ-Köhler theory (κ-KT) and Frenkel–Halsey–Hill (FHH) adsorption activation theory. This study has two main results: (1) κ-KT is the suitable framework to describe clay mineral nucleation activity. Apparent differences in κ with respect to size arise from an artifact introduced by improper size-selection methodology. For dust particles with mobility sizes larger than ~300 nm, i.e., ones that are within an atmospherically relevant size range, both κ-KT and FHH theory yield similar critical supersaturations. However, the former requires a single hygroscopicity parameter instead of the two adjustable parameters required by the latter. For dry-generated particles, the size dependence of κ is likely an artifact of the shape of the size distribution: there is a sharp drop-off in particle concentration at ~300 nm, and a large fraction of particles classified with a mobility diameter less than ~300 nm are actually multiply charged, resulting in a much lower critical supersaturation for droplet activation than expected. For wet-generated particles, deviation from κ-KT is likely a result of the dissolution and redistribution of soluble material. (2) Wet generation is found to be unsuitable for simulating the lofting of fresh dry dust because it changes the size-dependent critical supersaturations by fractionating and re-partitioning soluble material.United States. National Oceanic and Atmospheric Administration. Climate Program Office (award number NA11OAR4310159

From Teamchef Arminius to Hermann Junior: glocalised discourse about a national foundation myth

If for much of the nineteenth and twentieth centuries, the ‘Battle of the Teutoburg Forest’, fought in 9 CE between Roman armies and Germanic tribes, was predominantly a reference point for nationalist and chauvinist discourses in Germany, the first decade of the twenty-first century has seen attempts to link public remembrance with local/regional identities on the one hand and international/intercultural contact on the other. In the run up to and during the ‘anniversary year’ of 2009, German media, sports institutions and various other official institutions articulating tourist, economic and political interests attempted to create a new ‘glocalised’ version of the public memory of the Teutoburg battle. Combining methods of Cognitive Linguistics and Critical Discourse Analysis, the paper analyses the narrative and argumentative topoi employed in this re-orientation of public memory, with a special emphasis on hybrid, post-national identity-construction. Das zweitausendjährige Gedenkjahr der „Schlacht im Teutoburger Wald“ im Jahr 2009 bot eine günstige Gelegenheit, die bis in die zweite Hälfte des 20. Jahrhunderts dominante Tradition nationalistisch–chauvinistischer Deutungen des Sieges von germanischen Stämmen über drei römische Legionen zu korrigieren und zu überwinden. Der Aufsatz analysiert mit Hilfe diskurslinguistischer Methoden die Anstrengungen regionaler Institutionen und Medien, die nationale Vereinnahmung des historischen Gedenkens kritisch zu thematisieren sowie neue, zum eine lokal situierte, zum andern international orientierte Identifikationsangebote anzubieten. Die Analyse zeigt, dass solche „de-nationalisierten“ Identifikationsangebote zwar teilweise auch früher verwendet wurden, aber heutzutage rekontextualisiert und auf innovative Weise in den Vordergrund gestellt werden

Prebiotic Organic Microstructures

Micro- and sub-micrometer spheres, tubules and fiber-filament soft structures have been synthesized in our experiments conducted with 3 MeV proton irradiations of a mixture of simple inorganic constituents, CO, N2 and H2O. We analysed the irradiation products, with scanning electron microscopy (SEM) and atomic force microscopy (AFM). These laboratory organic structures produced wide variety of proteinous and non-proteinous amino acids after HCl hydrolysis. The enantiomer analysis for D-, L- alanine confirmed that the amino acids were abiotically synthesized during the laboratory experiment. Considering hydrothermal activity, the presence of CO2 and H2, of a ferromagnesian silicate mineral environment, of an Earth magnetic field which was much less intense during Archean times than nowadays and consequently of a proton excitation source which was much more abundant, we propose that our laboratory organic microstructures might be synthesized during Archean times. We show similarities in morphology and in formation with some terrestrial Archean microstructures and we suggest that some of the observed Archean carbon spherical and filamentous microstructures might be composed of abiogenic organic molecules. We further propose a search for such prebiotic organic signatures on Mars. This article has been posted on Nature precedings on 21 July 2010 [1]. Extinct radionuclides as source of excitation have been replaced by cosmic radiations which were much more intense 3.5 Ga ago because of a much less intense Earth magnetic field. The new version of the article has been presented at the ORIGINS conference in Montpellier in july 2011 [2] and has since been published in Origins of Life and Evolution of Biospheres 42 (4) 307-316, 2012. 
DOI: 10.1007/s11084-012-9290-5 

&#xa

Transformations in organic sulfur speciation during maturation of Monterey shale: Constraints from laboratory experiments

A series of hydrous pyrolysis experiments were conducted at temperatures ranging from 125 to 360C at 350 bars pressure to examine variations in sulfur speciation during thermal maturation of Monterey shale. The total sediment, kerogen and bitumen from each experiment in addition to unheated representatives were analyzed via x-ray absorption spectroscopy, pyrolysis-gas chromatography, {sup 30}NMR spectrometry, elemental analysis, thin-layer chromatography and reflected light microscopy. Based on these measurements, it was possible to recognize three distinct temperature regimes, within which the type and amount of sulfur in the analyzed fractions underwent transformations: (1) between 150 and 225C significant proportion of kerogen-bound sulfur is lost probably due to the collapse of polysulfide bridges; (2) between 225 and 275C, cleavage of -S-S- and -S-C- linkages within the kerogen is believed to occur, resulting in substantial production of polar sulfur-rich bitumen; (3) above 275C total bitumen yields as well as the proportion of bitumen sulfur decrease, while C-C bond scission leads to increased yields of saturated and aromatic hydrocarbons. The results from this study clearly and quantitatively establish a link between organically-bound sulfur, and more specifically, organic polysulfides, and the low-temperature evolution of soluble petroleum-like products (bitumen) from sulfur-rich source rocks

Chemistry of hot springs along the Eastern Lau Spreading Center

Author Posting. © The Author(s), 2010. 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 75 (2011): 1013-1038, doi:10.1016/j.gca.2010.12.008.The Eastern Lau Spreading Center (ELSC) is the southernmost part of the back-arc spreading axis in the Lau Basin, west of the Tonga trench and the active Tofua volcanic arc. Over its 397-km length it exhibits large and systematic changes in spreading rate, magmatic/tectonic processes, and proximity to the volcanic arc. In 2005 we collected 81 samples of vent water from six hydrothermal fields along the ELSC. The chemistry of these waters varies both within and between vent fields, in response to changes in substrate composition, temperature and pressure, pH, water/rock ratio, and input from magmatic gases and subducted sediment. Hot-spring temperatures range from 229º to 363ºC at the five northernmost fields, with a general decrease to the south that is reversed at the Mariner field. The southernmost field, Vai Lili, emitted water at up to 334°C in 1989 but had a maximum venting temperature of only 121ºC in 2005, due to waning activity and admixture of bottom seawater into the subseafloor plumbing system. Chloride varies both within fields and from one field to another, from a low of 528 mmol/kg to a high of 656 mmol/kg, and may be enriched by phase separation and/or leaching of Cl from the rock. Concentrations of the soluble elements K, Rb, Cs, and B likewise increase southward as the volcanic substrate becomes more silica-rich, especially on the Valu Fa Ridge. Iodine and δ7Li increase southward, and δ11B decreases as B increases, apparently in response to increased input from subducted sediment as the arc is approached. Species that decrease southward as temperature falls are Si, H2S, Li, Na/Cl, Fe, Mn, and 87Sr/86Sr, whereas pH, alkalinity, Ca, and Sr increase. Oxygen isotopes indicate a higher water/rock ratio in the three systems on Valu Fa Ridge, consistent with higher porosity in more felsic volcanic rocks. Vent waters at the Mariner vent field on the Valu Fa Ridge are significantly hotter, more acid and metal-rich, less saline, and richer in dissolved gases and other volatiles, including H2S, CO2, and F, than the other vent fields, consistent with input of magmatic gases. The large variations in geologic and geophysical parameters produced by back-arc spreading along the ELSC, which exceed those along mid-ocean ridge spreading axes, produce similar large variations in the composition of vent waters, and thus provide new insights into the processes that control the chemistry of submarine hot springs.We thank the U.S. National Science Foundation and its RIDGE 2000 Program for funding this study via grants OCE0241826 (to MJM), OCE0242902 (to PJM), OCE0241796 (to JSS, MKT), and OCE0242088 (to CGW), as well as the Deep Ocean Exploration Institute at WHOI (to GP, ER)

Chemical data quantify Deepwater Horizon hydrocarbon flow rate and environmental distribution

Author Posting. © The Author(s), 2011. This is the author's version of the work. It is posted here by permission of National Academy of Sciences for personal use, not for redistribution. The definitive version was published in Proceedings of the National Academy of Sciences of the United States of America (2012), doi:10.1073/pnas.1110564109.Detailed airborne, surface, and subsurface chemical measurements, primarily obtained in May and June 2010, are used to quantify initial hydrocarbon compositions along different transport pathways – in deep subsurface plumes, in the initial surface slick, and in the atmosphere – during the Deepwater Horizon (DWH) oil spill. Atmospheric measurements are consistent with a limited area of surfacing oil, with implications for leaked hydrocarbon mass transport and oil drop size distributions. The chemical data further suggest relatively little variation in leaking hydrocarbon composition over time. While readily soluble hydrocarbons made up ~25% of the leaking mixture by mass, subsurface chemical data show these compounds made up ~69% of the deep plume mass; only ~31% of deep plume mass was initially transported in the form of trapped oil droplets. Mass flows along individual transport pathways are also derived from atmospheric and subsurface chemical data. Subsurface hydrocarbon composition, dissolved oxygen, and dispersant data are used to provide a new assessment of release of hydrocarbons from the leaking well. We use the chemical measurements to estimate that (7.8±1.9) x106 kg of hydrocarbons leaked on June 10, 2010, directly accounting for roughly three-quarters of the total leaked mass on that day. The average environmental release rate of (10.1 ± 2.0) x106 kg/day derived using atmospheric and subsurface chemical data agrees within uncertainties with the official average leak rate of (10.2 ± 1.0) x106 kg/day derived using physical and optical methods.This research was supported by the National Science Foundation through grants to D. Blake (AGS-1049952), J. Kessler (OCE-1042650 and OCE-0849246), D. Valentine (OCE-1042097 and OCE-0961725), E. Kujawinski (OCE-1045811), and R. Camilli (OCE-1043976), by U.S. Coast Guard contract to R. Camilli (Contract HSCG3210CR0020), and by U.S. Department of Energy grant to D. Valentine (DE- NT0005667). The August, September, and October research cruises were funded by NOAA through a contract with Consolidated Safety Services, Incorporated. The NOAA P-3 oil spill survey flights were funded in part by NOAA and in part by a U.S. Coast Guard Pollution Removal Funding Authorization to NOAA

Effect of Cyclooxygenase(COX)-1 and COX-2 inhibition on furosemide-induced renal responses and isoform immunolocalization in the healthy cat kidney

BACKGROUND: The role of cyclooxygenase(COX)-1 and COX-2 in the saluretic and renin-angiotensin responses to loop diuretics in the cat is unknown. We propose in vivo characterisation of isoform roles in a furosemide model by administering non-steroidal anti-inflammatory drugs (NSAIDs) with differing selectivity profiles: robenacoxib (COX-2 selective) and ketoprofen (COX-1 selective). RESULTS: In this four period crossover study, we compared the effect of four treatments: placebo, robenacoxib once or twice daily and ketoprofen once daily concomitantly with furosemide in seven healthy cats. For each period, urine and blood samples were collected at baseline and within 48 h of treatment starting. Plasma renin activity (PRA), plasma and urinary aldosterone concentrations, glomerular filtration rate (GFR) and 24 h urinary volumes, electrolytes and eicosanoids (PGE(2), 6-keto-PGF1(α,) TxB(2)), renal injury biomarker excretions [N-acetyl-beta-D-glucosaminidase (NAG) and Gamma-Glutamyltransferase] were measured. Urine volume (24 h) and urinary sodium, chloride and calcium excretions increased from baseline with all treatments. Plasma creatinine increased with all treatments except placebo, whereas GFR was significantly decreased from baseline only with ketoprofen. PRA increased significantly with placebo and once daily robenacoxib and the increase was significantly higher with placebo compared to ketoprofen (10.5 ± 4.4 vs 4.9 ± 5.0 ng ml(−1) h(−1)). Urinary aldosterone excretion increased with all treatments but this increase was inhibited by 75 % with ketoprofen and 65 % with once daily robenacoxib compared to placebo. Urinary PGE(2) excretion decreased with all treatments and excretion was significantly lower with ketoprofen compared to placebo. Urinary TxB(2) excretion was significantly increased from baseline only with placebo. NAG increased from baseline with all treatments. Immunohistochemistry on post-mortem renal specimens, obtained from a different group of cats that died naturally of non-renal causes, suggested constitutive COX-1 and COX-2 co-localization in many renal structures including the macula densa (MD). CONCLUSIONS: These data suggest that both COX-1 and COX-2 could generate the signal from the MD to the renin secreting cells in cats exposed to furosemide. Co-localization of COX isoenzymes in MD cells supports the functional data reported here. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1186/s12917-015-0598-z) contains supplementary material, which is available to authorized users