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Nitrous oxide (N2O), a potent greenhouse gas, can be generated by multiple biological and abiotic processes in diverse contexts. Accurately tracking the dominant sources of N2O has the potential to improve our understanding of N2O fluxes from soils as well as inform the diagnosis of human infections. Isotopic "Site Preference" (SP) values have been used toward this end, as bacterial and fungal nitric oxide reductases (NORs) produce N2O with different isotopic fingerprints, spanning a large range. Here, we show that flavohemoglobin (Fhp), a hitherto biogeochemically neglected yet widely distributed detoxifying bacterial NO reductase, imparts a distinct SP value onto N2O under anoxic conditions (~+10) that correlates with typical environmental N2O SP measurements. Using Pseudomonas aeruginosa as a model organism, we generated strains that only contained Fhp or the dissimilatory NOR, finding that in vivo N2O SP values imparted by these enzymes differ by over 10. Depending on the cellular physiological state, the ratio of Fhp:NOR varies significantly in wild-type cells and controls the net N2O SP biosignature: When cells grow anaerobically under denitrifying conditions, NOR dominates; when cells experience rapid, increased nitric oxide concentrations under anoxic conditions but are not growing, Fhp dominates. Other bacteria that only make Fhp generate similar N2O SP biosignatures to those measured from our P. aeruginosa Fhp-only strain. Fhp homologs in sequenced bacterial genomes currently exceed NOR homologs by nearly a factor of four. Accordingly, we suggest a different framework to guide the attribution of N2O biological sources in nature and disease.
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Óxido Nitroso , Oxidorreductasas , Pseudomonas aeruginosa , Óxido Nitroso/metabolismo , Oxidorreductasas/metabolismo , Pseudomonas aeruginosa/metabolismo , Anaerobiosis , Proteínas Bacterianas/metabolismo , Proteínas Bacterianas/genética , Óxido Nítrico/metabolismoRESUMEN
The history of Earth's carbon cycle reflects trends in atmospheric composition convolved with the evolution of photosynthesis. Fortunately, key parts of the carbon cycle have been recorded in the carbon isotope ratios of sedimentary rocks. The dominant model used to interpret this record as a proxy for ancient atmospheric CO2 is based on carbon isotope fractionations of modern photoautotrophs, and longstanding questions remain about how their evolution might have impacted the record. Therefore, we measured both biomass (εp) and enzymatic (εRubisco) carbon isotope fractionations of a cyanobacterial strain (Synechococcus elongatus PCC 7942) solely expressing a putative ancestral Form 1B rubisco dating to â«1 Ga. This strain, nicknamed ANC, grows in ambient pCO2 and displays larger εp values than WT, despite having a much smaller εRubisco (17.23 ± 0.61 vs. 25.18 ± 0.31, respectively). Surprisingly, ANC εp exceeded ANC εRubisco in all conditions tested, contradicting prevailing models of cyanobacterial carbon isotope fractionation. Such models can be rectified by introducing additional isotopic fractionation associated with powered inorganic carbon uptake mechanisms present in Cyanobacteria, but this amendment hinders the ability to accurately estimate historical pCO2 from geological data. Understanding the evolution of rubisco and the CO2 concentrating mechanism is therefore critical for interpreting the carbon isotope record, and fluctuations in the record may reflect the evolving efficiency of carbon fixing metabolisms in addition to changes in atmospheric CO2.
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Dióxido de Carbono , Ribulosa-Bifosfato Carboxilasa , Isótopos de Carbono/metabolismo , Ribulosa-Bifosfato Carboxilasa/metabolismo , Dióxido de Carbono/metabolismo , Carbono/metabolismo , FotosíntesisRESUMEN
Subtle variations in stable isotope ratios at natural abundance are challenging to measure but can yield critical insights into biological, physical, and geochemical processes. Well-established methods, particularly multicollector, gas-source, or plasma isotope ratio mass spectrometry, are the gold standard for stable isotope measurement, but inherent limitations in these approaches make them ill-suited to determining site-specific and multiply substituted isotopic abundances of all but a few compounds or to characterizing larger intact molecules. Fourier transform mass spectrometry, namely, Orbitrap mass spectrometry, has recently demonstrated the ability to measure natural abundance isotope ratios with chemically informative accuracy and precision. Here, we report the first use of Fourier transform ion cyclotron resonance mass spectrometry for the accurate (<1) and precise (<1 standard error) simultaneous determination of δ13C and δ15N in caffeine isotopologues and provide a discussion of the critical instrumental parameters necessary to make such measurements. We further report the ability to make these measurements with online liquid chromatography, expanding the ability of this technique to explore mixtures in the future.
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Stable hydrogen isotope compositions (2H/1H ratios) have been an invaluable tool for studying biogeochemical processes in nature, but the diversity of molecular targets amenable to such analysis is limited. Here, we demonstrate a new technique for measuring δ2H of biomolecules via Orbitrap mass spectrometry (MS) using acetate as a model analyte. Acetate was chosen as a target molecule because its production and consumption are central to microbial carbon cycling, yet the mechanisms behind acetate turnover remain poorly understood. δ2H of acetate could provide a useful constraint on these processes; however, it remains uncharacterized in nature due to analytical challenges. Electrospray ionization (ESI)-Orbitrap MS circumvents these challenges and delivers methyl-specific H-isotope compositions of acetate with nanomole sensitivity, enough to enable analyses of environmental samples. This approach quantifies the methyl-specific δ2H and molecular-average δ13C of acetate simultaneously while achieving <3 and <0.5 uncertainty, respectively. Using optimized ionization and Orbitrap parameters, this level of precision is obtained within 15 min using only 15 nmol of acetate. As a demonstration of our analytical approach, we cultured three acetogenic bacteria and found a large 2H-fractionation between acetate and water (>310 depletion) associated with the Wood-Ljungdahl pathway, while fermentation expressed a muted (â¼80) fractionation. With its high precision and sensitivity, Orbitrap MS is a promising tool for investigating these signals in nature after offline purification. Furthermore, the ESI-Orbitrap method presented here could be applied to other molecules amenable to ESI, including central metabolites and sugars, greatly expanding the molecular targets used in hydrogen isotope biogeochemistry.
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Isótopos , Espectrometría de Masa por Ionización de Electrospray , Acetatos , Espectrometría de Masa por Ionización de Electrospray/métodosRESUMEN
RATIONALE: Position-specific 13 C/12 C ratios within amino acids remain largely unexplored in environmental samples due to methodological limitations. We hypothesized that natural-abundance isotope patterns in serine may serve as a proxy for plant metabolic fluxes including photorespiration. Here we describe an Orbitrap method optimized for the position-specific carbon isotope analysis of serine to test our hypothesis and discuss the generalizability of this method to other amino acids. METHODS: Position-specific carbon isotope ratios of serine were measured using a Thermo Scientific™ Q Exactive™ GC Orbitrap™. Amino acids were hydrolyzed from Arabidopsis biomass, purified from potential matrix interferences, and derivatized alongside standards. Derivatized serine (N,O-bis(trifluoroacetyl)methyl ester) was isolated using gas chromatography, trapped in a reservoir, and purged into the electron ionization source over tens of minutes, producing fragment ions containing different combinations of atoms from the serine-derivative molecule. The 13 C/12 C ratios of fragments with monoisotopic masses of 110.0217, 138.0166, and 165.0037 Da were monitored in the mass analyzer and used to calculate position-specific δ13 C values relative to a working standard. RESULTS: This methodology constrains position-specific δ13 C values for nanomole amounts of serine isolated from chemically complex mixtures. The δ13 C values of fragment ions of serine were characterized with ≤1 precisions, leading to propagated standard errors of 0.7-5 for each carbon position. Position-specific δ13 C values differed by up to ca 28 ± 5 between serine molecules hydrolyzed from plants grown under contrasting pCO2 , selected to promote different fluxes through photosynthesis and photorespiration. The method was validated using pure serine standards characterized offline. CONCLUSIONS: This study presents the first Orbitrap-based measurements of natural-abundance, position-specific carbon isotope variation in an amino acid isolated from a biological matrix. We present a method for the precise characterization of isotope ratios in serine and propose applications probing metabolism in plants. We discuss the potential for extending these approaches to other amino acids, paving the way for novel applications.
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Aminoácidos , Serina , Aminas/análisis , Aminoácidos/química , Isótopos de Carbono/análisis , Cromatografía de Gases y Espectrometría de Masas/métodosRESUMEN
The 18O/16O of calcite fossils increased by â¼8 between the Cambrian and present. It has long been controversial whether this change reflects evolution in the δ18O of seawater, or a decrease in ocean temperatures, or greater extents of diagenesis of older strata. Here, we present measurements of the oxygen and ?clumped" isotope compositions of Phanerozoic dolomites and compare these data with published oxygen isotope studies of carbonate rocks. We show that the δ18O values of dolomites and calcite fossils of similar age overlap one another, suggesting they are controlled by similar processes. Clumped isotope measurements of Cambrian to Pleistocene dolomites imply crystallization temperatures of 15-158 °C and parent waters having δ18OVSMOW values from -2 to +12. These data are consistent with dolomitization through sediment/rock reaction with seawater and diagenetically modified seawater, over timescales of 100 My, and suggest that, like dolomite, temporal variations of the calcite fossil δ18O record are largely driven by diagenetic alteration. We find no evidence that Phanerozoic seawater was significantly lower in δ18O than preglacial Cenozoic seawater. Thus, the fluxes of oxygen-isotope exchange associated with weathering and hydrothermal alteration reactions have remained stable throughout the Phanerozoic, despite major tectonic, climatic and biologic perturbations. This stability implies that a long-term feedback exists between the global rates of seafloor spreading and weathering. We note that massive dolomites have crystallized in pre-Cenozoic units at temperatures >40 °C. Since Cenozoic platforms generally have not reached such conditions, their thermal immaturity could explain their paucity of dolomites.
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Carbonato de Calcio/química , Cambio Climático/historia , Sedimentos Geológicos/química , Magnesio/química , Isótopos de Oxígeno/análisis , Oxígeno/análisis , Agua de Mar/química , Fósiles , Historia Antigua , Océanos y Mares , Temperatura , Factores de TiempoRESUMEN
The stable isotopes of sulfate, nitrate, and phosphate are frequently used to study geobiological processes of the atmosphere, ocean, as well as land. Conventionally, the isotopes of these and other oxyanions are measured by isotope-ratio sector mass spectrometers after conversion into gases. Such methods are prone to various limitations on sensitivity, sample throughput, or precision. In addition, there is no general tool that can analyze several oxyanions or all the chemical elements they contain. Here, we describe a new approach that can potentially overcome some of these limitations based on electrospray hyphenated with Quadrupole Orbitrap mass spectrometry. This technique yields an average accuracy of 1-2 for sulfate δ34S and δ18O and nitrate δ15N and δ18O, based on in-house and international standards. Less abundant variants such as δ17O, δ33S, and δ36S, and the 34S-18O "clumped" sulfate can be quantified simultaneously. The observed precision of isotope ratios is limited by the number of ions counted. The counting of rare ions can be accelerated by removing abundant ions with the quadrupole mass filter. Electrospray mass spectrometry (ESMS) exhibits high-throughput and sufficient sensitivity. For example, less than 1 nmol sulfate is required to determine 18O/34S ratios with 0.2 precision within minutes. A purification step is recommended for environmental samples as our proposed technique is susceptible to matrix effects. Building upon these initial provisions, new features of the isotopic anatomy of mineral ions can now be explored with ESMS instruments that are increasingly available to bioanalytical laboratories.
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Oxígeno/análisis , Aniones/análisis , Isótopos de Nitrógeno , Isótopos de Oxígeno , Espectrometría de Masa por Ionización de Electrospray , Isótopos de AzufreRESUMEN
The alanine transaminase enzyme catalyzes the transfer of an amino group from alanine to α-ketoglutarate to produce pyruvate and glutamate. Isotope fractionation factors (IFFs) for the reaction +H3NCH(CH3)COO- + -OOCCH2CH2C(O)COO- â CH3C(O)COO- + +H3NCH(CH2CH2COO-)COO- (zwitterionic neutral alanine + doubly deprotonated α-ketoglutarate â pyruvate + zwitterionic glutamate anion) were calculated from the partition functions of explicitly and implicitly solvated molecules at 298 K. Calculations were done for alanine (noncharge separated, zwitterion, deprotonated), pyruvic acid (neutral, deprotonated), glutamic acid (noncharge separated, zwitterion, deprotonated, doubly deprotonated), and α-ketoglutaric acid (neutral, deprotonated, doubly deprotonated). The computational results, calculated from gas phase- and aqueous-optimized clusters with explicit H2O molecules at the MP2/aug-cc-pVDZ and MP2/aug-cc-pVDZ/COSMO levels, respectively, predict that substitution of 13C at the C2 position of alanine and pyruvic acid and their various forms leads to the C2 position of pyruvic acid/pyruvate being enriched in 13C/12C ratio by 9. Simpler approaches that estimate the IFFs based solely on changes in the zero-point energies (ZPEs) are consistent with the higher-level model. ZPE-based IFFs calculated for simple analogues formaldehyde and methylamine (analogous to the C2 positions of pyruvate and alanine, respectively) predict a 13C enrichment in formaldehyde of 7-8 at the MP2/aug-cc-pVDZ and aug-cc-pVTZ levels. A simple predictive model using canonical functional group frequencies and reduced masses for 13C exchange between R2CâO and R2CH-NH2 predicted enrichment in R2CâO that is too large by a factor of two but is qualitatively accurate compared with the more sophisticated models. Our models are all in agreement with the expectation that pyruvate and formaldehyde will be preferentially enriched in 13C because of the strength of their >CâO bond relative to that of ≡C-NH2 in alanine and methylamine. 13C/12C substitution is also modeled at the methyl and carboxylic acid sites of alanine and pyruvic acid, respectively.
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Several large and rapid changes in atmospheric temperature and the partial pressure of carbon dioxide in the atmosphere--probably linked to changes in deep ocean circulation--occurred during the last deglaciation. The abrupt temperature rise in the Northern Hemisphere and the restart of the Atlantic meridional overturning circulation at the start of the Bølling-Allerød interstadial, 14,700 years ago, are among the most dramatic deglacial events, but their underlying physical causes are not known. Here we show that the release of heat from warm waters in the deep North Atlantic Ocean probably triggered the Bølling-Allerød warming and reinvigoration of the Atlantic meridional overturning circulation. Our results are based on coupled radiocarbon and uranium-series dates, along with clumped isotope temperature estimates, from water column profiles of fossil deep-sea corals in a limited area of the western North Atlantic. We find that during Heinrich stadial 1 (the cool period immediately before the Bølling-Allerød interstadial), the deep ocean was about three degrees Celsius warmer than shallower waters above. This reversal of the ocean's usual thermal stratification pre-dates the Bølling-Allerød warming and must have been associated with increased salinity at depth to preserve the static stability of the water column. The depleted radiocarbon content of the warm and salty water mass implies a long-term disconnect from rapid surface exchanges, and, although uncertainties remain, is most consistent with a Southern Ocean source. The Heinrich stadial 1 ocean profile is distinct from the modern water column, that for the Last Glacial Maximum and that for the Younger Dryas, suggesting that the patterns we observe are a unique feature of the deglacial climate system. Our observations indicate that the deep ocean influenced dramatic Northern Hemisphere warming by storing heat at depth that preconditioned the system for a subsequent abrupt overturning event during the Bølling-Allerød interstadial.
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Calor , Agua de Mar/análisis , Movimientos del Agua , Animales , Antozoos/fisiología , Océano Atlántico , Radioisótopos de Carbono , Calentamiento Global/historia , Historia Antigua , Cubierta de Hielo , Factores de TiempoRESUMEN
The release of methane into the atmosphere through destabilization of clathrates is a positive feedback mechanism capable of amplifying global warming trends that may have operated several times in the geological past. Such methane release is a hypothesized cause or amplifier for one of the most drastic global warming events in Earth history, the end of the Marinoan 'snowball Earth' ice age, â¼635 Myr ago. A key piece of evidence supporting this hypothesis is the occurrence of exceptionally depleted carbon isotope signatures (δ(13)C(PDB) down to -48; ref. 8) in post-glacial cap dolostones (that is, dolostone overlying glacial deposits) from south China; these signatures have been interpreted as products of methane oxidation at the time of deposition. Here we show, on the basis of carbonate clumped isotope thermometry, (87)Sr/(86)Sr isotope ratios, trace element content and clay mineral evidence, that carbonates bearing the (13)C-depleted signatures crystallized more than 1.6 Myr after deposition of the cap dolostone. Our results indicate that highly (13)C-depleted carbonate cements grew from hydrothermal fluids and suggest that their carbon isotope signatures are a consequence of thermogenic methane oxidation at depth. This finding not only negates carbon isotope evidence for methane release during Marinoan deglaciation in south China, but also eliminates the only known occurrence of a Precambrian sedimentary carbonate with highly (13)C-depleted signatures related to methane oxidation in a seep environment. We propose that the capacity to form highly (13)C-depleted seep carbonates, through biogenic anaeorobic oxidation of methane using sulphate, was limited in the Precambrian period by low sulphate concentrations in sea water. As a consequence, although clathrate destabilization may or may not have had a role in the exit from the 'snowball' state, it would not have left extreme carbon isotope signals in cap dolostones.
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Sedimentos Geológicos/química , Isótopos de Carbono/análisis , China , Sedimentos Geológicos/análisis , Isótopos de Oxígeno/análisis , Temperatura , Oligoelementos/análisisRESUMEN
Many aspects of Earth's early sulfur cycle, from the origin of mass-anomalous fractionations to the degree of biological participation, remain poorly understood--in part due to complications from postdepositional diagenetic and metamorphic processes. Using a combination of scanning high-resolution magnetic superconducting quantum interference device (SQUID) microscopy and secondary ion mass spectrometry (SIMS) of sulfur isotopes ((32)S, (33)S, and (34)S), we examined drill core samples from slope and basinal environments adjacent to a major Late Archean (â¼2.6-2.5 Ga) marine carbonate platform from South Africa. Coupled with petrography, these techniques can untangle the complex history of mineralization in samples containing diverse sulfur-bearing phases. We focused on pyrite nodules, precipitated in shallow sediments. These textures record systematic spatial differences in both mass-dependent and mass-anomalous sulfur-isotopic composition over length scales of even a few hundred microns. Petrography and magnetic imaging demonstrate that mass-anomalous fractionations were acquired before burial and compaction, but also show evidence of postdepositional alteration 500 million y after deposition. Using magnetic imaging to screen for primary phases, we observed large spatial gradients in Δ(33)S (>4) in nodules, pointing to substantial environmental heterogeneity and dynamic mixing of sulfur pools on geologically rapid timescales. In other nodules, large systematic radial δ(34)S gradients (>20) were observed, from low values near their centers increasing to high values near their rims. These fractionations support hypotheses that microbial sulfate reduction was an important metabolism in organic-rich Archean environments--even in an Archean ocean basin dominated by iron chemistry.
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Ambiente , Evolución Química , Microscopía de Interferencia/instrumentación , Microscopía de Interferencia/métodos , Isótopos de Azufre/química , Carbonatos/química , Fraccionamiento Químico , Geología , Historia Antigua , Espectrometría de Masas , SudáfricaRESUMEN
RATIONALE: Bulk and position-specific stable isotope characterization of nitrous oxide represents one of the most powerful tools for identifying its environmental sources and sinks. Constraining (14) N(15) N(18) O and (15) N(14) N(18) O will add two new dimensions to our ability to uniquely fingerprint N2 O sources. METHODS: We describe a technique to measure six singly and doubly substituted isotopic variants of N2 O, constraining the values of δ(15) N, δ(18) O, ∆(17) O, (15) N site preference, and the clumped isotopomers (14) N(15) N(18) O and (15) N(14) N(18) O. The technique uses a Thermo MAT 253 Ultra, a high-resolution multi-collector gas source isotope ratio mass spectrometer. It requires 8-10 hours per sample and ~10 micromoles or more of pure N2 O. RESULTS: We demonstrate the precision and accuracy of these measurements by analyzing N2 O brought to equilibrium in its position-specific and clumped isotopic composition by heating in the presence of a catalyst. Finally, an illustrative analysis of biogenic N2 O from a denitrifying bacterium suggests that its clumped isotopic composition is controlled by kinetic isotope effects in N2 O production. CONCLUSIONS: We developed a method for measuring six isotopic variants of N2 O and tested it with analyses of biogenic N2 O. The added isotopic constraints provided by these measurements will enhance our ability to apportion N2 O sources.
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The Moon is thought to be depleted relative to the Earth in volatile elements such as H, Cl and the alkalis. Nevertheless, evidence for lunar explosive volcanism has been used to infer that some lunar magmas exsolved a CO-rich and CO(2)-rich vapour phase before or during eruption. Although there is also evidence for other volatile species on glass spherules, until recently there had been no unambiguous reports of indigenous H in lunar rocks. Here we report quantitative ion microprobe measurements of late-stage apatite from lunar basalt 14053 that document concentrations of H, Cl and S that are indistinguishable from apatites in common terrestrial igneous rocks. These volatile contents could reflect post-magmatic metamorphic volatile addition or growth from a late-stage, interstitial, sulphide-saturated melt that contained approximately 1,600 parts per million H(2)O and approximately 3,500 parts per million Cl. Both metamorphic and igneous models of apatite formation suggest a volatile inventory for at least some lunar materials that is similar to comparable terrestrial materials. One possible implication is that portions of the lunar mantle or crust are more volatile-rich than previously thought.
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The East Asian monsoon is one of Earth's most significant climatic phenomena, and numerous paleoclimate archives have revealed that it exhibits variations on orbital and suborbital time scales. Quantitative constraints on the climate changes associated with these past variations are limited, yet are needed to constrain sensitivity of the region to changes in greenhouse gas levels. Here, we show central China is a region that experienced a much larger temperature change since the Last Glacial Maximum than typically simulated by climate models. We applied clumped isotope thermometry to carbonates from the central Chinese Loess Plateau to reconstruct temperature and water isotope shifts from the Last Glacial Maximum to present. We find a summertime temperature change of 6-7 °C that is reproduced by climate model simulations presented here. Proxy data reveal evidence for a shift to lighter isotopic composition of meteoric waters in glacial times, which is also captured by our model. Analysis of model outputs suggests that glacial cooling over continental China is significantly amplified by the influence of stationary waves, which, in turn, are enhanced by continental ice sheets. These results not only support high regional climate sensitivity in Central China but highlight the fundamental role of planetary-scale atmospheric dynamics in the sensitivity of regional climates to continental glaciation, changing greenhouse gas levels, and insolation.
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Cambio Climático/historia , Modelos Químicos , Temperatura , Ciclo Hidrológico , Exoesqueleto/química , Animales , Isótopos de Carbono/análisis , China , Simulación por Computador , Gastrópodos/química , Historia Antigua , Cubierta de Hielo , Isótopos de Oxígeno/análisis , Suelo/análisis , TermometríaRESUMEN
We present evidence that a rock sample found in the Koryak Mountains in Russia and containing icosahedrite, an icosahedral quasicrystalline phase with composition Al(63)Cu(24)Fe(13), is part of a meteorite, likely formed in the early solar system about 4.5 Gya. The quasicrystal grains are intergrown with diopside, forsterite, stishovite, and additional metallic phases [khatyrkite (CuAl(2)), cupalite (CuAl), and ß-phase (AlCuFe)]. This assemblage, in turn, is enclosed in a white rind consisting of diopside, hedenbergite, spinel (MgAl(2)O(4)), nepheline, and forsterite. Particularly notable is a grain of stishovite (from the interior), a tetragonal polymorph of silica that only occurs at ultrahigh pressures (≥ 10 Gpa), that contains an inclusion of quasicrystal. An extraterrestrial origin is inferred from secondary ion mass spectrometry (18)O/(16)O and (17)O/(16)O measurements of the pyroxene and olivine intergrown with the metal that show them to have isotopic compositions unlike any terrestrial minerals and instead overlap those of anhydrous phases in carbonaceous chondrite meteorites. The spinel from the white rind has an isotopic composition suggesting that it was part of a calcium-aluminum-rich inclusion similar to those found in CV3 chondrites. The mechanism that produced this exotic assemblage is not yet understood. The assemblage (metallic copper-aluminum alloy) is extremely reduced, and the close association of aluminum (high temperature refractory lithophile) with copper (low temperature chalcophile) is unexpected. Nevertheless, our evidence indicates that quasicrystals can form naturally under astrophysical conditions and remain stable over cosmic timescales, giving unique insights on their existence in nature and stability.
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The 3.45-billion-year-old Strelley Pool Formation of Western Australia preserves stromatolites that are considered among the oldest evidence for life on Earth. In places of exceptional preservation, these stromatolites contain laminae rich in organic carbon, interpreted as the fossil remains of ancient microbial mats. To better understand the biogeochemistry of these rocks, we performed microscale in situ sulfur isotope measurements of the preserved organic sulfur, including both Δ(33)S and . This approach allows us to tie physiological inference from isotope ratios directly to fossil biomass, providing a means to understand sulfur metabolism that is complimentary to, and independent from, inorganic proxies (e.g., pyrite). Δ(33)S values of the kerogen reveal mass-anomalous fractionations expected of the Archean sulfur cycle, whereas values show large fractionations at very small spatial scales, including values below -15. We interpret these isotopic patterns as recording the process of sulfurization of organic matter by H(2)S in heterogeneous mat pore-waters influenced by respiratory S metabolism. Positive Δ(33)S anomalies suggest that disproportionation of elemental sulfur would have been a prominent microbial process in these communities.
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Isótopos de Azufre/química , Archaea/fisiología , Australia , Fósiles , Sedimentos Geológicos , Geología/métodos , Sulfuro de Hidrógeno/química , Iones , Compuestos Orgánicos/química , Isótopos de Azufre/análisisRESUMEN
Perchlorate is a persistent and mobile contaminant in the environment with both natural and anthropogenic sources. Stable isotope ratios of oxygen (δ(18)O, Δ(17)O) and chlorine (δ(37)Cl) along with the abundance of the radioactive isotope (36)Cl were used to trace perchlorate sources and behavior in the Laurentian Great Lakes. These lakes were selected for study as a likely repository of recent atmospheric perchlorate deposition. Perchlorate concentrations in the Great Lakes range from 0.05 to 0.13 µg per liter. δ(37)Cl values of perchlorate from the Great Lakes range from +3.0 (Lake Ontario) to +4.0 (Lake Superior), whereas δ(18)O values range from -4.1 (Lake Superior) to +4.0 (Lake Erie). Great Lakes perchlorate has mass-independent oxygen isotopic variations with positive Δ(17)O values (+1.6 to +2.7) divided into two distinct groups: Lake Superior (+2.7) and the other four lakes (â¼+1.7). The stable isotopic results indicate that perchlorate in the Great Lakes is dominantly of natural origin, having isotopic composition resembling that measured for indigenous perchlorate from preindustrial groundwaters of the western USA. The (36)Cl/Cl ratio of perchlorate varies widely from 7.4 × 10(-12) (Lake Ontario) to 6.7 × 10(-11) (Lake Superior). These (36)ClO4(-) abundances are consistent with an atmospheric origin of perchlorate in the Great Lakes. The relatively high (36)ClO4(-) abundances in the larger lakes (Lakes Superior and Michigan) could be explained by the presence of (36)Cl-enriched perchlorate deposited during the period of elevated atmospheric (36)Cl activity following thermonuclear bomb tests in the Pacific Ocean.
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Lagos/química , Percloratos/química , Cloro/análisis , Great Lakes Region , Agua Subterránea , Isótopos/análisis , Percloratos/análisisRESUMEN
Despite evidence for liquid water at the surface of Mars during the Noachian epoch, the temperature of early aqueous environments has been impossible to establish, raising questions of whether the surface of Mars was ever warmer than today. We address this problem by determining the precipitation temperature of secondary carbonate minerals preserved in the oldest known sample of Mars' crust--the approximately 4.1 billion-year-old meteorite Allan Hills 84001 (ALH84001). The formation environment of these carbonates, which are constrained to be slightly younger than the crystallization age of the rock (i.e., 3.9 to 4.0 billion years), has been poorly understood, hindering insight into the hydrologic and carbon cycles of earliest Mars. Using "clumped" isotope thermometry we find that the carbonates in ALH84001 precipitated at a temperature of approximately 18 °C, with water and carbon dioxide derived from the ancient Martian atmosphere. Furthermore, covarying carbonate carbon and oxygen isotope ratios are constrained to have formed at constant, low temperatures, pointing to deposition from a gradually evaporating, subsurface water body--likely a shallow aquifer (meters to tens of meters below the surface). Despite the mild temperatures, the apparently ephemeral nature of water in this environment leaves open the question of its habitability.
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Carbon capture and storage (CCS) of CO2 is a key technology for substantially mitigating global greenhouse gas emissions. Determining the biogeochemical processes in host rocks after CO2 injection informs the viability of carbon storage as a long-term sink for CO2, the complexity of reservoir CH4 cycling, as well as the direct and indirect environmental impacts of this strategy. The doubly substituted ('clumped') isotopologues of methane (13CH3D and 12CH2D2) provide novel insights into methane origins and post-generation processing. Here, we report the chemical compositions of hydrocarbons (C1/C2+ molecular ratios), and methane bulk and clumped isotopes (δ13C, δD, Δ13CH3D and Δ12CH2D2) of a CO2 enhanced coal bed methane recovery (CO2-ECBM) area in Qinshui basin, China and is an analogue for carbon capture and storage. The clumped isotopologue compositions observed in the study area are generally consistent with a range of temperatures spanning 73 to 193 °C. The range in apparent temperature and correlations among clumped and bulk isotopic indices are best explained by mixing between a high maturity thermogenic methane (high in δ13C and δD, with a clumped isotope composition equilibrated near â¼249 °C) and biogenic methane formed or processed in the reservoir (low in δ13C and δD, with a clumped isotope composition equilibrated near 16-27 °C). We hypothesize that the biogenic endmember may result from slow methanogenesis and/or anaerobic oxidation of methane (AOM). This study demonstrates that the potential of methane clumped isotope approach to identify in situ microbial metabolic processes and their association with carbon cycling in CO2-ECBM area, improving our understanding of biogeochemical mechanisms in analogous geological reservoirs.
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Atmospheric carbon dioxide concentrations seem to have been several times modern levels during much of the Palaeozoic era (543-248 million years ago), but decreased during the Carboniferous period to concentrations similar to that of today. Given that carbon dioxide is a greenhouse gas, it has been proposed that surface temperatures were significantly higher during the earlier portions of the Palaeozoic era. A reconstruction of tropical sea surface temperatures based on the delta18O of carbonate fossils indicates, however, that the magnitude of temperature variability throughout this period was small, suggesting that global climate may be independent of variations in atmospheric carbon dioxide concentration. Here we present estimates of sea surface temperatures that were obtained from fossil brachiopod and mollusc shells using the 'carbonate clumped isotope' method-an approach that, unlike the delta18O method, does not require independent estimates of the isotopic composition of the Palaeozoic ocean. Our results indicate that tropical sea surface temperatures were significantly higher than today during the Early Silurian period (443-423 Myr ago), when carbon dioxide concentrations are thought to have been relatively high, and were broadly similar to today during the Late Carboniferous period (314-300 Myr ago), when carbon dioxide concentrations are thought to have been similar to the present-day value. Our results are consistent with the proposal that increased atmospheric carbon dioxide concentrations drive or amplify increased global temperatures.