Earth shaped by primordial H2 atmospheres.

Earth's water, intrinsic oxidation state and metal core density are fundamental chemical features of our planet. Studies of exoplanets provide a useful context for elucidating the source of these chemical traits. Planet formation and evolution models demonstrate that rocky exoplanets commonly formed with hydrogen-rich envelopes that were lost over time1. These findings suggest that Earth may also have formed from bodies with hydrogen-rich primary atmospheres. Here we use a self-consistent thermodynamic model to show that Earth's water, core density and overall oxidation state can all be sourced to equilibrium between hydrogen-rich primary atmospheres and underlying magma oceans in its progenitor planetary embryos. Water is produced from dry starting materials resembling enstatite chondrites as oxygen from magma oceans reacts with hydrogen. Hydrogen derived from the atmosphere enters the magma ocean and eventually the metal core at equilibrium, causing metal density deficits matching that of Earth. Oxidation of the silicate rocks from solar-like to Earth-like oxygen fugacities also ensues as silicon, along with hydrogen and oxygen, alloys with iron in the cores. Reaction with hydrogen atmospheres and metal-silicate equilibrium thus provides a simple explanation for fundamental features of Earth's geochemistry that is consistent with rocky planet formation across the Galaxy.

In Situ Quantification of Biological N2 Production Using Naturally Occurring 15N15N.

We describe an approach for determining biological N2 production in soils based on the proportions of naturally occurring 15N15N in N2. Laboratory incubation experiments reveal that biological N2 production, whether by denitrification or anaerobic ammonia oxidation, yields proportions of 15N15N in N2 that are within 1‰ of that predicted for a random distribution of 15N and 14N atoms. This relatively invariant isotopic signature contrasts with that of the atmosphere, which has 15N15N proportions in excess of the random distribution by 19.1 ± 0.1‰. Depth profiles of gases in agricultural soils from the Kellogg Biological Station Long-Term Ecological Research site show biological N2 accumulation that accounts for up to 1.6% of the soil N2. One-dimensional reaction-diffusion modeling of these soil profiles suggests that subsurface N2 pulses leading to surface emission rates as low as 0.3 mmol N2 m-2 d-1 can be detected with current analytical precision, decoupled from N2O production.

The First Samples from Almahata Sitta Showing Contacts Between Ureilitic and Chondritic Lithologies: Implications for the Structure and Composition of Asteroid 2008 TC3.

Almahata Sitta (AhS), an anomalous polymict ureilite, is the first meteorite observed to originate from a spectrally classified asteroid (2008 TC3). However, correlating properties of the meteorite with those of the asteroid is not straightforward because the AhS stones are diverse types. Of those studied prior to this work, 70-80% are ureilites (achondrites) and 20-30% are various types of chondrites. Asteroid 2008 TC3 was a heterogeneous breccia that disintegrated in the atmosphere, with its clasts landing on Earth as individual stones and most of its mass lost. We describe AhS 91A and AhS 671, which are the first AhS stones to show contacts between ureilitic and chondritic materials and provide direct information about the structure and composition of asteroid 2008 TC3. AhS 91A and AhS 671 are friable breccias, consisting of a C1 lithology that encloses rounded to angular clasts (<10 µm to 3 mm) of olivine, pyroxenes, plagioclase, graphite, and metal-sulfide, as well as chondrules (~130-600 µm) and chondrule fragments. The C1 material consists of fine-grained phyllosilicates (serpentine and saponite) and amorphous material, magnetite, breunnerite, dolomite, fayalitic olivine (Fo 28-42), an unidentified Ca-rich silicate phase, Fe,Ni sulfides, and minor Ca-phosphate and ilmenite. It has similarities to CI1 but shows evidence of heterogeneous thermal metamorphism. Its bulk oxygen isotope composition (δ18O = 13.53‰, δ17O = 8.93‰) is unlike that of any known chondrite, but similar to compositions of several CC-like clasts in typical polymict ureilites. Its Cr isotope composition is unlike that of any known meteorite. The enclosed clasts and chondrules do not belong to the C1 lithology. The olivine (Fo 75-88), pyroxenes (pigeonite of Wo ~10 and orthopyroxene of Wo ~4.6), plagioclase, graphite, and some metal-sulfide are ureilitic, based on mineral compositions, textures, and oxygen isotope compositions, and represent at least six distinct ureilitic lithologies. The chondrules are probably derived from type 3 OC and/or CC, based on mineral and oxygen isotope compositions. Some of the metal-sulfide clasts are derived from EC. AhS 91A and AhS 671 are plausible representatives of the bulk of the asteroid that was lost. Reflectance spectra of AhS 91A are dark (reflectance ~0.04-0.05) and relatively featureless in VNIR, and have an ~2.7 µm absorption band due to OH- in phyllosilicates. Spectral modeling, using mixtures of laboratory VNIR reflectance spectra of AhS stones to fit the F-type spectrum of the asteroid, suggests that 2008 TC3 consisted mainly of ureilitic and AhS 91A-like materials, with as much as 40-70% of the latter, and <10% of OC, EC and other meteorite types. The bulk density of AhS 91A (2.35 ± 0.05 g/cm3) is lower than bulk densities of other AhS stones, and closer to estimates for the asteroid (~1.7-2.2 g/cm3). Its porosity (36%) is near the low end of estimates for the asteroid (33-50%), suggesting significant macroporosity. The textures of AhS 91A and AhS 671 (finely comminuted clasts of disparate materials intimately mixed) support formation of 2008 TC3 in a regolith environment. AhS 91A and AhS 671 could represent a volume of regolith formed when a CC-like body impacted into already well-gardened ureilitic + impactor-derived debris. AhS 91A bulk samples do not show a solar wind (SW) component, so they represent sub-surface layers. AhS 91A has a lower cosmic ray exposure (CRE) age (~5-9 Ma) than previously studied AhS stones (11-22 Ma). The spread in CRE ages argues for irradiation in a regolith environment. AhS 91A and AhS 671 show that ureilitic asteroids could have detectable ~2.7 µm absorption bands.

Short time interval for condensation of high-temperature silicates in the solar accretion disk.

Chondritic meteorites are made of primitive components that record the first steps of formation of solids in our Solar System. Chondrules are the major component of chondrites, yet little is known about their formation mechanisms and history within the solar protoplanetary disk (SPD). We use the reconstructed concentrations of short-lived (26)Al in chondrules to constrain the timing of formation of their precursors in the SPD. High-precision bulk magnesium isotopic measurements of 14 chondrules from the Allende chondrite define a (26)Al isochron with (26)Al/(27)Al = 1.2(±0.2) × 10(-5) for this subset of Allende chondrules. This can be considered to be the minimum bulk chondrule (26)Al isochron because all chondrules analyzed so far with high precision (∼50 chondrules from CV and ordinary chondrites) have an inferred minimum bulk initial ((26)Al/(27)Al) ≥ 1.2 × 10(-5). In addition, mineral (26)Al isochrons determined on the same chondrules show that their formation (i.e., fusion of their precursors by energetic events) took place from 0 Myr to ∼2 Myr after the formation of their precursors, thus showing in some cases a clear decoupling in time between the two events. The finding of a minimum bulk chondrule (26)Al isochron is used to constrain the astrophysical settings for chondrule formation. Either the temperature of the condensation zone dropped below the condensation temperature of chondrule precursors at ∼1.5 My after the start of the Solar System or the transport of precursors from the condensation zone to potential storage sites stopped after 1.5 My, possibly due to a drop in the disk accretion rate.

Early Solar System hydrothermal activity in chondritic asteroids on 1-10-year timescales.

Chondritic meteorites are considered the most primitive remnants of planetesimals from the early Solar System. As undifferentiated objects, they also display widespread evidence of water-rock interaction on the parent body. Understanding this history has implications for the formation of planetary bodies, the delivery of water to the inner Solar System, and the formation of prebiotic molecules. The timescales of water-rock reactions in these early objects, however, are largely unknown. Here, we report evidence for short-lived water-rock reactions in the highly metamorphosed ordinary chondrite breccia Villalbeto de la Peña (L6). An exotic clast (d = 2cm) has coexisting variations in feldspar composition and oxygen isotope ratios that can only result from hydrothermal conditions. The profiles were modeled at T = 800 °C and P(H(2)O) = 1 bar using modified grain-boundary diffusion parameters for oxygen self-diffusion and reaction rates of NaSiCa(-1)Al(-1) exchange in a fumarole. The geochemical data are consistent with hydrothermal activity on the parent body lasting only 1-10 y. This result has wide-ranging implications for the geological history of chondritic asteroids.

High-precision determination of ¹³C-¹8O bonds in CO2 using multicollector peak hopping.

RATIONALE: Rapid development of the CO2 'clumped-isotope' temperature proxy (Δ47 ) has involved both resource- and labor-intensive analytical methods. We report strategies for measuring Δ47 on a conventional mass spectrometer, with the usual CO2 set of three Faraday collectors while reducing the time devoted to standardization with temperature-equilibrated CO2. METHODS: We measured Δ47 in CO2 on a mass spectrometer using only three Faraday cups by 'multicollector peak hopping', directing (46)CO2(+) and (47)CO2(+) ion beams into the Faraday cups normally used for m/z 44 and 45. Δ47 was calculated from the previously measured δ(13) C and δ(18) O values and we then measured (47)CO2(+)/(46)CO2(+). We invoke a protocol for correcting ion-beam intensities for secondary electrons to address common problems with compositional non-linearity and both long- and short-term measurement stability. RESULTS: Our method eliminates the need for six Faraday cups for measuring Δ47, a possible advantage for many laboratories. In addition, by using a correction based on removing the effects of secondary electrons, we remove the Δ47 dependence on δ(47)CO2. As a result, our methods are robust against mass spectrometer operating conditions. CONCLUSIONS: Δ47 can be precisely measured on mass spectrometers currently employed for measuring δ(13) C and δ(18) O values without significant resource investment. Accounting for ion scatter during measurements of CO2 results in improved external precision and long-term stability, while significantly increasing the machine time available for sample analysis.

Well-hidden methanogenesis in deep, organic-rich sediments of Guaymas Basin.

Deep marine sediments (>1mbsf) harbor ~26% of microbial biomass and are the largest reservoir of methane on Earth. Yet, the deep subsurface biosphere and controls on its contribution to methane production remain underexplored. Here, we use a multidisciplinary approach to examine methanogenesis in sediments (down to 295 mbsf) from sites with varying degrees of thermal alteration (none, past, current) at Guaymas Basin (Gulf of California) for the first time. Traditional (13C/12C and D/H) and multiply substituted (13CH3D and 12CH2D2) methane isotope measurements reveal significant proportions of microbial methane at all sites, with the largest signal at the site with past alteration. With depth, relative microbial methane decreases at differing rates between sites. Gibbs energy calculations confirm methanogenesis is exergonic in Guaymas sediments, with methylotrophic pathways consistently yielding more energy than the canonical hydrogenotrophic and acetoclastic pathways. Yet, metagenomic sequencing and cultivation attempts indicate that methanogens are present in low abundance. We find only one methyl-coenzyme M (mcrA) sequence within the entire sequencing dataset. Also, we identify a wide diversity of methyltransferases (mtaB, mttB), but only a few sequences phylogenetically cluster with methylotrophic methanogens. Our results suggest that the microbial methane in the Guaymas subsurface was produced over geologic time by relatively small methanogen populations, which have been variably influenced by thermal sediment alteration. Higher resolution metagenomic sampling may clarify the modern methanogen community. This study highlights the importance of using a multidisciplinary approach to capture microbial influences in dynamic, deep subsurface settings like Guaymas Basin.

Igneous meteorites suggest Aluminium-26 heterogeneity in the early Solar Nebula.

The short-lived radionuclide aluminium-26 (26Al) isotope is a major heat source for early planetary melting. The aluminium-26 - magnesium-26 (26Al-26Mg) decay system also serves as a high-resolution relative chronometer. In both cases, however, it is critical to establish whether 26Al was homogeneously or heterogeneously distributed throughout the solar nebula. Here we report a precise lead-207 - lead-206 (207Pb-206Pb) isotopic age of 4565.56 ± 0.12 million years (Ma) for the andesitic achondrite Erg Chech 002. Our analysis, in conjunction with published 26Al-26Mg data, reveals that the initial 26Al/27Al in the source material of this achondrite was notably higher than in various other well-preserved and precisely dated achondrites. Here we demonstrate that the current data clearly indicate spatial heterogeneity of 26Al by a factor of 3-4 in the precursor molecular cloud or the protoplanetary disk of the Solar System, likely associated with the late infall of stellar materials with freshly synthesized radionuclides.

The UCLA Cosmochemistry Database.

The UCLA Cosmochemistry Database was initiated as part of a data-rescue and -storage project aimed at archiving a variety of cosmochemical data acquired at University of California, Los Angeles (UCLA). The data collection includes elemental compositions of extraterrestrial materials analyzed by UCLA cosmochemists over the last five decades. The analytical techniques include atomic absorption spectrometry (AAS) and neutron activation analysis (NAA) at UCLA. The data collection is stored on the Astromaterials Data System (Astromat). We provide both interactive tables and downloadable datasheets for users to access all data. The UCLA Cosmochemistry Database archives cosmochemical data that are essential tools for increasing our understanding of the nature and origin of extraterrestrial materials. Future studies can reference the data collection in the examination, analysis, and classification of newly acquired extraterrestrial samples.

Samples returned from the asteroid Ryugu are similar to Ivuna-type carbonaceous meteorites.

Carbonaceous meteorites are thought to be fragments of C-type (carbonaceous) asteroids. Samples of the C-type asteroid (162173) Ryugu were retrieved by the Hayabusa2 spacecraft. We measured the mineralogy and bulk chemical and isotopic compositions of Ryugu samples. The samples are mainly composed of materials similar to those of carbonaceous chondrite meteorites, particularly the CI (Ivuna-type) group. The samples consist predominantly of minerals formed in aqueous fluid on a parent planetesimal. The primary minerals were altered by fluids at a temperature of 37° ± 10°C, about [Formula: see text] million (statistical) or [Formula: see text] million (systematic) years after the formation of the first solids in the Solar System. After aqueous alteration, the Ryugu samples were likely never heated above ~100°C. The samples have a chemical composition that more closely resembles that of the Sun's photosphere than other natural samples do.

Oxygen fugacities of extrasolar rocks: Evidence for an Earth-like geochemistry of exoplanets.

Oxygen fugacity is a measure of rock oxidation that influences planetary structure and evolution. Most rocky bodies in the Solar System formed at oxygen fugacities approximately five orders of magnitude higher than a hydrogen-rich gas of solar composition. It is unclear whether this oxidation of rocks in the Solar System is typical among other planetary systems. We exploit the elemental abundances observed in six white dwarfs polluted by the accretion of rocky bodies to determine the fraction of oxidized iron in those extrasolar rocky bodies and therefore their oxygen fugacities. The results are consistent with the oxygen fugacities of Earth, Mars, and typical asteroids in the Solar System, suggesting that at least some rocky exoplanets are geophysically and geochemically similar to Earth.

WITHDRAWN BY THE AUTHORS: Molecular mechanism of extracellular nucleotide-induced degranulation from human polymorphonuclear leukocytes: Role of leukotriene B4 and p38 MAP kinase as essential intermediates.

WITHDRAWN BY THE AUTHORS.

Early formation of the Moon 4.51 billion years ago.

Establishing the age of the Moon is critical to understanding solar system evolution and the formation of rocky planets, including Earth. However, despite its importance, the age of the Moon has never been accurately determined. We present uranium-lead dating of Apollo 14 zircon fragments that yield highly precise, concordant ages, demonstrating that they are robust against postcrystallization isotopic disturbances. Hafnium isotopic analyses of the same fragments show extremely low initial 176Hf/177Hf ratios corrected for cosmic ray exposure that are near the solar system initial value. Our data indicate differentiation of the lunar crust by 4.51 billion years, indicating the formation of the Moon within the first ~60 million years after the birth of the solar system.

Extreme enrichment in atmospheric 15N15N.

Molecular nitrogen (N2) comprises three-quarters of Earth's atmosphere and significant portions of other planetary atmospheres. We report a 19 per mil (‰) excess of 15N15N in air relative to a random distribution of nitrogen isotopes, an enrichment that is 10 times larger than what isotopic equilibration in the atmosphere allows. Biological experiments show that the main sources and sinks of N2 yield much smaller proportions of 15N15N in N2. Electrical discharge experiments, however, establish 15N15N excesses of up to +23‰. We argue that 15N15N accumulates in the atmosphere because of gas-phase chemistry in the thermosphere (>100 km altitude) on time scales comparable to those of biological cycling. The atmospheric 15N15N excess therefore reflects a planetary-scale balance of biogeochemical and atmospheric nitrogen chemistry, one that may also exist on other planets.

Oxygen isotopic evidence for vigorous mixing during the Moon-forming giant impact.

Earth and the Moon are shown here to have indistinguishable oxygen isotope ratios, with a difference in Δ'(17)O of -1 ± 5 parts per million (2 standard error). On the basis of these data and our new planet formation simulations that include a realistic model for primordial oxygen isotopic reservoirs, our results favor vigorous mixing during the giant impact and therefore a high-energy, high-angular-momentum impact. The results indicate that the late veneer impactors had an average Δ'(17)O within approximately 1 per mil of the terrestrial value, limiting possible sources for this late addition of mass to the Earth-Moon system.

Isotope geochemistry. Biological signatures in clumped isotopes of O2.

The abundances of molecules containing more than one rare isotope have been applied broadly to determine formation temperatures of natural materials. These applications of "clumped" isotopes rely on the assumption that isotope-exchange equilibrium is reached, or at least approached, during the formation of those materials. In a closed-system terrarium experiment, we demonstrate that biological oxygen (O2) cycling drives the clumped-isotope composition of O2 away from isotopic equilibrium. Our model of the system suggests that unique biological signatures are present in clumped isotopes of O2­and not formation temperatures. Photosynthetic O2 is depleted in (18)O(18)O and (17)O(18)O relative to a stochastic distribution of isotopes, unlike at equilibrium, where heavy-isotope pairs are enriched. Similar signatures may be widespread in nature, offering new tracers of biological and geochemical cycling.

Radar-enabled recovery of the Sutter's Mill meteorite, a carbonaceous chondrite regolith breccia.

Doppler weather radar imaging enabled the rapid recovery of the Sutter's Mill meteorite after a rare 4-kiloton of TNT-equivalent asteroid impact over the foothills of the Sierra Nevada in northern California. The recovered meteorites survived a record high-speed entry of 28.6 kilometers per second from an orbit close to that of Jupiter-family comets (Tisserand's parameter = 2.8 ± 0.3). Sutter's Mill is a regolith breccia composed of CM (Mighei)-type carbonaceous chondrite and highly reduced xenolithic materials. It exhibits considerable diversity of mineralogy, petrography, and isotope and organic chemistry, resulting from a complex formation history of the parent body surface. That diversity is quickly masked by alteration once in the terrestrial environment but will need to be considered when samples returned by missions to C-class asteroids are interpreted.

GC/multiple collector-ICPMS method for chlorine stable isotope analysis of chlorinated aliphatic hydrocarbons.

Stable isotopic characterization of chlorine in chlorinated aliphatic pollution is potentially very valuable for risk assessment and monitoring remediation or natural attenuation. The approach has been underused because of the complexity of analysis and the time it takes. We have developed a new method that eliminates sample preparation. Gas chromatography produces individually eluted sample peaks for analysis. The He carrier gas is mixed with Ar and introduced directly into the torch of a multicollector ICPMS. The MC-ICPMS is run at a high mass resolution of >/=10 000 to eliminate interference of mass 37 ArH with Cl. The standardization approach is similar to that for continuous flow stable isotope analysis in which sample and reference materials are measured successively. We have measured PCE relative to a laboratory TCE standard mixed with the sample. Solvent samples of 200 nmol to 1.3 micromol (24-165 microg of Cl) were measured. The PCE gave the same value relative to the TCE as measured by the conventional method with a precision of 0.12 per thousand (2x standard error) but poorer precision for the smaller samples.

Isotopic compositions of cometary matter returned by Stardust.

Hydrogen, carbon, nitrogen, and oxygen isotopic compositions are heterogeneous among comet 81P/Wild 2 particle fragments; however, extreme isotopic anomalies are rare, indicating that the comet is not a pristine aggregate of presolar materials. Nonterrestrial nitrogen and neon isotope ratios suggest that indigenous organic matter and highly volatile materials were successfully collected. Except for a single (17)O-enriched circumstellar stardust grain, silicate and oxide minerals have oxygen isotopic compositions consistent with solar system origin. One refractory grain is (16)O-enriched, like refractory inclusions in meteorites, suggesting that Wild 2 contains material formed at high temperature in the inner solar system and transported to the Kuiper belt before comet accretion.