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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.

As the field of zirconium (Zr) stable isotopes is rapidly expanding from the study of mass-independent to that of mass-dependent isotope effects, a variety of Zr standards have appeared in the literature. While several of these standards have been proposed as the ideal isotope reference material (iRM) against which all data should be reported, none of them have been shown to meet the compositional and/or conflict-of-interest-free distribution requirements put forth by the community. To remedy this situation, we report on a community-led effort to develop and calibrate a scale defining iRM for Zr isotopes: NIST RM 8299. Developed in partnership with the National Institute of Standards and Technology (NIST) from the widely used SRM 3169 Zirconium Standard Solution (certified for mass fraction), the candidate RM 8299 was calibrated through an inter-laboratory study involving three laboratories. Our data show that candidate RM 8299 meets all requirements of an ideal iRM. It is an isotopically homogeneous, high-purity reference material, that is free of isotope anomalies, and whose composition is identical to that of a major geological reservoir (Ocean Island Basalts). Furthermore, RM 8299 will be curated and distributed by NIST, a neutral, conflict-of-interest free organization, and was produced in sufficient quantities to last multiple decades. We recommend that all Zr isotope data be reported against RM 8299. Our results also show that SRM 3169 lots #130920 and #071226 have indistinguishable composition compared to candidate RM 8299. Therefore, using RM 8299 as the scale defining iRM will enable direct comparison of all future data with the vast majority of the existing literature data, both for mass-independent and mass-dependent isotope effects. To facilitate conversion of δ94/90Zr values reported against other Zr standards, we provide high-precision conversion factors to the RM 8299 scale obtained using the double-spike method. [ABSTRACT FROM AUTHOR]

The trapped melt fractional crystallization model for the IIIAB iron meteorites put forward by J. T. Wasson two decades prior is revisited. The basic precepts upon which the model was based remain true, and the model can be implemented using Ir and Au solid/liquid distribution coefficients that are broadly consistent with experimental data. For this reason, the difference between the Wasson model and some more recent trapped melt models lies mainly with inferences about the S concentrations of the core of the IIIAB iron meteorite parent body. For the Wasson model, S bulk concentrations of about 2 wt% are implied. For the more recent model, much greater concentrations of between about 12–15 wt% are indicated. The two different trapped melt models profoundly influence the interpretation of high δ57Fe values relative to chondrites in the IIIAB irons. The Wasson model suggests that there should be more variations in δ57Fe than are observed among these meteorites, while the more recent trapped melt model relies on the crystallization of FeS from the trapped melt to raise the δ57Fe of the latter, thus minimizing the variability. The interpretation of Fe isotope ratios in the IIIAB meteorites therefore depends critically on the S concentration of the parent body core. [ABSTRACT FROM AUTHOR]

Abstract: Apparent excesses in early-solar 26Al, 36Cl, 41Ca, and 60Fe disappear if one accounts for ejecta from massive-star winds concentrated into dense phases of the ISM in star-forming regions. The removal of apparent excesses is evident when wind yields from Wolf–Rayet stars are included in the plot of radionuclide abundances vs. mean life. The resulting trend indicates that the solar radionuclides were inherited from parental molecular clouds with a characteristic residence time of 108 yr. This residence time is of the same order as the present-day timescale for conversion of molecular cloud material into stars. The concentrations of these extinct isotopes in the early solar system need not signify injection from unusual proximal stellar sources, but instead are well explained by normal concentrations in average star-forming clouds. The results imply that the efficiency of capture is greater for stellar winds than for supernova ejecta proximal to star-forming regions. [Copyright &y& Elsevier]

The mass-dependent fractionation laws that describe the partitioning of isotopes are different for kinetic and equilibrium reactions. These laws are characterized by the exponent relating the fractionation factors for two isotope ratios such that α2/1 = α3/1β. The exponent β for equilibrium exchange is (1/m1 − 1/m2)/(1/m1 − 1/m3), where mi are the atomic masses and m1 < m2 < m3. For kinetic fractionation, the masses used to evaluate β depend upon the isotopic species in motion. Reduced masses apply for breaking bonds whereas molecular or atomic masses apply for transport processes. In each case the functional form of the kinetic β is ln(M1/M2)/ln(M1/M3), where Mi are the reduced, molecular, or atomic masses. New high-precision Mg isotope ratio data confirm that the distinct equilibrium and kinetic fractionation laws can be resolved for changes in isotope ratios of only 3‰ per amu. The variability in mass-dependent fractionation laws is sufficient to explain the negative Δ17O of tropospheric O2 relative to rocks and differences in Δ17O between carbonate, hydroxyl, and anhydrous silicate in Martian meteorites. (For simplicity, we use integer amu values for masses when evaluating β throughout this paper.) [Copyright &y& Elsevier]

First results from a new UV laser ablation MC-ICPMS method for measuring Mg isotope ratios in situ in meteoritical materials show that there are mass-dependent variations in δ25Mg and δ26Mg up to 1.5 ‰ per amu in chondrules and 0.3‰ per amu in a CAI from the Allende meteorite. In both cases the mass-dependent fractionation is associated with alteration. Comparisons with laser ablation O isotope data indicate that incorporation of pre-existing grains of forsterite with distinct Mg and O isotopic compositions and post-formation alteration both contributed to the variability in Mg isotope ratios in the chondrules, resulting in a correlation between high δ25Mg and low Δ17O. The laser ablation analyses of the CAI show that high-precision determinations of both δ25Mg and δ26Mg can be used to discriminate features of the 26Al-26Mg isotope system that are relevant to chronology from those that result from element mobility. [Copyright &y& Elsevier]

The article examines an analysis on chondrite meteorite, a primitive meteorite accreted during the earliest stage of solar system formation, depicting indications about the environment in which the solar system was formed. The author reveals that chondrite meteorites exhibit a variation of isotopes that go against the expectation of the exact ratio of oxygen isotopes. It is stated that a chondrite meteorite possess an abundance of oxygen-16 which is typical on Earth's rocks. The author believes that water is the key player in the origin of oxygen-16 anomaly and could pose as an evidence for the original isotopic composition of water in the early solar system.

Microbial anaerobic oxidation of methane (AOM) substantially mitigates atmospheric methane emissions on Earth and is a process to consider for astrobiological targets where methane has been detected. The measurement of doubly substituted, or "clumped", methane isotopes has proven useful in tracing processes of methane formation and oxidation. Both near-equilibrium and extreme disequilibrium methane clumped isotope signatures can be attributed to AOM, but, to date, understanding the mechanistic and environmental controls on those signatures has been lacking. We report measurements of methane clumped isotope compositions of residual methane in AOM-active microbial incubations using sediment slurries from Svalbard and Santa Barbara Channel methane seeps. Incubation experiments of Svalbard sediment slurries resulted in residual methane with very high Δ13CH 3 D and Δ12CH 2 D 2 values up to 19.5‰ and 65.1‰, respectively. We found similarly high Δ13CH 3 D and Δ12CH 2 D 2 values in fluid samples from the Chamorro Seamount, a serpentinite mud volcano in the Mariana forearc, suggesting that minimal reversibility of AOM intracellular reactions leads to kinetic fractionation of clumped isotopologues. When conditions were consistent with a low thermodynamic drive for AOM, however, methane isotopologues approached intra-species quasi-equilibrium. This was clearly observed in isotope exchange experiments with methyl-coenzyme M reductase (Mcr) and in microbial incubations of the Santa Barbara Channel sediment slurries. Using an isotopologue fractionation model, we highlight the critical role of reversibility in controlling the trajectory of gases in Δ13CH 3 D vs. Δ12CH 2 D 2 space during AOM. The near-equilibrium methane isotopologue signatures are generalized as a result of the Mcr-catalyzed intracellular isotope exchange operating under near-threshold free energy conditions, as shown in the deep-biosphere incubations. Our results show that the reversibility of the Mcr-catalyzed reaction is central to understanding the meaning of methane isotopologue ratios affected by microbial production and oxidation. [ABSTRACT FROM AUTHOR]

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 O2--and not formation temperatures. Photosynthetic O2 is depleted in 18O18O and 17O18O 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. [ABSTRACT FROM AUTHOR]

Calcium-aluminum-rich inclusions (CAIs) are highly refractory objects found in different chondrite groups and represent some of the oldest known solids of the Solar System. As such, CAIs provide key information regarding the conditions prevailing in the solar protoplanetary disk as well as subsequent mixing and transport processes. Many studies have investigated CAIs for their isotopic compositions and reported nucleosynthetic isotope anomalies in numerous elements, which are typically explained by the variable incorporation of isotopically highly anomalous presolar phases. However, with the exception of 54Cr-enriched nanospinels, the exact presolar phases responsible for the isotopic heterogeneities are yet to be identified. To address this issue, we here present in-situ Ti isotopic analyses obtained on a diverse set of CAIs from various CV3 chondrites. The in-situ measurements were performed by targeting individual mineral phases of 15 CAIs with laser-ablation mass spectrometry and indicate significant inter- and intra-CAI isotopic heterogeneity in the neutron-rich isotope 50Ti. This is particularly pronounced for primitive fine-grained CAIs, whereas coarse-grained CAIs, which have been subject to melting, exhibit smaller degrees of Ti isotopic heterogeneity. To further investigate this Ti isotopic heterogeneity, we additionally obtained Ti isotopic compositions of sequential acid leachates from two fine-grained and two coarse-grained CAIs derived from CV3 chondrites. In contrast to potential expectations from the first part of the study, we do not observe any significant intra-CAI Ti isotopic heterogeneity between the different leaching steps. The lack of intra-CAI Ti isotopic heterogeneity in the acid leachate samples of this study likely reflects that the leaching procedure is unable to efficiently separate the carriers of isotopically anomalous Ti in CAIs. By comparing the bulk CAI Ti isotope compositions with Ti isotope data for hibonite-rich objects from the literature, we find that the range of Ti isotope compositions recorded by CAIs from various chondrite groups can be accounted for by the averaging of hibonite grains. In turn, the variable Ti isotope compositions of hibonite grains can be explained by the averaging of isotopically diverse presolar grains present in the Sun's parental molecular cloud. This effect of averaging is statistically supported by the central limit theorem, and the concept has the potential to be useful for other isotopic systems. [ABSTRACT FROM AUTHOR]

Abstract: Transition metal stable isotope signatures can be useful for tracing both natural and anthropogenic signals in the environment, but only if the mechanisms responsible for fractionation are understood. To investigate isotope fractionations due to electrochemistry (or redox processes), we examine the stable isotope behavior of iron and zinc during the reduction reaction +2e− =Mmetal as a function of electrochemical driving force, temperature, and time. In all cases light isotopes are preferentially electroplated, following a mass-dependent law. Generally, the extent of fractionation is larger for higher temperatures and lower driving forces, and is roughly insensitive to amount of charge delivered. The maximum fractionations are δ56/54Fe=−4.0‰ and δ66/64Zn=−5.5‰, larger than observed fractionations in the natural environment and larger than those predicted due to changes in speciation. All the observed fractionation trends are interpreted in terms of three distinct processes that occur during an electrochemical reaction: mass transport to the electrode, chemical speciation changes adjacent to the electrode, and electron transfer at the electrode. We show that a large isotope effect adjacent the electrode surface arises from the charge-transfer kinetics, but this effect is attenuated in cases where diffusion of ions to the electrode surface becomes the rate-limiting step. Thus while a general increase in fractionation is observed with increasing temperature, this appears to be a result of thermally enhanced mass transport to the reacting interface rather than an isotope effect associated with the charge-transfer kinetics. This study demonstrates that laboratory experiments can successfully distinguish isotopic signatures arising from mass transport, chemical speciation, and electron transfer. Understanding how these processes fractionate metal isotopes under laboratory conditions is the first step towards discovering what role these processes play in fractionating metal isotopes in natural systems. [Copyright &y& Elsevier]

Methane generated by microorganisms is most often depleted in the doubly substituted isotopologue 12 CH 2 D 2 relative to the stochastic reference distribution. To constrain the controls on depleted Δ 12 CH 2 D 2 values, we experimentally isolated the root cause with microorganisms that produce methane from methylphosphonate via the C-P lyase pathway. This mechanism of methane production preserves the three hydrogens from methylphosphonate and adds one hydrogen from water. When maintaining the same methylphosphonate source, but varying the D/H composition of growth medium water, we observed significant shifts in methane Δ 12 CH 2 D 2 values, but little to no change in Δ 13 CH 3 D values. We reproduced these observations with a model that considers only the combinatorial isotope effect. The variation in Δ 12 CH 2 D 2 values of product methane resulted from the differences in D/H between reactants water and methylphosphonate. This work validates the hypothesis that combinatorial effects can strongly influence methane Δ 12 CH 2 D 2 values, and must be considered for low temperature, abiotic or biotic systems where methane hydrogen is derived from multiple reservoirs. [ABSTRACT FROM AUTHOR]

Abstract We determined the Fe isotope fractionation between the metal and silicate phases of two aubrite meteorites, Norton County and Mount Egerton. We find that the metallic phase is high in 57Fe/54Fe with respect to the silicate phase, with Δ57Fe metal-silicate = 0.08‰ ± 0.04 for Mount Egerton and 0.09 ± 0.02‰ for Norton County. These data, combined with new measurements of 57Fe/54Fe of IIIAB iron meteorites, are used to constrain the origins of the high 57Fe/54Fe exhibited by all classes of iron meteorites. We find that if the parent bodies of the iron meteorites had chondritic bulk 57Fe/54Fe values, their cores must have been unusually small (≤8% by mass). Relaxing the constraint that the bodies were chondritic in their bulk iron isotope ratios allows for larger core mass fractions commensurate with usual expectations. In this case, the elevated 57Fe/54Fe values of iron meteorites are due in part to evaporation of melt during the accretion stages of the parent bodies and not solely the result of metal-silicate differentiation. [ABSTRACT FROM AUTHOR]