We describe a unique and novel isotope ratio mass spectrometer (IRMS), the Panorama, developed explicitly for high-mass-resolution analysis of isotopologue ratios of gas samples. The double-focussing instrument routinely operates at a mass resolving power of 40,000 with a maximum useful MRP of similar to 80,000. The instrument achieves this exceptional MRP for a multi-collector using a Matsuda ion optical design with an ESA radius of 1018 mm and a magnetic sector radius of 800 mm. Collectors comprise 9 Faraday cups and a single channel of ion counting each with continuously variable collector slits. First results demonstrate both accuracy and precision comparable to, and in some cases, surpassing, other gas-source multi-collector IRMS instruments for singly-substituted species. For example, accurate bulk D/H and C-13/C-12 for methane gas measured with CH4 as the analyte are measured simultaneously with internal precision of 0.02-0.04 parts per thousand (1 std error) and similar to 0.006 parts per thousand (1 se), respectively. Ion counting with continuous rebalancing of sample and standard gases permits high-precision measurements of rare, multiply-substituted isotopologues with relative abundances as small as similar to 0.1 ppm. In the case of methane, both (CH3D)-C-13/(CH4)-C-12 and (CH2D2)-C-12/(CH4)-C-12 ratios are measured with precision of similar to 0.1 parts per thousand and similar to 0.5 parts per thousand, respectively. Accuracy of the multiply-substituted species measurements is demonstrated using isotope ratio mixing experiments. The ability to measure both Delta(CH3D)-C-13 and Delta CH2D2 (parts per thousand variations relative to the stochastic reference frame) provides heretofore unmatched capabilities to identify kinetic reaction pathways, isotope fractionation during transport, mixing, as well as temperatures of formation for methane gas. The high-resolution instrument can be used for a wide variety of applications. For example, it easily resolves Ar-36(+) from (OO+)-O-18-O-18 for oxygen bond-ordering studies. It also easily resolves (NO+)-N-14-O-16 from (NN+)-N-15-N-15 for measurements of the doubly-substituted N-2 species. (C) 2016 Elsevier B.V. All rights reserved.

We report measurements of resolved (CH2D2)-C-12 and (CH3D)-C-13 at natural abundances in a variety of methane gases produced naturally and in the laboratory. The ability to resolve (CH2D2)-C-12 from (CH3D)-C-13 provides unprecedented insights into the origin and evolution of CH4. The results identify conditions under which either isotopic bond order disequilibrium or equilibrium are expected. Where equilibrium obtains, concordant Delta (CH2D2)-C-12 and Delta (CH3D)-C-13 temperatures can be used reliably for thermometry. We find that concordant temperatures do not always match previous hypotheses based on indirect estimates of temperature of formation nor temperatures derived from CH4/H-2 D/H exchange, underscoring the importance of reliable thermometry based on the CH4 molecules themselves. Where Delta (CH2D2)-C-12 and Delta (CH3D)-C-13 values are inconsistent with thermodynamic equilibrium, temperatures of formation derived from these species are spurious. In such situations, while formation temperatures are unavailable, disequilibrium isotopologue ratios nonetheless provide novel information about the formation mechanism of the gas and the presence or absence of multiple sources or sinks. In particular, disequilibrium isotopologue ratios may provide the means for differentiating between methane produced by abiotic synthesis vs. biological processes. Deficits in (CH2D2)-C-12 compared with equilibrium values in CH4 gas made by surface-catalyzed abiotic reactions are so large as to point towards a quantum tunneling origin. Tunneling also accounts for the more moderate depletions in (CH3D)-C-13 that accompany the low (CH2D2)-C-12 abundances produced by abiotic reactions. The tunneling signature may prove to be an important tracer of abiotic methane formation, especially where it is preserved by dissolution of gas in cool hydrothermal systems (e.g., Mars). Isotopologue signatures of abiotic methane production can be erased by infiltration of microbial communities, and Delta (CH2D2)-C-12 values are a key tracer of microbial recycling. (C) 2017 Elsevier Ltd. All rights reserved.

Stable isotope compositions of methane (delta C-13 and delta D) and of short-chain alkanes are commonly used to trace the origin and fate of carbon in the continental crust. In continental sedimentary systems, methane is typically produced through thermogenic cracking of organic matter and/or through microbial methanogenesis. However, secondary processes such as mixing, migration or biodegradation can alter the original isotopic and composition of the gas, making the identification and the quantification of primary sources challenging. The recently resolved methane 'clumped' isotopologues Delta(CH3D)-C-13 and Delta(CH2D2)-C-12 are unique indicators of whether methane is at thermodynamic isotopic equilibrium or not, thereby providing insights into formation temperatures and/or into kinetic processes controlling methane generation processes, including microbial methanogenesis.

Silicon and Mg in differentiated rocky bodies exhibit heavy isotope enrichments that have been attributed to evaporation of partially or entirely molten planetesimals. We evaluate the mechanisms of planetesimal evaporation in the early solar system and the conditions that controlled attendant isotope fractionations.

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 mu m to 3 mm) of olivine, pyroxenes, plagioclase, graphite, and metal-sulfide, as well as chondrules (similar to 130-600 mu m) 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 (delta O-18 = 13.53 parts per thousand, delta O-17 = 8.93 parts per thousand) 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 similar to 10 and orthopyroxene of Wo similar to 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 similar to 0.04-0.05) and relatively featureless in VNIR, and have an similar to 2.7 mu m 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 OC, EC, and other meteorite types. The bulk density of AhS 91A (2.35 +/- 0.05 g cm(-3)) is lower than bulk densities of other AhS stones, and closer to estimates for the asteroid (similar to 1.7-2.2 g cm(-3)). 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 component, so they represent subsurface layers.

Methane generated by microorganisms is most often depleted in the doubly substituted isotopologue (CH2D2)-C-12 relative to the stochastic reference distribution. To constrain the controls on depleted Delta(CH2D2)-C-12 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 Delta(CH2D2)-C-12 values, but little to no change in Delta(CH3D)-C-13 values. We reproduced these observations with a model that considers only the combinatorial isotope effect. The variation in Delta(CH2D2)-C-12 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 Delta(CH2D2)-C-12 values, and must be considered for low temperature, abiotic or biotic systems where methane hydrogen is derived from multiple reservoirs. (C) 2020 Published by Elsevier Ltd.

Iron is a ubiquitous element in terrestrial and extra-terrestrial settings and can provide clues as to the conditions during which planetary scale processes occurred. One example of this is determining the conditions accompanying metal core formation in rocky planets and planetesimals. For at least two decades there has been a growing database of experimental and natural data aimed at understanding whether iron isotopes fractionate during the separation of silicate and metal. While it has been argued that the data are not in agreement with one another, it is apparent that once criteria are established that prove equilibrated samples, there is good agreement amongst the different studies when looked at as a function of the metallic composition. Proving equilibrium is critical in these types of experiments. The three-isotope experimental technique for establishing equilibrium is found to be both mathematically and fundamentally sound. Further it is clear that the question of whether there is an equilibrium iron isotope fractionation between metal and silicate is not straightforward and that it can vary significantly as a function of temperature, pressure, metallic composition, oxygen fugacity, and silicate composition.

The element beryllium is detected for the first time in white dwarf stars. This discovery in the spectra of two helium-atmosphere white dwarfs was made possible only because of the remarkable overabundance of Be relative to all other elements, heavier than He, observed in these stars. The measured Be abundances, relative to chondritic, are by far the largest ever seen in any astronomical object. We anticipate that the Be in these accreted planetary bodies was produced by spallation of one or more of O, C, and N in a region of high fluence of particles of MeV or greater energy.

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 pre-vailing 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 typ-ically 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 spec-trometry and indicate significant inter-and intra-CAI isotopic heterogeneity in the neutron-rich isotope 50Ti. This is partic-ularly pronounced for primitive fine-grained CAIs, whereas coarse-grained CAIs, which have been subject to melting, exhibit smaller degrees of Ti isotopic heterogeneity.