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At least 163 records · Page 9

Triple Oxygen Isotope Kinetics of Sulfate From Pyrite Oxidation

Sulfates from low temperature terrestrial and marine environments are out of equilibrium with their oxygen sources. Instead, oxygen isotope compositions of sulfate imply they are dominated by kinetic signatures of oxidative and reductive processes (Killingsworth et al., 2022) that are under-constrained compared to equilibrium effects (Hayles and Killingsworth, 2022). Consequently, the specific role of pyrite oxidation in setting the oxygen isotope composition of sulfate is also under-constrained. This scenario inhibits a more nuanced understanding of small variations in the oxygen isotopes of sulfate and their implications for tracing oxygen sources and sulfur cycle transformations, particularly in low-temperature relatively sulfate-limited freshwater systems such as rivers, lakes, aquifers, and mining-affected environments. To alleviate these knowledge gaps, we conduct pyrite oxidation experiments at time scales spanning minutes to years, analyze the triple oxygen isotope compositions (∆ 17 O and δ 18 O) of sulfate products, and interpret results using molecular modeling. Our preliminary results show isotopic relationships of 1) pyrite-derived sulfate ∆ 17 O reaching above the meteoric water line as its δ 18 O becomes lighter than water, and 2) sulfate ∆ 17 O and δ 18 O extending between water and O 2 . From these results we interpret a kinetic isotope effect between sulfate and water and mixing between sulfate end members containing most of their oxygen atoms from water and from O 2 .

Oxygen isotopes↗

Cosmic-ray isotopic composition

The 'age' of the cosmic rays and the origin of cosmic ray source matter are discussed. General approaches to the interpretation of the abundances of secondary radioactive nuclides are reviewed using Be-10 as an illustration. The present state of Be-10 based cosmic ray age determinations are summarized, briefly mentioning some recent results based on the isotope Al-26. The effects of nonhomogeneous propagation models on the interpretation of the radioactive isotope observations are mentioned. The cosmic ray source isotopic composition is discussed, emphasizing the neon composition. Mass histogram findings on the abundance of various elements in cosmic rays are described and possible reasons for some abundance enhancements are considered.

Wiedenbeck, M. E.↗

Carbon Isotope Fractionations Associated with Methanotrophic Growth with the Soluble and Particulate Methane Monooxygenases

Growth experiments with the RuMP-type methanotroph, Methylococcus capsulatus (Bath), have demonstrated that biomass and lipid biomarkers are significantly depleted in C-13 compared to the substrate methane and that the extent of fractionation is dependent on whether cells express the soluble (s) or particulate (p) methane monooxygenase (MMO). The presence or absence of the characteristic sMMO subunits was monitored using SDS-polyacrylamide gels. In M. capsulatus grown with no Cu supplementation, the characteristic sMMO subunits were observed in the soluble fraction throughout the entire growth period and biomass was depleted in C-13 by approximately 14,700 relative to substrate methane. In cells grown with 5uM Cu, no sMMO bands were observed and a greater fractionation of approximately 27,700 in resultant biomass was obtained. Methanol growth experiments with M. capsulatus and with a RuMP methylotroph, Methylophilus methylotrophus, in which biomass measurements yielded depletions in C-13 of 9 and 5%(sub o), respectively, suggest that oxidation of methane is the major fractionation step. Growth of M. capsulatus at a low level of oxygen, approximately 0.5%, had no significant effect on carbon isotope fractionation by either sMMO or pMMO. These observations are significant for identification of molecular biomarkers; and methanotrophic contributions to carbon isotope composition in natural environments.

Jahnke, Linda L.↗

Radioactive and magnetic investigations

Age and growth pattern determination of manganese nodules were explored. Two methods are discussed: (1) measurement of the presence of radioactive iodine isotopes; which is effective only up to 3.105 years, and (2) measurements of magnetism. The growth rates of three nodules were determined. The surface of the nodule was recent, and the overall age of the nodule could be determined with accuracy of better than 30%. Measurement of paleomagnetic effect was attempted to determine wider age ranges, however, the measured sign changes could not be interpreted as paleomagnetic reversals.

Heye, D.↗

Catalytic recombination of dissociation products with Pt/SnO2 for rare and common isotope long-life, closed-cycle CO2 lasers

This paper reports results on recombination of pulsed CO2 laser dissociation products with Pt/SnO2 catalysts, and supporting studies in a surrogate laboratory catalyst reactor. The closed-cycle, pulsed CO2 laser has been continuously operated for one million pulses with an overall power degradation of less than 5 percent by flowing the laser gas mixture through a 2-percent Pt/SnO2 catalyst bed. In the surrogate laboratory reactor, experiments have been conducted to determine isotopic exchange with the catalyst when using rare-isotope gases. The effects of catalyst pretreatment, sample weight, composition, and temperature on catalyst efficiency have also been determined.

Brown, Kenneth G.↗

The C2 Ballik-Ramsay transitions in carbon stars

The bands of C2 are an important source of opacity in the near-infrared spectral region of carbon stars. In the 2 micron spectral region, the Delta v = -1 and -2 transitions of the Ballik-Ramsay b 3Sigma(g)(-) - a 3Pi(u) system are especially important. A general method for calculating highly accurate transition parameters of the Ballik-Ramsay band is presented. This method allows the easy calculation of the satellite lines and the forbidden lines resulting from the perturbation of the upper b 3Sigma(g)(-) state by the X 1Sigma(0)(+) state. Included in the calculation is the effect of the isotopic molecules (C-12)2, (C-12)(C-13), and (C-13)2. Three consistency tests of the calculated strengths are presented. A comparison of synthetic spectra is made with an observed spectrum of WZ Cas in the 3940/cm spectral region.

Goorvitch, David↗

Grains of anomalous isotopic composition from novae

The effects of grain formation in nova ejecta are studied in order to model the optical and infrared luminosities schematically and to identify the anomalies of isotopic composition that should be present in large abundance in these grains. The large carbon concentration makes rapid and efficient grain formation possible and accounts for the peculiar luminosities observed in Nova Serpentis 1970. In the anticipated range of nova conditions, rapid addition of hot protons during the outburst produces large overabundances of C-13, O-18, Na-22, Al-26, Si-30, and perhaps others. Anomalous C-14 is expected subsequent to the C-13(alpha, n)O-16 reaction, and will be trapped in grains formed by subsequent atmospheric loss. Each of these anomalies may have been detected on the moon (due to accretion of interstellar dust) or in carbonaceous chondrites. Perhaps nova grains are responsible.

Clayton, D. D.↗

Workshop on Oxygen in Asteroids and Meteorites

Contents include the following: Constraints on the detection of solar nebula's oxidation state through asteroid observation. Oxidation/Reduction Processes in Primitive Achondrites. Low-Temperature Chemical Processing on Asteroids. On the Formation Location of Asteroids and Meteorites. The Spectral Properties of Angritic Basalts. Correlation Between Chemical and Oxygen Isotopic Compositions in Chondrites. Effect of In-Situ Aqueous Alteration on Thermal Model Heat Budgets. Oxidation-Reduction in Meteorites: The Case of High-Ni Irons. Ureilite Atmospherics: Coming up for Air on a Parent Body. High Temperature Effects Including Oxygen Fugacity, in Pre-Planetary and Planetary Meteorites and Asteroids. Oxygen Isotopic Variation of Asteroidal Materials. High-Temperature Chemical Processing on Asteroids: An Oxygen Isotope Perspective. Oxygen Isotopes and Origin of Opaque Assemblages from the Ningqiang Carbonaceous Chondrite. Water Distribution in the Asteroid Belt. Comparative Planetary Mineralogy: V Systematics in Planetary Pyroxenes and fo 2 Estimates for Basalts from Vesta.

Source record↗

Biologically mediated isotope fractionations - Biochemistry, geochemical significance and preservation in the earth's oldest sediments

Preferential metabolization of isotopically light carbon and sulfur has resulted in a fractionation of the stable isotopes of these elements on a global scale, with the light species (C-12, S-32) markedly concentrated in biogenic materials. Since the biological effects are basically retained when carbon and sulfur are incorporated in sediments, the respective fractionations are propagated into the rock section of the geochemical cycle, this having consequently caused a characteristic bipartition of both elements between 'light' and 'heavy' crustal reservoirs. Preservation of the biological isotope effects in sedimentary rocks makes it possible to trace the underlying biochemical processes back over most of the geological record. According to the available evidence, biological (autotrophic) carbon fixation arose prior to 3.5(if not 3.8) billion years ago, while the emergence of dissimilatory sulfate reduction antedates the appearance of the oldest presumably bacteriogenic sulfur isotope patterns in rocks between 2.7 and 2.8 billion years old. Hence, biological control of the terrestrial carbon and sulfur cycles has been established very early in the earth's history.

Schidlowski, M.↗

Stable Ni isotopes and Be-10 and Al-26 in metallic spheroids from Meteor Crater, Arizona

The Canyon Diablo spheroids, which are found around Meteor Crater, Arizona, are nickel-enriched objects with diameters from less than 0.1 to several mm. Previous studies have suggested that the enrichment of nickel resulted either from shock-melting of S-rich areas followed by solidification of the liquids under strongly non-equilibrium conditions at rapid cooling rates during flight outward from the crater or from the selective oxidation of iron. Isotopic studies are an effective tool for constraining the degree of open-system evaporation experienced by a system. The purpose of this study was to see whether Ni isotopes had been fractionated by volatilization during spheroid formation. In addition, the cosmogenic nuclides Be-10 and Al-26 were measured to try to estimate the depths in the parent meteorite from which the spheroids came.

Xue, S.↗

The relation between the age of the subconducting slab and the recycling of sediments into the mantle

The recycling of sediments into the mantle has become an important issue because recent papers have suggested that the geochemical inverse models of the evolution of radiogenic isotope abundances over the history of the Earth have nonunique solutions. Both the recycling of continent-derived sediments into the mantle and mixing in the mantle could produce similar geochemical effects in the mean isotopic ratios of new igneous material emplaced in continents. Recent models of Archaean heat flow and of plate tectonics during early Earth history have demonstrated that higher internal heat production of the early Earth was mainly dissipated through a higher creation rate of oceanic lithosphere. If the seafloor creation rate was higher on the early Earth, then the residence time of any one piece of oceanic lithosphere on the surface would have been shorter. It is possible that a higher rate of recycling of oceanic lithosphere into the mantle could have resulted in some transport of sediment into the mantle.

Abbott, D.↗

Sm-Nd and Rb-Sr isotope systematics of an Archean anorthosite and related rocks from the Superior Province of the Canadian Shield

Sm-Nd and Rb-Sr isotopic data for the Bad Vermilion Lake anorthosite in the Rainy Lake area of the Superior Province of northwesten Ontario show that direct ages of Archean anorthosites can be obtained with these isotopic systems despite the effects of low-grade metamorphism. There is sufficient spread in Sm/Nd between plagioclase megacrysts and coexisting mafic groundmass to allow the determination of reasonably precise internal Sm-Nd isochrons. Initial isotopic ratios of Nd and Sr add to the growing body of data indicating the Superior Province is underlain by depleted mantle.

Ashwal, L. D.↗

The Effects of High-Temperature Fractional Crystallization on Calcium Isotopic Composition

We report Ca isotope fractionation among a co-genetic suite of samples from the Mauritanian Guelb el Azib ultramafic-mafic-anorthosite complex (GAC), which represents the fractional crystallization sequence of an igneous magma chamber. We investigate how the composition of an evolving crystallizing liquid and the resultant mineralogy of co-crystallizing assemblages affects inter-phase Ca isotope fractionation. Because the GAC is an Archean metamorphosed complex, we first investigate the resistance of the Ca isotope signature to secondary hydrothermal alteration and to metamorphism. While we cannot conclude here that Ca isotopes are undisturbed at the mineral scale, we show that they are preserved at the bulk rock scale. This is adequate for our study where several samples are almost monomineralic at the bulk scale level. The δ(exp 44/40)Ca (relative to NIST standard SRM 915a) of GAC layers range from −1.53 to 1.61‰, with the earliest-formed ultramafic cumulate layer being isotopically heaviest and the later, more felsic layers being isotopically lighter. For the first time, we show that plagioclase is much more enriched in light Ca isotopes compared to olivine and (Ca-) pyroxene. Monte Carlo simulations suggest that Ca isotopes are fractionated among co-existing silicate minerals during fractional crystallization, possibly in relation with the residual liquid composition. In qualitative agreement with computational models based on first principles lattice dynamics, we observe that Ca isotope fractionation is mineralogically controlled and importantly, that the degree of fractionation can vary according to the CaO composition of the residual liquid. While previous studies have aimed to understand partial melting as a source of Ca isotope fractionation, our results suggest that fractional crystallization is also a source of Ca isotope variability among co-genetic samples.

Maria C. Valdes↗

The Effect of Europa and Enceladus Analog Seawater Composition on Isotopic Measurements of Volatile CO2

Science goals for icy ocean worlds missions include characterizing the chemical compositionof the surface and interior using remote sensing and in situ techniques. The next class of flightmass spectrometers for these missions will obtain compositional identifications and isotope ratiomeasurements of volatiles evolved from the ice surface (exosphere) and plumes. These massspectra will be combined with data from other flight instruments to infer the composition of theinterior from volatiles. To ensure accurate interpretation of these measurements, it is critical toverify whether the fundamental assumption that volatiles observed in icy ocean world exospheresor plumes will be a direct reflection of the sub-ice ocean. The present study evaluates whether isotopologues from an initial CO2 gas fractionate by interacting with seawater (brine) of varyingsalt composition and concentration. δ13CCO2 are affected by the pH of the brine and subsequentspeciation of {CO2}, where {CO2} represents the combination of CO2, H2CO3, HCO3-, and CO32-.{CO2} for low pH brines hypothesized for Europa will preferentially speciate as CO2. Analyzedδ13CCO2 for low pH brines are within error of the original δ13CCO2, demonstrating that volatile CO2in a low pH system will be a direct reflection of the original CO2. However, Europa’s radiativeenvironment and rapid depressurization due to plume ejection may impose fractionation effects.In contrast, high pH systems relevant to Enceladus or a more alkaline Europa are expected toform all carbonate species, while favoring speciation as HCO3-. High pH brines in theseexperiments include both an original CO2 gas and an isotopically distinct HCO3- (from NaHCO3salt). These alkaline experiments demonstrate that δ13CCO2 values are highly variable, and dependon the concentration of the dominant carbonate species, (Na)HCO3-. Mass balance estimatesindicate that measured δ13CCO2 is a thermodynamically predictable mixture of both carbonsources, suggesting that measurements of δ13C at Enceladus would directly reflect of the sourcesof CO2 and carbonate buffering in the ocean. δ18O measurements for CO2 interacting with KCland MgCl2 follow established models for δ18O-ionic strength. CO2 interacting with MgSO4,Na2SO4, and NaCl demonstrate an offset from established δ18O-ionic strength models dependingon the concentration of initial CO2. These results suggest that current predictive models for δ18Oin brines need to be resolved for changing concentrations of CO2

Ocean Worlds↗