The Sample Analysis at Mars instrument stepped combustion experiment on a Yellowknife Bay mudstone at Gale crater, Mars revealed the presence of organic carbon of Martian and meteoritic origins. The ...combustion experiment was designed to access refractory organic carbon in Mars surface sediments by heating samples in the presence of oxygen to combust carbon to CO
2
. Four steps were performed, two at low temperatures (less than ∼550 °C) and two at high temperatures (up to ∼870 °C). More than 950 μg C/g was released at low temperatures (with an isotopic composition of δ
13
C = +1.5 ± 3.8‰) representing a minimum of 431 μg C/g indigenous organic and inorganic Martian carbon components. Above 550 °C, 273 ± 30 μg C/g was evolved as CO
2
and CO (with estimated δ
13
C = −32.9‰ to −10.1‰ for organic carbon). The source of high temperature organic carbon cannot be definitively confirmed by isotopic composition, which is consistent with macromolecular organic carbon of igneous origin, meteoritic infall, or diagenetically altered biomass, or a combination of these. If from allochthonous deposition, organic carbon could have supported both prebiotic organic chemistry and heterotrophic metabolism at Gale crater, Mars, at ∼3.5 Ga.
Obtaining carbon isotopic information for organic carbon from Martian sediments has long been a goal of planetary science, as it has the potential to elucidate the origin of such carbon and aspects ...of Martian carbon cycling. Carbon isotopic values (δ
C
) of the methane released during pyrolysis of 24 powder samples at Gale crater, Mars, show a high degree of variation (-137 ± 8‰ to +22 ± 10‰) when measured by the tunable laser spectrometer portion of the Sample Analysis at Mars instrument suite during evolved gas analysis. Included in these data are 10 measured δ
C values less than -70‰ found for six different sampling locations, all potentially associated with a possible paleosurface. There are multiple plausible explanations for the anomalously depleted
C observed in evolved methane, but no single explanation can be accepted without further research. Three possible explanations are the photolysis of biological methane released from the subsurface, photoreduction of atmospheric CO
, and deposition of cosmic dust during passage through a galactic molecular cloud. All three of these scenarios are unconventional, unlike processes common on Earth.
Molecular dynamics simulations show that the desolvation rates of isotopes of Li ⁺, K ⁺, Rb ⁺, Ca ²⁺, Sr ²⁺, and Ba ²⁺ may have a relatively strong dependence on the metal cation mass. This inference ...is based on the observation that the exchange rate constant, k wₑₓ, for water molecules in the first hydration shell follows an inverse power-law mass dependence (k wₑₓ ∝ m ⁻ᵞ), where the coefficient γ is 0.05 ± 0.01 on average for all cations studied. Simulated water-exchange rates increase with temperature and decrease with increasing isotopic mass for each element. The magnitude of the water-exchange rate is different for simulations run using different water models i.e., extended simple point charge (SPC/E) vs. four-site transferrable intermolecular potential (TIP4P); however, the value of the mass exponent γ is the same. Reaction rate theory calculations predict mass exponents consistent with those determined via molecular dynamics simulations. The simulation-derived mass dependences imply that solids precipitating from aqueous solution under kinetically controlled conditions should be enriched in the light isotopes of the metal cations relative to the solutions, consistent with measured isotopic signatures in natural materials and laboratory experiments. Desolvation effects are large enough that they may be a primary determinant of the observed isotopic fractionation during precipitation.
Isotopic evidence of long-lived volcanism on Io de Kleer, Katherine; Hughes, Ery C; Nimmo, Francis ...
Science (American Association for the Advancement of Science),
2024-May-10, 2024-05-10, 20240510, Letnik:
384, Številka:
6696
Journal Article
Recenzirano
Jupiter's moon Io hosts extensive volcanism, driven by tidal heating. The isotopic composition of Io's inventory of volatile chemical elements, including sulfur and chlorine, reflects its outgassing ...and mass-loss history and thus records information about its evolution. We used submillimeter observations of Io's atmosphere to measure sulfur isotopes in gaseous sulfur dioxide and sulfur monoxide, and chlorine isotopes in gaseous sodium chloride and potassium chloride. We find
S/
S = 0.0595 ± 0.0038 (equivalent to δ
S = +347 ± 86‰), which is highly enriched compared to average Solar System values and indicates that Io has lost 94 to 99% of its available sulfur. Our measurement of
Cl/
Cl = 0.403 ± 0.028 (δ
Cl = +263 ± 88‰) shows that chlorine is similarly enriched. These results indicate that Io has been volcanically active for most (or all) of its history, with potentially higher outgassing and mass-loss rates at earlier times.
Distinguishing planetary formation and evolution pathways and understanding the origins of volatiles on planetary bodies requires determination of relative abundances and isotope ratios in the noble ...gases, and also of the isotope ratios in C, H, N, O and S at high precisions. Traditional planetary mass spectrometers uniquely provide excellent survey capability including the noble gas relative abundances and their isotope ratios. However, to distinguish planetary evolution models for the outer planets, stable isotope ratios in C and O require precisions of ∼10‰ or better, readily achievable with a tunable laser spectrometer (TLS). As demonstrated on the Mars Curiosity rover, and as planned for a now-selected NASA Venus mission, tunable laser spectrometers play a unique role synergistic with the capabilities of planetary mass spectrometers. The TLS technique of recording infrared absorption spectra at ultrahigh resolution (resolving power
λ
/
δ
λ
∼
5
million) provides unambiguous detection of a wide variety of gases such as H
2
O, H
2
O
2
, H
2
CO, HOCl, NO, NO
2
, HNO
3
, N
2
O, O
3
, CO, CO
2
, NH
3
, N
2
H
4
, PH
3
, H
2
S, SO
2
, OCS, HCl, HF, O
2
, HCN, and CH
4
, C
2
H
2
, C
2
H
4
, C
2
H
6
at parts-per-billion levels. Through line-depth or line-area ratio comparisons of adjacent spectral lines, planetary TLS instruments can achieve isotope ratio measurements in C, H, N, O, and S molecules at precisions of ∼1–2‰, including for the triple isotope components of O and S. Expected performance of TLS instruments for Venus, Saturn, Enceladus and Uranus will be described as constrained by actual measurements reported at Mars on the Curiosity rover.
NanoSIMS measurements of Ti, P, Y, Ce, and Hf in zircon separates from the Youngest Toba Tuff, the Bishop Tuff, the Quottoon Igneous Complex, the Sierra Nevada batholith, and an Adirondack migmatite ...show that micron-scale oscillatory zoning of Ti is common. The zircons we have studied typically display banded concentration gradients, having between 1 and 7 peaks in Ti abundance over length scales of 10–20 μm—the beam diameter commonly used for SIMS trace-element zircon analyses—with amplitudes of up to 4.5 ppm Ti (baseline values are ~1–4 ppm) and widths (measured at half-height) of between ~0.2 and 4 μm. Spatial correlations between concentrations of Ti and other trace elements (P, Y, and Ce) are also common, but variable in character, ranging from oscillatory co-variation of Ti, P, Y, and Ce to cases where only a subset of peaks for a given element is spatially correlated with peaks in Ti. There are also longer length-scale, generally positive correlations among concentrations of Ti, P, Y, and Ce (i.e., gradients on which narrower peaks are superimposed). In contrast, Hf concentrations are either uncorrelated or inversely correlated with these longer length-scale variations in Ti concentrations. The wide range in Ti concentrations over distances of less than 1 μm and the various correlations between Ti concentrations and those of the other analyzed elements suggest that on the micron scale and at temperatures between ~700 and 800 °C, zircon-liquid Ti partitioning is not controlled by bulk or lattice equilibrium. Treating our NanoSIMS Ti ion maps as though they were conventional SIMS analyses (i.e., generating an average Ti concentration for each map), we evaluate the hypothesis that while micron-scale variations in Ti concentrations might be kinetically controlled, when averaged over 100–400 μm
2
, such variations capture the thermal state of the growing zircon. Using these average Ti concentrations, independent petrologic pressure and temperature constraints, estimates of silica and titania activities based on phase assemblages as well as calculations using rhyolite-MELTS, we show that crystallization temperatures predicted by Ti-in-zircon geothermometry generally do not agree with the independently constrained temperatures for the samples.
The Deep Atmosphere Venus Investigation of Noble gases, Chemistry, and Imaging (DAVINCI) mission described herein has been selected for flight to Venus as part of the NASA Discovery Program. DAVINCI ...will be the first mission to Venus to incorporate science driven flybys and an instrumented descent sphere into a unified architecture. The anticipated scientific outcome will be a new understanding of the atmosphere, surface, and evolutionary path of Venus as a possibly once-habitable planet and analog to hot terrestrial exoplanets. The primary mission design for DAVINCI as selected features a preferred launch in summer/fall 2029, two flybys in 2030, and descent sphere atmospheric entry by the end of 2031. The in situ atmospheric descent phase subsequently delivers definitive chemical and isotopic composition of the Venus atmosphere during an atmospheric transect above Alpha Regio. These in situ investigations of the atmosphere and near infrared descent imaging of the surface will complement remote flyby observations of the dynamic atmosphere, cloud deck, and surface near infrared emissivity. The overall mission yield will be at least 60 Gbits (compressed) new data about the atmosphere and near surface, as well as the first unique characterization of the deep atmosphere environment and chemistry, including trace gases, key stable isotopes, oxygen fugacity, constraints on local rock compositions, and topography of a tessera.
Zoning of phosphorus in igneous olivine Milman-Barris, Margaret S.; Beckett, John R.; Baker, Michael B. ...
Contributions to mineralogy and petrology,
06/2008, Letnik:
155, Številka:
6
Journal Article
Recenzirano
We describe P zoning in olivines from terrestrial basalts, andesites, dacites, and komatiites and from a martian meteorite. P
2
O
5
contents of olivines vary from below the detection limit ...(≤0.01 wt%) to 0.2–0.4 wt% over a few microns, with no correlated variations in Fo content. Zoning patterns include P-rich crystal cores with skeletal, hopper, or euhedral shapes; oscillatory zoning; structures suggesting replacement of P-rich zones by P-poor olivine; and sector zoning. Melt inclusions in olivines are usually located near P-rich regions but in direct contact with low-P olivine. Crystallization experiments on basaltic compositions at constant cooling rates (15–30°C/h) reproduce many of these features. We infer that P-rich zones in experimental and natural olivines reflect incorporation of P in excess of equilibrium partitioning during rapid growth, and zoning patterns primarily record crystal-growth-rate variations. Occurrences of high-P phenocryst cores may reflect pulses of rapid crystal growth following delayed nucleation due to undercooling. Most cases of oscillatory zoning in P likely reflect internal factors whereby oscillating growth rates occur without external forcings, but some P zoning in natural olivines may reflect external forcings (e.g., magma mixing events, eruption) that result in variable crystal growth rates and/or P contents in the magma. In experimental and some natural olivines, Al, Cr, and P concentrations are roughly linearly and positively correlated, suggesting coupled substitutions, but in natural phenocrysts, Cr zoning is usually less intense than P zoning, and Al zoning weak to absent. We propose that olivines grow from basic and ultrabasic magmas with correlated zoning in P, Cr, and Al superimposed on normal zoning in Fe/Mg; rapidly diffusing divalent cations homogenize during residence in hot magma; Al and Cr only partially homogenize; and delicate P zoning is preserved because P diffuses very slowly. This interpretation is consistent with the fact that zoning is largely preserved not only in P but also in Al, Cr, and divalent cations in olivines with short residence times at high temperature (e.g., experimentally grown olivines, komatiitic olivines, groundmass olivines, and the rims of olivine phenocrysts grown during eruption). P zoning is widespread in magmatic olivine, revealing details of crystal growth and intra-crystal stratigraphy in what otherwise appear to be relatively featureless crystals. Since it is preserved in early-formed olivines with prolonged residence times in magmas at high temperatures, P zoning has promise as an archive of information about an otherwise largely inaccessible stage of a magma’s history. Study of such features should be a valuable supplement to routine petrographic investigations of basic and ultrabasic rocks, especially because these features can be observed with standard electron microprobe techniques.
Electron probe microanalyser measurements of trace elements with high accuracy are challenging. Accurate Al measurements in olivine are required to calibrate SIMS implant reference materials for ...measurement of Al in the solar wind. We adopt a combined EPMA/SIMS approach that is useful for producing SIMS reference materials as well as for EPMA at the ~ 100 µg g−1 level. Even for mounts not polished with alumina photoelectron spectroscopy shows high levels of Al surface contamination. In order to minimise electron beam current density, a rastered 50 × 100 µm electron beam was adequate and minimised sensitivity to small Al‐rich contaminants. Reproducible analyses of eleven SIMS‐cleaned spots on San Carlos olivine agreed at 69.3 ± 1.0 µg g−1. The known Al mass fraction was used to calibrate an Al implant into San Carlos. Accurate measurements of Al were made for olivines in the pallasites: Imilac, Eagle Station and Springwater. Our focus was on Al in olivine, but our technique could be refined to give accurate electron probe measurements for other contamination‐sensitive trace elements. For solar wind, it is projected that the Al/Mg abundance ratio can be determined to 6%, a factor of 2 more precise than the solar spectroscopic ratio.
Key Points
Determination of Al in the solar wind requires high‐accuracy calibration of SIMS implant reference materials.
Well‐cleaned, diamond‐polished olivine reference materials still showed high levels of surface Al contamination.
Our combined EPMA/SIMS approach is recommended for accurate quantification of SIMS reference materials and EPMA of trace elements.
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