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Ancient environmental conditions on Mars can be probed through the identification of minerals on its surface, including water-deposited salts and cements dispersed in the pore space of sedimentary rocks. Laser-induced breakdown spectroscopy (LIBS) analyses by the Martian rover Curiosity's ChemCam instrument can indicate salts, and ChemCam surveys aid in identifying and selecting sites for further, detailed in situ analyses. We performed laboratory LIBS experiments under simulated Mars conditions with a ChemCam-like instrument on a series of mixtures containing increasing concentrations of salt in a basaltic background to investigate the potential for identifying and quantifying chloride, carbonate, and sulfate salts found only in small amounts, dispersed in bulk rock with ChemCam, rather than concentrated in veins. Data indicate that the presence of emission lines from the basalt matrix limited the number of Cl, C, and S emission lines found to be useful for quantitative analysis; nevertheless, several lines with intensities sensitive to salt concentration were identified. Detection limits for the elements based on individual emission lines ranged from ~20 wt % carbonate (2 wt % C), ~5–30 wt % sulfate (1–8 wt % S), and ~5–10 wt % chloride (3–6 wt % Cl) depending on the basaltic matrix and/or salt cation. Absolute quantification of Cl, C, and S in the samples via univariate analysis depends on the cation-anion pairing in the salt but appears relatively independent of matrices tested, following normalization. These results are promising for tracking relative changes in the salt content of bulk rock on the Martian surface with ChemCam.

CO is thought to be the main reservoir of volatile carbon in protoplanetary disks, and thus the primary initial source of carbon in the atmospheres of forming giant planets. However, recent observations of protoplanetary disks point towards low volatile carbon abundances in many systems, including at radii interior to the CO snowline. One potential explanation is that gas phase carbon is chemically reprocessed into less volatile species, which are frozen on dust grain surfaces as ice. This mechanism has the potential to change the primordial C/H ratio in the gas. However, current observations primarily probe the upper layers of the disk. It is not clear if the low volatile carbon abundances extend to the midplane, where planets form. We have run a grid of 198 chemical models, exploring how the chemical reprocessing of CO depends on disk mass, dust grain size distribution, temperature, cosmic ray and X-ray ionization rate, and initial water abundance. Building on our previous work focusing on the warm molecular layer, here we analyze the results for our grid of models in the disk midplane at 12 au. We find that either an ISM level cosmic ray ionization rate or the presence of UV photons due to a low dust surface density are needed to chemically reduce the midplane CO gas abundance by at least an order of magnitude within 1 Myr. In the majority of our models CO does not undergo substantial reprocessing by in situ chemistry and there is little change in the gas phase C/H and C/O ratios over the lifetime of the typical disk. However, in the small sub-set of disks where the disk midplane is subject to a source of ionization or photolysis, the gas phase C/O ratio increases by up to nearly 9 orders of magnitude due to conversion of CO into volatile hydrocarbons., Accepted for publication in ApJ, 15 pages, 10 figures, 3 tables

The Mars Science Laboratory Curiosity rover is traversing a sequence of stratified sedimentary rocks in Gale crater that contain varied eolian, fluviodeltaic, and lake deposits, with phyllosilicates, iron oxides, and sulfate salts. Here, we report the chloride salt distribution along the rover traverse. Chlorine is detected at low levels (, Key Points Isolated Cl enrichments in bedrock, in nodular textures, and at calcium sulfate vein margins, correlated with Na, indicate haliteMapping of Cl along the Curiosity traverse in Gale Crater indicates Cl enrichments are more common in select Murray formation membersThe scattered, isolated occurrences of chlorides are consistent with late groundwater reworking and remobilization of original deposits

The Mars Science Laboratory rover, Curiosity, is equipped with ChemCam, a laser‐induced breakdown spectroscopy (LIBS) instrument, to determine the elemental composition of nearby targets quickly and remotely. We use a laboratory sample set including prepared mixtures of basalt with systematic variation in hydrated mineral content and compositionally well‐characterized, altered basaltic volcanic rocks to measure hydrogen by characterizing the H‐alpha emission line in LIBS spectra under Martian environmental conditions. The H contents of all samples were independently measured using thermogravimetric analysis. We found that H peak area increases with weight percent H for our laboratory mixtures with basaltic matrices. The increase is linear with weight percent H in the mixtures with structurally bound H up to about 1.25 wt.% H and then steepens for higher H‐content samples, a nonlinear trend not previously reported but potentially important for characterizing high water content materials. To compensate for instrument, environmental, and target matrix‐related effects on quantification of H content from the LIBS signal, we examined multiple normalization methods. The best performing methods utilize O 778‐ and C 248‐nm emission lines. The methods return comparable results when applied to ChemCam data of H‐bearing materials on Mars. The calibration and normalization methods tested here will aid in investigations of H by LIBS on Mars with ChemCam and SuperCam. Further laboratory work will aid quantification across different physical matrices and heterogeneous textures because of differences we observed in H in pelletized and natural rock samples of the same composition.

CO is commonly used as a tracer of the total gas mass in both the interstellar medium and in protoplanetary disks. Recently there has been much debate about the utility of CO as a mass tracer in disks. Observations of CO in protoplanetary disks reveal a range of CO abundances, with measurements of low CO to dust mass ratios in numerous systems. One possibility is that carbon is removed from CO via chemistry. However, the full range of physical conditions conducive to this chemical reprocessing is not well understood. We perform a systematic survey of the time dependent chemistry in protoplanetary disks for 198 models with a range of physical conditions. We varying dust grain size distribution, temperature, comic ray and X-ray ionization rate, disk mass, and initial water abundance, detailing what physical conditions are necessary to activate the various CO depletion mechanisms in the warm molecular layer. We focus our analysis on the warm molecular layer in two regions: the outer disk (100 au) well outside the CO snowline and the inner disk (19 au) just inside the midplane CO snow line. After 1 Myr, we find that the majority of models have a CO abundance relative to H$_2$ less than $10^{-4}$ in the outer disk, while an abundance less than $10^{-5}$ requires the presence of cosmic rays. Inside the CO snow line, significant depletion of CO only occurs in models with a high cosmic ray rate. If cosmic rays are not present in young disks it is difficult to chemically remove carbon from CO. Additionally, removing water prior to CO depletion impedes the chemical processing of CO. Chemical processing alone cannot explain current observations of low CO abundances. Other mechanisms must also be involved., 23 pages, 25 figures, 5 tables, accepted for publication in ApJ

The lifetime of gas in circumstellar disks is a fundamental quantity that informs our understanding of planet formation. Studying disk gas evolution requires measurements of disk masses around stars of various ages. Because H_2 gas is unobservable under most disk conditions, total disk masses are based on indirect tracers such as sub-mm dust and CO emission. The uncertainty in the relation between these tracers and the disk mass increases as the disk evolves. In a few well-studied disks, CO exhibits depletions of up to 100× below the assumed interstellar value. Thus, additional tracers are required to accurately determine the total gas mass. The relative lack of nitrogen found in solid solar system bodies may indicate that it persists in volatile form, making nitrogen-bearing species more robust tracers of gas in more evolved disks. Here we present Atacama Large Millimeter/submillimeter Array detections of N_2H^+ in two mature, ~5–11 Myr old disks in the Upper Scorpius OB Association. Such detections imply the presence of H_2-rich gas and sources of ionization, both required for N_2H^+ formation. The Upper Sco disks also show elevated N_2H^+/CO flux ratios when compared to previously observed disks with ≳10× higher CO fluxes. Based on line ratio predictions from a grid of thermochemical disk models, a significantly reduced CO/H_2 abundance of

The Earth and other rocky bodies in the inner solar system contain significantly less carbon than the primordial materials that seeded their formation. These carbon-poor objects include the parent bodies of primitive meteorites, suggesting that at least one process responsible for solid-phase carbon depletion was active prior to the early stages of planet formation. Potential mechanisms include the erosion of carbonaceous materials by photons or atomic oxygen in the surface layers of the protoplanetary disk. Under photochemically generated favorable conditions, these reactions can deplete the near-surface abundance of carbon grains and polycyclic aromatic hydrocarbons by several orders of magnitude on short timescales relative to the lifetime of the disk out to radii of ~20-100+ au from the central star depending on the form of refractory carbon present. Due to the reliance of destruction mechanisms on a high influx of photons, the extent of refractory carbon depletion is quite sensitive to the disk's internal radiation field. Dust transport within the disk is required to affect the composition of the midplane. In our current model of a passive, constant-alpha disk, where alpha = 0.01, carbon grains can be turbulently lofted into the destructive surface layers and depleted out to radii of ~3-10 au for 0.1-1 um grains. Smaller grains can be cleared out of the planet-forming region completely. Destruction may be more effective in an actively accreting disk or when considering individual grain trajectories in non-idealized disks., Comment: 15 pages, 9 figures, Accepted for publication in ApJ

International audience; We present observations of fine-structure line emission of atomic sulfur, iron, and rotational lines of molecular hydrogen in shocks associated with several Class 0 protostars obtained with the Infrared Spectrograph of the Spitzer Space Telescope. We use these observations to investigate the "missing sulfur problem," that significantly less sulfur is found in dense regions of the interstellar medium (ISM) than in diffuse regions. For sources where the sulfur fine-structure line emission is co-spatial with the detected molecular hydrogen emission and in the presence of weak iron emission, we derive sulfur and H2 column densities for the associated molecule-dominated C-shocks. We find the S I abundance to be gsim5%-10% of the cosmic sulfur abundance, indicating that atomic sulfur is a major reservoir of sulfur in shocked gas. This result suggests that in the quiescent dense ISM sulfur is present in some form that is released from grains as atoms, perhaps via sputtering, within the shock.