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Carbon Tracers of Aqueous Processes: Isotopic Analysis of Cr Carbonate Grains With Implications for Bennu Samples

Carbonate grains in carbonaceous chondrites record aqueous alteration events on the asteroidal parent bodies, including evidence for episodic alteration, timing of alteration, and time and temperature evolution of volatiles. Spectral features in the 3.4 μm region at asteroid Bennu have been interpreted as coming from carbonate minerals. Coordinated analysis of carbonate grains will be a valuable tool for analysis of Bennu samples, and related analysis of analog materials provides important context for understanding aqueous alteration of carbonaceous asteroids more broadly. To that end, our team is analyzing carbonates in Bennu analog materials, using Raman spectroscopy to identify carbonates and assess the maturity of related organic materials, vacuum reflectance spectroscopy from the ultraviolet through thermal infrared range to constrain contributions from carbonates and organics, X-ray microtomography and electron probe microanalysis (EPMA) to assess the distribution of void space, transmission electron microscopy to characterize space weathering effects, and EPMA and secondary ion mass spectrometry (SIMS) to measure composition and isotopic ratios. Here, we describe in situ analysis of carbon and oxygen isotopes from carbonates in Grosvenor Mountains (GRO) 95577.

K E Miller↗

Astrobiological Potential of Rocks Acquired By the Perseverance Rover at the Front of the Western Sediment Fan in Jezero Crater, Mars.

Major objectives of the Perseverance rover mission include identifying past habitable environments, collecting rocks that are likely to preserve biosignatures and using the rover’s instruments to look for potential biosignatures in these rocks. The recognition of the > 3.5 billion-year old habitable environments in Jezero crater, Mars (Fig. 1); promised that the mission could achieve these objectives. The western sedimentary fan deposit, the hydrated minerals therein and the carbonate minerals at the margin of this fan were identified as particularly compelling areas in which to search for the signs of past life and collect the oldest aqueously deposited rocks from another planet.

Mars 2020↗

Global stocks and capacity of mineral-associated soil organic carbon

Abstract Soil is the largest terrestrial reservoir of organic carbon and is central for climate change mitigation and carbon-climate feedbacks. Chemical and physical associations of soil carbon with minerals play a critical role in carbon storage, but the amount and global capacity for storage in this form remain unquantified. Here, we produce spatially-resolved global estimates of mineral-associated organic carbon stocks and carbon-storage capacity by analyzing 1144 globally-distributed soil profiles. We show that current stocks total 899 Pg C to a depth of 1 m in non-permafrost mineral soils. Although this constitutes 66% and 70% of soil carbon in surface and deeper layers, respectively, it is only 42% and 21% of the mineralogical capacity. Regions under agricultural management and deeper soil layers show the largest undersaturation of mineral-associated carbon. Critically, the degree of undersaturation indicates sequestration efficiency over years to decades. We show that, across 103 carbon-accrual measurements spanning management interventions globally, soils furthest from their mineralogical capacity are more effective at accruing carbon; sequestration rates average 3-times higher in soils at one tenth of their capacity compared to soils at one half of their capacity. Our findings provide insights into the world’s soils, their capacity to store carbon, and priority regions and actions for soil carbon management.

54 ENVIRONMENTAL SCIENCES↗

Isotopic Composition of Carbonates in Antarctic Ordinary Chondrites and Miller Range Nakhlites: Insights into Martian Amazonian Aqueous Alteration

The martian surface contains features of ancient fluvial systems. Stable isotope analysis of carbonates that form in aqueous systems can reveal their formation conditions. The Nakhlite meteorites originally formed on Mars 1.3 Ga and were later exposed to aqueous fluids that left behind carbonate minerals [1], thus analysis of these carbonates can provide data to understand Amazonian climate conditions on Mars. Carbonates found in the Nakhlite meteorites contain a range of delta(sup 13)C values, which may be either martian carbonates or terrestrial contamination. To better under-stand terrestrial weathering products and martian carbonate formation processes, we conducted a set of carbonate isotope analyses on Antarctic meteorites focusing on Miller Range (MIL) Nakhlites as well as Ordinary Chondrites (OCs) (Figure 1)[1-11] [12]. OCs of petrology type H, L, and LL 3-6 were selected since they are not expected to contain preterrestrial carbonates, yet they have visible evaporite minerals on the fusion crust indicating terrestrial alteration. These cryogenically formed terrestrial carbonates may also provide an analog for cryogenic carbonate formation on Mars.

Evans, M. E.↗

Mineralization of alkaline waste for CCUS

Ex-situ mineralization processes leverage the reaction of alkaline materials with CO 2 to form solid carbonate minerals for carbon capture, utilization, and storage. Annually, enough alkaline waste is generated to reduce global CO 2 emissions by a significant percentage via mineralization. However, while the reaction is thermodynamically favorable and occurs spontaneously, it is kinetically limited. Thus, a number of techniques have emerged to increase the efficiency of mineralization to achieve a scalable process. In this review, we discuss mineralization of waste streams with significant potential to scale to high levels of CO 2 sequestration. Focus is placed on the effect of operating parameters on carbonation kinetics and efficiency, methods, cost, and current scale of technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Soils' dirty little secret: Depth–based comparisons can be inadequate for quantifying changes in soil organic carbon and other mineral soil properties

Quantifying changes in soil organic carbon (SOC) stocks and other soil properties is essential for understanding how soils will respond to land management practices and global change. Although they are widely used, comparisons of SOC stocks at fixed depth (FD) intervals are subject to errors when changes in bulk density or soil organic matter occur. The equivalent soil mass (ESM) method has been recommended in lieu of FD for assessing changes in SOC stocks in mineral soils, but ESM remains underutilized for SOC stocks and has rarely been used for other soil properties. In this paper, we draw attention to the limitations of the FD method and demonstrate the advantages of the ESM approach. We provide illustrations to show that the FD approach is susceptible to errors not only for quantifying SOC stocks but also for soil mass-based properties such as SOC mass percent, C:N mass ratio, and δ 13 C. Here we describe the ESM approach and show how it mitigates the FD method limitations. Using bulk density change simulations applied to an empirical dataset from bioenergy cropping systems, we show that the ESM method provides consistently lower errors than FD when quantifying changes in SOC stocks and other soil properties. To simplify the use of ESM, we detail how the method can be integrated into sampling schemes, and we provide an example R computer script that can perform ESM calculations on large datasets. We encourage future studies, whether temporal or comparative, to utilize sampling methods that are amenable to the ESM approach. Overall, we agree with previous recommendations that ESM should be the standard method for evaluating SOC stock changes in mineral soils, but we further suggest that ESM may also be preferred for comparisons of other soil properties including mass percentages, elemental mass ratios, and stable isotope composition.

59 BASIC BIOLOGICAL SCIENCES↗

Emergent temperature sensitivity of soil organic carbon driven by mineral associations

Abstract Soil organic matter decomposition and its interactions with climate depend on whether the organic matter is associated with soil minerals. However, data limitations have hindered global-scale analyses of mineral-associated and particulate soil organic carbon pools and their benchmarking in Earth system models used to estimate carbon cycle–climate feedbacks. Here we analyse observationally derived global estimates of soil carbon pools to quantify their relative proportions and compute their climatological temperature sensitivities as the decline in carbon with increasing temperature. We find that the climatological temperature sensitivity of particulate carbon is on average 28% higher than that of mineral-associated carbon, and up to 53% higher in cool climates. Moreover, the distribution of carbon between these underlying soil carbon pools drives the emergent climatological temperature sensitivity of bulk soil carbon stocks. However, global models vary widely in their predictions of soil carbon pool distributions. We show that the global proportion of model pools that are conceptually similar to mineral-protected carbon ranges from 16 to 85% across Earth system models from the Coupled Model Intercomparison Project Phase 6 and offline land models, with implications for bulk soil carbon ages and ecosystem responsiveness. To improve projections of carbon cycle–climate feedbacks, it is imperative to assess underlying soil carbon pools to accurately predict the distribution and vulnerability of soil carbon.

54 ENVIRONMENTAL SCIENCES↗

Reduced accrual of mineral-associated organic matter after two years of enhanced rock weathering in cropland soils, though no net losses of soil organic carbon

Abstract Enhanced rock weathering (ERW), the application of crushed silicate rock to soil, can remove atmospheric carbon dioxide by converting it to (bi) carbonate ions or solid carbonate minerals. However, few studies have empirically evaluated ERW in field settings. A critical question remains as to whether additions of crushed rock might positively or negatively affect soil organic matter (SOM)—Earth’s largest terrestrial organic carbon (C) pool and a massive reservoir of organic nitrogen (N). Here, in three irrigated cropland field trials in California, USA, we investigated the effect of crushed meta-basalt rock additions on different pools of soil organic carbon and nitrogen (i.e., mineral-associated organic matter, MAOM, and particulate organic matter, POM), active microbial biomass, and microbial community composition. After 2 years of crushed rock additions, MAOM stocks were lower in the upper surface soil (0–10 cm) of plots with crushed rock compared to unamended control plots. At the 2 sites where baseline pre-treatment data were available, neither total SOC nor SON decreased over the 2 years of study in plots with crushed rock or unamended control plots. However, the accrual rate of MAOM-C and MAOM-N at 0–10 cm was lower in plots with crushed rock vs. unamended controls. Before ERW is deployed at large scales, our results suggest that field trials should assess the effects of crushed rock on SOM pools, especially over multi-year time scales and in different environmental contexts, to accurately assess changes in net C and understand the mechanisms driving interactions between ERW and SOM cycling.

58 GEOSCIENCES↗

Precision Oxygen Isotope Measurements of Two C-Rich Hydrated Interplanetary Dust Particles

Introduction: Chondritic-smooth IDPs (Interplanetary Dust Particles) are low porosity objects whose mineralogy is dominated by aqueous alteration products such as Mg-rich phyllosilicates (smectite and serpentine group) and Mg-Fe carbonate minerals. Their hydrated mineralogy combined with low atmospheric entry velocities have been used to infer an origin largely from asteroidal sources. Spectroscopic studies show that the types and abundance of organic matter in CS IDPs is similar to that in CP IDPs. Although CS IDPs show broad similarities to primitive carbonaceous chondrites, only a few particles have been directly linked to specific meteorite groups such as CM and CI chondrites based on the presence of diagnostic minerals. Many CS IDPs however, have carbon contents that greatly exceed that of known meteorite groups suggesting that they either may derive from comets or represent samples of more primitive parent bodies than do meteorites. It is now recognized that many large, dark primitive asteroids in the outer main belt, as well as some trans-Neptunian objects, show spectroscopic evidence for aqueous alteration products on their surfaces. Some CS IDPs exhibit large bulk D enrichments similar to those observed in the cometary CP IDPs. While hydrated minerals in comets have not been unambiguously identified to date, the presence of the smectite group mineral nontronite has been inferred from infrared spectra obtained from the ejecta from comet 9P/Tempel 1 during the Deep Impact mission. Recent observations of low temperature sulfide minerals in Stardust mission samples suggest that limited aqueous activity occurred on comet Wild-2. All of these observations, taken together, suggest that the high-carbon hydrated IDPs are abundant and important samples of primitive solar system objects not represented in meteorite collections. Oxygen isotopic compositions of chondrites reflect mixing between a 16O-rich reservoir and a 17O,18O-rich reservoir produced via mass-independent fractionation. The composition of the 16O-rich reservoir is well constrained but material representing the 17O,18O-rich end-member is rare. Self-shielding models predict that cometary water, presumed to represent this reservoir, should be enriched in 17O and 18O by greater than 200 per mille. The high-carbon hydrated IDPs may be among the best materials available to search for preserved "cometary" H2O signatures. In order to better understand the origin and evolution of these particles, we have obtained 10 hydrated interplanetary dust particles for coordinated mineralogical, isotopic and organic analyses. We have previously reported the results of mineralogical and O isotopic measurements of two hydrated IDPs; here we present results of O isotopic measurements of three additional IDPs. Samples and Methods: Three interplanetary dust particles (L2079C35, L2083D46 and L2083E46) were embedded in S and partially ultramicrotomed into approximately 70 nanometer sections for analysis via transmission electron microscopy (TEM). The remainders of the unsliced particles were removed from S and pressed into high purity Au foil that was cleaned with HF acid and annealed at 800 degrees Centigrade. The pressed IDPs were analyzed via electron microprobe analysis (EPMA) for quantitative bulk chemical analysis. After EPMA analysis, the IDPs were subjected to precision O isotope analysis with the UCLA Cameca IMS-1270 ion probe. A 20 kiloelectronvolt, 0.5 nanoangstrom Cs+ primary beam of approximately 15 micrometers diameter was used for each measurement. Small particles of San Carlos olivine and Burma spinel were pressed into the Au foil for use as standards to correct for instrumental mass fractionation. The detection system was configured for multicollection, with 16O measured on a Faraday cup, and 17O and 18O measured on electron multipliers (EMs). Individual analyses consisted of 15 cycles of 10 seconds per cycle. Additionally, two microtome thin sections were measured for H isotopic compositions with the JSC NanoSIMS 50L ion probe. An 8 picoangstrom, 16 kiloelectronvolt Cs plus primary beam was used. Measurements consisted of H, C, 12C, 16O, and 18O collected with EMs in multicollection. Terrestrial biotite and kerogen were used for isotopic standards. A significant challenge in O isotope measurement of hydrated minerals is the interference from 16OH at mass 17O. We ensured that the 17O and 16OH peaks were fully resolved by using a mass resolution of greater than 7000 and by careful analyses of San Carlos olivine, Burma spinel and chlorite hydrated mineral standards. The hydride was further suppressed with a cold finger attached to an LN2 dewar to trap volatiles in the sample chamber. All sputtered ions were counted (i.e. presputtering was not used); after applying background, yield and deadtime corrections, we performed a change-point analysis on our data via R in order to determine when the sample reached sputtering equilibrium; data points collected prior to the change point were excluded. Change-point analysis was also used to determine whether the IDP had completely sputtered. Results: Mineralogy. IDPs C35 and E46 exhibited hydrated mineralogies, Fe-Ni sulfide grains, nanoglobules and occasional enstatite grains distributed throughout a fine-grained Mg-Fe saponite matrix. C35 also contained breunnerite (Mg,Fe)CO3; solar flare tracks were observed in enstatite, indicating minimal atmospheric entry heating. The mineralogy of D46 is dominated by a large FeS grain with a minor component of adhering silicate material. D46 was strongly heated during atmorpheric entry as evidenced by a well-developed magnetite rim. EPMA analyses show that both C35 and E46 have high carbon contents of 20 weight percentage (approximately 6X CI). D46 contains approximately 6 wt.weight percentage C. A significant amount of the carbon is present as carbon nanoglobules. Results: Hydrogen isotopes: Although the bulk delta D values of both sections of L2079C35 were within error of SMOW (minus 33 plus or minus 19 per mille, 1 plus or minus 14 per mille 1 sigma), several delta D-rich hotspots were also identified, reaching 2000 per mille. As shown in Fig. 1, these hotspots are clearly associated with discrete carbonaceous inclusions that are akin to nanoglobules found in many meteorites and other IDPs. Oxygen Isotopes. Results of the oxygen isotope measurements are shown in Figure 1. The oxygen isotope composition for L2079C35 was delta 18O equals plus11.6 plus or minus 1.9per mille, delta 17O equals plus 7.9 plus or minus 1.9per mille (2 standard errors). The oxygen isotope composition for L2083D46 was delta 18O equals minus 8.1 plus or minus 1.9 per mille, delta 17O equals minus 6.4 plus or minus 3.1 per mille (2 standard errors). The oxygen isotope composition for L2083E46 was delta 18O equals plus 12.0 plus or minus 1.9 per mille, delta 17O equals plus 9.2 plus or minus 2.0 per mille (2 standard errors). Discussion: Despite mineralogical similarities to highly aqueously altered carbonaceous chondrites, the hydrated IDPs we analyzed have oxygen isotopic compositions that are distinct from matrix materials in the CI, CM, and CR chondrites. The IDPs plot along the Young-Russell line, with delta 17O values for C35 and E46 suggestive of interaction with a 16O-poor reservoir. However, we have thus far not observed evidence of extreme 16O-poor reservoirs expected from self-shielding models and observed in Acfer 094 simplectite. The high carbon contents of the IDPs also set them apart from known meteoritic samples. The lack of atmospheric entry heating effects are consistent with low encounter velocities and suggest either an asteroidal source, or a low inclination, low eccentricity cometary origin. Conclusions: The unusual oxygen isotopic compositions, high carbon contents, and the abundance of Drich nanoglobules, together, suggest that the high-carbon, hydrated IDPs are derived from a primitive source that is not yet represented in meteorite collections.

Snead, C. J.↗

Estimated Refractive Indices of Calcite, Dolomite, and Magnesite: ~0.3-500 M.

Carbonate minerals are germane to questions involving volatile and climate history on Mars [e.g., 1-2]. In particular, the abundance of carbonate-bearing minerals can provide broad useful bounds on the amount of CO2 out-gassed into the atmosphere over its history and their spatial distribution and mineralogy can yield constraints on the environments in which they were produced. Earth-based, orbital, and landed spectral observations provide evidence for the presence of carbonates in the Martian environment [3-6]. Infrared observations made from spacecraft near Mars were interpreted to indicate the presence of carbonates. [6] associated the carbonates with the surface dust and interpreted the mineralogy as being consistent with magnesite (MgCO3). Near- infrared observations from Mars orbit have been interpreted to suggest magnesite outcrops in restricted locations [7-9]. Quantitative estimates of the abundance of carbonates on Mars range from 0-3% [3], 2-5% [6], less than a few percent [10], and <10% [8]. With the growing evidence for magnesite on Mars additional quantitative estimates can be provided via theoretical modeling of the reflectance from the Martian surface. Calcite (CaCO3) and dolomite ((Ca,Mg)CO3) are identified in Asian dust [2-17%], [10] and calcite in Saharan dust [~8-10% [12-15]. The importance of op- tical constants at visible and near-infrared wavelengths as proxies for estimating the effects at infrared wave- lengths, has been investigated [15]. The growing evidence for Mg-carbonates on Mars, the presence of calcite and dolomite in terrestrial aero- sols, and general lack of optical constants for these materials in the visible- to mid-infrared (VMIR, ~0.3-6 ❍m) has motivated the current effort to estimate the optical constants of calcite, dolomite, and magnesite in the VMIR.

Roush, T. L.↗

Reactive Transport Modeling of Mineral Precipitation and Carbon Trapping in Discrete Fracture Networks

In this study we use numerical experiments to analyze reactive flow and transport behavior in discrete intersecting fracture networks, focusing on (a) how reaction-induced changes in physical and chemical properties affect flow connectivity and (b) how fracture networks developed in the Earth's critical zone contribute to carbon sequestration via mineral weathering reactions. In the first part of the study, we used two-dimensional reactive flow and transport simulations to analyze the impacts of mixing in a natural discrete fracture network. We concluded that reaction-induced changes can substantially alter the flow connectivity, especially at fracture intersections. The second set of simulations considered the problem of natural weathering of fractured mafic and ultramafic rocks in the partially saturated Earth's critical zone as a function of infiltration rates, fracture permeability, and partially saturated flow parameters. As a model system, we considered an incongruent reaction network with dissolution of forsterite and precipitation of magnesite. The behavior is complex in terms of the rate-controlling processes because of the multicomponent nature of the system as shown by the grid Peclet number: the CO 2 behavior is gas diffusion-controlled in the partially saturated zone, while the rate of water flow via the Damkӧhler number controls Mg 2+ transport through the fracture network. The amounts of carbon that can be trapped are modest, but the naturally fractured domain considered here provides a useful “base case” against which various engineered solutions can be compared.

58 GEOSCIENCES↗

Root carbon interation with soil minerals is dynamic, leaving a legacy of microbially derived residues

Minerals preserve the oldest most persistent soil carbon, and mineral characteristics appear to play a critical role in the formation of soil organic matter (SOM) associations. To test the hypothesis that carbon source and soil microorganisms also influence mineral-SOM associations, we incubated permeable minerals bags in soil microcosms with and without plants, in a 13CO2 labelling chamber. Mineral bags contained quartz, ferrihydrite, kaolinite, or native soil minerals isolated via density separation. Using 13C-NMR, FTICR-MS, and lipidomics, we traced plant-derived carbon onto minerals harvested from microcosms at three plant growth stages, characterizing total carbon, 13C enrichment, and SOM chemistry. While C accumulation was rapid and mineral-dependent, the accumulated amount was not significantly affected by the presence of plant roots. However, the rhizosphere did shape the chemistry of mineral-associated SOM. Minerals incubated in the rhizosphere were associated with a more diverse array of compounds with different C functional groups (carbonyl, aromatics, carbohydrates, lipids) than minerals incubated in a bulk soil control. These diverse rhizosphere-derived compounds may represent a “transient fraction” of mineral SOM, rapidly exchanging with mineral surfaces. Our results also suggest that many of the lipids which persist on minerals are microbially-derived with a large fraction of fungal lipids.

Rhizosphere, soil organic matter, grassland, 13C-N↗

Quantification of CO 2 Mineralization at the Wallula Basalt Pilot Project

In 2013, the Pacific Northwest National Laboratory led a geologic carbon sequestration field demonstration where ~1000 tonnes of CO 2 was injected into several deep Columbia River Basalt zones near Wallula, Washington. Rock core samples extracted from the injection zone two years after CO 2 injection revealed nascent carbonate mineralization that was qualitatively consistent with expectations from laboratory experiments and reactive transport modeling. In this study, we report on a new detailed analysis of the 2012 pre-injection and 2015 post-injection hydrologic tests that capitalizes on the difference in fluid properties between scCO 2 and water to assess changes in near-field, wellbore, and reservoir conditions that are apparent approximately two years following the end of injection. This comparative hydrologic test analysis method provides a new way to quantify the amount of injected CO 2 that was mineralized in the field test. Modeling results indicate that approximately 60% of the injected CO 2 was sequestered via mineralization within two years, with the resulting carbonates occupying ~4% of the available reservoir pore space. The method presented here provides a new monitoring tool to assess the fate of CO 2 injected into chemically reactive basalt formations but could also be adapted for long-term monitoring and verification within more traditional subsurface carbon storage reservoirs.

54 ENVIRONMENTAL SCIENCES↗

Interaction between dissolution and precipitation during olivine carbonation: Implications for CO 2 mineralization

Large-scale carbonation of olivine is considered a promising approach for in situ mineral carbonation, offering a permanent and stable method for CO 2 storage. A critical aspect of this process is understanding how dissolution and precipitation interact, as this could drive fracturing and enhance further reactions. In this study, we conducted carbonation experiments on olivine using CO 2 -saturated aqueous solutions of NaHCO 3 and NaCl. Two experimental setups were used: one representing an open geochemical system and the other a closed system, corresponding to reaction-limited and flow-limited scenarios, respectively. Further, post-reaction textural analysis using scanning electron microscopy (SEM) revealed surface coatings of reaction products in the closed system, while etch pits and etch channels were prevalent in the open system. Although no direct evidence of reaction-driven fracturing was observed, etch pits and etch channels may serve as initiation points for subcritical crack formation and growth, potentially maintaining permeability and exposing new unreacted surfaces. Using linear elastic fracture mechanics (LEFM) model, we estimate that microcracks could propagate under a pressure of 0.1 GPa if reaction products accumulate within the etch pits. Our findings offer new insights into the mechanisms governing olivine carbonation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carbonate and sulfate minerals in the Chassigny meteorite

SO2 and CO2 from pyrolysis and combustion of bulk Chassigny and infrared traces of sulfate and carbonate minerals have been previously reported. Using scanning electron microscopy (SEM) and energy-dispersive x ray spectrometry (EDS), portions of these samples are searched, and a Ca-sulfate/carbonate association is confirmed.

Wentworth, Susan J.↗

Hidden carbon dioxide on Mars

A recent proposal that much of the outgassed CO2 on Mars is tied up in the planet's crust in the form of carbonate mineral is discussed. According to this hypothesis, carbonate formation on Mars continued after open bodies of liquid water became unstable. A consequence of the hypothesis is that, in the absence of a recycling mechanism for CO2, the surface pressure on Mars will monotonically decrease until it reaches the minimum atmospheric overburden pressure required for liquid water to form. The theory explains Mars' low surface pressure, and also implies that the climate of Mars has evolved linearly over geologic time, rather than cyclically.

Haberle, R. M.↗