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At least 145 records · Page 8

Mineralogical and transport controls on the evolution of porous media texture using direct numerical simulation

The evolution of porous media due to mineral dissolution and precipitation can change the bulk properties of subsurface materials. The pore-scale structure of the media, including its physical and mineralogical heterogeneity, exerts controls on porous media evolution via transport limitations to reactive surfaces and mineral accessibility. Here in this paper we explore how these controls affect the evolution of the texture in porous media at the pore scale. For this purpose, a pore-scale flow and reactive transport model is developed that explicitly tracks mineral surfaces as they evolve using a direct numerical simulation approach. Simulations of dissolution in single-mineral domains provide insights into the transport controls at the pore scale, while the simulation of a fracture surface composed of bands of faster-dissolving calcite and slower-dissolving dolomite provides insights into the mineralogical controls on evolution. Transport-limited conditions at the grain-pack scale may result in unstable evolution, a situation in which dissolution is focused in a fast-flowing, fast-dissolving path. Due to increasing velocities, the evolution in these regions is like that observed under conditions closer to strict surface control at the pore scale. That is, grains evolve to have oblong shapes with their long dimensions aligning with the local flow directions. Another example of an evolving reactive transport regime that affects local rates is seen in the evolution of the fracture surface. As calcite dissolves, the diffusive length between the fracture flow path and the receding calcite surfaces increases. Thus, the calcite dissolution reaction becomes increasingly limited by diffusion.

36 MATERIALS SCIENCE↗

Chemistry, Mineralogy, and Grain Properties at Namib and High Dunes, Bagnold Dune Field, Gale Crater, Mars: A Synthesis of Curiosity Rover Observations: Bagnold Dune Sands Composition

The Mars Science Laboratory Curiosity rover performed coordinated measurements to examine the textures and compositions of aeolian sands in the active Bagnold dune field. The Bagnold sands are rounded to subrounded, very fine- to medium- sized (~45-500 µm) with ≥6 distinct grain colors. In contrast to sands examined by Curiosity in a dust-covered, inactive bedform called Rocknest and soils at other landing sites, Bagnold sands are darker, less red, better sorted, have fewer silt-sized or smaller grains, and show no evidence for cohesion. Nonetheless, Bagnold mineralogy and Rocknest mineralogy are similar with plagioclase, olivine, and pyroxenes in similar proportions comprising >90% of crystalline phases, along with a substantial amorphous component (35% ± 15%). Yet, Bagnold and Rocknest bulk chemistry differ. Bagnold sands are Si-enriched relative to other soils at Gale crater, and H 2 O, S, and Cl are lower relative to all previously measured martian soils and most Gale crater rocks. Mg, Ni, Fe, and Mn are enriched in the coarse-sieved fraction of Bagnold sands, corroborated by VNIR spectra that suggest enrichment of olivine. Together, patterns in major element chemistry and volatile release data indicate two distinctive volatile reservoirs in martian soils: (1) amorphous components in the sand-sized fraction (represented by Bagnold) that are Si-enriched, hydroxylated alteration products and/or impact or volcanic glasses; and (2) amorphous components in the fine fraction (<40 µm; represented by Rocknest and other bright soils) that are Fe-, S-, and Cl-enriched with low Si and adsorbed and structural H 2 O.

58 GEOSCIENCES↗

Concrete alteration due to 55 years of exposure to river water: Chemical and mineralogical characterisation

This article presents a study on concrete alteration mechanisms due to 55 years of exposure to river water. Many hydro power structures in cold regions suffer from concrete deterioration at the waterline. Progressive disintegration of the concrete surface leads to exposure of the coarse aggregate and eventually the reinforcing steel. Concrete cylinders drilled out at four vertically different locations on the upstream face of a concrete dam were analysed by electron microprobe analysis, X-ray diffraction, thermogravimetry and scanning electron microscopy. Long-term exposure to the river water, which is regarded as soft water, has led to chemical and mineralogical zonation of the cement paste. Up to five zones with different chemical and mineralogical composition, parallel to the upstream face, were observed in the outermost 8–9 mm of the concrete. Decalcification, precipitation of secondary ettringite and the formation of a magnesium-rich silica gel constitute the major changes that define the zones.

36 MATERIALS SCIENCE↗

Origin of 16 O-rich fine-grained Ca-Al-rich inclusions of different mineralogy and texture

We conducted a coordinated mineralogical and oxygen isotopic study of four fine-grained calcium-, aluminum-rich inclusions (CAIs) from the ALHA77307 CO3.0 carbonaceous chondrite. Three of the inclusions studied, 05, 1-65, and 2-119, all have nodular structures that represent three major groups, melilite-rich, spinel-rich, and hibonite-rich, based on their primary core mineral assemblages. A condensation origin was inferred for these CAIs. However, the difference in their primary core mineralogy reflects unique nebular environments in which multiple gas-solid reactions occurred under disequilibrium conditions to form hibonite, spinel, and melilite with minor perovskite and Al,Ti-rich diopside. A common occurrence of a diopside rim on the CAIs records a widespread event that marks the end of their condensation as a result of isolation from a nebular gas. An exception is a rare inclusion 2-112 that contains euhedral spinel crystals embedded in melilite, suggesting this CAI had been re-melted. All of the fine-grained CAIs analyzed in ALHA77307 are 16 O-rich with an average Δ 17 O value of ~-22 ± 5‰ (2σ), indicating no apparent correlation between their textures and oxygen isotopic compositions. We therefore conclude that a prevalent 16 O-rich gas reservoir existed in a region of the solar nebula where CO3 fine-grained CAIs formed, initially by condensation and then later, some of them were reprocessed by melting event(s).

58 GEOSCIENCES↗

Machine learning and deep learning for mineralogy interpretation and CO 2 saturation estimation in geological carbon Storage: A case study in the Illinois Basin

Carbon capture and storage (CCS) is a promising approach to simultaneously maintaining energy security and reducing carbon dioxide (CO 2 ) emissions under the current energy portfolio that is dominated by fossil fuel energy. Pre-injection formation characterization and post-injection CO 2 monitoring are two critical tasks to guarantee storage efficiency in CCS. The CCS projects in the Illinois Basin, the first large-scale CO 2 injection into saline aquifers in the United States, employed conventional and the latest pulsed neutron logging (PNL) tools for mineralogy interpretation and CO 2 saturation estimation, which provide valuable references for future CCS projects. Because of the inherent fuzziness of petrophysical measurements and complex subsurface heterogeneity, interpreting well-logging data is time-consuming, and its accuracy can be user-biased. In recent years, data-driven methods have been widely used to capture the non-linear patterns between input features and interpretation results. This work applied and evaluated four commonly used machine learning (ML) models, including ridge regression (RR), random forest (RF), gradient boosting regression (GBR), support vector regression (SVR), and one deep learning (DL) model, the artificial neural network (ANN). We optimized the hyperparameters of the four ML models and the DL model using the simulated annealing algorithm and the grid search strategy, respectively. The input features of the mineralogy interpretation models were eleven conventional well-logging parameters, and the label data (i.e., ground truth) were the porosity and volumetric fractions of six minerals, including quartz, feldspar, dolomite, calcite, clay, and iron minerals. The results demonstrated that the GBR and RF models were superior in predicting volumetric fractions of minerals and porosity; label data with low coefficient of variation (CV) values tended to yield better performance. For CO 2 saturation estimation, the RF was the best-performing model, followed by SVR, ANN, GBR, and RR. Furthermore, we conducted feature importance ranking using the permutation importance algorithm and found that the formation sigma and well pressure were the most important features in this study. In conclusion, the study of CCS projects in the Illinois Basin bridges the gap between the limited knowledge and understanding of geological carbon storage and the increasing demand for reliable, cost-effective, and sustainable energy solutions.

58 GEOSCIENCES↗

Mineralogy-dependent sulfide oxidation via polysulfide and thiosulfate pathways during weathering of mixed-sulfide bearing mine waste rock

Tracking the S oxidation pathway in sulfide-bearing mine waste-rock piles is complicated by variations in water content, O 2 and Fe 3+ concentrations, microbial diversity, mineralogy, the occurrence of a variety of S species associated with incomplete oxidation, and nonlinear coupling between physicochemical processes. Synchrotron-based S K-edge X-ray absorption near edge structure (XANES) spectroscopy facilitates the identification and quantification of S species (i.e., S 2– , $S_{2}O_{2}^{2–}$, S 8 , $S_{2}O_{3}^{2–}$, and $S_{2}O_{4}^{2–}$) in a weathered mine waste-rock pile containing pyrite, sphalerite, galena, pyrrhotite, and chalcopyrite. Mineralogy-dependent polysulfide and thiosulfate pathways both affect the S oxidation within the waste-rock pile. Currently, the polysulfide pathway, with S 8 as the intermediate S species, generates high concentrations of dissolved metals (from the rapid oxidation of monosulfides including sphalerite, galena, pyrrhotite, and chalcopyrite). As these monosulfides are depleted, the thiosulfate pathway of pyrite oxidation, including intermediate oxidation products (i.e., S 8 and $S_{2}O_{3}^{2–}$), will become the dominant oxidation pathway, resulting in the potential for generation of additional acidic drainage. This information highlights the importance of identifying the sulfide-mineral oxidation reaction pathways when attempting to estimate acid generation potential, and when developing remediation strategies for the storage and management of sulfide-bearing waste rock.

58 GEOSCIENCES↗

Mineralogical, magnetic and geochemical data constrain the pathways and extent of weathering of mineralized sedimentary rocks

The oxidative weathering of sulfidic rock can profoundly impact watersheds through the resulting export of acidity and metals. Weathering leaves a record of mineral transformation, particularly involving minor redox-sensitive phases, that can inform the development of conceptual and quantitative models. In sulfidic sedimentary rocks, however, variations in depositional history, diagenesis and mineralization can change or overprint the distributions of these trace minerals, complicating the interpretation of weathering signatures. Here we show that a combination of bulk mineralogical and geochemical techniques, micrometer-resolution X-ray fluorescence microprobe analysis and rock magnetic measurements, applied to drill core samples and single weathered fractures, can provide data that enable the development of a geochemically consistent weathering model. This work focused on one watershed in the Upper Colorado River Basin sitting within the Mesaverde Formation, a sedimentary sandstone bedrock with disseminated sulfide minerals, including pyrite and sphalerite, that were introduced during diagenesis and subsequent magmatic-hydrothermal mineralization. Combined analytical methods revealed the pathways of iron (Fe), carbonate and silicate mineral weathering and showed how pH controls element retention or release from the actively weathering fractured sandstone. Drill core logging, whole rock X-ray diffraction, and geochemical measurements document the progression from unweathered rock at depth to weathered rock at the surface. X-ray microprobe analyses of a 1-cm size weathering profile along a fracture surface are consistent with the mobilization of Fe(II) and Fe(III) into acidic pore water from the dissolution of primary pyrite, Fe-sphalerite, chlorite, and minor siderite and pyrrhotite. These reactions are followed by the precipitation of secondary minerals such as of goethite and jarosite, a Fe-(oxyhydr)oxide and hydrous Fe(III) sulfate, respectively. Microscale analyses also helped explain the weathering reactions responsible for the mineralogical transformations observed in the top and most weathered section of the drill core. For example, dissolution of feldspar and chlorite neutralizes the acidity generated by Fe and sulfide mineral oxidation, oversaturating the solution in both Fe-oxides. The combination of X-ray spectromicroscopy and magnetic measurements show that the Fe(III) product is goethite, mainly present either as a coating on fracture surfaces in the actively weathering region of the core or more homogeneously contained within the unconsolidated regolith at the top of the core. Low-temperature magnetic data reveal the presence of ferromagnetic Fe-sulfide pyrrhotite that, although it occurs at trace concentrations, could provide a qualitative proxy for unweathered sulfide minerals because the loss of pyrrhotite is associated with the onset of oxidative weathering. Pyrrhotite loss and goethite formation are detectable through room-temperature magnetic coercivity changes, suggesting that rock magnetic measurements can determine weathering intensity in rock samples at many scales. In conclusion, this work contributes evidence that the weathering of sulfidic sedimentary rocks follows a geochemical pattern in which the abundance of sulfide minerals controls the generation of acidity and dissolved elements, and the pH-dependent mobility of these elements controls their export to the ground- and surface-water.

58 GEOSCIENCES↗

Insights into Controls of Mineralogy and Pore Structure on the Density of Methane Adsorption Phase in Shales under Supercritical Conditions

With gradually increasing enhancing population and industrialization, exploitation of shale gas is enhancing in the world to satisfy the growing demand for energy worldwide. To exploit shale gas efficiently, accurate assessment of shale gas in place (GIP) is necessary for determining production strategies. Unlike free and dissolved gas, adsorbed gas contributes to the shale GIP up to 85% due to the well-developed surface area and micropores. Measured excess adsorption of methane (up to over 95% of subsurface shale gas) is often corrected to absolute adsorption to obtain the actual amount of adsorption under supercritical (or geological) conditions. During the correction, adsorption phase density (APD) is critical. However, the APD of subsurface shale gas and the effects of shale properties (e.g., mineralogy and pore structure) on APD remain poorly understood. A series of high-pressure methane adsorption isotherms (HPMAI) on Caney Shales were collected and analyzed in conjunction with other United States and Chinese shales from the literature at 35–125 °C and up to 15 MPa. Here, a three-layer Ono–Kondo (OK3) model is utilized to derive the temperature- and pressure-dependent APD coupling low-pressure nitrogen adsorption isotherms (LPNAI) and HPMAI. X-ray diffraction and organic geochemistry are combined to reveal the mineralogy. Brunauer–Emmett–Teller, Barrett–Joyner–Halenda, and Horvath–Kawazoe analyses via LPNAI are used to investigate the pore structures. Results show that APD increases with organic matter (OM) proxied by total organic carbon and decreases with clay minerals and the sum of quartz and feldspar. OM dramatically contributes to the APD as multiple-layer adsorption exists, and the APD for OM could be 1.4–8.5 times that for clay minerals. Other inorganic minerals contribute less to APD. The properties and constitution of the surface area instead of the volume fraction contribute to the APD in shales. APD does not show an obvious correlation with micropore volume, likely related to the ratio of micropore volume to the total pore volume. Here, we provide a significant and comprehensive study of petrological factors that impact the APD of subsurface shale gas, which will improve the estimation of supercritical adsorption and shale GIP under reservoir conditions. Also, the findings in this work can provide applications for subsurface carbon dioxide adsorption and storage.

58 GEOSCIENCES↗

Small-Angle Neutron Scattering Investigation of Oil Recovery in Mineralogically Distinct Wolfcamp Shale Strata

Understanding and improving hydrocarbon yields during enhanced oil recovery (EOR) in unconventional reservoirs is complicated by the intrinsic mineralogical and geochemical heterogeneity of shale formations. Here, in this study, we utilized small-angle neutron scattering (SANS) and ultra-small-angle neutron scattering (USANS) to investigate the degree of oil retention and its location in the nanoporous shale matrix for two mineralogically distinct shale samples. The two samples, dubbed “dark” and “light” based on their color, were taken from adjacent strata in a Wolfcamp shale core. While both samples contained kerogen, the dark sample contained more kerogen and clay (43.7 wt %) while the light sample contained more calcite (54.9 wt %). Samples were presaturated with decane, a model hydrocarbon, prior to pressure cycling with methane. Results showed significantly more retention of decane in 1.5–10 nm radius pores of both, likely indicating that oil is retained within kerogen nanopores. Although the dark sample had a higher porosity of 8.7%, versus 3.3% for the light sample, more pores were accessible to decane and a higher percentage of the imbibed decane was removable from the light sample compared to the dark sample. The majority of decane was not recoverable for the dark sample, indicating that EOR with methane can be challenging. These new findings can help to model expected recoveries of in-place oil from heterogeneous shale formations, as well as inform improved EOR strategies.

04 OIL SHALES AND TAR SANDS↗

Role of Mineralogy in Controlling Fracture Formation

The presence of fractures in caprocks can pose increased risks in subsurface energy systems and processes like CO 2 sequestration by introducing high-permeability leakage paths. Fracture apertures and permeability can be altered through mineral dissolution and precipitation reactions, but the reactive evolution of fractures is not well understood. In fractures, minerals that are otherwise inaccessible to reactive fluids can become exposed, resulting in mineral reactions unpredicted by bulk formation data. This work seeks to understand the relationship between mineralogy and fracture formation to enhance our understanding of reactive fracture evolution and CO 2 leakage potential. Here, the mineral compositions of mechanically induced fracture surfaces in samples of the Mancos and Marcellus shales have been quantified and compared to those of the near-fracture matrices using imaging and bulk X-ray diffraction (XRD) data. In the Mancos shale, the concentrations of clay minerals are enhanced along fracture surfaces with respect to the bulk, and the fracture is most likely to form at kaolinite–kaolinite interfaces. Further, evaluation of the mineralogical spatial variability through cross-correlation analysis of the surrounding matrix in images of samples cut perpendicular to the fracture shows that clay is 16.7 times more likely to be present than carbonate minerals near the fracture surface. The high correlation persists roughly 200 μm into the surrounding matrix for the Mancos sample and implies that the fracture formed within a defined clay-rich lithofacies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermal Pressure in the Laser‐Heated Diamond Anvil Cell: A Quantitative Study and Implications for the Density Versus Mineralogy Correlation of the Mantle

Abstract Thermal pressure is an inevitable thermodynamic consequence of heating a volumetrically constrained sample in the diamond anvil cell. Its possible influences on experimentally determined density‐mineralogy correlations are widely appreciated, yet the effect itself has never been experimentally measured. We present here the first quantitative measurements of the spatial distribution of thermal pressure in a laser‐heated diamond anvil cell (LHDAC) in both olivine and AgI. The observed thermal pressure is strongly localized and closely follows the distribution of the laser hotspot. The magnitude of the thermal pressure is of the order of the thermodynamic thermal pressure ( αK T Δ T ) with gradients between 0.5 and 1.0 GPa/10 μm. Remarkably, we measure a steep gradient in thermal pressure even in a sample that is heated close to its melting line. This generates consequences for pressure determinations in pressure‐volume‐temperature (PVT) equation of state measurements when using an LHDAC. We show that an incomplete account of thermal pressure in PVT experiments can lead to biases in the coveted depth versus mineralogy correlation. However, the ability to spatially resolve thermal pressure in an LHDAC opens avenues to measure difficult‐to‐constrain thermodynamic derivative properties, which are important for comprehensive thermodynamic descriptions of the interior of planets.

Yen, Connor Ethan↗

Mineralogical evidence for hydrothermal alteration of Bennu samples

Samples of asteroid (101955) Bennu delivered by the OSIRIS-REx mission offer the opportunity to study pristine planetary materials unchanged by exposure to the terrestrial environment. Here we use a combination of X-ray diffraction and various electron microscopy techniques to explore the detailed mineralogy of Bennu samples and determine the alteration history of the planetesimal protolith from which they originated. The samples consist largely of hydrated sheet-silicate minerals, namely nanoscale serpentine and saponite of varied grain size, which are decorated with micro- to nanoscale Fe-sulfides, magnetite and carbonates. We observe sheet silicates parallel and normal to sulfide surfaces and as inclusions in sulfides; sulfur-rich veins transecting the sheet-silicate matrix; zoned carbonates and phosphates and sulfide and magnetite grains exhibiting embayment. The mineralogical evidence indicates alteration of accreted minerals by a fluid that evolved with time, leading to etching, dissolution and reprecipitation. Sulfide compositions indicate alteration at ~25 °C, similar to conditions inferred for asteroid (162173) Ryugu and Ivuna-type (CI) chondrite meteorites. The fluid probably evolved from neutral to alkaline, culminating with the precipitation of highly soluble salts. We conclude that Bennu’s protolith comprised mainly nanometre to micrometre silicates, with fewer chondrules and calcium–aluminium-rich inclusions than those of most chondrite groups.

Zega, T J↗

Coupling among Microbial Communities, Biogeochemistry, and Mineralogy across Biogeochemical Facies

Physical properties of sediments are commonly used to define subsurface lithofacies and these same physical properties influence subsurface microbial communities. This suggests an (unexploited) opportunity to use the spatial distribution of facies to predict spatial variation in biogeochemically relevant microbial attributes. Here, we characterize three biogeochemical facies—oxidized, reduced, and transition—within one lithofacies and elucidate relationships among facies features and microbial community biomass, diversity, and community composition. Consistent with previous observations of biogeochemical hotspots at environmental transition zones, we find elevated biomass within a biogeochemical facies that occurred at the transition between oxidized and reduced biogeochemical facies. Microbial diversity—the number of microbial taxa—was lower within the reduced facies and was well-explained by a combination of pH and mineralogy. Null modeling revealed that microbial community composition was influenced by ecological selection imposed by redox state and mineralogy, possibly due to effects on nutrient availability or transport. As an illustrative case, we predict microbial biomass concentration across a three-dimensional spatial domain by coupling the spatial distribution of subsurface biogeochemical facies with biomass-facies relationships revealed here. We expect that merging such an approach with hydro-biogeochemical models will provide important constraints on simulated dynamics, thereby reducing uncertainty in model predictions.

Stegen, James C.↗

Effect of maturity and mineralogy on fluid-rock reactions in the Marcellus Shale

Natural gas extraction from the Appalachian Basin has significantly increased in the past decade. The push to properly dispose, reuse, or recycle the large amounts of produced fluids associated with hydraulic fracturing operations and design better fracturing fluids has necessitated a better understanding of the subsurface chemical reactions taking place during hydrocarbon extraction. Using autoclave reactors, this study mimics the conditions of deep subsurface shale reservoirs to observe the chemical evolution of fluids during the shut-in phase of hydraulic fracturing (HF), a period when hydraulic fracturing fluids (HFFs) remain confined in the reservoir. The experiment was conducted by combining a synthetic hydraulic fracturing fluid and powdered shale core samples in high temperature/pressure static autoclave reactors for 14 days. Shale samples of varying maturity and mineralogy were used to assess the effect of these variations on the proliferation of inorganic ions and low molecular weight volatile organic compounds (VOCs), mainly benzene, toluene, ethylbenzene and xylenes (BTEX) and monosubstituted carboxylic acids. Ion chromatography results indicate that the relative abundance of ions present was similar to that of water produced from HF operations in the Marcellus Shale basin. There was an increase of SO 4 2- and PO 4 3- and a decrease in Ba 2+ upon fluid-shale reaction. Major ionic shifts indicate calcite dissolution in two of the fluid-shale reactions and barite precipitation in all fluid-shale reactions. Toluene, xylene, and carboxylic acids were produced in the shale-free control experiment. The most substantial increase in BTEX analytes was observed in reactions with low maturity shale, while the high maturity shale reaction produced no measurable BTEX compounds. Total organic carbon decreased in all reactions including fracturing fluid and shale, suggesting adsorption onto the organic matter (OM) matrix. The results from this study highlight that both the nature of OM and mineralogy play a key role in determining the fate of inorganic and organic compounds during fluid–shale interactions in the subsurface shale reservoir. Overall this study aims to contribute to the growing understanding of complex chemical interactions that occur in the shale reservoirs during HF, which is vital for determining the potential environmental impacts of HF and designing more efficient HFF and produced water recycling techniques for environmentally conscious natural gas production.

58 GEOSCIENCES↗

Mineralogical effects on the detectability of the postperovskite boundary

The discovery of a phase transition in Mg-silicate perovskite (Pv) to postperovskite (pPv) at lowermost mantle pressure-temperature (P - T) conditions may provide an explanation for the discontinuous increase in shear wave velocity found in some regions at a depth range of 200 to 400 km above the core-mantle boundary, hereafter the D{double_prime} discontinuity. However, recent studies on binary and ternary systems showed that reasonable contents of Fe{sup 2+} and Al for pyrolite increase the thickness (width of the mixed phase region) of the Pv - pPv boundary (400-600 km) to much larger than the D{double_prime} discontinuity ({le} 70 km). These results challenge the assignment of the D{double_prime} discontinuity to the Pv - pPv boundary in pyrolite (homogenized mantle composition). Furthermore, the mineralogy and composition of rocks that can host a detectable Pv {yields} pPv boundary are still unknown. Here we report in situ measurements of the depths and thicknesses of the Pv {yields} pPv transition in multiphase systems (San Carlos olivine, pyrolitic, and midocean ridge basaltic compositions) at the P - T conditions of the lowermost mantle, searching for candidate rocks with a sharp Pv - pPv discontinuity. Whereas the pyrolitic mantle may not have a seismologically detectable Pv {yields} pPv transition due to the effect of Al, harzburgitic compositions have detectable transitions due to low Al content. In contrast, Al-rich basaltic compositions may have a detectable Pv - pPv boundary due to their distinct mineralogy. Therefore, the observation of the D{prime} discontinuity may be related to the Pv {yields} pPv transition in the differentiated oceanic lithosphere materials transported to the lowermost mantle by subducting slabs.

Grocholski, Brent↗

Mineralogy, fabric and deformation domains in D" across the southwestern border of the African LLSVP

Recent advances in seismic anisotropy studies that jointly use reflections and shear wave splitting have proven to place tight constraints on the plausible anisotropic and deformation scenarios in the D" region. We apply this novel methodology to a large area of the D" region beneath the South Atlantic, in proximity to and within the African large low seismic velocity province (LLSVP). This area of the mantle is characterized by a transition from fast to slow seismic velocity anomalies and it is thought to be the location of deep-seated plumes responsible for hotspot volcanism. Attempting to probe mantle composition and deformation along the LLSVP borders may provide key information on mantle dynamics. By analysing seismic phases sampling this region, we detect a D" discontinuity over a large area beneath the South Atlantic, with inferred depth ranges ~170 to ~240 km above the core–mantle boundary. We find evidence for a D" reflector within the area of the LLSVP. Shear wave splitting observations suggest that anisotropy is present in this region of the mantle, in agreement with previous studies that partially sampled this region. We model the observations considering lattice- and shape-preferred orientation of materials expected in the D" region. A regional variation of mineralogy, phase transition boundaries, and deformation direction is required to explain the data. We infer two distinct domains of mineralogy and deformation: aligned post-perovskite outside the LLSVP and aligned bridgmanite within the LLSVP. Finally, the scenario depicted by this study agrees well with the current hypotheses for the composition of the LLSVP and with the prevalence of vertical deformation directions expected to occur along the LLSVPs borders.

58 GEOSCIENCES↗

Climate, soil mineralogy and mycorrhizal fungi influence soil organic matter fractions in eastern US temperate forests

Identifying the primary controls of particulate (POM) and mineral-associated organic matter (MAOM) content in soils is critical for determining future stocks of soil carbon (C) and nitrogen (N) across the globe. However, drivers of these soil organic matter fractions are likely to vary among ecosystems in response to climate, soil type and the composition of local biological communities. We tested how soil factors, climate and plant–fungal associations influenced the distribution and concentrations of C and N in MAOM and POM in seven temperate forests in the National Ecological Observatory Network (NEON) across the eastern United States. Samples of upper mineral horizon soil within each forest were collected in plots representing a gradient of dominant tree–mycorrhizal association, allowing us to test how plant and microbial communities influenced POM and MAOM across sites differing in climate and soil conditions. We found that concentrations of C and N in soil organic matter were primarily driven by soil mineralogy, but the relative abundance of MAOM versus POM C was strongly linked to plot-level mycorrhizal dominance. Furthermore, the effect of dominant tree mycorrhizal type on the distribution of N among POM and MAOM fractions was sensitive to local climate: in cooler sites, an increasing proportion of ectomycorrhizal-associated trees was associated with lower proportions of N in MAOM, but in warmer sites, we found the reverse. As an indicator of soil carbon age, we measured radiocarbon in the MAOM fraction but found that within and across sites, Δ 14 C was unrelated to mycorrhizal dominance, climate, or soil factors, suggesting that additional site-specific factors may be primary determinants of long-term SOM persistence. Our results indicate that while soil mineralogy primarily controls SOM C and N concentrations, the distribution of SOM among density fractions depends on the composition of vegetation and microbial communities, with these effects varying across sites with distinct climates. Here we also suggest that within biomes, the age of mineral-associated soil carbon is not clearly linked to the factors that control concentrations of MAOM C and N.

54 ENVIRONMENTAL SCIENCES↗

Focused‐beam X‐ray fluorescence and diffraction microtomographies for mineralogical and chemical characterization of unsectioned extraterrestrial samples

Abstract This study describes the application of new synchrotron X‐ray fluorescence (XRF) and diffraction (XRD) microtomographies for the 3‐D visualization of chemical and mineralogical variations in unsectioned extraterrestrial samples. These improved methods have been applied to three compositionally diverse chondritic meteorite samples that were between 300 and 400 μm in diameter, including samples prepared from fragments of the CR2 chondrite LaPaz Icefield (LAP) 02342, H5 chondrite MacAlpine Hills (MAC) 88203, and the CM2 chondrite Murchison. The synchrotron‐based XRF and XRD tomographies used are focused‐beam techniques that measure the intensities of fluorescent and diffracted X‐rays in a sample simultaneously during irradiation by a high‐energy microfocused incident X‐ray beam. Measured sinograms of the emitted and diffracted intensities were then tomographically reconstructed to generate 2‐D slices of XRF and XRD intensity through the sample, with reconstructed pixel resolution of 1–2 μm, defined by the resolution of the focused incident X‐ray beam. For sample LAP 02342, primary mineral phases that were visualized in reconstructed slices using these techniques included isolated grains of α‐Fe, orthopyroxene, and olivine. For our sample of MAC 88203, XRF/XRD tomography allowed visualization of forsteritic olivine as a primary mineral phase, a vitrified fusion crust at the sample surface, identification of localized Cr‐rich spinels at spatial resolutions of several micrometers, and imaging of a plagioclase‐rich glassy matrix. In the sample of Murchison, major identifiable phases include clinoenstatite‐ and olivine‐rich chondrules, variable serpentine matrix minerals and small Cr‐rich spinels. Most notable in the tomographic analysis of Murchison is the ability to quantitatively distinguish and visualize the complex mixture of serpentine‐group minerals and associated tochilinite–cronstedtite intergrowths. These methods provide new opportunities for spatially resolved characterization of sample texture, mineralogy, crystal structure, and chemical state in unsectioned samples. This provides researchers an ability to characterize such samples internally with minimal disruption of sample micro‐structures and chemistry, possibly without the need for sample extraction from some types of sampling and capture media.

Geochemistry & Geophysics↗