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At least 1,189 records · Page 66

Crystal structure of calcium-ferrite type NaAlSiO4 up to 45 GPa

Abstract Alkali-rich aluminous high-pressure phases including calcium-ferrite (CF) type NaAlSiO4 are thought to constitute ~20% by volume of subducted mid-ocean ridge basalt (MORB) under lower mantle conditions. As a potentially significant host for incompatible elements in the deep mantle, knowledge of the crystal structure and physical properties of CF-type phases is therefore important to understanding the crystal chemistry of alkali storage and recycling in the Earth’s mantle. We determined the evolution of the crystal structure of pure CF-NaAlSiO4 and Fe-bearing CF-NaAlSiO4 at pressures up to ~45 GPa using synchrotron-based, single-crystal X-ray diffraction. Using the high-pressure lattice parameters, we also determined a third-order Birch-Murnaghan equation of state, with V0 = 241.6(1) Å3, KT0 = 220(4) GPa, and KT0′ = 2.6(3) for Fe-free CF, and V0 = 244.2(2) Å3, KT0 = 211(6) GPa, and KT0′ = 2.6(3) for Fe-bearing CF. The addition of Fe into CF-NaAlSiO4 resulted in a 10 ± 5% decrease in the stiffest direction of linear compressibility along the c-axis, leading to stronger elastic anisotropy compared with the Fe-free CF phase. The NaO8 polyhedra volume is 2.6 times larger and about 60% more compressible than the octahedral (Al,Si)O6 sites, with K0NaO8 = 127 GPa and K0(Al,Si)O6 ~304 GPa. Raman spectra of the pure CF-type NaAlSiO4 sample shows that the pressure coefficient of the mean vibrational mode, 1.60(7) cm–1/GPa, is slightly higher than 1.36(6) cm−1/GPa obtained for the Fe-bearing CF-NaAlSiO4 sample. The ability of CF-type phases to contain incompatible elements such as Na beyond the stability field of jadeite requires larger and less-compressible NaO8 polyhedra. Detailed high-pressure crystallographic information for the CF phases provides knowledge on how large alkali metals are hosted in alumina framework structures with stability well into the lowermost mantle.

Geochemistry & Geophysics↗

The iron spin transition of deep nitrogen-bearing mineral Fe3N1.2 at high pressure

Abstract Nitrogen is an essential element for life, one of the most abundant volatiles in the atmosphere, and an important component in the Earth’s interior, where iron nitride is an essential host of deep nitrogen. Here, we investigate the pressure-induced electronic spin-pairing transition of iron in siderazot (Fe3N1.2) at pressures up to 45.8 GPa at room temperature, using diamond-anvil cell techniques coupled with synchrotron X-ray emission spectroscopy. The integrated intensity of the satellite emission peak (K′β) decreases upon compression but remains unchanged at pressures greater than 30.5 GPa. In other words, the high-spin to low-spin transition of iron in Fe3N1.2 starts immediately at very low pressures and completes at ~30.5 GPa. The iron spin transition completion pressures increase with the nitrogen concentration of hexagonal close-packed iron nitrides (i.e., Fe3N1.2, Fe7N3, and Fe2N). Moreover, the identity and concentration of light elements in binary iron-rich compounds such as Fe3N, Fe3C, Fe3P, Fe3S, Fe7C3, and Fe7N3, together with their crystal structure, could affect the iron spin transition pressures. The spin transition of iron-rich alloys could alter the bonding nature and the physical properties, including the thermal and electrical conductivity, thereby influencing the thermal state and evolution of planetary interiors.

Geochemistry & Geophysics↗

Atomistic insight into the ferroelastic post-stishovite transition by high-pressure single-crystal X-ray diffraction

Abstract The post-stishovite transition is a classic pseudo-proper typed ferroelastic transition with a symmetry-breaking spontaneous strain. This transition has been studied using high-pressure spontaneous strains, optic modes, and elastic moduli (Cij) based on the Landau modeling, but its atomistic information and structural distortion remain poorly understood. Here we have conducted synchrotron single-crystal X-ray diffraction measurements on stishovite crystals up to 75.3 GPa in a diamond-anvil cell. Analysis of the data reveals atomic positions, bond lengths, bond angles, and variations of SiO6 octahedra across the transition at high pressure. Our results show that the O coordinates split at ~51.4 GPa, where the apical and equatorial Si-O bond lengths cross over, the SiO6 octahedral distortion vanishes, and the SiO6 octahedra start to rotate about the c axis. Moreover, distortion mode analysis shows that an in-plane stretching distortion (GM1+ mode) occurs in the stishovite structure at high pressure while a rotational distortion (GM2+ mode) becomes dominant in the post-stishovite structure. These results are used to correlate with elastic moduli and Landau parameters (symmetry-breaking strain e1–e2 and order parameter Q) to provide atomistic insight into the ferroelastic transition. When the bond lengths of two Si-O bonds are equal due to the contribution from the GM1+ stretching mode, C11 converges with C12, and the shear wave VS1[110] polarizing along [110] and propagating along [110] vanishes. Values of e1–e2 and Q are proportional to the SiO6 rotation angle from the occurrence of the GM1+ rotational mode in the post-stishovite structure. Our results on the pseudo-proper type transition are also compared with that for the proper type in albite and improper type in CaSiO3 perovskite. The symmetry-breaking strain, in all these types of transitions, arises as the primary effect from the structural angle (such as SiO6 rotation or lattice constant angle) and its relevant distortion mode in the low-symmetry ferroelastic phase.

Geochemistry & Geophysics↗

High-pressure behavior of 3.65 Å phase: Insights from Raman spectroscopy

Abstract The 3.65 Å phase [MgSi(OH)6] is a hydrous phase that is predicted to be stable in a simplified MgO-SiO2-H2O (MSH) ternary system at pressures exceeding 9 GPa. Along cold subduction zones, it is likely to transport water, bound in its crystalline lattice, into the Earth’s interior. The 3.65 Å phase consists of Mg and Si octahedral sites attached to the hydroxyl group that forms a hydrogen bond and is predicted to undergo pressure-induced symmetrization of the hydrogen bond. Therefore, in this study, we investigate the high-pressure behavior of the 3.65 Å phase using Raman spectroscopy. We have conducted five distinct compressions up to ~60 GPa using two different pressure-transmitting media—alcohol mixture and neon. At ambient conditions, we identified vibrational modes using complementary first-principles simulations based on density functional perturbation theory. Upon compression, we note that the first derivative of the vibrational modes in the lattice region stiffens, i.e., b1lattice > 0. In contrast, the hydroxyl region softens, i.e., b1OH > 0. This is indicative of the strengthening of hydrogen bonding upon compression. We noticed a significant broadening of vibrational modes related to hydroxyl groups that are indicative of proton disorder. However, within the maximum pressures explored in this study, we did not find evidence for pressure-induced symmetrization of the hydrogen bonds. We used the pressure derivative of the vibrational modes to determine the ratio of the bulk moduli and their pressure derivative. We note that the smaller bulk moduli of hydrous phases compared to the major mantle phases are compensated by significantly larger pressure derivatives of the bulk moduli for the hydrous phases. This leads to a significant reduction in the elasticity contrast between hydrous and major mantle phases. Consequently, the detection of the degree of mantle hydration is likely to be challenging at greater depths.

Geochemistry & Geophysics↗

Wave vector and field vector orientation dependence of Fe K pre-edge X-ray absorption features in clinopyroxenes

Abstract Pre-edge X-ray absorption features are commonly used to derive redox states for transition metal oxides in crystals and glasses. Several calibrations for Fe2+ and Fe3+ in silicate glasses have utilized the general relationships among pre-edge peak intensity, energy, and redox state. However, absorption variations complicate those relationships in anisotropic crystals. Although absorption anisotropy at and above the energy of the rising edge adheres to the typical cos2 relationship observed in absorption spectroscopies at other energies, the anisotropy of the pre-edge is far more complicated. Prior studies focusing on pre-edge absorption anisotropy demonstrate a 1-cos4φ dependence of absorption magnitudes with rotation. Experiments presented here show that absorption magnitudes of the pre-edge vary as a function of both electric field vector orientation and wave vector direction. However, rotations around the field vector axis or wave vector axis individually result in cos2 dependence of absorption magnitudes. Rotations where both wave vector and field vector orientation are varied are not well fit by either model in the pre-edge. The resulting anisotropy complicates the process of measuring characteristic absorption in the pre-edge, making valence state determinations challenging for strongly anisotropic crystal structures such as pyroxene.

Geochemistry & Geophysics↗

Thermal equation of state of ice-VII revisited by single-crystal X-ray diffraction

Abstract Ice-VII is a high-pressure polymorph of H2O ice and an important mineral widely present in many planetary environments, such as in the interiors of large icy planetary bodies, within some cold subducted slabs, and in diamonds of deep origin as mineral inclusions. However, its stability at high pressures and high temperatures and thermoelastic properties are still under debate. In this study, we synthesized ice-VII single crystals in externally heated diamond-anvil cells and conducted single-crystal X-ray diffraction experiments up to 78 GPa and 1000 K to revisit the high-pressure and high-temperature phase stability and thermoelastic properties of ice-VII. No obvious unit-cell volume discontinuity or strain anomaly of the high-pressure ice was observed up to the highest achieved pressures and temperatures. The volume-pressure-temperature data were fitted to a high-temperature Birch-Murnaghan equation of state formalism, yielding bulk modulus KT0 = 21.0(4) GPa, its first pressure derivative KT0′ = 4.45(6), dK/dT = –0.009(4) GPa/K, and thermal expansion relation αT = 15(5) × 10–5 + 15(8) × 10–8 × (T – 300) K–1. The determined phase stability and thermoelastic properties of ice-VII can be used to model the inner structure of icy cosmic bodies. Combined with the thermoelastic properties of diamonds, we can reconstruct the isomeke P-T paths of ice-VII inclusions in diamond from depth, offering clues on the water-rich regions in Earth’s deep mantle and the formation environments of those diamonds.

Geochemistry & Geophysics↗

Amorphous Mn2SiO4: A potential manganese phase in the stagnant slab

Abstract Tephroite (Mn2SiO4), together with some manganese (Mn)-rich mineral inclusions, has been found in ophiolite-hosted diamonds, possibly originating from Mn-nodules and sediments that were once deposited on the oceanic floor and later subducted into the deep mantle, which provides evidence for oceanic crustal recycling. However, the state and behavior of tephroite under high-pressure and high-temperature conditions remain poorly understood. In this study, we conducted in situ synchrotron single-crystal X-ray diffraction (XRD) and Raman spectroscopy of synthetic tephroite up to ~30 GPa and ~900 K. The XRD and Raman spectroscopy experiments in this study first show that tephroite undergoes a pressure-induced, irreversible, amorphous transformation above ~20 GPa. Temperature (<900 K) is found to be an insignificant factor governing the process of amorphous transformation. Amorphous tephroite may be a potential phase in a rapidly cooling oceanic lithospheric subduction slab stagnating at the bottom of the mantle transition zone.

Geochemistry & Geophysics↗

Temperature-induced densification in compressed basaltic glass revealed by in-situ ultrasonic measurements

Abstract Acoustic velocities of a model basalt glass (64 mol% CaMgSi2O6 + 36 mol% CaAl2Si2O8) were measured along different pressure-temperature (P-T) paths. One set of experiments involved isothermal compression-decompression cycles, performed at temperatures of 300, 641, 823, and 1006 K and pressures up to 12.2 GPa. The other set of experiments involved constant-load heating-cooling cycles at temperatures up to 823 K and pressures up to 7.5 GPa. Both sets of experiments were performed in a multi-anvil apparatus using a synchrotron-based ultrasonic technique. Our results show that the glass compressed isothermally at 300 K (cold-compression) displays anomalously decreasing compressional (VP) and shear (VS) wave velocities with increasing pressure until ~8 GPa. Beyond 8 GPa, both VP and VS start to increase sharply with pressure and irreversible densification of the glass occurred, producing large hysteresis loops of velocities upon decompression. However, for the glass compressed isothermally at increasingly higher temperatures (hot-compression), the velocity minima gradually shift to lower pressures. At temperature close to the glass transition temperature Tg, the velocity minima disappear completely, displaying a monotonic increase of velocities during compression and higher VP and VS during decompression. In addition, constant-load heating-cooling experiments show that velocities generally decrease slightly with increasing temperature, but start to increase once heated above a threshold temperature (~650 K). During cooling the velocities increase almost linearly with decreasing temperature, resulting in higher velocities (~1.5–2.5% higher) when returned to 300 K. This implies that a temperature-induced densification may have occurred in the glass at high pressures. Raman spectra on recovered samples show that the hot-compressed and high-P heated glasses contain distinctly densified and depolymerized structural signatures compared to the initial glass and the cold-compressed glass below the velocity transition pressure PT (~8 GPa). Such densification may be attributed to the breaking of bridging oxygen bonds and compaction in the intermediate-range structure. Our results demonstrate that temperature can facilitate glass densification at high pressures and point out the importance of P-T history in understanding the elastic properties of silicate glasses. Comparison with melt velocity suggests that hot-compressed glasses may better resemble the pressure dependence of velocity of silicate melts than cold-compressed glasses, but still show significantly higher velocities than melts. If the abnormal acoustic behaviors of cold-compressed glasses were used to constrain melt fractions in the mantle low-velocity regions, the melt fractions needed to explain a given velocity reduction would be significantly underestimated at high pressures.

Geochemistry & Geophysics↗

Sulfur speciation in dacitic melts using X-ray absorption near-edge structure spectroscopy of the S K -edge (S-XANES): Consideration of radiation-induced changes and the implications for sulfur in natural arc systems

Abstract The synchrotron technique of micro X-ray absorption near-edge structure spectroscopy at the sulfur K-edge (S-XANES) provides a unique opportunity to measure the proportion of different oxidation states of sulfur (S) in silicate glasses. Although applied extensively in the analysis of basaltic silicate glasses, few S-XANES studies have investigated variations in S oxidation states with fO2 in felsic silicate glasses. In addition, no study has systematically compared the S-XANES results obtained from the same samples at different photon flux densities to quantify the relationship between exposure time and changes in S speciation in silicate glass, as has been done for Fe and V. This study evaluates observed differences in S speciation measured in experimentally produced H2O-saturated dacitic glasses over a range of reducing to oxidizing conditions (from log fO2 = ΔFMQ-0.7 to ΔFMQ+3.3; FMQ is the fayalite-magnetite-quartz mineral redox buffer) and equilibrated at 1000 °C and 300 MPa. S-XANES spectra were collected at three different photon flux densities using three microspectroscopy beamlines. As is observed in S-XANES analyses of basaltic silicate glasses, beam-induced changes to the S6+/ΣS are observed as a function of photon flux density and beam exposure time. Our results demonstrate that silicate glasses of dacitic composition undergo beam-induced photo-reduction in samples equilibrated at ΔFMQ > +1.75 and photo-oxidation if equilibrated at ΔFMQ < +1. The time required to observe beam-induced changes in the spectra varies as a function of flux density, and our study establishes an upper photon density limit at ~1.0 × 1012 photons/µm2. The S6+/ΣS calculated from spectra collected below this absorbed photon limit at intermediate flux densities (~1–4 × 109 photons/s per µm2) are affected by beam damage, as no conditions were found to be completely free of beam-induced changes. However, the S6+/ΣS ratios calculated below the limit at intermediate flux densities are consistent with thermodynamic constraints, demonstrating that S6+/ΣS ratios calculated from S-XANES spectra can be considered reliable for estimating the oxygen fugacity. Our results carry important implications for the S budget of felsic magmas and dissolution mechanisms in evolved melts. While our results from all three flux densities show the presence of S4+ dissolved in relatively oxidized (ΔFMQ > +1.75) dacitic glass, even in the spectra exposed to the lowest photon densities, we are unable to rule out the possibility that the S4+ signal is the result of instantaneous X-ray irradiation induced beam damage using S-XANES alone. When our spectra are compared to S-XANES spectra from basaltic silicate glasses, important differences exist in the solubility of S2– and S6+ between dacitic silicate melts, pointing to differences in solubility mechanisms as melt composition changes. This study highlights the need for further investigation into beam damage systematics, presence of S4+, and the solubility mechanisms of different oxidation states of S as silicate melt composition changes.

Geochemistry & Geophysics↗

Pressure-induced phase transitions in Ni-bearing ferrosilite (Ni-En31Fs65)

Abstract Orthopyroxene is an abundant mineral in subducting slabs. Studying its phase transitions at high pressure is important to the understanding of mineralogy of subducting slabs in the deep Earth. Synchrotron-based single-crystal X-ray diffraction experiments were conducted on a synthetic Ni-bearing ferrosilite (Ni-En31Fs65) at pressures up to 33.8 GPa. Three phase transitions were observed at 12.1(6), 15.6(6), and 31.3(25) GPa. The first two phase transitions in Ni-En31Fs65 resemble the previously described phase transitions in Ni-free Fe-rich orthopyroxenes, i.e., the initial α-opx (Pbca) transforms to β-opx (P21/c), then the latter transforms to γ-opx (Pbca). This indicates that the incorporation of a few mol% NiSiO3 does not influence the phase transition path of Fe-rich orthopyroxene. After the third phase transition, the structure (P21ca) of Ni-En31Fs65 resembles the previously reported β-popx observed in En90 at high pressure, although the onset pressure of the phase transition in Ni-En31Fs65 is ~7 GPa lower than that in En90. β-popx has a post-pyroxene structure that contains fivefold- and sixfold-coordinated Si cations. Our results indicate that the post-pyroxene structure is β-popx (P21ca) for either Fe-poor or Fe-rich orthopyroxenes, although the phase transition path before the pyroxene → post-pyroxene is compositionally dependent. Additionally, unlike the second and third transitions, whose onset pressures are monotonously decreased by increasing Fe content, the Fe effect on shifting the first transition is much more significant for orthopyroxenes within En <50 mol% than that within En >50 mol%.

Geochemistry & Geophysics↗

Equation of state and structural evolution of manganese dolomite (kutnohorite) under high pressures

Abstract Understanding the structural evolution of carbonate minerals with increasing pressure is essential to decoding the role of Earth’s mantle in the global carbon cycle and long-term climate change. Here, we carried out synchrotron single-crystal X-ray diffraction measurements on a natural sample of manganese dolomite [kutnohorite, Ca1.11Mn0.89(CO3)2] in a diamond-anvil cell up to 51.2 GPa at room temperature with neon as the pressure-transmitting medium. The manganese dolomite sample remains stable in the rhombohedral structure from 1 bar to ~13.3 GPa. The equation of state of Ca1.11Mn0.89(CO3)2 was determined: V0 = 334.06 ± 0.29 Å3, K0 = 99.9 ± 4.7 GPa, and K0′ = 4.3 ± 0.9; when K0′ is fixed at 4.0, V0 = 334.04 ± 0.24 Å3, and K0 = 101.4 ± 1.5 GPa. Upon further compression at room temperature, the split and disappearance of diffraction spots were observed. That is, the rhombohedral structure of manganese dolomite becomes highly distorted to lose its long-range order at 13.3–51.2 GPa at room temperature. Moreover, our single-crystal X-ray diffraction results reveal the mechanisms of the reported lattice and internal Raman mode splits of the same manganese dolomite sample approximately at 13 and 24 GPa, respectively. These results suggest manganese-bearing carbonates may play a distinct role in the deep carbon cycle.

Geochemistry & Geophysics↗

Bobfinchite, Na[(UO2)8O3(OH)11]·10H2O, a new Na-bearing member of the schoepite family

Abstract The new mineral bobfinchite (IMA2020-082), Na[(UO2)8O3(OH)11]·10H2O, was found in the Burro mine, Slick Rock district, San Miguel County, Colorado, U.S.A., where it occurs as an oxidation product of uraninite on asphaltite matrix in intimate association with gypsum, natrozippeite, metaschoepite, and uranopilite. Bobfinchite crystals are transparent to translucent, yellow, lozenge-shaped disks up to 0.3 mm wide. Crystals are flattened on [100] and exhibit the forms {100}, {011}, {021}, {021}, and {011}. Bobfinchite has a pale-yellow streak and emits very dim yellow fluorescence under 365 nm ultraviolet illumination. The crystals are brittle with very good {100} cleavage and irregular, stepped fracture. The Mohs hardness is ca. 2 based on scratch tests. The calculated density is 5.044 g/cm3 based on the empirical formula and 5.036 g/cm3 for the ideal formula. Bobfinchite is optically biaxial (–), with α = 1.690(5), β = 1.7205(5), and γ = 1.730(5) (white light). The measured 2V, estimated from the interference figure, is 55(5)° and the calculated value is 59.1°. Dispersion is moderate, r > v; orientation: X = a, Y = b, Z = c; pleochroism: X nearly colorless, Y yellow, Z yellow; X < Y ≈Z. Electron microprobe analysis provided the empirical formula (Na0.99Pb0.02)[(UO2)7.99O3(OH)11]·10H2O. The five strongest X-ray powder diffraction lines are [dobs in Å(I)(hkl)]: 7.34(100)(200), 3.59(50)(024), 3.23(60)(224), 3.18(36)(240), and 2.01(23)(624,551,208,640,346). Bobfinchite is orthorhombic, Pbcn, a = 14.6249(9), b = 14.0389(10), c = 16.6923(10) Å, V = 3427.2(4) Å3, and Z = 4. The structure of bobfinchite (R1 = 0.0330 for 3770 I > 4σI) is built from uranyl oxide-hydroxide sheets that adopt the fourmarierite topology, with interlayer Na+ and H2O groups. Both the sheet and interlayer topology mimic those observed in natural and synthetic Na-metaschoepites studied previously, and as seen in other uranyl oxide hydrate minerals, charge balance is achieved at specific sites in the sheet through the substitution O2– ↔ (OH)–.

Geochemistry & Geophysics↗

A simple method for obtaining heat capacity coefficients of minerals

Abstract Heat capacity data are unavailable or incomplete for many minerals at geologically relevant temperatures. Despite the availability of entropy and enthalpy values in numerous thermodynamic tables (even sometimes at elevated temperatures), there remains need for extrapolation beyond, or interpolation between, temperatures. This approach inevitably results in estimates for entropy and enthalpy values because the heat capacity coefficients required for optimal thermodynamic treatment are less frequently available. Here we propose a simple method for obtaining heat capacity coefficients of minerals. This method requires only the empirically measured temperature-specific heat capacity for calculation via a matrix algorithm. The system of equations solver is written in the Python computing language and has been made accessible in an online repository. Thermodynamically, the solution to a system of equations represents the heat capacity coefficients that satisfy the mineral-specific polynomial. Direct coefficient calculation will result in more robust thermodynamic data, which are not subject to fitting uncertainties. Using hematite as an example, this method provides results that are comparable to conventional means and is applicable to any solid material. Coefficients vary within the traditional large 950 K temperature interval, indicating that best results should instead utilize a smaller 400 K temperature interval. Examples of large-scale implications include the refinement of geothermal gradient estimation in rapidly subsiding sedimentary basins or metamorphic and hydrothermal evolution.

Geochemistry & Geophysics↗

Real-Time Seismic System for Monitoring, Imaging, and Characterization (RT-SEISMIC)

The goal of this Laboratory Directed Research and Development (LDRD) project was to develop a borehole seismic source and sensor array to enable real-time seismic imaging at scales and conditions relevant to the energy industry including both fossil-energy and geothermal. In FY21 and FY22, we designed, built, and tested both a prototype impulse source module for generating seismic energy and a sensing module for recording ground motions generated by the source module array. A pneumatically driven vibratory source was also designed. The source modules were fabricated with all high temperature components and the team has worked to incorporate the current RT-SEISMIC electronics design into a commercially available, high temperature silicon-on-insulator chip integrated circuit. Several issues were identified during fabrication and lab testing that led to redesign of several system components and subsequent retesting. The final round of testing showed that while metal/graphite-based seals worked quite well for static seals, they were unable to provide an adequate gas seal for dynamic, reciprocating part movements which necessitated a final redesign using Kalrez. This change will result in a continuous temperature rating of approximately 275 degrees C for the system. While a field test of the RT-SEISMIC system was targeted in FY22, due to the extended lab testing and redesign efforts, field testing was not achieved. As a result of this LDRD investment, several sponsors have expressed interest in RT-SEISMIC and we expect to continue towards a field demonstration of the full system in the future.

58 GEOSCIENCES↗

UT-GOM2-2 Preliminary Report: Terrebonne Basin Northern Gulf of Mexico, 30 July-28 September 2023

In the summer and fall of 2023, the Gulf of Mexico Deepwater Hydrate Coring Expedition (UT-GOM2-2) drilled, cored, made downhole measurements, and analyzed samples from the seafloor to the base of the gas hydrate stability zone in one location (Site H, WR313) in the Terrebonne basin, deepwater Gulf of Mexico. Analyses of data and samples from the expedition will inform biological, geochemical, and geomechanical models to constrain the role of gas hydrates in the carbon cycle and the potential for gas hydrates as an energy resource. Pressure and conventional cores were collected continuously to a depth of 155.1 meters below the seafloor (mbsf). At deeper depths, cores were taken periodically from hydrate-bearing sands and their bounding muds to a total depth of 861.3 mbsf. 162.6 m of conventional core and 54.8 m of pressure core were obtained. Twelve temperature measurements were made between 27.1 and 144.5 mbsf to determine the geothermal gradient. At the seafloor, more than 4 m of sandy silt of unknown origin was encountered. Beneath this sand, to a depth of ~200 mbsf, the section was composed of interbedded mud and biogenic carbonate ooze. The biogenic ooze correlated to low density and high porosity intervals observed in the previously acquired logging while drilling (LWD) data and as measured. Calcareous nannofossil biostratigraphy constrains the entire record to the Pleistocene (< 0.91 million years) with a pronounced increase in sedimentation rate with depth. Beneath 200 mbsf, the section was predominantly composed of mud with two thicker, hydrate-bearing coarse-grained intervals, which are commonly known as the Blue and Orange sands. The dissolved gas concentration was quantified from pressure cores. In the shallow section, dissolved methane concentration increased below the sulfate-methane transition zone (SMTZ) and reaches saturation (the limit of solubility for methane) at 147 mbsf. Gas expansion was very common in conventional and depressurized pressure (conventionalized) cores below the SMTZ. At deeper depths, the methane concentration within muds bounding the Blue and Orange reservoirs was generally found to be less than saturation. The dissolved and hydrate gas composition is consistent with a microbial source, containing greater than 99.99% methane and only trace concentrations of ethane, propane, and butane. The methane to ethane ratio (C 1 /C 2 ) and the methane to ethane plus propane (C 1 /(C 2 +C 3 )) decrease with depth down to at least 678 mbsf, mainly driven by the increase in ethane with depth. It is unclear if this trend continues through the Orange sand interval. The δ 13 C isotopic signature of methane ranges between -69.9 and -78.5 ‰ Vienna Pee Dee Belemnite (VPDB). Pressure core recovery of all sandy intervals was poor. However, pressure core logs of the Orange sand show intervals of low density and high velocity, which are indicative of high hydrate saturation. One core from within the Orange sand was composed of interbedded graded sandy silt and mud. The sandy silts from this core are composed of mainly quartz and feldspar with some lithics. Most of the recovered pressure core samples are maintained at near in-situ pressure and temperature (within the hydrate stability field) at the University of Texas Pressure Core Center awaiting analysis. In the shallow section, samples will be used to determine the flux of organic carbon through the basin system, find the rate at which that carbon was consumed, and understand the microbial population responsible for these processes. In the deeper section, samples from in and around the hydrate reservoirs will be used to determine the petrophysical properties of the reservoir and bounding seals in these systems.

03 NATURAL GAS↗

Investigating Soil Organic Matter Complexation using Spectral Induced Polarization

Spectral induced polarization (SIP) laboratory experiments were conducted to determine the sensitivity of this method to the formation of soil organic matter (SOM) complexes, with a long-term goal of field-scale monitoring. There are few SIP experiments that have explored this topic, yet understanding the dynamic behavior and interactions of SOM at the field scale could provide insight into soil fertility and health which influences crop yields, microorganisms that degrade organic pollutants, and carbon stabilization. We present the results of three experiments where the iron oxide, ferrihydrite (Fhy), was used to coat different media, and then the OM compound pentaglycine (PG) was pulse injected to form SOM complexes. SIP data was collected during these injections to capture any surface complexation changes. These experiments were performed in 1) a fluidic cell containing a micromodel, 2) a column containing Fhy coated ceramic beads and 3) a column containing Fhy coated Accusand®. Our results show a higher frequency response (defined here as > 1 Hz) in all three experiments, with the largest amplitude response after the first PG injection (Figure S.1). The repeatability of this response is encouraging and supporting data collected on the Accusand® experiment provides preliminary insight into the mechanisms controlling the SIP signatures. Sampling of fluid conductivity $σ_w$ and pH may indicate deprotonation of SOM occurring or rapid adsorption and release of protons from the Fhy sites. However additional experiments are needed to identify and confirm the primary and secondary reactions impacting the SIP response. We are looking towards other opportunities to continue this work, particularly to repeat experiments while collecting supporting datasets.

58 GEOSCIENCES↗

Active Seismoelectric Monitoring of CO 2 Injection

Conference presentation at Carbon Capture, Utilization, and Storage (CCUS) Conference 2024, Houston, Texas, March 11–13, 2024. We investigated the use of active seismoelectric monitoring (ASE) to determine its effectiveness in detecting CO 2 injected deep underground and as an additional monitoring option for carbon storage projects. The EERC performed an ASE survey in February of 2023 at Pennel oil field near Baker, Montana, as part of the U.S. Department of Energy-sponsored Williston Basin CO 2 Field Laboratory in conjunction with operating partner Denbury Inc. The field site is part of the Cedar Creek Anticline geologic structure, with CO 2 planned for injection into a stacked storage complex (SSC) in the Interlake Formation containing both a residual oil zone and a conventional reservoir. The objective was to test the ASE method’s ability to characterize baseline fluid distribution in both the near surface and the SSC prior to CO 2 injection.

04 OIL SHALES AND TAR SANDS↗