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At least 667 records · Page 37

Underwater plasma breakdown characteristics with respect to highly pressurized drilling applications

Deep earth drilling is a key technique to extract oil, gas, and geothermal heat from the earth. Many complex energy focusing methods have been explored as an alternative approach to reach these resources but most of them require high energy. However, by utilizing short time span liquid plasma discharges, energy focusing can be achieved within traditional drilling systems. These discharges induce a rapid expansion process and a resulting shockwave. It is believed that this focused energy will lower the required cutting force to progress through the rock. Lowering the required cutting force will allow for lower drill bit wear, quicker rate of penetration, and an overall cost savings of the project. Plasma breakdown characteristics at drilling relevant pressures, ranging from 1 to 350 atm, were studied. A resistance–capacitance circuit with an air gapped spark switch was utilized to generate pulsed plasma between the pressurized electrodes. It was found that the required breakdown voltage increases as the pressure increases. It was also found that a plasma channel formation and an associated breakdown may or may not occur between the electrodes at different pressures due to variation in required breakdown voltages. Breakdown time-lag in the dielectric medium (tap water, 780 μS cm –1 ) increased as the pressure was increased, which indicated a higher voltage drop at higher pressures (>100 atm). The plasma generated cavitation bubble with an associated shockwave occurred as pressures were increased. However, the bubble radius and the bubble duration decreased as the pressure was increased. The plasma generated shockwave speeds fall within the expected speed of sound in water. Lastly, preliminary rock cracking tests were performed on granite at high pressures (340 and 272 atm) and it was found that plasma is able to create cracks in the rock.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Carbonate-hosted microbial communities are prolific and pervasive methane oxidizers at geologically diverse marine methane seep sites

At marine methane seeps, vast quantities of methane move through the shallow subseafloor, where it is largely consumed by microbial communities. This process plays an important role in global methane dynamics, but we have yet to identify all of the methane sinks in the deep sea. Here, we conducted a continental-scale survey of seven geologically diverse seafloor seeps and found that carbonate rocks from all sites host methane-oxidizing microbial communities with substantial methanotrophic potential. In laboratory-based mesocosm incubations, chimney-like carbonates from the newly described Point Dume seep off the coast of Southern California exhibited the highest rates of anaerobic methane oxidation measured to date. After a thorough analysis of physicochemical, electrical, and biological factors, we attribute this substantial metabolic activity largely to higher cell density, mineral composition, kinetic parameters including an elevated V max , and the presence of specific microbial lineages. Our data also suggest that other features, such as electrical conductance, rock particle size, and microbial community alpha diversity, may influence a sample’s methanotrophic potential, but these factors did not demonstrate clear patterns with respect to methane oxidation rates. Based on the apparent pervasiveness within seep carbonates of microbial communities capable of performing anaerobic oxidation of methane, as well as the frequent occurrence of carbonates at seeps, we suggest that rock-hosted methanotrophy may be an important contributor to marine methane consumption.

58 GEOSCIENCES↗

Microbially induced precipitation of silica by anaerobic methane-oxidizing consortia and implications for microbial fossil preservation

Authigenic carbonate minerals can preserve biosignatures of microbial anaerobic oxidation of methane (AOM) in the rock record. It is not currently known whether the microorganisms that mediate sulfate-coupled AOM—often occurring as multicelled consortia of anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB)—are preserved as microfossils. Electron microscopy of ANME-SRB consortia in methane seep sediments has shown that these microorganisms can be associated with silicate minerals such as clays [Chen et al., Sci. Rep. 4, 1–9 (2014)], but the biogenicity of these phases, their geochemical composition, and their potential preservation in the rock record is poorly constrained. Long-term laboratory AOM enrichment cultures in sediment-free artificial seawater [Yu et al., Appl. Environ. Microbiol. 88, e02109-21 (2022)] resulted in precipitation of amorphous silicate particles (~200 nm) within clusters of exopolymer-rich AOM consortia from media undersaturated with respect to silica, suggestive of a microbially mediated process. The use of techniques like correlative fluorescence in situ hybridization (FISH), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS), and nanoscale secondary ion mass spectrometry (nanoSIMS) on AOM consortia from methane seep authigenic carbonates and sediments further revealed that they are enveloped in a silica-rich phase similar to the mineral phase on ANME-SRB consortia in enrichment cultures. Like in cyanobacteria [Moore et al., Geology 48, 862–866 (2020)], the Si-rich phases on ANME-SRB consortia identified here may enhance their preservation as microfossils. Finally, the morphology of these silica-rich precipitates, consistent with amorphous-type clay-like spheroids formed within organic assemblages, provides an additional mineralogical signature that may assist in the search for structural remnants of microbial consortia in rocks which formed in methane-rich environments from Earth and other planetary bodies.

54 ENVIRONMENTAL SCIENCES↗

Correlative X-ray micro-nanotomography with scanning electron microscopy at the Advanced Light Source

Geological samples are inherently multi-scale. Understanding their bulk physical and chemical properties requires characterization down to the nano-scale. A powerful technique to study the three-dimensional microstructure is X-ray tomography, but it lacks information about the chemistry of samples. To develop a methodology for measuring the multi-scale 3D microstructure of geological samples, correlative X-ray micro- and nanotomography were performed on two rocks followed by scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS) analysis. The study was performed in five steps: (i) micro X-ray tomography was performed on rock sample cores, (ii) samples for nanotomography were prepared using laser milling, (iii) nanotomography was performed on the milled sub-samples, (iv) samples were mounted and polished for SEM analysis and (v) SEM imaging and compositional mapping was performed on micro and nanotomography samples for complimentary information. Correlative study performed on samples of serpentine and basalt revealed multiscale 3D structures involving both solid mineral phases and pore networks. Significant differences in the volume fraction of pores and mineral phases were also observed dependent on the imaging spatial resolution employed. This highlights the necessity for the application of such a multiscale approach for the characterization of complex aggregates such as rocks. Information acquired from the chemical mapping of different phases was also helpful in segmentation of phases that did not exhibit significant contrast in X-ray imaging. Adoption of the protocol used in this study can be broadly applied to 3D imaging studies being performed at the Advanced Light Source and other user facilities.

58 GEOSCIENCES↗

Direct evidence for eoarchean iron metabolism?

Metasedimentary rocks from Isua, West Greenland (> 3,700 million years old) contain carbonaceous compounds, compatible with a biogenic origin. The metamorphic mineral assemblage with garnet and quartz intergrowths contains layers of carbonaceous inclusions contiguous with carbon–rich sedimentary beds in the host rock. Previous studies on Isua rocks focused on testing the biogenic origin of the carbonaceous material, but here we searched for evidence which could provide new insights into the nature of the life that generated this carbonaceous material. We studied material trapped in inclusions armoured within quartz grains inside garnet porphyroblasts by non–destructive ptychographic X–ray nanotomography (PXCT). The 3D electron density maps generated by PXCT were correlated with maps from X–ray fluorescence tomography and micro–Raman spectroscopy. We found that the material trapped inside inclusions in the quartz grains consist of disordered carbon material encasing domains of iron–rich carbonaceous material. These results corroborate earlier claims for biogenic origins and are compatible with relics of metamorphosed biological material originally containing high iron/carbon ratios, comparable to ratios found in most extant organisms. Finally, these iron–rich domains represent the oldest evidence for organic iron complexes in the geologic record and are consistent with Fe–isotopic evidence for metabolic iron fractionation in > 3,700 Ma Isua banded iron formation.

58 GEOSCIENCES↗

Trace element geochemistry of coarse-grained angrites from Northwest Africa: Implications for their petrogenesis on the angrite parent body

The angrites are a class of achondrites that encompass a wide range of igneous textures from quenched, volcanic, and subvolcanic stones to slowly cooled, plutonic rocks. The compositions of the various geochemical reservoirs generating this variety of rocks have not been investigated fully because historically the numbers and masses of angrites available for study have been quite small. However, the rapid increase in meteorites from Northwest Africa (NWA) has enabled a renewed opportunity for such an investigation. In particular, three samples, NWA 2999, 4590, and 4801, have provided a new window into our understanding of the origin and petrogenesis of the coarse-grained (plutonic) angrites. We report here the trace element abundances in individual mineral grains of pyroxene, plagioclase, olivine/kirschsteinite, and phosphate and in the whole-rock samples. We utilize these data to constrain the petrogenetic history of each of these samples on the angrite parent body (e.g., parental melt compositions and oxygen fugacity conditions) and assess genetic relationships to previously investigated angrites. The trace element abundances in each of the three coarse-grained angrites studied here indicate a unique history for each. The observed trace element abundances and patterns in NWA 2999 show similarities with previously studied fine-grained, volcanic angrites and potentially indicate a common geochemical source reservoir, even though NWA 2999 is temporally distinct from the volcanic angrites. In contrast, NWA 4590 has trace element characteristics analogous to other coarse-grained angrites (e.g., Lewis Cliff [LEW] 86010), suggesting that these samples originated from geochemically similar source reservoirs. The third angrite, NWA 4801, exhibits geochemical characteristics most similar to the plutonic, coarse-grained angrites, but also appears to have some affinities in its trace element characteristics to the volcanic, fine-grained angrites. This suggests that NWA 4801 may represent a petrogenetic link between two distinct geochemical reservoirs on the angrite parent body. In aggregate, the trace element distributions in these three plutonic angrites suggest that while they may have originated up to several million years after the fine-grained angrites, they sampled a range of source reservoirs on the angrite parent body. Here, some of these source reservoirs were likely similar to those of the fine-grained angrites, but others had distinct geochemical characteristics.

79 ASTRONOMY AND ASTROPHYSICS↗

Askival: An altered feldspathic cumulate sample in Gale crater

Askival is a light-toned, coarsely crystalline float rock, which was identified near the base of Vera Rubin Ridge in Gale crater. We have studied Askival, principally with the ChemCam instrument but also using APXS compositional data and MAHLI images. Askival and an earlier identified sample, Bindi, represent two rare examples of feldspathic cumulate float rocks in Gale crater with >65% relict plagioclase. Bindi appears unaltered whereas Askival shows textural and compositional signatures of silicification, along with alkali remobilization and hydration. Askival likely experienced multiple stages of alteration, occurring first through acidic hydrolysis of metal cations, followed by deposition of silica and possible phyllosilicates at low T and neutral-alkaline pH. Through laser-induced breakdown spectroscopy compositional analyses and normative calculations, we suggest that an assemblage of Fe-Mg silicates including amphibole and pyroxene, Fe phases, and possibly Mg-rich phyllosilicate are present. Thermodynamic modeling of the more pristine Bindi composition predicts that amphibole and feldspar are stable within an upper crustal setting. This is consistent with the presence of amphibole in the parent igneous rocks of Askival and suggests that the paucity of amphiboles in other known Martian samples reflects the lack of representative samples of the Martian crust rather than their absence on Mars.

58 GEOSCIENCES↗

The Evolving Chronology of Moon Formation

Defining the age of the Moon has proven to be an elusive task because it requires reliably dating lunar samples using radiometric isotopic systems that record fractionation of parent and daughter elements during events that are petrologically associated with planet formation. Crystallization of the magma ocean is the only event that unambiguously meets this criterion because it probably occurred within tens of millions of years of Moon formation. There are three dateable crystallization products of the magma ocean: mafic mantle cumulates, felsic crustal cumulates, and late-stage crystallization products known as urKREEP (uniform residuum K, rare earth elements, and P). Although ages for these materials in the literature span 200 million years, there is a preponderance of reliable ages around 4.35 billion years recorded in all three lunar rock types. This age is also observed in many secondary crustal rocks, indicating that they were produced contemporaneously (within uncertainty of the ages), possibly during crystallization and overturn of the magma ocean. •The duration of planet formation is key information in understanding the mechanisms by which the terrestrial planets formed. •Ages of the oldest lunar rocks range widely, reflecting either the duration of Moon formation or disturbed ages caused by impact metamorphism. •Ages determined for compositionally distinct crust and mantle materials produced by lunar magma ocean differentiation cluster near 4.35 Gyr. •The repeated occurrence of 4.35 Gyr ages implies that Moon formation occurred late in Solar System history, likely by giant impact into Earth.

79 ASTRONOMY AND ASTROPHYSICS↗

Unraveling the Structure and Composition of Li 4 Mn 2 O 4.5 (Li 2 O·Li 0.667 Mn 1.333 O 2 ) Electrodes for Lithium Batteries Using a High-Temperature Synthesis Approach

This paper addresses the debate about the composition and structure of a lithium-rich manganese oxide electrode with a fully disordered rock salt component, Li 4 Mn 2 O 5 (or Li 2 O·2LiMnO 2 ), first reported by Freire et al. in 2016; it is typically prepared by a high-energy ball milling procedure. It has now been demonstrated that, when prepared at 800°C, the formula of this compound is Li 4 Mn 2 O 4.5 , alternatively Li 2 O·Li 0.667 Mn 1.333 O 2 , or close thereto. The cubic, disordered Li 0.667 Mn 1.333 O 2 (or Li 0.333 Mn 0.667 O) rock salt component, in which the manganese ions adopt an average oxidation state of 2.5+, transforms to a clearly-defined spinel configuration during electrochemical cycling. The electrochemical activation process that occurs during the initial charge reaction includes the oxidation of the manganese ions by oxygen released by the Li 2 O component between 4.5 and 4.6 V. In complete contrast, nickel- and nickel-cobalt-substituted electrodes, such as Li 2 O·2LiMn 0.5 Ni 0.5 O 2 (Li 4 MnNiO 5 ) and Li 2 O·2LiMn 0.475 Ni 0.475 Co 0.050 O 2 (Li 4 Mn 0.95 Ni 0.95 Co 0.10 O 5 ), in which the manganese ions adopt a tetravalent state, have completely disordered rock salt components that are electrochemically inactive.

25 ENERGY STORAGE↗

A New Model for Simulating the Imbibition of a Wetting-Phase Fluid in a Matrix-Fracture Dual Connectivity System

The imbibition experiment is an effective approach for measuring petrophysical properties of porous media, with many such experiments performed over the past decade. Quite some empirical, analytical, and numerical models have been developed to simulate spontaneous imbibition of the wetting phase fluid into porous media, but limitations still exist. In previous studies, the imbibition process has been considered to give a piston-like displacement or the porous medium modeled as multiply-sized pores linked with bonds; both approaches fail to yield comprehensive results due to their neglect of the presence of irregular fractures or nonuniform flow paths through the matrix. By building a numerical model for simulating laboratory-scale experimental data, we performed imbibition tests on several fractured Barnett Shale samples having fractures either parallel ( P ) or transverse ( T ) to the bedding plane and used MATLAB to build a new numerical model by combining the imbibition process in fractures and the matrix using concepts from percolation theory. The experimental data show that the rocks with P -direction fractures have a more steady increase of imbibition rates than the case of T -direction one. As the shale matrix with low pore connectivity hampers the upward water movement, the imbibition rate of shales with T -direction fractures will decrease suddenly after the bottom layer in contact with water is saturated during the initial period. This wetting phase movement (WPM) model can simulate 3D porous media with 2D fractures. The rate of imbibition by fractured porous media is associated with physical parameters such as porosity and fracture distribution (e.g., the number and angle of fractures). Using Monte Carlo methods, we examined fracture parameters and predicted elapsed time and cumulative water imbibition, for the Barnett Shale samples. The results show that the rate of imbibed water mass is sensitive to the number of fractures directly connected to water source, and the connectivity between two neighboring grid cells is a key parameter for the wetting-front progression. The findings of this study can help to better understand the imbibition process with multiple influencing processes and factors in fractured-matrix rocks. Although the experiments, data simulation, and prediction results are based only on Barnett Shale samples, the model is readily applicable to imbibition tests of other fractured rocks to show the spatial and temporal behavior during a dynamic imbibition process that are not easily captured experimentally.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Highly diverse and unknown viruses may enhance Antarctic endoliths’ adaptability

Abstract Background Rock-dwelling microorganisms are key players in ecosystem functioning of Antarctic ice free-areas. Yet, little is known about their diversity and ecology, and further still, viruses in these communities have been largely unexplored despite important roles related to host metabolism and nutrient cycling. To begin to address this, we present a large-scale viral catalog from Antarctic rock microbial communities. Results We performed metagenomic analyses on rocks from across Antarctica representing a broad range of environmental and spatial conditions, and which resulted in a predicted viral catalog comprising > 75,000 viral operational taxonomic units (vOTUS). We found largely undescribed, highly diverse and spatially structured virus communities which had predicted auxiliary metabolic genes (AMGs) with functions indicating that they may be potentially influencing bacterial adaptation and biogeochemistry. Conclusion This catalog lays the foundation for expanding knowledge of virosphere diversity, function, spatial ecology, and dynamics in extreme environments. This work serves as a step towards exploring adaptability of microbial communities in the face of a changing climate.

59 BASIC BIOLOGICAL SCIENCES↗

Stress analysis using direct-S wavelets produced by a vertical vibrator

We have determined how to extract the azimuth of maximum horizontal stress (SHmax) in deep rocks by doing a simple 360° mathematical rotation of a downgoing direct-S wavelet generated at the baseplate of a surface-based vertical vibrator. We worked with direct-S wavelets that travel through stressed rocks to a deep horizontal vertical seismic profile (VSP) geophone. We find that the azimuth where a polarity reversal occurs in mathematical rotations of this downgoing direct-S wavelet defines the azimuth of the SHmax in the overlying rocks. We tested this direct-S wavelet rotation method for determining the SHmax azimuth at a site in the Illinois Basin using legacy VSP data acquired in 2013. SHmax azimuths indicated by this simple wavelet-rotation method were determined when vertical vibrators were stationed at zero offset, at far offset, and at different azimuths around a VSP receiver well. These VSP-based SHmax azimuths agreed with the azimuth of the SHmax found by traditional minifrac tests in the VSP receiver well. This simple VSP data analysis procedure for detecting the azimuth of maximum horizontal stress has never, to our knowledge, been reported or discussed in the geophysical literature. This technical finding should be of interest to the worldwide geophysical community, especially to people who need to monitor how stress fields shift when fluids are injected into, or extracted from, deep porous reservoirs.

Geochemistry & Geophysics↗

EGS Collab Experiment 2: Continuous Broadband Seismic Waveform Data

Two broadband seismometers were installed on the 4100 level and recorded for the duration of EGS Collab Experiment #2. Inspired by published data from similar instruments installed in the Aspo Hard Rock Lab, these long-period instruments aimed to measure the tilting of the drift in response to the injection of fluid into the testbed. One instrument was installed underneath the wellheads in Site A (aka the "battery" alcove) and the other was installed along the east wall of the drift, south of Site B. Due to the feet of gravel (ballast) laid along the floor of the drift, we were unable to anchor the sensors directly to the rock. As a result, the coupling of the sensors to the experiment rock volume is likely poor. In addition, there are a number of noise sources that complicate the interpretation of the data. For example, sensor BBB is installed adjacent (within 3 ft) to the rail line that runs towards the Ross shaft. Trains (motors) run along this line almost daily and produce a large signal in these data. Careful extraction of periods of interest, as well as filtering for specific signals, is necessary. The sensors are Nanometrics Trillium Compact Posthole seismometers, sensitive down to 120 seconds period. They were installed as close to the drift wall and as deep as we could manually excavate (only about 1 ft or so). The holes were leveled with sand and the sensors were placed on a paver before backfilling with sand. The hole was then covered by a bucket filled with insulation to improve the sensor's isolation from daily temperature variations, which are minor but present due to drift ventilation from the surface. Data were recorded on Nanometrics Centaur digitizers at 100 Hz. The full response information is available in the StationXML file provided here, or by querying the sensors through the IRIS DMC (see links below). These instruments were provided free of charge through the IRIS PASSCAL instrument center. The network code is XP and the station codes are BBA and BBB. The waveform data can be queried through the IRIS FDSN server using any method the user likes. One convenient option is to use the Obspy python package: https://docs.obspy.org/packages/obspy.clients.fdsn.html

15 GEOTHERMAL ENERGY↗

Site Characterization of the Highest-Priority Geologic Formations for CO2 Storage in Wyoming

The project Site Characterization of the Highest-Priority Geologic Formations for CO2 Storage in Wyoming is one of 9 site characterization projects that were implemented as part of ARRA (American Recovery and Reinvestment Act). Data from this project was used to improve resolution of data in NATCARB in the area of study. Data related to this study has already been incorporated in NATCARB Atlas. The Wyoming Carbon Underground Storage Project (WY-CUSP) consisted of CO2 storage site characterization and evaluation, focusing on Wyoming’s most promising CO2 storage reservoirs (the Pennsylvanian Weber/Tensleep Sandstone and Mississippian Madison Limestone) and premier CO2 storage site (Rock Springs Uplift). Results from the WY-CUSP project suggest the two reservoirs could store up to 17,000 million tons of CO2. The WY-CUSP team drilled a stratigraphic test well and acquired a 3-D seismic survey covering 25 square miles of the Rock Springs Uplift site. The team retrieved 916 feet of core from the 12,810-foot-deep well, along with a complete log suite, borehole images, fluid samples, and other data. Project partners (1) provided continuous visual documentation of the core, including grain size, mineralogy, facies distribution, and porosity; (2) performed continuous permeability and velocity scans of selected reservoir intervals; and (3) chemically analyzed the fluid samples. WY-CUSP scientists integrated seismic attributes with observations from log suites, a VSP survey, core, fluid samples, and laboratory analyses, including continuous permeability scans. From these integrations, researchers constructed 3-D spatial distribution volumes of reservoir and seal properties that represent geological heterogeneity at the targeted CO2 storage site. The WY-CUSP team used this data to perform new CO2 plume migration simulations. Baker Hughes, Inc., completed a series of small-scale, in-situ water injectivity measurements. A database was formed when observations, analyses, and experiments from the stratigraphic test well were integrated. Correlation of these data allowed petrophysical parameters to be extrapolated from the test well out into the storage domain (5x5 mile 3-D seismic survey volume). This resulted in an improved, realistic understanding of performance assessments for potential CO2 storage scenarios. The WY-CUSP team worked on (1) improving CO2 storage resource estimates, (2) establishing long-term integrity and permanence of confining layers, (3) designing a profitable strategy for pressure management, and (4) evaluating the utilization of stored CO2 at the Rock Spring Uplift. Finally, Baker Hughes developed a microseismic baseline for the test site using in-bore geophones to complete field operations.

3-D seismic↗

Paleotopography controls weathering of Cambrian-age profiles beneath the Great Unconformity, St. Francois Mountains, SE Missouri, U.S.A.

ABSTRACT Precambrian (1.4 to 1.5 Ga) granite and rhyolite in the St. Francois Mountains at the northeast corner of the Ozark Plateau in Missouri has been altered down to a depth up to 8 meters below the Great Unconformity (the contact between Paleozoic sedimentary rock and underlying Precambrian). Petrographic, geochemical, and mineralogic data indicate that at least two events generated this alteration: 1) surficial weathering due to subaerial exposure of the granite before Cambrian burial—this material is preserved as a paleosol; and 2) alteration due to reaction with basinal fluids channeled along the unconformity from nearby sedimentary basins long after burial by Paleozoic strata. To assess the variation between surficial weathering and basinal fluid alteration, we measured and sampled for petrologic, geochemical, and mineralogic data in the rock at and just below the Great Unconformity at three paleoelevations. Whole-rock geochemical oxide and X-ray diffraction data indicate that K-metasomatism and highly crystalline illite occurred in each profile. The K increase reflects crystallization of authigenic feldspar and illite from basinal fluids that were channeled along the Great Unconformity during younger Paleozoic fluid-flow events. Each profile also exhibits an upward increase in altered feldspar crystals and highly crystalline kaolinite, and an upward decrease in Ca and Na. Such changes reflect soil formation due to reaction with meteoric water before Cambrian burial, indicating that the altered granite was a paleosol before Paleozoic basinal fluid-flow events. Notably, the paleosol at the highest paleoelevation displays the least amount of paleoweathering and the paleosol at the lowest displays the greatest amount of paleoweathering. These results demonstrate that not only can characteristics of the paleosol just below the Great Unconformity be recognized in the St. Francois Mountains, despite subsequent alteration, but also it is possible to detect variations in soil thickness that were controlled by slope steepness and, therefore, water availability and/or soil creep or failure. This spatial relationship is compatible with studies of modern soils which indicate that soil character varies with position on a slope.

Geology↗

Modeling Contact Angle vs. Temperature for the Quartz-Water-Decane System

Innovative approaches are needed to improve the efficiency of oil recovery technologies to meet the growing demands of fossil-fuel based energy consumption. Enhanced oil recovery (EOR) methods such as low-salinity waterflooding and chemically tuned waterflooding aim to optimize the reservoir’s wetting properties, detaching oil globules from rock surfaces and allowing easier oil flow through pore throats. This wetting behavior is commonly quantified by contact angle measurements of the rock-oil-brine interface, which have been thoroughly investigated and theorized for many systems at ambient temperatures and pressures. However, few studies exist for extending contact angle theories away from ambient conditions. In this paper, we model the contact angles of a quartz-water-decane system at elevated temperatures using the surface tension component (STC) approach. Temperature-dependent van der Waals [Lifshitz-van der Waals (LW)] interactions and hydrogen-bonding (acid-base) interactions were calculated and are incorporated into the model for the quartz-water-decane interface. Additionally, the Hough and White procedure was used to create temperature-dependent dielectric functions of quartz, water, and normal decane for calculations of Hamaker coefficients. Hamaker coefficients calculated this way are highly linear with temperature and agree well with Israelachvili’s approximation. The acid-base interactions likely contribute the most to system wettability changes. Resulting contact angles of the quartz-water-decane system shift from water-wet (16°) to slightly water-wet (57.4°) as temperature increases. The model was also successfully verified for the quartz-air-water system. Our results can be used in future studies to determine optimal injected water compositions for specific rock-oil-brine and other systems with consideration of reservoir temperature.

02 PETROLEUM↗

A Comprehensive Investigation into the Effect of a Low Surface Energy Treatment on Gas Hydrate, Asphaltene, and Wax Formation, Deposition, and Adhesion

The formation/precipitation and deposition of pipeline solids, such as gas hydrates, asphaltenes, and waxes have long plagued production fields. Given the vast differences in chemistries of these solids, any current prevention or mitigation strategy, particularly for cases in which multiple issues are a concern, is likely to involve an extensive assortment of chemical additives that are both costly and add complexity to the system. Surface treatments (coatings), on the other hand, present a relatively viable option for management strategies. A chemically and physically robust surface treatment with the ability to address deposition issues for multiple pipeline solids could not only decrease the operating expenditures for a field through material cost savings and obviation of downstream separation, but could also simplify produced fluids by eliminating additional chemicals from the mixture. The purpose of this study was to explore the feasibility of a particular surface treatment as part of a solids management strategy. This work used an omniphobic surface treatment to probe its effects on gas hydrate, asphaltene, and wax deposition. Specifically, an interfacial tensiometer (IFT) collected contact angle measurements for wettability studies. High-pressure rocking cells studied gas hydrate nucleation and deposition. A bench-scale flow loop quantified the deposition of oil and asphaltenes after a set time period. Finally, a mechanical shear device measured the adhesion force of wax deposits on untreated/treated surfaces. Static contact angle results showed that the omniphobic surface treatment had reduced surface interaction with water droplets in air, altering from the complete wetting on corroded surfaces to slightly hydrophobic conditions of greater than 100°. In addition, rocking-cell tests indicated that these omniphobic surface treatments may prevent gas hydrate deposition for up to 72 hours. The gas hydrate rocking-cell tests also demonstrated possible increases in induction time and occasional elimination of hydrate nucleation with the surface treatment. Finally, the surface treatment application, which also decreased surface roughness, showed that crude oil and asphaltene particles deposition, as well as the shear required to remove solidified wax deposits, could be reduced by a large factor. Overall, promising results were recorded for all major flow-assurance solids in the presence of the surface treatment.

Engineering↗

Eu speciation in apatite at 1 bar: An experimental study of valence-state partitioning by XANES, lattice strain, and Eu/Eu* in basaltic systems

Abstract Partition coefficients for rare earth elements (REEs) between apatite and basaltic melt were determined as a function of oxygen fugacity (fO2; iron-wüstite to hematite-magnetite buffers) at 1 bar and between 1110 and 1175 °C. Apatite-melt partitioning data for REE3+ (La, Sm, Gd, Lu) show near constant values at all experimental conditions, while bulk Eu becomes more incompatible (with an increasing negative anomaly) with decreasing fO2. Experiments define three apatite calibrations that can theoretically be used as redox sensors. The first, a XANES calibration that directly measures Eu valence in apatite, requires saturation at similar temperature-composition conditions to experiments and is defined by: ( E u 3 + ∑ E u ) Apatite = 1 1 + 10 - 0.10 ± 0.01 × l o g ⁡ ( f o 2 ) - 1.63 ± 0.16 . The second technique involves analysis of Sm, Eu, and Gd in both apatite and coexisting basaltic melt (glass), and is defined by: ( Eu E u * ) D Sm × Gd = 1 1 + 10 - 0.15 ± 0.03 × l o g ⁡ ( f o 2 ) - 2.46 ± 0.41 . The third technique is based on the lattice strain model and also requires analysis of REE in both apatite and basalt. This calibration is defined by ( Eu E u * ) D lattice strain = 1 1 + 10 - 0.20 ± 0.03 × l o g ⁡ ( f o 2 ) - 3.03 ± 0.42 . The Eu valence-state partitioning techniques based on (Sm×Gd) and lattice strain are virtually indistinguishable, such that either methodology is valid. Application of any of these calibrations is best carried out in systems where both apatite and coexisting glass are present and in direct contact with one another. In holocrystalline rocks, whole rock analyses can be used as a guide to melt composition, but considerations and corrections must be made to either the lattice strain or Sm×Gd techniques to ensure that the effect of plagioclase crystallization either prior to or during apatite growth can be removed. Similarly, if the melt source has an inherited either a positive or negative Eu anomaly, appropriate corrections must also be made to lattice strain or Sm×Gd techniques that are based on whole rock analyses. This being the case, if apatite is primary and saturates from the parent melt early during the crystallization sequence, these corrections may be minimal. The partition coefficients for the REE between apatite and melt range from a maximum DEu3+ = 1.67 ± 0.25 (as determined by lattice strain) to DLu3+ = 0.69 ± 0.10. The REE partition coefficient pattern, as observed in the Onuma diagram, is in a fortuitous situation where the most compatible REE (Eu3+) is also the polyvalent element used to monitor fO2. These experiments provide a quantitative means of assessing Eu anomalies in apatite and how they be used to constrain the oxygen fugacity of silicate melts.

Geochemistry & Geophysics↗