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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Relationship between clay minerals and microorganisms in underground hydrogen storage reservoirs: a mini review

Hydrogen (H 2 ) will play a vital role in the global shift towards sustainable energy systems. Due to the high cost and challenges associated with storing hydrogen in large quantities for industrial applications, Underground Hydrogen Storage (UHS) in geological formations has emerged as a promising solution. Clay minerals, abundant in subsurface environments, play a critical role in UHS by providing low permeability, cation exchange capacity, and stability, essential for preventing hydrogen leakage. However, microorganisms in the subsurface, particularly hydrogenotrophic species, interact with clay minerals in ways that can affect the integrity of these storage systems. Microbes form biofilms on clay surfaces, which can cause pore clogging and reduce the permeability of the reservoir, potentially stabilizing H 2 storage and limiting injectivity. Microbial-induced chemical weathering, through the production of organic acids and redox reactions, can degrade clay minerals, releasing metal ions and destabilizing the storage site. These interactions raise concerns about the long-term storage capacity of UHS, as microbial processes could lead to H 2 loss and caprock degradation, compromising the storage system’s effectiveness. This mini review aims to cover the current understanding of the interactions between clay minerals and microorganisms and how these dynamics can affect the safe and sustainable deployment of UHS .

Clark, Allison↗
DOE OSTI2024

Field Evaluation of the Caney Shale as an Emerging Unconventional Play, Southern Oklahoma

The Mississippian-age Caney Shale is an emerging unconventional oil and gas (UOG) resource play in the southern Midcontinent and is prospective in the Anadarko, Ardmore, Marietta and western Arkoma basins. This play is enigmatic in that time equivalent Fayetteville Shale in the eastern Arkoma basin and Barnett Shale in the Ft. Worth Basin are major unconventional plays, whereas Caney Shale production is sparse and unpredictable (Cardott, 2017). In the Anadarko, Ardmore and Marietta basins, the Caney Shale is in the oil window, but its resource potential has not been adequately assessed. The Caney reservoir is about 60-300 m thick, is rich in total organic carbon, contains a large oil resource base, and has a strong natural gas drive; however, development has been hampered by high clay content and reactivity of the formation with water. The main objective of this initial four-year research project was to address these issues by establishing a Caney Shale Field Laboratory in the Ardmore Basin of southern Oklahoma to (a) conduct a comprehensive field characterization (b) perform field experiments, and (c) validate cost-effective technologies that will lead to a comprehensive and efficient development strategy plan for Caney Shale.

02 PETROLEUM↗
DOE OSTI2020

Experimental evaluation of the role of redox during glauconite-CO 2 -brine interactions

Greensands formations are globally abundant sedimentary rocks rich in Fe clays (typically glauconite) that commonly contain natural hydrocarbon accumulations and may be important reservoirs for geologic storage of anthropogenic CO 2 . Diagenesis in greensands is commonly accompanied by the conversion of primary glauconite to siderite (FeCO 3 ), a process that could be exploited for the permanent trapping of CO 2 . Importantly, siderite formation after glauconite requires that the mostly oxidized Fe in the primary Fe clay minerals is reduced during diagenetic interactions. Here, we explore the effect of solution redox state on the stability of glauconite in sandstones with implications for the diagenetic and/or engineered formation of siderite. We performed two flow-through experiments on intact, glauconite-rich sandstone cores at 150 °C and 150 bar. Both experiments employed a 1 mol NaCl/kg, 0.1 mol NaHCO 3 /kg solution charged with ~0.58 mol CO 2 /kg solution, but the redox state of the injected fluid was manipulated between experiments in order to compare glauconite reactivity and siderite saturation state at oxidizing and reducing end-member conditions. After reaction with the oxidizing (O 2 (aq) ≈ 6 μmol/kg) fluid, chemical and Mӧssbauer spectroscopic analyses indicate the production of Fe(III)-oxy/hydroxide minerals from glauconite, whereas, in the reducing (H 2 (aq) ≈ 5–40 mmol/kg) experiment, thermodynamic calculations and coupled chemical, mineralogical, and Mӧssbauer analyses suggest glauconite dissolution and precipitation of an Fe(II) mineral, likely siderite, and minor magnetite formation. These experimental results, along with thermodynamic calculations, confirm that solution redox state is the master variable dictating siderite formation in greensands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

A model for discrete fracture-clay rock interaction incorporating electrostatic effects on transport

Abstract A model based on the code CrunchClay is presented for a fracture-clay matrix system that takes electrostatic effects on transport into account. The electrostatic effects on transport include those associated with the development of a diffusion potential as captured by the Nernst-Planck equation, and the formation of a diffuse layer bordering negatively charged clay particles within which partial anion exclusion occurs. The model is based on a dual continuum formulation that accounts for diffuse layer and bulk water pore space, providing a more flexible framework than is found in the classical mean electrostatic potential models. The diffuse layer model is obtained by volume averaging ion concentrations in the Poisson-Boltzmann equation, but also includes the treatment of longitudinal transport within this continuum. The calculation of transport within the bulk and diffuse layer porosity is based on a new formulation for the Nernst-Planck equation that considers averaging of diffusion coefficients and accumulation factors at grid cell interfaces. Equations for function residuals and the associated Jacobian matrix are presented such that the system of nonlinear differential-algebraic equations can be solved with Newton’s method. As an example, we consider a 2D system with a single discrete fracture within which flow and advective transport occurs that is coupled to diffusion in the clay-rich matrix. The simulation results demonstrate the lack of retardation for anions (e.g., 36 Cl − ) of the contaminant plume within the fracture flow system because they are largely excluded from the charged clay rock, while the migration of cations (e.g., 90 Sr ++ ) is more strongly attenuated. The diffusive loss of divalent cations in particular from the fracture is accentuated by their accumulation in the diffuse layer within the clay-rich matrix.

58 GEOSCIENCES↗
DOE OSTI2024

Fe-rich X-ray amorphous material records past climate and persistence of water on Mars

X-ray amorphous material comprises 15-73 wt.% of sedimentary rocks and eolian sediments in Gale crater. This material is variably siliceous and iron rich but aluminum poor. The presence of volatiles is consistent with the existence of incipient weathering products. To better understand the implications of this material for past aqueous conditions on Mars, here we investigate X-ray amorphous material formation and longevity within terrestrial iron rich soils with varying ages and environmental conditions using bulk and selective dissolution methods, X-ray diffraction, and transmission electron microscopy. Results indicate that in situ aqueous alteration is required to concentrate iron into clay-size fraction material. Cooler climates promote the formation and persistence of X-ray amorphous material whereas warmer climates promote the formation of crystalline secondary phases. Iron rich X-ray amorphous material formation and persistence on Mars are therefore consistent with past cool and relatively wet environments followed by long-term cold and dry conditions.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Analcime-wairakite formation during experimental cement-bentonite alteration at 200–300 °C

Engineered barrier system materials in nuclear waste repositories may undergo hydrothermal alteration in response to groundwater saturation and heating events over their long operational timescales. Hydrothermal interactions between engineered materials (e.g., bentonite buffers, cements, waste canister materials) and the host rock environment may drive alteration processes that affect the advantageous properties of some barrier materials. However, such alteration will also promote the formation of zeolites, hydrothermally formed minerals that may themselves act to isolate radionuclides. Understanding the environmental conditions that control radionuclide-sorbing properties of zeolites, such as Si/Al ratio or Na content, will be valuable for assessing the changing properties of engineered barrier materials in the case of an in situ heating event. Here, we present experimental work characterizing the formation of zeolites during hydrothermal interactions between generic clay and cement barrier materials, with a focus on the analcime-wairakite zeolite series, which has known radionuclide sorption and exchange properties. We present the results of hydrothermal experiments combining uncured ordinary Portland cement powder with steel and Wyoming bentonite in the presence of Opalinus clay and a synthesized Opalinus clay groundwater to simulate water-saturated conditions in an argillaceous rock repository. The experiments were conducted isothermally at 200 or 300 °C for 8 to 24 weeks. In contrast to analogous studies that did not include cement reactants, we observed the formation of analcime-group minerals in all experiments. The addition of cement resulted in lower Si/Al ratios in the zeolites compared to similar studies that did not include cement. The presence of cement as a reactant was interpreted to promote analcime formation at 200 °C. At 300 °C, we observed higher calcium and silica concentrations in the aqueous solutions as well as increased wairakite formation and decreased analcime formation compared to the experiments at 200 °C. These results show a fully realized analcime-wairakite solid solution that falls between Si/Al = 2 (ideal) and a trend of analcime minerals that have increasing Si/Al ratios with increasing Na/(Na+Ca). Our results show predictable relationships between the Si/Al ratio and the analcime-wairakite content under hydrothermal conditions and illustrate that repository material interactions may promote the formation of zeolites in the analcime-wairakite solid-solution series during heating events in the subsurface.

58 GEOSCIENCES↗
DOE OSTI2022

Metal (hydr)oxide surface precipitates and their effects on potassium sorption

Surface precipitation has been shown to occur on rapid time scales in clay and metal oxide mineral systems. The formation of surface precipitates is hypothesized to present new potential sorption sites for potassium (K), where K can become incorporated into newly formed interlayer spaces (e.g., between tetrahedral–octahedral–tetrahedral stacked sheets). The objective of this study is to determine the effects of newly formed mineral surface precipitates on K sorption. Potassium adsorption experiments were conducted by utilizing Al 2 O 3 and SiO 2 sorbents in the presence of various cations (magnesium, zinc, and nickel) that helped to catalyze the formation of surface precipitates. Dissolved concentrations of elements were monitored via inductively coupled plasma optical emission spectrometry (ICP-OES). Solids were characterized via X-ray diffraction (XRD), and K surface complexation was analyzed via X-ray absorption near edge structure (XANES) spectroscopy. X-ray diffraction analysis indicated bayerite, layered double hydroxides (LDH), and silicated LDH were formed as reaction products, thus creating new surface sites for potential K adsorption. The presence of Si increased K adsorption perhaps due to its role in the formation of LDH surface precipitates. When the differences between observed and theoretical surface area normalized K sorption densities were averaged, a 31% increase in K adsorption was observed in the presence of Si. XANES analysis indicated that the binding mechanism of K to Si is different than that of K to Al, perhaps due to the presence of inner-sphere complexation of K to Al-oxide. Samples reacted for one month versus one week yielded more intense XANES post-edge peaks which indicated that the K sorption complex changes over time. Altogether, our findings provide novel insights into the mechanisms of K fixation in soil and has high implication in providing improved K fertilizer recommendation to growers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Preparation of illite coated geomaterial microfluidic surfaces: Effect of salinity and heat treatment

Unique characteristics of clay (e.g., high surface area, deficiency in positive charges) make any clay abundant shales a good source of adsorbed gas. However, the presence of clay in porous media can also affect shale rock's producibility. The clay-water interaction can cause significant swelling and fines migration in the formation and impair the overall hydrocarbon recovery from shale. Geomaterial micromodels, developed by functionalizing traditional glass or PDMS surfaces with geomaterials (e.g., calcite, Quartz, clay), can represent the physicochemical properties of the natural porous media and have been used during the last few years to understand and evaluate the solid-fluid physicochemical interactions. Here, this study focuses on developing a clay-coated geomaterial surface and investigates the effect of base fluid's salinity on clay adsorption to the glass surface. Glass capillary tubes and straight channel borosilicate glass micromodels are coated with Illite clay to represent the pore-scale clay chemistry of Caney Shale, a Mississippian unconventional play in Southern Oklahoma, USA. 10 wt% of Illite clay slurries made with brines of four different salinities are used to coat the glass-capillary tubes to understand the effect of salinity in clay adsorption on the glass surface and overall coating quality. To achieve a stable coating and evaluate the impact of heat treatment on coating's stability, straight channel glass flow cells coated with Illite clay are heat-treated at low (25 °C) and high temperature (125 °C), and the results are compared with an untreated coated surface. Flooding tests were carried out with brines of different salinities on the coated surface to evaluate the stability of the coating. The experimental results indicated a strong relationship between the brine's salinity and the adsorption of clay particles on the glass surface. An increase in brine concentration resulted in improved adsorption of clay particles on the glass surface. Experiments involving heat treating the glass surface following the coating demonstrated significant improvement in the stability of the coating.

02 PETROLEUM↗
DOE OSTI2025

A comparative analysis of numerical approaches for the description of gas flow in clay-based repository systems: From a laboratory to a large-scale gas injection test

There is nowadays a consensus among many countries that geological disposal is a favourable solution for the long-term management. Although different host formations and different barrier systems are under consideration around the world, clay-based materials form an important component for waste isolation in most national programmes. Hence, a good comprehension of the effect of gas flow on the hydro-mechanical behaviour of clay-based soils is essential, both at laboratory and field scale. Task B under the international cooperative project DECOVALEX-2023 has recently shown that, after some enhancement, models can be employed to reproduce laboratory scale tests, even with different sample geometries 37 . However, further work is required to understand whether they can be applied to simulate a large-scale experiment. Up-scaling of models for the advective transport of gas through clay-based low permeable material presents a number of problems related to the difficulty in obtaining consistent hydrogeological parameters and constitutive relationships at both laboratory and field scale. Based on a unique dataset from a large-scale gas injection test (Lasgit) performed at the Äspö Hard Rock Laboratory (Sweden), Task B within DECOVALEX-2023 has explored the refinement of these numerical strategies applied to the simulation of gas flow. Work performed within the task reveals that codes do not need to be substantially modified from the laboratory models to reproduce full-scale tests: indeed, model parameters calibrated and validated at laboratory scale have been applied to predict field scale gas flow at Lasgit, including peak gas pressure and injected cumulative gas volume. By means of (1) the introduction of interfaces between blocks to reflect the experimental configuration and the (2) adjustment of some parameters (e.g., higher permeability), the updated models are able to represent most of the key features observed in the experimental data, even at a large scale.

Tamayo-Mas, E↗
DOE OSTI2021

Strength-promoting mechanism of alkanolamines on limestone-calcined clay cement and the role of sulfate

This paper reports the strength-promoting mechanism of alkanolamines on limestone-calcined clay cement (LC{sup 3}). The hydration kinetics, phase formation and microstructure of LC{sup 3} with triethanolamine (TEA) or triisopropanolamine (TIPA) were investigated. TEA enhanced the strength of LC{sup 3}, while TIPA was effective at 28 days, and a correct sulfate addition promoted their effects. Alkanolamines accelerated the aluminate reaction of LC{sup 3} during early hydration, increased sulfate slowed this reaction by producing more ettringite. TIPA favoured the hydration of ferrite in clinker, not only accelerated the silicate reaction of metakaolin, but also resulted in a rapid limestone reaction. Alkanolamines altered the morphology and chemical composition of the aluminate hydrates and C-A-S-H. Alkanolamines enabled the reduction of porosity of hardened pastes and the increased sulfate further refined them. It was the large pores being induced by TIPA at early ages that were considered to have an adverse impact on the early strength of LC{sup 3}.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Experimental Investigation of Inhibitive Drilling Fluids Performance: Case Studies from United States Shale Basins

Shale formations are attractive prospects due to their potential in oil and gas production. Some of the largest shale formations in the mainland US, such as the Tuscaloosa Marine Shale (TMS), have reserves estimated to be around 7 billion barrels. Despite their huge potential, shale formations present major concerns for drilling operators. These prospects have unique challenges because of all their alteration and incompatibility issues with drilling and completion fluids. Most shale formations undergo numerous chemical and physical alterations, making their interaction with the drilling and completion fluid systems very complex to understand. In this study, a high-pressure, high-temperature (HPHT) drilling simulator was used to mimic real time drilling operations to investigate the performance of inhibitive drilling fluid systems in two major shale formations (Eagle Ford Shale and Tuscaloosa Marine Shale). A series of drilling experiments using the drilling simulator and clay swelling tests were conducted to evaluate the drilling performance of the KCl drilling fluid and cesium formate brine systems and their effectiveness in minimizing drilling concerns. Cylindrical cores were used to mimic vertical wellbores. It was found that the inhibitive muds systems (KCl and cesium formate) provided improved drilling performance compared to conventional fluid systems. Among the inhibitive systems, the cesium formate brine showed the best drilling performances due to its low swelling rate and improved drilling performance.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2021

PREPARATION OF CLAY-COATED GLASS SURFACES FOR MICROFLUIDICS-BASED STUDY ON CLAY-FLUID INTERACTIONS

Unique characteristics of clay, even though make any clay abundant shales a good source of adsorbed gas, make them equally difficult to produce. The clay-water interaction can cause significant swelling and fines migration in the shale formation, both of which can significantly impair the overall hydrocarbon recovery from shale. Geomaterial micromodels, developed by functionalizing traditional glass or PDMS surface with geomaterials (e.g., calcite, quartz, clay) can represent the physico-chemical properties of the natural porous media and have been used during the last few years to understand and evaluate the solid-fluid physicochemical interactions. This study focuses on developing a clay-coated geomaterial surface and investigates the effect of base fluid's salinity on clay adsorption to the glass surface. Glass capillary tubes and straight channel borosilicate glass micromodels are coated with Illite clay minerals to represent the pore-scale clay chemistry of Caney Shale, a Mississippian unconventional play in Southern Oklahoma, USA. 10 wt.% of Illite clay slurries made with brines of four different salinities are used to coat the glass-capillary tubes to understand the effect of salinity in clay adsorption on the glass surface and overall coating quality. To achieve a stable coating and evaluate the impact of heat treatment on coating's stability, straight channel glass flow cells coated with Illite clay are heat-treated at low (25 °C) and high temperature (125 °C). Dynamic flooding tests were carried out with brines on the coated surface to evaluate the stability of the coating. The experiments' outcome indicated a strong relationship between the brine's salinity and the adsorption of clay particles on the glass surface. An increase in brine concentration resulted in improved adsorption of clay particles on the glass surface. Experiments involving heat treating the glass surface following the coating demonstrated significant improvement in the stability of the coating.

02 PETROLEUM↗
DOE OSTI2020

Small-angle Neutron Scattering (SANS) Characterization of Clay- and Carbonate-rich Shale at Elevated Pressures

Unconventional oil and gas from shale formations have emerged as some of the fastest growing energy resources in the United States, providing both cleaner energy to consumers and reducing the nation’s reliance on energy imports. To properly harness these important natural resources, the nanopore structure of associated shales must be fully understood, particularly under hydraulic fracturing conditions, where they are exposed to both overburden compressive and hydrostatic fluid pressures. The current study uses small-angle neutron scattering (SANS) to characterize pore structure, including porosity, pore accessibility, and pore size distribution, in the 1–100 nm regime at elevated pressures for mineralogically distinct clay- and carbonate-rich shales from the Permian Basin. Unlike typical porosity measurement techniques, SANS is uniquely capable of characterizing both open and closed porosity, allowing measurement of how pore accessibility changes with pressure and determination of the size range of accessible versus inaccessible pores. The porosity of the clay-rich shale was 7.7%, compared to 0.51% for the carbonate-rich shale. However, only 2.6% of the nanopores in the carbonate-rich shale were inaccessible to water at 8 kPSI (55.1 MPa) compared to 7.8% for the clay-rich shale. Furthermore, our analyses indicated that the closed pores fall within distinct size ranges, likely corresponding with the chemical nature of the pore host material. These results provide valuable insight into the effects of shale petrophysical properties on hydrocarbon extraction from unconventional reservoirs.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Comparative geochemistry of flowback chemistry from the Utica/Point Pleasant and Marcellus formations

Flowback/Produced fluid samples were collected from several wells from two Utica/Point Pleasant (UPP) sites (UPPW and UPPS) in Ohio, and one Marcellus (Marcellus Shale Energy and Environment Laboratory (MSEEL)) site in West Virginia over a period of approximately two years. Although these formations have different ages, depositional environments, diagenetic histories, and geochemical and mineralogical compositions (i.e. the UPP is significantly more carbonate rich than the Marcellus which is more siliceous), analysis of trends in fluid species over time shows that, overall, the TDS and major solubilized elements (Na, Ca, Cl) in the UPP and Marcellus brines are remarkably similar. Total dissolved solutes (TDS) in these brines ranged from approximately 40 to 250 g/L salt, and in general, concentrations increased with time elapsed since natural gas well completion and stimulation. The behavior of Na, Br, and Cl suggests that the produced water signatures from these formations are largely derived from the native formational brines which display evidence of originating from evaporated seawater. There is a strong correlation between Cl and Br, indicating that both species behave conservatively, and the similarity among each of these brines suggests no appreciable contribution of salt from halite dissolution because Br is excluded from the halite structure. Cl/Br ratios in the brines range from ~80 to 120 (mg/L/mg/L). Other elements, such as K, which readily reacts between fluids and ion exchange sites on clays, generally exhibit conservative behavior for an individual site, but show significant variations among each of the different well pads. The concentrations of Sr and Ba vary dramatically among well sites, and increase with respect to Cl- over time, suggesting increasing solubilization, presumably from desorption from clay minerals or dissolution of carbonates or sulfates from the source formation(s). The UPPW well site has very low Ba due to high-sulfate input fluid, which resulted in precipitation of barite/celestite in the brines. In contrast the UPPS well site had elevated Sr (~ 3500 mg/L), presumably due to the use of Sr-rich recycled brine used in hydraulic fracturing. The Marcellus site had the highest Ba concentrations (up to 10 g/L) and highest Ba/Sr ratios in the fluids, due to the high concentration of barium in the Marcellus target (~ 1000 ppm, as compared to ~200 ppm in the UPP). These observations suggest that solutes in the FP fluids are derived from native brines, water-rock interactions that have occurred over geologic time scales, as well as some contribution from contemporaneous reactions in the subsurface. The results also show that the composition of the injected fluid can influence flowback fluid chemistry and possibly production efficiency.

58 GEOSCIENCES↗
DOE OSTI2025

Inorganic Alterations in Unconventional Shale Reservoirs: Importance of Additive and Base Fluid Chemistry

The effective development of unconventional petroleum systems requires the use of significant water resources. In an effort to reduce the consumption of freshwater resources for hydraulic fracturing, highly saline produced waters are increasingly recycled for use as a base fluid. However, there are significant knowledge gaps regarding potential water–rock interactions resulting from the introduction of produced waters and associated additives into shale reservoirs such as formation and deposition of mineral scale, which can negatively affect hydrocarbon production through wellbore restriction and damage to hydraulically generated fractures. To assess the impacts of field stimulation practices in the subsurface, a series of laboratory experiments were completed using (a) three distinct sedimentary rock formations of the Midland Basin (Texas, USA) and (b) additives with two different base fluids: municipal fresh water and clean brine. The experimental approach used relevant injection sequences and mixing ratios in specialized reactors for 3 weeks. Static pressurized experiments and nonpressurized time-resolved experiments were undertaken. The resulting solids and liquids were analyzed by using a variety of laboratory- and synchrotron-based techniques. The use of an acid spearhead (15% HCl) resulted in texturing of both clay-rich and calcareous shales, which can temporarily enhance porosity but subsequently result in mineral scale deposition. The primary matrix scale was Fe(III)-bearing phases, which occurred in all experiments regardless of base fluid chemistry. Additionally, strontium sulfate (SrSO 4 ) precipitated on shale surfaces when clean brines were used. It was concluded that clean brine was the main source of Sr 2+ species, while persulfate breaker degradation and oxidation of pyrite were the sources of SO 4 2– . Sulfate scaling was more pronounced in clay-rich shales, suggesting that Sr sorption is important for promoting celestite formation. This work demonstrates that mineral scale deposition is a complex phenomenon, whereby the type and proportions of various mineral phases are determined from reservoir alteration processes and coprecipitation of constituents from injection fluids. In conclusion, the experimental results shown here should be considered when evaluating different base fluids and additives in order to mitigate mineral precipitation in unconventional shale reservoirs, which could result in reservoir degradation.

Jew, Adam D. [SLAC National Accelerator Laboratory↗
DOE OSTI2022

Fluid Induced Elemental and Mineralogy Alterations of Caney Shale

ABSTRACT: Studies were conducted on cores and rock cuttings recovered from two wells drilled in Caney shale in the Southern Oklahoma. Mineralogical compositions of these samples were obtained by X-Ray Diffraction (XRD) measurements using two methods of sample preparation: conventional powder (by crushing and grinding of rock fragments) and spray-drying of micronized rock powder method. Microstructure and microanalysis were acquired by Scanning Electron Microscopy/Energy Dispersive Spectroscopy (SEM/EDS). Batch experiments were then conducted using selected rock samples and fracturing fluid whilst deionized water was used as control sample for fluid/rock interaction. These were conducted at 95°C and ambient pressure for various time periods to assess the geochemical reactivity of the Caney shale. The rock samples were subsequently recovered from fluid, dried and analysis repeated using identical XRD and SEM/EDS measurements, following the same conditions. Preliminary experimental results show rock mineralogical compositions are predominantly quartz with relatively high clay content. The clay minerals are mainly illite. Carbonate content is less than 10% by weight for most samples, with other non-clay minerals pyrite, albite, dolomite, and some apatite. In general, sprayed samples showed more intense peaks and less full width at half maxima (FWHM) relative to conventional rock-powder samples. Post-experimental mineralogical changes were observed in samples with clay portions breaking down to amorphous entities. As expected, dissolution of carbonates (calcite and dolomite) was observed and newly detected dissolution of biogenic micro quartz resulted in formation of amorphous silica. 1.0 INTRODUCTION Formation of sedimentary rocks involves processes where rock sediments are emplaced with fluids starting interactions that persist over long periods. During the lithification process, sediments and fluids react and attain equilibrium state. This equilibrium is disturbed during drilling, completion, hydraulic fracturing and other operations that involve the introduction of engineered fluids into the subsurface. To return to equilibrium, dissolution and precipitation of minerals may occur. These reactions have implications on the petrophysical properties of the reservoir. Whiles dissolution and precipitation of minerals can enhance porosity and permeability, the reverse can also be true. For example, when acidic fluids are introduced into formations with high carbonate contents, carbonate minerals dissolve into solution thus increasing the porosity and permeability of the formation. In contrast, when alkaline fluids with pH above 11 are introduced into an illite-rich shale formation, the rock-fluid interaction leads to de-flocculation of illite platelets causing substantial increase in clay fines migration, consequently significant reduction in permeability (Salles et al., 2008).

Awejori, G.↗
DOE OSTI2021

Characterization of Nanoscale Pores in Tight Gas Sandstones Using Complex Techniques: A Case Study of a Linxing Tight Gas Sandstone Reservoir

Pore structures with rich nanopores and permeability in tight gas reservoirs are poorly understood up to date. Advanced techniques are needed to be employed to accurately characterize pore structures, especially tiny pores which include micron and nanopores. In this study, various experimental techniques such as scanning electron microscopy (SEM), nuclear magnetic resonance (NMR) T 2 , nitrogen adsorption method, and NMR cryoporometry (NMRC) are combined to interrogate the complex pore systems of the tight gas reservoir in the Linxing formation, Ordos Basin, China. Results show that tight gas sandstones are primarily comprised of residual interparticle and clay-dominated pores. Clay and quartz are two dominate minerals while pyrite occupies a nontrivial amount as well. The permeability of tight gas sandstones is very low, exhibiting an extremely poor positive correlation with porosity. While pore types and relative pore contents are more influential factors on the permeability, accurate characterization of pore size distribution is critical for the permeability of tight gas sandstones. Therefore, complementary characterization methods are carried out, indicating that neither small pores with radii < 100 nm (around peak 1 in NMR T 2 distribution) nor large pores with radii > 5 μ m (around peak 3 in NMR T 2 distribution) control the permeability by analyzing the connectivity of the pores in various size ranges, but rather pores averaging approximately 350 ± X nm (around peak 2 in NMR T 2 distribution) have sufficient connectivity to host and transmit hydrocarbons. The pore size of tight gas sandstones is dominated by the clay-rich mineral assemblage. The study shows that the NMRC technique can be a very promising method, especially when referred to as a promising “roadmap” on how to interrogate tight formations such as the tight gas sands or even shale especially for the nanopore characterization.

15 GEOTHERMAL ENERGY↗
DOE OSTI2026

Oxidation of biogenic U(IV) mediated by iron-bearing clay minerals, iron-reducing bacteria, and organic ligands

Bioreduction of hexavalent uranium (U(VI)) to tetravalent uranium (U(IV)) by dissimilatory metal-reducing bacteria (DMRB) is considered an effective strategy for uranium immobilization in contaminated environments. However, U(IV) can be reoxidized to U(VI) under fluctuating redox conditions and remobilized. This work investigates the oxidation behavior of biogenic U(IV) in the presence of bioreduced iron-bearing clay minerals (rNAu-2), iron-reducing bacteria (Shewanella putrefaciens CN32), and organic ligands (ethylenediaminetetraacetic acid (EDTA) and citrate). Results demonstrate that the presence of CN32 significantly inhibits U(IV) oxidation. rNAu-2 exerted a context-dependent influence on U(IV) oxidation: its effect was masked by bicarbonate-promoted U(VI) mobilization in the absence of active CN32, but became detectable when CN32-mediated microbial protection slowed U(IV) oxidation. EDTA and citrate markedly accelerate U(IV) oxidation via formation of soluble U(IV)-ligand complexes, changing U(IV) redox potentials, and by promoting clay mineral dissolution that enhances Fe(II)/Fe(III) redox cycling. Collectively, our findings constrain the roles that clay minerals, iron-reducing bacteria, and organic ligands play in governing U(IV) stability, emphasizing the need to account for these factors in developing robust bioremediation strategies.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗