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At least 145 records · Page 8

Characterization of paste microstructure for durability properties of concrete

In this study, paste samples from different cementitious systems were characterized by using X-Ray Micro Computed Tomography (µ-CT) and Fluorescence Microscopy techniques. Quantitative and qualitative aspects of defects from paste samples were investigated to develop indicators of durability related properties of corresponding concrete samples. In the first phase of this study, hour glass shaped 3D printed molds were used to investigate five cementitious combinations consisting of three cement types (Coarse Ground portland cement, Type IL Portland Limestone Cement and Type I/II ordinary portland cement) and fly ash as a supplementary cementitious material. In the second phase, metal molds were used to compare the results of Coarse Ground portland cement with Type I ordinary portland cement, 5% of which was replaced with colloidal nanosilica. Potential correlations between paste and concrete have been presented. This work was supported by US Department of Energy and North Dakota Department of Commerce.

36 MATERIALS SCIENCE↗

Optimization of matrix viscosity improves polypropylene fiber dispersion and properties of engineered cementitious composites

Engineered cementitious composites (ECC) is a durable cementitious material with high tensile ductility and strain-hardening characteristics. Although considered as a cost-effective fiber for ECC, polypropylene (PP) fiber is reportedly difficult to disperse in mortar matrix due to its high aspect ratio and hydrophobicity. In this study, the matrix viscosity of a low-carbon ECC based on limestone calcined clay cement was tailored as a variable to improve PP fiber dispersion under a pre-determined mixing protocol. The effect of matrix viscosity on the composite fresh and hardened properties was investigated experimentally. Results suggested an optimal range of matrix viscosity (10.3–11.5 Pa . s) favors the composite tensile strength and strain capacity at 28 days. At the optimal state with a 0.1 % viscosity modifying admixture (VMA)-to-binder mass ratio, PP-ECC achieved 7.0 % tensile strain capacity and 3.5 MPa ultimate tensile strength. When matrix viscosity falls outside the desired range, both ultimate tensile strength and strain capacity were diminished. By tailoring the VMA dosage, the matrix viscosity can be adjusted for desired fiber dispersion, workability, and mechanical properties. Finally, the findings of this study provide a technical reference for the practical design and application of PP-ECC.

36 MATERIALS SCIENCE↗

The impact of capillary heterogeneity on CO 2 flow and trapping across scales

Capillary heterogeneity has been identified over the last decade as a key control on subsurface CO 2 flow behavior during geological CO 2 sequestration. These heterogeneities can be formed in all sedimentary rocks, ranging from slight variations in the sand grain sizes to extensive sequences of interbedded sands, shales, and limestones. Capillary heterogeneity has been largely, although not entirely, overlooked in subsurface flow modeling because it is assumed to only directly influence fluid redistribution over scales of centimeters to meters. However, even small-scale fluid movements can result in dramatic impacts on the mobility and trapping of the CO 2 over kilometers. Therefore, neglecting capillary heterogeneity at multiple scales could potentially lead to errors in modeling and predicting field-scale plume migration. In this review paper, we aim to provide a consistent overview to (1) establish that capillary heterogeneity can have a major impact on CO 2 plume migration, (2) establish the respective length scales at which capillary heterogeneity matters, and (3) provide guidance for numerical modeling. This review covers pertinent literature and extracts key observations from the core to the field scales. Experimental studies have shown that millimeter-decimeter scale capillary heterogeneity can cause the so-called capillary heterogeneity trapping in addition to pore-scale residual trapping. Even at such a small scale, capillary heterogeneity can already lead to complex upscaled constitutive relationships, such as flow-rate dependent and anisotropic relative permeability, which affects field-scale CO 2 migration even when field-scale heterogeneities are present. Under gravity-dominated flow regimes, centimeter-meter scale capillary heterogeneity can entrap a significant amount of CO 2 at field scale, not just after imbibition but also during drainage. In certain cases, the presence of capillary heterogeneity can even completely stop the vertical movement of the CO 2 plume, hence greatly reducing leakage risks. At meter-kilometer scale, the influence of capillary heterogeneity is more pronounced and can hinder or redirect CO 2 migration in both lateral and vertical directions. The impact of capillary heterogeneity across multiple spatial scales poses a great challenge in modeling CO 2 migration at field scale, because it is practically impossible to build a field-scale earth model with grid blocks at millimeter scale. We recommend a hierarchical modeling approach to address this challenge. At field scale, earth models are built to capture geological features and heterogeneities in high but still practical grid resolutions. For each facies or rock type of the field-scale model, high- resolution meter-scale “conceptual” models are built with millimeter-scale grid blocks to capture representative fine-scale bedding geometries and heterogeneities in various environments of deposition, bridging the gap from subcore scale to the size of a field-scale simulation grid block. Upscaling is then used to preserve the smaller-scale flow dynamics of various rock types in field-scale simulations. Here, future work is needed to (1) refine, improve, and validate the hierarchical modeling approach; (2) build libraries of fine-scale bedding models for facies in various environments of deposition; (3) quantify multiscale capillary heterogeneity effects under subsurface uncertainties; (4) gain learning from different storage formations; and (5) establish best practices that balance accuracy and computational speed.

Capillary heterogeneity↗

Techno-economic feasibility of geothermal energy production using inactive oil and gas wells for district heating and cooling systems in Tuttle, Oklahoma

Oil and gas wells have been drilled in the United States and often encounter hot co-produced water possibly suitable for geothermal direct-use applications. Here this study evaluated geothermal resources, heating and cooling demand, and techno-economic potential of four oil and gas wells repurposed for geothermal energy production to serve two public schools and 250 nearby houses in Tuttle, Oklahoma, USA. Subsurface geology in the study area primarily consists of Permian to Mississippian sandstone and limestone formations approximately from 2 km to 3.5 km depth. With a geothermal gradient of 25.3 °C/km, the temperature of geothermal energy production was estimated as 68.2 °C at 2.1 km. The potential of calcite scaling within boreholes and pipes was minimal. Using the characterized reservoir properties, techno-economic analyses were conducted for evaluating levelized costs of geothermal energy production for direct-use heating and cooling and district heating systems with five different production scenarios. Heating and cooling demand in two schools and 250 houses and additional 0.3 MW and 0.6 MW base heating loads for potential geothermal direct-use applications in the study area were also incorporated in the modeling. Results indicated that the levelized cost of heating of geothermal district heating systems utilizing existing wells were significantly lower than those of conventional geothermal energy systems that include well drillings. The geothermal energy production with doublet and quartet configurations was generally sufficient to supply total annual heating demand in the district, while a peaking boiler was used to supply peak loads. Doublet configurations showed higher production temperature with a lower thermal drawdown than the quartet configurations. The doublet system at 2.1 km production depth with 9.3 kg/s flow rate represented the optimal levelized cost of $71/MWh and 91.2% utilization factor. These results imply that the Tuttle geothermal district heating system is techno-economically feasible and comparable to geothermal district heating systems in the United States and the regional natural gas rate for residentials by recycling inactive oil and gas wells with no drillings.

15 GEOTHERMAL ENERGY↗

Analyzing the upscaling potential and geospatial siting of calcination-free calcium hydroxide production in the United States

This study evaluates the techno-economic feasibility and the embodied carbon dioxide intensity (eCI) of a novel process for producing nominally pure (>95 mass %) calcium hydroxide without the need for the thermal calcination of limestone. The process relies on the aqueous extraction of calcium from alkaline industrial wastes following which portlandite (Ca(OH) 2 : CH, a.k.a. slaked lime or hydrated lime) is precipitated by application of a waste-heat based thermal swing. This approach takes advantage of the temperature dependent solubility of CH at ambient pressure. We evaluated the feasibility of implementing this process in the U.S. based on the geospatial availability of waste heat and slags as a Ca-source. For the base case, the cost of production of “Low-Temperature Portlandite (LTP)” is 2-to-3 times that of traditional portlandite (~$180/tonne). The main driver of cost is the electricity demand for reverse osmosis (RO) which is used to concentrate Ca-ions in solution, and the costs of membrane replacement. Our sensitivity analysis showed that parity with the cost of production of traditional portlandite is readily achievable by selecting membranes with better durability (i.e., better pH resistance) and flux (i.e., higher permeability) without sacrificing selectivity. Significantly, LTP features an eCI that is between 40%- and - 80 % lower than its traditional counterpart when electricity is sourced from natural gas combustion or wind power, respectively. Finally, our geospatial analysis reveals that there are three areas in the U.S. with the potential for implementation of industrial-scale facilities that could produce at least 50 tonnes of pure Ca(OH) 2 per day, while achieving a production cost of ~$270 per tonne of Ca(OH) 2 , owing to the proximity between slag feedstocks and waste heat sources.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Bedrock architecture, soil texture, and hyporheic zone characterization combining electrical resistivity and induced polarization imaging

The shallow (<15 m depth) subsurface environment of a short reach along a bedrock stream was investigated with electrical resistivity and induced polarization (IP) to map details of bedrock and soil sediments. The bedrock is mostly comprised of limestone, and is generally resistive compared to the overlying soil. The soil-bedrock interface was determined through a trial and error approach using a sharp boundary feature in the inversion model. The inferred bedrock surface determined from the inversions exhibited undulating patterns with troughs and ridges. A near continuous trough ran alongside the stream within the floodplain, and is suggestive of a paleochannel among other interpretations of this feature. The structure of the electrical resistivity above the bedrock showed small-scale elongated features. The chargeability from the IP method showed larger scale features. High values of chargeability were associated with the sediments in the floodplain, and low values were associated with bedrock, stream, and soil on the elevated banks above the stream. If the chargeability is associated with membrane polarization characteristic of clayey soils, then IP seems to highlight the mere existence of clay, while the resistivity may be more discernable of the relative proportion of clay. Vegetation differences may also explain the chargeability distribution, where parts of the survey with high chargeability had dense pine with no understory making the soils more organically rich.

54 ENVIRONMENTAL SCIENCES↗

Coupling geophysical, geological, geochemical and mineralogical assessments to examine preferential contaminant transport pathways in interbedded fractured bedrock

This study shows that a multi-faceted approach, combining borehole geophysical logging and surface seismic P-wave first-arrival tomography with confirmatory coring, well installation, and chemical and mineralogical analysis, is effective for identifying difficult-to-locate preferential contaminant transport pathways in deeper fractured bedrock. Seismic tomography detected porous 10–20 m wide elongated fractured conduits that allow acidic groundwater contaminated with uranium (U) and nitrate (NO 3 - ) to migrate within interbedded shale-limestone bedrock over 1000 m from a former disposal facility (S-3 Ponds site) located at the DOE Y-12 National Security Complex in Tennessee (USA). Conventional drilling techniques would easily miss these conduits because they are oriented parallel with fractured bedding planes. Synchrotron analysis of aquifer solids revealed that > 95 % of the U is hexavalent (U VI ). This uranyl (UO 2 2+ ) species is coordinated with carbonate, iron oxide, silicate and phosphate minerals within cemented white to yellow precipitates, which contain U concentrations as high as ∼21.6 % by weight fraction. Identifying the presence of these mineral phases, enables a further understanding of the potential effectiveness of remediation actions. The combination of methodologies presented here can also be applied to other explorations, such as the detection of water supply.

Fate and transport↗

Evidence for metal sources, fluid-mixing processes, and S isotope recycling within the feeder zone of an Irish type Zn-Pb deposit

The origin and evolution of fluids in Irish-type Zn-Pb deposits remains debated, particularly regarding the mobility of metals such as Cu and Ni, sources of sulphur, and the role of fluid mixing and replacement. The Lisheen Zn-Pb deposit, Ireland, offers a well-defined natural laboratory to investigate these questions. While most studies have focused on the Waulsortian Limestone Formation, the primary sulphide host, less is known about mineralisation in underlying units, such as the Lisduff Oolite Member (LOM). The LOM displays enrichment in Cu and Ni and displays intense replacement textures compared to other hosts at Lisheen, making it an ideal target for studying metal mobility and sulphur recycling in carbonate-hosted systems. Through characterising and studying LOM-hosted sulphides, valuable insights into mineralisation processes, especially related to Cu-Ni metals, can be defined. This study integrates petrography, EMPA, and in situ sulphur isotope (δ 34 S) analysis to investigate sulphide paragenesis, mineral chemistry, and fluid evolution across LOM ore zones. Results reveal a multistage mineralising system involving extensive replacement of early pyrite (Py0, δ 34 S = −28.4 to −21.9 ‰) by sphalerite and galena, with zoned pyrite (Py1) enriched in As-Cu-Ni-Tl. The δ 34 S values and trace element trends indicate mixing between hydrothermal and bacteriogenic sulphur-rich fluids, with evidence for sulphur recycling during replacement. Pyrite textures and compositions capture this evolving fluid regime, with trace element enrichment linked to paragenetic stage. The steel ore region, adjacent to major fault intersections, records intense hydrothermal fluid interaction, hosting Ni- and As-rich phases such as nickeline, gersdorffite, and arsenopyrite. These findings highlight the importance of structural controls and fluid mixing in metal transport and deposition, positioning the LOM as a key stratigraphic unit for understanding ore-forming processes in Irish-type systems. These results have implications for targeting similar carbonate-hosted systems globally, especially where deeper or structurally complex ore zones remain underexplored.

58 - GEOSCIENCES↗

Link Between CO 2 –Induced Wettability and Pore Architecture Alteration

Changes in pore (throat) size, surface roughness and mineralogy induced by supercritical-CO 2 -water-rock reactions impact petrophysical properties such as porosity, permeability, and especially wettability. Herein, we show that these changes directly impact relative permeability and capillary pressure curves, a fact rarely studied in the literature. In this work, we show that CO 2 contact angle changes emerge after Madison Limestone samples were soaked for 400 hours in CO 2 -enriched brine. Coreflooding results show that the water production rate and cumulative water production increased after the rock was exposed to carbonic acid. Moreover, the mercury capillary pressure decreased in meso- and macro-pores, indicating the increase of size in these pores due to reactions. This compounded wettability and pore network alteration can directly affect CO 2 injectivity, migration and storage capacity. Furthermore, this fundamental insight into CO 2 geological storage processes should aid practitioners to reduce uncertainties in forecasting CO 2 distribution via injection simulation.

58 GEOSCIENCES↗

Geoelectric Characterization of Hyporheic Exchange Flow in the Bedrock‐Lined Streambed of East Fork Poplar Creek, Oak Ridge, Tennessee

Abstract A multimethod geoelectric survey was implemented between January and March 2022 along a 220‐m long reach of the bedrock‐lined streambed of East Fork Poplar Creek in Oak Ridge, Tennessee to identify locations of surface‐water and groundwater exchange and characterize the subsurface flow paths that convey water between the stream and flood plain. A waterborne self‐potential (WaSP) survey was completed in January 2022 to measure the electric streaming‐potential field in the stream. Electric resistivity tomography (ERT) was performed in March 2022 on the flood plain adjacent to the WaSP survey reach to map the electric resistivity distribution and characterize the hydrogeology and subsurface flow paths that facilitate surface‐water and groundwater exchange in the bedrock‐lined stream. The combination of WaSP and ERT data support the qualitative interpretation that surface‐water and groundwater exchange likely occurs along fractures in outcropping bedrock and along two fault lines that intersect the limestone creek bed.

54 ENVIRONMENTAL SCIENCES↗

Measurement of the Static Nonlinear Third-Order Elastic Moduli of Rocks: Problems and Applicability

The third-order elastic (TOE) model has been used to describe the widely observed nonlinear mechanical behaviors of earth materials. In addition to linear elastic constants ( λ , μ ), three nonlinear elastic moduli ( A , B , C ) are required for isotropic rocks. Contrary to previous research on dynamic TOE moduli, this study followed the protocol to measure strain and stress under uniaxial and hydrostatic compressive tests statically, which were later used to invert for the full set of TOE moduli for four standard rock types with differing pore structures of a porous oolitic limestone, quartz-rich sandstones, and a dense crystalline basalt. The applicability of the TOE model to characterize nonlinearity depends on the fulfillment of path-independence and small-strain assumptions. Using the measured static TOE moduli, the finite element model demonstrates that the stress in the vicinity of the wellbore is more amplified than the stress in the linear elastic case, which leads to a wider zone of rock failure around the wellbore. Due to the long-standing discrepancy between static and dynamic moduli, the rarely reported full set of static TOE moduli is necessary and will benefit future research in understanding the effect of rock nonlinearity on geophysical and geomechanical applications, such as long-term safe storage of CO 2 and generating process of geohazards.

58 GEOSCIENCES↗

Radiation damages the silicates present in polyphasic mineral aggregates causing concrete’s degradation

While many U.S. nuclear power plants have submitted Subsequent License Renewal Application to operate beyond 60 years, others are already considering Operations Beyond Eighty years. In such cases, concrete biological shields are exposed to neutron and gamma radiation exceeding prescribed thresholds. Radiation-induced volumetric expansion (RIVE), extensively studied in single crystals, may also contribute to the degradation of polycrystalline aggregates. Since minerals differ in atomic structure and chemistry, radiation can affect them in distinct ways. This study examines quartzite, marble, and limestone to evaluate how irradiation affects their physical attributes and chemical reactivity. Results show crystalline silicates experience significant RIVE damage and enhanced reactivity in alkaline solutions compared to non-irradiated phases. Enhanced intra- and inter-granular dissolution could compromise aggregate integrity. An empirical correlation links silicate dissolution rate to atomic constraints (density, rigidity) and radiation dose, providing a predictive framework for estimating changes in silicate aggregate properties within radiation-exposed concrete.

Bouissonnié, Arnaud [Univ. of California, Los Ange↗

Chemical composition, coordination, and stability of Ca–organic associations in the presence of dissolving calcite

Environmental biotic and abiotic factors and soil physical, mineralogical, and chemical properties control the chemical composition of soil organic matter (SOM). Particularly, soil mineralogy and the presence of multivalent cations affect SOM labile fraction composition, stability, and environmental persistence. The persistence of SOM in aridic or limestone deposit derived soils, i.e., calcareous soils, has been partially attributed to SOM stabilization through adsorption or inclusion into the calcite mineral structure. Recently, however, it was shown that Ca(aq) released during calcite dissolution formed aqueous Ca–organic associations with OM components, which were unbound to mineral surface sites. This study investigates the structure, composition, and coordination of these associations by characterizing lyophilized Ca–organic containing solutions with spectromicroscopy [Scanning Transmission X-ray Microscopy (STXM)] and with a nanoimaging chemical probe [Infrared scattering-Scanning Nearfield Optical Microscopy (IR s-SNOM)]. Chemical stability of Ca–organic associations is furthermore determined with pyrolysis mass spectrometry analysis. The results demonstrate that Ca–organic associations are formed in the presence of dissolving calcite and OM components relevant to soil chemistry, i.e., lignin and amino acids. This study further reveals a spatial homogeneity of solution-derived (bi) carbonate in Ca–organic associations indicating for the first time that an inorganic anion, such as (bi)carbonate, may be part of these associations. Most likely, Ca ions are bound to both the (bi)carbonate and the organic components. These Ca (bi)carbonate–organic associations seem to have greater chemical stability than the pristine organic mixtures and, possibly, a higher environmental stability and reduced mineralization rate.

54 ENVIRONMENTAL SCIENCES↗

Effects of Cement Changes and Aggregate System on Mechanical Properties of Concrete

In this paper, mechanical properties of concrete mixtures containing different cementitious combinations and two aggregate systems were investigated under plastic and drying conditions. Emphasis was laid on durability and shrinkage of concrete. Life Cycle Analysis was also conducted by using Green Concrete LCA Webtool. Results indicated that the presence of larger aggregate sizes tend to enhance durability of concrete. The presence of nanosilica also imparted superior mechanical properties to concrete. A cementitious combination containing Portland Limestone Cement and fly ash with larger aggregate sizes emerged as a better performing mixture in terms of mechanical properties and with minimum environmental impact.

36 MATERIALS SCIENCE↗

Massive formation of early diagenetic dolomite in the Ediacaran ocean: Constraints on the “dolomite problem”

Paleozoic and Precambrian sedimentary successions frequently contain massive dolomicrite [CaMg(CO 3 ) 2 ] units despite kinetic inhibitions to nucleation and precipitation of dolomite at Earth surface temperatures (<60 °C). This paradoxical observation is known as the “dolomite problem.” Accordingly, the genesis of these dolostones is usually attributed to burial–hydrothermal dolomitization of primary limestones (CaCO 3 ) at temperatures of >100 °C, thus raising doubt about the validity of these deposits as archives of Earth surface environments. We present a high-resolution, >63-My-long clumped-isotope temperature (T Δ47 ) record of shallow-marine dolomicrites from two drillcores of the Ediacaran (635 to 541 Ma) Doushantuo Formation in South China. Our T ∆47 record indicates that a majority (87%) of these dolostones formed at temperatures of <100 °C. When considering the regional thermal history, modeling of the influence of solid-state reordering on our T Δ47 record further suggests that most of the studied dolostones formed at temperatures of <60 °C, providing direct evidence of a low-temperature origin of these dolostones. Furthermore, calculated δ 18 O values of diagenetic fluids, rare earth element plus yttrium compositions, and petrographic observations of these dolostones are consistent with an early diagenetic origin in a rock-buffered environment. We thus propose that a precursor precipitate from seawater was subsequently dolomitized during early diagenesis in a near-surface setting to produce the large volume of dolostones in the Doushantuo Formation. Our findings suggest that the preponderance of dolomite in Paleozoic and Precambrian deposits likely reflects oceanic conditions specific to those eras and that dolostones can be faithful recorders of environmental conditions in the early oceans.

58 GEOSCIENCES↗

A re-examination of the mechanism of whiting events: A new role for diatoms in Fayetteville Green Lake (New York, USA)

Whiting events—the episodic precipitation of fine-grained suspended calcium carbonates in the water column—have been documented across a variety of marine and lacustrine environments. Whitings likely are a major source of carbonate muds, a constituent of limestones, and important archives for geochemical proxies of Earth history. While several biological and physical mechanisms have been proposed to explain the onset of these precipitation events, no consensus has been reached thus far. Fayetteville Green Lake (New York, USA) is a meromictic lake that experiences annual whitings. Materials suspended in the water column collected through the whiting season were characterized using scanning electron microscopy and scanning transmission X-ray microscopy. Whitings in Fayetteville Green Lake are initiated in the spring within the top few meters of the water column, by precipitation of fine amorphous calcium carbonate (ACC) phases nucleating on microbial cells, as well as on abundant extracellular polymeric substances (EPS) frequently associated with centric diatoms. Whiting particles found in the summer consist of 5–7 μm calcite grains forming aggregates with diatoms and EPS. Simple calculations demonstrate that calcite particles continuously grow over several days, then sink quickly through the water column. In the late summer, partial calcium carbonate dissolution is observed deeper in the water column. Settling whiting particles, however, reach the bottom of the lake, where they form a major constituent of the sediment, along with diatom frustules. The role of diatoms and associated EPS acting as nucleation surfaces for calcium carbonates is described for the first time here as a potential mechanism participating in whitings at Fayetteville Green Lake. This mechanism may have been largely overlooked in other whiting events in modern and ancient environments.

54 ENVIRONMENTAL SCIENCES↗

Optimal band selection for target detection with a LWIR multispectral imager

Multispectral imaging can offer many benefits in cost, complexity, resolution, size, weight, and power, relative to hyperspectral imaging. When designing a multispectral system, spectral bandpasses can be selected using optimization algorithms configured to maximally separate target detection scores between target and background regions. A hyperspectral image (HSI) can serve as the source of data from which band groupings can be tested for optimality. The output of an adaptive cosine estimator target detection algorithm is used in an objective function. Three optimization algorithms are compared: particle swarm, dual annealing, and differential evolution. A global optimum is also found using a brute force approach on the Livermore Computing Syrah supercomputer. Three materials are investigated: calcite, gypsum, and limestone. This is done for 3-, 4-, and 5-band systems. The data originate from a longwave infrared HSI of a material display board. The optimization algorithms were run 30 times for every scenario. Performance statistics (maximum, minimum, mean, standard deviation, and median) based on the separation values are given. Additional characterization was performed using receiver operator characteristic (ROC) curves and the area under the ROC curve. While good performance was obtained for the three optimization algorithms, the dual annealing algorithm produced the highest and most consistent detection separation scores on average.

47 OTHER INSTRUMENTATION↗

Characterization of prokaryotic communities in Puerto Rican caves using 16S rDNA amplicon sequencing

The cave ecosystems host microbial communities adapted to extreme environments. This study utilized 16S rDNA to investigate the prokaryotic diversity across seven caves in Puerto Rico’s northern limestone karst belt. Microbial profiling revealed distinct subterranean communities, enhancing our understanding of cave microbiology and potential applications in environmental conservation and microbial research.

16S↗