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At least 811 records · Page 45

Binder-jetted AISI M2 tool steel during hot isostatic pressing: Densification and carbide transformation

Binder jetting (BJ) enables fabrication of complex components from high-alloy steels such as AISI M2; however, residual porosity after sintering limits mechanical performance. This study investigates the coupled effects of binder chemistry, sintering conditions, cooling rate, and subsequent hot isostatic pressing (HIP) on densification, microstructure, and mechanical response in binder-jetted M2 tool steel. HIP increased relative density from ∼93 to 95% to >99% and improved compressive strength by ∼40-70%. Densification was governed by initial pore morphology, where closed porosity was effectively eliminated, while interconnected porosity limited full consolidation. Microstructural analysis (XRD, EBSD, SEM) shows that HIP promotes dissolution of metastable carbides and redistribution of alloying elements (W, Mo, V), transforming heterogeneous carbide networks into finer and more uniformly distributed M 2 C, MC, and M 6 C phases through diffusion-assisted homogenization. Among the investigated conditions, the FluidFuse binder combined with sintering at 1270 °C for 60 min and furnace cooling produced the most balanced response, achieving ∼99.7% density, ∼855 HV hardness, ∼4130 MPa compressive strength, and ∼24% strain. In contrast, higher sintering temperatures promoted carbide coarsening, reducing ductility despite high density. HIP reduces microstructural heterogeneity and drives the system toward a near-equilibrium state with reduced sensitivity to prior processing history. A comparative assessment with conventional and additive manufacturing routes (LPBF, DED, EBM, FFF) shows that the BJ-HIP approach achieves competitive densification and mechanical performance. These findings provide a mechanistic basis for controlling densification and microstructure in high-alloy steels processed via BJAM.

AISI M2 tool steel↗

Oxidation of Ni-Rich Mangrove Sediments after Isolation from the Sea (Dumbea Bay, New Caledonia): Fe and Ni Behavior and Environmental Implications

Formation of Fe-sulfides in anoxic horizons of mangrove sediments makes this ecosystem a potential long-term sink for metal contaminants in the intertropical region. Increasing anthropogenic pressure on coastal areas can alter the physicochemical of mangrove sediments by modifying their redox state, affecting directly the rate of Fe-sulfides that mediate accumulation of metal contaminant. Here, we show that isolation from the sea, due to land use planning, directly modify the redox state of mangrove sediments from reducing condition to oxidizing condition, affecting the stability of Ni-accumulating Fe-sulfides. Unusual suboxic/oxic conditions are indeed observed at intermediate depths in these mangrove sediments and favor the oxidative dissolution of Ni-pyrite (Fe 1–x Ni x S 2 ) that initially formed under anoxic/suboxic conditions. This reaction leads to a significant release of aqueous HS – , Fe 2+ and Ni 2+ at the redox boundary. HS – and Fe 2+ oxidize into SO 4 2– and Fe 3+ and precipitate as schwertmannite (Fe 8 O 8 (OH) 6 SO 4 ), leading to acidification of the pore-waters. Meanwhile, aqueous Ni 2+ is mostly leached downward in the underlying anoxic layers of the sediment where it sorbs at the surface of pyrite and/or incorporates in the structure of newly formed pyrites. These results emphasize the potential of Fe-sulfides for mitigating the impact of the oxidation of former Ni-rich mangrove sediments, as long as the anoxic conditions are preserved at depth. Furthermore, this assumption can be expanded to other divalent metals and should be applicable to a larger set of mangrove ecosystems worldwide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Time-resolved cryogenic electron tomography for the study of transient cellular processes

Cryogenic electron tomography (cryo-ET) is the highest resolution imaging technique applicable to the life sciences, enabling sub-nanometer visualization of specimens preserved in their near native states. The rapid plunge freezing process used to prepare samples lends itself to time-resolved studies, which researchers have pursued for in vitro samples for decades. Here, we focus on developing a freezing apparatus for time-resolved studies in situ. The device mixes cellular samples with solution-phase stimulants before spraying them directly onto an electron microscopy grid that is transiting into cryogenic liquid ethane. By varying the flow rates of cell and stimulant solutions within the device, we can control the reaction time from tens of milliseconds to over a second prior to freezing. In a proof-of-principle demonstration, the freezing method is applied to a model bacterium, Caulobacter crescentus, mixed with an acidic buffer. Through cryo-ET we resolved structural changes throughout the cell, including surface-layer protein dissolution, outer membrane deformation, and cytosolic rearrangement, all within 1.5 seconds of reaction time. This new approach, Time-Resolved cryo-ET (TR-cryo-ET), enhances the capabilities of cryo-ET by incorporating a sub-second temporal axis and enables the visualization of induced structural changes at the molecular, organelle, or cellular level.

59 BASIC BIOLOGICAL SCIENCES↗

Assessment of shallow aquifer remediation capacity under different groundwater management conditions in CGS field

Because of unknown faults and fractures in the overlying rock, CO 2 stored deep underground may move upward, and the intrusion may impact shallow groundwater quality. After leakage of CO 2 has ceased, the affected aquifer may show remediation capacity under natural conditions and injections and extractions. Here, the reactive transport modeling software TOUGHREACT was used to simulate the remediation capacity of a study aquifer. The simulation results show that the intrusion of leaked CO 2 would decrease the pH of the target aquifer and trigger the dissolution of calcite minerals. After CO 2 leakage has ceased, the pH would increase as would the concentration of Ca because of the dissolution of calcite along the flow path. Scenario simulation results of amelioration of groundwater quality by water injection and extraction show that single injection is the best option and a combination approach of injection and extraction could control the range of the affected area. The pH value should not be regarded as the single indicator for remediation capacity assessment. Parameter sensitive analysis results show that the rates of injection and extraction affect the repair results significantly.

58 GEOSCIENCES↗

Environmental resistance of oxide tags fabricated on 304L stainless steel via nanosecond pulsed laser irradiation

Nanosecond pulsed laser irradiation was used to fabricate colored, mechanically robust oxide “tags” on 304L stainless steel. Immersion in simulated seawater solution, salt fog exposure, and anodic polarization in a 3.5% NaCl solution were employed to evaluate the environmental resistance of these oxide tags. Single layer oxides outside a narrow thickness range (~ 100–150 nm) are susceptible to dissolution in chloride containing environments. The 304L substrates immediately beneath the oxides corrode severely—attributed to Cr-depletion in the melt zone during laser processing. For the first time, multilayered oxides were fabricated with pulsed laser irradiation in an effort to expand the protective thickness range while also increasing the variety of film colors attainable in this range. Layered films grown using a laser scan rate of 475 mm/s are more resistant to both localized and general corrosion than oxides fabricated at 550 mm/s. Furthermore, in the absence of pre-processing to mitigate Cr-depletion, layered films can enhance environmental stability of the system.

54 ENVIRONMENTAL SCIENCES↗

Theoretical Calculation Guided Design of Single-Atom Catalysts toward Fast Kinetic and Long-Life Li–S Batteries

Lithium–sulfur (Li–S) batteries are enticing next-generation energy storage technologies due to their high theoretical energy density, environmental friendliness, and low cost. Yet, low conductivity of sulfur species, dissolution of polysulfides, poor conversion from sulfur reduction, and lithium sulfide (Li 2 S) oxidation reactions during discharge–charge processes hinder their practical applications. Herein, under the guidance of density functional theory calculations, we have successfully synthesized large-scale single atom vanadium catalysts seeded on graphene to achieve high sulfur content (80 wt % sulfur), fast kinetic (a capacity of 645 mAh g –1 at 3 C rate), and long-life Li–S batteries. Both forward (sulfur reduction) and reverse reactions (Li 2 S oxidation) are significantly improved by the single atom catalysts. This finding is confirmed by experimental results and consistent with theoretical calculations. The ability of single metal atoms to effectively trap the dissolved lithium polysulfides (LiPSs) and catalytically convert the LiPSs/Li 2 S during cycling significantly improved sulfur utilization, rate capability, and cycling life. Our work demonstrates an efficient design pathway for single atom catalysts and offers solutions for the development of high energy/power density Li–S batteries.

25 ENERGY STORAGE↗

Atomic steps on an ultraflat Si(111) surface upon sublimation

The kinetics of atomic steps on an ultraflat Si(111) surface is studied by in situ ultrahigh-vacuum reflection electron microscopy at temperatures of 1050–1350°C. For the first time it is experimentally shown that the rate of displacement of an atomic step during sublimation nonlinearly depends on the width of the adjacent terrace. It is established that the atomic mechanism of mass-transport processes at the surface at temperatures higher than 1200°C is controlled by nucleation and the diffusion of surface vacancies rather than of adsorbed Si atoms. The studies make it possible to estimate the activation energy of the dissolution of vacancies from the surface into the bulk of Si. The estimated activation energy is (4.3 ± 0.05) eV.

36 MATERIALS SCIENCE↗

Predictive modeling of CO2 sequestration in deep saline sandstone reservoirs: Impacts of geochemical kinetics

One idea for mitigating the increase in fossil-fuel generated CO{sub 2} in the atmosphere is to inject CO{sub 2} into subsurface saline sandstone reservoirs. To decide whether to try such sequestration at a globally significant scale will require the ability to predict the fate of injected CO{sub 2}. Thus, models are needed to predict the rates and extents of subsurface rock-water-gas interactions. Several reactive transport models for CO{sub 2} sequestration created in the last decade predicted sequestration in sandstone reservoirs of ~17 to ~90 kg CO{sub 2} m{sup -3|. To build confidence in such models, a baseline problem including rock + water chemistry is proposed as the basis for future modeling so that both the models and the parameterizations can be compared systematically. In addition, a reactive diffusion model is used to investigate the fate of injected supercritical CO{sub 2} fluid in the proposed baseline reservoir + brine system. In the baseline problem, injected CO{sub 2} is redistributed from the supercritical (SC) free phase by dissolution into pore brine and by formation of carbonates in the sandstone. The numerical transport model incorporates a full kinetic description of mineral-water reactions under the assumption that transport is by diffusion only. Sensitivity tests were also run to understand which mineral kinetics reactions are important for CO{sub 2} trapping. The diffusion transport model shows that for the first ~20 years after CO{sub 2} diffusion initiates, CO{sub 2} is mostly consumed by dissolution into the brine to form CO{sub 2,aq} (solubility trapping). From 20-200 years, both solubility and mineral trapping are important as calcite precipitation is driven by dissolution of oligoclase. From 200 to 1000 years, mineral trapping is the most important sequestration mechanism, as smectite dissolves and calcite precipitates. Beyond 2000 years, most trapping is due to formation of aqueous HCO{sub 3}{sup -}. Ninety-seven percent of the maximum CO{sub 2} sequestration, 34.5 kg CO{sub 2} per m{sup 3} of sandstone, is attained by 4000 years even though the system does not achieve chemical equilibrium until ~25,000 years. This maximum represents about 20% CO{sub 2} dissolved as CO{sub 2},aq, 50% dissolved as HCO{sub 3}{sup -}{sub ,aq}, and 30% precipitated as calcite. The extent of sequestration as HCO{sub 3}{sup -} at equilibrium can be calculated from equilibrium thermodynamics and is roughly equivalent to the amount of Na+ in the initial sandstone in a soluble mineral (here, oligoclase). Similarly, the extent of trapping in calcite is determined by the amount of Ca2+ in the initial oligoclase and smectite. Sensitivity analyses show that the rate of CO{sub 2} sequestration is sensitive to the mineral-water reaction kinetic constants between approximately 10 and 4000 years. The sensitivity of CO{sub 2} sequestration to the rate constants decreases in magnitude respectively from oligoclase to albite to smectite.

54 ENVIRONMENTAL SCIENCES↗

Flexible sulfur wires (Flex-SWs)—A new versatile platform for lithium-sulfur batteries

In this paper, a simple electrospinning methodology is described for generating novel fiber configurations of sulfur with the potential of yielding high performance sulfur electrodes for use in lithium-sulfur batteries. The unique fiber morphology derived by electrospinning has the capability of generating flexible sulfur yarns for the first time rendering them a highly attractive platform for small-scale mobile device applications such as textile-batteries. The electrospinning methodology reported herein also allows for the formation of a polymer-sulfur interface which acts as a physical barrier to liquid lithium electrolyte facilitating the reduction of polysulfide dissolution, a primary barrier to the progress of Li-S systems. Such flexible sulfur wire materials when converted into pellet sulfur electrodes, exhibit very stable capacities over 135 cycles with high areal capacities (~2.5 mAh cm -2 ). Finally, coating the electrodes with an inorganic lithium ion conductor coating results in further improvement of cycling behavior with electrodes of ~650 mAh g -1 capacity and an impressive low fade rate of ~0.003% fade cycle -1 demonstrating the promise of this unique platform.

25 ENERGY STORAGE↗

Reservoir scale reactive-transport modeling of a buoyancy-controlled CO 2 plume with impurities (SO 2 , NO 2 , O 2 )

We present that a demonstration project for the geological storage of CO 2 is currently being considered in the deep Precipice Sandstone formation of the Surat Basin, Queensland, Australia. Because of the presence of potential fresh water resources in this formation, a reservoir-scale two-dimensional reactive-transport model was developed to assess temporal and spatial changes in water quality imposed by co-injecting CO 2 with SO 2 , NO 2 , and O 2 at this location. The model shows that because the injection rate is relatively low (60,000 tons/year), flow is buoyancy-dominated and under these conditions the predicted CO 2 flow pattern is quite sensitive to fine-scale heterogeneities and the resolution of the numerical mesh. The model also shows that SO 2 and NO 2 readily partition into the aqueous phase in close vicinity of their injection point, lowering pH somewhat beyond the acidification from CO 2 dissolution. Only O 2 under redox disequilibrium conditions is modeled to persist in the CO 2 plume away from the injection point, however at sub-ppm levels. In conclusion, this modeling effort demonstrates acidification near the wellbore due to the preferential stripping of gas impurities, and accumulation of CO 2 around a lithostratigraphic boundary above the target formation, where relatively rapid mineral dissolution (muscovite, chlorite and calcite) and precipitation (ankerite, kaolinite and chalcedony) occur.

54 ENVIRONMENTAL SCIENCES↗

Heterogeneous Ni- and Cd-Bearing Ferrihydrite Precipitation and Recrystallization on Quartz under Acidic pH Condition

Ferrihydrite, as one of the most common naturally occurring iron oxides, can sequester toxic metals through co-precipitation. In this study, using grazing-incidence small-angle X-ray scattering, the heterogeneous precipitation of pure, Ni-, and Cd-bearing ferrihydrite on quartz was quantified in 0.1 mM Fe 3+ solutions in the absence and presence of 1 mM Ni 2+ or Cd 2+ (pH 3.8 ± 0.1). Under acidic condition, the limited hydrolysis of metal ions resulted in their small amounts of incorporation in ferrihydrite lattices (<0.1%), several orders of magnitude lower than those reported at neutral and alkaline pH conditions. The presence of Ni 2+ or Cd 2+ did not significantly affect the surface charges of either ferrihydrite pre-nucleation clusters (PNCs) or quartz surfaces. Therefore, with similar electrostatic interactions between PNCs and quartz, similar initial heterogeneous precipitation rates of pure and Ni- and Cd-bearing ferrihydrite on quartz were observed. Later on, continuous heterogeneous nucleation and growth of ferrihydrite nanoparticles resulted in their increased polydispersity, and the size-dependent solubility of ferrihydrite nanoparticles caused the Ostwald ripening process. The presence of Ni and Cd was found to retard the recrystallization of ferrihydrite, probably as a result of their structural incorporation, which could inhibit the dissolution of ferrihydrite. Furthermore, this study provided new kinetic and mechanistic insights for understanding the effects of metal ions on the heterogeneous precipitation and recrystallization processes of ferrihydrite nanoparticles on mineral surfaces, which can better predict the fate and transport of heavy metals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Role of aluminum as an oxygen-scavenger in zirconium based bulk metallic glasses

In order to investigate a way to diminish the impact of oxygen onto the critical cooling rate of Zr-based alloys, the bonding chemistry of the elements in Zr-Cu-Ni-Al-Nb-Si bulk metallic glasses with different oxygen contents is studied by x-ray photoelectron spectroscopy. Complementary undercooling experiments lead to continuous-cooling-transformation diagrams for the studied alloys. The experimental results demonstrate that Al not only acts as a scavenger for both absorbed and intrinsic oxygen but the dissolution of its oxide on atomic length scales refrains from heterogeneous nucleation. The combined effect is an enhancement of oxygen tolerance in the investigated alloy.

36 MATERIALS SCIENCE↗

Modifications of Carbonate Fracture Hydrodynamic Properties by CO 2 -Acidified Brine Flow

Acidic reactive flow in fractures is relevant in subsurface activities such as CO{sub 2} geological storage and hydraulic fracturing. Understanding reaction-induced changes in fracture hydrodynamic properties is essential for predicting subsurface flows such as leakage, injectability, and fluid production. In this study, x-ray computed tomography scans of a fractured carbonate caprock were used to create three dimensional reconstructions of the fracture before and after reaction with CO{sub 2}-acidified brine (Ellis et al., 2011, Greenhouse Gases: Sci. Technol., 1:248-260). As expected, mechanical apertures were found to increase substantially, doubling and even tripling in some places. However, the surface geometry evolved in complex ways including ‘comb-tooth’ structures created from preferential dissolution of calcite in transverse sedimentary bands, and the creation of degraded zones, i.e. porous calcite-depleted areas on reacted fracture surfaces. These geometric alterations resulted in increased fracture roughness, as measured by surface Z{sub 2} parameters and fractal dimensions D{sub f}. Computational fluid dynamics (CFD) simulations were conducted to quantify the changes in hydraulic aperture, fracture transmissivity and permeability. The results show that the effective hydraulic apertures are smaller than the mechanical apertures, and the changes in hydraulic apertures are nonlinear. Overestimation of flow rate by a factor of two or more would be introduced if fracture hydrodynamic properties were based on mechanical apertures, or if hydraulic aperture is assumed to change proportionally with mechanical aperture. The differences can be attributed, in part, to the increase in roughness after reaction, and is likely affected by contiguous transverse sedimentary features. Hydraulic apertures estimated by the 1D statistical model and 2D local cubic law (LCL) model are consistently larger than those calculated from the CFD simulations. In addition, a novel ternary segmentation method was devised to handle the degraded zones, allowing for a bounding analysis of the effects on hydraulic properties. We found that the degraded zones account for less than 15% of the fracture volume, but cover 70% to 80% of the fracture surface. When the degraded zones are treated as part of the fracture, the fracture transmissivities are two to four times larger because the fracture surfaces after reaction are not as rough as they would be if one considers the degraded zone as part of the rock. Therefore, while degraded zones created during geochemical reactions may not significantly increase mechanical aperture, this type of feature cannot be ignored and should be treated with prudence when predicting fracture hydrodynamic properties.

roughness↗

Multi-glass investigation of Stage III glass dissolution behavior from 22 to 90 °C triggered by the addition of zeolite phases

Evaluating the corrosion of glass waste forms for nuclear waste immobilization is a prime metric of their performance. Stage III behavior, the delayed acceleration of glass corrosion, remains the most potentially impactful aspect of glass corrosion behavior. Using the addition of various zeolite phases to trigger this effect, the properties of Stage III behavior were evaluated for three high-level waste glass compositions: SRL-202A, SON68, and AFCI. We demonstrate that Stage III behavior can occur at temperatures as low as 22°C, with rate acceleration observed at 90 and 70 °C for all studied glasses, and at 40 °C and 22 °C for two of the compositions (SRL-202A and SON68). Using an Arrhenius fit, the activation energy of the process was found to be highly uncertain, with values between 39 and 68 kJ·mol -1 . Stage III behavior was triggered for each of the glasses studied by the addition of each of the four zeolites studied (Na-P1, Na-P2, Analcime, and Chabazite). The rates of alteration during Stage III varied very little, from 0.0058 to 0.023 g·m -2 ·d -1 for the accelerated region immediately following zeolite addition. The acceleration was discovered to be transient, with the alteration rate decreasing and then accelerating again as the experiments proceeded. The solution composition was compared to the strong base/weak acid discriminator developed by Jantzen et al. and it was found that the addition of zeolites can overcome slightly non-optimal solution conditions for zeolite formation to trigger Stage III behavior.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Chemisorption of polysulfides through redox reactions with organic molecules for lithium–sulfur batteries

Lithium-sulfur battery possesses high energy density but suffers from severe capacity fading due to the dissolution of lithium polysulfides. Novel design and mechanisms to encapsulate lithium polysulfides are greatly desired by high-performance lithium-sulfur batteries towards practical applications. Herein, we report a strategy of utilizing anthraquinone, a natural abundant organic molecule, to suppress dissolution and diffusion of polysulfides species through redox reactions during cycling. The keto groups of anthraquinone play a critical role in forming strong Lewis acid-based chemical bonding. This mechanism leads to a long cycling stability of sulfur-based electrodes. With a high sulfur content of ~73%, a low capacity decay of 0.019% per cycle for 300 cycles and retention of 81.7% over 500 cycles at 0.5 C rate can be achieved. Here, this finding and understanding paves an alternative avenue for the future design of sulfur-based cathodes toward the practical application of lithium-sulfur batteries.

25 ENERGY STORAGE↗

Accelerated Leach Testing of Glass (ALTGLASS): II. Mineralization of hydrogels by leachate strong bases

The durability of high level nuclear waste glasses must be predicted on geological time scales. Waste glass surfaces form hydrogels when in contact with water for varying test durations. As the glass hydrogels age, some exhibit an undesirable resumption of dissolution at long times while others exhibit near steady-state dissolution, that is, nonresumption of dissolution. Resumption of dissolution is associated with the formation of zeolitic phases while nonresumption of dissolution is associated with the formation of clay minerals. Hydrogels with a stoichiometry close to that of imogolite, (Al 2 O 3 ·Si(OH) 4 ), with ferrihydrite (Fe 2 O 3 ·0.5H 2 O), have been shown to be associated with waste glasses that resume dissolution. Aluminosilicate hydrogels with a stoichiometry of allophane-hisingerite ((Al,Fe) 2 O 3 ·1.3-2Si(OH) 4 ) have been shown to be associated with waste glasses that exhibit near steady-state dissolution at long times. These phases are all amorphous and poorly crystalline and are also found on natural weathered basalt glasses. Interaction of these hydrogels with excess alkali and OH – (strong base) in the leachates, causes the Al 2 O 3 · n SiO 2 (where n=1-2) hydrogels to mineralize to zeolites. Excess alkali in the leachate is generated by alkali in the glass. As a result, preliminary rate-determining leach layer forming exchange reactions are hypothesized based on these findings.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The timescales of mineral redox reactions

Redox-reactive minerals can serve as electron donors or acceptors for abiotic reactants or microbial metabolic processes, and hence can play important roles in terrestrial and aquatic environments, particularly if their reaction rates are comparable to those of other biogeochemical processes. Under such circumstances, their reactions can control metal and contaminant bioavailability and change the permeability of soils and sediments. While the thermodynamic driving force for a mineral redox reaction is frequently a good predictor of relative rates of reaction, there are many examples in which kinetic factors limit reaction rate. Understanding the thermodynamic and kinetic aspects of mineral reaction rates, and their sensitivity to environmental conditions such as temperature or pH, is important for anticipating the biogeochemical evolution of natural environments subjected to change. Achieving this goal requires knowledge of the reaction pathway, the timescales of intermediate steps, and the lifetimes of metastable reaction states. Mineral redox reactions proceed through a combination of steps that can include electron and proton transfer, the breaking or formation of bonds, and mineral dissolution or phase transformation. The combination of conventional kinetics approaches, newly-developed ultrafast time-resolved methods and molecular simulation can provide elucidation of such complex reaction pathways. This chapter summarizes key concepts in mineral and interfacial redox reactions with illustrations from the rich geochemistry of iron and ironbearing minerals.

58 GEOSCIENCES↗

Geoscience Perspectives in Carbon Sequestration - Educational Training and Research Through Classroom, Field, and Laboratory Investigations

The most effective mechanism to limit CO 2 release from underground Geologic Carbon Sequestration (GCS) sites over multi-century time scales will be to convert the CO 2 into solid carbonate minerals. This report describes the results from four independent research investigations on carbonate mineralization: 1) Colloidal calcite particles forming in Maramec Spring, Missouri, provide a natural analog to evaluate reactions that may occur in a leaking GCS site. The calcite crystals form as a result of physiochemical changes that occur as the spring water rises from a depth of more than 190'. The resultant pressure decrease induces a loss of CO 2 from the water, rise in pH, lowering of the solubility of Ca 2+ and CO 3 2- , and calcite precipitation. Equilibrium modelling of the spring water resulted in a calculated undersaturated state with respect to calcite. The discontinuity between the observed occurrence of calcite and the model result predicting undersaturated conditions can be explained if bicarbonate ions (HCO 3 - ) are directly involved in precipitation process rather than just carbonate ions (CO 3 2- ). 2) Sedimentary rocks in the Oronto Group of the Midcontinent Rift (MCR) system contain an abundance of labile Ca-, Mg-, and Fe-silicate minerals that will neutralize carbonic acid and provide alkaline earth ions for carbonate mineralization. One of the challenges in using MCR rocks for GCS results from their low porosity and permeability. Oronto Group samples were reacted with both CO 2 -saturated deionized water at 90°C, and a mildly acidic leachant solution in flow-through core-flooding reactor vessels at room temperature. Resulting leachate solutions often exceeded the saturation limit for calcite. Carbonate crystals were also detected in as little as six days of reaction with Oronto Group rocks at 90oC, as well as experiments with forsterite-olivine and augite, both being common minerals this sequence. The Oronto Group samples have poor reservoir rock characteristics, none ever exceeded a permeability value of 2.0 mD even after extensive dissolution of calcite cement during the experiments. The overlying Bayfield Group – Jacobsville Formation sandstones averaged 13.4 ± 4.3% porosity and a single sample tested by core-flooding revealed a permeability of ~340 mD. The high porosity-permeability characteristics of these sandstones will allow them to be used for GCS as a continuous aquifer unit with the overlying Mt. Simon Formation. 3) Anaerobic sulfate reducing bacteria (SRB) can enhance the conversion rate of CO 2 into solid minerals and thereby improve long-term storage. SRB accelerated carbonate mineralization reactions between pCO 2 values of 0.0059 and 14.7 psi. Hydrogen, lactate and formate served as suitable electron donors for SRB metabolism. The use of a 13 CO 2 spiked gas source also produced carbonate minerals with ~53% of the carbon being derived from the gas phase. The sulfate reducing activity of the microbial community was limited, however, at 20 psi pCO 2 and carbonate mineralization did not occur. Inhibition of bacterial metabolism may have resulted from the acidic conditions or CO 2 toxicity. 4) Microbialite communities forming in the high turbidity and hypersaline water of Storrs’ Lake, San Salvador Island, The Bahamas, were investigated for their distribution, mineralogy and microbial diversity. Molecular analysis of the organic mats on the microbialites indicate only a trace amount of cyanobacteria, while anaerobic and photosynthetic non-sulfur bacteria of the phyla Chloroflexi and purple sulfur bacteria of class Gammaproteobacteria were abundant.

54 ENVIRONMENTAL SCIENCES↗