Model for Humidity-Mediated Diffusion on Aluminum Surfaces and Its Role in Accelerating Atmospheric Aluminum Corrosion.

Bare aluminum metal surfaces are highly reactive, which leads to the spontaneous formation of a protective oxide surface layer. Because many subsequent corrosive processes are mediated by water, the structure and dynamics of water at the oxide interface are anticipated to influence corrosion kinetics. Using molecular dynamics simulations with a reactive force field, we model the behavior of aqueous aluminum metal ions in water adsorbed onto aluminum oxide surfaces across a range of ion concentrations and water film thicknesses corresponding to increasing relative humidity. We find that the structure and diffusivity of both the water and the metal ions depend strongly on the humidity of the environment and the relative height within the adsorbed water film. Aqueous aluminum ion diffusion rates in water films corresponding to a typical indoor relative humidity of 30% are found to be more than 2 orders of magnitude slower than self-diffusion of water in the bulk limit. Connections between metal ion diffusivity and corrosion reaction kinetics are assessed parametrically with a reductionist model based on a 1D continuum reaction-diffusion equation. Our results highlight the importance of incorporating the properties specific to interfacial water in predictive models of aluminum corrosion.

Real Time 3D Observations of Portland Cement Carbonation at CO2 Storage Conditions.

Depleted oil reservoirs are considered a viable solution to the global challenge of CO2 storage. A key concern is whether the wells can be suitably sealed with cement to hinder the escape of CO2. Under reservoir conditions, CO2 is in its supercritical state, and the high pressures and temperatures involved make real-time microscopic observations of cement degradation experimentally challenging. Here, we present an in situ 3D dynamic X-ray micro computed tomography (µ-CT) study of well cement carbonation at realistic reservoir stress, pore-pressure, and temperature conditions. The high-resolution time-lapse 3D images allow monitoring the progress of reaction fronts in Portland cement, including density changes, sample deformation, and mineral precipitation and dissolution. By switching between flow and nonflow conditions of CO2-saturated water through cement, we were able to delineate regimes dominated by calcium carbonate precipitation and dissolution. For the first time, we demonstrate experimentally the impact of the flow history on CO2 leakage risk for cement plugging. In-situ µ-CT experiments combined with geochemical modeling provide unique insight into the interactions between CO2 and cement, potentially helping in assessing the risks of CO2 storage in geological reservoirs.

Impact of Chemical and Mechanical Processes on Leakage from Damaged Wells in CO2 Storage Sites.

The perceived risk of CO2 leakage through wells has been considered a potential limitation to commercial scale deployment of geologic CO2 storage. However, chemical and mechanical alteration of cement can reduce the permeability of leakage pathways. We conducted 100s of simulations spanning realistic operating conditions and well-damage characteristics to understand (1) under what conditions and time frames do fractures seal and (2) for fractures that do not seal, how quickly and to what extent is the permeability reduced. For the conditions simulated, fractures with apertures in the tens of microns seal while those greater than hundreds of microns may exhibit long-term leakage. Fractures with apertures between 10 and 500 µm took a few days to a couple of years to seal. For non-sealing fractures mechanical deformation of altered asperities can rapidly reduce permeability. A sealing criterion was developed to relate fracture aperture with the cemented length required for self-sealing. Longer cemented intervals can seal large fractures; however, they take longer to seal and leak larger volumes before sealing. While the results presented here are subject to uncertainties, the manuscript provides a framework in which a model can be used to quantitatively answer questions regarding well integrity to facilitate decision making.

Influence of Chemical, Mechanical, and Transport Processes on Wellbore Leakage from Geologic CO2 Storage Reservoirs.

Wells are considered to be high-risk pathways for fluid leakage from geologic CO2 storage reservoirs, because breaches in this engineered system have the potential to connect the reservoir to groundwater resources and the atmosphere. Given these concerns, a few studies have assessed leakage risk by evaluating regulatory records, often self-reported, documenting leakage in gas fields. Leakage is thought to be governed largely by initial well-construction quality and the method of well abandonment. The geologic carbon storage community has raised further concerns because acidic fluids in the CO2 storage reservoir, alkaline cement meant to isolate the reservoir fluids from the overlying strata, and steel casings in wells are inherently reactive systems. This is of particular concern for storage of CO2 in depleted oil and gas reservoirs with numerous legacy wells engineered to variable standards. Research suggests that leakage risks are not as great as initially perceived because chemical and mechanical alteration of cement has the capacity to seal damaged zones. Our work centers on defining the coupled chemical and mechanical processes governing flow in damaged zones in wells. We have developed process-based models, constrained by experiments, to better understand and forecast leakage risk. Leakage pathways can be sealed by precipitation of carbonate minerals in the fractures and deformation of the reacted cement. High reactivity of cement hydroxides releases excess calcium that can precipitate as carbonate solids in the fracture network under low brine flow rates. If the flow is fast, then the brine remains undersaturated with respect to the solubility of calcium carbonate minerals, and zones depleted in calcium hydroxides, enriched in calcium carbonate precipitates, and made of amorphous silicates leached of original cement minerals are formed. Under confining pressure, the reacted cement is compressed, which reduces permeability and lowers leakage risks. The broader context of this paper is to use our experimentally calibrated chemical, mechanical, and transport model to illustrate when, where, and in what conditions fracture pathways seal in CO2 storage wells, to reduce their risk to groundwater resources. We do this by defining the amount of cement and the time required to effectively seal the leakage pathways associated with peak and postinjection overpressures, within the context of oil and gas industry standards for leak detection, mitigation, and repairs. Our simulations suggest that for many damage scenarios chemical and mechanical processes lower leakage risk by reducing or sealing fracture pathways. Leakage risk would remain high in wells with a large amount of damage, modeled here as wide fracture apertures, where fast flowing fluids are too dilute for carbonate precipitation and subsurface stress does not compress the altered cement. Fracture sealing is more likely as reservoir pressures decrease during the postinjection phase where lower fluxes aid chemical alteration and mechanical deformation of cement. Our results hold promise for the development of mitigation framework to avoid impacting groundwater resources above any geologic CO2 storage reservoir by correlating operational pressures and barrier lengths.

Determination of diffusion profiles in altered wellbore cement using X-ray computed tomography methods.

The development of accurate, predictive models for use in determining wellbore integrity requires detailed information about the chemical and mechanical changes occurring in hardened Portland cements. X-ray computed tomography (XRCT) provides a method that can nondestructively probe these changes in three dimensions. Here, we describe a method for extracting subvoxel mineralogical and chemical information from synchrotron XRCT images by combining advanced image segmentation with geochemical models of cement alteration. The method relies on determining "effective linear activity coefficients" (ELAC) for the white light source to generate calibration curves that relate the image grayscales to material composition. The resulting data set supports the modeling of cement alteration by CO2-rich brine with discrete increases in calcium concentration at reaction boundaries. The results of these XRCT analyses can be used to further improve coupled geochemical and mechanical models of cement alteration in the wellbore environment.

Direct electrolytic dissolution of silicate minerals for air CO2 mitigation and carbon-negative H2 production.

We experimentally demonstrate the direct coupling of silicate mineral dissolution with saline water electrolysis and H2 production to effect significant air CO2 absorption, chemical conversion, and storage in solution. In particular, we observed as much as a 10(5)-fold increase in OH(-) concentration (pH increase of up to 5.3 units) relative to experimental controls following the electrolysis of 0.25 M Na2SO4 solutions when the anode was encased in powdered silicate mineral, either wollastonite or an ultramafic mineral. After electrolysis, full equilibration of the alkalized solution with air led to a significant pH reduction and as much as a 45-fold increase in dissolved inorganic carbon concentration. This demonstrated significant spontaneous air CO2 capture, chemical conversion, and storage as a bicarbonate, predominantly as NaHCO3. The excess OH(-) initially formed in these experiments apparently resulted via neutralization of the anolyte acid, H2SO4, by reaction with the base mineral silicate at the anode, producing mineral sulfate and silica. This allowed the NaOH, normally generated at the cathode, to go unneutralized and to accumulate in the bulk electrolyte, ultimately reacting with atmospheric CO2 to form dissolved bicarbonate. Using nongrid or nonpeak renewable electricity, optimized systems at large scale might allow relatively high-capacity, energy-efficient (<300 kJ/mol of CO2 captured), and inexpensive (<$100 per tonne of CO2 mitigated) removal of excess air CO2 with production of carbon-negative H2. Furthermore, when added to the ocean, the produced hydroxide and/or (bi)carbonate could be useful in reducing sea-to-air CO2 emissions and in neutralizing or offsetting the effects of ongoing ocean acidification.

Fracture-scale model of immiscible fluid flow.

We present a method for modeling immiscible fluid flow in narrow fractures. The method combines a parallel-plate flow model with a recoloration approach adapted from multiple-component lattice-Boltzmann methods. The resulting numerical method is straightforward to implement and accurately reproduces the relevant fluid behavior. To demonstrate the method, single-droplet simulations are compared to analytical solutions that isolate the contributions from the in-plane and normal curvature. Simulations reproducing capillary forces inside a widening aperture are also presented. Excellent agreement is found in all cases considered. Finally, the method's ability to model fracture flow is demonstrated by deriving relative permeability curves for flow through a heterogeneous aperture created between two fractal surfaces.

Chemical and mechanical properties of wellbore cement altered by CO2-rich brine using a multianalytical approach.

Defining chemical and mechanical alteration of wellbore cement by CO(2)-rich brines is important for predicting the long-term integrity of wellbores in geologic CO(2) environments. We reacted CO(2)-rich brines along a cement-caprock boundary at 60 °C and pCO(2) = 3 MPa using flow-through experiments. The results show that distinct reaction zones form in response to reactions with the brine over the 8-day experiment. Detailed characterization of the crystalline and amorphous phases, and the solution chemistry show that the zones can be modeled as preferential portlandite dissolution in the depleted layer, concurrent calcium silicate hydrate (CSH) alteration to an amorphous zeolite and Ca-carbonate precipitation in the carbonate layer, and carbonate dissolution in the amorphous layer. Chemical reaction altered the mechanical properties of the core lowering the average Young's moduli in the depleted, carbonate, and amorphous layers to approximately 75, 64, and 34% of the unaltered cement, respectively. The decreased elastic modulus of the altered cement reflects an increase in pore space through mineral dissolution and different moduli of the reaction products.

Evaporite caprock integrity: an experimental study of reactive mineralogy and pore-scale heterogeneity during brine-CO2 exposure.

We present characterization and geochemical data from a core-flooding experiment on a sample from the Three Fingers evaporite unit forming the lower extent of caprock at the Weyburn-Midale reservoir, Canada. This low-permeability sample was characterized in detail using X-ray computed microtomography before and after exposure to CO(2)-acidified brine, allowing mineral phase and voidspace distributions to be quantified in three dimensions. Solution chemistry indicated that CO(2)-acidified brine preferentially dissolved dolomite until saturation was attained, while anhydrite remained unreactive. Dolomite dissolution contributed to increases in bulk permeability through the formation of a localized channel, guided by microfractures as well as porosity and reactive phase distributions aligned with depositional bedding. An indirect effect of carbonate mineral reactivity with CO(2)-acidified solution is voidspace generation through physical transport of anhydrite freed from the rock matrix following dissolution of dolomite. The development of high permeability fast pathways in this experiment highlights the role of carbonate content and potential fracture orientations in evaporite caprock formations considered for both geologic carbon sequestration and CO(2)-enhanced oil recovery operations.

Reactivity of Mount Simon sandstone and the Eau Claire shale under CO2 storage conditions.

The Mount Simon sandstone and Eau Claire shale formations are target storage and cap rock formations for the Illinois Basin-Decatur Geologic Carbon Sequestration Project. We reacted rock samples with brine and supercritical CO(2) at 51 °C and 19.5 MPa to access the reactivity of these formations at storage conditions and to address the applicability of using published kinetic and thermodynamic constants to predict geochemical alteration that may occur during storage by quantifying parameter uncertainty against experimental data. Incongruent dissolution of iron-rich clays and formation of secondary clays and amorphous silica will dominate geochemical alterations at this CO(2) storage site in CO(2)-rich brines. The surrogate iron-rich clay in the model required significant adjustments to its thermodynamic constants and inclusion of incongruent reaction terms to capture the change in solution composition under acid CO(2) conditions. This result emphasizes the need for experiments that constrain the conceptual geochemical model, calibrate mean parameter values, and quantify parameter uncertainty in reactive-transport simulations that will be used to estimate long-term CO(2) trapping mechanisms and changes in porosity and permeability.

Probing the surface structure of divalent transition metals using surface specific solid-state NMR spectroscopy.

Environmental and geochemical systems containing paramagnetic species could benefit by using nuclear magnetic resonance (NMR) spectroscopy due to the sensitivity of the spectral response to small amounts paramagnetic interactions. In this study, we apply commonly used solid-state NMR spectroscopic methods combined with chemometrics analysis to probe sorption behavior of the paramagnetic cations Cu(2+) and Ni(2+)at the amorphous silica surface. We exploit the unique properties of paramagnets to derive meaningful structural information in these systems at low, environmentally relevant cation surface loadings by comparing the NMR response of sorption samples to paramagnetic free samples. These data suggest that a simple sorption model where the cation sorbs as inner sphere complexes at negatively charged, deprotonated silanol sites is appropriate. These results help constrain sorption models that are used to describe metal fate and transport.

Experimental Study of Cement - Sandstone/Shale - Brine - CO2 Interactions.

BACKGROUND: Reactive-transport simulation is a tool that is being used to estimate long-term trapping of CO2, and wellbore and cap rock integrity for geologic CO2 storage. We reacted end member components of a heterolithic sandstone and shale unit that forms the upper section of the In Salah Gas Project carbon storage reservoir in Krechba, Algeria with supercritical CO2, brine, and with/without cement at reservoir conditions to develop experimentally constrained geochemical models for use in reactive transport simulations. RESULTS: We observe marked changes in solution composition when CO2 reacted with cement, sandstone, and shale components at reservoir conditions. The geochemical model for the reaction of sandstone and shale with CO2 and brine is a simple one in which albite, chlorite, illite and carbonate minerals partially dissolve and boehmite, smectite, and amorphous silica precipitate. The geochemical model for the wellbore environment is also fairly simple, in which alkaline cements and rock react with CO2-rich brines to form an Fe containing calcite, amorphous silica, smectite and boehmite or amorphous Al(OH)3. CONCLUSIONS: Our research shows that relatively simple geochemical models can describe the dominant reactions that are likely to occur when CO2 is stored in deep saline aquifers sealed with overlying shale cap rocks, as well as the dominant reactions for cement carbonation at the wellbore interface.

Water challenges for geologic carbon capture and sequestration.

Carbon capture and sequestration (CCS) has been proposed as a means to dramatically reduce greenhouse gas emissions with the continued use of fossil fuels. For geologic sequestration, the carbon dioxide is captured from large point sources (e.g., power plants or other industrial sources), transported to the injection site and injected into deep geological formations for storage. This will produce new water challenges, such as the amount of water used in energy resource development and utilization and the "capture penalty" for water use. At depth, brine displacement within formations, storage reservoir pressure increases resulting from injection, and leakage are potential concerns. Potential impacts range from increasing water demand for capture to contamination of groundwater through leakage or brine displacement. Understanding these potential impacts and the conditions under which they arise informs the design and implementation of appropriate monitoring and controls, important both for assurance of environmental safety and for accounting purposes. Potential benefits also exist, such as co-production and treatment of water to both offset reservoir pressure increase and to provide local water for beneficial use.

Transformation of meta-stable calcium silicate hydrates to tobermorite: reaction kinetics and molecular structure from XRD and NMR spectroscopy.

Understanding the integrity of well-bore systems that are lined with Portland-based cements is critical to the successful storage of sequestered CO2 in gas and oil reservoirs. As a first step, we investigate reaction rates and mechanistic pathways for cement mineral growth in the absence of CO2 by coupling water chemistry with XRD and NMR spectroscopic data. We find that semi-crystalline calcium (alumino-)silicate hydrate (Al-CSH) forms as a precursor solid to the cement mineral tobermorite. Rate constants for tobermorite growth were found to be k = 0.6 (+/- 0.1) x 10(-5) s(-1) for a solution:solid of 10:1 and 1.6 (+/- 0.8) x 10(-4) s(-1) for a solution:solid of 5:1 (batch mode; T = 150 degrees C). This data indicates that reaction rates for tobermorite growth are faster when the solution volume is reduced by half, suggesting that rates are dependent on solution saturation and that the Gibbs free energy is the reaction driver. However, calculated solution saturation indexes for Al-CSH and tobermorite differ by less than one log unit, which is within the measured uncertainty. Based on this data, we consider both heterogeneous nucleation as the thermodynamic driver and internal restructuring as possible mechanistic pathways for growth. We also use NMR spectroscopy to characterize the site symmetry and bonding environment of Al and Si in a reacted tobermorite sample. We find two [4]Al coordination structures at delta iso = 59.9 ppm and 66.3 ppm with quadrupolar product parameters (PQ) of 0.21 MHz and 0.10 MHz (+/- 0.08) from 27Al 3Q-MAS NMR and speculate on the Al occupancy of framework sites by probing the protonation environment of Al metal centers using 27Al{1H}CP-MAS NMR.

Surface complexation model for strontium sorption to amorphous silica and goethite.

Strontium sorption to amorphous silica and goethite was measured as a function of pH and dissolved strontium and carbonate concentrations at 25 degrees C. Strontium sorption gradually increases from 0 to 100% from pH 6 to 10 for both phases and requires multiple outer-sphere surface complexes to fit the data. All data are modeled using the triple layer model and the site-occupancy standard state; unless stated otherwise all strontium complexes are mononuclear. Strontium sorption to amorphous silica in the presence and absence of dissolved carbonate can be fit with tetradentate Sr2+ and SrOH+ complexes on the beta-plane and a monodentate Sr2+complex on the diffuse plane to account for strontium sorption at low ionic strength. Strontium sorption to goethite in the absence of dissolved carbonate can be fit with monodentate and tetradentate SrOH+ complexes and a tetradentate binuclear Sr2+ species on the beta-plane. The binuclear complex is needed to account for enhanced sorption at hgh strontium surface loadings. In the presence of dissolved carbonate additional monodentate Sr2+ and SrOH+ carbonate surface complexes on the beta-plane are needed to fit strontium sorption to goethite. Modeling strontium sorption as outer-sphere complexes is consistent with quantitative analysis of extended X-ray absorption fine structure (EXAFS) on selected sorption samples that show a single first shell of oxygen atoms around strontium indicating hydrated surface complexes at the amorphous silica and goethite surfaces. Strontium surface complexation equilibrium constants determined in this study combined with other alkaline earth surface complexation constants are used to recalibrate a predictive model based on Born solvation and crystal-chemistry theory. The model is accurate to about 0.7 log K units. More studies are needed to determine the dependence of alkaline earth sorption on ionic strength and dissolved carbonate and sulfate concentrations for the development of a robust surface complexation database to estimate alkaline earth sorption in the environment.

Effect of solution saturation state and temperature on diopside dissolution.

Steady-state dissolution rates of diopside are measured as a function of solution saturation state using a titanium flow-through reactor at pH 7.5 and temperature ranging from 125 to 175 degrees C. Diopside dissolved stoichiometrically under all experimental conditions and rates were not dependent on sample history. At each temperature, rates continuously decreased by two orders of magnitude as equilibrium was approached and did not exhibit a dissolution plateau of constant rates at high degrees of undersaturation. The variation of diopside dissolution rates with solution saturation can be described equally well with a ion exchange model based on transition state theory or pit nucleation model based on crystal growth/dissolution theory from 125 to 175 degrees C. At 175 degrees C, both models over predict dissolution rates by two orders of magnitude indicating that a secondary phase precipitated in the experiments. The ion exchange model assumes the formation of a Si-rich, Mg-deficient precursor complex. Lack of dependence of rates on steady-state aqueous calcium concentration supports the formation of such a complex, which is formed by exchange of protons for magnesium ions at the surface. Fit to the experimental data yields [Formula in text] where the Mg-H exchange coefficient, n = 1.39, the apparent activation energy, Ea = 332 kJ mol(-1), and the apparent rate constant, k = 10(41.2) mol diopside cm(-2) s(-1). Fits to the data with the pit nucleation model suggest that diopside dissolution proceeds through retreat of steps developed by nucleation of pits created homogeneously at the mineral surface or at defect sites, where homogeneous nucleation occurs at lower degrees of saturation than defect-assisted nucleation. Rate expressions for each mechanism (i) were fit to [Formula in text] where the step edge energy (alpha) for homogeneously nucleated pits were higher (275 to 65 mJ m(-2)) than the pits nucleated at defects (39 to 65 mJ m(-2)) and the activation energy associated with the temperature dependence of site density and the kinetic coefficient for homogeneously nucleated pits (E b-homogeneous = 2.59 x 10(-16) mJ K(-1)) were lower than the pits nucleated at defects (E b-defect assisted = 8.44 x 10(-16) mJ K(-1)).