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Chemomechanical weakening of layered phyllosilicate muscovite mica was studied as a function of chemical environment via in situ liquid-nanoindentation under four conditions (dry, deionized water, and two NaCl solutions of different pH). While traditional indentation analyses of layered materials with extreme mechanical anisotropy have been limited due to displacement bursts (pop-ins), here the bursts were used as proxies for delamination, fracture, and spalling events. Since displacement bursts during an indent represent a stochastic process, 120 indents were conducted for each condition to generate statistically significant amounts of data. In total, over 9000 bursts were assessed using a load–displacement threshold criterion, classifying this as a high-throughput nanoscale fracture technique. For each burst, initiation load, initiation displacement, plastic zone volume at initiation, and energy dissipation were analyzed. A power-law relationship between the burst load and burst energy was noted which separated the bursts into two continuous distributions: (1) bursts due only to the mechanics of the indent and (2) bursts due to both the mechanics of the indent and the environment. By using a cumulative probability distribution, it was found that the NaCl solutions decreased the minimum plastic zone volume necessary to initiate a displacement burst by an order of magnitude relative to the dry condition. Finally, the underlying mechanisms explaining the trends in initiation volume as a function of environment were discussed, with a focus on the chemomechanical degradation processes via chemical attack and cation exchange.

We present a combined molecular dynamics (MD) simulation and X-ray absorption fine structure (XAFS) spectroscopic investigation of aqueous iron adsorption on nanoconfined amorphous silica surfaces. The simulation models examine the effects of pore size, pH (surface charge), iron valency, and counter-ion (chloride or hydroxide). The simulation methods were validated by comparing the coordination environment of adsorbed iron with coordination numbers and bond lengths derived from XAFS. In the MD models, nanoconfinement effects on local iron coordination were investigated by comparing results for unconfined silica surfaces and in confined domains within 2 nm, 4 nm, and 8 nm pores. Experimentally, coordination environments of iron adsorbed onto mesoporous silica with 4 nm and 8 nm pores at pH 7.5 were investigated. The effect of pH in the MD models was included by simulating Fe(II) adsorption onto negatively charged SiO2 surfaces and Fe(III) adsorption on neutral surfaces. The simulation results show that iron adsorption depends significantly on silica surface charge, as expected based on electrostatic interactions. Adsorption on a negatively charged surface is an order of magnitude greater than on the neutral surface, and simulated surface coverages are consistent with experimental results. Pore size effects from the MD simulations were most notable in the adsorption of Fe(II) at deprotonated surface sites (SiO−), but adsorption trends varied with concentration and aqueous Fe speciation. The coordination environment of adsorbed iron varied significantly with the type of anion. Considerable ion pairing with hydroxide anions led to the formation of oligomeric surface complexes and aqueous species, resulting in larger iron hydroxide clusters at higher surface loadings.

A quarter of Earth's land surface is covered by porous sedimentary silicate rocks, so silica–water interfaces are critical to the fate and transport of chemical species on a global-scale. However, while the physiochemical properties of unconfined silica–water interfaces are understood reasonably well, these properties have proven to be unpredictable when the interface is confined in nanometer-scale pores within sedimentary rocks. For example, the existing theories struggle to quantitatively predict how the energetics of adsorption reactions and the coordination environment of adsorbed species shift due to nanoconfinement of an interface. Here, we utilized gradual and known variations in the properties of trivalent lanthanide ions to decipher the chemical interactions that cause the nanoconfinement effects on chemistry at the silica–water interfaces. We discovered that the lanthanide's free energy of hydration (ΔGhydr) is a descriptor that can be used to predict the extent to which nanoconfinement will change the thermodynamics and products of interfacial reactions. We show that nanoconfinement promotes inner-sphere complexation between lanthanides and silica surface, as well as the formation of polymeric surface species. In nanoconfined domains lanthanide's ΔGhydr becomes less negative, reducing the energy required to dehydrate the ion during the formation of an inner-sphere surface complex. These nanoconfinement effects on chemistry become more pronounced for ions with lower hydration free energies.

Spatial confinement is prevalent in sedimentary rocks and can lead to changes in the chemical behavior at mineral–water interfaces. This includes both deviations in the physico-chemical properties of confined water, when compared to the bulk liquid phase, and subsequent alterations in adsorption chemistry of ions inside nano-scale mineral pores. Here we document contrasting adsorption mechanisms and differences in local coordination environments of copper (Cu2+), depending on whether the ion is adsorbed on non-porous silica surfaces, versus inside 8 nm and 4 nm pores in silica. X-ray absorption spectroscopy, flow micro-calorimetry, and batch adsorption methods together with molecular modeling are used to thoroughly describe the dependence of these adsorption processes on the pore size. We show that confinement within silica pores promotes Cu–Cu interactions and increases the formation of Cu–Cu polynuclear surface complexes. We also demonstrate that the mechanism of Cu2+ adsorption on non-porous versus porous silica is vastly different. The adsorption of Cu2+ on non-porous silica is an endothermic process, whereby Cu2+ undergoes dehydration prior to surface complexation. In contrast, adsorption within nano-scale pores is preceded by only partial dehydration, and significant formation of Cu–Cu polynuclear complexes, which leads to an overall exothermic signal. Interfacial confinement leads to dramatic changes in the adsorption mechanism and speciation, which in turn controls the fate and transport of chemical species in natural environments.

Reactions at solid-water interfaces play a foundational role in water treatment systems, catalysis, chemical separations, and in predicting chemical fate and transport in the environment. Over the last century, experimental measurements and computational models have made tremendous progress in capturing reactions at solid surfaces. The interfacial reactivity of a solid surface, however, can change dramatically and unexpectedly when it is confined to the nanoscale. Nanoconfinement can arise in different geometries such as pores/cages (3-D confinement), channels (2-D confinement) and slits (1-D confinement). Therefore, measurements on unconfined surfaces, and molecular models parameterized based on these measurements, fail to capture chemical behaviors under nanoconfinement. This review evaluates recent experimental and theoretical advances, with a focus on adsorption at solid-water interfaces. We review how nanoconfinement alters the physico-chemical properties of water, and how the structure and dynamics of nanoconfined water dictate energetics, pathways, and products of adsorption in nanopores. The implications of these findings and future research directions are discussed., Comment: Manuscript accepted for publication Annu. Rev. Phys. Chem (2023)

The lanthanide elements have well-documented similarities in their chemical behavior, which makes the valuable trivalent lanthanide cations (Ln(III)) particularly difficult to separate from each other in water. In this work, we apply ab initio molecular dynamics simulations to compare the free energies (Delta G(ads)) associated with the adsorption of lanthanide cations to silica surfaces at a pH condition where SiO- groups are present. The predicted Delta G(ads) for lutetium (Lu(III)) and europium (Eu(III)) are similar within statistical uncertainties; this is in qualitative agreement with our batch adsorption measurements on silica. This finding is remarkable because the two cations exhibit hydration free energies (Delta G(hyd}) that differ by >2 eV, different hydration numbers, and different hydrolysis behavior far from silica surfaces. We observe that the similarity in Lu(III) and Eu(III) Delta G(ads) is the result of a delicate cancellation between the difference in Eu(III) and Lu(III) hydration (Delta G(hyd})), and their difference in binding energies to silica. We propose that disrupting this cancellation at the two end points, either for adsorbed or completely desorbed lanthanides (e.g., via nanoconfinment or mixed solvents), will lead to effective Ln separation., 21 pages, 6 figures

Understanding lead (Pb) and antimony (Sb) speciation associated with the weathering of bullets at shooting ranges is essential for identifying species migration potential to local watersheds and for assessing the overall toxicity of shooting range soils. In the present study, we fired 2000 5.56 mm bullets into newly constructed and instrumented target berms composed of well-characterized test soils (sand, sandy loam, loamy sand, silt loam) and collected berm pore water runoff and soil samples over five summers (2011 to 2015). We tracked the chemical transformations of Pb and Sb released during bullet weathering as a function of time and soil properties. During 2014 summer, an amendment of ferrous chloride (FeCl2) with a calcium carbonate (CaCO3) buffer was added to a subset of the berms of each soil type to test this remediation strategy. Bulk speciation analysis coupled with micro-scale spectroscopic methods show that both Sb(III) and Sb(V) species are present in soil solution depending on the soil matrix type, but Sb(III) was not observed after 9 months of weathering. In general, Sb was found to be more mobile than Pb, attributable to the relatively low solubility of the dominant Pb phases present in the crust forming around bullet fragments and within soil. The oxidation of Pb(0) resulted in a mixture of lead oxide, lead carbonate, and lead sorbed onto iron(III) oxides. We found a higher degree of metal(loid) mobilization (higher dissolved metal concentrations) in the berms made from the sandy soils. In contrast, silt loam soil was found to be more effective at immobilizing metal(loid)s. Furthermore, we observed that an iron-oxide type amendment may be effective at further reducing Pb and Sb runoff. Results from this study provide insight into the fate and transport of metal(loid)s within small arms target ranges and address a potential method for metal(loid) immobilization.

Being the fourth most abundant element in the Earth's crust, iron (Fe) is a key player in myriad biogeochemical processes. Iron that resides in the structures of nano- to micron-scale clay mineral particles undergoes cycling between Fe(II) and Fe(III). This iron comprises a large redox-active pool in surface environments, controlling the fate and transport of nutrients and contaminants. The mechanism of electron transfer involving this iron species is poorly understood. We observe that Fe(III) in clay minerals does not oxidize arsenic As(III), unless a minor amount of Fe(II) is introduced into the predominantly-Fe(III) structure. These “activated” clay minerals are redox-active both in the presence and absence of oxygen. In the presence of oxygen, Fe(II) catalyzes the production of reactive oxygen species; however, the oxidation pathway in the absence of oxygen is unknown. Here we show that under oxygen-free conditions, the redox-active species in clay minerals is FeII–O–FeIII moieties at the edge sites. We used in situ and ex situ spectroscopic methods, including X-ray absorption, Mossbauer, and diffuse reflectance spectroscopies, as well as ab initio calculations. Our ab initio calculations show that desorption of water from an FeII–O–FeIII site in clay mineral requires less energy, compared to a fully-oxidized FeIII–O–FeIII site. We propose that this lower barrier for the desorption of water increases the apparent kinetics of redox reactions on clay mineral surfaces.

Water in nano-scale confining environments is a key element in many biological, material, and geological systems. The structure and dynamics of the liquid can be dramatically modified under these conditions. Probing these changes can be challenging, but vibrational spectroscopy has emerged as a powerful tool for investigating their behavior. A critical, evolving component of this approach is a detailed understanding of the connection between spectroscopic features and molecular-level details. In this paper, this issue is addressed by using molecular dynamics simulations to simulate the linear infrared (IR) and Raman spectra for isotopically dilute HOD in D2O confined in hydroxylated amorphous silica slit pores. The effect of slit-pore width and hydroxyl density on the silica surface on the vibrational spectra is also investigated. The primary effect of confinement is a blueshift in the frequency of OH groups donating a hydrogen bond to the silica surface. This appears as a slight shift in the total (measurable) spectra but is clearly seen in the distance-based IR and Raman spectra. Analysis indicates that these changes upon confinement are associated with the weaker hydrogen-bond accepting properties of silica oxygens compared to water molecules.

Lanthanide elements have well-documented similarities in their chemical behavior, which make the valuable trivalent lanthanide cations (Ln3+) particularly difficult to separate from each other in water. In this work, we apply ab initio molecular dynamics simulations to compare the free energies (ΔGads) associated with the adsorption of lanthanide cations to silica surfaces at a pH condition where SiO- groups are present. The predicted ΔGads for lutetium (Lu3+) and europium (Eu3+) are similar within statistical uncertainties; this is in qualitative agreement with our batch adsorption measurements on silica. This finding is remarkable because the two cations exhibit hydration free energies (ΔGhyd) that differ by2 eV, different hydration numbers, and different hydrolysis behavior far from silica surfaces. We observe that the similarity in Lu3+ and Eu3+ ΔGads is the result of a delicate cancellation between the difference in Eu3+ and Lu3+ hydration (ΔGhyd), and their difference in binding energies to silica. We propose that disrupting this cancellation at the two end points, either for adsorbed or completely desorbed lanthanides (e.g., via nanoconfinment or mixed solvents), will lead to effective Ln3+ separation.

Coastal erosion rates are increasing along the Alaskan Beaufort Sea coast due to increases in wave action, the increasing length of the ice-free season, and warming permafrost. These eroding permafrost coastlines transport organic matter and inorganic nutrients to the Arctic Ocean, likely fueling biological production and CO2 emissions. To assess the impacts of Arctic coastal erosion on nearshore carbon and nitrogen cycling, we examined geochemical profiles from eroding coastal bluffs and estimated annual organic matter fluxes from 1955 to 2018 for a 9 km stretch of coastline near Drew Point, Alaska. Additionally, we conducted a laboratory incubation experiment to examine dissolved organic carbon (DOC) leaching and biolability from coastal soils/sediments added to seawater.Three permafrost cores (4.5 – 7.5 m long) revealed that two distinct horizons compose eroding bluffs near Drew Point: Holocene age, organic-rich (~12-45% total organic carbon; TOC) terrestrial soils and lacustrine sediments, and below, Late Pleistocene age marine sediments with lower organic matter content (~1% TOC), lower carbon to nitrogen ratios, and higher δ13C-TOC values. Organic matter stock estimates from the cores, paired with remote sensing time-series data, show that erosional TOC fluxes from this study coastline averaged 1,369 kg C m−1 yr−1 during the 21st century, nearly double the average flux of the previous half century. Annual TOC flux from this 9 km coastline is now similar to the annual TOC flux from the Kuparuk River, the third largest river draining the North Slope of Alaska.Experimental work demonstrates that there are distinct differences in DOC leaching yields and the fraction of biodegradable DOC across soil/sediment horizons. When core samples were submerged in seawater for 24 hours, the Holocene age organic-rich permafrost leached the most DOC in seawater (~6.3 mg DOC g-1 TOC), compared to active layer soils and Late-Pleistocene marine-derived permafrost (~2.5 mg DOC g-1 TOC). Filtered leachates were then incubated aerobically in the dark for 26 and 90 days at 20°C to examine biodegradable DOC (i.e. the proportion of DOC lost due to microbial uptake or remineralization). Of this leached DOC, Late Pleistocene permafrost was the most biolabile over 90 days (31 ± 7%), followed by DOC from active layer soils (24 ± 5%) and Holocene-age permafrost (14% ± 3%). If we scale these results to a typical 4 m tall eroding bluff at Drew Point, we expect that ~341 g DOC m-2 will rapidly leach, of which ~25% is biodegradable. These results demonstrate that eroding permafrost bluffs are an increasingly important source of biolabile DOC, likely contributing to greenhouse gas emissions and marine production in the coastal environment.

Accelerating erosion of the Alaska Beaufort Sea coast is increasing inputs of organic matter from land to the Arctic Ocean, and improved estimates of organic matter stocks in eroding coastal permafrost are needed to assess their mobilization rates under contemporary conditions. We collected three permafrost cores (4.5–7.5 m long) along a geomorphic gradient near Drew Point, Alaska, where recent erosion rates average 17.2 m year−1. Down-core patterns indicate that organic-rich soils and lacustrine sediments (12–45% total organic carbon; TOC) in the active layer and upper permafrost accumulated during the Holocene. Deeper permafrost (below 3 m elevation) mainly consists of Late Pleistocene marine sediments with lower organic matter content (∼1% TOC), lower C:N ratios, and higher δ13C values. Radiocarbon-based estimates of organic carbon accumulation rates were 11.3 ± 3.6 g TOC m−2 year−1 during the Holocene and 0.5 ± 0.1 g TOC m−2 year−1 during the Late Pleistocene (12–38 kyr BP). Within relict marine sediments, porewater salinities increased with depth. Elevated salinity near sea level (∼20–37 in thawed samples) inhibited freezing despite year-round temperatures below 0°C. We used organic matter stock estimates from the cores in combination with remote sensing time-series data to estimate carbon fluxes for a 9 km stretch of coastline near Drew Point. Erosional fluxes of TOC averaged 1,369 kg C m−1 year−1 during the 21st century (2002–2018), nearly doubling the average flux of the previous half-century (1955–2002). Our estimate of the 21st century erosional TOC flux year−1 from this 9 km coastline (12,318 metric tons C year−1) is similar to the annual TOC flux from the Kuparuk River, which drains a 8,107 km2 area east of Drew Point and ranks as the third largest river on the North Slope of Alaska. Total nitrogen fluxes via coastal erosion at Drew Point were also quantified, and were similar to those from the Kuparuk River. This study emphasizes that coastal erosion represents a significant pathway for carbon and nitrogen trapped in permafrost to enter modern biogeochemical cycles, where it may fuel food webs and greenhouse gas emissions in the marine environment.

The success of geological carbon storage (GCS) depends on the sealing properties of caprocks, typically mudrocks, and their laminated variety – shales. In this study, we examined mineralogical changes in carbonate-rich Mancos Shale and corresponding changes in micro-mechanical properties following the reaction with carbon dioxide (CO2). Mineralogical changes of Mancos Shale depended on the pressure of CO2 during its exposure to the CO2-brine mixtures for up to 8 weeks. Dedolomitization was observed in the reactors pressurized with 100 psi of CO2, combined with the precipitation of gypsum. In the reactor pressurized with 2500 psi of CO2, the complete dissolution of calcite, partial dissolution of dolomite, and precipitation of magnesite and anhydrite were observed. Localized mechanical weakening was observed only for dolomite-muscovite-illite-rich laminae following whole shale puck alteration at 2500 psi of CO2, and a decrease of up to 50 ± 20% in scratch toughness was observed. The quartz-calcite-rich laminae did not exhibit a measurable difference in scratch toughness before and after reaction in CO2-rich brine. The predicted changes in mineralogy, porosity, density, and hardness of Mancos Shale are limited, according to the geochemical models describing alteration of shale by CO2-rich brine lasting for 5000 years. This study illustrates a coupled and localized chemical-mechanical response of caprock to the injection of CO2.

Calcite (CaCO3) is one of the most abundant minerals in the Earth’s crust, and it is susceptible to subcritical chemically-driven fracturing. Understanding chemical processes at individual fracture tips, and how they control the development of fractures and fracture networks in the subsurface, is critical for carbon and nuclear waste storage, resource extraction, and predicting earthquakes. Chemical processes controlling subcritical fracture in calcite are poorly understood. We demonstrate a novel approach to quantify the coupled chemical-mechanical effects on subcritical fracture. The calcite surface was indented using a Vickers-geometry indenter tip, which resulted in repeatable micron-scale fractures propagating from the indent. Individual indented samples were submerged in an array of aqueous fluids and an optical microscope was used to track the fracture growth in situ. The fracture propagation rate varied from 1.6 × 10−8 m s−1 to 2.4 × 10−10 m s−1. The rate depended on the type of aqueous ligand present, and did not correlate with the measured dissolution rate of calcite or trends in zeta-potential. We postulate that chemical complexation at the fracture tip in calcite controls the growth of subcritical fracture. Previous studies indirectly pointed to the zeta-potential being the most critical factor, while our work indicates that variation in the zeta-potential has a secondary effect.

The adsorption equilibrium constants of monovalent and divalent cations to material surfaces in aqueous media are central to many technological, natural, and geochemical processes. Cation adsorption/desorption is often proposed to occur in concert with proton-transfer on hydroxyl-covered mineral surfaces, but so far this cooperative effect has been inferred indirectly. This work applies Density Functional Theory (DFT)-based molecular dynamics simulations of explicit liquid water/mineral interfaces to calculate metal ion desorption free energies. Monodentate adsorption of Na(+), Mg(2+), and Cu(2+) on partially deprotonated silica surfaces are considered. Na(+) is predicted to be unbound, while Cu(2+) exhibits larger binding free energies to surface SiO(-) groups than Mg(2+). The predicted trends agree with competitive adsorption measurements on fumed silica surfaces. As desorption proceeds, Cu(2+) dissociates one of the H2O molecules in its first solvation shell, turning into Cu(2+)O(-)(H2O)(3), while Mg remains Mg(2+)(H2O)(6). The protonation state of the SiO(-) group at the initial binding site does not vary monotonically with cation desorption., Comment: 4 figures

A fluid flow in a nanochannel highly depends on the wettability of the channel surface to the fluid. The permeability of the nanochannel is usually very low, largely due to the adhesion of fluid at the solid interfaces. Using molecular dynamics (MD) simulations, we demonstrate that the flow of water in a nanochannel with rough hydrophilic surfaces can be significantly enhanced by the presence of a thin layer of supercritical carbon dioxide (scCO2) at the water-solid interfaces. The thin scCO2 layer acts like an atomistic lubricant that transforms a hydrophilic interface into a super-hydrophobic one and triggers a transition from a stick- to- a slip boundary condition for a nanoscale flow. This work provides an atomistic insight into multicomponent interactions in nanochannels and illustrates that such interactions can be manipulated, if needed, to increase the throughput and energy efficiency of nanofluidic systems.

Using molecular dynamics simulation, we studied the density fluctuations and cavity formation probabilities in aqueous solutions and their effect on the hydration of CO2. With increasing salt concentration, we report an increased probability of observing a larger than the average number of species in the probe volume. Our energetic analyses indicate that the van der Waals and electrostatic interactions between CO2 and aqueous solutions become more favorable with increasing salt concentration, favoring the solubility of CO2 (salting in). However, due to the decreasing number of cavities forming when salt concentration is increased, the solubility of CO2 decreases. The formation of cavities was found to be the primary control on the dissolution of gas, and is responsible for the observed CO2 salting-out effect. Our results provide the fundamental understanding of the density fluctuation in aqueous solutions and the molecular origin of the salting-out effect for real gas.

Heterogeneous redox reactions on clay mineral surfaces control mobility and bioavailability of redox-sensitive nutrients and contaminants. Iron (Fe) residing in clay mineral structures can either catalyze or directly participate in redox reactions; however, chemical controls over its reactivity are not fully understood. In our previous work we demonstrated that converting a minor portion of Fe(III) to Fe(II) (partial reduction) in the octahedral sheet of natural Fe-rich clay mineral nontronite (NAu-1) activates its surface, making it redox-active. In this study we produced and characterized synthetic ferric nontronite (SIP), highlighting structural and chemical similarities and differences between this synthetic nontronite and its natural counterpart NAu-1, and probed whether mineral surface is redox-active by reacting it with arsenic As(III) under oxic and anoxic conditions. We demonstrate that synthetic nontronite SIP undergoes the same activation as natural nontronite NAu-1 following the partial reduction treatment. Similar to NAu-1, SIP oxidized As(III) to As(V) under both oxic (catalytic pathway) and anoxic (direct oxidation) conditions. The similar reactivity trends observed for synthetic nontronite and its natural counterpart make SIP an appropriate analog for laboratory studies. The development of chemically pure analogs for ubiquitous soil minerals will allow for systematic research of the fundamental properties of these minerals.

Adsorption and redox transformations on clay mineral surfaces are prevalent in surface environments. We examined the redox reactivity of iron Fe(II)/Fe(III) associated with natural and synthetic ferric nontronites. Specifically, we assessed how Fe(II) residing in the octahedral sheets, or Fe(II) adsorbed at the edge sites alters redox activity of nontronites. To probe the redox activity we used arsenic (As) and selenium (Se). Activation of both synthetic and natural ferric nontronites was observed following the introduction of Fe(II) into predominantly-Fe(III) octahedral sheets or through the adsorption of Fe(II) onto the mineral surface. The oxidation of As(III) to As(V) was observed via catalytic (oxic conditions) and, to a lesser degree, via direct (anoxic conditions) pathways. We provide experimental evidence for electron transfer from As(III) to Fe(III) at the natural and synthetic nontronite surfaces, and illustrate that only a fraction of structural Fe(III) is accessible for redox transformations. We show that As adsorbed onto natural and synthetic nontronites forms identical adsorption complexes, namely inner-sphere binuclear bidentate. We show that the formation of an inner-sphere adsorption complex may be a necessary step for the redox transformation via catalytic or direct oxidation pathways.

Storing carbon dioxide in the subsurface as carbonate minerals has the benefit of long-term stability and immobility. Ultramafic rock formations have been suggested as a potential reservoir for this type of storage due to the availability of cations to react with dissolved carbon dioxide and the fast reaction rates associated with minerals common in ultramafic formations; however, the rapid reactions have the potential to couple with the mechanical and hydraulic behavior of the rocks and little is known about the extent and mechanisms of this coupling. In this study, we argue that the dissolution of primary minerals and the precipitation of secondary minerals along pre-existing fractures in samples lead to reductions in both the apparent Young's modulus and shear strength of aggregates, accompanied by reduction in permeability. Hydrostatic and triaxial deformation experiments were run on dunite samples saturated with de-ionized water and carbon dioxide-rich solutions while stress, strain, permeability and pore fluid chemistry were monitored. Sample microstructures were examined after reaction and deformation using scanning electron microscopy (SEM). The results show that channelized dissolution and carbonate mineral precipitation in the samples saturated with carbon dioxide-rich solutions modify the structure of grain boundaries, leading to the observed reductions in stiffness, strength and permeability. A geochemical model was run to help interpret fluid chemical data, and we find that the apparent reaction rates in our experiments are faster than rates calculated from powder reactors, suggesting mechanically enhanced reaction rates. In conclusion, we find that chemo-mechanical coupling during carbon mineralization in dunites leads to substantial modification of mechanical and hydraulic behavior that needs to be accounted for in future modeling efforts of in situ carbon mineralization projects.

Water is the universal solvent and plays a critical role in all known geological and biological processes. Confining water in nano-scale domains, as encountered in sedimentary rocks, in biological, and in engineered systems, leads to the deviations in water’s physicochemical properties relative to those measured for the non-confined phase. In our comprehensive analysis, we demonstrate that nano-scale confinement leads to the decrease in the melting/freezing point temperature, density, and surface tension of confined water. With increasing degree of spatial confinement the population of networked water, as evidenced by alterations in the O-H stretching modes, increases. These analyses were performed on two groups of mesoporous silica materials, which allows to separate pore size effects from surface chemistry effects. The observed systematic effects of nano-scale confinement on the physical properties of water are driven by alterations to water’s hydrogen-bonding network—influenced by water interactions with the silica surface — and has implications for how we understand the chemical and physical properties of liquids confined in porous materials.

The reactivity of co-occurring arsenic (As) and uranium (U) in mine wastes was investigated using batch reactors, microscopy, spectroscopy, and aqueous chemistry. Analyses of field samples collected in proximity to mine wastes in northeastern Arizona confirm the presence of As and U in soils and surrounding waters, as reported in a previous study from our research group. In this study, we measured As (< 0.500 to 7.77 μg/L) and U (0.950 to 165 μg/L) in waters, as well as mine wastes (< 20.0 to 40.0 mg/kg As and < 60.0 to 110 mg/kg U) and background solids (< 20.0 mg/kg As and < 60.0 mg/kg U). Analysis with X-ray fluorescence (XRF) and electron microprobe show the co-occurrence of As and U with iron (Fe) and vanadium (V). These field conditions served as a foundation for additional laboratory experiments to assess the reactivity of metals in these mine wastes. Results from laboratory experiments indicate that labile and exchangeable As(V) was released to solution when solids were sequentially reacted with water and magnesium chloride (MgCl(2)), while limited U was released to solution with the same reactants. The predominance of As(V) in mine waste solids was confirmed by X-ray absorption near edge (XANES) analysis. Both As and U were released to solution after reaction of solids in batch experiments with HCO(3)(−). Both X-ray photoelectron spectroscopy (XPS) and XANES analysis determined the predominance of Fe(III) in the solids. Mössbauer spectroscopy detected the presence of nano-crystalline goethite, Fe(II) and Fe(III) in (phyllo)silicates, and an unidentified mineral with parameters consistent with arsenopyrite or jarosite in the mine waste solids. Our results suggest that As and U can be released under environmentally relevant conditions in mine waste, which is applicable to risk and exposure assessment.

Geological carbon storage (GCS) is a promising technology for mitigating increasing concentrations of carbon dioxide (CO2) in the atmosphere. The injection of supercritical CO2 into geological formations perturbs the physical and chemical state of the subsurface. The reservoir rock, as well as the overlying caprock, can experience changes in the pore fluid pressure, thermal state, chemical reactivity and stress distribution. These changes can cause mechanical deformation of the rock mass, opening/closure of preexisting fractures or/and initiation of new fractures, which can influence the integrity of the overall geological carbon storage (GCS) systems over thousands of years, required for successful carbon storage. GCS sites are inherently unified systems; however, given the scientific framework, these systems are usually divided based on the physics and temporal/spatial scales during scientific investigations. For many applications, decoupling the physics by treating the adjacent system as a boundary condition works well. Unfortunately, in the case of water and gas flow in porous media, because of the complexity of geological subsurface systems, the decoupling approach does not accurately capture the behavior of the larger relevant system. The coupled processes include various combinations of thermal (T), hydrological (H), chemical (C), mechanical (M), and biological (B) effects. These coupled processes are time- and length-scale- dependent, and can manifest in one- or two-way coupled behavior. There is an undeniable need for understanding the coupling of processes during GCS, and how these coupled phenomena can result in emergent behaviors arising from the interplay of physics and chemistry, including self - focusing of flow, porosity collapse, and changes in fracture networks. In this chapter, the first section addresses the subsurface system response to the injection of CO2, examined at field and laboratory scales, as well as in model systems, addressed from a perspective of single disciplines. The second section reviews coupling between processes during GCS observed either in the field or anticipated based on laboratory results.

The long-term carbon dioxide storage capacity of reservoirs can be impacted by chemical reactions, mass transport, and mechanical deformation of the reservoir and caprock following the injection of CO 2 . Mineral mass removal can lead to microcracking and compaction, thus affecting the mechanical integrity of the reservoir–caprock system. The short-term (days, months) and long-term (hundreds to thousands of years) chemical effects, such as the dissolution of intergranular cement and mineral precipitation, can lead to a coupled chemical-mechanical response. This chemical-mechanical coupling occurs at multiple temporal and spatial scales. For instance, chemical processes at the crack-tip (micrometer) scale affect fracture networks with complex fracture architecture all the way to the reservoir scale. This chapter addresses chemical effects on the mechanical response of reservoir and caprock lithologies considered for geological carbon storage. Particular emphasis is on sandstone reservoir and mudrock (shale) caprock, as they are the most typical formations targeted for the injection of CO 2 . This chapter examines the existing laboratory, field, and modeling studies that address the coupled chemical-mechanical response of sandstone and mudrock lithologies to the injection of CO 2 . These coupled chemical-mechanical responses during geological carbon storage can result in the development of preferential flow paths and CO 2 leakage.

Geological carbon storage (GCS) is a rapidly evolving technology, which could become vital in mitigating the increasing concentrations of atmospheric carbon dioxide (CO2). While we understand overall phenomena associated with injecting and storing CO2 in porous subsurface formations, unknowns persist. For successful geological carbon storage, trapping of CO2 over extended time periods (103 to 104 years) is required. Existing predictive models examining these timescales include large uncertainties and require improvement. Addressing challenges associated with temporal and spatial scales, characterizing and controlling mechanisms, and kinetics of individual, as well as coupled, processes are central to this technology. One of the key future research areas is developing fundamental science to understand process coupling at relevant temporal and spatial scales, and being able to predict, anticipate, and mitigate emergent behavior (e.g., development of preferential flow paths). This chapter summarizes the current state-of-the-art knowledge detailed in the previous chapters and presents future research needs for successful GCS.

During the Frio-I Brine Pilot CO2 injection experiment in 2004, distinct geochemical changes in response to the injection of 1600 tons of CO2 were recorded in brine samples collected from the monitoring well. Previous geochemical modeling studies have considered dissolution of calcite and iron oxyhydroxides, or release of adsorbed iron, as the most likely sources of the increased ion concentrations. In this modeling study we explore possible alternative sources of the increasing calcium and iron, based on the data from the detailed petrographic characterization of the Upper Frio Formation “C”. Particularly, we evaluate whether dissolution of pyrite and oligoclase (anorthite component) can account for the observed geochemical changes. Due to kinetic limitations, dissolution of pyrite and anorthite cannot account for the increased iron and calcium concentrations on the time scale of the field test (10 days). However, dissolution of these minerals is contributing to carbonate and clay mineral precipitation on the longer time scales (1000 years). We estimated that during the field test dissolution of calcite and iron oxide resulted in ∼0.02 wt.% loss of the reservoir rock mass. The reactive transport models were constructed for 25 and 59 °C temperature and using Pitzer and B-dot activity correction methods. These models predict carbonate minerals, dolomite and ankerite, as well as clay minerals kaolinite, nontronite and montmorillonite, will precipitate in the Frio Formation “C” sandstone as the system progresses toward chemical equilibrium during a 1000-year period. Cumulative uncertainties associated with using different thermodynamic databases, activity correction models (Pitzer vs. B-dot), and extrapolating to reservoir temperature, are manifested in the difference in the predicted mineral phases. However, these models are consistent with regards to the total volume of mineral precipitation and porosity values which are predicted to within 0.002%.

The study of mineral–water interfaces is of great importance to a variety of applications including oil and gas extraction, gas subsurface storage, environmental contaminant treatment, and nuclear waste repositories. Understanding the fundamentals of that interface is key to the success of those applications. Confinement of water in the interlayer of smectite clay minerals provides a unique environment to examine the interactions among water molecules, interlayer cations, and clay mineral surfaces. Smectite minerals are characterized by a relatively low layer charge that allows the clay to swell with increasing water content. Montmorillonite and beidellite varieties of smectite were investigated to compare the impact of the location of layer charge on the interlayer structure and dynamics. Inelastic neutron scattering of hydrated and dehydrated cation-exchanged smectites was used to probe the dynamics of the interlayer water (200–900 cm–1 spectral region) and identify the shift in the librational edge as ...

Lead (Pb) and antimony (Sb) associated with bullets pose a long term contamination risk in shooting ranges because bullet fragments weather over years to decades. In this study we analyzed bullet and soil samples from a historic military shooting range in interior Alaska. Bulk speciation analysis coupled with micro-scale analytical methods demonstrate the presence of Sb(V) in octahedral coordination with 5.3(1) O and a second shell of 3(1) Fe atoms is the primary species present in the weathered bullet crust. However, trivalent Sb bound to 3.1(2) O atoms is likely the initial oxidation species as detected at the soil/alloy interface of a weathered bullet from this study. Similar analysis shows that cerussite (PbCO3), hydrocerussite (Pb3(CO3)2(OH)2), and litharge (PbO) comprise the majority of the Pb species in the weathering crust but Pb(II) adsorbed to Fe(III) oxides are also present in the soil distal to the source material. These results show differences in speciation between the weathering crust and soil fraction in shooting range samples and highlight the natural association of Pb and Sb with Fe. Understanding metal speciation is a critical first step in developing and implementing remediation strategies in small arms shooting ranges.

Geomechanics experiments were used to assess mechanical alteration of Boise Sandstone promoted by reactions with supercritical carbon dioxide (scCO2) and water vapor. During geologic carbon storage, scCO2 is injected into subsurface reservoirs, forming buoyant plumes. At brine-plume interfaces, scCO2 can dissolve into native brines, and water from brines can partition into scCO2, forming hydrous scCO2. This study investigates the effect of hydrous scCO2 on the strength of Boise Sandstone. Samples are first exposed to recirculating hydrous scCO2 for 24 h at 70 °C and 13.8 MPa scCO2 pressure. Samples are reacted with scCO2 with added water contents up to 500 mL. After scCO2 exposure, samples are deformed at room temperature under confining pressures of 3.4, 6.9, and 10.3 MPa. The results demonstrate that hydrous scCO2 induces chemical reactions in Boise Sandstone, with ions migrating from the solid into the hydrous scCO2 phase. At the longer time-scales, these reactions could lead to mechanical weakening in the samples; however, on the scale of our experiments, the strength changes are within sample variability. Because the solubility of water in scCO2 is extremely low (0.008 mol H2O per 1 mol CO2), the mineral dissolution of Boise Sandstone was under 0.002 wt.%. Additionally, mineral grains and pore throats in Boise Sandstone are cemented with quartz, which is not susceptible to dissolution at these conditions. Our results indicate that humidity in scCO2 plumes is unlikely to sustain chemical reactions and induce long term strength changes in quartz cemented sandstones due to resistant mineralogies and low water solubility.

The development of fractures in materials is controlled by stress, as well as chemical environment to which materials might be exposed. Chemical dissolution reactions have proven to affect the integrity of various materials, including porous rocks. The goal for this study is to develop a novel phase-field formulation to deal with fracture propagation in a chemically reactive environment. We formulated a numerical model for coupling chemical damage and mechanical damage defined based on the diffusive phase-field fracture method. Furthermore, the chemical damage is linked to the change in porosity due to dissolution. The developed theoretical framework was numerically implemented and applied to subsurface undergoing calcite dissolution due to exposure to CO 2 , as a real-world example where understanding chemo-mechanical damage is crucial. The chemical damage assists mechanical damage obtained from phase-field in degradation of the material. This application of the phase-field method to subsurface rocks demonstrates its ability to predict chemo-mechanical coupling, and to quantify the impact of chemical alteration on fracture behavior.

Nano-scale spatial confinement can alter chemistry at mineral–water interfaces. These nano-scale confinement effects can lead to anomalous fate and transport behavior of aqueous metal species. When a fluid resides in a nanoporous environments (pore size under 100 nm), the observed density, surface tension, and dielectric constant diverge from those measured in the bulk. To evaluate the impact of nano-scale confinement on the adsorption of copper (Cu2+), we performed batch adsorption studies using mesoporous silica. Mesoporous silica with the narrow distribution of pore diameters (SBA-15; 8, 6, and 4 nm pore diameters) was chosen since the silanol functional groups are typical to surface environments. Batch adsorption isotherms were fit with adsorption models (Langmuir, Freundlich, and Dubinin–Radushkevich) and adsorption kinetic data were fit to a pseudo-first-order reaction model. We found that with decreasing pore size, the maximum surface area-normalized uptake of Cu2+ increased. The pseudo-first-order kinetic model demonstrates that the adsorption is faster as the pore size decreases from 8 to 4 nm. We attribute these effects to the deviations in fundamental water properties as pore diameter decreases. In particular, these effects are most notable in SBA-15 with a 4-nm pore where the changes in water properties may be responsible for the enhanced Cu mobility, and therefore, faster Cu adsorption kinetics. Electronic supplementary material The online version of this article (10.1186/s12932-018-0057-4) contains supplementary material, which is available to authorized users.

© 2017 Elsevier B.V. Fine-grained sedimentary rocks – namely mudrocks, including their laminated fissile variety — shales – make up about two thirds of all sedimentary rocks in the Earth's crust and a quarter of the continental land mass. Organic-rich shales and mudstones are the source rocks and reservoirs for conventional and unconventional hydrocarbon resources. Mudrocks are relied upon as natural barriers for geological carbon storage and nuclear waste disposal. Consideration of mudrock multi-scale physics and multi-scale spatial and temporal behavior is vital to address emergent phenomena in shale formations perturbed by engineering activities. Unique physical characteristics of shales arise as a result of their layered and highly heterogeneous and anisotropic nature, low permeability fabric, compositional complexity, and nano-scale confined chemical environments. Barriers of lexicon among geoscientists and engineers impede the development and use of conceptual models for the coupled thermal-hydraulic-mechanical-chemical-biological (THMCB) processes in mudrock formations. This manuscript reviews the THMCB process couplings, resulting emergent behavior, and key modeling approaches. We identify future research priorities, in particular fundamental knowledge gaps in understanding the phase behavior under nano-scale confinement, coupled chemo-mechanical effects on fractures, the interplay between physical and chemical processes and their rates, and issues of non-linearity and heterogeneity. We develop recommendations for future research and integrating multi-disciplinary conceptual models for the coupled multi-scale multi-physics behavior of mudrocks. Consistent conceptual models across disciplines are essential for predicting emergent processes in the subsurface, such as self-focusing of flow, time-dependent deformation (creep), fracture network development, and wellbore stability.