Charged Mineral Surfaces Research Articles

Joint use of sodium silicate and polysaccharides in the flotation of talcose copper-nickel ores

The paper considers the combined effect of polysaccharides (carboxymethyl cellulose and carboxymethyl starch) with sodium silicate in the f lotation of talcose copper-nickel ore. The analysis of the f lotation results and the assessment of hydrophobicity and surface charge of minerals showed that the composition of carboxymethylated polysaccharides and sodium silicate hydrophilizes the talc surface more effectively than each of the reagents separately. Moreover, sodium silicate alone hardly depresses the talc surface at all. The depression of f lotation-active silicates is effective when polysaccharide and sodium silicate are sequentially supplied. Under these conditions, sodium silicate makes a significant contribution to increasing the negative charge on the talc particles surface. The effect is more pronounced for compositions with starch, characterized by a lower degree of substitution compared to cellulose. It results in a significantly reduced recovery of f lotation-active magnesium-containing silicates and a slight decrease in sulfide recovery. To determine the features of the mechanism of talc and sulfide minerals depression in f lotation, we performed calculations using the extended DLVO theory based on the obtained values of the zeta potential and force of detachment. We established that sulfide minerals have no potential barrier preventing their interaction with an air bubble, regardless of the compositions of the studied depressants used. We propose the following interaction mechanism: when sodium silicate is supplied first, the talc basal surface is very insignificantly hydrophilized as SiO(OH)– ions are not easy to fix. On the contrary, when the carboxymethylated polysaccharide is supplied first, significant hydrophilization of the talc surface with carboxyl groups occurs due to the hydrophobic interaction between the corresponding regions of the macromolecule and the talc basal surface.

Toward Modeling the Structure of Electrolytes at Charged Mineral Interfaces Using Classical Density Functional Theory.

The organization of water molecules and ions between charged mineral surfaces determines the stability of colloidal suspensions and the strength of phase-separated particulate gels. In this article, we assemble a density functional that measures the free energy due to the interaction of water molecules and ions in electric double layers. The model accounts for the finite size of the particles using fundamental measure theory, hydrogen-bonding between water molecules using Wertheim's statistical association theory, long-range dispersion interactions using Barker and Henderson's high-temperature expansion, electrostatic correlations using a functionalized mean-spherical approximation, and Coulomb forces through the Poisson equation. These contributions are shown to produce highly correlated structures, aptly rendering the layering of counterions and co-ions at highly charged surfaces and permitting the solvation of ions and surfaces to be measured by a combination of short-range associations and long-ranged attractions. The model is tested in a planar geometry near soft, charged surfaces to reproduce the structure of water near graphene and mica. For mica surfaces, explicitly representing the density of the outer oxygen layer of the exposed silica tetrahedra allows water molecules to hydrogen-bond to the solid. When electrostatic interactions are included, water molecules assume a hybrid character, being accounted for implicitly in the dielectric constant but explicitly otherwise. The disjoining pressure between approaching like-charged surfaces is calculated, demonstrating the model's ability to probe pressure oscillations that arise during the expulsion of ions and water layers from the interfacial gap and predict strong interattractive stresses that form at narrow interfacial spacing when the surface charge is overscreened. This interattractive stress arises not due to in-plane correlations under strong electrostatic coupling but due to the out-of-plane structuring of associating ions and water molecules.

Survival of environmental DNA in sediments: Mineralogic control on DNA taphonomy

AbstractThe extraction of environmental DNA (eDNA) from sediments is providing ground‐breaking views of past ecosystems and biodiversity. Despite this rich source of information, it is still unclear which sediments favor preservation and why. Here, we used atomic force microscopy and molecular dynamics simulations to explore the DNA‐mineral interaction to assess how mineralogy and interfacial geochemistry play a role in the preservation of environmental DNA on mineral substrates. We demonstrate that mineral composition, surface topography, and surface charge influence DNA adsorption behavior as well as preservation. Modeling and experimental data show that DNA damage can be induced by mineral binding if there is a strong driving force for adsorption. The study shows that knowledge of the mineralogical composition of a sediment and the environmental conditions can be useful for assessing if a deposit is capable of storing extracellular DNA and to what extent the DNA would be preserved. Our data adds to the understanding of eDNA taphonomy and highlights that, for some mineral systems, fragmented DNA may not represent old DNA.

Basalt mineral surface charge and the effect of mineralization on its colloidal stability: Implications of subsurface CO2 storage

Global concern over climate change caused by greenhouse gas emissions has received and is still receiving a lot of attention. Companies and nations have committed to reducing their carbon footprint to halt the consequences, and work is being done to create long-term strategies for CO2 usage. One of these goals is to use the CO2 that has been captured to make chemicals or to use it to make waste that can be buried or safely disposed of. One such endeavours is CO2 mineralization, which has been suggested as a method of CO2 utilization. It entails the creation of carbonates by the interaction of a fluid that contains CO2 with cations that are found in brines or rocks. However, the mineralization process is a protracted one, and until recently it was not believed that it could be completed in less than two years. Furthermore, little research has been done on how mineralization affects the electrokinetic and surface chemistry of cation-bearing rocks like basaltic rocks. Therefore, this study assesses how mineralization (carbonate precipitation) affects the colloidal and electrokinetic characteristics of basaltic rock.According to the study's findings, the electrical double layer (EDL) effect and protonation of the silanol group function as the two main controlling mechanisms of charge formation in the basaltic rock. More so, the rock sample is negatively charged over a range of pH and colloidally stable in freshwater. However, its colloidal stability is decreased in brines, and the EDL effect and potential determining ions (H+ and OH–) dominate its charge development. Additionally, different precipitates have distinct effects on the electrokinetic characteristics of basaltic rock, with the MgCO3 and FeCO3 precipitation having a more notable impact than the CaCO3 precipitation. Furthermore, at pH values of 3 – 4 (CO2 storage pH) in both freshwater and sweater environments, basaltic rocks exhibit near zero or low surface charge values indicating weak adhesion force. Thus, the question of if the near pH values of 2, can be considered as higher values of surface charge is observed in some cases. These findings raise questions about the structural integrity of basaltic rock, which has been touted as a prime candidate for the mineralization process due to its reactive nature, particularly in the case of colloidal stability after the mineralization process. The results of this study further provide new insight into the optimization of the mineralization process, which is dependent on the structural and petrophysical characteristics of the rocks and reservoirs that provide the cations for the process.

Relevance of charge interactions for contaminant transport in heterogeneous formations: a stochastic analysis

The electrostatic properties of clay (or other charged) mineral surfaces play a significant role in the fate, transport, persistence, and remediation of subsurface contaminant plumes. This study presents a stochastic assessment of the impact and relevance of microscale electrostatic effects on macroscopic, field-scale contaminant transport in heterogeneous groundwater systems involving spatially distributed clay zones. We present Monte Carlo simulations in two-dimensional heterogeneous fields, comprising heterogeneous distributions of physical (i.e., hydraulic conductivity, porosity, tortuosity) and electrostatic (i.e., surface charge) properties, and compare scenarios with different combination and extent of physical and electrostatic processes. The simulations were performed with the multi-continua based reactive transport code, MMIT-Clay, and considering an explicit treatment of the diffuse layer processes. The results reveal that the microscopic electrostatic mechanisms within clay’s diffuse layer can significantly accelerate or retard a particular contaminant depending on its charge, leading to considerably different solute breakthroughs and mass loading/release behaviors in low permeability inclusions. Furthermore, we show that such variations in the macroscale transport behavior, solely driven by charge interactions, are statistically significant over the ensembles of Monte Carlo realizations. The simulations also demonstrate that the omission of electrostatic processes, which is still a common practice in subsurface hydrology, can lead to substantial over- or underestimation of contaminant migration.

Y(III) Sorption at the Orthoclase (001) Surface Measured by X-ray Reflectivity.

Interactions of heavy metals with charged mineral surfaces control their mobility in the environment. Here, we investigate the adsorption of Y(III) onto the orthoclase (001) basal plane, the former as a representative of rare earth elements and an analogue of trivalent actinides and the latter as a representative of naturally abundant K-feldspar minerals. We apply in situ high-resolution X-ray reflectivity to determine the sorption capacity and molecular distribution of adsorbed Y species as a function of the Y3+ concentration, [Y3+], at pH 7 and 5. With [Y3+] ≥ 1 mM at pH 7, we observe an inner-sphere (IS) sorption complex at a distance of ∼1.5 Å from the surface and an outer-sphere (OS) complex at 3-4 Å. Based on the adsorption height of the IS complex, a bidentate, binuclear binding mode, in which Y3+ binds to two terminal oxygens, is proposed. In contrast, mostly OS sorption is observed at pH 5. The observed maximum Y coverage is ∼1.3 Y3+/AUC (AUC: area of the unit cell = 111.4 Å2) for all the investigated pH values and Y concentrations, which is in the expected range based on the estimated surface charge of orthoclase (001).

Adverse health and environmental outcomes of sewage treatment plant on surrounding groundwater with emphasis on some mitigation recommendations

Water quality deterioration hinders economic and social development in developing countries that are facing freshwater security and shortages. Based on the collection of 29 water samples, this study focused on the relationship between sewage treatment plant and groundwater system surrounding it using multidisciplinary approach that combines the characterization of groundwater system and its connection with surrounding canal and drains, using chemical and isotopic characterization revealing that there is a direct relation between the surface water system and surrounding groundwater system. About 58% of the groundwater samples and all surface water samples in the investigated area are threatened by high concentrations of trace elements. The multivariate statistical analysis elucidates that anthropogenic effect and fertilizers sewage contamination are the main causes of groundwater pollution. Nearly, 31% and 11.5% of groundwater samples were posing oral chronic non-carcinogenic health risk and dermal chronic risk for adult, respectively, while all surface water samples were posing oral chronic non-carcinogenic health risk, with no dermal hazard. The uncharged species of Fe and Al are expected to be more mobile in groundwater because they would not be attracted to the surface charge of minerals. Inorganic ligands (HCO3−, SO42−, Cl−, and NO3−) act as nucleation centers that were linked with those trace elements creating new species with higher solubility degree in water that are transported away randomly for long distances in the water path.

Ion Adsorption and Desorption at the CaF2 -Water Interface Probed by Flow Experiments and Vibrational Spectroscopy.

The dissolution of minerals in contact with water plays a crucial role in geochemistry. However, obtaining molecular insight into interfacial chemistry is challenging. Dissolution typically involves the release of ions from the surface, giving rise to a charged mineral surface. This charge affects the interfacial water arrangement, which can be investigated by surface-specific vibrational Sum Frequency Generation (v-SFG) spectroscopy. For the fluorite-water interface, recent spectroscopic studies concluded that fluoride adsorption/desorption determines the surface charge, which contrasts zeta potential measurements assigning this role to the calcium ion. By combining v-SFG spectroscopy and flow experiments with systematically suppressed dissolution, we uncover the interplay of dominant fluoride and weak calcium adsorption/desorption, resolving the controversy in the literature. We infer the calcium contribution to be orders of magnitude smaller, emphasizing the sensitivity of our approach.

Adsorption behavior and wettability alteration of bis-imidazolium salts on vermiculite: Experimental and theoretical studies

For further understanding the wettability alteration induced by organic salts, series of bis-imidazolium salts (EBMI, TBMI, HBMI, OBMI and DBMI) were employed for investigating their adsorption behavior and wettability alteration on vermiculite (Vt) by experimental and theoretical studies. The characterization results indicated that all bis-imidazolium salts had been loaded on Vts. The adsorption results showed that EBMI, TBMI, HBMI, OBMI and DBMI on Vt reached equilibrium of 0.159, 0.156, 0.145, 0.114 and 0.084 mmol g−1 around 30 min at 25 °C, respectively, which were sensitive to ionic strength and pH. Langmuir, statistical physical modelling and pseudo-second-order models could be well fitted with the adsorption data, and thermodynamic parameters suggested that the adsorption processes of bis-imidazolium salts were endothermic and spontaneous, indicating that the resultant bis-imidazolium salts could be self-assembled onto Vt in the form of the monolayer. Results of molecular dynamic simulation showed that bis-imidazolium salts were adsorbed on Vt with the lying-flat configuration, and the electrostatic interaction acted as the main interaction mechanism, which were consistent with that obtained experimentally. Changes of wettability of Vt induced by bis-imidazolium salts were verified by capillary rise experiments. Interestingly, the wettability of organo-Vts varied with the spacer length and the order was as follows: EBMI-Vt < TBMI-Vt < HBMI-Vt < OBMI-Vt < DBMI-Vt, which could be explained by their arrangements, hydrophobicity as well as the interaction energies. The longer the spacers of bis-imidazolium salts, the greater the absolute values of the interaction energy, the less the adsorbed bis-imidazolium salts, while the more hydrophobic of organo-Vt. This work aimed at revealing the adsorption behavior, mechanism as well as effect of bis-imidazolium salts on wettability alteration of negatively charged mineral surface, providing some information for the selection of flooding agent for enhanced oil recovery and wettability modifier.

Calcite–Brine Interface and Its Implications in Oilfield Applications: Insights from Zeta Potential Experiments and Molecular Dynamics Simulations

Carbonate reservoirs are made up of predominantly calcite and dolomite minerals and hold significant hydrocarbon reserves globally. However, the production from carbonate reservoirs is limited due to their wettability, which controls the production and fluid distribution. To develop efficient strategies for producing from these formations, it is necessary to understand the underlining mechanisms of carbonate rock wettability. We believe that understanding the native state of the rock mineral in the reservoir environment and how oilfield operations affect the wetting state of minerals is critical to demystifying the change in carbonate rock wettability. Thus, this study extends the understanding of the surface charge development of calcite minerals and provides useful insight into the mineral’s surface charge development. Zeta potential measurements and molecular dynamics (MD) simulations of calcite in different fluids of varying composition and salinity were investigated. We have considered both the mixed brine (seawater and reservoir water) and individual salt brine (i.e., NaCl, MgCl2, and CaCl2). The results show that the calcite mineral surface charge is controlled by the composition and salinity of the surrounding fluids. Indeed, we found that monovalent ions have dominant contributions to the total calcite surface charge. The adsorptions of Na+ and Cl– shape the stern layer structure in the first two calcite hydration monolayers. We found that the interplay between the calcite surface affinity to the brine ions and the hydration-free energies are the two critical parameters shaping the final mineral surface charge. We believe that our study provides essential atomic insights into the calcite–brine interfaces and how ions interact with the surface to control the surface charge, which are vital to the quest for wettability control.

Influence of Sandstone Mineralogy on the Adsorption of Polar Crude Oil Components and Its Effect on Wettability

The crude oil–brine–rock (COBR) system is a combination of contacting phases where polar organic molecules in crude oil, inorganic ions from the brine phase, and charged mineral surfaces participate in complex interactions. One of the surface phenomena that occur in the COBR system is the adsorption of polar crude oil components, which can directly affect the capillary forces and wettability of the rock. The purpose of this research work was to determine polar organic component (POC) adsorption trends for sandstones of different origins and mineralogical compositions. Adsorption preferences for acidic and basic POCs were quantified by potentiometric titration during dynamic core flooding tests using modified crude oil. The influence of POC adsorption on wettability was investigated by evaluating capillary forces during the displacement of oil in a spontaneous imbibition (SI) process. The results of this work showed a clear relationship between the intensity of POC adsorption and sandstone mineralogy. Greater adsorption capacity and a predominant affinity for bases compared to that for acids were found in the sandstone material containing a sufficient amount of reactive illite clay minerals. On the other hand, the sandstone material consisting mainly of quartz with an insignificant content of kaolinite clay did not show a pronounced tendency to adsorb POCs. All the studied rock materials have also shown a significant impact of POC adsorption on capillary forces and wettability, confirmed during SI tests. As a result, a detailed mineralogical analysis along with crude oil chemistry is required to properly evaluate sandstone wettability and competently plan core flooding laboratory studies.

Positively charged mineral surfaces promoted the accumulation of organic intermediates at the origin of metabolism.

Identifying plausible mechanisms for compartmentalization and accumulation of the organic intermediates of early metabolic cycles in primitive cells has been a major challenge in theories of life's origins. Here, we propose a mechanism, where positive membrane potentials elevate the concentration of the organic intermediates. Positive membrane potentials are generated by positively charged surfaces of protocell membranes due to accumulation of transition metals. We find that (i) positive membrane potentials comparable in magnitude to those of modern cells can increase the concentration of the organic intermediates by several orders of magnitude; (ii) generation of large membrane potentials destabilize ion distributions; (iii) violation of electroneutrality is necessary to induce nonzero membrane potentials; and (iv) violation of electroneutrality enhances osmotic pressure and diminishes reaction efficiency, resulting in an evolutionary driving force for the formation of lipid membranes, specialized ion channels, and active transport systems.

Effects of clay minerals on the transport of polystyrene nanoplastic in groundwater

Microplastics are widely detected in the soil-groundwater environment, which has attracted more and more attention. Clay mineral is an important component of the porous media contained in aquifers. The transport experiments of polystyrene nanoparticles (PSNPs) in quartz sand (QS) mixed with three kinds of clay minerals are conducted to investigate the effects of kaolinite (KL), montmorillonite (MT) and illite (IL) on the mobility of PSNPs in groundwater. Two-dimensional (2D) distributions of DLVO interaction energy are calculated to quantify the interactions between PSNPs and three kinds of clay minerals. The critical ionic strengths (CIS) of PSNPs-KL, PSNPs-MT and PSNPs-IL are 17.0 mM, 19.3 mM and 21.0 mM, respectively. Experimental results suggest KL has the strongest inhibition effect on the mobility of PSNPs, followed by MT and IL. Simultaneously, the change of ionic strength can alter the surface charge of PSNPs and clay minerals, thus affecting the interaction energy. Experimental and model results indicate both the deposition rate coefficient (k) and maximum deposition (Smax) linearly decrease with the logarithm of the DLVO energy barrier, while the mass recovery rate of PSNPs (Rm) exponentially increases with the logarithm of the DLVO energy barrier. Therefore, the mobility and associated kinetic parameters of PSNPs in complex porous media containing clay minerals can be predicted by 2D distributions of DLVO interaction energy. These findings could help to gain insight into understanding the environmental behavior and transport mechanism of microplastics in the multicomponent porous media, and provide a scientific basis for the accurate simulation and prediction of microplastic contamination in the groundwater system.

Effect of Sulfate-Based Scales on Calcite Mineral Surface Chemistry: Insights from Zeta-Potential Experiments and Their Implications on Wettability.

Scale formation and deposition in the subsurface and surface facilities have been recognized as a major cause of flow assurance issues in the oil and gas industry. Sulfate-based scales such as sulfates of calcium (anhydrite and gypsum) and barium (barite) are some of the commonly encountered scales during hydrocarbon production operations. Oilfield scales are a well-known flow assurance problem, which occurs mainly due to the mixing of incompatible brines. Researchers have largely focused on the rocks’ petrophysical property modifications (permeability and porosity damage) caused by scale precipitation and deposition. Little or no attention has been paid to their influence on the surface charge and wettability of calcite minerals. Thus, this study investigates the effect of anhydrite and barite scales’ presence on the calcite mineral surface charge and their propensity to alter the wetting state of calcite minerals. This was achieved vis-à-vis zeta-potential (ζ-potential) measurement. Furthermore, two modes of the scale control (slug and continuous injections) using ethylenediaminetetraacetic acid (EDTA) were examined to determine the optimal control strategy as well as the optimal inhibitor dosage. Results showed that the presence of anhydrite and barite scales in a calcite reservoir affects the colloidal stability of the system, thus posing a threat of precipitation, which would result in permeability and porosity damage. Also, the calcite mineral surface charge is affected by the presence of calcium and barium sulfate scales; however, the magnitude of change in the surface charge via ζ-potential measurement is insignificant to cause wettability alteration by the mineral scales. Slug and continuous injections of EDTA were implemented, with the optimal scale control strategy being the continuous injection of EDTA solutions. The optimal dosage of EDTA for anhydrite scale control is 5 and 1 wt % for the formation water and seawater environments, respectively. In the case of barite, in both environments, an EDTA dosage of 1 wt % suffices. Findings from this study not only further the understanding of the scale effects on calcite mineral systems but also provide critical insights into the potential of scale formation and their mechanisms of interactions for better injection planning and the development of a scale control strategy.

Mechanisms of Selected Anionic Dye Removal by Clinoptilolite

The extensive use of color dyes in modern society has resulted in serious concerns of water contamination. Many organic dyes bear charges; thus, materials of opposite charges have been tested for sorptive removal. However, the results from several studies also showed that anionic dyes methyl orange (MO) and alizarin red S (ARS) could be removed from water using minerals of negative charges, but the mechanisms were not addressed. In this study, negatively charged clinoptilolite was tested for its removal of anionic dyes MO and ARS from water under different physico-chemical conditions and to investigate the mechanism of Mo and ARS removal. The sorption capacities were 166 and 92 mmol/kg for MO and ARS, respectively, confirming the uptake of anionic dyes on negatively charged framework silicates. The influence of solution pH and ionic strength on MO removal was minimal, indicating the strong affinity of anionic dyes for clinoptilolite in comparison to other inorganic species. It was speculated that the N in the dimethyl group may bear a partial positive charge, which may have a net electrostatic attraction to the negatively charged mineral surfaces for MO sorption. For ARS, sorption may involve hydrogen bonding formation between the dye and the clinoptilolite. Moreover, under the experimental conditions, the MO molecules form dimers in solution via dimeric π-π interactions. Thus, the sorption of the dimers or aggregation of the MO monomers and dimers on clinoptilolite surface was attributed to additional MO removal, as suggested by molecular dynamic simulations. The speculation was supported by FTIR analyses and molecular dynamic simulations. As such, negatively charged Earth materials may be used as sorbents for the removal of certain anionic dyes via sorption, a new perspective for the innovative use of Earth materials.

Removal of toluidine blue from water using 1:1 layered clay minerals

Extensive use of color dyes in modern society resulted in their potential release into the environment. Dye removal often involved in sorption or reaction. For sorptive removal, materials with low cost and high efficiency are of great potential. In this study, the removal of toluidine blue (TB), a cationic dye, by 1:1 layered clay minerals kaolinite (KAO) and halloysite (HNC) was systematically studied under different physicochemical conditions. The TB removal was fast and equilibrium could be reached within an hour. The TB removal capacities were 47 and 149 mmol/kg by KAO and HNC slightly larger than their cation exchange capacity (CEC) of 37 and 120 meq/kg. The results indicated that both the CEC and specific surface area (SSA) of the minerals played a critical role in TB removal. Equilibrium solution pH and ionic strength had less effect on TB removal, suggesting preferred affinity of TB over other inorganic cations for mineral surfaces. X-ray diffraction data showed no interlayer expansion, indicating TB sorption sites were on the external surfaces of both minerals. The FTIR results indicated participation of N+ on the dimethyl group for TB sorption on negatively charged mineral surface. At the sorption capacities, TB may form a condensed monolayer on KAO surfaces, and a dimer or bilayer coverage on HNC surfaces, as suggested by molecular dynamic simulation. The results from this study suggest that clay minerals of high CEC and large SSA values would be good candidates for the removal of cationic dyes form water.

Investigation of Surface Charge at the Mineral/Brine Interface: Implications for Wettability Alteration

The reservoir rock ismade up of differentminerals which contribute to the overall formation wettability. These minerals in their natural state differ in chemistry and structure, and thus behave differently in an environment of varying composition and salinity. These have direct implications for enhanced oil recovery due to water flooding, or wettability alteration due to long-term exposure to brine. With the reservoir rock being a complex system of multiple minerals, the control of wettability alterations becomes difficult to manage. One of the dominant mechanisms responsible for wettability alteration is the mineral surface charge, which is dependent on pH, and fluid composition (salt type and salinity). For the first time, the surface charge development of barite, dolomite, and feldspar minerals in their native reservoir environments (accounting for the formation brine complexity) is presented. Also, the effect of oilfield operations (induced pH change) on minerals’ surface charge development is studied. This was achieved by using the zeta potential measurements. The zeta potential results show that barite and dolomite minerals possess positively charge surfaces in formation water and seawater, with feldspar having a near-zero surface charge. Furthermore, the surface charge development is controlled by the H+/OH− (pH), electrical double-layer effect, as well as ion adsorption on the mineral’s surfaces. These findings provide key insights into the role of fluid environment (pH, composition) and oilfield operations on mineral surface charge development. In addition, the results show that careful tuning of pH with seawater injection could serve as an operational strategy to control the mineral surface charge. This is important as negatively charged surfaces negate wettability alteration due to polar crude oil components. Also, the design of an ion-engineered fluid to control the surface charge of minerals was implemented, and the results show that reduction in the Ca2+ concentration holds the key to the surface charge modifications. Surface charge modifications as evidenced in this study play a critical role in the control of wettability alteration to enhance production.

Surface Complexation Modelling of Wettability Alteration during Carbonated Water Flooding

CO2 capture and utilization is an effective tool in reducing greenhouse gas emissions and hence, combating global warming. In the present study, surface complexation modeling (SCM) with the geochemistry solver, PHREEQ-C, was utilized to predict the wettability alteration of minerals, sandstone reservoir rocks (SRR), and pseudo-sandstone rocks (PSR) and mineral mixtures during carbonated water (CW) injection. The bond products, which is defined as the product of the mole fraction of oppositely charged mineral and oil surfaces, were calculated to estimate the wettability preferences. For the studied fluid systems, the results from SCM predicted that albite and quartz minerals were strongly water-wet while calcite was strongly oil-wet with formation water (FW). When it came to clay minerals, illite and montmorillonite were more oil-wet than quartz and less oil-wet than calcite. During CW injection (CWI), the wettability preferences of dominant minerals (considering weight and surface area) in SRR (i.e., quartz and calcite) were changed toward more water-wet, while for the clay minerals, the result was the opposite. The results from SCM showed that the wettability preferences of SRR were water-wet in both CW and FW. Moreover, increasing the amount of the water-wet minerals in mineral mixtures increased the rock’s tendency to become more water-wet.

Effect of Structural Fe Reduction on Water Sorption by Swelling and Non-Swelling Clay Minerals

Ferruginous clay minerals in saturated soils and within hydrocarbon deposits often exist in a reduced state. Upon introduction of dissolved oxygen, or other oxidants, the clay minerals oxidise and changes in mineral surface charge and sorption capacity occur, resulting in changes in hydration as well as flux of intercalated species. Here we examine the sorption of water to the Fe-containing clay minerals nontronite NAu-2 (23 wt% Fe) and illite IMt-2 (7 wt% Fe) as a function of Fe oxidation state and exchangeable cations by means of water vapour volumetry and N2 surface area analysis. The clay minerals were chemically reduced using sodium dithionite. Sorption isotherms of water vapour and nitrogen, controlled relative humidity diffractograms, and chemical analyses were recorded. The results show that, after reduction using sodium dithionite, increased amounts of water vapour and nitrogen were adsorbed to the high Fe content nontronite, despite decreased interlayer separation. Little change was observed for the non-swelling and low Fe content illite. Sodium from the reducing agent was found to exchange with calcium present in the starting clay minerals, and sodium balanced the additional mineral charge generated during reduction. The findings presented in this study deliver improved understanding of sorption at the surface of the reduced clay minerals, which aid constrain the role of clay mineral interfaces in subsurface environments.

Effect of Native Reservoir State and Oilfield Operations on Clay Mineral Surface Chemistry.

An understanding of clay mineral surface chemistry is becoming critical as deeper levels of control of reservoir rock wettability via fluid–solid interactions are sought. Reservoir rock is composed of many minerals that contact the crude oil and control the wetting state of the rock. Clay minerals are one of the minerals present in reservoir rock, with a high surface area and cation exchange capacity. This is a first-of-its-kind study that presents zeta potential measurements and insights into the surface charge development process of clay minerals (chlorite, illite, kaolinite, and montmorillonite) in a native reservoir environment. Presented in this study as well is the effect of fluid salinity, composition, and oilfield operations on clay mineral surface charge development. Experimental results show that the surface charge of clay minerals is controlled by electrostatic and electrophilic interactions as well as the electrical double layer. Results from this study showed that clay minerals are negatively charged in formation brines as well as in deionized water, except in the case of chlorite, which is positively charged in formation water. In addition, a negative surface charge results from oilfield operations, except for operations at a high alkaline pH range of 10–13. Furthermore, a reduction in the concentrations of Na, Mg, Ca, and bicarbonate ions does not reverse the surface charge of the clay minerals; however, an increase in sulfate ion concentration does. Established in this study as well, is a good correlation between the zeta potential value of the clay minerals and contact angle, as an increase in fluid salinity results in a reduction of the negative charge magnitude and an increase in contact angle from 63 to 102 degree in the case of chlorite. Lastly, findings from this study provide vital information that would enhance the understanding of the role of clay minerals in the improvement of oil recovery.