A robust model for pore-water chemistry of clayrock

The chemistry of pore water is an important property of clayrocks being considered as host rocks for long-term storage of radioactive waste. It may be difficult, if not impossible, to obtain water samples for chemical analysis from such rocks because of their low hydraulic conductivity. This paper presents an approach for calculating the pore-water compositions of clayrocks from laboratory-measured properties of core samples, including their leachable Cl and SO₄ concentrations and analysed exchangeable cations, and from mineral and cation exchange equilibria based on the formation mineralogy. New core sampling and analysis procedures are presented that reduce or quantify side reactions such as sample oxidation (e.g. pyrite) and soluble mineral dissolution (celestite, SrSO₄) that affect measured SO₄ concentrations and exchangeable cation distributions. The model considers phase equilibria only with minerals that are observed in the formation including the principal clay phases. The model has been used to calculate the composition of mobile pore water in the Callovo-Oxfordian clayrock and validated against measurements of water chemistry made in an underground research laboratory in that formation. The model reproduces the measured, in situ pore-water composition without any estimated parameters. All required parameters can be obtained from core sample analysis. We highlight the need to consider only those mineral phases which can be shown to be in equilibrium with contacting pore water. The consequence of this is that some conceptual models available in the literature appear not to be appropriate for modelling clayrocks, particularly those considering high temperature and/or high pressure detrital phases as chemical buffers of pore water. The robustness of our model with respect to uncertainties in the log K values of clay phases is also demonstrated. Large uncertainties in log K values for clay minerals have relatively small effects on modelled pore-water compositions.     

Determining Biogenic Silica in Marine Samples by Tracking Silicate and Aluminium Concentrations in Alkaline Leaching Solutions

This study introduces an alkaline leaching technique for the simultaneous analysis of biogenic silica and aluminium in sediments. Measuring aluminium facilitates the discrimination between silica from the biogenic (BSiO₂) and the non-biogenic fraction, because it originates almost solely from the lithogenic phase. The method was tested using fine-grained silicagel, standard clay minerals, artificial sediments, and natural samples ranging from fresh diatoms to aged sediment from different depositional settings. To determine the BSiO₂ content, four different models each describing the dissolution curves, but of increasing complexity, were applied and for each different type of sample the optimum model was selected on the basis of F-test statistics. For mixtures of silicagel and clay minerals, the contribution of Si from the dissolution of clay was negligible compared to Si originating from silicagel. For natural samples with high clay content, complex dissolution curves were observed and single-phase first order dissolution was the exception. This deviation from `ideal' behavior could only be recognized because of high-resolution sampling, especially in the first 20 minutes of the experiment. For most of the samples, the distinction between the biogenic silica fraction and the silica originating from dissolution of clays could be made on the basis of the Si/Al ratios and reactivity constants of the dissolving phases calculated with the models. Clay minerals typically dissolve slowly at a Si/Al ratio close to 1–2, depending on the type of clay mineral. In contrast, biogenic silica displays a wide range of reactivities and Si/Al ratios. Fresh biogenic silica from the water column usually has a high reactivity and a low Al content. Aged biogenic silica from the sediments has a lower reactivity, but Si/Al ratios as low as 5 were found. The method as described here therefore presents an accurate method to analyze biogenic silica in marine sediments with a relatively high clay mineral content.     

The products of the interaction of feldspars with aqueous solutions at 25°C

Chemical analyses of 300 solutions produced by the artificial weathering of eight different feldspars in fourteen experiments of up to 1200hr duration were used to study the evolution of water during weathering. The range of pH was between 4 and 5·5. Within 4 hr of dissolution, the activity of Al was controlled by the pH and the solubility of microcrystalline gibbsite. After 100 hr of dissolution, the pH and microcrystalline halloysite controlled the activities of Al and silicic acid in all of the solutions.Microcrystalline halloysite was the only phase identified in the weathering of plagioclases in distilled water and 1 atm CO₂ partial pressure. Montmorillonites, halloysite and other clay minerals were produced from oligoclase in aqueous solutions containing high initial concentrations of Ca. Mg, K and SiO₂.The experimentally determined log solubility product of microcrystalline gibbsite was ?32·78 ± 0·04 and log $\text{K}$ for the hydrolysis of microcrystalline halloysite was 11.58 ± 0·05. The results suggest that very poorly crystalline metastable phases may control the initial compositions of some waters in contact with rocks containing feldspar minerals.     

Influence of the alteration processes on the origin of uranium and europium anomalies in trachyte, central Eastern Desert, Egypt

El Atshan mining area, central Eastern Desert, represents one of the uranium occurrences related to alkaline volcanic rocks in Egypt. Based on the plot of total alkali elements versus silica, these rocks are classified as trachytes. The U and Eu anomalies appear to be derived from trachyte exposed to a long period of alteration and rock–fluid interaction. The trachyte has been subjected to two phases of alteration. The pronounced chemical changes include the mobility of Si, Na, Fe, U, Zn and REE and the immobility of Mg, Th, Hf, Ta and Sc. The late stage hydrothermal solutions caused the breakdown of the feldspars by losing sodium, potassium and partially silica and eventually formation of argillic alteration products, dissolution of iron-bearing sulphides, formation of iron-oxy hydroxides and corrosion of primary uranium minerals forming uranyl oxide hydrates. The acidic water percolating through the fractured trachyte rock leached not only available major or trace elements, but also REE. Eu originally incorporated in feldspars as Eu⁺² has been oxidized to Eu⁺³ and subsequently leached away leaving a negative anomaly in the host rock. The leached U and Eu were then transported most probably as carbonate complexes. The second phase of alteration occurred at the near surface profile when the late stage hydrothermal fluids cool to the temperature of meteoric water and may have mixed with it, the pH of the fluids would shift to more alkaline values and at these conditions U and Eu were precipitated into the fracture system mainly by being adsorbed on the clay minerals and probably coprecipitated with iron oxy-hydroxides.     

Evaluation of silica-water surface chemistry using NMR spectroscopy

We have combined traditional batch and flow-through dissolution experiments, multinuclear nuclear magnetic resonance (NMR) spectroscopy, and surface complexation modeling to re-evaluate amorphous silica reactivity as a function of solution pH and reaction affinity in NaCl and CsCl solutions. The NMR data suggest that changes in surface speciation are driven by solution pH and to a lesser extent alkali concentrations, and not by reaction time or saturation state. The ²⁹Si cross-polarization NMR results show that the concentration of silanol surface complexes decreases with increasing pH, suggesting that silanol sites polymerize to form siloxane bonds with increasing pH. Increases in silica surface charge are offset by sorption of alkali cations to ionized sites with increasing pH. It is the increase in these ionized sites that appears to control silica polymorph dissolution rates as a function of pH. The ²³Na and ¹³³Cs NMR results show that the alkali cations form outersphere surface complexes and that the concentration of these complexes increases with increasing pH. Changes in surface chemistry cannot explain decreases in dissolution rates as amorphous silica saturation is approached. We find no evidence for repolymerization of the silanol surface complexes to siloxane complexes at longer reaction times and constant pH.     

The effect of high pH alkaline solutions on the mineral stability of the Boom Clay – Batch experiments at 60 °C

Boom Clay is currently viewed as a reference host formation for studies on deep geological disposal of radioactive waste in Belgium. The interactions between bulk rock Boom Clay and 0.1 M KOH, 0.1 M NaOH, 0.1 M Ca(OH)₂, young cement water and evolved cement water solutions, ranging in pH from 12.5 to 13.2, were examined as static batch experiments at 60 °C to simulate alkaline plume perturbations, which are expected to occur in the repository due to the presence of concrete. Both liquids and solids were investigated at specific times between 90 and 510 days in order to control the elemental budget and to search for potential mineralogical alterations. Also, the clay fraction was separated from the whole-rock Boom Clay at the end of each run and characterized for its mineralogical composition. Thereby, the importance of the mineral matrix to buffer the alkaline attack and the role of organic matter to protect clay minerals were also addressed. The results indicate that the degree of geochemical perturbation in Boom Clay is dependent on the initial pH of the applied solution together with the nature of the major cation in the reactant fluids. The higher the initial pH of the media, the stronger its interaction with Boom Clay. No major non-clay mineralogical alteration of the Boom Clay was detected, but dissolution of kaolinite, smectite and illite occurred within the studied experimental conditions. The dissolution of clays is accompanied by the decrease in the layer charge, followed by a decrease in the cation-exchange capacity. The highest TOC values coincide with the highest total elemental concentrations in the leachates, and correspondingly, the highest dissolution degree. However, no quantitative link could be established between the degree of organic matter decomposition and clay dissolution.     

Dissolution–precipitation reactions in hydrothermal experiments with quartz–feldspar aggregates

Batch and flow-through experiments were performed on quartz–feldspar granular aggregates at hydrothermal conditions (up to ≈150 °C, up to 5 MPa effective pressure, and near-neutral pH) for up to 141 days. The effect of dissolution–precipitation reactions on the surface morphology of the mineral grains was investigated. The starting materials as well as the solids and fluids resulting from the experiments were characterized using BET, energy dispersive X-ray spectroscopy, electron microprobe analysis, inductively coupled plasma-optical emission spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, and X-ray fluorescence spectroscopy. The electrical conductivity of fluid samples was used as a proxy for the evolution of the fluid composition in the experiments. The chemical analyses of the fluids in combination with hydrogeochemical simulations with PHREEQC suggested the precipitation of Al–Si-bearing solid phases. Electron microscopy confirmed the formation of secondary amorphous Al–Si-bearing solid phases. The microscopic observations are consistent with a process of stoichiometric dissolution of the mineral grains, transport of dissolved ions in the fluid phase, and spatially coupled precipitation of sub-μm sized amorphous particles on mineral surfaces. These findings shed light onto early stages of diagenesis of quartz–feldspar sands and indicate that amorphous phases may be precursors for the formation of crystalline phases, for example, clay minerals.     

Geochemical process regulating groundwater quality in a coastal region with complex contamination sources: Barka,Sultanate of Oman

An investigation was carried out to evaluate the geochemical processes regulating groundwater quality in a coastal region, Barka, Sultanate of Oman. The rapid urban developments in Barka cause depletion of groundwater quantity and deterioration of quality through excessive consumption and influx of pollutants from natural and anthropogenic activities. In this study, 111 groundwater samples were collected from 79 wells and analysed for pH, EC, DO, temperature, major ions, silica and nutrients. In Barka, water chemistry shows large variation in major ion concentrations and in electrical conductivity, and implies the influence of distinguished contamination sources and hydrogeochemical processes. The groundwater chemistry in Barka is principally regulated by saline sources, reverse ion exchange, anthropogenic pollutants and mineral dissolution/precipitation reactions. Due to ubiquitous pollutants and processes, groundwater samples were classified into two groups based on electrical conductivity. In group1, water chemistry is greatly influenced by mineral dissolution/precipitation process and lateral recharge from upstream region (Jabal Al-Akdar and Nakhal mountains). In group 2, the water chemistry is affected by saline water intrusion, sea spray, reverse ion exchange and anthropogenic pollutants. Besides, high nitrate concentrations, especially in group 2 samples, firm evidence for impact of anthropogenic activities on groundwater quality, and nitrate can be originated by the effluents recharge from surface contamination sources. Ionic ratios such as SO₄/Cl, alkalinity/Cl and total cation/Cl indicate that effluents recharged from septic tank, waste dumping sites and irrigation return flow induce dissolution of carbonate minerals, and enhances solute load in groundwater. The chemical constituents originating from saline water sources, reverse ion exchange and mineral dissolution are successfully differentiated using ionic delta, the difference between the actual concentration of each constituent and its theoretical concentration for a freshwater–seawater mix calculated from the chloride concentration of the sample, and proved that this approach is a promising tool to identify and differentiate the geochemical processes in coastal region. Hence, both regular geochemical methods and ionic delta ensured that groundwater quality in Barka is impaired by natural and human activities.     

Textural evidences for dissolution of silica-rich rocks of the Ypresian phosphatic series,Gafsa-Metlaoui basin,southwestern Tunisia: implication of biogenic silica supply on genesis of fibrous clays

The present work aimed to determine the mineralogical composition of Ypresian series and to clarify the influence of the dissolution of siliceous frustules on the genesis of fibrous clay minerals. The specimens sampled from CPG trench are mainly constituted of silica-rich rocks at Mides area located at the western part of Gafsa-Metlaoui basin. The samples were investigated using X-ray diffraction (XRD) and scanning electron microscopy (SEM) in order to determine texture of constituents. The data obtained indicate that the bulk rock samples are mainly made up of opal CT and clay minerals. The latter consists of palygorskite-sepiolite minerals associated with smectite and few amount of illite. The trend of mineralogical composition indicates that fibrous clay minerals are more concentrated at the upper part. SEM observations indicated that palygorskite mineral appears as thread-like facies, which surround foliated texture of smectite in the lower part of the Mides section, although with the low Mg activity confirmed by the absence of dolomite. But, at the upper part of the Mides section, SEM observations revealed the occurrence of siliceous frustules, which have numerous dissolved areas and replacement of carbonate tests by silica. The dissolution saturated the depositional environment with silica which is required for the formation of palygorskite and sepiolite minerals, in addition to high Mg activity confirmed by the presence of dolomite in the bulk rock, which is required basically for the formation of sepiolite. Although the genesis mode of palygorskite and sepiolite is similar with very little difference, the genesis of sepiolite needs a high alkalinity than the formation of palygorskite.     

Mineral Surface after Reaction with Aqueous Solution at High Temperatures and Pressures

This work presents new experimental results on surface chemistry of reacting minerals and interface kinetics between mineral and aqueous solutions. These experiments were carried out using a flow reactor (packed bed reactor) of an open system as well as a continuous stirred tank reactor, CSTR. The authors measured reaction rates of such minerals as zeolite, albite and carbonate (rhodochrosite, dolomite) in various solutions, and tested corresponding mineral surface by using SEM, XPS, SIMS, etc. This paper mainly presents the experimental results of zeolite dissolution in water and in low pH solutions at room temperature, and dolomite dissolution at elevated temperatures. The results show that the release rates of Si, Al and Na of zeolite are different in most cases. The incongruent dissolution of zeolite is related to surface chemical modifications. The Na, Al and Si release rates for dissolution of albite and zeolite in water and various solutions were measured as a function of temperature, flow veloci     

Oxytetracycline sorption onto Iraqi montmorillonite

This paper assesses the use of certified Iraqi montmorillonite clay as a potential sorbent for the removal of oxytetracycline (OTC) from aqueous solutions. The clay is characterized by a cation exchange capacity of 0.756 meq g^?1 and a zero point charge at pH 8.7. Aqueous solutions of OTC were equilibrated with montmorillonite under various experimental conditions, such as OTC concentration, pH and clay content, for 24 h at fixed ionic strength. Two forms of montmorillonite were evaluated: regular and iron-modified form. The effect of pH was minor on OTC adsorption. Kinetic study revealed that the sorption follows a pseudo-second-order model. Sorption isotherm showed a good fit with the Freundlich model. OTC sorption onto Fe-saturated montmorillonite was analyzed statistically using a response surface design to study the effects of experimental conditions. The introduction of iron improved the adsorption characteristics of the clay due to the ability of ferric ions to make stable complexes with OTC. The most favorable operating conditions for the treatment were deemed as follows: clay content, 6.85 g L^?1, oxytetracycline concentration, 1.0 mmol L^?1 and pH, 5.5 for the iron-modified form.     

Processes controlling acid attenuation in the unsaturated zone of a Triassic sandstone aquifer (U.K.), in the absence of carbonate minerals

Continuous core samples were taken through the unsaturated zone at three sites on the outcrop of Permo-Triassic sandstone in the British West Midlands. Sample sites were chosen for lack of recent, direct anthropogenic disturbance, and for differing vegetation: heathland, birch woodland and conifer forest. Interstitial water was extracted and analyzed for 32 major and trace elements. Solid phases were analyzed for exchangeable cations and mineralogy. The rate of recharge calculated using a Cl mass balance method was three times greater below heathland than below afforested sites owing to higher evapotranspiration rates in the woodlands.Carbonate minerals were absent from the unsaturated zone at each site. Soil solutions were acidic and soils at the woodland sites were more acidic (pH 4.0) than those at the heathland site (pH 4.5). Acidic interstitial water solutions were found to up to 5.0 m depth in the unsaturated zone and are partially neutralized by two aluminosilicate mineral reactions in the unsaturated zone: cation exchange and K-feldspar dissolution. The rate at which these acid neutralizing reactions act to neutralize acidity is revealed by the rate of depletion of base cations from the unsaturated zone in recharge solutions; K⁺ (dissolution), Ca⁺² + Mg⁺² (cation exchange). The total base cation depletion rate was greatest below heathland; this can be attributed mainly to the greater rate of SO₄ assimilation by the woodland biome.     

A surface complexation and ion exchange model of Pb and Cd competitive sorption on natural soils

The bioavailability and fate of heavy metals in the environment are often controlled by sorption reactions on the reactive surfaces of soil minerals. We have developed a non-electrostatic equilibrium model (NEM) with both surface complexation and ion exchange reactions to describe the sorption of Pb and Cd in single- and binary-metal systems over a range of pH and metal concentration. Mineralogical and exchange properties of three different acidic soils were used to constrain surface reactions in the model and to estimate surface densities for sorption sites, rather than treating them as adjustable parameters. Soil heterogeneity was modeled with >FeOH and >SOH functional groups, representing Fe- and Al-oxyhydroxide minerals and phyllosilicate clay mineral edge sites, and two ion exchange sites (X⁻ and Y⁻), representing clay mineral exchange. An optimization process was carried out using the entire experimental sorption data set to determine the binding constants for Pb and Cd surface complexation and ion exchange reactions.Modeling results showed that the adsorption of Pb and Cd was distributed between ion exchange sites at low pH values and specific adsorption sites at higher pH values, mainly associated with >FeOH sites. Modeling results confirmed the greater tendency of Cd to be retained on exchange sites compared to Pb, which had a higher affinity than Cd for specific adsorption on >FeOH sites. Lead retention on >FeOH occurred at lower pH than for Cd, suggesting that Pb sorbs to surface hydroxyl groups at pH values at which Cd interacts only with exchange sites. The results from the binary system (both Pb and Cd present) showed that Cd retained in >FeOH sites decreased significantly in the presence of Pb, while the occupancy of Pb in these sites did not change in the presence of Cd. As a consequence of this competition, Cd was shifted to ion exchange sites, where it competes with Pb and possibly Ca (from the background electrolyte). Sorption on >SOH functional groups increased with increasing pH but was small compared to >FeOH sites, with little difference between single- and binary-metal systems. Model reactions and conditional sorption constants for Pb and Cd sorption were tested on a fourth soil that was not used for model optimization. The same reactions and constants were used successfully without adjustment by estimating surface site concentrations from soil mineralogy. The model formulation developed in this study is applicable to acidic mineral soils with low organic matter content. Extension of the model to soils of different composition may require selection of surface reactions that account for differences in clay and oxide mineral composition and organic matter content.     

Sorption of Trace Elements on Mineral Surfaces: Modern Perspectives from Spectroscopic Studies,and Comments on Sorption in the Marine Environment

The partitioning (or sorption) of trace elements from aqueous solutions onto mineral surfaces and natural organic matter (NOM) has played a major role in determining the trace element content of natural waters. This review examines sorption processes on mineral surfaces for nine trace elements (Cr, Co, Ni, Cu, Zn, Sr, Cd, Hg, Pb), focusing on the results of modern x-ray spectroscopic studies. Such studies provide unique information on the structure and composition of sorption products, including their mode of attachment to mineral surfaces or functional groups in NOM under in situ conditions (i.e., with aqueous solution present at 25°C). The types of chemical reactions (acid-base, ligand exchange, redox, dissolution/reprecipitation) that can occur at mineral-aqueous solution interfaces are also reviewed, and some of the factors that affect the reactivity of mineral surfaces are discussed, including changes in the geometric and electronic structures of mineral surfaces when they first react with aqueous solutions and constraints on the bonding of adions to surface functional groups imposed by Pauling bond valence sums. A summary of electrical double layer (EDL) theory is presented, including the results of several recent x-ray spectroscopic and parameter regression studies of the EDL for metal-(oxyhydr) oxide-aqueous solution interfaces. The effects of common inorganic and organic complexants on the sorption of trace metal cations at mineral-solution interfaces are considered, in the context of spectroscopic studies where possible. The results of sorption studies of trace metal cations on NOM, common bacteria, and marine biomass are reviewed, and the effects of coatings of NOM and microbial biofilms on cation uptake on mineral surfaces are discussed, based on macroscopic and spectroscopic data. The objective here is to assess the relative importance of inorganic versus organic sorption processes in aquatic systems. The paper concludes with a discussion of the effects of water composition on trace element removal mechanisms, with the aim of providing an understanding of the effects of the high salinity of seawater on trace element sorption processes. The information presented in this review indicates that sorption processes on mineral, NOM, and microbial and algal surfaces, including true adsorption and precipitation, are highly effective at removing trace elements from natural waters and generally supports Krauskopf's (1956) conclusion that such processes are likely responsible for the present trace element concentrations in seawater.     

Rapid clay transformations in Delaware salt marshes

Salt marshes are the major areas for net sedimentation in many estuaries such as the Delaware Bay, and their diagenetic chemistry is harsh and extreme with large seasonal excursions in chlorinity (1–50 ppt), pH (4–6), and Eh (−240+120). Such diagenesis is driven by organic matter decomposition using redox cycles of S and Fe materials imported primarily as tidal sea water SO₄ and Fe silicates, respectively.Important and quantitative changes in clay mineralogy occur within a decade at the redox boundary in a high marsh sediment near Lewes, Delaware. The clay mineralogy consists initially of a micaceous illite and chlorite mixture accumulating at the salt marsh surface. It is comprised of relic glacial sediments deposited on the continental slope during their net tidal movement from the sea to land. Once buried, these detrital clays are transformed into a new assemblage containing an illite/smectitic mixed layer mineral of poor crystallinity. Using curve decomposition techniques on complex X-ray traces, it is estimated that this new phase constitutes 45–55% of the clay fraction.The redox boundary where the sharp transition occurs is only about 20 a old as determined by ²¹⁰Pb and ¹³⁷Cs geochronology, and, thus, the clay mineral transformation is rapid. The occurrence of the new, abundant clay mineral is very abrupt (less than 1 cm at 12 cm in depth) and, thus, may itself occur in as little as three years. Once formed, the new mixed layer phase remains stable during the subsequent 40 a of burial from the time of formation at the oxic/anoxic boundary.Slow transformations of unstable primary clay reactants such as illite and chlorite are a common process of soil formation. However such rapid clay reactions have rarely been documented in either subaerial or submerged soil settings. The formation of a smectite mineral product of high chemical reactivity for a significant portion of the clays in a soil is unusual. In fact, the abrupt change in clay mineralogy in the salt marsh occurs precisely at the sharp evolution in salt marsh geochemistry from oxidized to reducing conditions where there is extensive redox cycling of Fe and S phases. A large seasonal oscillation in interstitial pH and Eh probably contributes to the rapid clay transformation. Such clay transformations may have important implications for the retention of other trace elements entering the salt marsh by atmospheric fallout and tidal cycles, or the release of such metal inventories after burial.     

Mechanism of pyroxene and amphibole weathering—I. Experimental studies of iron-free minerals

The short term (2–40 days) dissolution of enstatite, diopside, and tremolite in aqueous solution at low temperatures (20–60°C) and pH 1–6 has been studied in the laboratory by means of chemical analyses of reacting solutions for Ca²⁺, Mg²⁺, and Si(OH)₄ and by the use of X-ray photoelectron spectroscopy (XPS) for detecting changes in surface chemistry of the minerals. All three minerals were found to release silica at a constant rate (linear kinetics) providing that ultrafine particles, produced by grinding, were removed initially by HF treatment. All three also underwent incongruent dissolution with preferential release of Ca and/or Mg relative to Si from their outermost surfaces. The preferential release of Ca, but not Mg for diopside at pH 6 was found by both XPS and solution chemistry verifying the theoretical prediction of greater mobility of cations located in M₂ structural sites. Loss mainly from M₂ sites also explains the degree of preferential loss of Mg from enstatite at pH 6; similar structural arguments apply to the loss of Ca and Mg from the surface of tremolite. In the case of diopside and tremolite initial incongruency was followed by essentially congruent cation-plus-silica dissolution indicating rapid formation of a constant-thickness, cation-depleted surface layer. Cation depletion at elevated temperature and low pH (~ 1) for enstatite and diopside was much greater than at low temperature and neutral pH, and continued reaction resulted in the formation of a surface precipitate of pure silica as indicated by solubility calculations, XPS analyses, and scanning electron microscopy.From XPS results at pH 6, model calculations indicate a cation-depleted altered surface layer of only a few atoms thickness in all three minerals. Also, lack of shifts in XPS peak energies for Si, Ca, and Mg, along with undersaturation of solutions with respect to all known Mg and Ca silicate minerals, suggest that cation depletion results from the substitution of hydrogen ion for Ca²⁺ and/or Mg²⁺ in a modified silicate structure and not from the precipitation of a new, radically different surface phase. These results, combined with findings of high activation energies for dissolution, a non-linear dependence on a_H⁺ for silica release from enstatite and diopside, and the occurrence of etch pitting, all point to surface chemical reaction and not bulk diffusion (either in solution or through altered surface layers) as the rate controlling mechanism of iron-free pyroxene and amphibole dissolution at earth surface temperatures.     

Do clay mineral dissolution rates reach steady state?

The temporal evolution of natural illite du Puy dissolution rates was measured from Si release rates in single-pass flow-through experiments lasting at least 100 days at 25°C and pH ranging from 2 to 12. Si release rates decreased by a factor of five and three at pH 12 and 2, respectively, during the experiments. These observations are interpreted to stem from changes in illite du Puy reactive surface area during these experiments. As the edges of clay minerals dissolve faster than the basal planes, dissolution tends to change clay mineral morphology decreasing the percentage of reactive edge sites. This continuously changing morphology prevents illite dissolution rates from attaining steady state during laboratory experiments lasting 100 to 200 days. A similar temporal decrease in dissolution rates is evident for many different sets of clay mineral dissolution rate data available in the literature. It seems reasonable, therefore, to expect that clay mineral dissolution does not attain steady state in nature, but rather their dissolution rates decrease continuously during their dissolution.     

CO2-water-basalt interaction. Numerical simulation of low temperature CO2 sequestration into basalts

The interaction between CO₂-rich waters and basaltic glass was studied using reaction path modeling in order to get insight into the water-rock reaction process including secondary mineral composition, water chemistry and mass transfer as a function of CO₂ concentration and reaction progress (ξ). The calculations were carried out at 25-90 °C and pCO₂ to 30 bars and the results were compared to recent experimental observations and natural systems. A thermodynamic dataset was compiled from 25 to 300 °C in order to simulate mineral saturations relevant to basalt alteration in CO₂-rich environment including revised key aqueous species for mineral dissolution reactions and apparent Gibbs energies for clay and carbonate solid solutions observed to form in nature. The dissolution of basaltic glass in CO₂-rich waters was found to be incongruent with the overall water composition and secondary mineral formation depending on reaction progress and pH. Under mildly acid conditions in CO₂ enriched waters (pH <6.5), SiO₂ and simple Al-Si minerals, Ca-Mg-Fe smectites and Ca-Mg-Fe carbonates predominated. Iron, Al and Si were immobile whereas the Mg and Ca mobility depended on the mass of carbonate formed and water pH. Upon quantitative CO₂ mineralization, the pH increased to >8 resulting in Ca-Mg-Fe smectite, zeolites and calcite formation, reducing the mobility of most dissolved elements. The dominant factor determining the reaction path of basalt alteration and the associated element mobility was the pH of the water. In turn, the pH value was determined by the concentration of CO₂ and extent of reaction. The composition of the carbonates depended on the mobility of Ca, Mg and Fe. At pH <6.5, Fe was in the ferrous oxidation state resulting in the formation of Fe-rich carbonates with the incorporation of Ca and Mg. At pH >8, the mobility of Fe and Mg was limited due to the formation of clays whereas Ca was incorporated into calcite, zeolites and clays. Competing reactions between clays (Ca-Fe smectites) and carbonates at low pH, and zeolites and clays (Mg-Fe smectites) and carbonates at high pH, controlled the availability of Ca, Mg and Fe, playing a key role for low temperature CO₂ mineralization and sequestration into basalts. Several problems of the present model point to the need of improvement in future work. The determinant factors linking time to low temperature reaction path modeling may not only be controlled by the primary dissolving phase, which presents challenges concerning non-stoichiometric dissolution, the leached layer model and reactive surface area, but may include secondary mineral precipitation kinetics as rate limiting step for specific reactions such as retrieved from the present reaction path study.     

The surface chemistry of multi-oxide silicates

The surface chemistry of natural wollastonite, diopside, enstatite, forsterite, and albite in aqueous solutions was characterized using both electrokinetic techniques and surface titrations performed for 20 min in batch reactors. Titrations performed in such reactors allow determination of both proton consumption and metal release from the mineral surface as a function of pH. The compositions, based on aqueous solution analysis, of all investigated surfaces vary dramatically with solution pH. Ca and Mg are preferentially released from the surfaces of all investigated divalent metal silicates at pH less than ∼8.5-10 but preferentially retained relative to silica at higher pH. As such, the surfaces of these minerals are Si-rich and divalent metal poor except in strongly alkaline solutions. The preferential removal of divalent cations from these surfaces is coupled to proton consumption. The number of protons consumed by the preferential removal of each divalent cation is pH independent but depends on the identity of the mineral; ∼1.5 protons are consumed by the preferential removal of each Ca atom from wollastonite, ∼3 protons are consumed by the preferential removal of each Mg or Ca atom from diopside or enstatite, and ∼4 protons are consumed by the preferential removal of each Mg from forsterite. These observations are interpreted to stem from the creation of additional ‘internal’ adsorption sites by the preferential removal of divalent metal cations which can be coupled to the condensation of partially detached Si. Similarly, Na and Al are preferentially removed from the albite surface at 2 > pH > 11; mass balance calculations suggest that three protons are consumed by the preferential removal of each Al atom from this surface over this entire pH range. Electrokinetic measurements on fresh mineral powders yield an isoelectric point (pH_IEP) 2.6, 4.4, 3.0, 4.5, and <1, for wollastonite, diopside, enstatite, forsterite, and albite, respectively, consistent with the predominance of SiO₂ in the surface layer of all of these multi-oxide silicates at acidic pH. Taken together, these observations suggest fundamental differences between the surface chemistry of simple versus multi-oxide minerals including (1) a dependency of the number and identity of multi-oxide silicate surface sites on the aqueous solution composition, and (2) the dominant role of metal-proton exchange reactions on the reactivity of multi-oxide mineral surfaces including their dissolution rate variation with aqueous solution composition.