Quantification of drying induced acidity at the mineral-water interface using ATR-FTIR spectroscopy

Drying induced pH changes were quantified on the surface of Na⁺, Ca²⁺, Mg²⁺ and Al³⁺ saturated smectite and kaolinite clays. This was achieved using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy to measure real time changes to a pH indicator, sorbed to the clay mineral surface, during wetting and drying events. Using this technique it was possible to measure how low the pH of the surface drops during dehydration, the critical water content at which acidification of the surface begins and lastly how reversible the pH decrease is. The results show that only Al³⁺-smectite shows acidification below pH 4.8 with drying. The pH starts to decrease on the Al³⁺-smectite surface even when significantly hydrated (gravimetric water content ∼ 125 mg/m²), and falls to between 1.2 and 1.4 when completely air dry. The drying induced pH decrease is completely reversible on rewetting, suggesting large pH oscillations may occur on smectite surfaces with appreciable exchangeable Al³⁺. Aluminium saturated kaolinite did not show significant acidification in response to drying (pH > 3.5), however, a 0.1 M AlCl₃ solution evaporated to a final pH of 2.8. The enhanced acidification observed on an Al-smectite clay compared to a solution containing free Al³⁺ ions highlights the role of highly charged surfaces in the hydrolysis reaction that occurs within the hydration shell of exchangeable Al³⁺ ions.     

The dissolution rates of gibbsite in the presence of chloride, nitrate, silica, sulfate, and citrate in open and closed systems at 20°C

The dissolution of well crystallized gibbsite far at from equilibrium was studied in batch and mixed flow through reactors. The dissolution experiments were carried out between pH 2 and 6 in the presence of 10 mmol L⁻¹ citrate, at pH 2 and 3 in the presence of 10 mmol L⁻¹ chloride, nitrate, and sulfate, and at pH 2 and 3 in the presence of 1.5 mmol L⁻¹ silica at 20°C. The dissolution rate of gibbsite, R_Al (mol m⁻² s⁻¹), increases in the order of chloride ≈ nitrate < silica < sulfate ≈ citrate. In presence of silica, sulphate, and citrate dissolution is catalysed by the formation of aluminium complexes at the gibbsite surface (pH 2 and 3). From pH 2 to 3 no effect of R_Al on hydrogen activity is predicted as singly coordinated surface sites at the edges of the platy gibbsite crystals, [≡AlOH₂^+0.5] ≈ [≡AlOH], are almost saturated with protons. However at pH >3 dissolution is slowed by a decrease of [≡AlOH₂^+0.5].Gibbsite dissolution rates measured in closed and open systems were identical within the experimental and analytical uncertainty. This observation indicates that gibbsite dissolution is a surface controlled process. If dissolution of gibbsite occurs close to equilibrium R_Al values may be predicted by an approximately linear function of ΔG_r.     

Studies on the solid acidity of heated and cation-exchanged montmorillonite using n-butylamine titration in non-aqueous system and diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy

The effects of heating and cation exchange on the solid acidity of montmorillonite were investigated using n-butylamine titration in non-aqueous system and diffuse reflectance Fourier transform infrared spectroscopy. The number of total, Brønsted, and Lewis acid sites showed the same modulation tendency with increasing heating temperature, reaching a maximum at 120 °C and subsequently decreasing until it reaches a minimum at 600 °C. The Lewis acid sites result from unsaturated Al³⁺ cations, and their number increased with the heating temperature due to the dehydration and dehydroxylation of montmorillonite. The generation and evolution of Brønsted acidity were mainly related to interlayer-polarized water molecules. Water adsorbed on the unsaturated Al³⁺ ions also acted as a Brønsted acid. The acid strength of the Brønsted acid sites was dependent on the polarization ability of the exchangeable cation, the amount of interlayer water, and the degree of dissociation of the interlayer water coordinated to exchangeable cations. All cation-exchanged montmorillonites exhibited different numbers of acid sites and various distributions of acid strength. Brønsted acidity was predominant in Al³⁺-exchanged montmorillonite, whereas the Na⁺- and K⁺-exchanged montmorillonites showed predominantly Lewis acidity. Moreover, Mg²⁺- and Li⁺-exchanged montmorillonites exhibited approximately equal numbers of Brønsted and Lewis acid sites. The Brønsted acidity of cation-exchanged montmorillonite was positively correlated with the charge-to-radius ratios of the cations, whereas the Lewis acidity was highly dependent on the electronegativity of the cations. The acid strengths of Al³⁺- and Mg²⁺-exchanged montmorillonites were remarkably higher than those of monovalent cation-exchanged montmorillonites, showing the highest acid strength (H ₀ ≤ ?3.0). Li⁺- and Na⁺-exchanged montmorillonites exhibited an acid strength distribution of ?3.0 < H ₀ ≤ 4.8, with the acid strength ranging primarily from 1.5 to 3.3 in Li⁺-exchanged montmorillonite, whereas only weaker-strength acid sites (1.5 < H ₀ ≤ 4.8) were present in K⁺-exchanged montmorillonite. The results of the catalysis experiments indicated that montmorillonite promoted the thermal decomposition of the model organic. The catalytic activity showed a positive correlation with the solid acidity of montmorillonite and was affected by cation exchange, which occurs naturally in geological processes.     

Gibbsite solubility and thermodynamic properties of hydroxy-aluminum ions in aqueous solution at 25°C

Solubility curves were determined for a synthetic gibbsite and a natural gibbsite (Minas Gerais, Brazil) from pH 4 to 9, in 0.2% gibbsite suspensions in 0.01 M NaNO₃ that were buffered by low concentrations of non-complexing buffer agents. Equilibrium solubility was approached from oversaturation (in suspensions spiked with Al(NO₃)₃ solution), and also from undersaturation in some synthetic gibbsite suspensions. Mononuclear Al ion concentrations and pH values were periodically determined. Within 1 month or less, data from over-and undersaturated suspensions of synthetic gibbsite converged to describe an equilibrium solubility curve. A downward shift of the solubility curve, beginning at pH 6.7, indicates that a phase more stable than gibbsite controls Al solubility in alkaline systems. Extrapolation of the initial portion of the high-pH side of the synthetic gibbsite solubility curve provides the first unified equilibrium experimental model of Al ion speciation in waters from pH 4 to 9.The significant mononuclear ion species at equilibrium with gibbsite are Al³⁺, AlOH²⁺, Al(OH)⁺₂ and Al(OH)^?₄, and their ion activity products are $\text{1K}{}_{50}\text{= 1.29 × 10}{}^8$, $\text{1K}{}_{\mathrm{s1}}\text{= 1.33 × 10}{}^3$, $\text{1K}{}_{\mathrm{s2}}\text{= 9.49 × 10}{}^{\mathrm{?3}}$ and $\text{1K}{}_{\mathrm{s4}}\text{= 8.94 × 10}{}^{\mathrm{?15}}$. The calculated standard Gibbs free energies of formation (ΔG°_f) for the synthetic gibbsite and the A1OH²⁺, Al(OH)⁺₂ and Al(OH)^?₄ ions are ?276.0, ?166.9, ?216.5 and ?313.5 kcal mol^?1, respectively. These ΔG°_f values are based on the recently revised ΔG°_f value for Al³⁺ (?117.0 ± 0.3 kcal mol_?1) and carry the same uncertainty. The ΔG°_f of the natural gibbsite is ?275.1 ± 0.4 kcal mol^?, which suggests that a range of ΔG°_f values can exist even for relatively simple natural minerals.     

Solubility relationships of aluminum and iron minerals associated with acid mine drainage

The ability to properly manage the oxidation of pyritic minerals and associated acid mine drainage is dependent upon understanding the chemistry of the disposal environment. One accepted disposal method is placing pyritic-containing materials in the groundwater environment. The objective of this study was to examine solubility relationships of Al and Fe minerals associated with pyritic waste disposed in a low leaching aerobic saturated environment. Two eastern oil shales were used in this oxidizing equilibration study, a New Albany Shale (unweathered, 4.6 percent pyrite), and a Chattanooga Shale (weathered, 1.5 percent pyrite). Oil shale samples were equilibrated with distilled-deionized water from 1 to 180 d with a 1∶1 solid-to-solution ratio. The suspensions were filtered and the clear filtrates were analyzed for total cations and anions. Ion activities were calculated from total concentrations. Below pH 6.0, depending upon SO ₄ ²⁻ activity, Al³⁺ solubility was controlled by AlOHSO₄ (solid phase) for both shales. Initially, Al³⁺ solubility for the New Albany Shale showed equilibrium with amorphous Al(OH)₃. The pH decreased with time, and Al³⁺ solubility approached equilibrium with AlOHSO_4(s). Below pH 6.0, Fe³⁺ solubility appeared to be regulated by a basic iron sulfate solid phase with the stoichiometric composition of FeOHSO_4(s). The results of this study indicate that below pH 6.0, Al³⁺ solubilities, are limited by basic Al and Fe sulfate solid phases (AlOHSO_4(s) and FeHSO_4(s)). The results from this study further indicate that the acidity in oil shale waters is produced from the hydrolysis of Al³⁺ and Fe³⁺ activities in solution. These results indicate a fundamental change in the stoichiometric equations used to predict acidity from iron sulfide oxidation. The results of this study also indicate that water quality predictions associated with acid mine drainage can be based on fundamental thermodynamic relationships. As a result, waste management decisions can be based on waste-specific/site-specific test methods.     

Pollution caused by metallic fragments introduced into soils because of World War I activities

 The influence of parent rock and soil material on the corrosion rate of metallic fragments that remained in soil after World War I in the Soča front area (Slovenia), as well as the corrosion products of these fragments, were studied. The results of corrosion tests did not indicate appreciable differences in corrosion rates between various corrosion media. Consequently, the corrosion rates are influenced mostly by soil aeration, soil humidity and also by microstructures of alloys. Soil type seems to have the most influence on corrosion products. For the pH and Eh ranges that prevail in the studied soils, goethite is the only stable iron mineral. Lead minerals are not stable, and lead, in a Pb²⁺ cation form, is probably adsorbed onto some minerals – especially goethite – or is bound with organic matter. In distric brown soil, lead stays in the cation form as Pb²⁺ because of high soil acidity. Cuprite is stable in rendzina and brown soil on limestone, whereas in distric brown soil copper stays in solution as Cu²⁺. Received: 7 October 1999 · Accepted: 8 March 2000     

Seasonal variation in nature and chemical compositions of spring water in Cuihua Mountain,Shaanxi Province,central China

Two springs (Cuihua Spring, Shuiqiuchi Spring) in Cuihua Mountain of the Qinling Mountains were observed and sampled monthly during 2004 and 2005 to trace their physical properties and chemical compositions with seasons. Although both pH values and cation (Ca²⁺, Mg²⁺, K⁺, and Na⁺) contents of Cuihua Spring are higher than those of Shuiqiuchi Spring, seasonal variations in both springs are obvious. The pH values of both spring waters are between 5.69 and 6.98, lower than that of rainwater during summer and autumn. From January to November, the pH values of both springs similarly vary from high to low and then to high again. Variations in electric conductivities of two spring waters are contrary, although their electric conductivities are positively correlative with the cation content respectively. This can be attributed to different water sources of the two springs or different acidic rocks they passed. The contents of HCO₃ ⁻, Ca²⁺, Mg²⁺, K⁺, and Na⁺ are low, indicating a low silicate weathering that the strata in this district are mainly composed of granite and schist of quartz and mica. Differing from change in spring water in karst regions of South China where abundant precipitation and dilution of rainwater cause low pH and electric conductivity in summer and autumn, the seasonal variations in the pH values and the electric conductivities of two springs in Qinling Mountains are attributed to seasonal changes in CO₂ produced by microorganisms’ activity in soil within respective year, rather than rainfall. The microorganisms’ activity in soil produces more CO₂ during summer and autumn. Therefore, the water nature of springs in silicate regions chiefly reflects the seasonal changes of CO₂ produced by the microorganisms in soil.     

安徽栏杆含金刚石基性岩中石榴子石矿物学特征

在中国东部皖北地区分布着新元古代镁铁质岩,其中一些碱性基性岩为金刚石的赋矿岩石。为了确定安徽栏杆金刚石矿区的石榴子石种类,对矿区内不同类型的石榴子石进行系统采样,测定了62件石榴子石微区化学成分。结果显示,安徽栏杆石榴子石矿物化学式A_3~(2+)B_2~(3+)(SiO_4)_3中的A组阳离子由Mg~(2+)、Fe~(2+)和Ca~(2+)离子占位,B主要由Al~(3+)、Fe~(3+)、Mn~(3+)和Cr~(3+)离子占位,三价阳离子主要为Al~(3+),二价阳离子主要为Ca~(2+),表明研究区石榴子石主要为钙铝-钙铁-镁铝石榴子石系列。在62个样品中,发现了超硅石榴子石。经过计算其形成的压力范围为12.1～12.8GPa,深度可达300km。     

Calcium isotope constraints on the uptake and sources of Ca in a base-poor forest: A new concept of combining stable (δCa) and radiogenic (εCa) signals

Plant-available reserves of major base cations, Ca²⁺ and Mg²⁺, decreased markedly in soils over the past century, thus posing a potential threat to forest ecosystem health. Trees are thought to obtain dissolved Ca²⁺ ions mainly from an easily accessible soil-water reservoir also termed the ‘exchangeable cation pool’. The status of Ca reserves in this soil pool is sensitive to anthropogenic perturbations such as soil acidification induced by acid rain and/or excessive timber harvesting. Here we show that in a base-poor forest of the northeastern USA (i.e. Wachusett Mountain, Massachusetts) the ‘exchangeable Ca pool’ of deeper mineral soils has a unique isotope signature that is significantly enriched in the radiogenic ⁴⁰Ca, due to the dissolution of K-rich silicate minerals such as biotite. Using a simple isotope mass balance, and assuming that the input of Ca from biotite has a ε_Ca signature of ∼16, the results of our calculation indicate that the weathering of biotite may supply a sizeable fraction, up to 25%, of Ca²⁺ ions into the ‘exchangeable cation pool’ of deeper mineral soils. Importantly, samples of local vegetation (i.e. woody tissues of red oak) show no detectable excess of the radiogenic ⁴⁰Ca, and based on our model the upper limit of a possible biotite-derived Ca contribution in vegetation is estimated at ∼5%. We also found no evidence of the radiogenic ⁴⁰Ca signal in the samples of forest floor and the uppermost organic-rich soils (0-15 cm depth), which in turn suggest that over the long-term development of the forest and its organic matter accumulation, the vegetation growth must have also relied primarily on the non-radiogenic Ca sources. Based on our experimental data, such sources may include (i) wet atmospheric deposition, (ii) the organically-complexed Ca in topsoil horizons, and (iii) chemical weathering and/or fungal-mediated dissolution of apatite and Ca-rich plagioclase. Hence, our stable and radiogenic Ca isotope data indicate that the studied base-poor forest is able to bypass the ‘exchangeable cation pool’ of deeper (i.e. below 15 cm) mineral soils, and still manages to meet its nutritional requirements with respect to Ca. Another important implication of this study is that the organically-complexed Ca in the topsoil horizon (0-15 cm depth) has to be tightly bound to the ion exchange sites, otherwise the large radiogenic ⁴⁰Ca signatures present in the ‘exchangeable cation pool’ of deep mineral soils would be swamped by the downward gravitational flux of non-radiogenic Ca from the decaying organic matter and litterfall. Hence, the limited mobility of the organically-complexed Ca in soils and its tight biological cycling could explain the lack of a significant impact of vegetation on the Ca isotope systematics observed in large rivers.     

DFT study of the cation arrangements in the octahedral and tetrahedral sheets of dioctahedral 2:1 phyllosilicates

Quantum mechanical calculations based on the density functional theory (DFT) are used to study the crystal structures of dioctahedral 2:1 phyllosilicates. The isomorphous cation substitution is investigated by exploring different substitutions of octahedral Al³⁺ by Mg²⁺ or Fe³⁺, tetrahedral substitution of Si⁴⁺ by Al³⁺, and different interlayer cations (IC) (Na⁺, K⁺, Ca²⁺, and Mg²⁺). Samples with different kinds of layer charges are studied: only tetrahedrally charged, only octahedrally charged, or mixed octahedral/tetrahedral charged. The effect of the relative arrangements of these substitutions on the lattice parameters and total energy is studied. The experimental observation of segregation tendency of Fe³⁺ and dispersion tendency of Mg²⁺ in the octahedral sheet is reproduced and explained with reference to the relative energies of the octahedral cation arrangements. These energies are higher than those due to the IC/tetrahedral and IC/octahedral relative arrangements. The tetrahedral and octahedral substitutions that generate charged layers also tend to be dispersed. The octahedral cation exchange potentials change with the IC-charge/ionic radius value.     

Mechanism and numerical simulation of multicomponent solute transport in sodic soils reclaimed by calcium sulfate

The mechanism for reclaiming sodic soils using calcium sulfate (CaSO₄) could provide a theoretical basis for the field application of CaSO₄ substitutes, including the by-products of flue gas desulfurization (BFGD), fly ash, and phosphorus gypsum. In this study, Ca²⁺ application experiment was conducted to analyze the dynamic changes of the cations in the reclamation of sodic soils with CaSO₄. A multicomponent solute transport model (UNSATCHEM) that considers ion adsorption exchange and dynamic changes in the soil’s hydraulic conductivity was subsequently used to simulate and predict the movement of ions. The Ca²⁺ application experiment consisted of four treatments with four CaSO₄ concentrations (0.5, 1, 1.5, and 2 g L^?1). When the Ca²⁺ concentrations in the supplied water were 14.71, 22.06, and 29.41 mmol L^?1, Ca²⁺ achieved penetration, and this process was faster when the Ca²⁺ concentration in the supplied water was higher. Ca²⁺ did not achieve penetration when the Ca²⁺ concentration was 7.35 mmol L^?1. UNSATCHEM was able to simulate the transportation mechanism of Ca²⁺ and Na⁺ in the soil solution in the Ca²⁺ application experiment, the adsorption and exchange between the Na⁺ in the soil colloid and Ca²⁺ in the soil solution, and the precipitation and dissolution of CaSO₄ with a high degree of accuracy. Sodic soil reclamation with CaSO₄ was not a short-term process. Compared with applying CaSO₄ only once, applying CaSO₄ in batches decreased the accumulation of soil salts and promoted its dissolution.     

Hydrogeochemistry and water quality assessment of shallow aquifers in the western flanks of Southern Western Ghats,SW India

The present study deals with the hydrogeochemistry and water quality of shallow aquifers in two important river basins—the Ithikkara and Kallada river basins—draining the south western flanks of Western Ghats in Kerala, South West India. Well water samples were collected from 20 dug wells with a depth range of 1 m below ground level (mbgl) to 18.2 mbgl during pre-monsoon, monsoon, and post-monsoon seasons of the year 2011–2012. These samples were analyzed for various physico-chemical parameters following standard methods and were evaluated for their interrelations and drinking water suitability. The pH of the water samples shows wide variation from highly acidic to highly alkaline water. About 80% of pre-monsoon samples recorded Fe²⁺ concentration above the permissible limit of drinking water standard. Water Quality Index (WQI) shows that majority of the well water samples fall in the category of excellent–good for drinking purpose. The results of the irrigation suitability assessment using the procedures like Percent Sodium, Sodium Absorption Ratio, Residual Sodium Carbonate, Kelly Index, Permeability Index, and Magnesium Hazard reveal that the well waters of the study area are fit for irrigation purpose. Na⁺/Cl^? ratio reflects the release of sodium to water due to silicate weathering. The samples have a Ca²⁺/Mg²⁺ ratio equal or greater than 2 indicating the effect of silicate minerals in contributing Ca²⁺ and Mg²⁺ ions to the well water. The saturation indices reveal that groundwater is supersaturated with SiO₂. Among the causative factors that determine the hydrochemical quality of well water samples, silicate weathering plays a pivotal role with significant input of ions from anthropogenic sources.     

Hydrogeochemical processes controlling fluoride enrichment within alluvial and hard rock aquifers in a part of a semi-arid region of Northern India

Rock–water interaction along with mineral dissolution/ precipitation plays a profound role in the control of fluoride ion concentration within the alluvial groundwater in a part of semi-arid northern India. In the premonsoon season, the alluvial region experiences evaporative processes leading to increase in Na⁺ ions which through reverse ion exchange processes are adsorbed onto suitable sites within the aquifer matrix in exchange for Ca²⁺ ion in solution. Increase in Ca²⁺ ions in solution inhibits fluorite mineral dissolution, thereby controlling premonsoon fluoride ion concentration within alluvial groundwaters (1.40?±?0.5 mg/l). In the postmonsoon season, however, higher average fluoride ion concentration within the alluvial aquifer samples (2.33?±?0.80 mg/l) is observed mainly due to increase in silicate weathering of fluoride-bearing rocks and direct ion exchange processes enabling Ca²⁺ ion uptake from solution accompanied with the release of fluoride ions. Combined effect of these processes results in average fluoride ion concentration falling above the WHO drinking water permissible limit (1.5 mg/l). Alternatively, the hard rock aquifer samples within the study area have an average fluoride ion concentration falling below the permissible limit in both the seasons.     

On local structural changes in lizardite-1T: {Si4+/Al3+}, {Si4+/Fe3+}, [Mg2+/Al3+], [Mg2+/Fe3+] substitutions

Geometrical changes induced by cation substitutions {Si⁴⁺/Al³⁺}[Mg²⁺/Al³⁺], {2Si⁴⁺/2Al³⁺} [2Mg²⁺/2Al³⁺], {Si⁴⁺/Fe³⁺} [Mg²⁺/Al³⁺] or [Mg²⁺/Fe³⁺], where {} and [] indicate tetrahedral and octahedral sheet in lizardite 1T, are studied by ab-initio quantum chemistry calculations. The majority of the models are based on the chemical compositions reported for various lizardite polytypes with the amount of Al in the tetrahedral sheets reported to vary from 3.5% to 8% in the 1T and 2H ₁, up to ~30% in the 2H ₂ polytype. Si⁴⁺ by Fe³⁺ substitution in the tetrahedral sheet with an Al³⁺ (Fe³⁺) in the role of a charge compensating cation in the octahedral sheet is also examined. The cation substitutions result in the geometrical changes in the tetrahedral sheets, while the octahedral sheets remain almost untouched. Substituted tetrahedra are tilted and their basal oxygens pushed down from the plane of basal oxygens. Ditrigonal deformation of tetrahedral sheets depends on the substituting cation and the degree of substitution.     

Metal release from dolomites at high partial-pressures of CO2

The potential for metal release associated with CO₂ leakage from underground storage formations into shallow aquifers is an important consideration in assessment of risk associated with CO₂ sequestration. Metal release can be driven by acidification of groundwaters caused by dissolution of CO₂ and subsequent dissociation of carbonic acid. Thus, acidity is considered one of the main drivers for water quality degradation when evaluating potential impacts of CO₂ leakage. Dissolution of carbonate minerals buffers the increased acidity. Thus, it is generally thought that carbonate aquifers will be less impacted by CO₂ leakage than non-carbonate aquifers due to their high buffering potential. However, dissolution of carbonate minerals can also release trace metals, often present as impurities in the carbonate crystal structure, into solution. The impact of the release of trace metals through this mechanism on water quality remains relatively unknown. In a previous study we demonstrated that calcite dissolution contributed more metal release into solution than sulfide dissolution or desorption when limestone samples were dissolved in elevated CO₂ conditions. The study presented in this paper expanded our work to dolomite formations and details a thorough investigation on the role of mineral composition and mechanisms on trace element release in the presence of CO₂. Detailed characterization of samples from dolomite formations demonstrated stronger associations of metal releases with dissolution of carbonate mineral phases relative to sulfide minerals or surface sorption sites. Aqueous concentrations of Sr²⁺, CO²⁺, Mn²⁺, Ni²⁺, Tl⁺, and Zn²⁺ increased when these dolomite rocks were exposed to elevated concentrations of CO₂. The aqueous concentrations of these metals correlate to aqueous concentrations of Ca²⁺ throughout the experiments. All of the experimental evidence points to carbonate minerals as the dominant source of metals from these dolomite rocks to solution under experimental CO₂ leakage conditions. Aqueous concentrations of Ca²⁺ and Mg²⁺ predicted from numerical simulation of kinetic dolomite dissolution match those observed in the experiments when the surface area is three to five orders of magnitude lower than the surface area of the samples measured by gas adsorption.     

Iron sulfide oxidation and the chemistry of acid generation

Acid mine drainage, produced from the oxidation of iron sulfides, often contains elevated levels of dissolved aluminum (AI), iron (Fe), and sulfate (SO₄) and low pH. Understanding the interactions of these elements associated with acid mine drainage is necessary for proper solid waste management planning. Two eastern oil shales were leached using humidity cell methods. This study used a New Albany Shale (4.6 percent pyrite) and a Chattanooga Shale (1.5 percent pyrite). The leachates from the humidity cells were filtered, and the filtrates were analyzed for total concentrations of cations and anions. After correcting for significant solution species and complexes, ion activities were calculated from total concentrations. The results show that the activities of Fe³⁺, Fe²⁺, Al³⁺, and SO₄ ²⁻ increased due to the oxidation of pyrite. Furthermore, the oxidation of pyrite resulted in a decreased pH and an increased pe+pH (redox-potential). The Fe³⁺ and Fe²⁺ activities appeared to be controlled by amorphous Fe(OH)₃ solid phase above a pH of 6.0 and below pe+pH 11.0. The Fe³⁺, Fe²⁺, and SO₄ ²⁻ activities reached saturation with respect to FeOHSO₄ solid phase between pH 3.0 and 6.0 and below pe+pH 11.0 Below a pH of 3.0 and above a pe+pH of 11.0, Fe²⁺, Fe³⁺, and SO₄ ²⁻ activities are supported by FeSO₄·7H₂O solid phase. Above a pH of 6.0, the Al³⁺ activity showed an equilibrium with amorphous Al(OH)₃ solid phase. Below pH 6.0, Al³⁺ and SO₄ ²⁻ activities are regulated by the AlOHSO₄ solid phase, irrespective of pe+pH. The results of this study suggest that under oxidizing conditions with low to high leaching potential, activities of Al and Fe can be predicted on the basis of secondary mineral formation over a wide range of pH and redox. As a result, the long-term chemistry associated with disposal environments can be largely predicted (including trace elements).     

The importance of unsaturated zone biogeochemical processes in determining groundwater composition, southeastern Australia

Analysis of soil, soil water and groundwater in the Mount William Creek catchment, southeastern Australia, shows that Mg²⁺ and Ca²⁺ within infiltrating rainfall are rapidly depleted by plant uptake and adsorption on clay minerals. Na⁺ and K⁺ may exhibit minor enrichment at shallow depths but are quickly readsorbed, so that cation/Cl^– ratios typical of groundwater are observed in soil water within the upper 200 cm of the soil profile for all species. The concentrations of K⁺ and Ca²⁺ in soil and groundwater are more depleted than Na⁺ and Mg²⁺ due to preferential uptake by vegetation. Removal of organic matter results in a continuing, long-term export of all major cations from the soil profiles. The processes of biogeochemical fractionation within the unsaturated zone rapidly modify the cation/Cl^– ratios of infiltrating rainfall to values characteristic of seawater. These mechanisms may have reached steady state, because groundwaters with seawater ion/Cl^– ratios are thousands of years old; the exchange sites on the soil clays are probably saturated, so cations supplied in rainfall are exported in organic matter and incorporated into recharge infiltrating into the groundwater. Much of the chemical evolution of groundwater traditionally attributed to processes within the aquifer is complete by the time recharge occurs; this evolutionary model may have broad application.     

Calcium adsorption at the rutile-water interface: a potentiometric study in NaCl media to 250°C

Calcium adsorption by rutile was studied potentiometrically from 25 to 250°C, at ionic strengths of 0.03 and 0.30 m in NaCl media, using two complementary experimental methodologies. In the first, net proton adsorption in the presence and absence of Ca²⁺ was monitored, and in the second, samples were periodically withdrawn during the course of a titration to determine Ca²⁺ adsorption directly. These experiments revealed that Ca²⁺adsorption systematically increased with temperature relative to the pH of zero net proton charge in NaCl media alone (pH_znpc(NaCl) – pH). That is, as temperature increased, Ca²⁺ adsorption commenced at progressively more positive pH_znpc(NaCl) – pH values. Increasing ionic strength from 0.03 to 0.30 m NaCl suppressed Ca²⁺ adsorption at all temperatures as a result of either increased competition from Na⁺ or greater complexation of Ca²⁺ by Cl⁻. Finally, there was no apparent trend in the proton stoichiometric ratios (moles H⁺ released / moles Ca²⁺ adsorbed) with increasing temperature. This suggests that the electrostatic and/or chemical processes involved in Ca²⁺ adsorption do not change greatly with increasing temperature. Favorable entropic effects, related to the increasing ease of releasing Ca²⁺ waters of hydration, are believed to be primarily responsible for the increase in adsorption with temperature.