A hydrogeochemical transport model for an oxidation experiment with pyrite/calcite/exchangers/organic matter containing sand

We report the hydrogeochemical modeling of a complicated suite of reactions that take place during the oxidation of pyrite in a marine sediment. The sediment was equilibrated in a column with MgCl₂ solution and subsequently oxidized with H₂O₂. The oxidation of pyrite triggers dissolution of calcite, cation and proton exchange, and CO₂ sorption. The composition of the column effluent was modeled with PHREEQC, a hydrogeochemical transport model. The model was extended with a formal ID transport module which includes dispersion and diffusion. The algorithm solves the advection-reaction-dispersion equation with explicit finite differences in a split-operator scheme. Also, kinetic reactions for pyrite oxidation, calcite dissolution and precipitation, and organic C oxidation were included. Kinetic relations for pyrite oxidation and calcite dissolution were taken from the literature, and a coefficient equivalent to the ratio A/V (surface over volume), was adjusted to fit the experimental data. The comparison of model and experiment shows that ion exchange and sorption are dominant chemical processes in regulating and buffering water quality changes upon the oxidation of pyrite. Cation exchange was assigned to the colloidal fraction ( < 2 μm) and deprotonated organic matter, proton buffering to organic matter, and CO₂ sorption to amorphous Fe-oxyhydroxide. These processes have been neglected in earlier modeling studies of pyrite oxidation in natural sediments.     

Diagenetic reactions in reservoir strata and geochemical properties of pore fluid and its origin in Songliao Basin

The reservoirs of the SOngliao Basin are composed of typical unstable sandstones,with high percentages of volcanic fragments and feldspar,In the course of sedimentation and burying,a series of physical and chemical reactions took place between minerals and pore water and water-rock reactions and ion exchange caused changes in ion assemblage of pore water,Hydration-hydrolysis,dissolution and the albitization of feldspar made many ions free from their framework and inter into the pore water,and induced the precipitation of a large amount of authigenic minerals such as smectite and chlorite,During the diagenesis of sandstone.diagenetic reactions involved several stages with increasing depth,and so did the precipitation of authigenic minerals and the transformaiton of minerals.The migration of ions is related with the precipitation,transformation and dissolution of authigenic minerals.Thus,to deepen our study on sandstone diagenesis is an important link for the analysis of ion migration in the evolution of pore water ,the origin and evolution of pore water could be tracked in terms of the geochemistry of fluid inclusions in authigenic minerals.And the isotopic composition of the authigenic mineral calcite can provide its genetic information.     

Biogeochemical processes in a clay formation in situ experiment: Part A - Overview, experimental design and water data of an experiment in the Opalinus Clay at the Mont Terri Underground Research Laboratory, Switzerland

An in situ test in the Opalinus Clay formation, termed porewater chemistry (PC) experiment, was carried out for a period of 5 years. It was based on the concept of diffusive equilibration whereby a traced water with a composition close to that expected in the formation was continuously circulated and monitored in a packed-off borehole. The main original focus was to obtain reliable data on the pH/pCO₂ conditions of the porewater, but because of unexpected microbiologically-induced redox reactions, the objective was extended to elucidate the biogeochemical processes occurring in the borehole and to understand their impact on pH/pCO₂ and porewater chemistry in the low permeability clay formation.The behaviour of the conservative tracers ²H and Br⁻ could be explained by diffusive dilution in the clay and moreover the results showed that diffusive equilibration between the borehole water and the formation occurred within about 3 year’s time. However, the composition and pH/pCO₂ conditions differed considerably from those of the in situ porewater. Thus, pH was lower and pCO₂ was higher than indicated by complementary laboratory investigations. The noted differences are explained by microbiologically-induced redox reactions occurring in the borehole and in the interfacial wall area which were caused by an organic source released from the equipment material. The degradation of this source was accompanied by sulfate reduction and - to a lesser extent - by methane generation, which induced a high rate of acetogenic reactions corresponding to very high acetate concentrations for the first 600 days. Concomitantly with the anaerobic degradation of an organic source, carbonate dissolution occurred and these processes resulted in high pCO₂ and alkalinities as well as drop in pH. Afterwards, the microbial regime changed and, in parallel to ongoing sulfate reduction, acetate was consumed, leading to a strong decrease in TOC which reached background levels after about 1200 days. In spite of the depletion of this organic perturbation in the circuit water, sulfate reduction and methanogenesis continued to occur at a constant rate leading to near-to-constant concentrations of sulfate and bicarbonate as well as pH/pCO₂ conditions until the end of the experiment. The main sink for sulphur was iron sulfide, which precipitated as FeS (am) and FeS₂.The chemical and isotopic composition was affected by the complex interplay of diffusion, carbon degradation rates, mineral equilibria and dissolution rates, iron sulfide precipitation rates, and clay exchange reactions. The ¹³C signals measured for different carbon species showed significant variations which could only be partly explained. The main cations, such as Na, Ca and Mg remained remarkably constant during the experiment, thus indicating the strong buffering of the formation via cation and proton exchange as well as carbonate dissolution/precipitation reactions.     

Navajo Sandstone–brine–CO<Subscript>2</Subscript> interaction: implications for geological carbon sequestration

The injection of CO₂ into deep saline aquifers is being considered as an option for greenhouse gas mitigation. However, the response of an aquifer to the injected CO₂ is largely unknown. Experiments involving the reaction of Navajo Sandstone with acidic brine were conducted at 200°C and 25 or 30 MPa to evaluate the extent of fluid–rock interactions. The first experiment examined sandstone interaction with CO₂-impregnated brine; the second experiment examined sandstone dissolution in CO₂-free acidic brine; the third one is carried out in a mixed-flow reactor and designed to measure sandstone dissolution rates based on time-series Si concentrations. The solution chemistry data indicate that the SiO₂(aq) increases gradually and pH increases slowly with reaction progress. Silicate minerals in the sandstone display textures (dissolution features, secondary mineralization), indicating that these phases are reacting strongly with the fluid. Dissolution of feldspars and conversion of smectite to illite are likely to be the two reactions that contribute to the release of SiO₂(aq). The product minerals present at the end of the experiments are illite, illite/smectite, allophane, and carbonate minerals (for the CO₂-charged system). Dissolved CO₂ is likely to acidify the brine and to provide a source of carbon for the precipitation of carbonate minerals. Mineral trapping through the precipitation of carbonate minerals is favored thermodynamically and was observed in the experiments. The chemical reactions likely increase the bulk porosity of the sandstone due to dissolution of silicate minerals. However, allophane and illite/smectite fill voids in sandstone grains. There is no evidence for the removal of clay coatings due to chemical reactions. It is uncertain whether the mechanical forces near an injection well would mobilize the smectite and allophane and clog pore throats. Trace amounts of metals, including Cu, Zn, and Ba, were mobilized.     

Timescales of interface-coupled dissolution-precipitation reactions on carbonates

In the Earth's upper crust, where aqueous fluids can circulate freely, most mineral transformations are controlled by the coupling between the dissolution of a mineral that releases chemical species into the fluid and precipitation of new minerals that contain some of the released species in their crystal structure, the coupled process being driven by a reduction of the total free-energy of the system. Such coupled dissolution-precipitation processes occur at the fluid-mineral interface where the chemical gradients are highest and heterogeneous nucleation can be promoted, therefore controlling the growth kinetics of the new minerals. Time-lapse nanoscale imaging using Atomic Force Microscopy (AFM) can monitor the whole coupled process under in situ conditions and allow identifying the time scales involved and the controlling parameters. We have performed a series of experiments on carbonate minerals (calcite, siderite, dolomite and magnesite) where dissolution of the carbonate and precipitation of a new mineral was imaged and followed through time. In the presence of various species in the reacting fluid (e. g. antimony, selenium, arsenic, phosphate), the calcium released during calcite dissolution binds with these species to form new minerals that sequester these hazardous species in the form of a stable solid phase. For siderite, the coupling involves the release of Fe²⁺ ions that subsequently become oxidized and then precipitate in the form of Fe^III oxyhydroxides. For dolomite and magnesite, dissolution in the presence of pure water (undersaturated with any possible phase) results in the immediate precipitation of hydrated Mg-carbonate phases. In all these systems, dissolution and precipitation are coupled and occur directly in a boundary layer at the carbonate surface. Scaling arguments demonstrate that the thickness of this boundary layer is controlled by the rate of carbonate dissolution, the equilibrium concentration of the precipitates and the kinetics of diffusion of species in a boundary layer. From these parameters a characteristic time scale and a characteristic length scale of the boundary layer can be derived. This boundary layer grows with time and never reaches a steady state thickness as long as dissolution of the carbonate is faster than precipitation of the new mineral. At ambient temperature, the surface reactions of these dissolving carbonates occur on time-scales of the order of seconds to minutes, indicating the rapid surface rearrangement of carbonates in the presence of aqueous fluids. As a consequence, many carbonate-fluid reactions in low temperature environments are controlled by local thermodynamic equilibria rather than by the global equilibrium in the whole system.     

Calcium isotope evidence for suppression of carbonate dissolution in carbonate-bearing organic-rich sediments

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (δ^44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of δ^44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, δ^44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the δ^44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.     

布隆湖水化学成分的形成机制

在对研究区地质及水文地质条件进行分析的基础上,根据对各类水样水质资料的分析,得出与补给水相比,布隆湖水中各组分含量普遍升高、TDS显著增大、水化学类型由HCO3.Cl型变为Cl.SO4.HCO3型、水质由良好的饮用水变为多种组分含量超标的不可饮水;认为布隆湖水的化学成分是在补给水化学成分的基础上,经过蒸发浓缩作用、溶解/沉淀及阳离子交替吸附作用而形成的。使用离子比值分析方法,估算出河水进入布隆湖后,蒸发比例高达71.43%,使各组分含量增大了约3.5倍;质量平衡模拟结果表明,形成湖水化学成分的主要化学作用是岩盐、石膏的溶解、方解石的沉淀以及CO2的逸出,此外还发生了少量的阳离子交替吸附作用。     

Using non-conservative tracers to characterise karstification processes in the Merinos-Colorado-Carrasco carbonate aquifer system (southern Spain)

The systematic sampling of the chemical composition of the groundwater from five karst springs (including an overflow spring) and one outflowing borehole have permitted to determine distinctive chemical changes in the waters that reflect the geochemical processes occurring in a carbonate aquifer system from southern Spain. The analysis of the dissolution parameters revealed that geochemical evolution of the karst waters basically depends on the availability of the minerals forming aquifer rocks and the residence time within the aquifers. In the three proposed scenarios in the aquifers, which include the preferential flow routines, the more important geochemical processes taking place during the groundwater flow from the recharge to the discharge zones are: CO₂ dissolution and exsolution (outgassing), calcite net dissolution, calcite and dolomite sequential dissolution, gypsum/anhydrite and halite dissolution, de-dolomitization and calcite precipitation. A detailed analysis of the hydrochemical data set, saturation indices of the minerals and partial pressure of CO₂ in the waters joined to the application of geochemical modelling methods allowed the elaboration of a hydrogeochemical model of the studied aquifers. The developed approach contributes to a better understanding of the karstification processes and the hydrogeological functioning of carbonate aquifers, the latter being a crucial aspect for the suitable management of the water resources.     

Identification and evolution of hydrogeochemical processes in the groundwater environment in an area of the Palar and Cheyyar River Basins,Southern India

The Palar and Cheyyar River Basins in Tamil Nadu state of Southern India are characterised by different geological formations, and groundwater is the major source for domestic, agricultural and other water-related activities. Hydrogeochemical studies were carried out in this area with the objective of identifying the geochemical processes and their relation to groundwater quality. Groundwater samples were collected once a month from 43 groundwater wells in this area from January 1998 to July 1999. Sampling procedures and chemical analysis were carried out as per the standard methods. Chemical data are used for mathematical calculations and graphical plots to understand the chemical process and its relation to the groundwater quality. The chemical composition of groundwater in the central part of the study area mainly depends on the recharge from lakes and the river, which is explained by a mixing mechanism. In addition, weathering of silicate minerals controls the concentration of major ions such as sodium, calcium, magnesium and potassium in the groundwater of this area. Further, the activity ratios indicate that the groundwater is in equilibrium with kaolinite, smectite and montmorrillonite. The reverse ion exchange process controls the concentration of calcium, magnesium and sodium in hard rock formations, and dissolution of carbonate minerals and accessory minerals is the source of Ca and Mg, in addition to cation exchange in the sedimentary formations. In general, the chemical composition of the groundwater in this area is influenced by rock–water interaction, dissolution and deposition of carbonate and silicate minerals, ion exchange, and surface water interactions.     

Diagenetic processes in Holocene carbonate sediments: Florida Bay mudbanks and islands

The sedimentology, mineralogy and pore fluid chemistry of seven cores from the Holocene sediments of Florida Bay were studied to determine the physical processes and diagenetic reactions affecting the sediments. The cores were taken in a transect from a shallow mudbank onto a small adjacent island, Jimmy Key. Steady state models of pore fluid chemistry are used to estimate the rates of various reactions. In the mudbank sediments, little carbonate mineral diagenesis is taking place. No change in sediment mineralogy is detectable and pore water profiles of Ca²⁺, Mg²⁺ and Sr²⁺ show only minor variation. Chloride concentrations indicate substantial biological mixing of seawater from the bay into the sediments in one of the cores. Pore water analyses of sulphate and alkalinity show only a low degree of sulphate depletion and a decreasing extent of sulphate reduction downcore. Models of sulphate reduction in the mudbank show that there is substantial chemical exchange between the sediment pore fluids and water from the bay probably as a result of bio-irrigation. The sulphate and alkalinity data also suggest that the underlying Pleistocene rocks contain water of near normal seawater composition. Stratigraphic analysis and δ¹³C analyses of the organic carbon in the sediments of the island cores show that the sediments were primarily deposited in a subtidal mudbank setting; only the upper 20–30 cm is supratidal in origin. Nevertheless, island formation had a significant effect on pore fluid chemistry and the types of diagenetic reactions throughout the sediment column. Chloride in the sediment pore fluids is more than twice the normal seawater concentrations over most of the depth of the cores. The constant, elevated chloride concentrations indicate that hypersaline fluids which formed in ponds on the island are advected downward through the sediments. Models of the chloride profiles yield an estimate of 2·5 cm yr^?1 as a minimum advective velocity. Changes in pore water chemistry with depth are interpreted as indicating the following sequence of reactions: (1) minor high-Mg calcite dissolution and low-Mg calcite precipitation, from 0 to 35 cm; (2) Ca- or Mg-sulphate dissolution and low-Mg calcite precipitation, from 5 to 35 cm; (3) dolomite or magnesite precipitation together with sulphate reduction, from 35 to 55 cm; and (4) little reaction below 55 cm. In addition, one or more as yet unidentified reactions must be taking place from 5 to 55 cm depth as an imbalance in possible sources and sinks of alkalinity is observed. The imbalance could be explained if chloride is not completely conservative. Despite the pore fluid chemical evidence for diagenetic reactions involving carbonate minerals, no changes in sediment mineralogy were detected in X-ray diffraction analyses, probably because of the comparatively young age of the island.     

Ennoyage des mines de fer lorraines : impact sur la qualité de l'eau

The flooding of the abandoned iron mines of Lorraine leads to a degradation of the groundwater quality. Laboratory experiments allowed us to build a kinetic chemical model based on simple chemical mechanisms. During mining operations, pyrite oxidation and carbonate dissolution lead to the precipitation of gypsum. The local decrease of pH favours local dissolutions of minerals and releases ions that are fixed on cationic exchange sites. During the flooding of the mine workings, the dissolution of the newly precipitated gypsum, the precipitation of carbonates and cationic exchange reactions are responsible for the increase of the concentrations of sulphate, magnesium, sodium, potassium and strontium in water. Thereafter, these concentrations would decrease with the natural leaching of the mining reservoir. To cite this article: P. Collon et al., C. R. Geoscience 336 (2004).     

Hydrothermal mixing,carbonate dissolution and sulfide precipitation in Mississippi Valley-type deposits

A large number of Mississippi Valley-Type (MVT) deposits are located within dissolution zones in carbonate host rocks. Some genetic models propose the existence of cavities generated by an earlier event such as a shallow karstification, that were subsequently filled with hydrothermal minerals. Alternative models propose carbonate dissolution caused by the simultaneous precipitation of sulfides. These models fail to explain either the deep geological setting of the cavities, or the observational features which suggest that the dissolution of carbonates and the precipitation of minerals filling the cavities are not strictly coeval. We present a genetic model inspired by the textural characteristics of MVT deposits that accounts for both the dissolution of carbonate and precipitation of sulfides and later carbonates in variable volumes. The model is based on the mixing of two hydrothermal fluids with a different chemistry. Depending on the proportion of the end members, the mixture dissolves and precipitates carbonates even though the two mixing solutions are both independently saturated in carbonates. We perform reactive transport simulations of mixing of a regional groundwater and brine ascending through a fracture, both saturated in calcite, but with different overall chemistries (Ca and carbonate concentrations, pH, etc). As a result of the intrinsic effects of chemical mixing, a carbonate dissolution zone, which is enhanced by acid brines, appears above the fracture, and another zone of calcite precipitation builds up between the cavity and the surrounding rock. Sulfide forms near the fracture and occupies a volume smaller than the cavity. A decline of the fluid flux in the fracture would cause the precipitation of calcite within the previously formed cavities. Therefore, dissolution of carbonate host rock, sulfide precipitation within the forming cavity, and later filling by carbonates may be part of the same overall process of mixing of fluids in the carbonate host rock.Editorial handling: C. Everett     

Estimation of reactive mineral surface area during water-rock interaction using fluid chemical data

Mineral dissolution and precipitation reactions actively participate to control fluid chemistry during water-rock interaction. However, it is difficult to estimate and normalize bulk reaction rates if the mineral surface area effectively participating in the reactions is unknown. In this study, we evaluated the changing of the reactive mineral surface area during the interaction between CO₂-rich fluids and albitite rock reacting under flow-through conditions. Our methodology, adopting an inverse modelling approach, is based on the measured chemical fluid composition as raw data. We estimated the rates of dissolution and the reactive surface areas of the different minerals by reconstructing the chemical evolution of the interacting fluids. This was done by a reaction process schema that was defined by a fractional degree of advance of the irreversible mass-transfer process and by attaining the continuum limit during the water-rock interaction. Calculations were carried out for albite, microcline, biotite and calcite assuming that the ion activity of dissolved silica and aluminium ions was limited by the equilibrium with quartz and kaolinite.We found that the absolute dissolution rate of albite, microcline, biotite and calcite remains essentially constant as a function of time, and the calcite dissolution rate is orders of magnitude higher than silicate minerals. On the contrary, the reactive surface area of the parent minerals varied by more than two orders of magnitude during the observed reaction time, especially for albite. We propose that the reactive surface area depends mainly on the stability of the secondary mineral coating that may passivate the effective reactive surface area of the parent minerals.     

Devolatilization of metabasic rocks during greenschist–amphibolite facies metamorphism

The production of large volumes of fluid from metabasic rocks, particularly in greenstone terranes heated across the greenschist–amphibolite facies transition, is widely accepted yet poorly characterized. The presence of carbonate minerals in such rocks, commonly as a consequence of sea‐floor alteration, has a strong influence, via fluid‐rock buffering, on the mineral equilibria evolution and fluid composition. Mineral equilibria modelling of metabasic rocks in the system Na₂O‐CaO‐FeO‐MgO‐Al₂O₃‐SiO₂‐CO₂‐H₂O (NCaFMASCH) is used to constrain the stability of common metabasic assemblages. Calculated buffering paths on T–X_CO2 pseudosections, illustrate the evolution of greenstone terranes during heating across the greenschist‐amphibolite transition. The calculated paths constrain the volume and the composition of fluid produced by devolatilization and buffering. The calculated amount and composition of fluid produced are shown to vary depending on P–T conditions, the proportion of carbonate minerals and the X_CO2 of the rocks prior to prograde metamorphism. In rocks with an initially low proportion of carbonate minerals, the greenschist to amphibolite facies transition is the primary period of fluid production, producing fluid with a low X_CO2. Rocks with greater initial proportions of carbonate minerals experience a second fluid production event at temperatures above the greenschist to amphibolite facies transition, producing a more CO₂‐rich fluid (X_CO2 = 0.2–0.3). Rocks may achieve these higher proportions of carbonate minerals either via more extensive seafloor alteration or via infiltration of fluids. Fluid produced via devolatilization of rocks at deeper crustal levels may infiltrate and react with overlying lower temperature rocks, resulting in external buffering of those rocks to higher X_CO2 and proportions of carbonate minerals. Subsequent heating and devolatilization of these overlying rocks results in buffering paths that produce large proportions of fluid at X_CO2 = 0.2–0.3. The production of fluid of this composition is of importance to models of gold transport in Archean greenstone gold deposits occurring within extensive fluid alteration haloes, as these haloes represent the influx of fluid of X_CO2 = 0.2–0.3 into the upper crust.     

广汉市平原区浅层地下水化学演化及其控制因素

为在广汉市城乡规划过程中提供地下水资源开发利用的基础信息,采用矿物风化系统分析、相关性分析、主成分分析和PhreeQC反向水文地球化学模拟等方法对广汉市平原区的浅层地下水的地下水水化学组分进行分析,确定了浅层地下水的水化学演化及控制因素,完成了地下水资源的质量及时空分布特征分析。分析表明：Gibbs图显示岩石风化主导该区地下水水化学特征,风化过程产生离子和次生矿物又经历水解作用,在矿物风化系统稳定场图中显示水样中铝硅酸盐矿物逐渐趋于溶解,碳酸盐矿物处于饱和状态;PhreeQC反向水文地球化学模拟结果显示在水流模拟路径上主要发生了钙蒙脱石、钾长石溶解和高岭石、石英、钠长石的沉淀,以及Ca-Na₂之间的阳离子交换吸附作用;离子相关性和主成分分析进一步的验证了溶滤作用、蒸发浓缩作用和阳离子交换吸附作用是引起浅层地下水水化学过程和矿物组成改变的主要原因。研究区地下水水质总体不会对人体健康造成不良影响。     

热液成矿分带的溶解－沉淀波结构

热液成矿分带是一种输运－反应问题。热液成矿分带基本属于渗滤交代分带性质，它是溶解－沉淀波在可渗透介质中形成和传播的结果。本文应用物理化学流体动力学中的渗滤与溶解－沉淀反应耦合过程理论研究溶解－沉淀波的结构特征，并进一步应用多组分耦合系统动力学中的用于原理揭示其形成的动力学机制，最后提出了一种热流成矿分带理论，对热液成矿分带问题的性质、热液成矿分带的本质和热液成矿分带的结构特征与形成机制提出了新认识。     

How does the water–rock interaction of marly rocks affect its mechanical properties in the Three Gorges reservoir area,China?

Marly rock is a sensitive rock group of landslides in the Three Gorges reservoir area, China. It is composed predominantly of carbonate and clay minerals, water–rock interaction (WRI) of which could activate landslides in the reservoir area. To study the mechanism by which WRI affects the mechanical properties of marly rock, samples were collected from two boreholes (depth 301.78 and 307.14 m) and slope surface. Then, laboratory tests were designed to study the quantitative relationship between mineral contents and mechanical properties of intact rock, to analyze both change process of mineral composition and microstructure under short-term and long-term WRI. Finally, the change in mechanical properties and its effect on slope stability are suggested. This study indicates that the uniaxial compressive strength and Poisson ratio can be estimated by linear regression equations: (1) σ _c = 8.959 × (C/Q) ? 0.744 × CM + 58.516; (2) μ = 0.014 × (C/Q) ? 0.001 × CM + 0.234. The chemical reactions of WRI mainly included dissolution and ion exchange. On the slope surface, dissolution mainly acts on calcite, illite, dolomite, feldspar and other minerals dissolved in water. Underground, both chemical reactions of dissolution and ion exchange easily approach equilibrium with long-term seepage. Small-size minerals and micropores damage the stable microstructure of marly rock. These changes of minerals and microstructure can trigger shallow slope failure and develop deep creep deformation along some crash zones in the reservoir shoreline.     

Dissolution of basaltic glass in seawater: Mechanism and rate

Basaltic glasses are considered as natural analogues for nuclear waste glasses. Thermodynamic computer codes used to evaluate long term behavior of both nuclear waste and basaltic glasses require the knowledge of the dissolution mechanism of the glass network (congruent dissolution or ion exchange in a residual hydrated structure).The paper presents the results of a series of experiments designed to study the structure and chemical composition of alteration layers formed on the surface of artificial tholeiitic glass altered in artificial seawater. Experiments were performed at 60°C, 1 bar and 350 bars in non-renewed conditions. A natural sample from Palagonia (Sicily) has been studied by electron microscopy and comparison between natural and experimental palagonitic layers is made.The behavior of dissolved silica during experiments, and both the structure and the chemical composition of the palagonitic layers, indicate that they form by precipitation of secondary minerals from solution after a total breakdown of the glassy network, i.e., congruent dissolution of the glass. Hence the dissolution equation necessary for thermodynamic modelling of basaltic glass dissolution in seawater at low temperature must be written as a simple stoichiometric process.For the first 2.10⁵ years of reaction the palagonitic layers do not constitute a diffusional barrier to the mass transfer between the glass and the bulk solution. The growth of these layers is linearly dependent on time.These experiments indicate that the transformation of glass to palagonitic material is not isovolumetric. Hence it is preferable to use Fe or Ti as conservative elements for chemical budget calculations.     

Geochemical processes,evidence and thermodynamic behavior of dissolved and precipitated carbonate minerals in a modern seawater/freshwater mixing zone of a small tropical island

The geochemical processes and thermodynamic behavior of dissolved and precipitated carbonate minerals controlling the hydrochemistry of an aquifer in the seawater/freshwater mixing zone of a small island are identified. Field and laboratory analyses, geochemical modeling (PHREEQC) and multivariate statistical analysis (MSA) provide a quantitative interpretation for the geochemistry of the carbonate-dominated aquifer. Geochemical analyses and modeling results show that dissolution and re-precipitation of CaCO₃ are the prevalent processes governing geochemical reactions in the mixing zone. Furthermore, this was confirmed by coherent statistical output that incorporates Principle Component Analysis (PCA) and k-means Cluster Analysis (k-CA). Generally, the composition of the lowland sandy soil was rather homogeneous and was primarily composed of quartz, aragonite, calcite and Mg-calcite. Thermodynamic model calculations indicate that the carbonate minerals calcite, aragonite and dolomite are supersaturated in the mixing zone. Nevertheless, Powder X-ray Diffraction (PXRD) and Scanning Electron Microscope (SEM) examination verified the occurrence of low-Mg-calcite (LMC) and the absence of dolomite, attributed to thermodynamic/kinetic hindrance, cation disorder and the presence of dolomite crystal growth rate inhibitors (such as SO₄). The results suggest that dissolution of aragonite and precipitation of LMC drives the solid phase geochemistry in the small tropical island aquifer.     

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.