The evolution of clay rock/cement interfaces in a cementitious repository for low- and intermediate level radioactive waste

In Switzerland, deep geological storage in clay rich host rocks is the preferred option for low- and intermediate-level radioactive waste. For these waste types cementitious materials are used for tunnel support and backfill, waste containers and waste matrixes. The different geochemical characteristics of clay and cementitious materials may induce mineralogical and pore water changes which might affect the barrier functionality of host rocks and concretes.We present numerical reactive transport calculations that systematically compare the geochemical evolution at cement/clay interfaces for the proposed host rocks in Switzerland for different transport scenarios. We developed a consistent set of thermodynamic data, simultaneously valid for cementitious (concrete) and clay materials. With our setup we successfully reproduced mineralogies, water contents and pore water compositions of the proposed host rocks and of a reference concrete.Our calculations show that the effects of geochemical gradients between concrete and clay materials are very similar for all investigated host rocks. The mineralogical changes at material interfaces are restricted to narrow zones for all host rocks. The extent of strong pH increase in the host rocks is limited, although a slight increase of pH over greater distances seems possible in advective transport scenarios. Our diffusive and partially also the advective calculations show massive porosity changes due to precipitation/dissolution of mineral phases near the interface, in line with many other reported transport calculations on cement/clay interactions. For all investigated transport scenarios the degradation of concrete materials in emplacement caverns due to diffusive and advective transport of clay pore water into the caverns is limited to narrow zones.A specific effort has been made to improve the geochemical setup and the extensive use of solid solution phases demonstrated the successful application of a thermodynamically consistent union of very different materials like hydrated cement and clay phases. A reactive system utilizing a novel solid-solution approach is used, where cation exchange is an intrinsic property of the mineral phase definition. Although such features were not the primary aim of the study, they offer a large potential for studies where ion exchange and changing sorption properties are of interest.     

Water-rock interactions drive chemostasis

The western U.S. is experiencing shifts in recharge due to climate change, and it is currently unclear how hydrologic shifts will impact geochemical weathering and stream concentration–discharge (C–Q) patterns. Hydrologists often use C–Q analyses to assess feedbacks between stream discharge and geochemistry, given abundant stream discharge and chemistry data. Chemostasis is commonly observed, indicating that geochemical controls, rather than changes in discharge, are shaping stream C–Q patterns. However, few C–Q studies investigate how geochemical reactions evolve along groundwater flowpaths before groundwater contributes to streamflow, resulting in potential omission of important C–Q controls such as coupled mineral dissolution and clay precipitation and subsequent cation exchange. Here, we use field observations—including groundwater age, stream discharge, and stream and groundwater chemistry—to analyse C–Q relations in the Manitou Experimental Forest in the Colorado Front Range, USA, a site where chemostasis is observed. We combine field data with laboratory analyses of whole rock and clay x-ray diffraction and soil cation-extraction experiments to investigate the role that clays play in influencing stream chemistry. We use Geochemist's Workbench to identify geochemical reactions driving stream chemistry and subsequently suggest how climate change will impact stream C–Q trends. We show that as groundwater age increases, C–Q slope and stream solute response are not impacted. Instead, primary mineral dissolution and subsequent clay precipitation drive strong chemostasis for silica and aluminium and enable cation exchange that buffers calcium and magnesium concentrations, leading to weak chemostatic behaviour for divalent cations. The influence of clays on stream C–Q highlights the importance of delineating geochemical controls along flowpaths, as upgradient mineral dissolution and clay precipitation enable downgradient cation exchange. Our results suggest that geochemical reactions will not be impacted by future decreasing flows, and thus where chemostasis currently exists, it will continue to persist despite changes in recharge.     

Geochemical impact of a low-pH cement liner on the near field of a repository for spent fuel and high-level radioactive waste

In Switzerland the geological storage in the Opalinus Clay formation is the preferred option for the disposal of spent fuel (SF) and high-level radioactive waste (HLW). The waste will be encapsulated in steel canisters and emplaced into long tunnels that are backfilled with bentonite. Due to uncertainties in the depth of the repository and the associated stress state, a concrete liner might be used for support of emplacement tunnels.Numerical reactive transport calculations are presented that investigate the influence of a concrete liner on the adjacent barrier materials, namely bentonite and Opalinus Clay. The geochemical setup was tailored to the specific materials foreseen in the Swiss repository concept, namely MX-80 bentonite, low-pH concrete (ESDRED) and Opalinus Clay. The heart of the bentonite model is a new conceptual approach for representing thermodynamic properties of montmorillonite which is formulated as a multi-component solid solution comprised of several end-members.The presented calculations provide information on the extent of pH fronts, on the sequence and extent of mineral phase transformations, and on porosity changes on cement–clay interfaces. It was found that the thickness of the zone containing significant mineralogical alterations is at most a few tens of centimeters thick in both the bentonite and the Opalinus Clay adjacent to the liner. Near both interfaces, bentonite–concrete liner and concrete liner–Opalinus Clay, the precipitation of minerals causes a reduction in the porosity. The effect is more pronounced and faster at the concrete liner–Opalinus Clay interface. The simulations reveal that significant pH-changes (i.e. pH > 9) in bentonite and Opalinus Clay are limited to small zones, less than 10 cm thick at the end of the simulations. It is not to be expected that the zone of elevated pH will extend much further at longer times.     

Geochemical evolution of groundwater in hard-rock aquifers of South India using statistical and modelling techniques

ABSTRACT

Multivariate statistical analysis and inverse geochemical modelling techniques were employed to deduce the mechanism of groundwater evolution in the hard-rock terrain of Telangana, South India. Q-mode hierarchical cluster analysis (HCA) and principal component analysis (PCA) were used to extract the hydrogeochemical characteristics and classify the groundwater samples into three principal groups. Use of thermodynamic stability diagrams and inverse geochemical modelling in PHREEQC identified the chemical reactions controlling hydrogeochemistry of each of the groups obtained from statistical analysis. The model output showed that a few phases are governing the water chemistry in this area and the geochemical reactions responsible for evolution of groundwater chemistry along the flow path are (i) dissolution of evaporite minerals (dolomite, halite); (ii) dissolution of primary silicate minerals (albite, anorthite, K-feldspar, biotite); (iii) precipitation of secondary silicate minerals (kaolinite, quartz, gibbsite, Ca-montmorillonite) along with anhydrite and calcite; and (iv) reverse ion exchange processes.     

Effect of mineral reactions on the hydraulic properties of unsaturated soils: Model development and application

The selective radius shift model was used to relate changes in mineral volume due to precipitation/dissolution reactions to changes in hydraulic properties affecting flow in porous media. The model accounts for (i) precipitation/dissolution taking place only in the water-filled part of the pore space and further that (ii) the amount of mineral precipitation/dissolution within a pore depends on the local pore volume. The pore bundle concept was used to connect pore-scale changes to macroscopic soil hydraulic properties. Precipitation/dissolution induces changes in the pore radii of water-filled pores and, consequently, in the effective porosity. In a time step of the numerical model, mineral reactions lead to a discontinuous pore-size distribution because only the water-filled pores are affected. The pore-size distribution is converted back to a soil moisture characteristic function to which a new water retention curve is fitted under physically plausible constraints. The model equations were derived for the commonly used van Genuchten/Mualem hydraulic properties. Together with a mixed-form solution of Richards’ equation for aqueous phase flow, the model was implemented into the geochemical modelling framework PHREEQC, thereby making available PHREEQC’s comprehensive geochemical reactions. Example applications include kinetic halite dissolution and calcite precipitation as a consequence of cation exchange. These applications showed marked changes in the soil’s hydraulic properties due to mineral precipitation/dissolution and the dependency of these changes on water contents. The simulations also revealed the strong influence of the degree of saturation on the development of the saturated hydraulic conductivity through its quadratic dependency on the van Genuchten parameter α. Furthermore, it was shown that the unsaturated hydraulic conductivity at fixed reduced water content can even increase during precipitation due to changes in the pore-size distribution.     

Velocity–porosity relationships: Predictive velocity model for cemented sands composed of multiple mineral phases

Computer simulations are used to calculate the elastic properties of model cemented sandstones composed of two or more mineral phases. Two idealized models are considered – a grain‐overlap clay/quartz mix and a pore‐lining clay/quartz mix. Unlike experimental data, the numerical data exhibit little noise yet cover a wide range of quartz/cement ratios and porosities. The results of the computations are in good agreement with experimental data for clay‐bearing consolidated sandstones. The effective modulus of solid mineral mixtures is found to be relatively insensitive to microstructural detail. It is shown that the Hashin–Shtrikman average is a good estimate for the modulus of the solid mineral mixtures. The distribution of the cement phase is found to have little effect on the computed modulus–porosity relationships. Numerical data for dry and saturated states confirm that Gassmann's equations remain valid for porous materials composed of multiple solid constituents. As noted previously, the Krief relationship successfully describes the porosity dependence of the dry shear modulus, and a recent empirical relationship provides a good estimate for the dry‐rock Poisson's ratio. From the numerical computations, a new empirical model, which requires only a knowledge of system mineralogy, is proposed for the modulus–porosity relationship of isotropic dry or fluid‐saturated porous materials composed of multiple solid constituents. Comparisons with experimental data for clean and shaly sandstones and computations for more complex, three‐mineral (quartz/dolomite/clay) systems show good agreement with the proposed model over a very wide range of porosities.     

Approaches to modelling coupled flow and reaction in a 2D cementation experiment

Porosity evolution at reactive interfaces is a key process that governs the evolution and performances of many engineered systems that have important applications in earth and environmental sciences. This is the case, for example, at the interface between cement structures and clays in deep geological nuclear waste disposals. Although in a different transport regime, similar questions arise for permeable reactive barriers used for biogeochemical remediation in surface environments.The COMEDIE project aims at investigating the coupling between transport, hydrodynamics and chemistry when significant variations of porosity occur. The present work focuses on a numerical benchmark used as a design exercise for the future COMEDIE-2D experiment. The use of reactive transport simulation tools like Hytec and Crunch provides predictions of the physico-chemical evolutions that are expected during the future experiments in laboratory. Focus is given in this paper on the evolution during the simulated experiment of precipitate, permeability and porosity fields.A first case is considered in which the porosity is constant. Results obtained with Crunch and Hytec are in relatively good agreement. Differences are attributable to the models of reactive surface area taken into account for dissolution/precipitation processes. Crunch and Hytec simulations taking into account porosity variations are then presented and compared. Results given by the two codes are in qualitative agreement, with differences attributable in part to the models of reactive surface area for dissolution/precipitation processes. As a consequence, the localization of secondary precipitates predicted by Crunch leads to lower local porosities than for predictions obtained by Hytec and thus to a stronger coupling between flow and chemistry. This benchmark highlights the importance of the surface area model employed to describe systems in which strong porosity variations occur as a result of dissolution/precipitation. The simulation of highly non-linear reactive transport systems is also shown to be partly dependent on specific numerical approaches.     

Quantification and spatial distribution of pore-filling materials through constrained rock physics template and fluid response modelling in Paleogene clastic reservoir from Cauvery basin,India

Sands belonging to Kamalapuram Formation of Paleocene-Eocene age are deposited in Cauvery basin as incised valley fill during a regressive cycle. Here we attempt to quantify the influence of diagenesis on pore-filling materials using rock physics template constrained by geohistory modelling. Primarily, porosity–velocity and acoustic impedance – the ratio of P-wave and S-wave velocity (V_P/V_s) cross-plots are used as rock physics templates. Rock physics template has efficiently quantified pore-filling materials namely; contact cement and non-contact cement. The estimated contact cement and non-contact cement are correlated with conventional petrophysical logs within the selected depth interval. Further, this correlation is used to interpret the composition of pore-filling materials. Shallower depth intervals (I and II) exhibit moderate non-contact cement (4–5%) and insignificant contact cement (1–2% approx.) depositions. However, deeper interval (III) records a significant amount of pore-filling materials amounting average of 12% non-contact cement and 4% contact cement. Pore-filling materials demonstrate a positive correlation with the depth of burial. The fluid response is substantially affected by the degree of diagenesis, composition and spatial distribution of pore-filling materials. Shallower depth intervals (1770–1786 m and 1858–1878 m) are relatively more sensitive to fluid changes as it is affected by insignificant contact cement. The depth interval 1770–1786 m shows class II (oil) and class III (gas) amplitude variation with offset anomalies. The sand occurring in depth interval 1858–1878 m demonstrates class IIP (oil) and II (gas) anomaly. The deeper interval (2118–2170 m) is comparatively stiffer and demonstrates class I amplitude variation with offset (oil and gas sand) anomaly.     

Estimation of clay content in soil based on resistivity modelling and laboratory measurements

The determination of clay content in near‐surface formations is crucial for geotechnical, hydrogeological and oil‐contamination studies. We have developed a technique for estimating clay content that consists of the minimization of the difference between the theoretically calculated and measured soil resistivities as a function of water salinity. To calculate the resistivity, we used a model that takes into account the electrochemical processes in the clay micropores. The experimental measurements of soil resistivity were performed on soil samples, completely saturated by brines at different concentrations of NaCl salt in the range 0.6–100 g/l, to obtain the resistivity versus salinity curve. The parameters obtained with this curve inversion are the clay content, the total porosity and the cation exchange capacity. To verify the new technique, we determined clay concentrations of artificial mixtures of calibrated sand and clay. The relative mean error in the clay content does not exceed 20% for a 5% fitting error of the resistivity versus salinity curves. Such evaluations allow the correct separation of the main lithological groups (sand, sandy loam, loam, and light, medium and heavy clay). We applied this technique to estimate the petrophysical parameters of soils (clay content, porosity and cation exchange capacity) at various sites in Mexico. The results improved the interpretation of the vertical electrical soundings, the lithological soil characterization and the delineation of oil‐contaminated areas.     

Rates of dissolution of aluminosilicates in seawater

Dissolution of eight clay minerals, four zeolites, and quartz in seawater has been monitored for81/2 years. For most of the minerals, dissolution can be described as a first-order reaction in which dissolved silica approaches from undersaturation steady concentration values with time. Characteristic reaction rate constants (k₁) are of the order of 10^?7 sec^?1. One of the zeolites, clinoptilolite, shows a different dissolution behavior: SiO₂ concentration in solution reaches a high value within one year, followed by a decline to a lower value, suggestive of precipitation of another silicate phase (possibly sepiolite).A mathematical solution is given for a kinetic equation combining the parabolic-rate and first-order rate processes. It is shown that in a wide range of silicate dissolution reactions taking place over long periods of time, the presence of the parabolic-rate dissolution processes cannot be detected, thereby making its inclusion in the kinetic equations unnecessary. The experimental rates of dissolution are comparable to the SiO₂^? dissolution rates in oceanic sediments near the sediment/water interface. But deeper in the sediment, the calculated dissolution rates are significantly lower than the near-interface and experimental values.     

ANDRA underground research laboratory: interpretation of the mineralogical and geochemical data acquired in the Callovian–Oxfordian formation by investigative drilling

Under the ANDRA Meuse/Haute Marne underground research laboratory scientific programme, two boreholes (EST204 and EST205) were drilled to a depth of 510 m for the purposes of scientific characterisation. Twenty-nine core samples were taken in borehole EST205 every 3 m between 422 and 504 m depth. Physical property measurements (water content, porosity, density, specific surface), geochemical analyses (major and trace elements, cation exchange capacity [CEC] and surface cation occupancy, leaching anions, redox state, organic matter concentration), and a semi-quantitative mineralogical study were conducted on the samples.As the rocks are in a reduced state, the core samples were stored under nitrogen immediately after drilling. All the steps of the sampling and of the characterisation are done with a research of limitation of the oxidation to obtain representative samples of the in situ conditions.The top of the formation is more carbonate-rich, with interbedded clayey layers and carbonate rock. The formation is more homogeneous in its central section with a clay mineral concentration of 45–50%, which corresponds to a maximum of flooding within the area. In the upper part of this section, micas and mixed-layer illite/smectite R0 dominate, whereas in the lower part of the section we find an abrupt transition to mixed-layer illite/smectite R1 associated with kaolinite.A statistical analysis, including the data of major and trace elements with the semi-quantitative mineralogy, enabled the identification of some mineralogical traps for trace elements. The values of cation occupancy at the surface of the clay minerals provided a good image of the pore water chemistry; pore water is in equilibrium with the clay surfaces. Leaching experiments revealed the pore water salinity and provided profiles of Cl and Br concentrations. Cl/Br values in the centre of the formation are close to the present-day seawater ratio, which could indicate a seawater origin of the pore water. Some measurements of total reduced capacity, provide quantified results of the reduced state of the rock.Processing the data on water content, helium and petroleum pycnometry enabled calculation of total rock porosity and gave an uncertainty range for this value. Finally, the high BET(N₂) specific surfaces are consistent with the clayey nature of the rock.     

Geochemistry of meteoric diagenesis in carbonate islands of the northern Bahamas: 2. Geochemical modelling and budgeting of diagenesis

Geochemical characterization and numerical modelling of surface water and ground water, combined with hydrological observations, provide quantitative estimates of meteoric diagenesis in Pleistocene carbonates of the northern Bahamas. Meteoric waters equilibrate with aragonite, but water‐ rather than mineral‐controlled reactions dominate. Dissolutional lowering of the undifferentiated bedrock surface is an order of magnitude slower than that within soil‐filled topographic hollows, generating small‐scale relief at a rate of 65–140 mm ka^?1 and a distinctive pocketed topography. Oxidation of organic matter within the subsoil and vadose zones generates an average P of 4·0 × 10^?3 atm, which drives dissolution during vadose percolation and/or at the water table. However, these dissolution processes together account for <60% of the average rock‐derived calcium in groundwaters pumped from the freshwater lens. The additional calcium may derive from oxidation of organic carbon within the lens, accounting for the high P of the lens waters. Mixing between meteoric waters of differing chemistry is diagenetically insignificant, but evapotranspiration from the shallow water table is an important drive for subsurface cementation. Porosity generation in the shallow vadose zone averages 1·6–3·2% ka^?1. Phreatic meteoric diagenesis is focused near the water table, where dissolution generates porosity at 1·4–2·8% ka^?1. Maximum dissolution rates, however, are similar to those of evaporation‐driven precipitation, which occludes porosity of 4·0 ± 0·6% ka^?1. This drives porosity inversion, from primary interparticle to secondary mouldic, vug and channel porosity. In the deeper freshwater lens, oxidation of residual organic carbon and reoxidation of reduced sulphur species from deeper anaerobic oxidation of organic carbon may generate porosity up to 0·06% ka^?1. Meteoric diagenesis relies critically on hydrological routing and vadose thickness (controlled by sea level), as well as the geochemical processes active. A thin vadose zone permits direct evaporation from the water table and drives precipitation of meteoric phreatic cements even where mineral stabilization is complete. Copyright © 2007 John Wiley & Sons, Ltd.     

A numerical procedure for geochemical compaction in the presence of discontinuous reactions

The process by which rocks are formed from the burial of a fresh sediment involves the coupled effects of mechanical compaction and geochemical reactions. Both of them affect the porosity and permeability of the rock and, in particular, geochemical reactions can significantly alter them, since dissolution and precipitation processes may cause a structural transformation of the solid matrix. Often, the differential problems that arise from the modeling of these chemical reactions may present a discontinuous right hand side, where the discontinuity depends on the solution itself. In this work we have developed a numerical model to simulate this complex multi-physics problem by treating the discontinuous right hand side with a specially tailored event-driven numerical scheme. We show the performance of this strategy in terms of positivity and mass conservation, also in comparison with a more traditional approach that relies on a regularization of the discontinuous terms.     

The effect of microporosity on transport properties in porous media

Sizeable amounts of connected microporosity with various origins can have a profound effect on important petrophysical properties of a porous medium such as (absolute/relative) permeability and capillary pressure relationships. We construct pore-throat networks that incorporate both intergranular porosity and microporosity. The latter originates from two separate mechanisms: partial dissolution of grains and pore fillings (e.g. clay). We then use the reconstructed network models to estimate the medium flow properties. In this work, we develop unique network construction algorithms and simulate capillary pressure–saturation and relative permeability–saturation curves for cases with inhomogeneous distributions of pores and micropores. Furthermore, we provide a modeling framework for variable amounts of cement and connectivity of the intergranular porosity and quantifying the conditions under which microporosity dominates transport properties. In the extreme case of a disconnected inter-granular network due to cementation a range of saturations within which neither fluid phase is capable of flowing emerges. To our knowledge, this is the first flexible pore scale model, from first principles, to successfully approach this behavior observed in tight reservoirs.     

Hydrochemical and isotopic characterization of groundwater in the southeastern part of the Plateaux Region,Togo

Hydrochemical, inverse geochemical modelling and isotopic approaches are used to assess the hydrogeochemical evolution of groundwater from the basement aquifers in the southeastern part of the Plateaux Region, Togo. Groundwater originates from present-day rainwater infiltration and is mostly fresh and slightly acidic to neutral. Hydrochemical facies are predominantly mixed cations-HCO₃ associated with Ca/Mg-Cl, Na-HCO₃ and Na-Cl water types in equilibrium with kaolinite and Ca/Mg-smectites. They are related to silicates hydrolysis, anthropogenic contamination, nitrification/denitrification, mixing along flowpaths and dissolution/precipitation of secondary minerals. The pattern of flow paths is in accordance with an increasing trend in total dissolved solids (TDS) toward the potentiometric depression located in the central and southern parts of the aquifer system. Inverse geochemical modelling using the NETPATH-WIN model showed the relative importance of biotite, plagioclase and amphibole weathering and dissolution of secondary carbonate minerals along the flowpath, suggesting that an abundance of minerals is not necessarily the main factor controlling the groundwater chemistry evolution.     

Structure of weathered clastic crust and its petroleum potential

Weathered clastic crust can be subdivided into weathered clay and leached zone in terms of variable weathering of different minerals and mobility of weathered products.On the basis of clastic outcrops and well cores in the Junggar Basin,the dark red Fe-rich weathered clay is formed in an arid environment,whereas the light blue Al-rich weathered clay under humid conditions.According to the geochemical analysis,a new weathering index for weathered clastic crust is built mainly on Fe and Al contents,accurately indicating the weathered clay,sandy leached zone,and muddy leached zone in the Junggar Basin.The breaking pressure of weathered clay is rather large,the same as that of normal muddy cap,effectively to seal oil or gas.The porosity of underlying leached zone is greatly enhanced by weathering and leaching,but its permeability is a function of clay mineral content,i.e.,the higher the clay content,the worse the permeability.Weathered crust provides effective sealing conditions for both top and bottom layers of a petroleum reservoir,and is important in the clastic hydrocarbon exploration.     

Using hydrogeochemical data to trace groundwater flow paths in a cold alpine catchment

Significant uncertainty remains in understanding the groundwater flow pathways in the northeastern Qinghai–Tibet Plateau. Hydrogeochemical and isotopic data as well as hydrogeological data were combined to explore the groundwater flow path in a representative cold alpine catchment in the headwater region of the Heihe River. The results indicate that the suprapermafrost groundwater chemical components were mainly affected by calcite dissolution and evaporation, whereas the geochemistry of subpermafrost groundwater was controlled by dolomite and gypsum dissolution, calcite precipitation, and albite and halite dissolution. Distinct hydrogeochemical characteristics and controlling processes suggest a poor hydraulic connectivity between the suprapermafrost and subpermafrost groundwater. The hydraulic connectivity between permafrost groundwater and groundwater in the seasonally frozen area was confirmed by their similar hydrogeochemical features. In the seasonally frozen area, a silty clay layer with low permeability separates the aquifer into the deep (depth >20 m) and shallow (depth <20 m) flow paths. The deep groundwater was characterized by the enhanced dedolomitization and enhanced cation exchange processes compared with the shallow groundwater. Groundwater in the seasonally frozen area finally discharges as base flow into the stream. These results provide useful information about the groundwater flow systems in the unique alpine gorge catchments in Qinghai–Tibet Plateau. The above findings suggest that the permafrost distribution and the aquifer structures within the seasonally frozen area have significant impact on groundwater flow paths. Cross‐validation by drilling work and hydrograph data confirms that the hydrogeochemical and isotopic tracers combined with field investigations can be relatively low‐cost tools in interpreting the groundwater flow paths in similar alpine catchments.     

Significance of isotopic and geochemical methods to determine the evolution of inland brackish and bitter water: An example from the Zuli river in the upper reaches of the Yellow River,China

With the increasing demand for water resources, the utilization of marginal water resources of poor-quality has become a focus of attention. The brackish water developed in the Loess Plateau is not only salty but also famous for its ‘bitterness’. In the present work, multi-isotope analysis (Sr, B) was combined with geochemical analysis to gain insight into the hydrogeochemical evolution and formation mechanisms of brackish water. These results demonstrate that groundwater in the headwater is influenced by carbonate weathering. After the confluence of several tributaries in the headwater, the total dissolved solids (TDS) of water is significantly increased. The dissolution of evaporates is shown to be the main source of salinity in brackish water, which also greatly affects the strontium isotopic composition of water. This includes the dissolution of Mg-rich minerals, which is the main cause of the bitterness. Furthermore, the release of calcium from the dissolution of gypsum may induce calcite precipitation and incongruent dissolution of dolomite, which also contributes to the enrichment of magnesium. The highly fractionated boron isotopic values observed in the upstream groundwater were explained by the absorption with clay minerals. The inflow of brackish groundwater is the source of river water. Then evaporation further aggravates the salinization of river water, with water quality evolving to saline conditions in the lower reach. When the river reaches the valley plain, the ⁸⁷Sr/⁸⁶Sr ratios decreases significantly, which is primarily related to erosion of the riverbanks during runoff. These results indicate that water resource sustainability could be enhanced by directing focus to mitigating salinization in the source area of the catchment.     

泥质砂岩中接触胶结泥质定量估算及对砂岩弹性的影响

在泥质砂岩的岩石物理建模中,明确泥质砂岩中泥质胶结物的接触类型及其含量对正确认识泥质的胶结作用对泥质砂岩声速的影响以及合理地建立岩石物理模型至关重要.现阶段,尚未有实验室定量估算胶结泥质的方法,导致应用胶结砂岩理论模型预测胶结砂岩地层的声速时往往由于胶结物含量被高估从而导致预测声速结果偏高.本文通过观察铸体薄片中泥质与颗粒之间的接触关系和相对分布提出了一种区分胶结泥质和分散泥质的方法:与两个或两个以上颗粒接触的连续分布的泥质为胶结泥质;与一个颗粒接触或者不与颗粒接触的泥质为分散泥质.基于这一准则,本文基于像素拾取法估算了人造泥质砂岩的胶结泥质含量,并将胶结泥质含量作为胶结砂岩模型的输入参数优化CCT模型.对比原始模型,本文方法声速误差下降了20%,预测准确度显著提高.本文方法适用于弱胶结地层的岩石物理建模,能够准确的预测声速以结合地震和测井资料识别有利储层,定量评价储层参数.     

Influence of mineral weathering reactions on the chemical composition of soil water,Springs, and ground water,Catoctin Mountains,Maryland

During 1983 and 1984, wet precipitation was primarily a solution of dilute sulphuric acid, whereas calcium and bicarbonate were the major ions in springs and ground water in two small watersheds with a deciduous forest cover in central Maryland. Dominant ions in soil water were calcium, magnesium, and sulphate. The relative importance of mineral weathering reactions on the chemical composition of these subsurface waters was compared to the contribution from wet precipitation, biological processes, and road deicing salts. Mineral reaction models, developed from geochemical mass-balance relationships, involved reactions of primary and secondary minerals in metabasalt and metarhyolite with hydrogen ion. Geochemical weathering reactions account for the majority of total ion equivalents in soil water (46 per cent), springs (51 per cent), and ground water (68 to 77 per cent). The net contribution of total ion equivalents from biological processes was 20 and 16 per cent for soil water and springs, respectively, but less than 10 per cent for ground water. The contribution of total ion equivalents from deicing salts (10 to 20 per cent) was related to proximity to roads. Strong acids in precipitation contributed 44 per cent of the total amount of hydrogen ions involved in mineral-weathering reactions for ground water in contact with metarhyolite compared to 25 per cent for ground water in contact with metabasalt, a less resistant rock type to weathering.