Geochemistry of arsenic during low-temperature water–rock interaction

High arsenic water has been a global focus of both scientists and water supply managers because of its serious adverse impact on human health and wide distribution in the world. Processes of redox, sorption, precipitation, and dissolution release arsenic in both natural systems and in environments intensely modified by human activities. In natural systems, groundwater arsenic is controlled by lithologic geochemistry, sedimentation conditions, hydrogeologic setting and groundwater chemistry. However, in the intensely human-affected systems (such as mining and tilling areas), arsenic mobilization is dependent on the composition of the primary materials, treatment methods, storage design, and local climate. Well-designed experimental systems aid in characterizing sorption, precipitation, and redox processes associated with arsenic dynamics during water-rock interaction. Continued investigations of field sites will further refine understanding of the processes favoring arsenic mobility in the range of natural and man-made systems. The combination of field and experimental studies will lead to better understanding of arsenic cycling in all systems and sustainable management of water resources in arsenic-affected areas.     

Geochemical modelling of CO2–water–rock interactions in a potential storage formation of the North German sedimentary basin

The lower Triassic/Bunter sandstone and lower Jurassic/Rhät formations of the Northern Germany sedimentary basin constitute feasible reservoirs for the storage of CO₂ from combustion of fossil fuels or industrial production processes. This study presents analyses of geochemical interactions between CO₂, formation fluid and rock of these potential reservoirs using geochemical modelling in order to assess the short and long term impact of CO₂ sequestration. Batch equilibrium modelling was performed first for assessing the consistency of fluid and mineralogy field data and for identifying potential secondary minerals under the influence of injected CO₂. Inclusion of reaction kinetics in the batch models allowed an observation of reaction paths and to estimate the time frame of geochemical reactions. Finally, one-dimensional equilibrium reactive transport modelling was used in order to investigate the direction of reactions under conditions of fluid flow and mass transport and to quantify feedbacks of reactions on transport processes.Results of the simulations performed show that dawsonite may act as the main CO₂ storage mineral in both formations, while the carbonates calcite and dolomite dissolve over time. Also, changes in porosity and permeability are significant in the equilibrium reactive transport simulations. The time scale of kinetically controlled reactions observed in the kinetic batch modeling, however, suggests that CO₂ mineral trapping in both formations requires very long time frames, and hence other mechanisms such as structural or solubility trapping seem to be more relevant within the injection or early post-injection phase for the studied formations.     

Oxidative–reductive photodecomposition of perfluorooctanoic acid in water

This article aims to elucidate on usefulness of vacuum ultraviolet (VUV) for photoreductive degradation of perfluorooctanoic acid (PFOA), a representative perfluorinated compound (PFC), in water for the first time. Bench-scale tests were conducted on oxidative and reductive (with aquated electron: e _aq ^? ) mineralization of PFOA using low-pressure UV (LPUV) lamps and potassium iodide. Unlike with 254 nm wavelength (UVC), the reductive mineralization with VUV was very inefficient compared to the corresponding oxidative mineralization. The inefficiency is attributed to low reactivity of e _aq ^? with PFOA and its fluorinated products than that of 185 nm photons. Direct VUV photolysis of PFOA and its products in reductive reaction conditions was not apparent due to a very big difference in reactivity of 185 and 254 nm photons with iodide. The results demonstrated that highly energetic VUV photons are not suitable for photoreductive degradations of PFCs involving e _aq ^? , but they can be best used for oxidative degradations. These findings should serve as an important reference on VUV usage to decompose refractory micropollutants.     

A novel approach for modelling soil–water characteristic curves with hysteresis

Soil–water characteristic curves can be defined as the relationship between the degree of saturation and suction of an unsaturated soil. Geomaterials, such as clays, sands, and geotextiles, usually exhibit hysteresis between drying and wetting curves. In addition, each drying and wetting curve is nonlinear in shape, which may be approximated by sigmoid curves. In geotechnical engineering, it is common to adopt analytical expressions for these curves that must be calibrated iteratively by trying different values for the constitutive parameters. In this paper, a novel approach for modelling the nonlinear saturation–suction response with hysteresis is presented, where a simple differential equation is introduced to describe the shapes of the curves. The great advantage of this new technique is the ease with which the parameters can be determined. In addition, the implementation of the resulting equations into fully hydro-mechanical models for numerical analyses is straightforward. Some features of the behaviour predicted with the new representation are studied and validations against real laboratory curves for soils are presented. The technique is simple, yet versatile due to the rational basis used in the deduction of the equations, which allows for future extensions to soils displaying more complex unsaturated behaviour.     

Geochemical tracing and hydrogeochemical modelling of water–rock interactions during salinization of alluvial groundwater (Upper Rhine Valley,France)

In the southern Upper Rhine Valley, groundwater has undergone intensive saline pollution caused by the infiltration of mining brines, a consequence of potash extraction carried out during the 20th century. Major and trace elements along with Sr and U isotopic ratios show that groundwater geochemical characteristics along the saline plumes cannot reflect conservative mixing between saline waters resulting from the dissolution of waste heaps and one or more unpolluted end-members. The results imply the occurrence of interactions between host rocks and polluted waters, and they suggest that cationic exchange mechanisms are the primary controlling process. A coupled hydrogeochemical model has been developed with the numerical code KIRMAT, which demonstrates that cationic exchange between alkalis from polluted waters and alkaline-earth elements from montmorillonite present in the host rock of the aquifer is the primary process controlling the geochemical evolution of the groundwater. The model requires only a small amount of montmorillonite (between 0.75% and 2.25%), which is in agreement with the observed mineralogical composition of the aquifer. The model also proves that a small contribution of calcite precipitation/dissolution takes places whereas other secondary mineral precipitation or host rock mineral dissolution do not play a significant role in the geochemical signature of the studied groundwater samples. Application of the model demonstrates that it is necessary to consider the pollution history to explain the important Cl, Na and Ca concentration modifications in groundwater samples taken over 2 km downstream of waste heaps. Additionally, the model shows that the rapidity of the cationic exchange reactions insures a reversibility of the cation fixation on clays in the aquifer.     

Geochemical characterization of surface water and spring water in SE Kashmir Valley,western Himalaya: Implications to water–rock interaction

Water samples from precipitation, glacier melt, snow melt, glacial lake, streams and karst springs were collected across SE of Kashmir Valley, to understand the hydrogeochemical processes governing the evolution of the water in a natural and non-industrial area of western Himalayas. The time series data on solute chemistry suggest that the hydrochemical processes controlling the chemistry of spring waters is more complex than the surface water. This is attributed to more time available for infiltrating water to interact with the diverse host lithology. Total dissolved solids (TDS), in general, increases with decrease in altitude. However, high TDS of some streams at higher altitudes and low TDS of some springs at lower altitudes indicated contribution of high TDS waters from glacial lakes and low TDS waters from streams, respectively. The results show that some karst springs are recharged by surface water; Achabalnag by the Bringi stream and Andernag and Martandnag by the Liddar stream. Calcite dissolution, dedolomitization and silicate weathering were found to be the main processes controlling the chemistry of the spring waters and calcite dissolution as the dominant process in controlling the chemistry of the surface waters. The spring waters were undersaturated with respect to calcite and dolomite in most of the seasons except in November, which is attributed to the replenishment of the CO₂ by recharging waters during most of the seasons.     

Geochemical features of the utilization of buried wastes of the Tyrnyauz Tungsten–Molybdenum Plant using acid leaching

The decontamination of buried wastes of the Tyrnyauz Tungsten–Molybdenum Plant is complicated by the geochemical features of the waste composition: low sulfide and high carbonate content, polyelemental composition, and considerable amounts of technogenic admixtures (kerosene, oils, soda, and soluble glasses). These circumstances result in sufficient complication of the suggested technology of waste treatment, including the sulfuric-acid leaching and separate sorption recovery of hazardous and useful elements from the working solution.     

The effect of methanogenesis on the geochemistry of low temperature water–Fe0–basalt reactions

Hydrogen gas produced in the subsurface from the hydration of mafic rocks is known to be a major energy source for chemolithotrophic life in extreme environments such as hydrothermal vents. The possibility that in situ anaerobic microorganisms present in the deep subsurface are sustained by low temperature H₂-generating water–rock reactions taking place around them is being investigated. Whether the growth and activity of H₂-utilizing microbes directly influences aqueous geochemistry, rates of mineral dissolution, and the chemical composition of the alteration products is also being quantitatively evaluated.To explore how microorganisms are affected by water–rock reactions, and how their activity may in turn affect reaction progress, laboratory experiments have been conducted to monitor the growth of a methanogenic Archaea in the presence of H_2(g) produced from low temperature water–Fe⁰–basalt reactions. In these systems, the conversion of Fe(II) to Fe(III) and subsequent hydrolysis of water is responsible for the production of H_2(g). To characterize key components of the geochemical system, time series measurements of H₂ and CH₄ gas concentrations, Fe and Si aqueous concentrations, and spatially resolved synchrotron-based analyses of microscale Fe distribution and speciation were conducted. Culture experiments were compared with an abiotic control to document changes in the geochemistry both in the presence and absence of the methanogen.In the control abiotic batch experiment, H₂ was continuously produced, until the headspace became saturated, while in the biotic experiments, microbial consumption of H₂ for methanogenesis draws H₂ down and produces CH₄. Purging the headspace gas reinitiates H₂ and CH₄ production in abiotic and culture experiments, respectively. Mass balance analysis of the amount of CH₄ produced suggests that the total H₂ production in microbial experiments does not exceed the abiotic experiment. Soluble Si concentrations, while buffered to relatively constant values, were higher in culture experiments than the abiotic control.Iron_(aq) concentrations appear to respond to perturbations of H₂ and CH₄ gas concentrations in both culture experiments and the abiotic control. A pulse of Fe preceded the rise in either H₂ or CH₄ production, and as the gas concentrations increased the Fe_(aq) decreased. Iron-bearing mineral assemblages change with increasing reaction time and mineral assemblages vary between culture experiments and the abiotic control. These geochemical trends suggest that there are different reaction paths between the culture experiments and the abiotic control.The hydration of mafic rocks is a common geologic reaction and one that has taken place on Earth for the majority of its history and is postulated to occur on Mars. These reactions are important because of their effect on the rheology and geochemistry of the ocean crust. While most often studied at temperatures of ～250 °C, this work suggests that at lower temperatures microorganisms may have a profound effect on what has long been thought to be solely an abiotic reaction, and may produce diagnostic mineral assemblages that will be preserved in the geological record.     

Arsenate adsorption at the sediment–water interface: sorption experiments and modelling

Arsenate adsorption was studied in three clastic sediments, as a function of solution pH (4.0–9.0) and arsenate concentration. Using known mineral values, protolytic constants obtained from the literature and K _ads values (obtained by fitting experimental adsorption data with empirical adsorption model), the constant capacitance surface complexation model was used to explain the adsorption behavior. The experimental and modelling approaches indicate that arsenate adsorption increases with increased pH, exhibiting a maximum adsorption value before decreasing at higher pH. Per unit mass, sample S₃ (smectite–quartz/muscovite–illite sample) adsorbs more arsenate in the pH range 5–8.5, with 98% of sites occupied at pH 6. S₁ and S₂ have less adsorption capacity with maxima adsorption in the pH ranges of 6–8.5 and 4–6, respectively. The calculation of saturation indices by PHREEQC at different pH reveals that the solution was undersaturated with respect to aluminum arsenate (AlAsO₄2H₂O), scorodite (FeAsO₄2H₂O), brucite and silica, and supersaturated with respect to gibbsite, kaolinite, illite and montmorillonite (for S₃ sample). Increased arsenate concentration (in isotherm experiments) may not produce new solid phases, such as AlAsO₄2H₂O and/or FeAsO₄2H₂O.     

Geochemical modelling of fluid–rock interactions in the context of the Soultz-sous-Forêts geothermal system

The development of the Enhanced Geothermal System (EGS) at Soultz-sous-Forêts (France) has given to scientists an interesting opportunity for the application of geochemical modelling of water–rock interactions, combining theoretical studies with field and experimental data. The main results of four successive and complementary studies are summarized: geochemical modelling of fluid–rock interactions with prediction of dissolution/precipitation of minerals, feed-back effects on the mineralogy and petrography of the rock (major role of silicates in the geological past and of carbonates in the near future of the exploitation), experimental control of the dynamics of silicates under thermal gradient and relation between the evolution of the petrophysics of the rocks and the heat and mass transfers. The thermal cycle of the fluid, between 200 °C and 65 °C in the geothermal loop, may be responsible for dissolution/precipitation of minerals which modify the porosity and permeability of the granite, as it happened in the geological past, in relation with hydrothermal circulations in the Rhine Graben.     

A case-study of complex gas–water–rock–pollutants interactions in shallow groundwater: Šalek Valley (Slovenia)

The complex geochemical interactions in the groundwater of the industrial area of Šalek Valley (Slovenia) between natural and anthropogenic fluids were studied by means of major (Ca, Mg, Na, K, HCO₃ ⁻, Cl⁻ and SO₄ ²⁻) and trace elements’ (As , Cd, Cu, Pb, Zn, Hg, Se and V) abundances, geochemical classification and statistical analysis of data. Cation abundances indicate mixing between a dolomitic end-member and an evaporitic or geothermal end-member. Anion abundances indicate mixing between bicarbonate waters and either sulphate-enriched waters (suggesting hydrothermalism) or chlorine-rich waters. Principal component analysis (PCA) allowed the extraction of seven factors, which describe, respectively: water–rock interaction mainly on dolomitic rocks; redox conditions of water; Cd–Zn enrichment in chlorine-rich waters (probably from industrial wastes); hydrothermal conditions in waters close to major faults; Pb and Cu pollution; V and K enrichments, indicating their common organic source; the role of partial pressure of CO₂ dissolved in water, which is highest in three wells with bubbling gases. Average underground discharge rates of solutes from the Valley range between 0.09 t/a (V) and 1.8 × 104 t/a (HCO₃ ⁻) and indicate how natural fluids can significantly contribute to the levels of elements in the environment, in addition to the amount of elements released by human activities.     

Regional fluid characterisation and modelling of water–rock equilibria in the Boom clay Formation and in the Rupelian aquifer at Mol,Belgium

Interstitial water from the Boom clay Formation around the HADES (high activity disposal experimental site, an underground research facility belonging to the Nuclear research centre, SCK·CEN, at Mol-Dessel, Belgium.) underground research facility at Mol, Belgium, and waters sampled at different locations in the Rupelian aquifer, underlying the clay formation, have been studied. The Boom clay is a Tertiary mudrock containing about 55 % clay and the Rupelian aquifer is located in a silty layer. Special care was taken to adapt or improve measurement, sampling, conservation and analysis methods to get a reliable regional and local database, for the purpose of testing a general model describing the regulation and acquisition of the composition of these fluids. The isotopic and chemical composition of the waters allows them to be assigned to a common origin, namely mixing between a marine endmember and the clay interstitial water, followed by reequilibration with the host rock through dissolution–precipitation reactions involving identified secondary minerals. Oxidation–reduction state and trace element behavior are also discussed and the limits of the model are outlined.     

Thermodynamic modelling of a cooling C–O–H fluid–graphite system: implications for hydrothermal graphite precipitation

Carbon-saturated crustal fluids in the C–O–H system comprise H₂O, CO₂ and CH₄ as the most important fluid species. Graphite precipitation from a cooling C–O–H is discussed for two different systems, namely for a fluid–rock system in which no transfer of atomic oxygen and hydrogen between the fluid and the rock is possible (closed fluid system), and for an open fluid system. Thermodynamic model calculations show that the graphite-forming reactions and the graphite precipitation potential are different for these two systems. Furthermore, the calculations demonstrate that for both systems, the following factors play a role in determining the graphite precipitation potential, i.e. (1) the redox state of the fluid, (2) the initial pressure and temperature conditions and (3) whether cooling is combined with decompression. Open and closed fluid system graphite precipitation can be distinguished from each other using fluid inclusion and stable carbon isotope studies. The results of this study provide insight in the formation of hydrothermal graphite deposits.     

The colloid chemistry of acid rock drainage solution from an abandoned Zn–Pb–Ag mine

Acid rock drainage (ARD) solution from an abandoned ore mine (pH 2.7, SO²⁻₄ concentration 411 mmol/l, Fe concentration 93.5 mmol/l) was investigated by photon correlation spectroscopy, centrifugation, filtration, ultrafiltration, scanning electron microscopy, ICP–MS, AAS, ion chromatography, TOC analysis, and extended X-ray absorption fine structure (EXAFS) spectroscopy. A colloid concentration of ⩾1 g/l was found. The prevailing particle size was <5 nm. Iron, As and Pb were the metal constituents of the colloidal particles. The most probable mineralogical composition of the particles is a mixture of hydronium jarosite and schwertmannite. A small amount of a relatively coarse precipitate was formed in the ARD solution during the months after sampling. The colloid particles are obviously an intermediate in the precipitate formation process. The results suggest that the arsenate is bound to the colloids by the formation of a bidentate binuclear inner-sphere surface complex. However, the transformation of the colloidal material to the more aggregated long-term precipitate results in the incorporation of the arsenate into the interior of the Fe hydroxy sulfate crystal structures. Lead seems to occur as anglesite.     

Origin and evolution of formation water at the Jujo–Tecominoacán oil reservoir,Gulf of Mexico. Part 1: Chemical evolution and water–rock interaction

The origin and evolution of formation water from Upper Jurassic to Upper Cretaceous mudstone–packstone–dolomite host rocks at the Jujo–Tecominoacán oil reservoir, located onshore in SE-Mexico at a depth from 5200 to 6200 m.b.s.l., have been investigated, using detailed water geochemistry from 12 producer wells and six closed wells, and related host rock mineralogy. Saline waters of Cl–Na type with total dissolved solids from 10 to 23 g/L are chemically distinct from hypersaline Cl–Ca–Na and Cl–Na–Ca type waters with TDS between 181 and 385 g/L. Bromine/Cl and Br/Na ratios suggest the subaerial evaporation of seawater beyond halite precipitation to explain the extreme hypersaline components, while less saline samples were formed by mixing of high salinity end members with surface-derived, low salinity water components. The dissolution of evaporites from adjacent salt domes has little impact on present formation water composition. Geochemical simulations with Harvie-Mφller-Weare and PHRQPITZ thermodynamic data sets suggest secondary fluid enrichment in Ca, HCO₃ and Sr by water–rock interaction. The volumetric mass balance between Ca enrichment and Mg depletion confirms dolomitization as the major alteration process. Potassium/Cl ratios below evaporation trajectory are attributed to minor precipitation of K feldspar and illitization without evidence for albitization at the Jujo–Tecominoacán reservoir. The abundance of secondary dolomite, illite and pyrite in drilling cores from reservoir host rock reconfirms the observed water–rock exchange processes. Sulfate concentrations are controlled by anhydrite solubility as indicated by positive SI-values, although anhydrite deposition is limited throughout the lithological reservoir column. The chemical variety of produced water at the Jujo–Tecominoacán oil field is related to a sequence of primary and secondary processes, including infiltration of evaporated seawater and original meteoric fluids, the subsequent mixing of different water types and the formation of secondary minerals by water–rock interaction. A best fit between measured and calculated reservoir temperatures was obtained with the Mg–Li geothermometer for high salinity formation water (TDS > 180 g/L), whereas Na–K, Na–Ka–Ca and quartz geothermometers are partially applicable for less salinite water (TDS < 23 g/L).     

The Guarani Aquifer System: estimation of recharge along the Uruguay–Brazil border

The cities of Rivera and Santana do Livramento are located on the outcropping area of the sandstone Guarani Aquifer on the Brazil–Uruguay border, where the aquifer is being increasingly exploited. Therefore, recharge estimates are needed to address sustainability. First, a conceptual model of the area was developed. A multilayer, heterogeneous and anisotropic groundwater-flow model was built to validate the conceptual model and to estimate recharge. A field campaign was conducted to collect water samples and monitor water levels used for model calibration. Field data revealed that there exists vertical gradients between confining basalts and underlying sandstones, suggesting basalts could indirectly recharge sandstone in fractured areas. Simulated downward flow between them was a small amount within the global water budget. Calibrated recharge rates over basalts and over outcropping sandstones were 1.3 and 8.1% of mean annual precipitation, respectively. A big portion of sandstone recharge would be drained by streams. The application of a water balance yielded a recharge of 8.5% of average annual precipitation. The numerical model and the water balance yielded similar recharge values consistent with determinations from previous authors in the area and other regions of the aquifer, providing an upper bound for recharge in this transboundary aquifer.     

An embedded bond-slip model for finite element modelling of soil–nail interaction

Soil nailing has been widely used as a reinforcing technique to retain excavations and stabilise slopes. Proper assessment of the interaction between the nails and the surrounding soil is central to safe and economical design of the composite reinforced soil structure. In this note, a new interface model, denoted as “embedded bond-slip model”, is proposed to model the soil–nail interaction numerically in a simplified manner. Combining the key features of the embedded element technique and the conventional interface element method, the proposed plane–strain interface model has the advantages that no special considerations have to be given to the arrangement of the finite element mesh for the soil nails, and that possible tangential slippage along the interface can be modelled. The formulation also allows pore water flow across the soil nails to be incorporated into the analysis. The proposed model has been implemented into a finite element code and verified by simple element tests under different uni-direction loading conditions. Using the proposed interface model, back analyses of a field test involving a soil-nailed cut slope subjected to a rise in groundwater table have been conducted. This note presents the details of the embedded bond-slip model and the numerical results which demonstrate that the proposed model is capable of simulating soil–nail interaction conveniently and realistically.