Generation of hydrogen ions and hydrogen gas in quartz–water crushing experiments: an example of chemical processes in active faults

To understand the fundamental chemical processes of fluid–rock interaction during the pulverization of quartz grains in fault zones, quartz grains were crushed within pure water. The crushing experiments were performed batch style using a shaking apparatus. The crushing process induced a decrease in pH and an increase in hydrogen gas with increased shaking duration. The amount of hydrogen ions generated was five times larger than that of the hydrogen gas, which was consistent with the amount of Si radicals estimated from electron spin resonance measurements by Hochstrasser and Antonini (1972). This indicates that hydrogen gas was generated by consuming most of the Si radicals. The generation of hydrogen ions was most likely related to the presence of silanols on the newly formed mineral surface, implying a change of proton activities in the fluid after pulverization of quartz.     

Orthopyroxene rim growth between olivine and quartz at low temperatures (750–950°C) and low water concentration

Orthopyroxene reaction rims were synthesized between polished plates of natural olivine or synthetic forsterite and quartz at 1.9 GPa and temperatures of 750–950°C. The experiments were performed in a piston-cylinder apparatus after drying the samples at 600°C. Each experiment comprised 4 or 7 quartz-olivine contacts that were positioned along a temperature gradient. As a monitor for water content in the samples, the water concentration in the two olivines was determined by FTIR before and after the experiments. The orthopyroxene layers show two different structural variants. Type one (normal layers) has very constant thickness at each contact and formed with equal growth rates at both interfaces. Type two (bulging layers) comprises more irregular areas with 3–5 times thicker rims where porosity provides evidence for the local presence of a fluid. In the bulging layers the growth rate at the olivine-orthopyroxene interface exceeds that at the quartz-orthopyroxene interface. The relative growth rates at the interfaces are in accordance with SiO₂-immobile growth of the normal layers and SiO₂-mobile growth of the bulging layers. The natural olivine contains about 60 wt-ppm intracrystalline water before and after experiment and took up about 20 wt-ppm water molecular adsorbed to micro- and nanocracks and -pores during the runs. The synthetic forsterite contains about 7 wt-ppm internally adsorbed molecular water before and after experiment, and during the runs took up hydrogen equivalent to 3 wt-ppm adsorbed water. The IR spectra indicate that large parts of the point defects (possibly tetrahedral) were frozen-in at the conditions of the experiments. In both olivines a new band appeared at 3,355 or 3,357 cm^?1, respectively, equivalent to about 3 wt-ppm water that at the high pressure of the experiments and opx-buffered aSiO₂ of the experiments might already mean water saturation of the olivines. Despite the effective drying before experiment and the absence of porosity, the bulk diffusivity derived from the rim growth rates is perfectly in line with data from water-bearing piston-cylinder experiments at higher temperatures. The bulk diffusivity during rim growth is 4 to 7 orders of magnitude higher than an extrapolation of really dry experiments to the temperature range of this study.     

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.     

Characteristics of isotope in precipitation,river water and lake water in the Manasarovar basin of Qinghai–Tibet Plateau

The stable hydrogen and oxygen of lake, river, rain and snow waters were investigated to understand the water cycle characteristics of the drainage basin of Manasarovar Lake in Tibet. Both δD and δ ¹⁸O of river water are larger than those of lake water and the effect of altitude on both δD and δ ¹⁸O is not very significant. This phenomenon was suggested to occur because Manasarovar basin is located in Qinghai–Tibet Plateau which has low latitude, high altitude, abundant glaciers, thin air and intensive solar radiation, resulting in higher evaporation in lake water.     

Zircon–quartz–calcite segregations in carbonate–alkaline metasomatic rocks of the western Baikal region and their petrogenetic implications

Fine-grained segregations up to 5 mm in size composed of graphic intergrowths of zircon, quartz, calcite and containing up to 0.8 wt % SrO have been found in albite–riebeckite and dolomite–biotite metasomatic rocks formed after alaskite granite. They contain magnetite, titanomagnetite (25.4 wt % TiO₂), cerite-(Ce,Nd), rutile (up to 1.2 wt % Nb₂O₅), as well as rare micrograins of monazite-(Ce), bastnaesite-(Ce), and barite (up to 5.7 wt % SrO). The fine-grained structure of mineral aggregates suggests a metacolloidal nature. It is assumed that the zircon–quartz–calcite assemblage was formed due to exchange decomposition reaction between the salt phase of hydrothermal solution with predominant Na₂CO₃, elevated Zr and, to a lesser extent, Fe, Ti, LREE, Nb contents and dissolved calcium and silica compounds of a Na₂SiO₃ type.     

Re-equilibration of natural H2O–CO2–salt-rich fluid inclusions in quartz—Part 1: experiments in pure water at constant pressures and differential pressures at 600 °C

Re-equilibration processes of natural H₂O–CO₂–NaCl-rich fluid inclusions quartz are experimentally studied by exposing the samples to a pure H₂O external fluid at 600 °C. Experimental conditions are selected at nearly constant pressure conditions (309 MPa) between fluid inclusions and pore fluid, with only fugacity gradients in H₂O and CO₂, and at differential pressure conditions (394–398 MPa, corresponding to an internal under-pressure) in addition to similar CO₂ fugacity gradients and larger H₂O fugacity gradients. Modifications of fluid inclusion composition and density are monitored with changes in ice dissolution temperature, clathrate dissolution temperature and volume fraction of the vapour phase at room temperature. Specific modification of these parameters can be assigned to specific processes, such as preferential loss/gain of H₂O and CO₂, or changes in total volume. A combination of these parameters can clearly distinguish between modifications according to bulk diffusion or deformation processes. Bulk diffusion of CO₂ according to fugacity gradients is demonstrated at constant pressure conditions. The estimated preferential loss of H₂O is not in accordance with those gradients in both constant pressure and differential pressure experiments. The development of deformation halos in quartz around fluid inclusions that are either under-pressurized or over-pressurized promotes absorption of H₂O from the inclusions and inhibits bulk diffusion according to the applied fugacity gradients.     

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.     

Contamination of water and soil by the Erdenet copper–molybdenum mine in Mongolia

As one of the largest copper–molybdenum (Cu–Mo) mines in the world, the Erdenet Mine in Mongolia has been active since 1978 and is expected to continue operations for at least another 30 years. In this study, the potential impacts of mining activities on the soil and water environments have been evaluated. Water samples showed high concentrations of sulfate, calcium, magnesium, Mo, and arsenic, and high pH values in the order of high to low as follows: tailing water > Khangal River > groundwater. Statistical analysis and the δ²H and δ¹⁸O values of water samples indicate that the tailing water directly affects the stream water and indirectly affects groundwater through recharge processes. Soil and stream sediments are highly contaminated with Cu and Mo, which are major elements of ore minerals. Based on the contamination factor (CF), the pollution load index (PLI), and the degree of contamination (C_d), soil appears to be less contaminated than stream sediments. The soil particle size is similar to that of tailing materials, but stream sediments have much coarser particles, implying that the materials have different origins. Contamination levels in stream sediments display a tendency to decrease with distance from the mine, but no such changes are found in soil. Consequently, soil contamination by metals is attributable to wind-blown dusts from the tailing materials, and stream sediment contamination is caused by discharges from uncontained subgrade ore stock materials. Considering the evident impact on the soil and water environment, and the human health risk from the Erdenet Mine, measures to mitigate its environmental impact should be taken immediately including source control, the establishment of a systematic and continuous monitoring system, and a comprehensive risk assessment.     

Dumortierite- and corundum-bearing quartz–feldspar–mica rocks of the Belomorian eclogite province: An example of melting of phengite + quartz

In the Salma eclogite of the Belomorian eclogite province, a dumortierite–phengite–corundum–bearing quartz–feldspar rock has been studied: its primary HP mineral paragenesis included garnet, phengite, and quartz. The phengite–quartz rocks were formed during dehydration and/or melting of boroncontaining rocks when they were dipped in the Meso- Neoarchaean subduction zone to a depth of not less than 70 km. As a result of the subsequent superimposed high-temperature metamorphic events under PT conditions of high-pressure granulite facies, the phengite in quartz underwent incongruent dehydration melting with formation of complex polymineral pseudomorphs, consisting of feldspars, biotite, newly formed muscovite, kyanite, corundum, and dumortierite. New estimates of the metamorphic temperature (850–900°C according to the melting reactions of phengite and the dumortierite field of stability; about 1000°C by the reintegrated composition of feldspar–mesoperthite) that affected the HP parageneses of Salma eclogitized rocks are at least 50–100°C (or even more) higher than them estimated earlier.

     

Solid–water partitioning of elements in Czech freshwaters

Partitioning of 41 elements between solids and water was studied by filtration and dialysis in situ in Czech freshwaters. Field-based distribution (partition) coefficients, K_D, between suspended particulate matter (SPM) and filtrate (‘dissolved’ fraction) differed by 4 orders of magnitude. The highest K_D values (log K_D>2.0 l/g) were exhibited by Zr, Al, Ce, Pb, La, Ti, Fe, Sm, Th and Cr which are extremely insoluble in near-neutral water or generally poorly soluble (Zr,Ti). The K_Ds decrease with element and DOC loading due to the relative increase of the element in the low molecular fraction. Log K_D mostly increased linearly with pH within a range from 3.5 to 9. K_D^U decreased at pH >6 due to carbonate complexation. The colloidal fraction (>1 kDa <0.4 μm) in a reservoir with a pH of 6.8 was mainly preferred by Fe, Pb, Be, Nb, Y, Al, Ni, U and Zr. When the colloidal fraction is not differentiated from true solution, then incorrect information about partitioning may be obtained and the highest K_D may decrease.     

Geochemical features of gold–quartz veins in granitoid intrusives and terrigenous masses of the Yana–Kolyma folded belt in the northeast of Russia

The main task of this study was to reveal geochemical and distinctive features of gold–quartz vein ores of deposits in granitoid intrusive bodies and in terrigenous black-schist masses of the Yana-Kolyma folded belt. The results obtained point to the significant role of metamorphism of the enclosing terrigenous carbonaceous masses in ore formation of both types of deposits. The established facts are not contradictory to the metamorphic–magmagene model of the formation of gold deposits in the Yana–Kolyma belt. The geochemical similarity of both types of deposits shows that these are products of the same orogenic system, which confirms the validity of combining these deposits to form a unified gold–quartz formation.     

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.     

The solubility of calcite in water at 6–16 kbar and 500–800 °C

The solubility of calcite in H₂O was measured at 6–16 kbar, 500–800 °C, using a piston-cylinder apparatus. The solubility was determined by the weight loss of a single crystal and by direct analysis of the quench fluid. Calcite dissolves congruently in the pressure (P) and temperature (T) range of this study. At 10 kbar, calcite solubility increases with increasing temperature from 0.016±0.005 molal at 500 °C to 0.057±0.022 molal at 750 °C. The experiments reveal evidence for hydrous melting of calcite between 750 and 800 °C. Solubilities show only a slight increase with increasing P over the range investigated. Comparison with work at low P demonstrates that the P dependence of calcite solubility is large between 1 and 6 kbar, increasing at 500 °C from 1.8×10^–5 molal at 1 kbar to 6.4×10^–3 molal at 6 kbar. The experimental results are described by:

SPH study of the evolution of water–water interfaces in dam break flows

Natural Hazards - The mixing process of upstream and downstream waters in the dam break flow could generate significant ecological impact on the downstream reaches and influence the environmental...     

Sr isotopes in natural waters: Applications to source characterisation and water–rock interaction in contrasting landscapes

Strontium isotopes (⁸⁷Sr/⁸⁶Sr) are routinely measured in hydrochemical studies to determine sources and mixing relationships. They have proved particularly useful in determining weathering processes and quantifying end-member mixing processes. A number of routine case studies are presented which highlight that Sr isotopes represent a powerful tool in the geochemists toolbox helping to constrain weathering reactions, weathering rates, flow pathways and mixing scenarios. Differences in methodologies for determining the weathering component in natural environments, inherent differences in weathering rates of different minerals, and mineral heterogeneity often cause difficulties in defining the weathering component of different catchments or aquifer systems. Nevertheless, Sr isotopes are useful when combined with other hydrochemical data, to constrain models of water–rock interaction and mixing as well as geochemical processes such as ion-exchange. This paper presents a summary of recent work by the authors in constraining the sources of waters and weathering processes in surface catchments and aquifers, and indicates cases where Sr isotopes alone are insufficient to solve hydrological problems.     

Elevated critical micelle concentration in soil–water system and its implication on PAH removal and surfactant selecting

Triton X-100 (TX100) and Brij 35 (B35) were used to investigate the elevated critical micelle concentration (CMC) induced by surfactant sorption and its influence on PAH removal in soil washing systems. The surface tension technique was applied to determine the CMC and the apparent CMC (CMC_soil) in soil–water systems. Surfactant sorption experiments were conducted by the batch equilibration technique. Surfactants sorbed on the soil at concentrations below the CMC_soil were quantified with data from the surface tension experiments for both an aqueous system and a soil–water system. Due to sorption, the CMC_soil values of the two surfactants are 2.75 and 6.31 times their corresponding CMC values in aqueous solutions, respectively. At concentrations below CMC_soil, the loss of B35 (92–99.7 %) was greater than that of TX100 (63–92 %). The PAH removal efficiencies are greatly dependent on the CMC_soil value. At surfactant concentrations below CMC_soil, the PAH removal is very low and remains almost invariable. Whereas, at concentrations above CMC_soil, the PAH removal increases greatly. B35 inhibited PAH desorption at concentrations below its CMC_soil. For TX100, some degree of PAH desorption enhancement was observed at concentrations below its CMC_soil. CMC_soil is a key parameter while selecting a surfactant for a specific soil washing system, only surfactant concentrations above their CMC_soil should be evaluated.     

Optimal water and waste load allocation in reservoir–river systems: a case study

In this paper, a new methodology is developed for optimization of water and waste load allocation in reservoir–river systems considering the existing uncertainties in reservoir inflow, waste loads and water demands. A stochastic dynamic programming (SDP) model is used to optimize reservoir operation considering the inflow uncertainty, and another model called PSO-SA is developed and linked with the SDP model for optimizing water and waste load allocation in downstream river. In the PSO-SA model, a particle swarm optimization technique with a dynamic penalty function for handling the constraints is used to optimize water and waste load allocation policies. Also, a simulated annealing technique is utilized for determining the upper and lower bounds of constraints and objective function considering the existing uncertainties. As the proposed water and waste load allocation model has a considerable run-time, some powerful soft computing techniques, namely, Regression tree Induction (named M5P), fuzzy K-nearest neighbor, Bayesian network, support vector regression and an adaptive neuro-fuzzy inference system, are trained and validated using the results of the proposed methodology to develop real-time water and waste load allocation rules. To examine the efficiency and applicability of the methodology, it is applied to the Dez reservoir–river system in the south-western part of Iran.     

Characteristics of Piezometric heads and determination of fresh water–salt water interface in the coastal zone near Beihai,China

Changes in hydraulic heads with space and time and evolution of the location of fresh water–salt water interface are important for groundwater development in coastal aquifers. Measurements of piezometric heads at 11 well clusters consisting of three piezometric wells of different depths with a 5-day interval for 15 months show that the piezometric heads at nearly all the wells near the northwestern coast in Beihai decrease with increasing depth and increase with increasing distance from the coast. Changes in piezometric heads at the wells during the measurement period were caused by seasonal precipitation and induced by the tide. The depth of the sharp interface between fresh water–salt water can be estimated based on measurements of piezometric heads at a piezometric well tapping at a point in the salt water zone below the interface and measurements of the water table at the same well. The calculations of the interface for well H5 range from 40 to 80 m below sea level in the measurement period, which are believed to be more reasonable than those estimated with the Ghyben–Herzberg relation. An erratum to this article can be found at