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1.
《Geochimica et cosmochimica acta》1999,63(19-20):3261-3275
Studies on the dissolution kinetics of kaolinite were performed using batch reactors at 25°C and in the pH range from 1 to 13. A rapid initial dissolution step was first observed, followed by a linear kinetic stage reached after approximately 600 hr of reaction during which the kaolinite dissolves congruently at pH < 4 and pH > 11. The apparent incongruency between pH 5 and 10 was due to the precipitation of an Al–hydroxide phase. The true dissolution rates were computed from the amount of Si released into solution. The rate dependence on pH can be described by: r = 10−12.19aH+0.55 + 10−14.36 + 10−10.71aOH−0.75Between pH 5 and 10, the rate is approximately constant, although a smooth minimum was observed at pH close to 9. mAn attempt was made to obtain a general rate law based on the coordination theory, which was first applied to the mineral dissolution studies by Stumm and co-workers. The kinetic data were combined with the results obtained for the surface speciation by Huertas et al. (1998). It is possible to express the linear dissolution rate as a simple power function of the concentration of the surface sites active in various pH ranges: r = 10−8.25 [>Al2OH2+] + 10−10.82 [>AlOH2+]0.5 + 10−9.1 [>Al2OH + >AlOH + >SiOH] + 103.78 [>Al2O− + >AlO−]3This equation assumes that the dissolution mechanism is mainly controlled by the two Al surface sites (external and internal structural hydroxyls, and aluminol at the crystal edges) under both acidic and alkaline conditions. The model reflects well the important contribution of the crystal basal planes to the dissolution of kaolinite.  相似文献   

2.
Reactive-transport models are developed here that produce dolomite via two scenarios: primary dolomite (no CaCO3 dissolution involved) versus secondary dolomite (dolomitization, involving CaCO3 dissolution). Using the available dolomite precipitation rate kinetics, calculations suggest that tens of meters of thick dolomite deposits cannot form at near room temperature (25-35°C) by inorganic precipitation mechanism, though this mechanism will provide dolomite aggregates that can act as the nuclei for dolomite crystallization during later dolomitization stage. Increase in supersaturation, Mg+2/Ca+2 ratio and CO3-2 on the formation of dolomite at near room temperature are subtle except for temperature.This study suggests that microbial mediation is needed for appreciable amount of primary dolomite formation. On the other hand, reactive-transport models depicting dolomitization (temperature range of 40 to 200°C) predicts the formation of two adjacent moving coupled reaction zones (calcite dissolution and dolomite precipitation) with sharp dolomitization front, and generation of >20% of secondary porosity. Due to elevated temperature of formation, dolomitization mechanism is efficient in converting existing calcite into dolomite at a much faster rate compared to primary dolomite formation.  相似文献   

3.
《Applied Geochemistry》1999,14(5):569-579
Potential human intrusion into the Waste Isolation Pilot Plant (WIPP) might release actinides into the Culebra Dolomite where sorption reactions will affect of radiotoxicity from the repository. Using a limited residence time reactor the authors have measured Ca, Mg, Nd adsorption/exchange as a function of ionic strength, PCO2, and pH at 25°C. By the same approach, but using as input radioactive tracers, adsorption/exchange of Am, Pu, U, and Np on dolomite were measured as a function of ionic strength, PCO2, and pH at 25°C. Metal adsorption is typically favored at high pH. Calcium and Mg adsorb in near-stoichiometric proportions except at high pH. Adsorption of Ca and Mg is diminished at high ionic strengths (e.g., 0.5M NaCl) pointing to association of Na+ with the dolomite surface, and the possibility that Ca and Mg sorb as hydrated, outer-sphere complexes. Sulfate amplifies sorption of Ca and Mg, and possibly Nd as well. Exchange of Nd for surface Ca is favored at high pH, and when Ca levels are low. Exchange for Ca appears to control attachment of actinides to dolomite as well, and high levels of Ca2+ in solution will decrease Kds. At the same time, to the extent that high PCO2s increase Ca2+ levels, Kds will decrease with CO2 levels as well, but only if sorbing actinide-carbonate complexes are not observed to form (Am-carbonate complexes appear to sorb; Pu-complexes might sorb as well. U-carbonate complexation leads to desorption). This indirect CO2 effect is observed primarily at, and above, neutral pH. High NaCl levels do not appear to affect to actinide Kds.  相似文献   

4.
This study investigated the potential for the uranium mineral carnotite (K2(UO2)2(VO4)2·3H2O) to precipitate from evaporating groundwater in the Texas Panhandle region of the United States. The evolution of groundwater chemistry during evaporation was modeled with the USGS geochemical code PHREEQC using water-quality data from 100 groundwater wells downloaded from the USGS National Water Information System (NWIS) database. While most modeled groundwater compositions precipitated calcite upon evaporation, not all groundwater became saturated with respect to carnotite with the system open to CO2. Thus, the formation of calcite is not a necessary condition for carnotite to form. Rather, the determining factor in achieving carnotite saturation was the evolution of groundwater chemistry during evaporation following calcite precipitation. Modeling in this study showed that if the initial major-ion groundwater composition was dominated by calcium-magnesium-sulfate (>70 precent Ca + Mg and >50 percent SO4 + Cl) or calcium-magnesium-bicarbonate (>70 percent Ca + Mg and <70 percent HCO3 + CO3) and following the precipitation of calcite, the concentration of calcium was greater than the carbonate alkalinity (2mCa+2 > mHCO3− + 2mCO3−2) carnotite saturation was achieved. If, however, the initial major-ion groundwater composition is sodium-bicarbonate (varying amounts of Na, 40–100 percent Na), calcium-sodium-sulfate, or calcium-magnesium-bicarbonate composition (>70 percent HCO3 + CO3) and following the precipitation of calcite, the concentration of calcium was less than the carbonate alkalinity (2mCa+2 < mHCO3- + 2mCO3−2) carnotite saturation was not achieved. In systems open to CO2, carnotite saturation occurred in most samples in evaporation amounts ranging from 95 percent to 99 percent with the partial pressure of CO2 ranging from 10−3.5 to 10−2.5 atm. Carnotite saturation occurred in a few samples in evaporation amounts ranging from 98 percent to 99 percent with the partial pressure of CO2 equal to 10−2.0 atm. Carnotite saturation did not occur in any groundwater with the system closed to CO2.  相似文献   

5.
Mineral dissolution rates have been rationalized in the literature by surface complexation models (SCM) and morphological and geometric models (GM), and reconciliation of these conceptually different yet separately highly successful models is an important goal. In the current work, morphological alterations of the surface are observed in real time at the microscopic level by atomic force microscopy (AFM) while dissolution rates are simultaneously measured at the macroscopic level by utilizing the AFM fluid cell as a classic flow-through reactor. Rhodochrosite dissolution is studied from pH = 2 to 11 at 298 K, and quantitative agreement is found between the dissolution rates determined from microscopic and macroscopic observations. Application of a SCM model for the interpretation of the kinetic data indicates that the surface concentration of >CO3H regulates dissolution for pH < 7 while the surface concentration of >MnOH2+ regulates dissolution for pH > 7. A GM model explains well the microscopic observations, from which it is apparent that dissolution occurs at steps associated with anisotropic pit expansion. On the basis of the observations, we combine the SCM and GM models to propose a step-site surface complexation model (SSCM), in which the dissolution rates are quantitatively related to the surface chemical speciation of steps. The governing SSCM equation is as follows: R = χ1/2(kco + kca)[>CO3H] + χ1/2(kmo + kma)[>MnOH2+ ], where R is the dissolution rate (mol m−2 s−1), 2χ1/2 is the fraction of surface sites located at steps, [>CO3H] and [>MnOH2+ ] are surface concentrations (mol m−2), and kco, kca, kmo, and kma are the respective dissolution rate coefficients (s−1) for the >CO3H and the >MnOH2+ surface species on obtuse and acute steps. We find kco = 2.7 s−1, kca = 2.1 × 10−1 s−1, kmo = 4.1 × 10−2 s−1, kma = 3.7 × 10−2 s−1, and χ1/2 = 0.015 ± 0.005. The rate coefficients quantify the net result of complex surface step processes, including double-kink initiation and single-kink propagation. We propose that the SSCM model may have general applicability for dissolution far from equilibrium of flat mineral surfaces of ionic crystals, at least those that dissolve by step retreat.  相似文献   

6.
On the basis of the mechanism of formation of mineral inclusions, it may be assumed that a certain relation exists between the compositions of fluid inclusions in various minerals formed at the same stage of hydrothermal activity. In order to study the genetic relationships between different minerals in the Bayan Obo iron deposit, the compositions(K~+, Na~+, Ca~+, Mg~+, F~+, Cl~+, CO_2~(2-), ΣSO_4~(2-) and pH) of inclusions in fluorite(23), hematite(13), magnetite(3), sodium pyroxene(2) and dolomite(5) from the main mine and the eastern mine were determined by using the vacuum decrepitation and leaching methods, and cluster analyses of the data on the compostions were made. The Q-mode cluster analysis indicates that some iron oxide minerals in the deposit are related to dolomite of sedimentary origin, while others are related to fluorite and sodium pyroxene--products of hydrothermal activity. The R-mode cluster analysis shows that the components of the leaching solution may be divided into two groups: one includes CO_2~(2-), Mg~(2+) and H~+(pH), which are obviously associated with dolomite; the other comprises Na~+, K~+, Ca~+, F~+, Cl~+ and SO_4~(2-), which may possibly represent the composition of hydrothermal solutions.The reaction of the Na-F-Cl solution(pH 4.72) with hematite dolomite at 300℃ and 5 × 10~7 Pa and under alternately"static and dynamic" conditions produced large amounts of hematite and fluorite and small amounts of smectite and Na(Fe) silicates, and the hematite-fluorite assemblage accords with the actual geological conditions in the deposit. From a comparison between the compositions of"static" and"dynamic" solution samples, it may be known that the flow reaction facilitates the migration of Fe, F, Ca and other components as well as Na-metasomatism(Na and Si are fixed in a solid phase).The study of the compositions of mineral inclusions and simulation experiments on hydrothermal metasomatism have provided new evidence for the hypothesis of metamorphosed-sedimentary and hydrothermal-remoulding origin of the Bayan Obo deposit, and pointed out emphatically that hydrothermal metasomatism plays an important role in the formation of the mineral deposit, particularly in the main and the east mine.  相似文献   

7.
《Applied Geochemistry》2001,16(9-10):1067-1082
Thermodynamic data for all fate-determining processes are needed in order to predict the fate and transport of metals in natural systems. The surface complexation properties of a synthetic MnO2, δ-MnO2, have accordingly been investigated using glass electrode potentiometry. Experimental data were interpreted according to the surface complexation model in conjunction with the diffuse double layer model of the solid/solution interface. Adsorption constants were determined using the non-linear optimisation program FITEQL. Surface complexation parameters determined in this way were validated against results obtained from the literature. Best fits of alkalimetric titration data were obtained with a 2-site, 3 surface-species model of the δ-MnO2 surface. Site concentrations of 2.23×10−3 mol g−1 and 7.66×10−4 mol g−1 were obtained. Corresponding logarithms of formation constants for the postulated surface species are −1.27 (≡XO−), −5.99 (≡YO−) and 3.52 (≡YOH2+) at I=0.1 M. The surface speciation of δ-MnO2 is dominated by ≡XO− over the pH range investigated. Metal adsorption was modelled with surface species of the type ≡XOM+, ≡XOMOH, ≡YOM+, ≡YOMOH (M=Cu, Ni, Zn, Cd and Pb) and ≡XOM2OH2+ (M=Pb). For Cu, Ni and Zn, titration data could be modelled with ≡XOM+, ≡XOMOH, ≡YOM+ and ≡YOMOH, whereas for Cd, ≡XOM+ and ≡YOM+ were sufficient. Lead data were best modelled by assuming the dinuclear species ≡XOM2OH2+ to be the only surface species to form. Adsorption constants determined for Ni, Cu and Zn follow the Irving-Williams sequence. The model suggests an adsorption order of (Pb, Cu) > (Ni, Zn) > Cd. The discrepancy between model predictions and published adsorption results is similar to the variability observed in experimental results from different laboratories.  相似文献   

8.
Geochemical processes that take place in the aquifer have played a major role in spatial and temporal variations of groundwater quality. This study was carried out with an objective of identifying the hydrogeochemical processes that controls the groundwater quality in a weathered hard rock aquifer in a part of Nalgonda district, Andhra Pradesh, India. Groundwater samples were collected from 45 wells once every 2 months from March 2008 to September 2009. Chemical parameters of groundwater such as groundwater level, EC and pH were measured insitu. The major ion concentrations such as Ca2+, Mg2+, Na+, K+, Cl−, and SO4 2− were analyzed using ion chromatograph. CO3 − and HCO3 − concentration was determined by acid–base titration. The abundance of major cation concentration in groundwater is as Na+ > Ca2+ > Mg2+ > K+ while that of anions is HCO3 − > SO4 2− > Cl− > CO3 −. Ca–HCO3, Na–Cl, Ca–Na–HCO3 and Ca–Mg–Cl are the dominant groundwater types in this area. Relation between temporal variation in groundwater level and saturation index of minerals reveals the evaporation process. The ion-exchange process controls the concentration of ions such as calcium, magnesium and sodium. The ionic ratio of Ca/Mg explains the contribution of calcite and dolomite to groundwater. In general, the geochemical processes and temporal variation of groundwater in this area are influenced by evaporation processes, ion exchange and dissolution of minerals.  相似文献   

9.
The chemistry of the rainwater indirectly reflects the composition of the ions in the atmosphere. The study of the rainwater gains its own importance as it forms the basis for the agricultural, domestic and drinking water. Twelve rainwater samples were collected along the southeastern coast of India during southwest monsoon. The samples were analyzed for the major anions (Cl?, SO4 2?, PO4 3? and HCO3 ?) and cations (Na+, K+, Ca2+ and Mg2+). The majority of the samples reflect acidic pH. The general dominance of the cations is in the order of Na+ > Ca2+ > K+ > Mg2+ and that of anions is HCO3 ? > Cl? > SO4 2? > PO4 3?. The water is classified as calcium bicarbonate to sodium bicarbonate type. The decrease of pH value also increases the pCO2. In order to study the impact of acidic and alkaline species on rainwater, correlation coefficients were determined for establishing the relationship between different ions. Good correlation was established between cations, and sulfate has no correlation with other ions and pH. Factor analysis reveals that land use pattern, marine source and methanogenesis from the tidal influenced mangroves play a major role in determining the rainwater chemistry of the region.  相似文献   

10.
Dissolution of CO2 into deep subsurface brines for carbon sequestration is regarded as one of the few viable means of reducing the amount of CO2 entering the atmosphere. Ions in solution partially control the amount of CO2 that dissolves, but the mechanisms of the ion's influence are not clearly understood and thus CO2 solubility is difficult to predict. In this study, CO2 solubility was experimentally determined in water, NaCl, CaCl2, Na2SO4, and NaHCO3 solutions and a mixed brine similar to the Bravo Dome natural CO2 reservoir; ionic strengths ranged up to 3.4 molal, temperatures to 140 °C, and CO2 pressures to 35.5 MPa. Increasing ionic strength decreased CO2 solubility for all solutions when the salt type remained unchanged, but ionic strength was a poor predictor of CO2 solubility in solutions with different salts. A new equation was developed to use ion hydration number to calculate the concentration of electrostricted water molecules in solution. Dissolved CO2 was strongly correlated (R2 = 0.96) to electrostricted water concentration. Strong correlations were also identified between CO2 solubility and hydration enthalpy and hydration entropy. These linear correlation equations predicted CO2 solubility within 1% of the Bravo Dome brine and within 10% of two mixed brines from literature (a 10 wt % NaCl + KCl + CaCl2 brine and a natural Na+, Ca2+, Cl− type brine with minor amounts of Mg2+, K+, Sr2+ and Br−).  相似文献   

11.
The frictional properties of anhydrite-dolomite fault gouges, and the effects of CO2 upon them, are of key importance in assessing the risks associated with CO2 storage in reservoir formations capped by anhydrite-dolomite sequences, and in understanding seismicity occurring in such formations (such as the Italian Apennines). Therefore, we performed velocity-stepping direct-shear experiments on simulated dolomite, anhydrite and 50:50 anhydrite/dolomite gouges, at representative in-situ conditions (120 °C and σne = 25 MPa). They were conducted under vacuum, or else using water or CO2-saturated water as pore fluid (Pf = 15 MPa). Friction coefficients varied between 0.55 and 0.7. All dry samples exhibited velocity-weakening behavior, whereas all wet samples exhibited velocity-strengthening behavior, without or with CO2. This is consistent with trends previously reported for such gouges. A compilation of literature data shows that the transition from velocity-strengthening to velocity-weakening occurs in these materials between 80 and 120 °C when dry, and between 100 and 150 °C when wet. This implies little seismogenic potential for wet dolomite, anhydrite and mixed gouges under CO2 storage conditions at 2–4 km depth. Seismic slip in the Italian Apennines at depths of ∼6 km and beyond may be explained by the velocity-weakening behavior expected in anhydrite and especially dolomite at temperatures above 150 °C.  相似文献   

12.
Whether carbonate weathering could produce a stable carbon sink depends primarily on the utilization of dissolved inorganic carbon (DIC) by aquatic phototrophs (the so-called Biological Carbon Pump-BCP effect). On this basis, water temperature (T), pH, electrical conductivity (EC) and dissolved oxygen (DO) were synchronously monitored at 15-min resolution for one and two days respectively in January and October 2013 in Maolan Spring and the spring-fed midstream and downstream ponds in Maolan Nature Reserve, China. A thermodynamic model was used to link the continuous data to allow calculation of CO2 partial pressures (pCO2) and calcite saturation indexes (SIC). A floating static chamber was placed on the water surface successively at all sites to quantify CO2 exchange flux between atmosphere and water so as to evaluate the BCP effect. Results show that, in both winter and autumn, remarkable diel variations of hydrochemical parameters were present in the midstream pond where DO, pH, and SIC increased in the day and decreased during the night while EC, [HCO3−], [Ca2+] and pCO2 showed inverse changes mainly due to the metabolic processes of the flourishing submerged plants, with photosynthesis dominating in the day and respiration dominating at night. However, hydrochemical parameters in the spring and downstream pond show less change since few submerged plants developed there. It was determined that the BCP effect in the midstream pond was 285 ± 193 t C km−2 a−1 in winter and 892 ± 300 t C km−2 a−1 in autumn, indicating a potential significant role of terrestrial aquatic photosynthesis in stabilizing the carbonate weathering-related carbon sink.  相似文献   

13.
In situ measured microprofiles of Ca2+, pCO2, pH and O2 were performed to quantify the CaCO3 dissolution and organic matter mineralization in marine sediments in the eastern South Atlantic. A numerical model simulating the organic matter decay with oxygen was used to estimate the calcite dissolution rate. From the oxygen microprofiles measured at four stations along a 1300-m isobath of the eastern African margin and one in front of the river Niger at a water depth of 2200 m the diffusive oxygen uptake (DOU) and oxygen penetration depth (OPD) was calculated. DOU rates were in the range of 0.3 to 3 mmol m−2 d−1 and showed a decrease with increasing water depth, corresponding to an increase in OPD. The calculated amount of degradated organic matter is in the range of 1 to 8.5 gC m−2 a−1. The metabolic CO2, released from mineralization of the organic matter drives calcite dissolution in these sediments overlain by calcite-supersaturated water. Fluxes across the sediment water interface calculated from the in situ Ca2+ microprofiles were 0.6 mmol m−2 d−1 for two stations at a water depth of 1300 m. The ratio of calcite dissolution flux and organic C degradation is 0.53 and 0.97, respectively. The microprofiles indicate that CO2 produced within the upper oxic sediment layer dissolves up to 85% of the calcite rain to the seafloor. Modeling our O2, pH and Ca2+ profiles from one station predicted a calcite dissolution rate constant for this calcite-poor site of 1000 mol kgw−1 a−1 (mol per kg water and year), which equals 95% d−1. This rate constant is at the upper end of reported in situ values.  相似文献   

14.
The paired chemical reactions, Ca2+ + 2HCO3 ? ? CaCO3 + CO2 + H2O, overestimate the ratio of CO2 flux to CaCO3 flux during the precipitation or dissolution of CaCO3 in seawater. This ratio, which has been termed ??, is about 0.6 in surface seawater at 25°C and at equilibrium with contemporary atmospheric CO2 and increases towards 1.0 as seawater cools and pCO2 increases. These conclusions are based on field observations, laboratory experiments, and equilibrium calculations for the seawater carbonate system. Yet global geochemical modeling indicates that small departures of ?? from 1.0 would cause dramatic, rapid, and unrealistic change in atmospheric CO2. ?? can be meaningfully calculated for a water sample whether or not it is in equilibrium with the atmosphere. The analysis presented here demonstrates that the atmospheric CO2 balance can be maintained constant with respect to seawater CaCO3 reactions if one considers the difference between CaCO3 precipitation and burial and differing values for ?? (both <1.0) in regions of precipitation and dissolution within the ocean.  相似文献   

15.
《Applied Geochemistry》2002,17(4):399-408
The sorption of U(VI) onto the surface of olivine has been experimentally investigated at 25 °C under an air atmosphere as a function of pH, solid surface to volume ratio and total U concentration. Sorption has been observed to decrease as the extent of carbonate complexation of U(VI) in solution increases, which is attributed to the competition between aqueous and solid ligands for the coordination of U. The experimental results have been interpreted by means of two different approaches: (1)a semi-empirical model, exemplified by the application of a Langmuir isotherm and (2) a non-electrostatic thermodynamic surface complexation model which includes the formation of the surface species: >SO–UO2+ and >SO–UO2(OH). The following stability constants for these species have been determined from the thermodynamic analysis: K(>SO–UO2+)=289±71 and K(>SO–UO2(OH))=(3.4±0.4)×10−6. The comparison of the sorption of U onto olivine with granites of different origin indicate that the use of this mineral as additive to the backfill of deep high level nuclear waste repositories could retard the migration of U from the repository to the geosphere.  相似文献   

16.
Hydrochemical investigations were carried out in Damagh area, Hamadan, western Iran, to assess chemical composition of groundwater. Forty representative groundwater samples were collected from different wells to monitor the water chemistry of various ions. Chemical analysis of the groundwater showed that the mean concentration of the cations is in the order Na+ > Ca2+ > Mg2+ > K+, while that for anions was HCO3− > Cl− > SO42 − > NO3−. All of the investigated groundwaters present two different chemical facies (Ca–HCO3 and Na–HCO3) which is in relation with their interaction with the geological formations of the basin, cation exchange between groundwater and clay minerals and anthropogenic activities. The principal component analysis (PCA) performed on groundwater identified three principal components controlling their variability in groundwater. Electrical conductivity, Mg2+, Na+, SO42−, and Cl− content were associated in the same component (PC1) (salinity), determined principally by anthropogenic activities. The pH, CO32 −, HCO3−, and Ca2+ (PC2) content were related to the geogenic factor. Finally, the NO3−, Cl− and K+ (PC3) were controlled by anthropogenic activity as a consequence of inorganic fertilizers.  相似文献   

17.
Sabkhas are ubiquitous geomorphic features in eastern Saudi Arabia. Seven brine samples were taken from Sabkha Jayb Uwayyid in eastern Saudi Arabia. Brine chemistry, saturation state with respect to carbonate and evaporate minerals, and evaporation-driven geochemical reaction paths were investigated to delineate the origin of brines and the evolution of both brine chemistry and sabkha mineralogy. The average total dissolved solids in the sabkha brines is 243 g/l. The order of cation dominance is Na+   >>  Mg2+ >>  Ca2+>K+, while anion dominance is Cl− >> SO4 2− >> HCO3 −. Based on the chemical divide principle and observed ion ratios, it was concluded that sabkha brines have evolved from deep groundwater rather than from direct rainfall, runoff from the surroundings, or inflow of shallow groundwater. Aqueous speciation simulations show that: (1) all seven brines are supersaturated with respect to calcite, dolomite, and magnesite and undersaturated with respect to halite; (2) three brines are undersaturated with respect to both gypsum and anhydrite, while three brines are supersaturated with respect to both minerals; (3) anhydrite is a more stable solid phase than gypsum in four brines. Evaporation factors required to bring the brines to the halite phase boundary ranged from 1.016 to 4.53. All reaction paths to the halite phase boundary follow the neutral path as CO2 is degassed and dolomite precipitates from the brines. On average, a sabkha brine containing 1 kg of H2O precipitates 7.6 g of minerals along the reaction path to the halite phase boundary, of which 52% is anhydrite, 35.3% is gypsum, and 12.7% is dolomite. Bicarbonate is the limiting factor of dolomite precipitation, and sulfate is the limiting factor of gypsum and anhydrite precipitation from sabkha brines.  相似文献   

18.
Assessing the influence of CO2 on soil and aquifer geochemistry is a task of increasing interest when considering risk assessment for geologic carbon sequestration. Leakage and CO2 ascent can lead to soil acidification and mobilization of potentially toxic metals and metalloids due to desorption or dissolution reactions. We studied the CO2 influence on an Fe(III) (oxyhydr)oxide rich, gleyic Fluvisol sampled in close vicinity to a Czech mofette site and compared the short-term CO2 influence in laboratory experiments with observations on long-term influence at the natural site. Six week batch experiments with/without CO2 gas flow at 3 different temperatures and monitoring of liquid phase metal(loid) concentrations revealed two main short-term mobilization processes. Within 1 h to 1 d after CO2 addition, mobilization of weakly adsorbed metal cations occurred due to surface protonation, most pronounced for Mn (2.5–3.3 fold concentration increase, mobilization rates up to 278 ± 18 μg Mn kgsoil−1 d−1) and strongest at low temperatures. However, total metal(loid) mobilization by abiotic desorption was low. After 1–3 d significant Fe mobilization due to microbially-triggered Fe(III) (oxyhydr)oxide dissolution began and continued throughout the experiment (up to 111 ± 24 fold increase or up to 1.9 ± 0.6 mg Fe kgsoil−1 d−1). Rates increased at higher temperature and with a higher content of organic matter. The Fe(III) mineral dissolution was coupled to co-release of incorporated metal(loid)s, shown for As (up to 16 ± 7 fold, 11 ± 8 μg As kgsoil−1 d−1). At high organic matter content, re-immobilization due to resorption reactions could be observed for Cu. The already low pH (4.5–5.0) did not change significantly during Fe(III) reduction due to buffering from sorption and dissolution reactions, but a drop in redox potential (from > +500 mV to minimum +340 ± 20 mV) occurred due to oxygen depletion. We conclude that microbial processes following CO2 induction into a soil can contribute significantly to metal(loid) mobilization, especially at optimal microbial growth conditions (moderate temperature, high organic carbon content) and should be considered for carbon sequestration monitoring and risk assessment.  相似文献   

19.
Far from equilibrium enstatite dissolution rates both open to atmospheric CO2 and CO2 purged were measured as a function of solution pH from 8 to 13 in batch reactors at room temperature. Congruent dissolution was observed after an initial period of incongruent dissolution with preferential Si release from the enstatite. Steady-state dissolution rates in open to atmospheric CO2 conditions decrease with increase in solution pH from 8 to 12 similar to the behavior reported by other investigators. Judging from the pH 13 dissolution rate, rates increase with pH above pH 12. This is thought to occur because of the increase in overall negative surface charges on enstatite as Mg surface sites become negative above pH 12.4, the pH of zero surface charge of MgO.Steady-state dissolution rates of enstatite increase above pH 10 when CO2 was purged by performing the experiments in a N2 atmosphere. This suggests inhibition of dissolution rates above pH 10 when experiments were open to the atmosphere. The dissolved carbonate in these solutions becomes dominantly CO32− above pH 10.33. It is argued that CO32− forms a >Mg2-CO3 complex at positively charged Mg surface sites on enstatite, resulting in stabilization of the surface Si-O bonds. Therefore, removal of solution carbonate results in an increase in dissolution rates of enstatite above pH 10. The log rate of CO2-purged enstatite dissolution in moles per cm2 per s as a function of increasing pH above pH 10 is equal to 0.35. This is consistent with the model of silicate mineral dissolution in the absence of surface carbonation in alkaline solutions proposed earlier in the literature.  相似文献   

20.
Fifty groundwater samples were collected from Al-Hasa to analyze the pH, electrical conductivity (EC, dS m?1), total dissolved solids (TDS), major anions (HCO3?, CO32?, Cl?, SO42?, and NO3?), major cations (Ca2+, Mg2+, Na+, and K+), and total hardness. The analyzed data plotted in the Piper, Gibbs, and Durov diagrams, and water quality index (WQI) were calculated to evaluate the groundwater geochemistry and its water quality. The results reveal that most of the investigated samples are Ca2+, Mg2+, SO42?, Cl? and Na+, and HCO3? water types using the Piper diagram. Na+?>?Ca2+?>?Mg2+ are the dominant cations, while Cl??>?HCO3??>?SO42??>?CO32? are the dominant anions. Sodium adsorption ratio (SAR) values varied from 0.79 to 10; however, the Kelly ratio (KR) ranged between 0.1 and 2.2. The permeability index (PI) showed that well water is suitable for irrigation purposes with 75% or more of maximum permeability. The US salinity diagram revealed that the water quality classes of studied waters were CIII-SI, CIII-SII, and CIV-SII, representing height hazards of salinity and medium- to low-sodium hazard. The water quality index (WQI) results indicated that total dissolved solids are out of the drinking water standard limits in Saudi Arabia. The WQI revealed that 38% of the studied wells were considered as poor water (class III), 52% are found as very poor water class (IV), and 10% are unsuitable water for drinking class (V).  相似文献   

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