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1.
This work presents new experimental results on the kinetics of mineral dissolution in near-critical and supercritical water in a temperature range (T) from 25 to 400℃ and a constant pressure of 23 MPa. Kinetic experiments were carried out by using a flow reactor (packed bed reactor) of an open system. The dissolution rates of albite and magnetite were measured under these experimental conditions. Na, Al and Si release rates for albite dissolution in water were measured as a function of the temperature and flow velocity in the reaction system. The maximum release rates of Na, AI and Si of albite dissolution in the hydrothermal flow systems under different flow velocities were always obtained at 300℃, that is to say, the maximum albite dissolution rates in the flow systems, regardless of different flow rates, were repeatedly measured at 300℃. Results indicate a wide fluctuation in albite dissolution rates occurring close to the critical point of water. The dissolution rates increased when the temperatu  相似文献   

2.
The dissolution kinetics of a simulated lunar glass were examined at pH 3, 5, and 7. Additionally, the pH 7 experiments were conducted in the presence of citric and oxalic acid at concentrations of 2 and 20 mM. The organic acids were buffered at pH 7 to examine the effect of each molecule in their dissociated form. At pH 3, 5, and 7, the dissolution of the synthetic lunar glass was observed to proceed via a two-stage process. The first stage involved the parabolic release of Ca, Mg, Al, and Fe, and the linear release of Si. Dissolution was incongruent, creating a leached layer rich in Si and Ti which was verified by transmission electron microscopy (TEM). During the second stage the release of Ca, Mg, Al, and Fe was linear. A coupled diffusion/surface dissolution model was proposed for dissolution of the simulated lunar glass at pH 3, 5, and 7. During the first stage the initial release of mobile cations (i.e., Ca, Mg, Al, Fe) was limited by diffusion through the surface leached layer of the glass (parabolic release), while Si release was controlled by the hydrolysis of the Si-O-Al bonds at the glass surface (linear release). As dissolution continued, the mobile cations diffused from greater depths within the glass surface. A steady-state was then reached where the diffusion rate across the increased path lengths equalled the Si release rate from the surface. In the presence of the organic acids, the dissolution of the synthetic lunar glass proceeded by a one stage process. The release of Ca, Mg, Al, and Fe followed a parabolic relationship, while the release of Si was linear. The relative reactivity of the organic acids used in the experiments was citrate > oxalate. A thinner leached layer rich in Si/Ti, as compared to the pH experiments, was observed using TEM. Rate data suggest that the chemisorption of the organic anion to the surface silanol groups was responsible for enhanced dissolution in the presence of the organic acids. It is proposed that the increased rate of Si release is responsible for the one stage parabolic release of mobile cations and the relatively thin leached layer compared to experiments at pH 3 and 5.  相似文献   

3.
The effect of oxalate, a strong chelator for Al and other cations, on the dissolution rates of oligoclase feldspar and tremolite amphibole was investigated in a flow-through reactor at 22°C. Oxalate at concentrations of 0.5 and 1 mM has essentially no effect on the dissolution rate of tremolite, nor on the steady-state rate of release of Si from oligoclase. The fact that oxalate has no effect on dissolution rate suggests that detachment of Si rather than Al or Mg is the rate-limiting step. At pH 4 and 9, oxalate has no effect on the steady-state rate of release of Al, and dissolution is congruent. At pH 5 and 7, oligoclase dissolution is congruent in the presence of oxalate, but in the absence of oxalate Al is preferentially retained in the solid relative to Si.Large transient “spikes” of Al or Si are observed when oxalate is added to or removed from the system. The cause of the spikes is unknown; we suggest adsorption on feldspar surfaces away from sites of active dissolution as a possibility. Solutions in the reactors are undersaturated with respect to both gibbsite and kaolinite, so neither the spikes nor the incongruent dissolution can be explained by formation of a secondary precipitate.The rate of dissolution of tremolite is independent of pH over the pH range 2–5, and decreases at higher pH. The rate of dissolution of oligoclase in our experiments was independent of pH over the pH range 4–9. Since the dissolution rate of these minerals is independent of pH and organic ligand concentration, the effect of acid deposition from the atmosphere on the rate of supply of cations from weathering of granitic rocks should be minor.  相似文献   

4.
This study reports the kinetic experimental results of albite in water and in KCI solution at 22 MPa in the temperature range of 25 to 400℃. Kinetic experiments have been carried out in an open flow-through reaction system (packed bed reactor). Albite dissolution is always incongruent in water at most temperatures, but becomes congruent at 300℃ (close to the critical point 374℃). At temperatures from 25 to 300℃, the incongruent dissolution of albite is reflected by the fact that sodium and aluminum are easily dissolved into water; from 300 to 400℃ it is reflected by silicon being more easily dissolved in water than Al and Na. Maximum albite dissolution rates in the flow hydrothermal systems have been repeatedly observed at 300℃, independent of flow rates.The kinetic experiments of albite dissolution in a KCl aqueous solution (0.1 mol KCl) indicate that the dissolution rate of albite increases with increasing temperature. Maximum silicon release rates of albite have been observed at 400℃, while ma  相似文献   

5.
模拟不同气候条件下碳酸盐岩风化作用的淋溶实验研究   总被引：3，自引：3，他引：0  
通过模拟干热、湿热与干冷3种气候条件,以饱和CO2水作为淋溶液,对黔中岩溶区3条碳酸盐岩风化壳岩-土界面的岩粉层试样进行了淋溶实验(其中干热、湿热条件下淋溶到残余酸不溶物阶段),对淋出液的pH值以及主要造岩元素的浓度进行了动态分析。结果表明,碳酸盐岩风化壳岩-土界面由岩到土的转变过程中,伴随碳酸盐的溶蚀,酸不溶物已表现出明显的风化倾向。碳酸盐的溶蚀强度表现为干冷>干热>湿热的变化趋势。温度低,碳酸盐的溶解速率大;排水条件好,碳酸盐溶解释放的Ca、Mg易随风化流体排出体系。对于酸不溶物组分,淋溶实验中有:(1)K、Na、Mg、Si、P的载体矿物风化强度在干热条件下最大(至于Ca,由于方解石与白云石均是其主要的载体矿物,酸不溶物相中的Ca难以在淋出液中有效识别)。在干冷与湿热之间,K、Na、Mg等盐基离子的溶出能力大多表现为湿热>干冷,指示了温度对盐基离子释放强度的重要制约作用;而Si和P未表现出一致的变化趋势,可能源于淋溶体系微环境的差异。(2)Fe与Mn表现出弱迁移性。其中,Fe在干冷环境下淋出强度最弱,说明温度是制约含Fe矿物分解速率的重要因素。而Fe在干热与湿热之间,以及Mn在3种淋溶条件下,未呈现出一致的变化趋势。(3)Al和Ti在碳酸盐岩风化过程中表现出强烈的惰性。   相似文献   

6.
Laboratory experiments were carried out continuously for 30–35 days at 25 and 5°C in three different buffer solutions of pH 4.0, 2.2 and 8.4 to calculate dissolution rates of two minerals, calcite (CC) and dolomite (DM) and two rocks, leucogranite (LG) and gneiss (GN) from the Himalayan range. Calculated rates in terms of release of targeted elements versus time (Ca for CC; Mg for DM; Si for LG and GN) demonstrate direct correlation with temperature. Dissolution rates are higher at 25°C compared to 5°C. CC and DM were experimented only at pH 8.4 and results show that both undergo congruent dissolution with CC dissolving ∼5 times faster than DM. Ca and Mg exhibit average apparent activation energies (E a) of 13.98 and 9.98 kcal mol−1 respectively at pH 8.4 which reflects greater sensitivity of CC dissolution than DM dissolution towards an increase in temperature. Scanning Electron Microscope attached with Energy Dispersive X-Ray Analyser (SEM-EDX) data indicates that dissolution is controlled primarily by surface-reaction processes, with dislocation sites contributing maximum to the dissolution. As compared to CC and DM dissolution, LG and GN undergo relatively slower incongruent dissolution with precipitation of some secondary minerals as revealed from X-ray diffractometer (XRD) results. Rates of dissolution of LG is maximum at pH 2.2, moderate at pH 8.4 and least at pH 4.0, whereas GN shows maximum dissolution at pH 2.2, moderate at pH 4.0 and least at pH 8.4. A comparison in dissolution behavior of LG and GN at experimental conditions reveals that increase in Si-release rate in the temperature range between 5 and 25°C is maximum at pH 8.4 (∼3.4–4.5 times), moderate at pH 4.0 (∼3–1.8 times) and least at pH 2.2 (∼1.0–1.5 times). Within the experimental temperature range, calculated values of E a for Si release during LG and GN dissolution advocates positive correlation with pH. A substantial decrease in initial values of Brunauer–Emmett–Teller (BET) surface area of DM, LG, and GN has been encountered at the end of the experiment, except for CC for which an increase is observed. The study clearly demonstrates the dissolution behavior of pure minerals and rocks under controlled conditions. The dissolution rates assume enormous significance for the release of trace elements from rocks/minerals to the reacting water.  相似文献   

7.
The dissolution rate of illite, a common clay mineral in Australian soils, was studied in saline-acidic solutions under far from equilibrium conditions. The clay fraction of Na-saturated Silver Hill illite (K1.38Na0.05)(Al2.87Mg0.46Fe3+0.39Fe2+0.28Ti0.07)[Si7.02Al0.98]O20(OH)4 was used for this study. The dissolution rates were measured using flow-through reactors at 25 ± 1 °C, solution pH range of 1.0-4.25 (H2SO4) and at two ionic strengths (0.01 and 0.25 M) maintained using NaCl solution. Illite dissolution rates were calculated from the steady state release rates of Al and Si. The dissolution stoichiometry was determined from Al/Si, K/Si, Mg/Si and Fe/Si ratios. The release rates of cations were highly incongruent during the initial stage of experiments, with a preferential release of Al and K over Si in majority of the experiments. An Al/Si ratio >1 was observed at pH 2 and 3 while a ratio close to the stoichiometric composition was observed at pH 1 and 4 at the higher ionic strength. A relatively higher K+ release rate was observed at I = 0.25 in 2-4 pH range than at I = 0.01, possibly due to ion exchange reaction between Na+ from the solution and K+ from interlayer sites of illite. The steady state release rates of K, Fe and Mg were higher than Si over the entire pH range investigated in the study. From the point of view of the dominant structural cations (Si and Al), stoichiometric dissolution of illite occurred at pH 1-4 in the higher ionic strength experiments and at pH ?3 for the lower ionic strength experiments. The experiment at pH 4.25 and at the lower ionic strength exhibited lower RAl (dissolution rate calculated from steady state Al release) than RSi (dissolution rate calculated from steady state Si release), possibly due to the adsorption of dissolved Al as the output solutions were undersaturated with respect to gibbsite. The dissolution of illite appears to proceed with the removal of interlayer K followed by the dissolution of octahedral cations (Fe, Mg and Al), the dissolution of Si is the limiting step in the illite dissolution process. A dissolution rate law showing the dependence of illite dissolution rate on proton concentration in the acid-sulfate solutions was derived from the steady state dissolution rates and can be used in predicting the impact of illite dissolution in saline acid-sulfate environments. The fractional reaction orders of 0.32 (I = 0.25) and 0.36 (I = 0.01) obtained in the study for illite dissolution are similar to the values reported for smectite. The dissolution rate of illite is mainly controlled by solution pH and no effect of ionic strength was observed on the dissolution rates.  相似文献   

8.
A continuous reactor based on the fluidized bed technique was developed in order to study the kinetics and the mechanisms of the initial stages of weathering of albite. Simultaneous determination of Si, Al and Na and the observed low concentrations of the dissolved elements which were always at levels below saturation with respect to possible secondary precipitates, indicate that formation of a residual layer of a few tens of angstroms occurred at the surface of the feldspar. The composition of this layer, enriched in Si and/or Al, is strongly dependent on the pH of the aqueous solution. The formation of the layer is followed by the establishment of a quasi-steady state during which the dissolution of albite tends to become stoichiometric.  相似文献   

9.
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   

10.
The surface chemistry of natural wollastonite, diopside, enstatite, forsterite, and albite in aqueous solutions was characterized using both electrokinetic techniques and surface titrations performed for 20 min in batch reactors. Titrations performed in such reactors allow determination of both proton consumption and metal release from the mineral surface as a function of pH. The compositions, based on aqueous solution analysis, of all investigated surfaces vary dramatically with solution pH. Ca and Mg are preferentially released from the surfaces of all investigated divalent metal silicates at pH less than ∼8.5-10 but preferentially retained relative to silica at higher pH. As such, the surfaces of these minerals are Si-rich and divalent metal poor except in strongly alkaline solutions. The preferential removal of divalent cations from these surfaces is coupled to proton consumption. The number of protons consumed by the preferential removal of each divalent cation is pH independent but depends on the identity of the mineral; ∼1.5 protons are consumed by the preferential removal of each Ca atom from wollastonite, ∼3 protons are consumed by the preferential removal of each Mg or Ca atom from diopside or enstatite, and ∼4 protons are consumed by the preferential removal of each Mg from forsterite. These observations are interpreted to stem from the creation of additional ‘internal’ adsorption sites by the preferential removal of divalent metal cations which can be coupled to the condensation of partially detached Si. Similarly, Na and Al are preferentially removed from the albite surface at 2 > pH > 11; mass balance calculations suggest that three protons are consumed by the preferential removal of each Al atom from this surface over this entire pH range. Electrokinetic measurements on fresh mineral powders yield an isoelectric point (pHIEP) 2.6, 4.4, 3.0, 4.5, and <1, for wollastonite, diopside, enstatite, forsterite, and albite, respectively, consistent with the predominance of SiO2 in the surface layer of all of these multi-oxide silicates at acidic pH. Taken together, these observations suggest fundamental differences between the surface chemistry of simple versus multi-oxide minerals including (1) a dependency of the number and identity of multi-oxide silicate surface sites on the aqueous solution composition, and (2) the dominant role of metal-proton exchange reactions on the reactivity of multi-oxide mineral surfaces including their dissolution rate variation with aqueous solution composition.  相似文献   

11.
库车坳陷白垩系深层致密砂岩储层溶蚀作用实验模拟研究   总被引：1，自引：1，他引：0  
库车坳陷前陆区白垩系发育特低物性、强非均质性和高稳产砂岩储层,溶蚀作用显著,但成因机制尚不是很明确。利用高温高压热模拟实验还原了目的层在成岩演化过程中1种表生流体和2种埋藏流体环境下溶蚀作用差异,揭示了成岩矿物演化过程及储集空间结构变化特征。结果表明,表生成岩期大气淡水淋滤弱酸性流体环境（CO2饱和溶液,pCO2=1 MPa）溶蚀作用最为显著,长石类矿物发生明显溶蚀,石英和黏土矿物相对难溶,Na+、Ca2+和K+等离子析出明显,Si4+和Al3+析出较少,样品表面沉淀出较多的疑似多边形石英和铝硅酸类矿物;成岩晚期油气充注酸性流体环境（乙酸溶液,2 mL/L）溶蚀作用其次,易于溶解白云石、石膏和长石类矿物,Ca2+、Mg2+、Na+和Si4+等离子析出明显,样品表面无沉淀;成岩早-中期碱性流体环境（NaHCO3溶液,pH=7.46、HCO3-=0.6 mol/L）溶蚀作用相对较弱,石英、长石和部分黏土矿物均发生了不同程度的溶蚀,且随着温度、压力的增加,溶蚀作用程度增加。综合分析表明:表生流体是研究区砂岩储层溶蚀孔隙发育的关键因素,其次为有机酸和碱性埋藏流体。这一认识能够丰富致密砂岩储层孔隙成岩演化理论,为下一步寻找规模储层发育区和气田有效开发提供理论支撑。  相似文献   

12.
The mineralogy and geochemistry data are presented for thirty-seven shales,four concretions,two carbonate sediments and seven lignites from the Marathousa coal field of the Megalopolis Basin in Greece.The argillaceous rocks consist of chlorite,illite,kaolinte,albite,quartz.opal-A,calcite and dolomite;the concretions of aragonite,gypsum and pyrite;and the carbonate rocks of calcite,quartz and illite.The mineral matter in the lignites consists of gypsum,quartz,albite,chlorite,illite,opal-A,dolomite,pyrite,and rarely calcite and kaolinite Athree-factor model explains the total variaition of major and trace elements in the argillaceous sediments.The first factor is an aluminosilicate factor and involves the following elements:Al,Si,Mg,Na,K,Ti,Mn,Nb,Y,Rb,Zn,Cu,Ni,Cr,Nband V,associated with chlorite,albite and illite.The second factor involves the elements Ca,Sr,Ba,Znand Sc and is related to carbonate lithology and mainly the carbonate concretions with gypsum.The third factor involves Fe and Ce with a weak association with Mn.The diagenesis of the Marathousa sediments and lignites was not very advanced as indicated by (a) the total thickness of the sequence (500m),(b) the presence of biogenic silica(opal-A) and (c) the age of the deposit(Pleistocene).FOr these reasons the rpresence of chlorite,illite and kaolinite in the sediments and lignite is due not to diagenetic reactions but to weathering of the flysch and metamorphic rocks at the edges of the Megalopolis Basin and transport of the weathering products(illite,chlorite,kaolinite)into the basin of deposition.The diagenetic minerals of the Marathousa sequence include pyrite,gypsum,dolomite and aragonite.  相似文献   

13.
Palygorskite is a fibrous, magnesium‐bearing clay mineral commonly associated with Late Mesozoic and Early Cenozoic dolomites. The presence of palygorskite is thought to be indicative of warm, alkaline fluids rich in Si, Al and Mg. Palygorskite has been interpreted to form in peritidal diagenetic environments, either as a replacement of detrital smectite clay during a dissolution–precipitation reaction or solid‐state transformation, or as a direct precipitate from solution. Despite a lack of evidence, most diagenetic studies involving these two minerals posit that dolomite and palygorskite form concurrently. Here, petrological evidence is presented from the Umm er Radhuma Formation (Palaeocene–Eocene) in the subsurface of central Qatar for an alternative pathway for palygorskite formation. The Umm er Radhuma is comprised of dolomitized subtidal to peritidal carbonate cycles that are commonly capped by centimetre‐scale beds rich in palygorskite. Thin section, scanning electron microscopy and elemental analyses demonstrate that palygorskite fibres formed on both the outermost surfaces of dissolved euhedral dolomite crystals and within partially to completely dissolved dolomite crystal cores. These observations suggest that dolomite and palygorskite formed sequentially, and support a model by which the release of Mg2+ ions and the buffering of solution pH during dolomite dissolution promote the formation of palygorskite. This new diagenetic model explains the co‐occurrence of palygorskite and dolomite in the rock record, and provides valuable insight into the specific diagenetic conditions under which these minerals may form.  相似文献   

14.
Stoichiometry of smectite dissolution reaction   总被引：1，自引：0，他引：1  
The dissolution stoichiometry of smectite-rich bentonites SAz-1, STx-1 and SWy-1 was studied at 50°C and pH 2 and 3 using flow-through reactors. In addition to smectite, these samples contain considerable amounts of silica phases (quartz, cristobalite and/or amorphous silica). As a result, the molar Al/Si ratios of the bulk samples are significantly lower than those of the pure smectite.Smectite dissolution was highly incongruent during the first few hundred to few thousand hours of the experiments. Release rates of Si, Mg, Ca and Na underwent a distinct transition from an initial period of rapid release to significantly lower release rate at steady state. A reversed trend was observed for release of Al, which gradually increased from very low starting release rate to higher release rate at steady state. At steady state the ratio of released Al to released Si was found to be constant and independent of the experimental conditions. We suggest that this ratio represents the Al/Si ratio of the smectite itself, and it is not influenced by the presence of accessory phases in the sample.The rapid release of calcium, sodium and magnesium from the interlayer sites is explained by ion-exchange reactions, whereas the fast release of silicon is explained by dissolution of amorphous silica. We interpret the initial slow release of Al as the result of inhibition of smectite dissolution due to coating or cementation of the smectite aggregates by amorphous silica. As the silica is dissolved, the aggregates fall apart and more smectite surfaces are exposed, resulting in an increase in the smectite dissolution rate. Thereafter, the system approaches steady state, in which the major tetrahedral and octahedral cations of smectite are released congruently.  相似文献   

15.
The short term (2–40 days) dissolution of enstatite, diopside, and tremolite in aqueous solution at low temperatures (20–60°C) and pH 1–6 has been studied in the laboratory by means of chemical analyses of reacting solutions for Ca2+, Mg2+, and Si(OH)4 and by the use of X-ray photoelectron spectroscopy (XPS) for detecting changes in surface chemistry of the minerals. All three minerals were found to release silica at a constant rate (linear kinetics) providing that ultrafine particles, produced by grinding, were removed initially by HF treatment. All three also underwent incongruent dissolution with preferential release of Ca and/or Mg relative to Si from their outermost surfaces. The preferential release of Ca, but not Mg for diopside at pH 6 was found by both XPS and solution chemistry verifying the theoretical prediction of greater mobility of cations located in M2 structural sites. Loss mainly from M2 sites also explains the degree of preferential loss of Mg from enstatite at pH 6; similar structural arguments apply to the loss of Ca and Mg from the surface of tremolite. In the case of diopside and tremolite initial incongruency was followed by essentially congruent cation-plus-silica dissolution indicating rapid formation of a constant-thickness, cation-depleted surface layer. Cation depletion at elevated temperature and low pH (~ 1) for enstatite and diopside was much greater than at low temperature and neutral pH, and continued reaction resulted in the formation of a surface precipitate of pure silica as indicated by solubility calculations, XPS analyses, and scanning electron microscopy.From XPS results at pH 6, model calculations indicate a cation-depleted altered surface layer of only a few atoms thickness in all three minerals. Also, lack of shifts in XPS peak energies for Si, Ca, and Mg, along with undersaturation of solutions with respect to all known Mg and Ca silicate minerals, suggest that cation depletion results from the substitution of hydrogen ion for Ca2+ and/or Mg2+ in a modified silicate structure and not from the precipitation of a new, radically different surface phase. These results, combined with findings of high activation energies for dissolution, a non-linear dependence on aH+ for silica release from enstatite and diopside, and the occurrence of etch pitting, all point to surface chemical reaction and not bulk diffusion (either in solution or through altered surface layers) as the rate controlling mechanism of iron-free pyroxene and amphibole dissolution at earth surface temperatures.  相似文献   

16.
近地表温压条件下白云岩溶解过程的实验研究   总被引：4，自引：2，他引：2  
与溶解作用有关的次生孔隙是碳酸盐岩最主要的油气储集空间,从实验模拟角度研究碳酸盐溶解机制具有重要的理论与应用价值。本文在近地表的温度和压力条件下,进行了具相同成分和结构的白云岩在CO2和乙酸介质中的对照溶解实验,两种类型的具相同成分和不同结构的白云岩在CO2介质中添加和不添加硬石膏的对照溶解实验,以及方解石含量50%的岩石在CO2介质中添加和不添加硬石膏的对照溶解实验。实验结果表明:(1)近地表温压条件的酸性环境中,乙酸对碳酸盐矿物的溶解能力显著大于CO2流体,乙酸对白云石的溶解是接近化学计量的,而CO2流体则是非化学计量的,白云石中Ca优先溶出而Mg滞留;(2)溶解CaSO4的加入会显著改善近地表温压条件下CO2流体对白云石的溶解效果,使得白云石溶解接近化学计量组成,该过程是通过抑制Ca的溶出和加速Mg的溶出来实现的;(3)对于白云石含量大于90%的较纯的白云岩来说,溶解CaSO4的加入会使得白云岩溶出离子的Ca、Mg合量增加,因而总体上有利于白云岩溶解,与之相反,溶液中CaSO4的沉淀可能导致白云石的沉淀。实验结果可以帮助我们更深刻理解近地表环境白云岩的溶解过程,尤其是与膏盐伴生的白云岩的溶解及相应岩溶过程和次生孔隙的形成机制。   相似文献   

17.
Steady-state element release rates from crystalline basalt dissolution at far-from-equilibrium were measured at pH from 2 to 11 and temperatures from 5 to 75 °C in mixed-flow reactors. Steady-state Si and Ca release rates exhibit a U-shaped variation with pH where rates decrease with increasing pH at acid condition but increase with increasing pH at alkaline conditions. Silicon release rates from crystalline basalt are comparable to Si release rates from basaltic glass of the same chemical composition at low pH and temperatures ?25 °C but slower at alkaline pH and temperatures ?50 °C. In contrast, Mg and Fe release rates decrease continuously with increasing pH at all temperatures. This behaviour is interpreted to stem from the contrasting dissolution behaviours of the three major minerals comprising the basalt: plagioclase, pyroxene, and olivine. Calcium is primarily present in plagioclase, which exhibits a U-shaped dissolution rate dependence on pH. In contrast, Mg and Fe are contained in pyroxene and olivine, minerals whose dissolution rates decrease monotonically with pH. As a result, crystalline basalt preferentially releases Mg and Fe relative to Ca at acidic conditions. The injection of acidic CO2-charged fluids into crystalline basaltic terrain may, therefore, favour the formation of Mg and Fe carbonates rather than calcite. Element release rates estimated from the sum of the volume fraction normalized dissolution rates of plagioclase, pyroxene, and olivine are within one order of magnitude of those measured in this study.  相似文献   

18.
Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH 1 experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost ∼9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >∼2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction.  相似文献   

19.
Biotite dissolution under conditions of high pH and high aluminum, sodium, and nitrate concentrations analogous to those found in tank wastes at the Hanford Site was investigated using continuously stirred flow-through reactors at 22 to 25 °C. Experiments were designed to simulate tank leaks into the Hanford vadose zone where Fe(II) from biotite is the dominant reducing agent available to immobilize certain contaminants. Both non-steady-state and steady-state dissolution kinetics were quantified; interest in non-steady-state kinetics derives from the inherently transitory nature of tank leaks. Biotite was conditioned in pH 8 solutions to simulate the alkaline environment of the Hanford sediment, and then reacted in pH 10-14 solutions, some including 0.055 M Al(NO3)3 and/or 2 M or 6 M NaNO3. Initial dissolution transients (intervals of rapid release rates that decay to slower steady-state rates) showed fast preferential release of K followed by near-stoichiometric release of Si, Al, and Mg, and slower release of Fe. Each increase in pH resulted in a second transient with the greatest amounts of Si, Al, and K released at pH 14, followed by pHs 13, 12, 11, and 10. Fe release also was highest at pH 14, but unchanging at pHs 10-13 within experimental error. Transient releases at high pH are attributed to dissolution of amphoteric secondary phases such as ferrihydrite that are inferred from saturation calculations and solid analyses to form during the conditioning interval. Transient release of Si was inhibited by the presence of 0.055 M Al(NO3)3; the effects of Al(NO3)3 and NaNO3 on the release rates of Al, Fe, Mg, and K were variable and generally outweighed by the effect of pH. Quasi-steady-state release rates were slowest at pH 11-12 (10−12.2 mol biotite m−2 s−1 for Si) and increased in either direction in pH away from this minimum (to 10−11.5 at pHs 8 and 14 for Si). Fe release rates at high pH were sufficient to account for observed Cr(VI) reduction at Hanford. The net release rates of the major framework cations, from which the biotite dissolution rate is inferred, may reflect the precipitation of secondary phases or the alteration of biotite to vermiculite. The most extensive solid-phase alterations were observed in Na-enriched solutions.  相似文献   

20.
The present investigation tests a model to explain the behavior of dissolved Si during early diagenesis in sediments. The model assumes that low-Fe clays and other minerals can be treated simply as Al hydroxides, having attached silica. When the minerals are placed in seawater solutions, Si is released, causing exposure of fresh Al-octahedra. which are reactive toward Si and other elements in solution. Standard clays (kaolinite, montmorillonite) and solid silicic acid were suspended in seawater solutions in various combinations and dissolved Al, Si, Ca, pH and alkalinity were determined as a function of time. The theoretical model correctly predicts the behavior of Si in mixtures of the different minerals, based upon the dissolution behavior of the minerals in suspension alone. Further, the decrease in the alkalinity of kaolinitecontaining seawater solutions, where carbonate dissolution, organic matter decomposition and reduced sulfur oxidation are apparently unimportant, can be predicted from a simple extrapolation of the silica model results. The alkalinity changes observed in this study, as well as the pH changes observed in standard clay suspensions by other researchers, can be explained simply by equilibration of the charge on exposed Al-octahedra with the pH of the surrounding waters. The results of this study indicate that theoretical models of Si diagenesis in sediments should have general usefulness for predicting the effects of clay dissolution on sediment properties.  相似文献   

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