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31.
本文利用中国南极科学考察航次获得的沉积物样品,采用分批(batch)实验方法,获取实验室生物硅溶解度,并结合间隙水中可溶性硅剖面,对普里兹湾沉积物中生物硅的溶出过程进行了初步研究。研究结果如下:在25℃,pH 8条件下,普里兹湾IV-10、 IS-4站表层沉积物中生物硅的实验室溶解度分别为1936、1539μmol/dm3,不同层次沉积物溶出结果显示随深度增加溶解度值降低。根据实验室溶解度数据与间隙水硅酸盐Cd的分析比较,表明研究站位沉积物生物硅的早期成岩过程中生物硅的溶出还伴随有其他化学过程。  相似文献   
32.
以合成花岗岩、水、不同浓度的盐酸溶液、氢氟酸溶液作为反应初始物,在850℃,100 MPa,接近于NNO的条件下开展了金在不同花岗质熔体中溶解度的实验研究,实验固液相产物中的金含量使用石墨炉原子吸收法测定。实验结果显示,金在花岗质熔体中的溶解度变化范围为1.87~156.62μg/g,流体相中金的溶解度为0.31~6.92μg/g;金在熔体相中的溶解度较其在共存液相中的高。花岗质熔体相中金的溶解度明显受熔体化学组成的影响,过碱性富钠花岗质熔体中金的溶解度明显高些;金在花岗质熔体中的溶解度随着熔体中Na2O/K2O摩尔比增大而增大;在氟氯共存岩浆体系中,氟含量变化对金在熔体相中的溶解度影响不明显,而液相中氯含量增大有利于提高金在流体相中的含量。  相似文献   
33.
运用热力学原理和方法,研究了CO2-H2O流体不混溶作用对Au的溶解度的影响。结果表明,贵州水银洞金矿床的成矿流体是一种富含挥发分(fCO2=70.79MPa)、酸性(pH=3.71)、还原性(fO2=0.50×10-36MPa)、中温(267℃)、具有超压(180MPa)性质的含Au(a∑Au=3.744×10-8mol/L)流体。当超压流体的封闭层——炭质页岩因断裂作用而被破坏时,热液体系的压力发生骤降(28.50~35.30MPa),CO2-H2O流体发生不混溶作用,并有大量CO2溢出。CO2的流失可使成矿溶液的CO2逸度和O2逸度降低(fCO2=0.80MPa、fO2=2.512×10-42MPa),酸碱度升高(pH=4.32),同时伴随温度的下降(224℃),成矿热液中Au溶解度的降低(a∑Au=3.790×10-9mol/L),从而快速沉淀下来成矿。  相似文献   
34.
磷石膏物理力学特性初探   总被引:4,自引:0,他引:4  
通过大量的室内试验,研究了磷石膏的烘烤温度与含水率的关系、烘烤时间与含水率关系、溶解度与温度关系。按土工试验规范进行试验,测得磷石膏的含水率随着烘烤温度的升高而增加,也随着烘烤时间的增长而增加,但是含水率应该是一个恒定的指标,所以磷石膏的含水率的测定不能按照现行规范进行,必须加以改进。建议在55~60℃条件下烘烤36 h或更长时间来测定磷石膏的含水率。从试验还可以得知磷石膏有一定的溶解度,且其溶解度随着温度的升高而降低。也正是由于磷石膏的溶解特性,所以在进行渗透试验和三轴剪切试验时要使用室温条件下的饱和磷石膏溶液替代水,从渗透试验结果来看,磷石膏坝渗透特性不同于一般的尾矿坝,其垂直渗透系数要大于水平渗透系数。从磷石膏的固结不排水三轴剪切试验可知,磷石膏是一种有明显的剪胀性的材料,在剪切条件下其破坏发生在孔隙水压力为负的情况下,且其破坏时的应变受围压的影响不明显。利用磷石膏的剪切破坏发生在负孔压的这一特性,理论上可以通过坝体内孔压变化的监测来预测磷石膏坝的安全性。  相似文献   
35.
Abstract: The solubility of gold was studied in water and aqueous NaCl (1– 5 m) solutions under oxygen and sulfur buffered conditions between 300–500C at a constant pressure 1 kb. Two buffer assemblages HMP and PPM were used. Analysis of the scatter in measured values in log mAu–mNaCl–T frame fixed linear dependence between log mAu and T at any studied iso‐pleth (mNaCl) in the form of log mAu = a. T(C) + b. Coefficients of the equation were calculated for water and NaCl (1, 3, 5 m) solutions. The maximum solubility characterizes the NaCl‐free system in the presence of HMP. In the case, Au solubility increases from (log mAu) –6. 72 to –5. 04 at 300 and 500C, respectively. In the presence of PPM, maximum of Au solubility was obtained for the 5 mNaCl solution. In a similar manner solubility rises from –6. 54 to –5. 77 at 300 and 500C, accordingly. In studied fO2/fS2 area the behavior of Au solubility testified that: (i) – a composite interaction between chloride and hydrosulfide speciation of gold affects its total solubility; (ii) – in addition of NaCl up to about 1. 5 m the solubility decreases, more pronounced in the presence of HMP; (iii) – the contribution of chloride in total Au solubility is more for PPM despite of lower fO2value, than for HMP. The solubility of platinum was studied in the Pt–Cl–S–H2O system between 300 and 500C, 1 kb. PPM solid buffer controlled oxidation state, pH and sulfur activity of solutions (H2O, 1 mNaCl and 0. 1 mHCl). Under the conditions, PtS precipitated from the solutions with increasing temperature and acidity. The PtS solubility in the 0. 1 mHCl solutions lowers slightly in the range of 300–500C from –5. 30 to –5. 60 (in log mPt) that is typical to the hydrosulfide species. It was deduced that reducing media, regulated by the PPM assemblage, suppress activity of chloride species of Pt. More oxidizing conditions were modeled in runs using mixtures of Mn(II), Mn(III) and Mn(IV) oxides to buffer the aqueous‐chloride solutions between 300 and 500C, 1 kb. It was found that MnO tends to oxidize at T below 400C forming intermediate Mn‐hydroxides (β–MnOOH, Mn (OH)2 and Mn2(OH)3Cl). These phases are metastable and transfer to Mn3O4 with increasing duration. Generation of the Mn‐hydroxides leads to a change of physical‐chemical parameters of the solutions, such as water activity, pH and Eh. The last results in abrupt increase in the noble metals dissolution. At stable existence of only Mn3O4, the solubility of both Pt and Au lowers to equilibrium values. Essential catalysis effect of Pt on intensity and rate of Mn(II) oxidation was found. The dominant role of chloride of Pt and Au was defined under most oxidized conditions, specified by Mn2O3–MnO2 buffer. So at 400C, dissolved Au (log mAu) increases from –4. 40 in water to –1. 00 in 0. 1 mHCl, and ones of Pt (log mPt) from –4. 80 to –2. 90 accordingly. Thus, mixing of hydrosulfide and chloride solutions, as well as transformation of the systems to the stable state act upon total solubility of the noble metals.  相似文献   
36.
Since 1980 when F. Lippmann's seminal paper appeared, ourunderstanding of solubility equilibria involving ionic solidsolutions has been advanced by theoretical considerations as wellas careful experimental studies designed to determine excess Gibbsfunctions. A unified theory of solid-solution aqueous-solutionequilibria as well as the thermodynamic background of thephenomenon of ``stoichiometric saturation' are reviewed.It is shown that Lippmann diagrams effectively summarize thethermodynamic basis of solid-solute aqueous-solution equilibria ofsparingly soluble metal carbonate systems. Clearly, the predictivepower of these diagrams may be limited due to kineticrestrictions. Only when dissolution and precipitation areessentially reversible, favourable conditions to synthesizehomogeneous solid phases can be derived from studies of equilibria.  相似文献   
37.
天然水CaCO3侵蚀量与沉淀量的计算是岩溶地球化学研究中的一个重要问题,本文在指出有关文献对这一问题的处理存在严重问题的同时,提出了天然水CaCO3侵蚀量与沉淀量计算的新方法。该方法以水溶液相对CSCO3饱和度的计算为基础,对CaCO3溶解或沉淀所引起的水溶液pH值、组分的活度系数以及水溶液中各组分存在形式含量的变化统一地作了考虑,且区分开放系统与封闭系统两种不同的情况分别进行了计算。实际水样的计算结果表明,计算中若不考虑上述的种种变化,则计算结果的误差将是相当大的。  相似文献   
38.
Carbonate minerals and water (or geofluids) reactions are important for modeling of geochemical processes and have received considerable attention over the past decades.The calcite dissolution rates from 50℃to 250℃at 10 MPa in deionized water with a flow rate varying from 0.2 to 5 mL/min were experimentally measured in a continuous flow column pressure vessel reactor.The dissolution began near the equilibrium with c/c_(eq)>0.3 and finally reached the equilibrium at 100℃-250℃,so the corresponding solubility was also determined as 1.87,2.02,2.02 and 1.88×10~(-4)·mol/L at 100℃,150℃,200℃and 250℃respectively,which was first increasing and then switching to decreasing with temperature and the maximum value might occur between 150℃and 200℃.The experimental dissolution rate not only increased with temperature,but also had a rapid increase between 150℃and 200℃at a constant flow rate of 4 mL/min.The measured dissolution rates can be described using rate equations of R=k(1-c/c_(eq))n or R=kc~(-n).In these equations the reaction order n changed with temperature,which indicates that n was a variable rather than a constant,and the activation energy was 13.4 kJ/mol calculated with R=k(1-c/c_(eq))~n or 18.0 k J/mol with R=kc~(-n),which is a little lower than the surface controlled values.The varied reaction order and lower activation energy indicates that calcite dissolution in this study is a complex interplay of diffusion controlled and surface controlled processes.  相似文献   
39.
Henry's law constants KH (mol kg–1 atm–1) for the reaction HOCl(g)=HOCl(aq) near room temperature, literature data for the associated enthalpy change, and solubilities of HOCl in aqueous H2SO4 (46 to 60 wt%) at temperatures relevant to the stratosphere (200 KT230 K) are shown to be thermodynamically consistent. Effective Henry's law constants [H*=mHOCl/pHOCl, in mol kg–1 atm–1] of HOCl in aqueous H2SO4 are given by: ln(H*)=6.4946–mH2SO4(–0.04107+54.56/T)–5862 (1/To–1/T) where T(K) is temperature and To=298.15K. The activity coefficient of HOCl in aqueous H2SO4 has a simple Setchenow-type dependence upon H2SO4 molality.  相似文献   
40.
At Bangriposi, variable stages in replacement of staurolite by chloritoid – Na–K–Ca mica shimmer aggregates in muscovite schists provides insight into the complex interplay between fluid flow, mass transfer, and dissolution–precipitation during pseudomorph growth. Idioblastic chloritoid growing into mica caps without causing visible deformation, and monomineralic chloritoid veins (up to 300 μm wide) within shimmer aggregates replacing staurolite attest to chloritoid nucleation in fluid‐filled conduits along staurolite grain boundaries and crystallographic planes. The growth of shimmer aggregates initiated along staurolite margins, and advanced inwards into decomposing staurolite along networks of crystallographically controlled fluid‐filled conduits. Coalescence among alteration zones adjacent to channel fills led to dismemberment and the eventual demise of staurolite. Mass balance calculation within a volume‐fixed, silica‐conserved reference frame indicate the shimmer aggregates grew via precipitation from fluids in response to mass transport that led to the addition of H2O, K2O, Na2O and CaO in the reaction zone, and Al2O3 was transported outward from the inward‐retreating margin of decomposing staurolite. This aided precipitation of chloritoid in veins and in the outer collars, and as disseminated grains in the shimmer aggregates at mid‐crustal condition (~520 ± 20 °C, 5.5 ± 2.0 kbar). Computation using one‐dimensional transport equation suggests that staurolite decomposition involved advection dominating over diffusive transport; the permeation of externally derived H2O caused flattening of chemical potential gradients in H2O and aqueous species, for example, and , computed using the Gibbs method. This suggests that staurolite decomposition was promoted by the infiltration of a large volume of H2O that flattened existing chemical potential gradients. In the initial stages of replacement, chloritoid super‐saturation in fluid caused preferential nucleation and growth of chloritoid at staurolite grain boundaries and in crystallographic planes. As reaction progressed, further chloritoid nucleation was halted, but chloritoid continued to grow as the 3‐mica aggregates continued to replace the remaining staurolite in situ, while the chloritoid‐compatible elements were transported in the water‐rich phase facilitating continued growth of the existing chloritoid grains.  相似文献   
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