相山矿田邹家山铀矿床碱交代矿化蚀变岩地球化学

相山矿田邹家山铀矿床成矿作用与碱交代关系密切。钠、钾的带入和带出极大地影响铀成矿作用过程,钠交代和钾交代对铀成矿的影响差异明显。本文以邹家山铀矿床中典型的钠化和钾化矿体为研究对象,通过比较两矿体剖面的地球化学特征,研究其异同,探讨钠交代、钾交代与铀成矿作用关系,得出以下认识:(1)与矿体两侧的围岩相比,钠交代和钾交代矿石中都富U和Mo,而Ba含量明显降低;(2)钠交代对原岩化学成分的改变不强。除了钠含量明显增高、钾含量明显降低、钠钾摩尔比M(Na2O/K2O)明显增大外,矿石与原(或围)岩的化学成分相差不大,总碱摩尔数M(Na2O+K2O)几乎不变;(3)钾交代对原岩的矿物及化学成分改变很大。除钾高、钠低等含量变化外,强烈去Si和Na,M(Na2O+K2O)有20%~30%的减少,而且许多微量(成矿)元素含量明显增加,特别是稀土元素明显增高,且重稀土增加更快;(4)两类碱交代中行为反差最大的组分是Na2O、K2O、Si O2和REE。钠交代过程中,Na2O和Si O2增加,K2O和REE减少,M(Na2O/K2O)明显增大;而钾交代过程正相反;(5)在相山铀成矿过程中,仅有钠交代时铀的含量较低,强钾交代是形成富铀矿的必要条件。     

Rock-Forming feldspars of the Khibiny alkaline pluton,Kola Peninsula,Russia

This paper describes the structural-compositional zoning of the well-known Khibiny pluton in regard to rock-forming feldspars. The content of K-Na-feldspars increases inward and outward from the Main foidolite ring. The degree of coorientation of tabular K-Na-feldspar crystals sharply increases in the Main ring zone, and microcline-dominant foyaite turns into orthoclase-dominant foyaite. The composition of K-Na-feldspars in the center of the pluton and the Main ring zone is characterized by an enrichment in Al. This shift is compensated by a substitution of some K and Na with Ba (the Main ring zone) or by an addition of K and Na cations to the initially cation-deficient microcline (the central part of the pluton). Feldspars of volcanosedimentary rocks occurring as xenoliths in foyaite primarily corresponded to plagioclase An_15–40, but high-temperature fenitization and formation of hornfels in the Main ring zone gave rise to the crystallization of anorthoclase subsequently transformed into orthoclase and albite due to cooling and further fenitization. Such a zoning is the result of filling the Main ring fault zone within the homogeneous foyaite pluton with a foidolite melt, which provided the heating and potassium metasomatism of foyaite and xenoliths of volcanosedimentary rocks therein. The process eventually led to the transformation of foyaite into rischorrite-lyavochorrite, while xenoliths were transformed into aluminum hornfels with anorthoclase, annite, andalusite, topaz, and sekaninaite.     

电感耦合等离子体发射光谱法测定膨润土中的交换性阳离子钙镁钾钠

对膨润土交换性阳离子和阳离子交换容量的测试是评价膨润土矿的主要指标之一,传统的测定膨润土交换性阳离子通常采用原子吸收光谱法或容量法,操作手续复杂繁琐。本文用氯化铵-乙醇交换液交换出试样中的可交换性阳离子钙、镁、钾、钠,分取蒸至湿盐状,制备成盐酸介质的溶液,电感耦合等离子体发射光谱法测定。通过正交试验确定了最佳实验条件为交换1次,加入25 mL交换液,搅拌30 min,沉淀洗涤2次。分别选择315.887 nm、279.079 nm、766.490 nm、589.592 nm作为钙、镁、钾、钠的分析谱线,绘制的标准曲线中钾、钠的浓度在0～0.6 mmol/L,钙、镁的浓度在0～3.0 mmol/L呈良好的线性关系。方法检出限为0.012～0.048 mmol/100 g。经国家标准物质验证,测定值与标准值吻合,精密度为0.5%～2.5%(RSD,n=11),准确度为-6.1%～10%,加标回收率为97.0%～100.0%。本方法样品处理方法程序简单快速,分析重现性好,克服了传统分析方法测定手续繁琐、时间冗长且成本高等缺点,适用于批量样品的分析。     

Etude des solutions solides des néphélines (Na,K)AlSiO4 et (Na,Rb)AlSiO4

Ion exchange equilibrium of nepheline solid solutions (Na, K)AlSiO₄ and (Na, Rb)AlSiO₄ with hydrothermal solutions has been studied at 600°C and 2000 bars. The behaviour of dilute solid solutions was specially investigated.Na-Rb ion exchange data can be represented satisfactorily by a model taking into account the existence of two different sites in the structure of nepheline. At 600°C Rb atoms substitute almost exclusively for Na atoms situated in the larger sites. On the other hand, this model only partially applies to Na-K ion exchange equilibrium.Finally, the importance of the ion exchange data concerning extremely dilute solutions to calculate activity-composition diagrams is emphasized with special reference to the nepheline solid solutions.     

The kinetics of dissolution of muscovites at 25°C and 1 atm CO2 partial pressure

Two different dry-ground muscovites were placed separately in deionized water saturated with 1 atm partial pressure of carbon dioxide at room temperature and pressure for about 1000 hr. The carbonic acid formed buffered the bulk solution between 4.6 and 5.1 during the whole time of the experiment. K and Na were rapidly released by a reaction with hydrogen ions in the solution, which is usually attributed to a surface exchange reaction. The cation exchange capacity is close to the amount of K and Na released to the solution. However, measurement of surface areas of the micas both before and after the rapid release of K and Na, indicate that only one third of the cation exchange capacity can be attributed to release from the outer surfaces, whereas two thirds must be attributed to removal from within deeper parts of the structure.Approximately 2.5% of total K and Na from the interlayer regions, 1.5% of Mg from the octahedral sheets, and 0.5% of Si from the tetrahedral sheets were released by the end of the experiment, indicating that dissolution was incongruent in both cases. Si showed the slowest total release rate of all the ions. In the later stages (after 400 hr), the release rate of Si becomes a linear function of time. The linear release rate of Si was found to be 2.4 × 10^?17 mol/cm²/sec for the ruby mica, and 2.7 × 10^?17 mol/cm²/sec for the green mica. The rate-controlling mechanism in the dissolution of muscovite in the later stages is probably related to the rate of destruction of the tetrahedral sheets (Si-O bonds) which in turn is reflected by the rate of release of Si into the solution.     

Ion exchange between tectosilicates with the nepheline-kalsilite framework and molten MNO3 or MO (M = Li,Na, K,Ag)

Natural nepheline, a synthetic Na-rich nepheline, and synthetic kalsilite were ion exchanged in molten MNO₃ or MCl (M = Li, Na, K, Ag) at 220–800° C. Crystalline products were characterized by wet chemical and electron microprobe analysis, single crystal and powder X-ray diffraction, and transmission electron microscopy and diffraction. Two new compounds were obtained: Li-exchanged nepheline with a formula near (Li,K_0.3,□)Li₃[Al₃(Al,Si)Si₄O₁₆] and a monoclinic unit cell with a = 951.0(6) b = 976.1(6) c = 822.9(5)pm γ = 119.15°, and Ag-exchanged nepheline with a formula near (K,Na,□)Ag₃[Al₃(Al,Si)Si₄O₁₆] and a hexagonal unit cell with a = 1007.4(8) c = 838.2(1.0) pm. Both compounds apparently retain the framework topology of the starting material. Ion exchange isotherms and structural data show that immiscibility between the end members is a general feature in the systems Na-Li, Na-Ag, and Na-K. For the system Na-K, a stepwise exchange is observed with (K,D)Na₃[Al₃(Al,Si)Si₄O₁₆] as an intermediate composition which has the nepheline structure and is miscible with the sodian end member (Na,□)Na₃[Al₃(Al,Si)Si₄O₁₆], but not with the potassian end member (K,□)₄[Al₃(Al,Si)Si₄O₁₆] which shows the kalsilite structure; there was no indication for the formation of trior tetrakalsilite (K/(K + Na)≈0.7) at the temperatures studied (350 and 800° C). The exact amount of vacancies □ on the alkali site depends upon the starting material and was found to be conserved during exchange, with ca 0–0.2 and 0.3–0.4 vacancies per 16 oxygen atoms for the synthetic and natural precursors, respectively. Thermodynamic interpretation of the Na-K exchange isotherms shows, as one important result, that the sodian end member is unstable with respect to the intermediate at K/(K+Na)≈0.25 by an amount of ca 45 kJ/mol Na in the large cavity at 800° C (52 kJ/mol at 350° C).     

Experimental and modelling studies of caesium sorption on illite

A natural illite (illite du Puy) was purified and converted to the homo-ionic Na form. The conditioned Na–illite was characterised in terms of its mineralogy, chemical inventory, and surface properties. The structural formula was determined from EDS analyses (SEM/TEM) and bulk chemistry. A cation exchange capacity of 127 mEq/kg was determined by the Na isotope dilution method at neutral pH.The sorption of Cs was measured as a function of NaClO₄ background electrolyte concentration (1.0, 0.1 and 0.01 M), Cs concentration and pH in the range ≈3 to ≈10. Before obtaining these measurements the kinetics of Cs uptake were determined at initial concentrations of 2 × 10⁻⁸ M and 7 × 10⁻⁵ M, representing the extremes of the range investigated, and was found to be concentration dependent. The supernatant solutions after centrifugation were analysed for major cations in all of the sorption tests.A two-site cation exchange model was developed to describe the sorption of Cs over the whole range of experimental conditions. The two-site types were termed frayed edge sites, FES (high affinity/low capacity) and type II sites (low affinity/high capacity). At low NaClO₄ concentrations, Cs sorption decreased at pH values less than neutral. This was interpreted in terms of competitive effects from H, and K released by the partial dissolution of illite, which cannot be avoided at low and high pH values. Selectivity coefficient values for Cs–Na, Cs–K, K–Na, and H–Na exchange equilibria on the FES sites, and Cs–Na exchange on the type II sites are given for illite together with the corresponding site capacities.     

电感耦合等离子体发射光谱法同时测定卤水中锂钠钾钙镁硼硫氯

建立了电感耦合等离子体发射光谱法(ICP-AES)同时测定碳酸盐型、硫酸盐型、氯化物型三种类型卤水中Li、Na、K、Ca、Mg、B、S、Cl等高低含量元素的分析方法。选择仪器最佳的工作条件为射频功率1400W,炬管位置位于-3,载气流量0.60 L/min。确定了各元素测定谱线,使用ICP-AES的双向观测模式、轴向观测模式测定Li、Ca、B、S、Cl以及低含量的K、Mg,径向观测模式测定高含量的Na、K、Mg,可确保卤水中不同含量的元素同时检出。Li、Na、K、Ca、Mg、B、S的检测下限为0.07～3.00 mg/L,Cl的测定下限为165mg/L。方法精密度(RSD,n=10)均小于5%,回收率为92.4%～109.7%。其中Na、K、Mg、S、Cl测定结果与传统方法测定结果基本吻合。     

The crystal chemistry of silica-rich,alkali-deficient nepheline

Coarse crystals of an extremely silica-rich, potassium-deficient nepheline have been synthesized hydrothermally with albite. Electron microprobe analysis yielded the formula: □_1.76K_o.24Na_6.00Al_6.24-Si_9.76O₃₂. A crystal structure analysis of this nepheline has revealed (1) a disordered Si-Al distribution, (2) full occupancy of the smaller cavity site by sodium atoms, and (3) the larger cavity is vacant except for the minor potassium content, with the size of this cavity being the same as when largely occupied with potassium atoms. In addition, the crystal structure of another nepheline prepared by alkali exchange in molten NaCl showed that when Na atoms replace the K atoms of the large cavity: (1) this cavity does not collapse around the smaller atoms, and therefore, (2) the sodium atoms occupy an offcenter position displaced by about 0.3 Å from the cavity center in order to form a rather one-sided bonding configuration with some of the cavity wall oxygen atoms. These structures further support the strong site preference indicated earlier by Buerger and coworkers and restated by Barth: that for the large cavity K > □ ? Na and for the small cavity site Na>Ca(?)?K, □. Perfect compliance with this site preference scheme would tend to restrict nephelines to the Barth compositional join: □₂Na₆Al₆Si₁₀O₃₂-K₂Na₆Al₈Si₈O₃₂, neglecting the minor Ca component usually present. Thirteen new electron microprobe analyses of nephelines from a variety of occurrences and sixteen additional microprobe analyses from the literature which comply with nepheline-structure allowed stoichiometry, are plotted showing that (1) natural nephelines closely conform to this site preference scheme with less than 10% of the large cavity sites containing sodium atoms, that is, the analyses cluster near the Barth join, and (2) examples of natural nephelines can be found at nearly all intermediate compositions along this join.     

河北省赤城县独石口沸石岩矿物学特征及其性能研究

独石口沸石岩共生矿物组合为斜发沸石、蒙脱石、α-方石英和少量丝光沸石。斜发沸石呈微晶产于玻璃质岩屑和火山尘中,也呈板状产于玻屑和珍珠岩溶解形成的孔洞中,沸石总量大于70％;化学成分显示高Si、高Al、富K、富Ca、贫Na的特征;阳离子交换容量高,交换性阳离子以Ca为主,其次为K,Na,Mg;阳离子选择交换顺序为NH_4~+>K~+>Ca~(2+)>Na~+>Mg~(2+);不同阳离子类型的沸石岩其热稳定性和吸附性有差异,K型和Na型沸石岩可稳定至700℃,而Ca型沸石岩在500℃时结构被破坏;Ca型沸石岩吸附性好,而K型差。     

Heating experiments relevant to the depletion of Na,K and Mn in the Earth and other planetary bodies

We have studied the evaporation of Na, K and Mn from Al-Na-K- and Mn-rich silicates at various conditions. Total alkali oxide contents ranged from 5 to 20%. The evaporation rate of Na increases with temperature and decreasing oxygen fugacity and decreases with duration of heating. The loss of K is in all cases less pronounced than for Na. Heating in an evacuated vacuum furnace is more effective in removing Na and K from melt droplets than in furnaces with one atm gas flow of air or gas mixtures controlling the oxygen fugacity. The strong pumping required to keep the vacuum removes Na and K atoms very effectively. In all experiments, the rate of evaporation is determined by quasi-equilibrium between a thin layer of Na and K rich gas above the molten silicates. The results of the experiments are in agreement with several other studies.In experiments with more than one sample in the furnace, equilibration of Na- and K-rich samples with Na- and K-poor samples occurred rapidly, mediated by the ambient gas phase.The results of experiments with Mn in starting compositions showed much stronger losses of Na than Mn under a variety of conditions.Thus the nearly chondritic Mn/Na ratios in the Earth cannot be the result of evaporation of Na and Mn in Earth-making materials, as the Mn/Na ratios in evaporation residues would be much higher than chondritic ratios. Such evaporation processes may have occurred in the parent material of Moon, Vesta and Mars.The data suggest, in agreement with earlier hypotheses, that the high and variable contents of Na and K in chondrules require a gas phase high in Na and K equilibrating with chondrule melts. The volume of nebular gas parental to a certain type of chondrites was heated and Na and K were lost from the chondrule precursors to the gas phase. Subsequently the nebular parcel was compressed leading to higher partial pressures of Na and K. Flash heating then produced chondrule melts which incorporated some of the gaseous Na and K and then cooled rapidly. The large range of Na and K contents in chondrule melts reflects very local enrichments of Na and K in the gas phase. Despite these variations bulk chondritic meteorites have well defined bulk Na and K contents, implying a closed system during formation of chondrules and matrix.     

27Al, 29Si,and 23Na MAS NMR study of an Al,Si ordered alkali feldspar solid solution series

Solid-state ²⁷Al, ²⁹Si and ²³Na MAS NMR spectra have been obtained for an Al,Si ordered low albite to low microcline ion exchange series for which unit-cell parameters and ²⁹Si NMR data have previously been reported. ²⁷Al δ_i vary continuously with composition from 63.4 (±0.5) ppm for albite to 58.9 (±0.5) ppm for microcline, and parallel the ²⁹Si chemical shifts assigned to the T2m-site. The ²⁷Al and ²⁹Si chemical shifts for this series correlate well with composition-dependent lattice parameters, most notably cell volume and the angle [201]¹b. The linewidths of the ²⁹Si and ²⁷Al resonances indicate a significant amount of structural disorder in the intermediate compositions due to Na, K substitution. The 1 σ width of the distribution of average Si-O-T angles for each T-site is estimated to be about 1° for the Or33 sample. The average ²³Na δ_i varies monotonically from -8.5 (±1) ppm for albite to -24.3 (±1)ppm for Or83. Similarly, the average ²³Na nuclear quadrupole coupling constant decreases from 2.60 to 1.15 (±0.05) MHz and the asymmetry parameter of the electric field gradient increases from 0.25 to 0.6 with increasing K-content from albite to Or83. The observed variations in the quadrupole coupling parameters are consistent with simple electrostatic calculations. Higher resolution ²³Na spectra of the intermediate compositions obtained at 11.7 T indicate the presence of an inhomogeneous linebroadening which is related to the distribution of Na-environments. A model based on a random distribution of local compositions does not simulate the spectra, suggesting that the distribution of Na is skewed toward Na-rich clusters. Observation of the ²³Na NMR lineshape of Or49 after short periods of heat treatment indicate that ²³Na NMR is very sensitive to the changes in the Na, K distribution accompanying the early stages of exsolution. Reversible changes occur after heating at 530° C for 3 h, whereas heating at 600° C produces no changes, possibly bracketing the position of the coherent spinodal for Al, Si ordered alkali feldspars at this composition.     

Chemical evolution of a gas-capped deep aquifer,southwest of Iran

The Kangan Aquifer (KA) is located below a gas reservoir in the crest of the Kangan Anticline, southwest of Iran. This aquifer is composed of Permo-Triassic limestone, dolomite, sandstone, anhydrite and shale. It is characterized by a total dissolved solid of about 332,000 mg/L and Na–Ca–Cl-type water. A previous study showed that the source of the KA waters is evaporated seawater. Chemical evolution of the KA is the main objective of this study. The major, minor and trace element concentrations of the KA waters were measured. The chemical evolution of KA waters occurred by three different processes: evaporation of seawater, water–rock and water–gas interactions. Due to the seawater evaporation process, the concentration of all ions in the KA waters increased up to saturation levels. In comparison to the evaporated seawater, the higher concentrations of Ca, Li, Sr, I, Mn and B and lower concentrations of Mg, SO₄ and Na and no changes in concentrations of Cl and K ions are observed in the KA waters. Based on the chemical evolution after seawater evaporation, the KA waters are classified into four groups: (1) no evolution (Cl, K ions), (2) water–rock interaction (Na, Ca, Mg, Li and Sr ions), (3) water–gas interaction (SO₄ and I ions) and (4) both water–rock and water–gas interactions (Mn and B ions). The chemical evolution processes of the KA waters include dolomitization, precipitation, ion exchange and recrystallization in water–rock interaction. Bacterial reduction and diagenesis of organic material in water–gas interaction also occur. A new type of chart, Ca_excess versus Mg_deficit, is proposed to evaluate the dolomitization process.     

Chemistry of polar snows. Estimation of rates of deposition in Antarctica

In this study, we report analyses of chlorine, sodium, magnesium, potassium, calcium, manganese and iron in ten surface firn samples collected along the profile Mirny (66°30′S, 93°E, near the sea)-Vostok (78°27′S, 107°E, 1295 km from the sea, altitude 3420 m) in Antarctica, and brought back to the laboratory in the frozen state. The analyses were carried out by atomic absorption after preconcentration in the presence of aqua regia and HF (Na, Mg, K, Ca and Fe) and neutron activation in the frozen state (Cl, Na and Mn).     

Potassium induced salinity tolerance in wheat (Triticum aestivum L.)

Water culture experiments were conducted to study the response of ten wheat genotypes to external K application (10 mmol KCI dm^?3) at seedling stage under saline condition (0 and 100 mmol NaCl dm^?3). The data showed that there was an increase in the shoot and root length with the application of external K. The increase was more pronounced under control than under saline conditions. The better performing genotypes under two treatments were Bhitai, NIAB-41, NIAB-I076 and Khirman. The enhanced growth of these genotypes under saline condition might be due to the quick response to external K application, resulting in high K/Na ratio. The results indicated that the genotypes, which have the ability of enhanced K/Na discrimination, might perform better under saline conditions when sufficient potassium is applied in the rooting medium.     

A Comparative geochemical study of pelitic schists and metamorphosed carbonate rocks from south-central Maine,USA

Whole-rock major element chemical analyses of progressively metamorphosed impure carbonate rocks and pelitic schists, collected from the same metamorphic terrain, reveal similarities and differences in the chemical response of these rock types to the metamorphic event. Relative to a constant aluminum reference frame, both schist and carbonate exhibit no detectable change in their contents of Fe, Mg, Ti, Si, and Ca with change in metamorphic grade. Carbonate rocks become progressively depleted in K and Na with increasing grade of metamorphism, while schists exhibit no statistically significant change in their contents of K and Na. Both rock types become depleted in volatiles (principally CO₂ and H₂O) with increasing grade.Whole-rock chemical data permit two mechanisms for migration of K and Na from the carbonate rocks during metamorphism: (a) diffusion of alkalis from carbonate to adjacent schist; (b) transport of alkalis by through-flowing metamorphic fluid (infiltration). Mineral equilibria in schist and metacarbonate rock from the same outcrops allow calculation of the affinity for cation exchange between the two rock types during metamorphism. Measured affinities indicate that if mass transport of K and Na occurred by diffusion, chemical potential gradients would have driven the alkalis from schist into carbonate rock. Because diffusion cannot produce the observed chemical trends in the metacarbonates, K and Na are believed to have been removed during metamorphism by infiltration.The disparity in chemical behavior between the pelitic schists and metacarbonate rocks may be a result of enhanced fluid flow through the carbonates. The carbonate rocks may have acted as metamorphic aquifers; the greater flow of fluid through them would then have had a correspondingly greater effect on their whole-rock chemistry.     

Two-feldspar geothermometry: a review and revision for slowly cooled rocks

Recent improvements in the experimental and thermodynamic basis of two-feldspar geothermometry allow one to recover temperatures of coexistence more reliably. Some problems, however, persist: (1) the experimental solvi by Seck (1971a) and Elkins and Grove (1990) differ from each other; (2) it is not known to what extent Na–K–Ca exchange equilibrium is approached; (3) both solvi are probably metastable with regard to Al, Si order; (4) it is difficult to judge how closely high-temperature natural feldspars compare to this situation; (5) the thermodynamic treatment neglects phase transformations; (6) the temperature dependence of the Margules parameters used to model non-ideal mixing behaviour may not be linear; (7) it is not clear which expressions should be used to describe ideal activities. With these caveats in mind we treat the problem of retrograde resetting in high-grade metamorphic rocks that were slowly cooled under essentially dry conditions. Coexisting feldspars from such rocks commonly do not plot on a common isotherm. Thus temperatures derived from such pairs using any of the proposed two-feldspar geothermometers will necessarily be in error. We suggest that the non-equilibrium compositions result from retrograde intercrystalline K–Na exchange. This exchange continues after the plagioclase and alkali feldspar have already become essentially closed systems with respect to Al–Si exchange, which is a prerequisite for (Na,K)–Ca exchange. We use a modified version of the Fuhrman and Lindsley (1988) programme to reverse the K–Na exchange and derive concordant temperatures.     

Assessment of chemical properties and hydro-geochemical coefficients at the Qareh Sou Basin,Golestan Province,Iran

This paper focuses on the Qareh Sou Basin in Golestan Province, Iran. Golestan Province is the third largest cereal producer in Iran and water scarcity and salinity are major problems in this area. This study attempts to facilitate the comprehension of system behavior with respect to water quality issues and hydro-geochemical coefficients within the Qareh Sou Basin. This study was carried out during the year 2010. Various parameters, such as pH, EC, chloride, sulfate, bicarbonate, sodium, potassium, calcium and magnesium have been determined for evaluation purposes. Then, Ca/Mg, Na/Cl, Mg/(Ca + Mg), Ca/HCO₃, (Ca + Mg)–(HCO₃ + SO₄), (Na + K)–Cl, (Ca + Mg + Na + K)–Cl, HCO₃ + SO₄, Ca + Mg and chloro-alkaline indices (CAI) were calculated. Results show that cation exchange probably is an important factor in the hydrochemistry and silicate mineral weathering. Also, CAI-1 plot against CAI-2 demonstrates that most of samples have positive values which suggest normal ion exchange in the system. The carbonic acid is the main agent of calcite, limestone and dolomite weathering which occurs in some stations. According to Chadha’s diagram, the type of water is determined as Ca–Mg–HCO₃.     

含蛭石晶层间层矿物的可交换性阳离子及交换容量研究

对采自新疆尉犁蛭石矿、河南灵宝-陕西潼关蛭石矿的工业蛭石矿物样品进行了可交换性阳离子与交换容量研究，发现新疆尉犁蛭石矿金云母-蛭石中可交换性阳离子主要为Na^ 和Ca^2 ，其次为Mg^2 、K^ 、Ba^2 和Sr^2 ；而河南灵宝-陕西潼关蛭石矿工业蛭石样品的可交换性阳离子主要为Ca^2 和Mg^2 ，其次为Na^ 、K^ 等。金云母-蛭石和绿泥石-蛭石间层矿物的阳离子交换容量随间层结构中蛭石晶层的含量增加而增大，一般在56．92～98．95mmol／100g之间，仅为蛭石最大阳离子交换容量的一半。金云母-蛭石样品阳离子交换容量大小与K2O含量呈负相关关系，与(Na2O CaO)含量呈正相关关系。     

Experimentally determined partitioning of Rb between richterites and aqueous (Na, K)-chloride solutions

The distribution of Rb-Na and Rb-K between richterite and a 2-molal aqueous (Na, K, Rb)-chloride solution has been investigated with hydrothermal experiments at 800^∘C and 200 MPa. Experiments were performed as syntheses in which amphiboles grew in the presence of an excess fluid containing the exchangeable cations Na⁺-Rb⁺ or Na⁺-K⁺-Rb⁺. The obtained amphiboles were large enough (up to 20 m in width) for reliable EMP analysis. They were chemically homogeneous and HRTEM investigations showed that they were structurally well ordered. The Rb, Na, K, Ca and Mg concentrations in coexisting fluids were measured by ICP-AES. According to the possible incorporation of Na, K and Rb on the A-site, solid solutions in the ternary Na(NaCa) Mg₅[Si₈O₂₂/(OH)₂] (richterite)-K(NaCa)Mg₅[Si₈O₂₂/(OH)₂] (K-richterite)-Rb(NaCa)Mg₅[Si₈O₂₂/(OH)₂] (Rb-richterite) were expected. However, Rb-rich richterites always had significant amounts of A-site vacancy concentrations (X _□ ^amph=□ ^A /(Rb^A+K^A +Na^A+□^A) of up to 0.42 in the K-free (Na,Rb)-richterites and of up to 0.67 in the (Na, K, Rb)-richterites which corresponds to the same content of tremolite+cummingtonite-component. Amphiboles containing practically only Rb besides vacancies and no Na and/or K on the A-site were also synthesized, however. The Rb-Na and Rb-K exchange coefficients between fluid and richterites are similar. Rubidium always fractionated strongly into the fluid phase. For low Rb-concentrations in richterite (X _Rb ^amph<0.1) a linear correlation between X _Rb ^fluid and X _Rb ^amph exists. In this concentration range, the derived exchange coefficients K _D(Rb−K) ^amph−fluid and K _D(Rb−Na) ^amph−fluid were 0.08 ± 0.04 and 0.04 ± 0.02, respectively. These low exchange coefficients show that significant amounts of Rb in amphiboles require a Rb-rich fluid phase. The results indicate that K-Rb fractionation between alkali amphiboles and fluids is significantly different from K-Rb fractionation between alkali feldspar/ phlogopite and fluid, with K_Ds of about 0.5 and 1.2, respectively. Formation of richterites will drastically alter the K/Rb-ratios of fluids or melts. These results may have important implications for the genetical interpretation of various geological settings, e.g., MARID-type rocks. Received: 6 October 1997 / Accepted: 7 July 1998