蒙脱石+伊/蒙混层+伊利石等粘土矿物混合物相X射线定量分析方法—模拟定量法

本文提出粘土矿物(特别是含伊/蒙不规则混层粘土矿物)混合物相的X射线定量分析方法——模拟定量法。着重解决在蒙脱石-不规则伊/蒙混层粘土矿物-伊利石组合中,伊/蒙混层粘土矿物的定量分析计算。模拟定量法是对以前的各种粘土矿物X射线定量分析方法的补充。用纯净的蒙脱石、伊利石、高岭石、绿泥石及各种伊/蒙混层比的伊/蒙混层粘土矿物,配制了各种不同组合的粘土矿物混合样品,制成定向薄膜片,进行了X射线分析,讨论了各种组合的粘土矿物混合物相X射线衍射图谱的特征,并在此基础上提出了粘土混合物相定量分析的方法。     

中国含油气盆地粘土矿物的某些矿物学特征

本文总结归纳了２０多个含油气盆地粘土矿物的类型，讨论了８种较常见的、６种较少见的和３种极少见的粘土矿物的Ｘ射线衍射特征及其成分、形态和分布等方面的矿物学特征．     

Geochemical and mineralogical impacts of H2SO4 on clays between pH 5.0 and −3.0

Natural and constructed clay liners are routinely used to contain waste and wastewater. The impact of acidic solutions on the geochemistry and mineralogy of clays has been widely investigated in relation to acid mine drainage systems at pH > 1.0. The impact of H₂SO₄ leachate characterized by pH < 1.0 and potentially negative pH values on the geochemistry and mineralogy of clays is, however, not clear. Thus, laboratory batch experiments were conducted on three natural clay samples with different mass ratios of smectite, illite and kaolinite to investigate the impact of H₂SO₄ on the geochemistry and mineralogy of aluminosilicates from pH 5.0 to −3.0. Batch testing was conducted at seven pH treatments (5.0, 3.0, 1.0, 0.0, −1.0, −2.0 and −3.0) using standardized H₂SO₄ solutions for four exposure periods (14, 90, 180, and 365 d). Aqueous geochemical and XRD analyses showed: increased dissolution of aluminosilicates with decreasing pH and increasing exposure period, that smectite was more susceptible to dissolution than illite and kaolinite, precipitation of an amorphous silica phase occurred at pH ? 0.0, and anhydrite precipitated in Ca-rich clays at pH ? −1.0. In addition, global dissolution rates were calculated for the clays and showed good agreement to literature smectite, illite and kaolinite dissolution rates, which suggests global dissolution rates for complex clays could be determined from monomineralic studies. A stepwise conceptual model of the impact of H₂SO₄ on aluminosilicate geochemistry and mineralogy between pH 5.0 and −3.0 is proposed.     

The effect of iron on montmorillonite stability. (II) Experimental investigation

Several designs proposed for high-level nuclear waste (HLW) repositories include steel waste canisters surrounded by montmorillonite clay. This work investigates montmorillonite stability in the presence of native Fe, magnetite and aqueous solutions under hydrothermal conditions. Two series of experiments were conducted. In the first, mixtures of Na-montmorillonite, magnetite, native Fe, calcite, and NaCl solutions were reacted at 250 °C, P_sat for between 93 and 114 days. In the second series, the starting mixtures included Na-montmorillonite, native Fe and solutions of FeCl₂ which were reacted at temperatures of 80, 150, and 250 °C, P_sat, for 90-92 days. Experiments were analysed using XRD, FT-IR, TEM, ICP-AES, and ICP-MS. In the first series of experiments, native Fe oxidised to produce magnetite and the starting montmorillonite material was transformed to Fe-rich smectite only when the Fe was added predominantly as Fe metal rather than Fe oxide (magnetite). The Fe-rich smectite was initially Fe(II)-rich, which oxidised to produce an Fe(III)-rich form on exposure to air. The expansion of this material on ethylene glycol solvation was much reduced compared to the montmorillonite starting material. TEM imaging shows that partial loss of tetrahedral sheets occurred during transformation of the montmorillonite, resulting in adjacent layers becoming H-bonded with a 7 Å repeat. The reduced swelling property of the Fe-smectite product may be due predominantly to the structural disruption of smectite layers and the formation of H-bonds. Solute activities corresponded to the approximate stability field calculated for hypothetical Fe(II)-saponite. In the second series of experiments, significant smectite alteration was only observed at 250 °C and the product contained a small proportion of a 7 Å repeat structure, observable by XRD. In these experiments, solute activities coincide with berthierine. The experiments indicate that although bentonite is still a desirable choice of backfill material for HLW repositories, some loss of expandability may result if montmorillonite is altered to Fe-rich smectite at the interface between steel canisters and bentonite.     

Patterns of mineral transformations in clay gouge,with examples from low-angle normal fault rocks in the western USA

Neoformed minerals in shallow fault rocks are increasingly recognized as key to the behavior of faults in the elasto-frictional regime, but neither the conditions nor the processes which wall-rock is transformed into clay minerals are well understood. Yet, understanding of these mineral transformations is required to predict the mechanical and seismogenic behavior of faults. We therefore present a systematic study of clay gouge mineralogy from 30 outcrops of 17 low-angle normal faults (LANF's) in the American Cordillera to demonstrate the range and type of clay transformations in natural fault gouges. The sampled faults juxtapose a wide and representative range of wall rock types, including sedimentary, metamorphic and igneous rocks under shallow-crustal conditions. Clay mineral transformations were observed in all but one of 28 faults; one fault contains only mechanically derived clay-rich gouge, which formed entirely by cataclasis.Clay mineral transformations observed in gouges show four general patterns: 1) growth of authigenic 1M_d illite, either by transformation of fragmental 2M₁ illite or muscovite, or growth after the dissolution of K-feldspar. Illitization of fragmental illite–smectite is observed in LANF gouges, but is less common than reported from faults with sedimentary wall rocks; 2) ‘retrograde diagenesis’ of an early mechanically derived chlorite-rich gouge to authigenic chlorite–smectite and saponite (Mg-rich tri-octahedral smectite); 3) reaction of mechanically derived chlorite-rich gouges with Mg-rich fluids at low temperatures (50–150 °C) to produce localized lenses of one of two assemblages: sepiolite + saponite + talc + lizardite or palygorskite +/− chlorite +/− quartz; and 4) growth of authigenic di-octahedral smectite from alteration of acidic volcanic wall rocks. These transformation groups are consistent with patterns observed in fault rocks elsewhere. The main controls for the type of neoformed clay in gouge appear to be wall-rock chemistry and fluid chemistry, and temperatures in the range of 60–180 °C.     

Dissolution of illite in saline-acidic solutions at 25 °C

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 (K_1.38Na_0.05)(Al_2.87Mg_0.46Fe³⁺_0.39Fe²⁺_0.28Ti_0.07)[Si_7.02Al_0.98]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 R_Al (dissolution rate calculated from steady state Al release) than R_Si (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.     

Rare earth element sorption by basaltic rock: Experimental data and modeling results using the “Generalised Composite approach”

Sorption of the 14 rare earth elements (REE) by basaltic rock is investigated as a function of pH, ionic strength and aqueous REE concentrations. The rock sample, originating from a terrestrial basalt flow (Rio Grande do Sul State, Brazil), is composed of plagioclase, pyroxene and cryptocrystalline phases. Small amounts of clay minerals are present, due to rock weathering. Batch sorption experiments are carried out under controlled temperature conditions of 20 °C with the <125 μm fraction of the ground rock in solutions of 0.025 M and 0.5 M NaCl and at pH ranging from 2.7 to 8. All 14 REEs are investigated simultaneously with initial concentrations varying from 10⁻⁷ to 10⁻⁴ mol/L. Some experiments are repeated with only europium present to evaluate possible competitive effects between REE. Experimental results show the preferential retention of the heavy REEs at high ionic strength and circumneutral pH conditions. Moreover, results show that REE sorption increases strongly with decreasing ionic strength, indicating two types of sorption sites: exchange and specific sites. Sorption data are described by a Generalised Composite (GC) non-electrostatic model: two kinds of surface reactions are treated, i.e. cation exchange at >XNa sites, and surface complexation at >SOH sites. Total site density (>XNa + >SOH) is determined by measuring the cation exchange capacity (CEC = 52 μmol/m²). Specific concentrations of exchange sites and complexation sites are determined by fitting the Langmuir equation to sorption isotherms of REE and phosphate ions. Site densities of 22 ± 5 and 30 ± 5 μmol/m² are obtained for [>XNa] and [>SOH], respectively. The entire set of REE experimental data is modeled using a single exchange constant (log K_ex = 9.7) and a surface complexation constant that progressively increases from log K = −1.15 for La(III) to −0.4 for Lu(III).The model proves to be fairly robust in describing other aluminosilicate systems. Maintaining the same set of sorption constants and only adjusting the site densities, we obtain good agreement with the literature data on REE/kaolinite and REE/smectite sorption. The Generalised Composite non-electrostatic model appears as an easy and efficient tool for describing sorption by complex aluminosilicate mineral assemblages.     

准噶尔盆地南缘新生界粘土矿物分布及影响因素

根据粘土矿物的相对含量研究了准噶尔盆地南缘新生界砂岩粘土矿物类型、组合特征及纵、横向分布规律及其主要影响因素。划分出无序伊/蒙混层型、部分有序伊/蒙混层型、伊利石+伊/蒙混层型、蒙皂石型以及含坡缕石型等5类粘土矿物组合。按照伊/蒙混层相对含量的变化,粘土矿物纵向上演化呈正常转化型(伊/蒙混层相对含量降低)、反向转化型(伊/蒙混层相对含量增加)和“S”型(伊/蒙混层相对含量呈曲线变化)3种形式。平面上,伊/蒙混层和伊利石这两类主要粘土矿物从湖盆的边缘向中心分别呈现减少和增多的趋势,湖盆边缘相带以无序伊/蒙混层型、蒙皂石型和含坡缕石型为主,湖盆中心则为部分有序伊/蒙混层型和伊利石+伊/蒙混层型组合等类型。上述分布规律的控制因素主要有沉积环境、构造运动及层序发育等。     

Bioreduction of Fe-bearing clay minerals and their reactivity toward pertechnetate (Tc-99)

⁹⁹Technetium (⁹⁹Tc) is a fission product of uranium-235 and plutonium-239 and poses a high environmental hazard due to its long half-life (t_1/2 = 2.13 × 10⁵ y), abundance in nuclear wastes, and environmental mobility under oxidizing conditions [i.e., Tc(VII)]. Under reducing conditions, Tc(VII) can be reduced to insoluble Tc(IV). Ferrous iron, either in aqueous form (Fe²⁺) or in mineral form [Fe(II)], has been used to reduce Tc(VII) to Tc(IV). However, the reactivity of Fe(II) from clay minerals, other than nontronite, toward immobilization of Tc(VII) and its role in retention of reduced Tc(IV) has not been investigated. In this study the reactivity of a suite of clay minerals toward Tc(VII) reduction and immobilization was evaluated. The clay minerals chosen for this study included five members in the smectite-illite (S-I) series, (montmorillonite, nontronite, rectorite, mixed layered I-S, and illite), chlorite, and palygorskite. Surface Fe-oxides were removed from these minerals with a modified dithionite-citrate-bicarbonate (DCB) procedure. The total structural Fe content of these clay minerals, after surface Fe-oxide removal, ranged from 0.7% to 30.4% by weight, and the structural Fe(III)/Fe(total) ratio ranged from 45% to 98%. X-ray diffraction (XRD) and Mössbauer spectroscopy results showed that after Fe oxide removal the clay minerals were free of Fe-oxides. Scanning electron microscopy (SEM) revealed that little dissolution occurred during the DCB treatment. Bioreduction experiments were performed in bicarbonate buffer (pH-7) with structural Fe(III) in the clay minerals as the sole electron acceptor, lactate as the sole electron donor, and Shewanella putrefaciens CN32 cells as a mediator. In select tubes, anthraquinone-2,6-disulfate (AQDS) was added as electron shuttle to facilitate electron transfer. In the S-I series, smectite (montmorillonite) was the most reducible (18% and 41% without and with AQDS, respectively) and illite the least (1% for both without and with AQDS). The extent and initial rate of bioreduction were positively correlated with the percent smectite in the S-I series (i.e., layer expandability). Fe(II) in the bioreduced clay minerals subsequently was used to reduce Tc(VII) to Tc(IV) in PIPES buffer. Similar to the trend of bioreduction, in the S-I series, reduced NAu-2 showed the highest reactivity toward Tc(VII), and reduced illite exhibited the least. The initial rate of Tc(VII) reduction, after normalization to clay and Fe(II) concentrations, was positively correlated with the percent smectite in the S-I series. Fe(II) in chlorite and palygorskite was also reactive toward Tc(VII) reduction. These data demonstrate that crystal chemical parameters (layer expandability, Fe and Fe(II) contents, and surface area, etc.) play important roles in controlling the extent and rate of bioreduction and the reactivity toward Tc(VII) reduction. Reduced Tc(IV) resides within clay mineral matrix, and this association could minimize any potential of reoxidation over long term.     

Modelling of Cs sorption in natural mixed-clays and the effects of ion competition

Cs migration in the environment is mainly controlled by sorption onto mineral surfaces, in particular on clay minerals. With the objective of designing a geochemical reactive barrier to treat ¹³⁷Cs accidental pollution in an industrial waste repository, different natural clayrocks were studied to analyse their capacity to retain Cs.The simple semi-empiric K_d-approach for experimental data analysis, is unsatisfactory to describe the variability of sorption upon chemical changes. Indeed, due to the high salinity of the site, the effects of competitive ions must be evaluated and quantified. Thus, the development of sorption models, capable of reproducing experimental data obtained under conditions representative of the contaminated site, and applicable to reactive transport studies, is needed.In this study, a model for Cs sorption, which takes into account the main mineralogy of the sorbent, the composition of the natural water (and ion competition) was successfully applied to interpret the non-linear Cs sorption under natural conditions.The selectivity coefficients of Cs with respect to the most important cations present in the site water (Na, K, NH₄, Ca) were derived by means of experiments in single clay minerals and synthetic mono-component solutions. Then, these parameters were tested in systems of increasing complexity.Considering the mineralogical composition of raw materials, it was shown that the principal contribution to Cs sorption is given by the mineral illite, while smectite starts to be relevant only at very high Cs loadings. Kaolinite, even in concentrations around 10 wt% of the clayey fraction, played only a minor role.With respect to the solution composition, the model was able to predict Cs sorption in electrolyte concentrations up to twice than that of seawater and up to 500 mg/L NH₄⁺. The effect of highly competing ions, especially NH₄⁺ and K⁺, on Cs retention is more important at low ionic strengths and low Cs loadings, where adsorption is dominated by illite selective frayed edge sites, FES. Divalent cations are not especially relevant as competing cations for Cs.     

Volcanic Activity, Hydrothermal Alteration and Epithermal Gold-Silver Mineralization in the Ryuo Mine Area in the Kitami Metallogenic Province, Hokkaido, Japan

Abstract: Characterization of Neogene magmatism in the Ryuo mine area in the Kitami metallogenic province was carried out on the basis of K-Ar data for felsic–to–mafic terrestrial extrusive and intrusive volcanism from Late Miocene to Early Pliocene. The Ryuo epithermal gold-silver deposit occurs primarily in the felsic volcaniclastic rocks of the Ikutahara Formation and in Ryuo Rhyolite. The Ryuo mineralization age of 7. 7 – 8. 1 Ma coincides well with the hydrothermal alteration age (7. 7 Ma) of Ryuo Rhyolite hosting ore veins. It is concluded that the Ryuo mineralization was essentially accompanied by felsic volcanic activity during the sedimentation of the Ikutahara Formation, and was closely related both temporally and spatially to the intrusive activity of Ryuo Rhyolite. Hydrothermal alteration related to the epithermal gold-silver mineralization of the Ryuo deposit is primarily characterized by early regional and vein-related alterations, and late steam-heated alteration. Early regional alteration consists of a smectite halo (smectite+pyrite±quartz±opal–CT±mordenite°Clinoptilolite–heulandite series mineral). Early vein-related alteration is primarily marked by potassic alteration. This alteration halo can be subdivided into a K-feldspar halo (quartz+adular–ia+pyrite±illite±interstratified illite/smectite±smectite), an illite halo (quartz+illite + chlorite + pyrite ± interstratified illite/smec–tite±smectite) and an interstratified illite/smectite halo (quartz + interstratified illite/smectite+pyrite±smectite). Late steam-heated alteration characterized by kaolinite or alunite locally overprints the early K-feldspar halo. The style of the Ryuo gold-silver deposit is a low-sulfidation epithermal type. The gold–silver–bearing quartz vein precipitates during boiling of ore fluid. The origin of the ore fluid might be meteoric water. The temperature and sulfur fugacity conditions during precipitation of electrum and acanthite are estimated to be 206°– 238°C and 10^-13.5 – 10^-11.6 atm, respectively.     

粘土矿物地温计在沉积盆地热演化研究中的应用

在成岩过程中形成的粘土矿物真实地记录了地层形成的成岩温度及其盆地热演化的信息,可以作为沉积盆地的热史指标。本文主要介绍了伊利石/蒙皂石间层矿物（以下简称伊/蒙间层或I/S间层）、伊利石结晶度、绿泥石化学成分三种常用的粘土矿物地温计的发展历史、基本原理和影响因素;回顾了我国沉积盆地热演化研究中粘土矿物地温计的应用现状,并对未来的应用推广工作提出了若干参考建议。     

贵州绿豆岩中粘土矿物特征及其成因探讨

本文应用Ｘ射线衍射、红外光谱、差热分析，电子显微镜、化学分析、沉积相分析等方法，详细研究了贵州早、中三叠世间绿豆岩及其粘土矿物组成，确定了贵州绿豆岩中主要粘土矿物为伊利石、蒙脱石、高岭和伊利石／蒙脱石混层矿物。由于各地沉积环境和成岩条件的差异，分别形成伊利石粘土岩、蒙脱石粘土岩和高岭石粘土岩。探讨了绿豆及其粘土矿物的形成机理，为绿豆岩的开发利用提供了系统的新资料。     

Alteration and mass transfer in cataclasites and mylonites in 6.6 km of granitic crust at the Siljan impact structure,central Sweden

Granitic rocks deformed by cataclasis and mylonitization on macro- (a few meters) and micro- (thin section) scales are found at depths down to 6.6km in the Siljan impact structure in central Sweden. Granites near fault planes exhibit: (1) fracturing, kinking, fragmentation, and recrystallization of feldspars into pure K and Na endmember varieties, (2) fragmentation, polygonization and development of undulose extinction in quartz, and (3) kinking, appearance of wavy extinction and alteration of biotite, chlorite, amphibole, and alteration of ilmenite and magnetite. Whole-rock chemical analyses of deformed and undeformed rocks show that deformed rocks are enriched in SiO₂ (by about 5 wt.%) and depleted in other oxides by variable percentages. Apart from Rb and Co, the concentrations of other trace elements (including Ba, Sr, Zn, Zr, Pb, Cd, Cu, Cr, Ni, V, U, Th, La, and Li) are lower in deformed relative to undeformed rocks. Mass-balance calculations for a 1000 cm³ model granite which were based on modal mineralogy, whole-rock chemistry, and mineral analyses suggest that the break down of primary biotite, chlorite, and amphibole in deformed zones released elements to circulating fluids. These calculations also indicate liberation of water and a doubling of porosity (from 1 to 2%) during the deformation episodes. Later precipitation of minerals in shear and tension fractures reduced this porosity. Within the upper 2000 m of the Gravberg-1 well, the formation of fracture-filling minerals (smectite, calcite, hematite, chlorite, and albite) is impact-related, and was favored by active circulation of meteoric water. Fracture-filling minerals in the upper 2000 m of the borehole formed at temperatures of 70° to 200°C. Between depths of 2000 and 3500 m, fracture-filling mineral assemblages (dominated by Fe–Mg chlorite, sphene and epidote) suggest formation temperatures in the range of 150° to 300°C. Occurrence of pumpellyite and prehnite in some altered biotite and chlorite of the deformed zones between 3500 and 5500 m suggest preimpact metamorphism and formation temperature above 150°C. Below 5500 m, the mineral assemblages in the fractures are dominated by quartz, sphene, epidote, and some muscovite and chlorite, indicating a temperature range between 300° and 450°C. One of the possible origins for the CH₄ and H₂ gases detected in the Gravberg-1 well is a combination of hydrogen ions released by decomposition of hydrated silicates (biotite, chlorite, hornblende) with carbon. The presence of iron in the deformed granitic rocks prevented the resulting CH₄ from being oxidized.     

Chemico-mineralogical attributes of clays from the late Cretaceous–early Palaeogene succession of the Um Sohryngkew river section of Meghalaya,India: Palaeoenvironmental inferences and the K/Pg boundary

A continuous shallow marine 10 m thick succession within the Langpar Formation in the Um Sohryngkew river section of Meghalaya, containing late Maastrichtian through early Danian planktonic foraminiferal zones – CF4, CF3, CF2, CF1, P0, Pα and P1a and the K/Pg boundary (between CF1 and P0) that makes unique of its kind. The section has been re-studied and sampled for clay mineralogy to understand the palaeoenvironmental conditions prevalent in the region and to assess the K/Pg transition. The relative abundances of the clay mineral phases permitted a threefold sub-division of the studied section with a illite, illite/ smectite dominated lower part, illite, kaolinite and abundance of montmorillonite dominated middle part and kaolinite–montmorillonite dominated upper part. Enriched HREEs in the lower part of the succession suggest variations in the pH of alteration solutions. Most of the samples show positive cerium (δCe) and europium (δEu) anomalies, the former reflecting oxidizing conditions at the time of clay formation. Illite dominated clays present a positive Eu anomaly, formed at relatively higher temperatures than the clays with less illite and without Eu anomalies, whereas clays occurring in the lower and upper parts exhibit a prominent negative Eu anomaly. Shifts in the redox condition found in this section are more or less similar to the foraminiferal changes and Au, Pt, Pd anomalies. Clay mineralogical attributes and REE patterns, comparable to those of the known K/Pg boundaries, appeared within the CF3 and CF2 zones in the Um Sohryngkew river section. The sample at the boundary between CF3 and CF2 is marked by a negative <delta>Ce anomaly, high La/Yb and TOC values, suggesting that sea level rise during the upper part of CF3 was caused by tectonism rather than warming. The similar characteristics of clay minerals and REE patterns, attributed to the initiation of tectonic events during the CF3 zone, indicate environmental changes that affected the shelf area and the provenance of these sediments.     

The effect of high pH alkaline solutions on the mineral stability of the Boom Clay – Batch experiments at 60 °C

Boom Clay is currently viewed as a reference host formation for studies on deep geological disposal of radioactive waste in Belgium. The interactions between bulk rock Boom Clay and 0.1 M KOH, 0.1 M NaOH, 0.1 M Ca(OH)₂, young cement water and evolved cement water solutions, ranging in pH from 12.5 to 13.2, were examined as static batch experiments at 60 °C to simulate alkaline plume perturbations, which are expected to occur in the repository due to the presence of concrete. Both liquids and solids were investigated at specific times between 90 and 510 days in order to control the elemental budget and to search for potential mineralogical alterations. Also, the clay fraction was separated from the whole-rock Boom Clay at the end of each run and characterized for its mineralogical composition. Thereby, the importance of the mineral matrix to buffer the alkaline attack and the role of organic matter to protect clay minerals were also addressed. The results indicate that the degree of geochemical perturbation in Boom Clay is dependent on the initial pH of the applied solution together with the nature of the major cation in the reactant fluids. The higher the initial pH of the media, the stronger its interaction with Boom Clay. No major non-clay mineralogical alteration of the Boom Clay was detected, but dissolution of kaolinite, smectite and illite occurred within the studied experimental conditions. The dissolution of clays is accompanied by the decrease in the layer charge, followed by a decrease in the cation-exchange capacity. The highest TOC values coincide with the highest total elemental concentrations in the leachates, and correspondingly, the highest dissolution degree. However, no quantitative link could be established between the degree of organic matter decomposition and clay dissolution.     

Immobilization of Ni by Al-modified montmorillonite: A novel uptake mechanism

The sorption capacity of montmorillonite clay minerals for small cations, such as Ni²⁺, can be greatly enhanced by modifying the clay mineral with Al(III). In this study, the mechanisms of Ni uptake by Al-modified montmorillonite were studied using extended x-ray absorption fine structure (EXAFS) spectroscopy of powders and polarized EXAFS spectroscopy of self-supporting clay films to delineate the binding structure of Ni formed as a function of the reaction conditions. Analysis of powder EXAFS spectra of wet pastes, collected from Ni-treated Al-modified montmorillonites reacted at pH 5-8, 25°C or 80°C (to accelerate the reaction process), and reaction times ranging from 1 month to 9 yrs, showed that Ni was surrounded on average by 6 O atoms at a distance of 2.05 Å and 6 Al atoms at 3.01 Å, suggesting the incorporation of Ni into a gibbsite-like structure. Only at pH 8, Ni-containing precipitates were congruently formed. Polarized EXAFS spectroscopy of self-supporting Ni-reacted Al-modified montmorillonite clay films showed a pronounced angular dependency of the spectra of the Ni-doped gibbsite, indicating that the orientation of this Ni-doped gibbsite coincided with the layering of the montmorillonite. Data analysis suggested that Ni is included slightly above and below the vacant octahedral sites of the postulated interstitial gibbsite monolayer. This newly identified mechanism of metal uptake by Al-modified montmorillonite provides a large metal sorption capacity and, because the metal is included in a monolayer gibbsite or gibbsite “islands” formed in the interstitial space of the clay mineral, it potentially leads to a permanent sequestration of the metal from the environment.     

Microstructures and compositional variation in the intravolcanic bole clays from the eastern Deccan volcanic province: Palaeoenvironmental implications and duration of volcanism

Clay minerals associated with intra-volcanic bole horizons of varied colours and thicknesses contain montmorillonite, halloysite and kaolinite, show distinct microstructures and microaggregates. In kaolinite, Fe³⁺ ions substitute for Al³⁺ at octahedral sites. Most of these clays are dioctahedral type, show balance between net layer and interlayer charges. The interstratified illite — smectite (I/S) mixed layers containing variable proportions of montmorillonite. Illite contains sheet-like, well oriented microaggregates. The parallel stacks of chlorite sheets show chlorite/smectite (C/S) mixed layers. Progressive enrichment of Fe and depletion of Al ions with the advancement of kaolinization process is observed. High order of structural and compositional maturity observed in these bole clays, indicate long hiatus between the two volcanic episodes.     

云南腾冲地热区主要蚀变矿物含量与蚀变母岩的关系

腾冲地热区出露有众多热泉泉群,地热活动频繁,岩石发生强烈蚀变,形成的主要蚀变矿物包括高岭石、绢云母、蒙脱石、I/M间层矿物、石英和蛋白石。主要蚀变矿物的种类和含量受蚀变母岩性质的控制,花岗质砂砾岩和花岗岩形成高岭石,玄武岩形成伊利石和蒙托石,安山岩中发育硅化作用。泥化作用增强的趋势是安山岩→花岗岩→玄武岩→花岗质砂砾岩。由于花岗质砂砾岩在热区内广泛分布,通过蚀变作用形成了有经济价值的高岭土矿床。     

粘土矿物在油气初次运移中作用的探讨

本文在大量实际分析资料基础上,总结出我国含油气盆地中蒙脱石的转化类型,并讨论了它们在油气初次运移中的作用。在蒙脱石向伊利石连续转化型的盆地中,矿物转化对初次运移有明显作用;在蒙脱石向伊利石不连续转化或少量转化类型盆地中,由于矿物转化与生油期不相匹配或可转化的蒙脱石含量太少,对初次运移的作用不明显;在蒙脱石无转化和缺少蒙脱石的盆地中,基本不存在蒙脱石的转化过程,因而对初次运移不起作用。