The kinetics of chlorite dissolution

A model for the dissolution of chlorite has been developed based on fast ligand assisted proton attack of the alumina tetrahedra within the alumina-silica lattice followed by slower dissolution of the remnant silica lattice. While the rate determining step is within the silica dissolution regime, the rate is a function of the H⁺ and Al³⁺ concentrations and the dominant aqueous Al species. Individual rates may be described by a generic rate equation applicable across the spectrum of Al species:

     

Polarized EXAFS of biotite and chlorite

Polarized Fe K-edge EXAFS spectra of biotite and chlorite monocrystals have been recorded using the Synchrotron radiation at LURE, Orsay. The anisotropic contribution of the nearest cation shell is clearly brought to evidence. In the limit case in which the electric field vector would be disposed normal to the layer plane, the contribution of cations belonging to octahedral sheets would not be sampled. At this orientation, the Fe-(Si, Al) contribution is selected and it is then possible by extrapolation of spectra taken at lower angles to extract phase and amplitude functions associated with this atomic pair. Two applications of this experiment are presented, (i) In chlorite, the amplitude of the Fe-(Si, Al) contribution is directly proportional to the distribution of Fe atoms between the TOT layer and the interlayer. It is found that about 25 percent of the iron is located in the interlayer. (ii) In the biotite structure, the contribution of the (Si, Al) shell is almost constant for a wide range of Fe-containing phyllosilicates and can be subtracted from their EXAFS spectrum. Such an operation will permit a more accurate analysis of the reality of solid solutions.     

绿泥石片岩各向异性特性研究

为研究十堰地区片岩的各向异性特性,开展了武当群绿泥石片岩长方体试样的单轴压缩和圆盘试样的间接拉伸试验,探讨了试样各向异性的力学特性和在不同受力状态下的变形破裂特性,揭示了不同变形破裂的力学机制。研究表明,武当群绿泥石片岩具有明显的各向异性性质,平行片理方向强度高,垂直片理方向强度低。该片岩特殊的定向排列片束状构造和片理间的弱胶结作用,致使不同方向上的破坏特征具有明显差异,其力学机制也不相同。在压应力作用下,泊松效应容易引起平行片理面的张拉劈裂和压杆失稳,垂直片理方向容易发生片理面间的剪切破坏。在同一方向上强度具有一致性,即平行片理面抗压和抗拉强度均较垂直片理面强度大。由于片理面间的抗拉承载力极低,在小角度劈裂荷载下,容易发生张拉劈裂和拉剪破坏,因此,实际工程中应尽可能避免片理面间的受拉破坏和沿片理的拉剪破坏。研究结果可以为隧道、边坡支护加固和防水处理提供参考。     

Alpha particle haloes in chlorite and cordierite

Summary Effects of the impact of natural long-term irradiation with alpha particles in one chamosite and one cordierite sample were characterised in detail using electron microprobe, Raman microprobe, optical absorption spectroscopy (cordierite only), and transmission electron microscopy (TEM; cordierite only) analysis. In both cases, the impact of ⁴He cores (alpha particles) that were emitted from actinide-bearing mineral inclusions has caused the formation of radiation damage haloes in the host mineral. These haloes have maximum radii of about 33 μm (chamosite) and 47 μm (cordierite). They show notably changed optical properties, i.e., intensified absorption of light as recognised by brown (chamosite) and yellow (cordierite) pleochroism and enhanced or even anomalous interference colours. In spite of the significant disturbance of their short range order, alpha particle haloes are characterised by generally low degrees of structural radiation damage. This is indicated by rather moderate broadening of vibrational bands and, in the case of cordierite, apparently undisturbed electron diffraction patterns in the TEM. Intensive damage, virtually close to an amorphous state, was only found in cordierite up to a few tens of nanometres away from actinide-bearing inclusions. This damage is mainly assigned to recoils of heavy nuclei upon emission of an alpha particle, which have particle trajectory lengths that are three orders of magnitude shorter than those of the alpha particles. Similar to observations on biotite, alpha particle haloes in chamosite and cordierite as observed in the optical microscope may be considered as representative of a very early stage of the metamictisation process.     

Identification of chlorite and chlorite-related minerals in sediments

A scheme is presented for the identification and classification of chlorite and related minerals in sediments which is mainly based on X-ray characteristics of the orginal sample and the sample heated at 350°C and treated with K⁺ and with glycerol. Examples are given. It is emphasized that additional data about clay mineral genesis, electron microscopy, infrared spectroscopy and chemical analyses are needed for the ordening of a certain mineral in the proposed scheme. Many names of minerals so far found to occur in the clay separate of sediments proved to be synonymous (52 of a total of 88) and thus should be abandoned. They only give confusion and needlessly increase the many difficulties which already exist in the identification, classification and quantitative determination of this complicated group of minerals of about 36 well defined specimens which may be found in sediments.     

Ni(II) sorption on natural chlorite

Sorption of Ni(II) onto chlorite surfaces was studied as a function of pH (5–10), ionic strength (0.01–0.5 M) and Ni concentration (10⁻⁸–10⁻⁶ M) in an Ar atmosphere using batch sorption with radioactive ⁶³Ni as tracer. Such studies are important since Ni(II) is one of the major activation products in spent nuclear fuel and sorption data on minerals such as chlorite are lacking. The sorption of Ni(II) onto chlorite was dependent on pH but not ionic strength, which indicates that the process primarily comprises sorption by surface complexation. The maximum sorption was at pH ∼ 8 (K_d = ∼10⁻³ cm³/g). Desorption studies over a period of 1–2 weeks involving replacement of the aqueous solution indicated a low degree of desorption. The acid–base properties of the chlorite mineral were determined by titration and described using a non-electrostatic surface complexation model in FITEQL. A 2-pK NEM model and three surface complexes, Chl_OHNi²⁺, Chl_OHNi(OH)⁺ and Chl_OHNi(OH)₂, gave the best fit to the sorption results using FITEQL. The high K_d values and low degree of desorption observed indicate that under expected groundwater conditions, a large fraction of Ni(II) that is potentially leachable from spent nuclear fuel may be prevented from migrating by sorption onto chlorite surfaces.     

57Fe Mössbauer spectroscopic analysis of chlorite

Five chlorite samples have been studied by ⁵⁷Fe Mössbauer spectroscopy at different temperatures. The spectra are consistently described by a superposition of one ferric and three ferrous quadrupole doublets. All hyperfine data exhibit only minor variations from sample to sample, meaning that the structural and electronic properties of chlorite are rather insensitive to compositional changes and local cation disorder. Two of the ferrous doublets are ascribed to cis and trans co-ordinations in the T-O-T layers. The third ferrous doublet is interpreted as being due to ferrous ions in the hydroxide sheets. Its hyperfine parameters are close to those of the former doublets and the observed deviations from the parameter values found for pure brucite are discussed. Approximately 20 to 25 percent of the total iron is situated in the hydroxide sheets. All five chlorites contain about 10 percent Fe³⁺ which is most probably located on octahedral sites. The temperature dependence of the ferrous quadrupole splittings for two chlorites has been interpreted on the basis of the thermal populations of the two lowest electronic states of the Fe²⁺ ions. From this, the deformations of the different octahedral co-ordinations could be estimated.     

Regional retrograde alteration of sub-greenschist facies chlorite to smectite

Dioctahedral smectite is present as a retrograde alteration product of chlorite in Permian-Triassic red slates of the Malaguide Complex in Sierra de Espuña (Betic Cordillera). Mineral assemblages and textures, illite crystallinity indices, and fluid inclusion data indicate sub-greenschist facies conditions that reached at least 180°C in the higher-grade tectonic unit of the Malaguide Complex, preceding formation of smectite. Smectite, having K as the dominant interlayer cation, occurs ubiquitously intercalated with trioctahedral chlorite as thin packets of layers and as individual layers that commonly change to chlorite along layers. Although some chlorite is typically homogeneous and trioctahedral, much chlorite shows signs of alteration and has compositions corresponding to different degrees of smectite contaimination. The incompatibility of metamorphic grade with the occurrence of smectite, the general association of chlorite and smectite, and the textural relations collectively show that dioctahedral smectite is derived through replacement of trioctahedral chlorite. Such replacement occurs on a regional basis and demonstrates that caution must be used in interpreting the occurrence of smectite in pelites as being due to prograde processes. Alteration of trioctahedral chlorite under oxidizing conditions due to introduction of phreatic water after uplift of the Betic Cordillera is proposed as the cause of formation of smectite.     

A recalibration of the chlorite—biotite—muscovite geobarometer

Massonne (1981) reported experiments on the composition of muscovite in the assemblage phlogopite-muscovite-K-feldspar-quart. The experimental data have been used to recalculate the equilibrium conditions for the chlorite-muscovite-biotite-quartz assemblage which has been proposed as a new geobarometer by Powell and Evans (1983).The recalculated equilibrium shows much steeperdp/dT slopes than those calculated by Powell and Evans (1983). Nevertheless, with the necessary precautions it is suggested that the barometer may provide the critical user with valuable pressure estimates.     

A new chlorite geothermometer for diagenetic to low-grade metamorphic conditions

The evolution of chlorite composition with temperature (and pressure) serves as basis to a number of chlorite chemical thermometers, for which the oxidation state of iron has been recognised as a recurrent issue, especially at low temperature (T). A new chlorite geothermometer that does not require prior Fe³⁺ knowledge is formulated, calibrated on 161 analyses with well-constrained T data covering a wide range of geological contexts and tested here for low-T chlorites (T < 350 °C and pressures below 4 kbar). The new solid-solution model used involves six end-member components (the Mg and Fe end-members of ‘Al-free chlorite S’, sudoite and amesite) and so accounts for all low-T chlorite compositions; ideal mixing on site is assumed, with an ordered cationic distribution in tetrahedral and octahedral sites. Applied to chlorite analyses from three distinct low-T environments for which independent T data are available (Gulf Coast, Texas; Saint Martin, Lesser Antilles; Toyoha, Hokkaido), the new pure-Fe²⁺ thermometer performs at least as well as the recent models, which require an estimate of Fe³⁺ content. This relief from the ferric iron issue, combined with the simple formulation of the semi-empirical approach, makes the present thermometer a very practical tool, well suited for, for example, the handling of large analytical datasets—provided it is used in the calibration range (T < 350 °C, P < 4 kbar).     

Thermodynamic properties of chlorite and berthierine derived from calorimetric measurements

In the context of the deep waste disposal, we have investigated the respective stabilities of two iron-bearing clay minerals: berthierine ISGS from Illinois [USA; (Al_0.975FeIII_0.182FeII_1.422Mg_0.157Li_0.035Mn_0.002)(Si_1.332Al_0.668)O₅(OH)₄] and chlorite CCa-2 from Flagstaff Hill, California [USA; (Si_2.633Al_1.367)(Al_1.116FeIII_0.215Mg_2.952FeII_1.712Mn_0.012Ca_0.011)O₁₀(OH)₈]. For berthierine, the complete thermodynamic dataset was determined at 1 bar and from 2 to 310 K, using calorimetric methods. The standard enthalpies of formation were obtained by solution-reaction calorimetry at 298.15 K, and the heat capacities were measured by heat-pulse calorimetry. For chlorite, the standard enthalpy of formation is measured by solution-reaction calorimetry at 298.15 K. This is completing the entropy and heat capacity obtained previously by Gailhanou et al. (Geochim Cosmochim Acta 73:4738–4749, 2009) between 2 and 520 K, by using low-temperature adiabatic calorimetry and differential scanning calorimetry. For both minerals, the standard entropies and the Gibbs free energies of formation at 298.15 K were then calculated. An assessment of the measured properties could be carried out with respect to literature data. Eventually, the thermodynamic dataset allowed realizing theoretical calculations concerning the berthierine to chlorite transition. The latter showed that, from a thermodynamic viewpoint, the main factor controlling this transition is probably the composition of the berthierine and chlorite minerals and the nature of the secondary minerals rather than temperature.     

考虑硬化软化和剪胀特性的绿泥石片岩力学模型

绿泥石片岩是一种典型的软岩,开挖过程中出现的围岩大变形和塌方对工程安全危害极大。为了深入研究绿泥石片岩的力学特征并建立其合理的力学模型,首先进行了不同围压下的三轴压缩试验,并考虑应力状态对塑性演化的影响,定义了新的内变量;分析了凝聚力和内摩擦角随内变量的演化规律,结果表明,凝聚力先近似呈线性减小,而后近似呈抛物线递减至残余破坏;而内摩擦角一直近似呈抛物线递增;研究了绿泥石片岩的剪胀特性,分析了剪胀角随内变量演化规律,结果表明,剪胀角与内摩擦角呈相反的演化趋势。考虑硬化、软化和剪胀特性,建立了绿泥石片岩的力学模型,对室内三轴压缩试验结果的模拟分析表明,该力学模型可以较好地描述绿泥石片岩的硬化、软化规律和剪胀等性质,为工程安全性分析提供了基本的力学模型,对于类似软岩力学性质的研究也具有重要的参考意义。     

碎屑岩储集层中绿泥石包膜的研究现状*

绿泥石包膜在国内外碎屑岩储集层中常有发现,其对石英次生加大的抑制及对储集层物性的影响一直是国内外学者的研究热点。本文回顾了绿泥石包膜的研究历史,总结了其研究成果,包括微观赋存状态、形成时间和机理、控制因素、对石英次生加大的抑制和对储集层物性的影响等。结果表明:(1)储集层中绿泥石包膜主要偏富铁,具连续生长的双层结构,符合“Ostwald”熟化过程,始于早期富铁黏土包膜,早成岩期转化为平行或斜切颗粒表面的内层包膜,逐渐向外生长为垂直颗粒表面的孔隙衬里绿泥石,并可在埋藏成岩过程持续生长;(2)富含铁镁矿物的火山物质(火山岩岩屑和火山灰)及暗色矿物(黑云母和角闪石等)是形成绿泥石包膜的主要物质来源,并主要富集在三角洲入海(湖)的高能水动力相带,如三角洲前缘水下分流河道及河口坝等沉积微相中,烃类充注影响孔隙衬里绿泥石的生长形态;(3)中低温环境绿泥石包膜明显抑制石英次生加大的生长,高温环境抑制效果减弱;(4)绿泥石包膜的发育有利于粒间孔隙的保护,但易降低孔隙喉道的连通性。最后指出了绿泥石包膜在目前研究中存在的问题和今后的研究趋势。     

Deformation microstructures of olivine and chlorite in chlorite peridotites from Almklovdalen in the Western Gneiss Region,southwest Norway,and implications for seismic anisotropy

Chlorite peridotites from Almklovdalen in southwest Norway were studied to understand the deformation processes and seismic anisotropy in the upper mantle. The lattice preferred orientation (LPO) of olivine and chlorite was determined using electron backscattered diffraction (EBSD)/scanning electron microscopy. A sample with abundant garnet showed [100] axes of olivine aligned sub-parallel to lineation, and [010] axes aligned subnormal to foliation: A-type LPO. Samples rich in chlorite showed different olivine LPOs. Two samples showed [001] axes aligned sub-parallel to lineation, and [010] axes aligned subnormal to foliation: B-type LPO. Two other samples showed [100] axes aligned sub-parallel to lineation, and [001] axes aligned subnormal to foliation: E-type LPO. Chlorite showed a strong LPO characterized by [001] axes aligned subnormal to foliation with a weak girdle subnormal to lineation. Fourier transform infrared (FTIR) spectroscopy of the specimens revealed that the olivines with A-type LPO contain a small amount (170 ppm H/Si) of water. In contrast, the olivines with B-type LPOs contain a large amount (340 ppm H/Si) of water.

The seismic anisotropy of the olivine and chlorite was calculated. Olivine showed Vp anisotropy of up to 3.8% and a maximum Vs anisotropy of up to 2.7%. However, the chlorite showed a much stronger Vp anisotropy, up to 21.1%, and a maximum Vs anisotropy of up to 31.7%. A sample with a mixture of 25% of olivine and 75% of chlorite can produce a Vp anisotropy of 14.2% and a maximum Vs anisotropy of 22.9%. Because chlorite has a wide stability field at high pressure and high temperature in the subduction zone, the strong LPO of chlorite can be a source of the observed trench-normal or trench-parallel seismic anisotropy in the mantle wedge as well as in subducting slabs depending on the dipping angle of slab in a subduction zone where chlorite is stable.     

Distribution of chlorite and kaolinite in eastern Atlantic sediments off North Africa

Chlorite in the Atlantic sediments is predominantly derived from the Atlas Mountains, kaolinite originates in the southern Sahara and Sahel zone. These minerals may be used to reconstruct the tracks of two superimposed wind systems (Trade Winds and Harmattan Wind). A modified method for determining relative abundances of chlorite and kaolinite is presented.     

甘肃龙首山碱交代型铀矿床绿泥石特征及意义

绿泥石化是龙首山铀矿床重要的蚀变类型之一。通过对龙首山碱交代型铀矿床的绿泥石等蚀变矿物进行的岩相学和电子探针成分分析研究,确定了龙首山地区绿泥石的化学类型主要为铁镁绿泥石,少数为蠕绿泥石。依据绿泥石成因或与共生矿物的关系,绿泥石可被划分为黑云母蚀变型、长石蚀变型、沥青铀矿共生型和副矿物共生型等4种类型。泥质岩是本区绿泥石的主要原岩类型,是多期次地质作用形成的产物。研究认为,龙首山地区碱交代型铀矿床的成矿过程可表述为矿前期在相对较高温度的热液流体作用下,黑云母发生绿泥石化蚀变,随后热液继续交代长石,形成长石蚀变型绿泥石,进而在成矿期热液温度相对较低的条件下形成与沥青铀矿紧密共生的绿泥石。绿泥石在铀成矿过程中不但活化了花岗岩里的铀,而且还给铀矿化供应了相对良好的积淀环境。     

A chlorite solid solution geothermometer the Los Azufres (Mexico) geothermal system

Chlorite constitutes a major hydrothermal alteration product of metamorphism of andesites, in the active geothermal system of Los Azufres (Mexico). Electron microprobe analyses performed on a set of crystals from each sample show wide variations in composition. Correlation coefficients among chemical constituents were calculated. It is shown that the tetrahedral charge is positively correlated with the octahedral vacancy and negatively with the iron content, and there is almost no correlation with the octahedral aluminium and magnesium content. A procedure is proposed to select end-members and substitution vectors, and to give a general formula for these chlorites.Their formation temperatures are estimated with great accuracy, combining results of microthermometric data on fluid inclusions from gangue minerals of chlorites (quartz, calcite), direct measurements in wells (Kuster equipment), and chemical geothermometers. Correlations between chlorite compositions, range and nature of site occupancy, and temperature are good. Formation temperatures of chlorites range from 130° C to 300° C. As no other thermodynamic parameter varies significantly in the studied field (composition of the host rocks, nature of the geothermal fluids, pressure, ...), these variations of site occupancy (mainly Al(IV) and the octahedral occupancy (6-Al(VI)-(Mg+Fe(2+)) = VAC) are considered mainly as temperature dependent.Molar fractions of each end-member show very different variations with increasing temperature: X-kaolinite decreases, and X-chamosite increases, while X-talc-3 brucite does not show significant change. From these data, activity coefficients and standard state chemical potential of major components, and molar free energy formation of chlorite have been calculated for each temperature of crystallisation.     

The anisotropy of magnetic susceptibility in biotite, muscovite and chlorite single crystals

The anisotropy of magnetic susceptibility (AMS) of single crystals of biotite, muscovite and chlorite has been measured in order to provide accurate values of the magnetic anisotropy properties for these common rock-forming minerals. The low-field AMS and the high-field paramagnetic susceptibility are defined. For the high-field values, it is necessary to combine the paramagnetic deviatoric tensor obtained from the high-field torque magnetometer with the paramagnetic bulk susceptibility measured from magnetization curves of the crystals. This leads to the full paramagnetic susceptibility ellipsoid due to the anisotropic distribution of iron cations in the silicate lattice. The ellipsoid of paramagnetic susceptibility, which was obtained for the three phyllosilicates, is highly oblate in shape and the minimum susceptibility direction is subparallel to the crystallographic c-axes. The anisotropy of the susceptibility within the basal plane of the biotite has been evaluated and found to be isotropic within the accuracy of the instrumental measurements. The degree of anisotropy of biotite and chlorite is compatible with previously reported values while for muscovite the smaller than previously published values. The shape of the chlorite AMS ellipsoid for all the samples is near-perfect oblate in contrast with a wide distribution of oblate and prolate values reported in earlier studies. Reliable values are important for deriving models of the magnetic anisotropy where it reflects mineral fabrics and deformation of rocks.     

Equations for the dissolution reaction rates of montmorillonite,illite, and chlorite

The available experimental data on the dissolution kinetics of montmorillonite, illite, and chlorite were analyzed. The reliability of the data was assessed and possible reasons for discrepancies were discussed. The dissolution rates of the minerals were described by quantitative and qualitative dependencies on various parameters. The quantitative relations were described by various equations, which were proposed in other studies or derived by the author on the basis of the mathematical processing of the raw data. General equations were obtained for the dissolution rate of each of the minerals as a function of temperature, pH, and the degree of saturation of the solution. For the dependencies that were not constrained by experiments, experimental data for structurally similar minerals or theoretical equations were invoked.     

Modification to the crystal structure of chlorite during early stages of its dissolution

Early stage processes of Mg-rich chlorite (clinochlore) dissolution were examined, focusing especially on the structural modification at grain edges during dissolution. Focused ion beam transmission electron microscopy sample preparation was applied to crystals dissolved in a flow-through reaction system at pH 3.0 and 25°C for 31 days. The obtained Si and Mg dissolution rates are −11.49 and −11.14 (logR, mol/(m²/s)), respectively, implying dissolution is non-stoichiometric. TEM-EDX analyses of dissolved samples reveal the development of 20–50-nm thick amorphous zone at an outermost rim with a chemical gradient of Mg, lower towards the solid surface, and Si enrichment in this amorphous zone. Crystalline material is partially interwoven with amorphous one at the interface between the amorphous and crystalline regions. These results indicate that the amorphous zone was produced by selective leaching of cations except for Si. Chlorite dissolution may proceed via the formation and thickening of leached layer as a by-product of release to solution of Si at slightly slower rate than Mg.