Dissolution of basaltic glass in seawater: Mechanism and rate

Basaltic glasses are considered as natural analogues for nuclear waste glasses. Thermodynamic computer codes used to evaluate long term behavior of both nuclear waste and basaltic glasses require the knowledge of the dissolution mechanism of the glass network (congruent dissolution or ion exchange in a residual hydrated structure).The paper presents the results of a series of experiments designed to study the structure and chemical composition of alteration layers formed on the surface of artificial tholeiitic glass altered in artificial seawater. Experiments were performed at 60°C, 1 bar and 350 bars in non-renewed conditions. A natural sample from Palagonia (Sicily) has been studied by electron microscopy and comparison between natural and experimental palagonitic layers is made.The behavior of dissolved silica during experiments, and both the structure and the chemical composition of the palagonitic layers, indicate that they form by precipitation of secondary minerals from solution after a total breakdown of the glassy network, i.e., congruent dissolution of the glass. Hence the dissolution equation necessary for thermodynamic modelling of basaltic glass dissolution in seawater at low temperature must be written as a simple stoichiometric process.For the first 2.10⁵ years of reaction the palagonitic layers do not constitute a diffusional barrier to the mass transfer between the glass and the bulk solution. The growth of these layers is linearly dependent on time.These experiments indicate that the transformation of glass to palagonitic material is not isovolumetric. Hence it is preferable to use Fe or Ti as conservative elements for chemical budget calculations.     

单斜星叶石矿物的穆斯堡尔光谱学研究

本文对产于俄罗斯希宾地区的单斜星叶石进行了不同的温度条件下的穆斯堡尔光谱效应研究,通过在温度分别在298 K,180 K和80 K条件下的分析,发现单斜星叶石由2个Fe~(2 )和1个Fe~(3 )四极双峰组成,并进行了单斜星叶石中的畸变参数包括八面体键角(σ~2)和键长变量(Δ)的计算。但是,在两个畸变参数之间存在着明显的差异,将无法对它们的穆斯堡尔参数和四极双峰进行指派。本文对温度在同质异能位移和四极分裂中的作用进行了探讨,根据通过穆斯堡尔效应和f(Fe~(3 )(O))/f(Fe~(2 )(O))的平均值获得的三价铁对全铁的比值,改写了单斜星叶石的化学式。     

A review on the synthesis and applications of green rust for environmental pollutant remediation

This paper discusses the various approaches to the synthesis of green rust. Green rusts are synthesized by changing the average oxidation state of iron compounds so that the ratio of ferric/ferrous ions is between 0.25 and 0.33. This can be achieved by mixing ferrous and ferric hydroxides, oxidation of ferrous compounds or reduction of ferric compounds. Characterization of the samples with analytical methods such as Mossbauer spectroscopy, X-ray diffraction spectroscopy, scanning electron microscopy, transmission electron microscopy and atomic-force microscopy is discussed. Green rusts have a layered double hydroxide structure, with an interchangeable anion layer and a mixed ferrous–ferric cation layer. This structure can adsorb ions by intercalation or exchange anions with its environment. The cation layer can oxidize, which gives a reducing nature to green rusts. These properties make them excellent candidates for the reduction and immobilization of several inorganic pollutants. Green rusts also have applications in dechlorination of organic compounds and in the synthesis of nanohybrid materials. These environmental and nanochemistry applications are also covered in this paper.     

Iron in a post-glacial lake sediment core; a Mössbauer effect study

The distribution of iron in a 6-m core of post-glacial sediment from an oligotrophic lake (Connistonwater, England) was determined, principally by Mossbauer spectroscopy on dried samples. The immediate post-glacial deposits contain 4.8 wt. % of iron, with a Fe²⁺; Fe³⁺ ratio ～- 4. The iron there is predominantly in the form of chlorite, but there are small amounts in hematite and illite. The distribution of iron is different, and very variable in the recent sediments (~ < 13,000 BP), which contain 25–35 per cent organic matter and 5.2 wt. % of iron relative to the inorganic fraction. Typically half the iron is present there as chlorite, and the rest is ferric, mostly in the form of an amorphous gel which is also present in undried samples. To explain the observed ferrous:ferric profile, it is proposed that the latter includes iron which was once mobile, having been leached from the Fe²⁺-bearing clays under reducing conditions in the soils of the drainage basin, or in the sediment itself. It was subsequently precipitated as ferric hydroxide on contact with the oxic lake water. In contrast, the ferrous iron in the sediments is immobile iron, which remained locked in the chlorite phase of the clay particles as they were carried from soil to sediment intact.All the sediments are rather inhomogeneous. Chlorite, and especially hematite, are mechanically concentrated in pink varves in the immediate post-glacial deposits. In the partly inorganic sediments, the concentration of ferrous iron (chlorite) is approximately uniform, but the ferric content may differ by a factor of five between regions only a few millimeters apart.     

基于Apollo15月壤和普通球粒与碳质球粒陨石模拟实验的太空风化特征产物成因分析

月球、小行星等无大气行星体具有独特的反射光谱太空风化改造特征,其成因主要被归结于纳米级—亚微米级不透明颗粒等太空风化特征产物.本研究结合Apollo 返回月壤样品、普通球粒和碳质球粒陨石样品的模拟实验结果,综合分析了太空风化特征产物的来源和成因,并讨论了其可能的光谱效应.研究结果表明,np-Fe0 (纳米级单质金属铁)是铁镁硅酸盐等矿物经过微陨石轰击引起的气化沉积作用和原位还原作用形成.np-FeNi(纳米级铁镍金属)的成因主要包括FeNi金属和陨硫铁的气化沉积与冲击分散成因.np-FeNiS(纳米级铁镍金属的硫化物)和sm-FeNiS(亚微米级铁镍金属的硫化物)主要形成于陨硫铁的冲击分散过程.上述不透明颗粒是形成月球与S型小行星紫外—近红外波段光谱反射率降低、特征吸收峰减弱和连续统红移等特征的主要原因.气泡结构主要形成于层状硅酸盐等矿物在微陨石轰击过程中的挥发分逃逸,推测是含水量较高的小行星(如Bennu)紫外-近红外波段光谱反射率增加和连续统蓝移等特征的主要成因.实验结果预期对月球与小行星返回样品分析以及反射光谱的太空风化改造特征的解释提供一定的参考.     

The use of water-extractable Cu,Mo, Zn,As, Pb concentrations and automated mineral analysis of flue dust particles as tools for impact studies in topsoils exposed to past emissions of a Cu-smelter

An exploratory study has been conducted to test the utility of automated mineral analysis observations to identify flue dust particles in topsoils exposed for several decades to emissions of a copper smelter. The methods used are readily available in mining countries. To identify the most impacted sites, the Cu, Zn, Pb, Mo and As levels in water and diluted sulphuric acid extractions of four topsoil size fractions (833–495 μm, 246–148 μm; 74–38 μm; <38 μm) were analysed. X-ray diffraction analyses were used to demonstrate the mineralogical degradation of smectite phases when approaching the smelter. Flue dust particles in different states of conservation in topsoils were directly observed by scanning electron microscopy (SEM) aided by energy dispersive detection of X-rays. Qemscan^® scanning of dispersed topsoil preparations (10,000 particles) pinpoints smelter particles by their density; flue dust pearls can be tracked by sorting particles according to their sphericity, clearly identifying them as pyrometallurgical products. When sorting soil particles by mineral groups (e.g. sulphides), an increase in this phase group can be observed when approaching the smelter. SEM resolution limits observations to particles larger than 2–3 μm. Smaller particles can be observed by transmission electron microscopy, although observer experience and the availability of equipment time are essential as is the case for SEM.     

Calibration and Applications of Spinel Equilibria in the System FeO-Al2O3-SiO2

A new thermobarometer, based on the equilibrium: has been calibrated with experiments carried out in the piston-cylinderapparatus. Reversed equilibria were obtained using well-calibrated2.54 cm NaCl furnace assemblies and Ag₈₀Pd₂₀capsules with f_O2bufferedat or near iron-wustite. The equilibrium is located between5.2–5.4, 6.6–6.8, and 8.6–8.8 kb at 880, 940,and 1020?C, respectively, and at 5.2 and 8.8 kb between 865–880and 1020–1030?C, respectively. X-ray refinement data indicate that the hercynite (a = 8.15546?) has approximately 18 per cent inverse character. M?ssbauerspectra reveal that 4 mol per cent of the Fe is ferric (2 percent magnetite component). Broad Mossbauer lines and a Fe²+energy level splitting of 3.7 kJ mol^–1 calculated fromthe Mossbauer spectra are consistent with the X-ray determineddegree of inversion, although no separate octahedral Fe²⁺ spectraldoublet is resolved. Calibration of this equation allows calculation of the equilibrium: Thermobarometers based on the above equilibria are widely applicablein granulite fades rocks and yield pressure/temperature datathat are consistent with other well-calibrated barometers andthermometers.     

The stoichiometric effects of ferric iron substitutions in serpentine from microprobe data

ABSTRACT

Given that secondary magnetite is common in serpentinites, it is clear that serpentinites are oxidized rocks. Questions remain, however, concerning the distribution of ferric iron among magnetite and serpentine minerals and the role of ferric iron-rich serpentine in the formation of secondary magnetite. Direct determination of ferric iron in serpentine is not possible using an electron microprobe. We show, however, that the stoichiometic effects of ferric iron substitutions are detectable, although not quantifiable, by microprobe. First, we demonstrate that for studies that provide both microprobe analyses of major elements of serpentine and Mössbauer analysis of ferric iron, substitution effects are obvious. Next, it is equally clear that the early veins forming at the onset of olivine hydration (type 1 veins) show no indication of the presence of ferric serpentine, although a small amount of ferric ‘brucite’ may occur. Finally, we show that secondary (type 2) veins, which form as the system becomes open to fluids in equilibrium with plagioclase or pyroxene, contain, in addition to significant alumina, stoichiometric indications of ferric iron substitution. The serpentine in these veins is magnesian, usually with Mg#s around 96–98. Thus, even if a significant proportion of this iron is ferric, it comprises only a small fraction of the total ferric iron budget of the rock. Given that reduced iron is known to be abundant in early-formed brucite and early-formed serpentine and given that brucite, in particular, is absent from evolved serpentine veins, we propose that most magnetite in serpentinites forms as a tertiary product via oxidation of brucite.     

Fe3+纳米胶体颗粒的光吸收边蓝移与溶液中Al/Fe比的关系

合成了n（Al）／n（Fe）和碱化度不同的45个聚合氯化铝铁（PAFC）样品,进行了光谱分析,结果显示光吸收边蓝移或红移以及Fe（Ⅲ）羟基氧化物和Al-Fe共聚体纳米胶体颗粒大小分布与溶液的Al／Fe比和碱化度（B=[OH]／[Al＋Fe]）密切相关。电镜观察和电子衍射分析表明：Al（Ⅲ）的加入使Fe（Ⅲ）羟基氧化物和Al-Fe共聚体纳米胶体颗粒变小、有序度降低是造成PAFE光吸收边蓝移和保持胶体颗粒在亚稳定状态下存在的重要原因。当n（Al）／n（Fe）〉8：2后,PAFC溶液中Fe（Ⅲ）羟基氧化物和Al-Fe共聚体胶体主要以〈10m的纳米颗粒形态存在,对应的光谱能级提高到26000cm^-1以上,且各种曰值下Fe^3＋的光谱能级趋于一致。这表明,在大量Al（Ⅲ）存在条件下,PAFE中Fe3^＋的所处的化学环境相似。点能谱分析显示,n（Al）／n（Fe）=4：6的样品中颗粒物的化学计量比最接近AlOOH,FeOOH,溶液的稳定性最差。     

Oxygen Thermobarometry of Orogenic Lherzolite Massifs

The oxidation state has been determined for spinel peridotitesfrom 13 orogenic lherzolite massifs including Beni Bousera,Ronda, and 11 smaller massifs in the French Pyrenees. The oxygenfugacity (f_o2) was calculated for 67 samples from microprobeanalyses using a set of secondary spinel standards to correctthe ferric iron content in the spinels. The utility of thismethod is confirmed by the good agreement between the calculatedvalues and those determined by Mossbauer spectroscopy on 28samples. The spinel peridotites of Ronda and Beni Bousera are relativelyreduced, averaging -11 and -1.5 log units relative to fayalite-magnetite-quartz(FMQ) respectively, which is in agreement with values from abyssalperidotites and mid-ocean ridge basalt (MORB) glasses. The Pyreneanmassifs are relatively oxidized and are intermediate between the abyssal peridotites and continentalxenolith suites. No systematic gradients are observable. Instead,variations of up to 2 log units in f_o2 occur at a localizedscale. This type of variation is also observed for trace elementsand radiogenic isotopes. The harzburgites at Beni Bousera recordthe most reduced conditions. Local oxidation coincides withthe appearance of amphibolc, indicating that metasomatizingfluids or melts are generally oxidized compared with the hostperidotites. Partial re-equilibration in the plagioclase peridotitefades has occurred at Ronda, causing the spinels to become Crrich. Re-equilibration is extremely heterogeneous. Mild oxidationappears to attend the crystallization of fine-grained plagioclase. The similarity in fo₂ values at Beni Bousera and Ronda indicatesa fairly uniform oxidation state at a scale of {small tilde}200 km. This scale of homogeneity is also observed in the Pyrenees,where no significant variation in f_o2 is apparent along 200km of strike in the Northern Pyrenean Zone.     

Oxidation of arsenopyrite and deposition of gold on the oxidized surfaces: A scanning probe microscopy, tunneling spectroscopy and XPS study

We have used ex situ atomic force microscopy (AFM), scanning tunneling microscopy and spectroscopy (STM/STS) and X-ray photoelectron spectroscopy (XPS) to study the surfaces of natural arsenopyrite samples that were electrochemically polarized in 1 M HCl, or leached in acidic solutions containing ferric iron salts, and then reacted with aqueous gold (III) chloride at ambient temperatures. For arsenopyrite oxidized on a positive-going potential sweep, progressively increasing amounts of surface Fe(III)-O and As-O species, and of S/Fe and S/As ratios in a non-stoichiometric sulfidic layer were found. The products formed in the sweep to a potential of 0.6 V (Ag/AgCl) of the passivity region are shaped in about 100 nm protrusions of two sorts, which are arranged in micrometer-size separate areas, while they are largely mixed at higher, “transpassive” potentials. The quantities of surface alteration substances notably decrease after leaching in ferric chloride and ferric sulfate acidic solutions. Passivation of arsenopyrite was suggested to associate with the disordered, metal-deficient surface layer having moderate excess of sulfur rather than with the products of arsenopyrite oxidation. Exposure of arsenopyrite to 10⁻⁵-10⁻³ M (pH 2) solutions results in the deposition of 8-50 nm gold particles; only a small fraction of the gold is present as Au(I)-S species. The electrochemical oxidation at 0.6 V or ageing of arsenopyrite in air promotes the subsequent gold deposition; in contrast, the amount of Au deposited on arsenopyrite that was treated by leaching in ferric chloride and sulfate solutions was about 10 times smaller than with polished arsenopyrite samples. It has been concluded that reducing agents formed as intermediates of arsenopyrite decomposition facilitate the Au⁰ cementation although other factors related to the surface state of the arsenopyrite play a role as well. A decrease in the tunneling current magnitudes with decreasing the Au⁰ particle size has been revealed using STS. This effect along with the increase by 0.2-0.5 eV in the XPS Au 4f binding energies were tentatively ascribed to retarding the electron transitions by emerging electrostatic charge on gold nanoparticles (Coulomb blockade). Possible mechanisms for the effects, and their potential role in the deposition and hydrometallurgy of “invisible” gold are discussed.     

Micro-XANES determination of ferric iron and its application in thermobarometry

Micro-X-ray absorption near-edge structure (XANES) analysis was employed to determine the content of ferric iron in minerals formed in ultrahigh-pressure (UHP) eclogites. It is observed that omphacite and phengite contain significant amounts of Fe³⁺/Fe_tot (0.2–0.6), whereas only very low contents are present in garnet (Fe³⁺/Fe_tot=0.0–0.03), the latter being consistent with results from stoichiometric charge-balance calculations. Furthermore, considerable variations in the Fe³⁺/Fe_tot ratios of omphacite and phengite are observed depending on the textural sites and local bulk chemistry (eclogite and calc-silicate matrix) within one thin section. The oxidation state of isofacial minerals is thus likely to depend on the local fluid composition, which, in the studied case, is controlled by calcareous and meta-basic mineral compositions. These first in-situ measurements of ferric iron in an eclogite sample from the Dabie Shan, E China, are used to recalculate geothermobarometric data. Calculations demonstrate that the temperature during UHP metamorphism was as high as 780 °C, about 80–100 °C higher than previously estimated. Temperatures based on charge balance calculations often give erroneous results. Pressure estimates are in good agreement with former results and confirm metamorphism in the stability field of diamond (43.7 kbar at 750 °C). These P–T data result in a geothermal gradient of ca. 6 °C/km during UHP metamorphism in the Dabie Shan. However, accounting for ferric iron contents in geothermobarometry creates new difficulties inasmuch as calibrations of geothermometers may not be correctable for Fe³⁺ and the actual effect on Mg–Fe²⁺ partitioning is unknown. The present study further shows that micro-XANES is a promising technique for the in situ determination of ferric iron contents without destroying the textural context of the sample: a clear advantage compared to bulk methods.     

Characterization of magnetite particles in shocked quartz by means of electron- and magnetic force microscopy: Vredefort, South Africa

Submicroscopic opaque particles from highly shocked granite-gneisses close to the core of the Vredefort impact structure have been investigated by means of micro-analytical techniques with high spatial resolution such as electron diffraction, orientation contrast imagery and magnetic force microscopy. The opaque particles have been identified as nano- to micro-sized magnetite that occur in several distinct modes. In one sample magnetite occurs along relict planar deformation features (PDFs) in quartz, generally accepted as typical shock lamellae. The magnetite particles along shock lamellae in quartz grains virtually all show uniform crystallographic orientations. In most instances, the groups of magnetite within different quartz grains are systematically misorientated such that they share a subparallel <101> direction. The magnetite groups of all measured quartz grains thus appear to have a crystallographic preferred orientation in space. In a second sample, orientations of magnetite particles have been measured in microfractures (non-diagnostic of shock) of quartz, albite and in the alteration halos, (e.g. biotite grains breaking down to chlorite). The crystallographic orientations of magnetite particles are diverse, with only a minor portion having a preferred orientation. Scanning electron microscopy shows that magnetite along the relict PDFs is invariably associated with other microcrystalline phases such as quartz, K-feldspar and biotite. Petrographic observations suggest that these microcrystalline phases crystallized from locally formed micro-melts that intruded zones of weakness such as microfractures and PDFs shortly after the shock event. The extremely narrow widths of the PDFs suggest that heat may have dissipated rapidly resulting in melts crystallizing relatively close to where they were generated. Magnetic force microscopy confirms the presence of magnetic particles along PDFs. The smallest particles, <5 μm with high aspect ratios 15:1 usually exhibit intense, uniform magnetic signals characteristic of single-domain magnetite. Consistent offsets between attractive and repulsive magnetic signals of individual single-domain particles suggest consistent directions of magnetization for a large proportion of particles. Received: 16 November 1998 / Accepted: 17 May 1999     

Effect of phosphate, silicate, and Ca on the morphology, structure and elemental composition of Fe(III)-precipitates formed in aerated Fe(II) and As(III) containing water

We investigated Fe(III)-precipitates formed from Fe(II) oxidation in water at pH 7 as a function of dissolved Fe(II), As(III), phosphate, and silicate in the absence and presence of Ca. We used transmission electron microscopy (TEM), including selected area electron diffraction (SAED) and energy dispersive X-ray spectroscopy (EDX) to characterize the morphology, structure and elemental composition of the precipitates. Results from our companion X-ray absorption spectroscopy (XAS) study suggested that the oxidation of Fe(II) leads to the sequential formation of distinct polymeric units in the following order: Fe(III)-phosphate oligomers in the presence of phosphate, silicate-rich hydrous ferric oxide (HFO-Si) at high Si/Fe (>0.5) or 2-line ferrihydrite (2L-Fh) at lower Si/Fe (∼0.1-0.5), and lepidocrocite (Lp) in the absence of phosphate at low Si/Fe (<0.1). Results from this study show that the size of the polymeric units increased along the same sequence and that the aggregation of these polymeric units resulted in spherical particles with characteristic surface textures changing from smooth to coarse. The diameter of the spherical particles increased from 15 to 380 nm as the molar ratio (P + Si + As)/Fe(II) in the starting solution decreased and larger spherical particles precipitated from Ca-containing than from Ca-free solutions. These trends suggested that the size of the spherical particles was controlled by the charge of the polymeric units. Spherical particles coagulated into flocs whose size was larger in the presence than in the absence of Ca. Further observations pointed to the importance of Fe(II) oxidation and polymerization versus polymer aggregation and floc formation kinetics in controlling the spatial arrangement of the different polymeric units within Fe(III)-precipitates. The resulting structural and compositional heterogeneity of short-range-ordered Fe(III)-precipitates likely affects their colloidal stability and their chemical reactivity and needs to be considered when addressing the fate of co-transformed trace elements such as arsenic.     

The form,distribution and mobility of arsenic in soils contaminated by arsenic trioxide,at sites in southeast USA

Soils from many industrial sites in southeastern USA are contaminated with As because of the application of herbicide containing As₂O₃. Among those contaminated sites, two industrial sites, FW and BH, which are currently active and of most serious environmental concerns, were selected to characterize the occurrence of As in the contaminated soils and to evaluate its environmental leachability. The soils are both sandy loams with varying mineralogical and organic matter contents. Microwave-assisted acid digestion (EPA method 3051) of the contaminated soils indicated As levels of up to 325 mg/kg and 900 mg/kg (dry weight basis) for FW and BH soils, respectively. However, bulk X-ray powder diffraction (XRD) analysis failed to find any detectable As-bearing phases in either of the studied soil samples. Most of the soil As was observed by scanning electron microscopy, coupled with energy dispersive X-ray spectroscopy (SEM/EDX), to be disseminated on the surfaces of fine-grained soil particles in close association with Al and Fe. A few As-bearing particles were detected in BH soil using electron microprobe analysis (EMPA). Synchrotron micro-XRD and X-ray absorption near-edge structure (XANES) analyses indicated that these As-rich particles were possibly phaunouxite, a mineral similar to calcium arsenate, which could have been formed by natural weathering after the application of As₂O₃. However, the scarcity of those particles eliminated them from playing any important role in As sequestration.     

安徽巢湖凤凰山石炭系黄龙组红色灰岩矿物地球化学特征

安徽巢湖凤凰山晚石炭世黄龙组的地层主体为肉红色生物屑微晶灰岩,顶部为夹灰岩条带的泥岩。矿物学分析显 示,肉红色生物屑微晶灰岩的矿物主要为方解石,含少量针铁矿和赤铁矿。漫反射光谱分析表明,常用的古气候指标“红 度”与灰岩中铁氧化物、氢氧化物的光谱强度具显著的正相关性,而与岩石的全铁含量相关性较低,据此推测铁的氧化物 和氢氧化物是灰岩呈肉红色的重要原因。元素地球化学分析结果显示,黄龙组灰岩相对富Fe,Mn,而贫Co,Ni,在 Al-Fe-Mn,Fe-Mn-(Cu+Co+Ni)以及Cu-Pb-Zn三角判别图上,均靠近或落入热液成因区。综合地球化学特征与前人研究成 果,该文认为巢湖凤凰山黄龙组肉红色灰岩的形成很可能受到海底热液活动的影响。     

几种锡矿物的穆斯堡尔谱研究

本文对我国一些地区的锡石、黄锡矿、辉锑锡铅矿等锡矿物样品进行了化学成分分析、穆斯堡尔谱测试,并利用穆斯堡尔谱方法区分了这些锡矿物中锡的价态。实测结果表明,锡石中的锡全是Sn~(4+)(六配位),黄锡矿中的锡是Sn~(4+)(四配位),辉锑锡铅矿中的锡有Sn~(4+)及少量 的Sn~(2+)。钙铁榴石中的锡是Sn~(4+),它是以类质同像替换方式进入[Y]位替换Fe~(3+)。同时,讨论了同质异能位移值与价态的关系,I.S值的增大顺序为:Sn~(4+)→Sn~0→Sn~(2+)。根据经验公式,估算了一些锡矿物中氧和硫配位基的电负性,     

Scanning electron microscope observation of dislocations in olivine

Dislocations in olivine decorated by oxidation in air were observed with a scanning electron microscope (SEM) using a backscattered electron image (BEI). The decorated dislocations (and grain boundaries) were found to give clear bright images in this mode, indicating an increase of mean atomic number near the dislocation cores (and grain boundaries). This method of dislocation observation has a resolution of ca. 0.1 μm, about an order of magnitude better than optical microscopic observation, and is particularly useful in the study of the overall dislocation distribution of naturally and experimentally deformed olivines with relatively high dislocation densities.     

富水水库中微生物成因的显微针铁矿及其对微量元素的富集

通过对湖北省富水水库坝基渗漏水及其析出物的研究，探讨了现代沉积环境（水库）中显微铁矿物形成的机理及微生物在铁的生物矿化中的作用和意义。对析出物中微量元素的富集特征也进行了初步研究。用化学分析方法测试出坝基渗漏水中阳离子以Ca^2 、Mg^2 、K^ 、Na^ 为主，Fe^2 和Fe^3 含量极少，阴离子以HCO3^-为主。析出物的化学成分以铁的氧化物为主。采用X射线衍射、差热分析、红外光谱和穆斯堡尔谱，以及透射电镜和扫描电镜等测试手段，分析研究了析出物的物相和形貌特征。析出物的主要矿物相为针铁矿、石英、伊利石、蒙脱石和微量方解石，呈弱结晶状态。由析出物中显微针铁矿特殊的形貌特征及其特征的穆斯堡尔谱图推测出富水水库沉积环境中显微针铁矿是由铁细菌形成。ICP－MS测试测试结果表明，析出物中不仅富集了铁，还富集了Yb、Pb、Dy、Zn、Co、Be、Eu、Sm和Tb等微量元素。微量元素的富集是微生物与显微针铁矿共同作用的结果。     

Natural and synthetic leucites studied by solid state 29-Si and 27-Al NMR and 57-Fe Mossbauer spectroscopy

The 29-Si NMR spectra of natural and synthetic leucites (KAlSi₂O₆) are found to contain a number of resonances which are interpreted in terms of the known structure of low-temperature (tetragonal) leucite. Computer simulation of the spectra suggests that the most distorted tetrahedral lattice site T ₁ contains a higher proportion of Al than the other two tetrahedral sites. The occurrence of some ordering of the tetrahedral Si and Al in leucite is confirmed by Mossbauer studies of synthetic iron-containing leucites, including the fully ferric end-member KFeSi₂O₆, in which the three tetrahedral sites can be distinguished. On replacement of about half this Fe by Al, the most distorted of these sites is lost from the spectrum, reflecting the preference of Al for this site. A linear relationship is found between the unit cell dimensions of all these leucites and their iron content.