水铁矿的结构、组成及环境地球化学行为

水铁矿广泛分布于水、土壤、沉积物和生物体中,它具有大比表面积和高表面活性,控制和影响着环境中某些污染物质和营养元素的形态、迁移和转化。此外,它也是环境中其他晶质铁(氢)氧化物形成的前驱体。然而,人们对水铁矿在环境中的作用和重要性的认识还存在不足,主要表现在：(1)水铁矿通常被混淆为无定形铁氢氧化物或水合铁氧化物,环境中的水铁矿因难以分离和进行定量分析而使其含量常被低估;(2)水铁矿结晶弱,结构表征困难,对其在环境中的分布、组成、结构及性质的认识较欠缺。水铁矿以弱晶质的纳米颗粒形式存在,其XRD(X射线衍射)线少且宽、强度弱。根据衍射线的条数可将水铁矿分为结晶较弱的2 线水铁矿(2LFh)和结晶较好的6 线水铁矿(6LFh)。目前,普遍接受的水铁矿化学式为Fe5HO8·4H2O,但大量实验表明H2O不是水铁矿结构的必要成分,且容易被吸附的外来物质取代。有人提出水铁矿是一种二元结构,中心为八面体配位Fe,表面以四面体配位Fe为主,这有待论证。最近,通过PDF(配对分布函数)研究水铁矿的结构表明,理想水铁矿结构包含20%四面体配位Fe和80%八面体配位Fe,化学式为Fe10O14(OH)2。然而, 不少学者对这一新的水铁矿结构模型提出了质疑。对近年来水铁矿的分布、组成、结构和环境行为方面的研究和存在的问题进行了综述和讨论,并且对水铁矿的未来研究方向进行了展望。     

Analysis of cation distribution in the octahedral sheet of dioctahedral 2:1 phyllosilicates by using inverse Monte Carlo methods

An inverse Monte Carlo (MC) method was developed to determine the distribution of octahedral cations (Al³⁺, Fe³⁺, and Mg²⁺) in bentonite illite–smectite (I–S) samples (dioctahedral 2:1 phyllosilicates) using FT–IR and ²⁷Al MAS NMR spectroscopies. FT–IR allows determination of the nature and proportion of different cation pairs bound to OH groups measuring the intensities of OH-bending bands. ²⁷Al MAS NMR data provide information about cation configuration because ²⁷Al MAS NMR intensity depends on Fe distribution. MC calculations based on FT–IR data alone show Fe segregation by short-range ordering (Fe clusters within 9 to 15?Å from a given Fe atom). Fe segregation increases with illite proportion. MC calculations based on IR and ²⁷Al NMR simultaneously yield similar configurations in which Fe clusters are smaller. The latter calculations fail to build appropriate cation distributions for those samples with higher number of illite layers and significant Fe content, which is indicative of long-range Fe ordering that cannot be detected by FT–IR and ²⁷Al MAS NMR. The proportion of Mg–Mg pairs is negligible in all samples, and calculations, in which the number of Mg atoms, as second neighbours, is minimised, create appropriate configurations.     

古盐度对塔北隆起泥岩中粘土矿物组合和绿泥石成分的影响

粘土矿物组合和绿泥石成分常被用来讨论盆地沉积物的成岩作用和埋藏古温度。许多沉积盆地的研究结果显示,泥 岩和页岩中的粘土矿物组合和绿泥石的成分与埋藏深度/温度有关。但也见有例外的现象存在。文中主要探讨了新疆塔北隆 起泥岩中的粘土矿物组合和绿泥石成分的特征,以及与盆地古盐度的关系。研究结果表明：（1）在塔北隆起泥岩中,埋藏 深度2777.37~4604.41m,地层单位为J1-N2的粘土矿物组合为I+Chl和I+Chl+Ka; 埋藏深度5071.52~5299.37m,地层单位为 T1的粘土矿物组合为R0I/S+I+Chl和R0I/S+Chl。（2）研究区的成岩绿泥石为Ⅱb型铁镁绿泥石,其成分特征主要表现为： ①配位八面体中阳离子的占位数为11.532(总平均值);②ⅥAl含量明显大于ⅣAl含量;③（Fe+Mg）为4.016（总平均值）;④ Si/Al比值>1。（3）根据研究区盐类矿物的分布范围以及古盐度的数据,讨论了古盐度对该区粘土矿物组合和绿泥石成分的 影响,指出古盐度是影响本区粘土矿物组合和绿泥石成分变化的主要因素。用古盐度解释了<5000m深度的粘土矿物组合 中不含无序伊/蒙混层（R0I/S）矿物,而>5000m深度粘土矿物组合中含有无序伊/蒙混层（R0I/S）矿物的异常现象。揭示了 在一定的深度范围（2777.37~4405.27m）,一定的古盐度条件下（Sr/Ba比值≥0.4,并有盐类矿物出现）,绿泥石成分受到 古盐度的制约,并且随着古盐度的增高,绿泥石成分中的Al、ⅣAl、Na、Na2O、Al/Si随之增高,而Si/Al则随之降低。由 绿泥石成分温度计获得的温度值也伴随着古盐度的增高而增高。因此,由绿泥石成分温度计所计算的温度不能代表本区实 际埋藏的古温度。（4）研究区内绿泥石成分中的SiO2和FeO与母岩的对应成分之间有一定的相关性,其SiO2绿泥石与SiO2岩石、 FeO绿泥石与FeO岩石呈负相关的线性关系,并且这种关系在古盐度的干扰下也未受到影响。     

Distribution of Fe in the octahedral sheet of trioctahedral micas by polarized EXAFS

The distribution of Fe atoms within the octahedral sheet of a series of trioctahedral micas has been investigated by polarized Fe K-edge EXAFS spectroscopy. Single crystals have been oriented in the X-ray beam with the layer plane at 35° with respect to the electric field vector. At this “magic angle”, contributions to the EXAFS spectrum of nearest cation shells are equal to those recorded on a completely disoriented powder. The average number of Fe and Mg cations surrounding each Fe atom has been determined and compared with those deduced from NMR spectra. It is shown that the distribution of Fe atoms is not random, the deviation from this distribution depending on the fluorine content. The agreement between these independent results proves the reliability of the structural information deduced from EXAFS and NMR spectra as well as the usefulness of these two methods in analyzing the local distribution of cations in minerals.     

蒙脱石中铁的赋存状态的研究

通过对徐闻、三水、高州等地五个样品的Ｘ射线衍射分析，化学全分析，分析它们为含铁量不同的蒙脱石，层间可交换阳离子主要为Ｃａ＾２＋。几个样品穆斯堡尔谱表明铁主要以Ｆｅ＾３＋的形式存在，含铁量较高的样品ＸＧＡ、ＸＳＡ、ＳＳ的谱可以拟合出Ｆｅ＾３＋的二对四级双峰，表明铁在蒙脱石中占据两种不等同的八面体位置。     

Crystal chemistry of Fe3+-bearing (Mg,Fe)SiO3 perovskite: a single-crystal X-ray diffraction study

Magnesium silicate perovskite is the predominant phase in the Earth’s lower mantle, and it is well known that incorporation of iron has a strong effect on its crystal structure and physical properties. To constrain the crystal chemistry of (Mg, Fe)SiO₃ perovskite more accurately, we synthesized single crystals of Mg_0.946(17)Fe_0.056(12)Si_0.997(16)O₃ perovskite at 26 GPa and 2,073 K using a multianvil press and investigated its crystal structure, oxidation state and iron-site occupancy using single-crystal X-ray diffraction and energy-domain Synchrotron Mössbauer Source spectroscopy. Single-crystal refinements indicate that all iron (Fe²⁺ and Fe³⁺) substitutes on the A-site only, where \( {\text{Fe}}^{ 3+ } /\Upsigma {\text{Fe}}\sim 20\,\% \) based on Mössbauer spectroscopy. Charge balance likely occurs through a small number of cation vacancies on either the A- or the B-site. The octahedral tilt angle (Φ) calculated for our sample from the refined atomic coordinates is 20.3°, which is 2° higher than the value calculated from the unit-cell parameters (a = 4.7877 Å, b = 4.9480 Å, c = 6.915 Å) which assumes undistorted octahedra. A compilation of all available single-crystal data (atomic coordinates) for (Mg, Fe)(Si, Al)O₃ perovskite from the literature shows a smooth increase of Φ with composition that is independent of the nature of cation substitution (e.g., \( {\text{Mg}}^{ 2+ } - {\text{Fe}}^{ 2+ } \) or \( {\text{Mg}}^{ 2+ } {\text{Si}}^{ 4+ } - {\text{Fe}}^{ 3+ } {\text{Al}}^{ 3+ } \) substitution mechanism), contrary to previous observations based on unit-cell parameter calculations.     

岩浆母质对蚀变粘土矿物的约束:以贵州新民剖面P-T界线附近火山灰层为例

目前对于粘土层中伊蒙混层矿物的堆垛结构、单元层含量与岩浆母质及环境条件关系的了解等,仍然十分匮乏.一定沉积环境下火山灰层中粘土矿物组合、以及伊蒙混层堆垛方式精细结构特征,可能记录了沉积(包括成岩作用) 环境对火山物质蚀变产物的影响.采用X射线衍射(XRD)、扫描电子显微镜(SEM)、元素地球化学分析、氧同位素分析方法等方法,对贵州新民深海相二叠系-三叠系(P-T) 界线附近蚀变火山灰层的地球化学特征、粘土矿物精细结构特征等进行了深入研究.结果表明,4个火山灰粘土层均含有2种具有R3结构、不同混层比的伊蒙混层矿物相,且均出现粘土矿物集合体取代原先的火山碎屑颗粒或在颗粒表面生长的现象,粘土矿物形成于沉积-成岩阶段因而其泥质结构被保留;样品XM-5-1和XM-5-2的Fe3+原子数分别为0.16和0.17个且具有明显Eu负异常和较低的K₂O含量,而XM-5-3和XM-5-4的Fe3+原子数均为0.14个,说明相对于前2个粘土层,后2个的岩浆母质更加偏向酸性而表现为成岩蚀变程度更强.粘土矿物的氧同位素组成为17.3‰~18.1‰,与常温下蒙脱石与海水的平衡数值相近,表明粘土矿物化学组成与海底成岩蚀变环境有关,而不同火山灰层的粘土矿物学特征则主要取决于岩浆岩母质以及成岩蚀变强度.      

Clay Minerals in an Active Hydrothermal Field at Iheya‐North‐Knoll,Okinawa Trough

Iheya‐North‐Knoll is one of the small knolls covered with thick sediments in the Okinawa Trough back‐arc basin. At the east slope of Iheya‐North‐Knoll, nine hydrothermal vents with sulfide mounds are present. The Integrated Ocean Drilling Program (IODP) Expedition 331 studied Iheya‐North‐Knoll in September 2010. The expedition provided us with the opportunity to study clay minerals in deep sediments in Iheya‐North‐Knoll. To reveal characteristics of clay minerals in the deep sediments, samples from the drilling cores at three sites close to the most active hydrothermal vent were analyzed by X‐ray diffraction, scanning electron microscope and transmission electron microscope. The sediments are classified into Layer 0 (shallow), Layer 1 (deep), Layer 2 (deeper) and Layer 3 (deepest) on the basis of the assemblage of clay minerals. Layer 0 contains no clay minerals. Layer 1 contains smectite, kaolinite and illite/smectite mixed‐layer mineral. Layer 2 contains chlorite, corrensite and chlorite/smectite mixed‐layer mineral. Layer 3 is grouped into three sub‐layers, 3A, 3B and 3C; Sub‐layer 3A contains chlorite and illite/smectite mixed‐layer mineral, sub‐layer 3B contains chlorite/smectite and illite/smectite mixed‐layer minerals, and sub‐layer 3C contains chlorite and illite. Large amounts of di‐octahedral clay minerals such as smectite, kaolinite, illite and illite/smectite mixed‐layer mineral are found in Iheya‐North‐Knoll, which is rarely observed in hydrothermal fields in mid‐ocean ridges. Tri‐octahedral clay minerals such as chlorite, corrensite and chlorite/smectite mixed‐layer mineral in Iheya‐North‐Knoll have low Fe/(Fe + Mg) ratios compared with those in mid‐ocean ridges. In conclusion, the characteristics of clay minerals in Iheya‐North‐Knoll differ from those in mid‐ocean ridges; di‐octahedral clay minerals and Fe‐poor tri‐octahedral clay minerals occur in Iheya‐North‐Knoll but not in mid‐ocean ridges.     

The crystal chemistry of pumpellyite: An X-ray Rietveld refinement and 57Fe Mössbauer study

Pumpellyite of the general formula W₈X₄Y₈-Z₁₂O_56-n(OH)_n contains Fe, Al and Mg in two crystallographically different octahedral sites. Three different pumpellyite samples covering the known compositional field from Al- to Fe-rich have been studied to determine the valence state and intracrystalline partitioning of the Fe cations between the two independent octahedral sites. Fe⁺² and Fe⁺³ cation partitioning is interpreted on the basis of results obtained by ⁵⁷Fe Mössbauer spectroscopy at 293 and 77 K and from Rietveld structure analysis performed on powder X-ray diffraction data. Pumpellyite from low-grade metamorphic rocks typically contains a majority of iron in the Fe⁺³ oxidation state, which is found in the smaller and less symmetrical octahedral Y-site. Fe⁺² was also present in all pumpellyite samples studied and it is located in the larger and more symmetrical octahedral X-site.     

Palygorskite from cave sediments: case study from Wadi Haqil,United Arab Emirates

The x-ray powder diffraction identification of clay minerals both in bulk samples and in separated clay fraction confirmed the presence of palygorskite in samples of cave sediments from Wadi Haqil (the western slopes of Musandam Mountains; Ras Al-Khaimah Emirate, UAE). Samples contain quartz, gypsum, smectite, kaolinite, calcite, and palygorskite, some of them chlorite, illite, feldspars, and goethite. Calcite dominates in most samples; smectite prevails in clay fraction. After heating, the 001 reflection of chlorite shifts to higher diffraction angles and its intensity decreases; these features indicate that the chlorite represent a Fe-dominant species. Unit-cell dimensions of major phases as refined by the Rietveld method are in agreement with literature data. Chemical composition of palygorskite was derived from unit-cell dimensions as follows: MgO content is 11–14 wt% and Al₂O₃ 10–13 wt%. Clay mineralogy is only hard to ascertain from the scanning electron microscope (SEM) images even after being combined with the energy-dispersive spectrometer data. The SEM was also used to characterize gypsum grains; they often display flow deformation features. Studied cave sediments represent palygorskite-bearing weathering products and desert soils re-deposited from the cave surroundings by slope processes and wind and/or surface runoff. The mixture with other clay minerals, quartz, feldspars, etc. supports this interpretation. Fine-grained quartz fraction is probably wind-blown. Gypsum and calcite are the precipitates (crusts and/or cements), although gypsum can also be re-deposited from omnipresent gypsum-cemented surface sediments.     

The geochemistry of iron in Recent tidal-flat sediments of the Wash area,England: a mineralogical,Mössbauer,and magnetic study

Undisturbed core samples of Recent sediments from the Wash tidal flats, East Anglia, England, obtained using a Delft corer, were studied with special reference to the diagenesis and geochemical behaviour of iron. The Mössbauer effect in ⁵⁷Fe was used to monitor the distribution of Fe between different phases as a function of depth, together with the magnetic mineralogy and palaeomagnetic properties.The cores consist of, successively downwards: 0.36 m brown clay; 1.5 m finely laminated silts and fine sands, and 7.14 m homogeneous fine sands. The dominant minerals are quartz, feldspar, calcite and clay minerals, and chemical analysis for Al, Si, Mg, Mn, Ca, Fe, Na, K showed variations closely linked to lithological changes. Illite is the most abundant clay mineral (mean 48%), followed by mixed layer illite-montmorillonite and montmorillonite, kaolinite and chlorite. Chlorite is the major iron-bearing clay mineral and represents 4 to 10% of the <2 μm fraction throughout the core. Sulphide minerals are present throughout the core, including framboidal pyrite.Computer fit analysis of the Mössbauer spectra of best quality showed contributions from Fe²⁺ and Fe³⁺ in clay minerals (essentially chlorite), low-spin Fe²⁺ in pyrite, and magnetically ordered iron in greigite (Fe₃S₄). Systematic variations, as a function of sample depth, indicate a relative increase in the amount of Fe in pyrite at the expense of the clay minerals.Magnetite and titanium-bearing magnetite are the carriers of natural magnetic remanence in these sediments.The direction and intensity of natural remanence in the samples compare well with the known secular variation of the Earth's magnetic field derived from the historic-archaeomagnetic record and this enables the samples to be dated and sedimentation rates to be determined (1.5 mm yr^?1 for the upper 2 m and ~7.7 mm yr^?1 for the lower 7 m).     

Crystal chemistry of ferric iron in (Mg,Fe)(Si,Al)O<Subscript>3</Subscript> majorite with implications for the transition zone

Fifteen samples of (Mg,Fe)SiO₃ majorite with varying Fe/Mg composition and one sample of (Mg,Fe)(Si,Al)O₃ majorite were synthesized at high pressure and temperature under different conditions of oxygen fugacity using a multianvil press, and examined ex situ using X-ray diffraction and Mössbauer and optical absorption spectroscopy. The relative concentration of Fe³⁺ increases both with total iron content and increasing oxygen fugacity, but not with Al concentration. Optical absorption spectra indicate the presence of Fe²⁺–Fe³⁺ charge transfer, where band intensity increases with increasing Fe³⁺ concentration. Mössbauer data were used in conjunction with electron microprobe analyses to determine the site distribution of all cations. Both Al and Fe³⁺ substitute on the octahedral site, and charge balance occurs through the removal of Si. The degree of Mg/Si ordering on the octahedral sites in (Mg,Fe)SiO₃ majorite, which affects both the c/a ratio and the unit cell volume, is influenced by the thermal history of the sample. The Fe³⁺ concentration of (Mg,Fe)(Si,Al)O₃ majorite in the mantle will reflect prevailing redox conditions, which are believed to be relatively reducing in the transition zone. Exchange of material across the transition boundary to (Mg,Fe) (Si,Al)O₃ perovskite would then require a mechanism to oxidize sufficient iron to satisfy crystal-chemical requirements of the lower-mantle perovskite phase.     

Iron isotope systematics in estuaries: The case of North River, Massachusetts (USA)

Recent studies have suggested that rivers may present an isotopically light Fe source to the oceans. Since the input of dissolved iron from river water is generally controlled by flocculation processes that occur during estuarine mixing, it is important to investigate potential fractionation of Fe-isotopes during this process. In this study, we investigate the influence of the flocculation of Fe-rich colloids on the iron isotope composition of pristine estuarine waters and suspended particles. The samples were collected along a salinity gradient from the fresh water to the ocean in the North River estuary (MA, USA). Estuarine samples were filtered at 0.22 μm and the iron isotope composition of the two fractions (dissolved and particles) were analyzed using high-resolution MC-ICP-MS after chemical purification. Dissolved iron results show positive δ⁵⁶Fe values (with an average of 0.43 ± 0.04‰) relative to the IRMM-14 standard and do not display any relationships with salinity or with percentage of colloid flocculation. The iron isotopic composition of the particles suspended in fresh water is characterized by more negative δ⁵⁶Fe values than for dissolved Fe and correlate with the percentage of Fe flocculation. Particulate δ⁵⁶Fe values vary from −0.09‰ at no flocculation to ∼0.1‰ at the flocculation maximum, which reflect mixing effects between river-borne particles, lithogenic particles derived from coastal seawaters and newly precipitated colloids. Since the process of flocculation produces minimal Fe-isotope fractionation in the dissolved Fe pool, we suggest that the pristine iron isotope composition of fresh water is preserved during estuarine mixing and that the value of the global riverine source into the ocean can be identified from the fresh water values. However, this study also suggests that δ⁵⁶Fe composition of rivers can also be characterized by more positive δ⁵⁶Fe values (up to 0.3‰) relative to the crust than previously reported. In order to improve our current understanding of the oceanic iron isotope cycling, further work is now required to determine the processes controlling the fractionation of Fe-isotopes during continental run-off.     

57Fe M?ssbauer spectroscopy study of organic rich sediments (source rocks) from test well CT-1, Chinnewala structure of Jaisalmer basin, India

~(57)Fe M?ssbauer spectroscopic study was carried out on the organic rich sedimentary samples collected at different depth intervals from newly drilled test well Chinnewala Tibba-1(CT-1) located in Jaisalmer Petroliferous basin India. It is found that iron is mainly distributed in high spin Fe3tand Fe2tstate in clay minerals. The plot of Fe2t/(Fe2tt Fe3t) indicates the presence of poor redox conditions in the samples.Results obtained are also compared with those already reported in the literature. This comparison shows that there may exist a correlation between prospecting of the basin, the redox environment in sediments and the nature of iron bearing minerals distributed in the sedimentary sequence.     

Evaluation of redox-active iron sites in smectites using middle and near infrared spectroscopy

Redox processes of structural Fe in clay minerals play an important role in biogeochemical cycles and for the dynamics of contaminant transformation in soils and aquifers. Reactions of Fe(II)/Fe(III) in clay minerals depend on a variety of mineralogical and environmental factors, which make the assessment of Fe redox reactivity challenging. Here, we use middle and near infrared (IR) spectroscopy to identify reactive structural Fe(II) arrangements in four smectites that differ in total Fe content, octahedral cationic composition, location of the negative excess charge, and configuration of octahedral hydroxyl groups. Additionally, we investigated the mineral properties responsible for the reversibility of structural alterations during Fe reduction and re-oxidation. For Wyoming montmorillonite (SWy-2), a smectite of low structural Fe content (2.8 wt%), we identified octahedral AlFe(II)-OH as the only reactive Fe(II) species, while high structural Fe content (>12 wt%) was prerequisite for the formation of multiple Fe(II)-entities (dioctahedral AlFe(II)-OH, MgFe(II)-OH, Fe(II)Fe(II)-OH, and trioctahedral Fe(II)Fe(II)Fe(II)-OH) in iron-rich smectites Ölberg montmorillonite, and ferruginous smectite (SWa-1), as well as in synthetic nontronite. Depending on the overall cationic composition and the location of excess charge, different reactive Fe(II) species formed during Fe reduction in iron-rich smectites, including tetrahedral Fe(II) groups in synthetic nontronite. Trioctahedral Fe(II) domains were found in tetrahedrally charged ferruginous smectite and synthetic nontronite in their reduced state while these Fe(II) entities were absent in Ölberg montmorillonite, which exhibits an octahedral layer charge. Fe(III) reduction in iron-rich smectites was accompanied by intense dehydroxylation and structural rearrangements, which were only partially reversible through re-oxidation. Re-oxidation of Wyoming montmorillonite, in contrast, restored the original mineral structure. Fe(II) oxidation experiments with nitroaromatic compounds as reactive probes were used to link our spectroscopic evidence to the apparent reactivity of structural Fe(II) in a generalized kinetic model, which takes into account the presence of Fe(II) entities of distinctly different reactivity as well as the dynamics of Fe(II) rearrangements.     

Distribution and Influence of Iron Phases on the Physico—Chemical Properties of Phyllosilicates

Clay minerals from different Cretaceous stratigraphic successions of Egypt were investigated using XRD,DTA,dissolution analysis(DCB),IR,Moessbauer and X-band Electron Spin Resonance(ESR) spectroscopies.The purity of the samples and the degree of structural order were determined by XRD.The location of Fe in the octahedral sheet is characterized by absorption bands at-875cm^-1 assigned as Al-OH-Fe which is present after chemical dissolution of free iron.The Moessbauer spectra of these clays sow two doublets with isomer shift and quadrupole splitting typical of octahedral coordinated Fe^3 ,in addition to third doubler with hyperfine parameter typical of Fe^2 in the spectra of Abu-Had kaolinite (H)sample.6-lines magnetic hyperfine components which are consistent with those of hematite are confirmed in the spectra of both Isel and Rish kaolinite samples.Goethite was confirmed by both IR and DTA.Multiple nature of ESR of these clays suggested structural Fe in distorted octaedral symmetry and as non-structural Fe.Little dispersion and low swelling indices as well as incomplete activaiton of investigated montmorillonite samples by NaCO3 appear to be due to incomplete disaggregation of montmorillonite particles.This can be explained by the ability of Fe-gel to aggregate the montmorillonite into pseudo-particles and retard the rigid-gel structure.However,extraction of this ferric amorphous compound by dithonite treatment recovers the surface properties of the montmorillonite samples.On the other hand,amounts and site occupation of Fe associated with kaolinite samples show a negative correlation with the parameters used to describe the degree of crystalline perfection,color,brightness and vitrification range of these kaolinite samples.     

The CaGeO3–Ca3Fe2Ge3O12 garnet join: an experimental study

Germanate garnets are often used as isostructural analogues of silicate garnets to provide insight into the crystal chemistry and symmetry of the less accessible natural garnet solid solutions. We synthesised two series of germanate garnets at 3 GPa along the join^VIIICa₃^VI(CaGe)^IVGe₃O₁₂–^VIIICa₃^VIFe₂^IVGe₃O₁₂ at 900 °C and 1,100 °C. Samples with compositions close to the CaGeO₃ end-member consist of tetragonal garnet with a small amount of triclinic CaGe₂O₅. Samples with nominal compositions between X_Fe=0.4 and 1.0 consist of a mixture of tetragonal and cubic garnets; whereas, single-phase cubic garnets were obtained for compositions with X_Fe>1.2 (X_Fe gives the iron content expressed in atoms per formula unit, and varies between 0 and 2 along the join). Run products which were primarily single-phase garnet were investigated using Mössbauer spectroscopy. Spectra from samples synthesised at 1,100°C consist of one well-resolved doublet that can be assigned to Fe³⁺ in the octahedral site of the garnet structure. A second doublet, present primarily in samples synthesised at 900°C, can be assigned to Fe²⁺ at the octahedral sites of the garnet structure. The relative abundance of Fe²⁺ decreases with increasing iron content. Transmission electron microscopy analyses confirm this tendency and show that the garnets are essentially defect-free. The unit-cell parameters of tetragonal ^VIIICa₃^VI(CaGe)^IVGe₃O₃ garnet decrease with increasing synthesis temperature, and the deviation from cubic symmetry becomes smaller. Cubic garnets show a linear decrease of unit-cell parameter with increasing iron content. The results are discussed in the context of iron incorporation into ^VIIIMg₃^VI(MgSi)^IVSi₃O₃ majorite.     

安徽官山两种坡缕石粘土的成分与红外吸收谱

本文采用多种成分分析手段对官山两种不同颜色坡缕石全粘土进行了研究。全粘土湿化学分析扣除SiO2含量计算得到的坡缕石阳离子数与电子探针获得的阳离子数一致。配位八面体阳离子计算表明，粉红色坡缕石为三八面体矿物，灰白色坡缕石是介于三八面体矿物和二八面体矿物间的中间类型。X射线粉末衍射的K值法对全粘土矿物定量分析有着较高的精度，同时用电子探针波谱可准确测定坡缕石粘土的成分。官山两种不同颜色含坡缕石的全粘土红外吸收谱能反映其中坡缕石的吸收谱特征。对X射线光电子能谱研究表明两种不同颜色的坡缕石中的铁主要是Fe^3 ，这与全岩湿化学分析的结果是一致的，同时也还可以作为电子探针成分分析的补充。     

Mössbauer studies of structural features in tourmaline of various genesis

Nuclear gamma ray (Mössbauer) spectroscopy (ngr) was used to examine 114 samples of tourmaline from different deposits. The absorption curve shape of the ngr spectra was found to depend not only on tourmaline composition, but also on the character of cation distribution in the crystal structure. The complex superpositional nature of the spectra corresponds to a statistical distribution of iron ions, whereas a minimum number of doublets is observed in an ordered distribution of these ions in the structure. The existence of nonequivalent Fe sites with statistical cation distribution in Y and Z positions was confirmed by experiments on iron oxidation in tourmaline, temperature studies of quadrupole splitting, and probability analysis of formation of nonequivalent sites in accordance with the tourmaline structure. We established experimentally that iron ions in Y positions have a lower ionization potential than in Z positions. The coefficient of iron oxidation in tourmaline, the occupancy of crystallographic positions, and the nature of cation distribution in the structure are features permitting identification of the particular genetic type to which the test sample belongs.     

墨铜矿的穆斯堡尔谱特征

墨铜矿是典型的异类矿物结构基元层间层矿物．在其结构中，Ｆｅ可占据硫化物层中四次配位和氢氧化物层中六次配位两种位置。本文通过穆斯堡尔谱研究，确定了墨铜矿的穆斯堡尔谱谱型，并认为高自旋的Ｆｅ２＋占据四次配位位置，与Ｃｕ离子一起可能呈无序占位，配位环境的对称性较低，谱参数为：ＩＳ＝０．４２－０．４８ｍｍ／ｓ、ＱＳ＝０．８１－１．２８ｍｍ／ｓ及Ｈｉ约为２４０ＫＯｅ；低自旋的Ｆｅ３＋占据六配位位置，ＩＳ值为０．３２－０．３６ｍｍ／ｓ、ＱＳ值为０．４４－０．５９ｍｍ／ｓ。