Microanalysis of Fe3+/ΣFe in oxide and silicate minerals by investigation of electron energy-loss near-edge structures (ELNES) at the Fe M 2,3 edge

The Fe M _2,3-edge spectra of solid solutions of garnets (almandine-skiagite Fe₃(Al_1–xFe_x)₂[SiO₄]₃ and andradite-skiagite (Fe_1–xCa_x)₃Fe₂[SiO₄]₃), pyroxenes (acmite-hedenbergite (Ca_1–xNa_x)(Fe²⁺ _1−xFe³⁺ _x)Si₂O₆), and spinels (magnetite-hercynite Fe(Al_1–xFe_x)₂O₄) have been measured using the technique of parallel electron energy-loss spectroscopy (EELS) conducted in a transmission electron microscope (TEM). The Fe M _2,3 electron energy-loss near-edge structures (ELNES) of the minerals exhibit a characteristic peak located at 4.2 eV and 2.2 eV for trivalent and divalent iron, respectively, prior to the main maximum at about 57 eV. The intensity and energy of the pre-edge feature varies depending on Fe³⁺/ΣFe. We demonstrate a new quantitative method to extract the ferrous/ferric ratio in minerals. A systematic relationship between Fe³⁺/ΣFe and the integral intensity ratio of the main maximum and the pre-edge peak of the Fe M _2,3 edge is observed. Since the partial cross sections of the Fe M _2,3 edges are some orders of magnitude higher than those of the Fe L _2,3 edges, the Fe M _2,3 edges are interesting for valence-specific imaging of Fe. The possibility of iron valence-specific imaging is illustrated by Fe M _2,3-ELNES investigations with high lateral resolution from a sample of ilmenite containing hematite exsolution lamellae that shows different edge shapes consistent with variations in the Fe³⁺/ΣFe ratio over distances on the order of 100 nm. Received: 14 April 1998 / Revised, accepted: 8 March 1999     

An infrared spectroscopic and single-crystal X-ray study of malayaite, CaSnSiO5

Powder infrared spectroscopy and X-ray diffraction techniques on single crystals were used to study the thermal behaviour of malayaite, CaSnSiO₅. Infrared spectra show a discontinuity in the temperature evolution of phonon frequencies and absorbance near 500 K. However, crystal structure data collected at 300, 450, 550, 670, and 750 K show no evidence of a symmetry-breaking phase transition and no split positions. The most obvious change with heating is a tumbling motion of the SnO₆ octahedra and an increase of the anisotropic displacement factors of Ca. The thermal evolution of the mean-square vibrational amplitude of the Ca atom shows a pronounced change in slope near 500 K. The evidence suggests that the 500 K anomaly in malayaite is more similar in character to the 825 K (β-γ) transition as opposed to the 496 K (α-β) transition in synthetic titanite. Received: 26 March 1998 / Revised, accepted: 23 December 1998     

Calculation of reflectance values for two models of texture of carbon materials

This paper presents two models of texture of carbon materials possessing porosity. For both models, R_MAX, R_INT and R_MIN values of reflectance have been calculated by modified Ting's 3A method [Ting, F.T.C., 1978. Petrographic techniques in coal analysis. In: C. Karr (Ed.), Analytical Methods for Coal and Coal Products, Vol. 1. Academic Press, New York, 1978, pp. 3–25]. It has been found that the reflectance indicating surface (RIS) for the studied models of texture changes from a biaxial negative up to a biaxial positive one (the type A texture) depending on the shape and size of pores. In particular case, for the type B texture and the isometry of pores, a uniaxial negative RIS is merely obtained.     

悬沙水体不同波段反射比的分布特征及悬沙量估算实验研究

我国沿岸、河口附近水域具有高悬沙量的特点.悬沙的分布、扩散、沉降过程影响港口、航道水深的维持,影响生态环境.利用卫星遥感资料开展悬沙遥感及定量算法研究,在我国已取得诸多成果,挥才兴等[1]提出了几种悬沙定量的经验和半经验模式.“七五”攻关分别对黄河口和长江口提出了对数模式、线性分析模式和双峰比模式,Ma等[2]将模式识别方法应用于悬沙遥感.90年代后期,国际上陆续发射多颗海色卫星,我国也计划发射海色卫星,为有效地利用海色卫星资料,进一步开展悬沙定量算法及传感器谱段选择研究具有重要意义.     

秋季太湖悬浮物高光谱估算模型

2004年10月,在太湖设置67个采样点,现场测量了水体遥感反射比、后向散射系数和辅助参数,实验室分析了水体的悬浮物浓度和水色要素吸收系数.本文在对遥感反射比光谱分析的基础上,比较了几种水体遥感反射比光谱估算悬浮物浓度的方法,结果发现广泛应用的带比值项的算法,虽然可以应用于太湖总悬浮物浓度估算,但是普遍存在相对误差较高的弱点.通过对光谱的分析,确定了750hm单波段算法的参数,并提出了利用近红外812nm波峰高度来估算水体悬浮物的方法.文中还详细阐述了为什么比值算法等在太湖水体悬浮物浓度估算中相对误差比较高,并解释了利用近红外估算精度高的原因,并指明以上算法在遥感应用中的优点和不足,以及现实水体(水质)遥感对现有遥感器配置和遥感算法的需求.     

海带对重金属的吸附位点研究

用甲醇、甲醛处理海带藻粉,对其吸附重金属时羧基和氨基的作用进行研究,经藻粉的红外光谱及吸附实验的分析结果表明;羧基和氨基均参入了吸附过程;化学处理降低了重金属的吸附量。     

大洋多金属结核中铁锰质矿物拉曼光谱特征初探

拉曼光谱是一种快速无损的分析手段,它既可观察样品的显微结构构造,也可分析样品的成分和结构。为了丰富多金属结核的岩石矿物学特征,文章对西太平洋某海山区的多金属结核样品进行了X射线粉末衍射分析和拉曼光谱分析。X射线分析结果显示该区域样品主要含有水羟锰矿、钡镁锰矿、斜长石、钙十字沸石和石英,显微构造主要有纹层状构造、柱状构造、树枝状构造、充填构造等。通过分析对比潮湿样品和烘干样品铁锰质矿物的拉曼特征谱峰,得出结核中水羟锰矿的特征谱峰位于490 cm~(-1)、570 cm~(-1)和626 cm~(-1)附近,钡镁锰矿的特征谱峰则位于640 cm~(-1)附近,与陆地上对应矿物的特征拉曼谱峰不同。结核中的钡镁锰矿结构不稳定,经过风干或者抛磨后部分产生相变,不同显微结构中,相变情况不同。经与RRUFF数据库比对,识别出钙十字沸石、斜长石等自形晶,多分布于结核最内层,往结核外层总体减少。矿物微晶多见铁锰质矿物微晶和钙十字沸石微晶,铁锰质矿物绕其向外生长。     

四川米易海塔地区混合岩型铀矿流体包裹体特征

混合岩型铀矿是康滇地轴上最有希望取得找矿突破的铀矿类型,海塔地区的铀矿化即是该类型铀矿的典型代表。本文针对区内的长英质脉矿石、富晶质铀矿石英脉矿石和含矿热液石英脉中的石英流体包裹体进行了研究。结果表明,海塔地区混合岩型铀矿的成矿作用可分为2个阶段:早期混合岩化热液成矿阶段为高温、中低盐度流体,流体包裹体均一温度集中在380~540℃,盐度变化范围为16.15%~23.18%NaCl eqv,是区内铀成矿的主要阶段;晚期热液叠加改造成矿阶段为中低温、低盐度流体,流体包裹体均一温度集中在140~220℃,盐度变化范围为5.56%~23.18%NaCleqv,是区内富铀矿的形成阶段。流体包裹体的气相成分测试表明,长英质脉矿石石英包裹体中以CH4、CO2为主,其次为H2O和N2;而富晶质铀矿石英脉及含矿热液石英脉石英包裹体中以H2为主,部分含有CO2、CH4、H2O。氢、氧同位素研究表明,早期混合岩化成矿阶段的成矿流体可能为岩浆水与变质水的混合,而晚期热液叠加改造成矿阶段成矿流体中可能有大气降水的加入。     

Provenance discrimination of fine sediments by mid-infrared spectroscopy: Calibration and application to fluvial palaeo-environmental reconstruction

Determining sediment provenance allows a better understanding of fluvial palaeo-dynamics, and identifying involved watersheds, at broad spatio-temporal scales. Conventional approaches for source identification are usually based on the physical, mineralogical, geochemical, magnetic or isotopic properties of sediments. Rapid, non-destructive and, in well-established contexts, highly accurate, mid-infrared spectroscopy is an alternative method for investigating sediment sources. The present research objectives are: (i) to use the mid-infrared spectroscopy method to discriminate the provenance of fine sediments, by applying discriminant analysis on a large set of reference samples from three different watersheds in the Upper Rhine area (associated with the Rhine, Ill and Vosges tributaries); (ii) to clarify whether the provenance spectra signatures are influenced by riverine depositional contexts (bars versus banks) and, to some extent, by grain size and/or high organic matter content; and (iii) to apply the mid-infrared spectroscopy – discriminant analysis method to a study of fluvial palaeo-dynamics and determine the provenance of palaeo-channel infillings. Three main sedimentary sources, divided into eight sub-categories, have been characterized by 196 modern reference samples from 78 collecting sites. Discriminant analysis displayed a strong separating power by classifying correctly the origin of samples without any inter-group overlap, independently from the geomorphological context (bar or bank) and associated slight changes in organic matter contents or grain size. Mid-infrared spectroscopy – discriminant analysis investigations of the palaeo-channel infill, complemented by radiocarbon dates and mineralogical data, allowed reconstructing general trends for the local morpho-sedimentary dynamics over the last ca 12 millennia.     

A new occurrence of retrogressed eclogite from the Sanbagawa belt of southwest Japan and its significance

The present paper reports, for the first time, the occurrence of an omphacite‐bearing mafic schist from the Asemi‐gawa region of the Sanbagawa belt (southwest Japan). The mafic schist occurs as thin layers within pelitic schist of the albite–biotite zone. Omphacite in the mafic schist only occurs as inclusions in garnet, and albite is the major Na phase in the matrix, suggesting that the mafic schist represents highly retrogressed eclogite. Garnet grains in the sample show prograde‐type compositional zoning with no textural or compositional break, and contain mineral inclusions of omphacite, quartz, glaucophane, barroisite/hornblende, epidote and titanite. In addition to the petrographic observations, Raman spectroscopy and focused ion beam system–transmission electron microscope analyses were used for identification of omphacite in the sample. The omphacite in the sample shows a strong Raman peak at 678 cm^?1, and concomitant Raman peaks are all consistent with those of the reference omphacite Raman spectrum. The selected area electron diffraction pattern of the omphacite is compatible with the common P2/n omphacite structure. Quartz inclusions in the mafic schist preserve high residual pressure values of Δω₁ > 8.5 cm^?1, corresponding to the eclogite facies conditions. The combination of Raman geothermobarometries and garnet–clinopyroxene geothermometry gives peak pressure–temperature (P–T) conditions of 1.7–2.0 GPa and 440–540 °C for the mafic schist. The peak P–T values are comparable to those of the schistose eclogitic rocks in other Sanbagawa eclogite units of Shikoku. These findings along with previous age constraints suggest that most of the Sanbagawa schistose eclogites and associated metasedimentary rocks share similar simple P–T histories along the Late Cretaceous subduction zone.