Polarized EXAFS, distance-valence least-squares modeling (DVLS), and quantitative texture analysis approaches to the structural refinement of Garfield nontronite

This paper reports on the new application of polarized extended X-ray absorption fine structure (P-EXAFS) spectroscopy to fine-grained layer silicates taking the Garfield nontronite as a case study. Up to now application of P-EXAFS to structural studies of layer silicates has been restricted to single phyllosilicate crystals (Manceau et al. 1988; Manceau et al. 1990), but we show here that P-EXAFS can rigorously be applied to self-supporting clay films without loss of spatial resolution. The quantitative analysis of P-EXAFS requires however the preparation of highly oriented clay films, the orientation distribution of which can be assessed by texture goniometry. The Fe K-edge linear dichroism measurements were simulated by ab initio EXAFS modeling performed on a nontronite cluster whose structure was refined by distance-valence least-squares calculations. It is shown that ab initio modeling quantitatively accounts for the angular dependence of experimental EXAFS spectra. These calculations allowed for the identification of the fundamental character of single- and multiple-scattering paths of the photoelectron, and the structural interpretation of all spectral features observed up to 6.5?Å for the in-plane and out-of-plane radial structure functions of nontronite. In practice, P-EXAFS measurements allow the determination of the flattening angle of Fe(O,OH)₆ octahedra, cations distribution in the octahedral sheet with an enhanced sensitivity, and differentiation between dioctahedral and trioctahedral structures.     

The distribution of [O/Na] in globular clusters

The results of [O/Na] abundance modelling in globular clusters NGC 2808 and NGC 6752 are presented. An evolutionary scenario that is able to reproduce the characteristic observational peculiarities of the [O/Na] distribution function for the stars is proposed, which assumes that the source of the observed chemical anomalies is slow winds from massive rotating stars. The peculiarities of the chemical compositions of globular clusters can be explained in amodel with partialmixing of the stellar-wind material and the surrounding interstellar gas; i.e., second-generation stars are born in the vicinity of individual massive first-generation stars, from the heterogeneously distributed material ejected from their surfaces.     

Electron Density distribution and bonding in silicates

This paper summarizes the recent results of the investigation of bonding in silicates obtained by precision X-ray diffraction. The experimental electron density distribution is compared with theoretical electron density maps calculated for model silicate molecules. The characteristic features of the chemical bonds in ortho-, ring-, chain- and framework silicates are discussed.     

中国二八面体含铝蒙皂石矿物化学和晶体化学的特征

通过对我国６４个二八面体含铝蒙皂石矿物化学及晶体化学数据的统计分析，研究了它们的矿物化学及晶体化学的基本特征，并得出八面体组分是影响蒙皂石矿物学及物理化学性质的主要因素，在此基础上，利用ＡｌＡｌ－ＡｌＦｅ－ＡｌＭｇ三角图划分了我国二八面体含铝蒙皂石的晶体化学类型，并对原分类图进行了模式化处理，使ＡｌＡｌ－ＡｌＦｅ－ＡｌＭｇ图更具实际意义，蒙皂石的阳离子交换容量与晶体化学模型有对应性，并受八面体三价     

Polytype and polymorph identification of finely divided aluminous dioctahedral mica individual crystals with SAED. Kinematical and dynamical electron diffraction

This work investigates the potential of selected-area electron diffraction (SAED) for the polytype and polymorph identification of finely divided K-bearing aluminous dioctahedral mica. Individual mica crystals may indeed differ by their layer-stacking sequence and by the inner structure of their octahedral sheets (polytypic and polymorphic variants, respectively). This diversity of natural mica is commonly considered to be responsible for their morphological variety. The present article thus analyzes the intensity distribution between hk0 beams as a function of the crystal structure and thickness. The comparison of ED calculations with experimental diffraction data shows that predicted dynamical effects are not observed for finely divided dioctahedral mica. The influence of different structure defects on calculated intensities is analyzed, and their widespread occurrence in natural mica is hypothesized to be responsible for the limitation of dynamical diffraction effects. SAED may thus be used to identify the structure of individual dioctahedral mica crystals using the kinematical approximation to simulate and qualitatively interpret the observed intensities.     

Cathodoluminescence (CL) and electron paramagnetic resonance (EPR) studies of clay minerals

Summary ?Sheet silicates of the serpentine–kaolin-group (serpentine, kaolinite, dickite, nacrite, halloysite), the talc–pyrophyllite-group (talc, pyrophyllite), the smectite-group (montmorillonite), and illite (as a mineral of the mica-group) were investigated to obtain information concerning their cathodoluminescence behaviour. The study included analyses by cathodoluminescence (CL microscopy and spectroscopy), electron paramagnetic resonance (EPR), X-Ray diffraction (XRD), scanning electron microscopy (SEM) and trace element analysis. In general, all dioctahedral clay minerals exhibit a visible CL. Kaolinite, dickite, nacrite and pyrophyllite have a characteristic deep blue CL, whereas halloysite emission is in the greenish-blue region. On the contrary, the trioctahedral minerals (serpentine, talc) and illite do not show visible CL. The characteristic blue CL is caused by an intense emission band around 400 nm (double peak with two maxima at 375 and 410 nm). EPR measurements indicate that this blue emission can be related to radiation induced defect centres (RID), which occur as electron holes trapped on apical oxygens (Si–O centre) or located at the Al–O–Al group (Al substituting Si in the tetrahedron). Additional CL emission bands were detected at 580 nm in halloysite and kaolinite, and between 700 and 800 nm in kaolinite, dickite, nacrite and pyrophyllite. Time-resolved spectral CL measurements show typical luminescence kinetics for the different clay minerals, which enable differentiation between the various dioctahedral minerals (e.g. kaolinite and dickite), even in thin section. Received December 3, 2001; revised version accepted February 27, 2002     

SAED and HRTEM Investigation of Palygorskite

The microstructure of palygorskite from Longwang Mountain of Xuyu County, Jiangsu Province, was studied by energy dispersive X-ray analysis （EDX）, selected-area electron diffraction （SAED） and high-resolution transmission electron microscopy （HRTEM）. The average composition of the palygorskite studied is （Si7.38A10.62） （A10.96Fe^3＋ 0.62Mg2.86 0.56）Ca0.03K0.06O20（OH）2（OH2）4, which is rich in Mg. Several SAED patterns from a single crystal of palygorskite were obtained with different zone axes. The polymorphs （monoclinic and orthorhombic） are unequivocally distinguished by distant interplanar angles, even though they possess similar sets of d-values. High-resolution images of three principal zones （[010], [100] and [110]） were obtained. The lattice fringes on HRTEM images along [010] have spacings of 0.319 nm. These fringes are interpreted as periodic alterations of two tetrahedral （T） sheets and one octahedral （O） sheet （-TT-O-TT-O-）. We have directly observed trioctahedral and dioctahedral individual palygorskite particles along [100]. They are all presented as dark lines along [001], but the width of dark lines corresponding to trioctahedral crystals （0.913 nm） is twice that of the dioctahedral ones （0.456 nm）. This is because the trans.sites are occupied by cations in trioctahedral palygorskite. The width of dark lines along [110] is 1.024 nm, a bit thinner than the theoretical spacing （1.044 nm）. This is because water molecules quickly leave the structure upon the irradiation by the electron beam.     

用红外吸收光谱确定层状硅酸盐中羟基键的方向

层状硅酸盐样品用于红外二色性研究,当射线的电场矢量与振动的偶极矩方向成一角度时,这吸收与角度成比例,当某振动的偶极矩与电场矢量平行时,产生最大吸收,而这两矢量彼此垂直时将不产生吸收。在云母和有关晶体中可看到,在二八面体组成中,在改变电场矢量时倾斜OH团的OH振动强度保持不变,而与在三八面体组成中垂直于解理面方向的八面体OH团相比,当层状定向颗粒方向改变时显示强度大大增加,由此能获得层状硅酸盐OH键的方向,在晶体结构分析中能提供有价值的信息。     

Mineral composition of the fine-dispersed fractions of loess and soil processes developed in them

Of the stable indications of elementary soil processes those are to be identified which are taking place in the fine-dispersed fractions of soil by transformations of layer silicates and primarily of interstratified formations.Instrumental detection of transformations in the fine-dispersed material and of its migration along paleosol profiles allows a comparison with changes in recent soils and a judgement about the conditions of paleosol formation. This presumption is supported by data on the mineral composition of the fine-dispersed fractions of the Mikulino interglacial soils as a product of the first phase of pedogenesis within the Mezin loess- paleosol complex (Morozova et al. 1979) and, in general, of the loess-paleosol sequence developed above the ground moraine of the Don glacier tongue containing paleosols formed in the Early, Middle and Late Pleistocene (Velichko et al. 1965).     

Interstratification and other reaction microstructures in the chlorite-berthierine series

 Transmission electron microscopy (TEM) results show there is a series of periodically and nonperiodically interstratified structures composed of berthierine and chlorite layers in low-temperature “chlorite” that is one of the alteration products of granulite-facies Archean ironstone from the eastern border of the Beartooth Mountains, Montana. An antiphase domain structure suggests that the interstratified structures are intermediate transformation products formed by reaction from berthierine (serpentine structure) to chlorite. Periodically interstratified structures consisting of chlorite (C) and serpentine-like (S) (or berthierine) layers include (CS), (CCS), (CCCS), (CCCCS), and (CCCCCCS). The layer sequences in interstratified chlorite-berthierine are indicative of the reaction mechanisms that produce the interstratified structures (e.g., crystallization from solution or solid-state transformation). The reaction from berthierine to chlorite is crystallographically much like a cell-preserved phase transformation, even though it is highly reconstructive. Berthierine can be considered a polymorph of the Fe-rich chlorite mineral chamosite, with berthierine as the los-temperature phase. Interstratification and integrowths in the chlorite-berthierine series may be common phenomena in low-temperature layer silicates resembling chlorite. Although such relations are difficult to recognize from chemical analyses or powder X-ray diffraction patterns, they can be observed readily with TEM method. Received: 25 April 1995/Accepted 5 April 1996     

GEOCHEMISTRY OF THE PLIOCENE SHOSHONITIC ROCKS FROM OIYUG BASIN, CENTRAL TIBET

GEOCHEMISTRY OF THE PLIOCENE SHOSHONITIC ROCKS FROM OIYUG BASIN, CENTRAL TIBET     

Siderite layers in the fresh-water Neogene sediments of Vietnam

Siderites forming beds and lenses in the Neogene lacustrine—swampy sediments of the Rinh Chua Formation (northern Vietnam) are considered in detail. Results of the mineralogical and chemical study of siderites and host terrigenous–clayey siltstones are reported. New analytical data characterize the composition and structure of microbiomorphic (bacterial) bodies in the siderites and terrigenous sediments. Microstructures (porosity) and compositional peculiarities (up to 18% P₂O₅) of individual horizons of the sediments testify to their lacustrine-swampy genesis. It is established that the siderites in association with the layer silicates were formed during the microbiochemogenic decomposition of terrigenous components, including quartz.     

In situ anaerobic degradation of petroleum alkanes in marine sediments: preliminary results

The degradation of acyclic petroleum hydrocarbons was studied during a 24-month experiment in Mediterranean coastal sediments (Gulf of Fos). Sediment cores entirely contaminated with oil (Arabian Light Crude Oil) were incubated in situ. The use of conservative tracers of sediment's particles reworking (luminophores) allowed the distinction of the reworked layer from the anoxic deeper sediments. Using the 17α,21βC₃₀ hopane (C₃₀H) as an inert internal reference, we could demonstrate that, after 24 months of experiment, acyclic petroleum hydrocarbons can be degraded under natural anaerobic conditions. The reactivity of individual alkanes appeared to depend on their chemical structure. To cite this article: D. Massias et al., C. R. Geoscience 335 (2003).To cite this article: D. Massias et al., C. R. Geoscience 335 (2003).     

Stability of phyllosilicates in Ca(OH)2 solution: Influence of layer nature,octahedral occupation,presence of tetrahedral Al and degree of crystallinity

This paper presents the results of a comprehensive investigation of the interaction of layered silicates with Ca(OH)₂ in hydrothermal conditions. The study is intended to evaluate the stability of the clay buffer in radioactive waste repositories, at the intermediate stages of concrete leaching, when the pH is controlled by the dissolution of portlandite. The influence of layer nature, octahedral occupation, presence of tetrahedral Al and degree of crystallinity will be assessed by analysing the behaviour of a set of well-selected phyllosilicates and using the combined capabilities of ²⁹Si and ²⁷Al MAS-NMR spectroscopy, powder X-ray diffraction and SEM/EDX. The results show that the main factor affecting the stability of the clay is the octahedral occupation, so that trioctahedral phyllosilicates are much more stable than dioctahedral ones. The nature and expandability of the layer does not seem to much influence the stability of the clay, so that a 2:1 expandable phyllosilicate shows the same stability as a chemically analogous 1:1 non-expandable phyllosilicate. However other factors like the poor crystallinity of the starting material or the presence of Al in the tetrahedral sheet of trioctahedral phyllosilicates weaken the clay structure in alkaline conditions and favour the transformation towards other phases.     

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。     

含方霜晶石的羟硅铝石-地开石粘土脉——一种新型的低温热液蚀变岩脉

铁锂云母钠长花岗岩中发现了新型的低温热液蚀变产物——含方霜晶石的羟硅铝石-地开石粘土脉。描述了粘土脉的地质背景、岩石学特征,以及方霜晶石、羟硅铝石的矿物学特征。讨论了这一发现的岩石学和矿物学的意义。     

Crystal-chemical microheterogeneity of Precambrian globular dioctahedral mica minerals

The paper presents a novel method for determining the crystal-chemical heterogeneity of finely dispersed dioctahedral 2: 1 mica mineral phases based on the modeling of their powder diffraction patterns. We used three samples, which were taken from Lower-Middle Riphean rock sections of the Anabar and Olenek uplifts in northern Siberia, and one sample from the Upper Riphean Inzer Formation in the southern Urals. Choice of globular samples was determined by contrast features of their chemical composition and different lithological types of the host terrigenous rocks that are commonly transformed at the level of deep catagenesis.Based on structural formulas, unit cell parameters, and coordinates of atoms occupying the cells, we modeled powder diffractograms that made it possible to determine the sizes of coherent scattering domains and probability parameters, which characterize the type, content, and distribution of stacking faults in each of the studied samples. The modeling results demonstrated that each sample represents a physical mixture of individual micaceous phases of different compositions. The paper discusses scales and modes of the crystalchemical heterogeneity of micaceous varieties, which make up globules in the coarse- and fine-grained terrigenous sediments, as well as their various specific crystal-chemical characteristics. The probable physicochemical settings, which were responsible for specific features of the structural and crystal-chemical heterogeneity of micaceous varieties in each of the studied four samples, are also discussed.     

Geochronology of Granitoid Rocks and Geochemistry,Petrogenesis of Volcanic Rocks in the Dahalajunshan Formation Towards a Genetic Model for the Associated Iron Ore Deposits,Xinjiang, NW China

<正>There are many skarn deposits that occur in volcanic rocks as stratiform and lentoid bodies,for example the Lower Yangtze River Valley,Western Tianshan Mountains and Lhasa Terrane in China,the Nuuk in West Greeland and the Austroalpine Alps(e.g.Xv et al.,1984;Appel,1994;Raith and Stein,2000;Wang et al.,2001;Gu et al.,2007;Hou et al.,2011;Zhou et al.,2011;Jiang et al.,2012;Xu et al.,2010;Wang et al.,2012;Yu et al.,2011).Despite     

Place-based learning and knowing: critical pedagogies grounded in Indigeneity

For Indigenous peoples, knowledge and science are written onto the landscapes our languages ??talk into being?? through the ??individual and collective consciousness of our communities (Cajete 2000, 284).?? Our landscapes are the storied histories, cosmogonies, philosophies and sciences of those Indigenous knowledges which are increasingly being pushed aside by the ??gray uniformity?? of globalization and its progenitor, European colonization. It is within storied places that we can still glimpse alternatives to this gray uniformity of globalization which brings with it a rhetoric of capitalism, modernism, abstract space and Western science. It is this rhetoric produced through globalization which erases the storied landscapes, destroying the libraries embedded within Indigenous toponyms, creating a terra nullius: an empty land awaiting a colonial/neo-colonial history and economy. As Paulo Freire has challenged us to see, critical consciousness requires us to ??read our world,?? decoding the images of our own concrete, situated experiences with the world (Freire and Macedo 1987, 35). A critical pedagogy of place recognizes the concrete experiences of communities grounded in shared histories, stories and challenges based within a politics of place. A critical pedagogy of place seeks to decolonize and reinhabit the storied landscape through ??reading?? the ways in which Indigenous peoples?? places and environment have been injured and exploited. This paper seeks to discuss how through reading the places in the world as ??political texts,?? one may engage in reflection and praxis in order to understand, and where necessary, to change the world.     

Geochemical Characteristics of Mid-oceanic Ridge Volcanic Glass from Lau Basin: Evidence from the Major Elements Variation

Orientale size craters are not recognized on Earth nor expected for Phanerozoic and Proterozoic eons from conventional crater size frequency distributions (Ivanov et al., 2002). Here suggested are three such Phanerozoic craters, modified by plate tectonics, and tentatively correlated with extinction and “ophiolite obduction” events. Hypothesis testing is proposed and plate tectonics implications are discussed. Such basins might manifest:

• circular to elliptical rims (or rim segments), with exposed lithospheric mantle, as strain markers for plate boundary motion;
• thick ejecta near rim expressed as “ophiolitic melange”;
• power law decay of ejecta thickness with radial distance from rim (McGetchin et al., 1973) and/or systematic azimuthal variation of ejecta thickness for low angle impacts (Schultz, 1999);
• weathering resistant shocked mantle minerals (Bohor et al., 1990) in ejecta;? global spherule layer with PGE anomalies (Alvarez et al., 1980);
• rim structures consistent with cratering mechanics (Melosh, 1989; Kenkmann, 2014);
• impact melt basement (Grieve et al., 1992; Pierazzo et al. 2000) recording uniform cooling age and Earth's magnetic polarity of the time. Tentatively suggested Phanerozoic impact basins:
• Yucatan Basin: Greater Antilles ophiolite rim – KPg Boundary? Maastrichtian ophiolite obduction in southeast Cuba (Iturralde‐Vinent et al., 2006).
• Sulu Sea Basin: Palawan, Sabah etc. ophiolite rim – Middle Miocene Disruption? MM ophiolitic mélange emplacement in Sabah (Clennell, 1991).
• Loyalty Basin: New Caledonia ophiolite and d'Entrecasteaux ridge rim – EO Boundary? EO ophiolite obduction in New Caledonia (Cluzel et al., 2012).