Raman and infrared study of hydroxyl sites in natural uvite,fluor-uvite,magnesio-foitite,dravite and elbaite tourmalines

We present the Raman and infrared spectra of different tourmaline species in the spectral range associated with the hydroxyl stretching modes, investigated through polarized Raman spectroscopy. Different lineshapes are observed for the OH spectra in uvite, fluor-uvite, magnesio-foitite, dravite and elbaite samples, and can be related to the coordination of OH in the two different structural V[O(3)]- and W[O(1)]-occupied sites. Local arrangements around the two different OH sites were assigned, and different ion substitutions for these five tourmaline species were identified. Our work with polarized Raman spectroscopy revealed that OH-stretching modes are described by totally symmetric, irreducible representations.     

Measurements of volcanic SO2 and CO2 fluxes by combined DOAS,Multi-GAS and FTIR observations: a case study from Turrialba and Telica volcanoes

Over the past few decades, substantial progress has been made to overcome the technical difficulties of continuously measuring volcanic SO₂ emissions. However, measurements of CO₂ emissions still present many difficulties, partly due to the lack of instruments that can directly measure CO₂ emissions and partly due to its strong atmospheric background. In order to overcome these difficulties, a commonly taken approach is to combine differential optical absorption spectroscopy (DOAS) by using NOVAC scan-DOAS instruments for continuous measurements of crateric SO₂ emissions, and electrochemical/NDIR multi-component gas analyser system (multi-GAS) instruments for measuring CO₂/SO₂ ratios of excerpts of the volcanic plume. This study aims to quantify the representativeness of excerpts of CO₂/SO₂ ratios measured by Multi-GAS as a fraction of the whole plume composition, by comparison with simultaneously measured CO₂/SO₂ ratios using cross-crater Fourier transform infrared spectroscopy (FTIR). Two study cases are presented: Telica volcano (Nicaragua), with a homogenous plume, quiescent degassing from a deep source and ambient temperature, and Turrialba volcano (Costa Rica), which has a non-homogeneous plume from three main sources with different compositions and temperatures. Our comparison shows that in our “easier case” (Telica), FTIR and Multi-GAS CO₂/SO₂ ratios agree within a factor about 3 %. In our “complicated case” (Turrialba), Multi-GAS and FTIR yield CO₂/SO₂ ratios differing by approximately 13–25 % at most. These results suggest that a fair estimation of volcanic CO₂ emissions can be provided by the combination of DOAS and Multi-GAS instruments for volcanoes with similar degassing conditions as Telica or Turrialba. Based on the results of this comparison, we report that by the time our measurements were made, Telica and Turrialba were emitting approximately 100 and 1,000 t day^?1 of CO₂, respectively.     

The quantitative analysis of OH in vesuvianite: a polarized FTIR and SIMS study

A well-characterized suite of vesuvianite samples from the volcanic ejecta (skarn or syenites) from Latium (Italy) was studied by single-crystal, polarized radiation, Fourier-transform infrared (FTIR) spectroscopy and secondary-ion mass-spectrometry (SIMS). OH-stretching FTIR spectra consist of a rather well-defined triplet of broad bands at higher-frequency (3,700–3,300 cm^–1) and a very broad composite absorption below 3,300 cm^–1. Measurements with E//c or Ec show that all bands are strongly polarized with maximum absorption for E//c. They are in agreement with previous band assignments (Groat et al. Can Mineral 33:609, 1995) to the two O(11)–H(1) and O(10)–H(2) groups in the structure. Pleochroic measurements with changing direction of the E vector of the incident radiation show that the orientation of the O(11)–H(1) dipole is OHc~35°, in excellent agreement with the neutron data of Lager et al. (Can Mineral 37:763, 1999). A SIMS-based calibration curve at ~10% rel. accuracy has been worked out and used as reference for the quantitative analysis of H₂O in vesuvianite by FTIR. Based on previous SIMS results for silicate minerals (Ottolini and Hawthorne in J Anal At Spectrom 16:1266, 2001; Ottolini et al. in Am Mineral 87:1477, 2002) the SiO₂ and FeO content of the matrix were assumed as the major factors to be considered at a first approximation in the selection of the standards for H. The lack of vesuvianite standards for quantitative SIMS analysis of H₂O has been here overcome by selecting low-silica elbaite crystals (Ottolini et al. in Am Mineral 87:1477, 2002). The resulting integrated molar absorption FTIR coefficient for vesuvianite is _i=100.000±2.000 l mol^–1 cm^–2. SIMS data for Li, B, F, Sr, Y, Be, Ba REE, U and Th are also provided in the paper.     

A combined FTIR and TPD study on the bulk and surface dehydroxylation and decarbonation of synthetic goethite

The thermal dehydroxylation of a goethite-carbonate solid solution was studied with combined Fourier-transform infrared (FTIR)-Temperature programmed desorption (TPD) experiments. The TPD data revealed dehydroxylation peaks involving the intrinsic dehydroxylation of goethite at 560 K and a low temperature peak at 485 K which was shown to be associated to the release of non-stoichiometric water from the goethite bulk and surface. The FTIR and the TPD data of goethite in the absence of adsorbed carbonate species revealed the presence of adventitious carbonate mostly sequestered in the goethite bulk. The release of carbonate was however not only related to the dehydration of goethite but also from the crystallization of hematite at temperatures exceeding 600 K. The relative abundance of surface hydroxyls was shown to change systematically upon goethite dehydroxylation with a preferential stripping of singly-coordinated OH sites followed by a dramatic change in the dominance of the different surface hydroxyls upon the formation of hematite.     

Thermal stability of wind near a hot star

We present computations of the ionization and thermal balance in the wind from WR and OB stars. The star’s radiation field is modeled using a Planck function with a temperature from 2 to 6 eV. We assume that the principal contribution from gas heating and cooling is from ions and atoms of hydrogen, carbon, nitrogen, oxygen, and neon. We take into account photoionization from the ground state and excited states, ionization by electron collisions, radiative and two-electron recombination, and excitation and de-excitation of discrete levels by the star’s dilute radiation and electron collisions. It is demonstrated that the thermal regime of gas in the conditions typical of the winds near WR and OB stars is stable.     

Microtremor survey and stability analysis of a soil-rock mixture landslide: a case study in Baidian town,China

Soil-rock mixtures (S-RM) are widely distributed in mountainous regions, and there are different genetic types and scales of S-RM slopes. The stability of these slopes is very important for slope safety during the construction and operation of engineering projects. Since the mechanical properties of an S-RM are mainly dominated by its random component, accurately investigating the structure of an S-RM slope is the fundamental basis for evaluating the mechanism of a landslide. In this paper, in situ direct shear tests are used to obtain the “soil” strength parameters of the S-RM, the microtremor survey method (MSM) is introduced to detect the S-RM slope and the numerical method of FEM is utilised to simulate the failure characteristics and stability of the S-RM slope. Based on the MSM, the strata structure and proportions of solitary rock blocks in the S-RM slope are investigated, and three possible models of the S-RM slope are established. By using the strength reduction method in numerical simulations, the potential failure surface and stability of a slope of homogeneous soil and that with solitary rock blocks are discussed. The study results show that the MSM is an effective method to estimate the proportion of rock blocks in the S-RM slope. The presence of solitary rock blocks makes the slope potential slide surface complicated. The factor of safety of the S-RM slope is higher than that of the homogeneous soil slope, the rock blocks at the toe of the slope are favourable for slope stability and the rock blocks near the surface of the slope squeeze the lower soil and improve the safety factor of the slope.     

Dehydroxylation induced structural transformations in montmorillonite: an isothermal FTIR study

Fourier transform infrared (FTIR) measurements on thermally shocked (290T<1100 k,="">t=1 and 24 h) and thermally soaked (T=803 K, 0t<25 h)="" ca-montmorillonite="" from="" texas="" show="" that="" the="" dehydroxylation="" temperature="" for="" this="" mineral="" is="" much="" lower="" than="" previously="" reported="" in="" the="" literature="" and="" depends="" upon="" the="" thermal="" soak="" time="" used.="" the="" effect="" of="" thermal="" shock="" temperature="" on="" vibrational="" frequencies,="" originating="" from="" the="" silicate="" sheet,="" and="" the="" intensity="" of="" al-oh-al="" stretching="" mode="" suggest="" that="" camontmorillonite="" dehydroxylates="" at="" 903="">T<923 k="" and="">T<823 k="" for="" 1="" h="" and="" 24="" h="" thermally="" shocked="" samples,="" respectively.="" our="" similar="" measurements="" on="" the="" mn="" and="" fe="" exchanged-montmorillomte="" from="" texas="" demonstrate="" that="" the="" dehydroxylation="" temperature="" range="" is="" also="" affected="" by="" the="" type="" of="" cations="" present="" in="" the="" interlayer.="" the="" thermal="" soak="">T=803 K, 0t<25 h)="" measurement="" on="" ca-montmorillonite="" indicates="" that="" the="" dehydroxylation="" of="" this="" montmorillonite="" proceeds="" via="" the="" development="" of="" intermediate="" structural="" phases.="" as="" noted="" by="" previous="" authors,="" the="" dehydroxylation="" of="">²⁺ and Fe³⁺ octahedral sites does not affect the overall structure. However, if 75 percent of the hydroxyls attached to Al³⁺ are lost, then the lattice manifests an intermediate structural phase. In this intermediate phase, the structure of both octahedral and silicate layers is affected. On a further loss of hydroxyls (90% of Al³⁺ hydroxyls), the final montmorillonite dehydroxylate phase develops. The vibrational analysis of an isothermally treated sample suggests that the final phase is induced due to the rearrangement of the silicate oxygens, which leave the coordination around Al to be 5. The dehydroxylation results of montmorillonite (Texas) have been discussed in terms of known mechanisms, and it appears that the dehydroxylation starts at the surface and proceeds via proton delocalization at trans hydroxyl positions, followed by the protons' migration across the vacant cation sites with the formation of H₂O molecules below the hexagonal holes.     

Thermal expansion and decomposition of jarosite: a high-temperature neutron diffraction study

The structure of deuterated jarosite, KFe₃(SO₄)₂(OD)₆, was investigated using time-of-flight neutron diffraction up to its dehydroxylation temperature. Rietveld analysis reveals that with increasing temperature, its c dimension expands at a rate ~10 times greater than that for a. This anisotropy of thermal expansion is due to rapid increase in the thickness of the (001) sheet of [Fe(O,OH)₆] octahedra and [SO₄] tetrahedra with increasing temperature. Fitting of the measured cell volumes yields a coefficient of thermal expansion, α = α₀ + α₁ T, where α₀ = 1.01 × 10⁻⁴ K⁻¹ and α₁ = −1.15 × 10⁻⁷ K⁻². On heating, the hydrogen bonds, O1···D–O3, through which the (001) octahedral–tetrahedral sheets are held together, become weakened, as reflected by an increase in the D···O1 distance and a concomitant decrease in the O3–D distance with increasing temperature. On further heating to 575 K, jarosite starts to decompose into nanocrystalline yavapaiite and hematite (as well as water vapor), a direct result of the breaking of the hydrogen bonds that hold the jarosite structure together.     

碱性玄武岩中长石巨晶的结构水：红外光谱和核磁共振谱研究

运用傅立叶变换红外光谱技术（ＦＴＩＲ,红外区和近红外区）和质子魔角旋转核磁共振技术（＾１ＨＭＡＳＮＭＲ）对来自安徽女山,江苏盘石山和河北汉诺坝新生代大恶性玄武岩中的４个歪长石巨晶进行了观察,结果显示,这些巨晶含有结构水,主要以Ｈ２Ｏ的形式存在,其中３个样品的结构水含量（Ｈ２Ｏ）分别为４０５μｇ／ｇ,９１５μｇ／ｇ,μｇ／ｇ。这些数据和文献中已有的资源表明,名义上无水的长石族矿物可以是地球上的水储库     

Slope stability analysis on a regional scale using GIS: a case study from Dhading,Nepal

A spatially distributed physically based slope stability model combined with a hydrological model is presented and applied to a 350-km² area located in Dhading district, Nepal. Land slide safety factor maps are generated for five cases, including three steady state conditions assuming either completely dry soils, half saturated soils, or fully saturated soils, and two quasi-dynamic conditions, i.e. soil wetness resulting from storm events with, respectively a 2 or 25-year return period. For the quasi-dynamic cases, two methods are used, one based on accumulation of groundwater flow from upstream areas, and the other on accumulation of soil water from direct infiltration. The methodology delineates areas most prone to shallow land sliding in function of readily available data as topography, land-use and soil types. For the study area only 29% of the soils are unconditionally stable, while 25% of the soils are found to be unstable under fully saturated conditions. The comparison between the methods based on contributing area or on infiltration for quasi-dynamic conditions show that the approach based on infiltration is more reliable for the study area. The proposed methodology for predicting landslide susceptibility on a regional scale, based on basic data in GIS form, may be useful for other remote regions where detailed information is not available.     

Influence of rainfall on the deformation and stability of a slope in overconsolidated clays: a case study

The behaviour of an instrumented unstable slope in a profile of weathered overconsolidated clay has been analysed. Available field investigation data and laboratory tests were integrated in a coupled hydromechanical model of the slope. Particular attention was given to the unsaturated soil conditions above the water table and to the influence of the rainfall record. Recorded pore-water pressures helped to identify the hydrogeological conditions of the slope. The coupled model was used to compute slope deformations and the variation of safety with time. Actual rainfall records were also integrated into the analysis. Comparison of measurements and calculations illustrate the nature of the slope instability and the complex relationships between mechanical and hydraulic factors. Electronic Publication     

Distribution of platinum-group elements in the Platreef at Overysel,northern Bushveld Complex: a combined PGM and LA-ICP-MS study

Detailed mineralogical and laser ablation-inductively coupled plasma-mass spectrometry studies have revealed the physical manifestation of the platinum-group elements (PGE) within the Platreef at Overysel, northern Bushveld Complex, South Africa. The PGE in the Platreef were originally concentrated in an immiscible sulfide liquid along with semi-metals such as Bi and Te. As the sulfide liquid began to crystallize, virtually all the Os, Ir, Ru and Rh partitioned into monosulfide solid solution (mss), which on further cooling, exsolved to form pyrrhotite and pentlandite with Os, Ir and Ru remaining in solid solution in both phases with Rh prefentially partitioning into pentlandite. Platinum, some Pd and Au were concentrated in the residual sulfide liquid after mss crystallization, and were then concentrated in an immiscible late stage melt along with semi metals, which was expelled to the grain boundaries during crystallization of intermediate solid solution (iss) to form Pt and Pd tellurides and electrum around the margins of the sulfide grains. Tiny droplets of this melt trapped in the crystallizing mss and iss cooled to form Pt–Bi–Te microinclusions in all sulfide phases, whilst the excess Pd was accommodated in solid solution in pentlandite. Minor redistribution and recrystallization by hydrothermal fluids occurred around xenoliths and at the very base of the mineralized zone within the footwall, however, the overall lack of secondary alteration coupled with the volatile-poor nature of the gneissic footwall have allowed the preservation of what may be the most ‘primary’ style of Platreef mineralization. The lack of PGM inclusions within early liquidus phases suggests very early sulfur saturation in the Platreef, lending support to theories involving S saturation occurring prior to intrusion of the Platreef, possibly within a staging chamber.     

Slope stability assessment and design of remedial measures for Tungnath Temple at Uttarakhand,India: a case study

Natural Hazards - The present paper assesses the slope&nbsp;stability of the Tungnath Temple at Rudraprayag District, in the Indian state of Uttarakhand, and suggests the remedial measures. The...     

Nodular chert from the Arbuckle Group, Slick Hills, SW Oklahoma: a combined field, petrographic and isotopic study

Nodular chert from the middle and upper Arbuckle Group (Early Ordovician) in the Slick Hills, SW Oklahoma, was formed by selective replacement of grainstones, burrow fillings, algal structures, and evaporite nodules. Chert nodules are dominantly microquartz with minor fibrous quartz (both quartzine and chalcedony), megaquartz, and microflamboyant quartz. Lepisphere textures of an opal-CT precursor are preserved in many (especially in finely-crystalline) chert nodules. The δ¹⁸O values of microquartz chert range from +23.4 to + 28.8^0/00 (SMOW), significantly lower than those of Cenozoic and Mesozoic microquartz chert formed both in the deep sea and from near-surface sea water. The δ¹⁸O values of chert decrease with increasing quartz crystal size. Silicification in the Arbuckle Group occurred during early diagenesis, with the timing constrained by the relative temporal relationships among silicification, burial compaction, and early dolomite stabilization. Silica for initial chert nucleation may have been derived from both dissolution of sponge spicules and silica-enriched sea water. Chert nucleation appears to have been controlled by the porosity, permeability, and organic matter content of precursor sediments. This conclusion is based on the fact that chert selectively replaced both porous grainstones and burrows and algal structures enriched in organic matter. Growth of chert probably occurred by a maturation process from opal-A(?), to opal-CT, to quartz, as indicated by the presence of opal-CT precursor textures in many chert nodules. Although field and petrographic evidence argues for an early marine origin for chert in the Arbuckle Group, the light δ¹⁸O values are inconsistent with this origin. Meteoric resetting of the δ¹⁸O values of the chert during exposure of the carbonate platform best explains the light δ¹⁸O values because: (i) the δ¹⁸O values of chert nodules decrease with decreasing δ¹⁸O values of host limestones, and (ii) chert nodules from early dolomite, which underwent more extensive meteoric modification than associated limestones, have lighter δ¹⁸O values than chert nodules from limestones. Increasing recrystallization of chert nodules by meteoric water resulted in progressive ¹⁸O depletion and (quartz) crystal enlargement.     

多年冻土区不同路面材料路基热稳定性分析

针对多年冻土区路基路面病害多发的现状,从路面材料入手,对水泥混凝土和沥青两种路面下路基温度场的变化规律进行研究。研究结果表明,在计算高度范围内,对于8.5 m路面宽幅的路基来说,沥青路面下的最大融深大于混凝土路面下的最大融深,尤其在路基高度较低时两种路面下的融深差异更大。最大融化深度和最大融化深度发展速率均与路基高度和路面宽幅有紧密关系,通过研究可以提出有效的措施来保持路基热稳定性,从而减少路基路面病害的发生和公路的运营成本,为今后类似工程提供参考     

氯羟磷灰石中羟基的FTIR研究

通过固相法合成了一系列氯羟磷灰石(ClHAp)固溶体,经FTIR表征发现,纯羟基磷灰石(HAp)的羟基振动频率为3572cm-1和632cm-1。当Cl-进入HAp晶体结构后,在3494cm-1和673cm-1处各出现新的吸收谱带,说明在其通道结构中形成[Cl…HO]氢键,导致羟基的伸缩振动向低频偏移,弯曲振动向高频偏移。与氟羟磷灰石的FTIR谱比较可知:ClHAp的羟基振动谱带的位置与数量主要受氢键和周围结构环境变化程度影响。     

Overcoming problems of density and thickness measurements in FTIR volatile determinations: a spectroscopic approach

The Beer–Lambert law is traditionally used to determine water and carbon concentrations in glasses from their infrared (IR) spectra. In practice, this method requires estimation of the thickness and density of the glass as well as the calibration of the molecular absorptivities of the species concerned. All of these parameters can be sources of practical difficulties and analytical uncertainty. These weaknesses in the application of the Beer–Lambert law have been overcome by an empirical analysis of the infrared spectra. Using a set of 292 spectra obtained on 113 natural and experimental tholeiitic glasses (SiO₂ 48.5–51 wt%; water contents 0–4000 ppm H₂O), it can be shown that the thickness–density (ρ d) product of a glass sample can be directly and reliably inferred from its IR spectrum. This allows the Beer–Lambert law to be rewritten. The new form no longer requires thickness or density estimations to determine volatile contents. Moreover, if needed, the thickness of the glass slab can also be accurately determined from the IR spectra. This new method is developed for quantitative determination of water concentrations in MORB glasses but can also be applied to any minor species (carbon, sulfur, etc.) provided it is active in the IR domain and that a suitable independent frequency of IR absorption can be identified. Precision is about 60 ppm H₂O on O–H⁻ contents. This method, tested on natural and experimental MORB-type glasses, can be applied to any chemical composition provided a set of reference spectra is available. Received: 16 September 1999 / Accepted: 18 February 2000