Modelling the OH stretch envelope shape and temperature effects in infrared spectra of hydrous silica and silicate glasses

Simple model calculations show that the reversible temperature effects reported for broad OH-stretching bands in infrared spectra of silica, aluminosilicate, and similar glasses can be explained, in essentials, by homogeneous thermal broadening of the ν(OH) envelope constituents and a decrease in intensity with increasing temperature taking place uniformly across the band. This means that these effects are reasonably consistent with the temperature behaviour of narrow ν(OH) bands of crystalline OH-bearing minerals. These findings leave little room for the previously agreed interpretation in terms of a change in hydrogen-bonding strength, although the dependence of integrated intensity on temperature still remains to be understood. Received: 16 April 1999 / Accepted: 4 April 2000     

Transport properties of low-sanidine single-crystals, glasses and melts at high temperature

Thermal diffusivity (D) was measured using laser-flash analysis from oriented single-crystal low-sanidine (K_0.92Na_0.08Al_0.99Fe³⁺ _0.005Si_2.95O₈), and three glasses near KAlSi₃O₈. Viscosity measurements of the three supercooled liquids, in the range 10^6.8 to 10^12.3 Pa s, confirm near-Arrhenian behavior, varying subtly with composition. For crystal and glass, D decreases with T, approaching a constant near 1,000 K: D _sat ∼ 0.65 ± 0.3 mm² s⁻¹ for bulk crystal and ∼0.53 ± 0.03 mm² s⁻¹ for the glass. A rapid decrease near 1,400 K is consistent with crossing the glass transition. Melt behavior is approximated by D = 0.475 ± 0.01 mm² s⁻¹. Thermal conductivity (k _lat) of glass, calculated using previous heat capacity (C _P) and new density data, increases with T because C _P strongly increases with T. For melt, k _lat reaches a plateau near 1.45 W m⁻¹ K⁻¹, and is always below k _lat of the crystal. Melting of potassium feldspars impedes heat transport, providing positive thermal feedback that may promote further melting in continental crust.     

A pre-edge analysis of Mn K-edge XANES spectra to help determine the speciation of manganese in minerals and glasses

High-resolution manganese K-edge X-ray absorption near edge structure spectra were collected on a set of 40 Mn-bearing minerals. The pre-edge feature information (position, area) was investigated to extract as much as possible quantitative valence and symmetry information for manganese in various “test” and “unknown” minerals and glasses. The samples present a range of manganese symmetry environments (tetrahedral, square planar, octahedral, and cubic) and valences (II to VII). The extraction of the pre-edge information is based on a previous multiple scattering and multiplet calculations for model compounds. Using the method described in this study, a robust estimation of the manganese valence could be obtained from the pre-edge region at 5% accuracy level. This method applied to 20 “test” compounds (such as hausmannite and rancieite) and to 15 “unknown” compounds (such as axinite and birnessite) provides a quantitative estimate of the average valence of manganese in complex minerals and silicate glasses. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

An infrared and <Superscript>1</Superscript>H MAS NMR investigation of strong hydrogen bonding in ussingite,Na<Subscript>2</Subscript>AlSi<Subscript>3</Subscript>O<Subscript>8</Subscript>(OH)

The mineral ussingite, Na₂AlSi₃O₈(OH), an interrupted tectosilicate, has strong hydrogen bonding between OH and the other nonbridging oxygen atom in the structure. Infrared spectra contain a strongly polarized, very broad OH-stretching band with an ill-defined maximum between 1500 and 1800 cm^–1, and a possible OH librational bending mode at 1295 cm^–1. The IR spectra confirm the orientation of the OH vector within the triclinic unit cell as determined from X-ray refinement (Rossi et al. 1974). There are three distinct bands in the ¹H NMR spectrum of ussingite: a predominant band at 13.5 ppm (TMS) representing 90% of the structural hydrogen, a second band at 15.9 ppm corresponding to 8% of the protons, and a third band at 11.0 ppm accounting for the remaining 2% of structural hydrogen. From the correlation between hydrogen bond length and ¹H NMR chemical shift (Sternberg and Brunner 1994), the predominant hydrogen bond length (H...O) was calculated to be 1.49 Å, in comparison to the hydrogen bond length determined from X-ray refinement (1.54 Å). The population of protons at 15.9 ppm is consistent with 5–8% Al–Si disorder. Although the ussingite crystal structure and composition are similar to those of low albite, the bonding environment of OH in low albite and other feldspars, as characterized through IR and ¹H NMR, is fundamentally different from the strong hydrogen bonding found in ussingite.     

玻璃和熔体包裹体中水含量的拉曼光谱定量测定方面的进展评述

This paper is focused on the progress in the determination of water in glasses and melt inclusions with Raman spectroscopy. Using the presented ＂Comparator Technique＂ the water content of a sample is determined by siruple comparison with a known standard. A calibration curve is not necessary. Furthermore, with this technique the water concentration in silicate melt inclusions can be determined without exposing the inclusions for measurements. This is very important for extremely water-rich melt inclusions, which would loose H2O on exposure.     

Refined relationship between the position of the fundamental OH stretching and the first overtones for clays

The aim of this paper is to determine a relationship between the wavenumbers of the first OH-stretching overtones (W_2OH) and the wavenumbers of the OH-stretching fundamentals (W_OH) to help to interpret the near-infrared (NIR) spectra. The first overtone (2OH) bands appear at wavenumbers less than twice those of the fundamental bands (OH), due to the anharmonic character of vibrations, X = W_2OH/2 - W_OH, with X being the anharmonicity constant. Talc samples with various crystal chemistries are used to solve the equation and the experimental data are well fitted with X = –85.6 cm^–1. As far as the authors are aware, it is the first time that the anharmonicity constant for the OH-stretching vibrations is determined for phyllosilicates. The anharmonicity constant remains almost unchanged for several types of clay samples. Therefore the relation, established from talc samples because their absorption bands are narrow and their wavenumber range of OH vibrations is wide, can be used for any other clay minerals.     

俯冲带温度条件下橄榄石中硅氧四面体的非谐振动:透射红外光谱研究

橄榄石既是上地幔的主要矿物,又是俯冲板块的主要矿物。在正常地幔温度条件下,橄榄石中原子之间的振动是非谐振动,这已成为学界共识;然而,对于俯冲带的较低温情况,橄榄石中原子之间的振动的非谐性是否重要,目前还没有比较一致的结论。本研究利用透射红外光谱的方法,系统研究了室温下不同厚度橄榄石中硅氧四面体的红外光谱特征,并着重对其在2100~1500cm-1区域形成的二倍频峰/合频峰进行了指认。在此基础上,本研究通过采集不同温度下的透射红外光谱数据(最高温度达约450℃),确立了橄榄石中硅氧四面体的相应基频峰及二倍频峰峰位对温度的依赖性,进而得出其相应红外振动的非谐系数(χ)随温度(T)的变化关系,具体为:χ838=6.37(2)×10-7×T+0.0014(1)及χ993=7.86(3)×10-7×T+0.0015(1),其中温度的单位为℃。外推到600℃时,有χ838=0.0018(1)及χ993=0.0020(2)。这些结果表明,在俯冲带的较低温条件下,橄榄石中硅氧四面体的内部振动的非谐性可能不重要。     

Oxygen sites in hydrous aluminosilicate glasses: the role of Al-O-Al and H2O

We describe here high-field ¹⁷O magic-angle-spinning (MAS) and triple-quantum MAS (3QMAS) NMR spectra for several alkali silicate and Na, K, and Ca aluminosilicate glasses containing up to 10 wt.% water. The H₂O site appears to have a large quadrupolar coupling constant, and its chemical shift increases from Na- to K- glasses, suggesting significant cation-H₂O interactions. In ¹⁷O one-pulse MAS and 3QMAS and ²⁷Al one-pulse NMR experiments, major differences were seen between spectra for anhydrous and hydrous calcium aluminosilicate glasses. The changes in the ¹⁷O MAS spectra can be explained by the addition of an H₂O peak and to the disappearance of an Al-O-Al peak from the ¹⁷O NMR spectrum for the hydrous glass. The ²⁷Al results are consistent with this interpretation.     

LiFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript> and NaFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript> at low temperatures: an infrared spectroscopic study

 Synthetic aegirine LiFeSi₂O₆ and NaFeSi₂O₆ were characterized using infrared spectroscopy in the frequency range 50–2000 cm⁻¹, and at temperatures between 20 and 300 K. For the C2/c phase of LiFeSi₂O₆, 25 of the 27 predicted infrared bands and 26 of 30 predicted Raman bands are recorded at room temperature. NaFeSi₂O₆ (with symmetry C2/c) shows 25 infrared and 26 Raman bands. On cooling, the C2/c–P2₁/c structural phase transition of LiFeSi₂O₆ is characterized by the appearance of 13 additional recorded peaks. This observation indicates the enlargement of the unit cell at the transition point. The appearance of an extra band near 688 cm⁻¹ in the monoclinic P2₁/c phase, which is due to the Si–O–Si vibration in the Si₂O₆ chains, indicates that there are two non-equivalent Si sites with different Si–O bond lengths. Most significant spectral changes appear in the far-infrared region, where Li–O and Fe–O vibrations are mainly located. Infrared bands between 300 and 330 cm⁻¹ show unusually dramatic changes at temperatures far below the transition. Compared with the infrared data of NaFeSi₂O₆ measured at low temperatures, the change in LiFeSi₂O₆ is interpreted as the consequence of mode crossing in the frequency region. A generalized Landau theory was used to analyze the order parameter of the C2/c–P2₁/c phase transition, and the results suggest that the transition is close to tricritical. Received: 21 January 2002 / Accepted: 22 July 2002     

阿尔山地区近300年来brGDGTs记录的温度变化与火山喷发记录之间的关系

火山活动被认为是影响全球温度百年到千年时间尺度上变化的最主要因素。本研究对我国东北阿尔山地区鹿鸣湖的一支长约85 cm沉积物中支链甘油二烷基甘油四醚类化合物（brGDGTs）相关指标进行分析和计算,重建了近300年来阿尔山地区的生长季节（5~9月）温度变化。结果显示近300年来,研究区生长季温度的平均值在13.8℃左右,温度变幅为3.0℃左右。18世纪到20世纪初,阿尔山地区生长季温度呈波动趋势,20世纪初至20世纪90年代从14.0℃左右持续下降到了12.0℃,降温趋势较好地响应了大型火山喷发事件发生频率的增加,20世纪90年代之后表现出较为明显的增温趋势。相关性分析的结果表明近300年来大型火山喷发事件的发生频率和阿尔山地区的生长季温度变化有较好的相关性,火山喷发事件是阿尔山地区百年尺度上生长季温度变化的重要控制因素。

     

Application of infrared spectroscopy to studies of silicate glass structure: Examples from the melilite glasses and the systems Na2O-SiO2 and Na2O-Al2O3-SiO2

Infrared (IR) and Raman spectroscopic methods are important complementary techniques in structural studies of aluminosilicate glasses. Both techniques are sensitive to small-scale (<15 Å) structural features that amount to units of several SiO₄ tetrahedra. Application of IR spectroscopy has, however, been limited by the more complex nature of the IR spectrum compared with the Raman spectrum, particularly at higher frequencies (1200–800 cm^?1) where strong antisymmetric Si-O and Si-O-Si absorptions predominate in the former. At lower frequencies, IR spectra contain bands that have substantial contributions from ‘cage-like’ motions of cations in their oxygen co-ordination polyhedra. In aluminosilicates these bands can provide information on the structural environment of Al that is not obtainable directly from Raman studies. A middle frequency envelope centred near 700 cm^?1 is indicative of network-substituted AlO₄ polyhedra in glasses with Al/(Al+Si)>0·25 and a band at 520–620cm^?1 is shown to be associated with AlO₆ polyhedra in both crystals and glasses. The IR spectra of melilite and melilite-analogue glasses and crystals show various degrees of band localization that correlate with the extent of Al, Si tetrahedral site ordering. An important conclusion is that differences in Al, Si ordering may lead to very different vibrational spectra in crystals and glasses of otherwise gross chemical similarity.     

Evidence for kinks in structural and thermodynamic properties across the forsterite–fayalite binary from thin-film IR absorption spectra

Infrared absorbance spectra over ∼100 to 1,800 cm⁻¹ were collected from optically thin films of 21 samples with compositions spanning the forsterite–fayalite binary. Polarization information from previous specular reflectance data on end-members was used in tracing the peaks across the entire binary. Peak positions (ν_i) were constrained by Lorentzian decompositions. Fitting also constrained widths for singlet peaks but for doublets and triplets, variation in ν_i with composition among the constituent polarizations alters widths from intrinsic. Because film thicknesses of 0.6–1.4 μm were estimated, our band strengths are approximate; however, relative intensities should be correct. Only for a few peaks does ν_i vary smoothly across the entire binary; instead, distinct linear trends exist for Fe- and Mg-rich olivines. Discontinuities and kinks in ν_i(X) occur at X = Mg/(Fe + Mg) = 0.7 and are accompanied by a change in intensity patterns. This interesting behavior was not revealed in previous spectra of powder dispersions. The contrasting character of IR vibrations for Fe- and Mg-rich olivines is inferred to arise from structural variations because (1) frequency is related to bond length, (2) other factors affecting frequency (cation mass and probably bonding type) vary linearly across the binary, and (3) available data on unit cell parameters are consistent with distinct trends for forsterites and fayalites. Vibrational components of heat capacity (C _V) and enthalpy (H) calculated from ν_i, were found to be slightly more negative than linear interpolations between values for forsterite and fayalite. Our computations give smaller negative excesses from ideality in H than do previous calorimetric measurements, but are equal within experimental uncertainties.     

不锈钢内衬技术在江阴市供水管网改造中的应用

本文结合不锈钢内衬技术在江阴市玻璃钢供水管道改造中的应用,介绍了不锈钢内衬玻璃钢管施工工艺流程和施工技术措施,分析了不锈钢内衬施工效果和优势。展望了不锈钢内衬技术在城市供水管网改造中的应用前景。     

宝石的红外反射光谱及红外光谱鉴定系统

红外透过光谱技术是当前鉴别翡翠是否有聚合物充填的最好方法，而红外反射光谱技术是一种快速、无损伤的测试方法，主要提供矿物的基频振动光谱信息，在宝石学研究方面特别是鉴定宝石种属方面显示出新的应用可能性。本文介绍红外反射光谱技术的宝石学应用和包含318个光谱的数据库以及检索、鉴定程序的宝石红外光谱鉴定系统。     

Electronic absorption spectra of Fe2+ ions in oxygen-based rock-forming minerals at temperatures between 297 and 600 K

 Polarized electronic single crystal spectra of natural Fe²⁺ ion-bearing oxygen-based minerals, in which ferrous ions enter octahedral sites of different symmetry and distortion (olivine, cordierite, ortho- and clinopyroxene, amphibole), eightfold sites in garnet (almandine) and clinopyroxene (M2), and tetrahedral sites in spinel, were studied at temperatures from 300 to ca. 600 K. In the minerals studied, the spin-allowed bands of Fe²⁺ display rather variable temperature behaviour. In most cases, due to the thermal expansion of the Fe²⁺-bearing polyhedra, bands shift to lower energies upon increasing temperature, though there are some exceptions to this rule: in cases of other than sixfold octahedral or close to octahedral coordination, in almandine and spinel the bands shift to higher energies, which can be explained by an increase in distortions of the Fe²⁺-bearing polyhedra. Splitting of the excited ⁵ E _g-level of Fe²⁺ ions usually, but not always, increases with temperature, reflecting thermally induced increase in distortion of the Fe²⁺-bearing sites in the minerals studied. Integral intensities of the bands in question do not always obey the general rule, according to which intensity should increase with temperature, when the 3d ^N-centred site is centrosymmetric, or should remain unchanged when the 3d ^N site lacks an inversion centre. The experimental results show that the response of the characteristics of absorption bands such as width, intensity and energy caused by dd transitions of Fe²⁺ in oxygen-based minerals to increasing temperature is not always uniform and is at variance with expectation. This temperature dependence cannot be used directly to solve band assignment problems, as earlier proposed in the literature. Received: 22 December 1999 / Accepted: 30 October 2000     

南极半岛近百年气温的年代际振荡

利用南极半岛及邻近地区(30°～70°W,50°S以南)气象观测资料较好的12个站,建立了该地区近百年的气温距平序列.结果表明:1)近百年南极半岛气温有3个跃变点,分别在1919-1923年1947-1953年和1976-1982年之间,两个跃变点之间的稳定气候阶段的平均长度约30a左右;2)各阶段平均气温成阶梯式的上升,近百年年气温增加了0.730℃,但增温幅度各季不同:冬季最大,夏季最小;3)南极半岛年冰密集度指数倾向率为-0.2053·(10a)^-1,而且夏半年(12～翌年5月)比冬半年(6～11月)大;4)南极半岛温度与它的冰密集度指数呈反相关,夏季、秋季和年的相关系数都超过了5%信度.     

Experimental and theoretical study of the structural environment of magnesium in minerals and silicate glasses using X-ray absorption near-edge structure

X-ray absorption spectroscopy at the Mg K-edge is used to obtain information on magnesium environment in minerals, silicate and alumino-silicate glasses. First-principles XANES calculations are performed for minerals using a plane-wave density functional formalism with core-hole effects treated in a supercell approach. The good agreement obtained between experimental and theoretical spectra provides useful information to interpret the spectral features. With the help of calculation, the position of the first peak of XANES spectra is related to both coordination and polyhedron distortion changes. In alumino-silicate glasses, magnesium is found to be mainly 5-fold coordinated to oxygen whatever the aluminum saturation index value. In silicate glasses, magnesium coordination increases from 4 in Cs-, Rb- and K-bearing glasses to 5 in Na- and Li-bearing glasses but remains equal as the polymerization degree of the glass varies. The variation of the C feature (position and intensity) is strongly related to the alkali type providing information on the medium range order.

过去千年东亚与全球百年尺度温度同步性变化的模拟研究

利用美国国家大气研究中心（NCAR）提供的过去千年（850~2005年）集合模拟试验（CESM-LME）资料,在与重建资料、现代观测/再分析资料进行对比验证的基础上,分析了过去千年不同世纪东亚与全球地表温度变化的同步性,并结合单因子敏感性试验结果,分析了造成东亚与全球地表温度各个世纪同步性及变化幅度差异的原因。结果表明：过去千年里,在20世纪以前,东亚地区与全球均经历了中世纪暖期与小冰期,温度变化在百年尺度上整体一致,10世纪、11世纪、13世纪、18世纪和19世纪东亚与全球温度变化同步性较高,差异较小;但在12世纪、14~17世纪中,其变化振幅存在显著差异,东亚地区温度变化幅度总体上小于全球,太阳辐射和火山活动等自然外强迫及内部变率对差异的形成可能起到了主导作用;而20世纪以来,两者变化显示出较大的不同步性,东亚地区温度增长没有全球温度增长剧烈,甚至出现了降温,人为外强迫在这一时期起主导作用。温室气体浓度变化对温度的影响在两极有明显的放大效应,是东亚与全球温度变化差异形成的主要原因,同时,人为气溶胶排放使得东亚地区温度降低也是东亚与全球温度变化不同步的原因之一。

     

Recognition and characterisation of high-grade ignimbrites from the Neoproterozoic rhyolitic volcanism in southernmost Brazil

Neoproterozoic magmatism in southern Brazil is associated with translithospheric shear belts and strike-slip basins in a post-collisional setting related to the last stages of the Brasilian-Pan African Orogenic Cycle. It evolved from an association of high-K calc-alkaline, leucocratic-peraluminous and continental tholeiitic magmas, to an association with shoshonitic magmas and, eventually, to an association with magmas of the sodic mildly alkaline series. This magmatism varies from metaluminous to peralkaline and exhibits alkaline sodic affinity. A large volcanism is related to this alkaline sodic magmatism and is named the Acampamento Velho Formation. This unit was coeval with subaerial siliciclastic sedimentation in post-collisional basins preserved in the region. The Acampamento Velho Formation consists of pyroclastic and effusive volcanic deposits, which are mainly silicic, emplaced under subaerial conditions. The best exposures of this volcanism occur on the Ramada and Taquarembó plateaus, located southwest of Rio Grande do Sul in southernmost Brazil. The pyroclastic flow deposits are composed mainly of juvenile fragments such as pumices, shards and crystal fragments. Welding is very effective in these units. High-grade ignimbrites occur at the base and intermediate portions of the deposits and rheoignimbrites are observed at the top. The pre-eruptive temperature calculations, which were obtained at the saturation of zircon, revealed values between 870 °C and 978 °C for Taquarembó Plateau and 850 °C–946 °C for Ramada Plateau. The calculated viscosity values vary from 6.946 to 8.453 log η (Pas) for the rheoignimbrites and 7.818 to 10.588 log η (Pas) for the ignimbrites. Zr contents increase toward the top of the pyroclastic sequence, which indicates an increase in peralkalinity and determines the reduction in viscosity for clasts at the upper portions of the flows. The patterns of the structures of the ignimbrites and rheoignimbrites in the Taquarembó and Ramada plateaus accords well with successive pyroclastic flows that halts en masse. In this model the entire pyroclastic flow halts en masse, so complex vertical changes in grain size and composition are interpreted as recording deposition from successive discrete pyroclastic flows. The stratification observed in intermediate units in Taquarembó Plateau might reflect in this case variation in eruptive dynamics and short pauses.     

Ammonium ion behaviour in feldspar: variable-temperature infrared and 2H NMR studies of synthetic buddingtonite, N(D,H)4AlSi3O8

The behaviour of the ammonium ion in synthetic buddingtonite, N(D,H)₄AlSi₃O₈, has been studied by infrared (IR) spectroscopy from 20 K to 298 K and by ²H NMR spectroscopy from 120 K to 298 K. IR spectra were collected from 500 to 3500 cm^–1. Static ²H NMR spectra collected at 298 K and 120 K are very similar, consisting of a single sharp isotropic resonance, indicating complete averaging of quadrupolar interactions and implying that at these temperatures the ammonium ion is in rapid (<1 s) randomised motion within the M-site cavity of the feldspar framework. NMR spectroscopy indicates that the splitting of the internal modes of the ammonium ion observed by IR spectroscopy is not due to freezing in of the ammonium ion. This observation rules out the formation of a preferred N–H...O hydrogen bond, with precession of the ion about it, as proposed by Kimball and Megaw (1978), because any N–H...O hydrogen bond must be very weak and transient in nature. Contraction of the cavity site upon cooling imposes a distortion upon the ammonium ion that affects vibrational modes. This distortion does not affect the motion of the ammonium ion as observed on the NMR time-scale.