IR active orientation of OH bending mode in topaz

Infrared (IR) and nearinfrared (NIR) absorption spectra of hydrous and F-rich topazes were measured to assign an OH bending mode of topaz. Three absorption peaks at 1165, 3650, and 4803 cm⁻¹ are assigned to OH related absorption peaks. Since a peak at 4803 cm⁻¹ can be assigned to a combination mode of 1165 and 3650 cm⁻¹, the 1165 cm⁻¹ peak is harmonic with the 3650 cm⁻¹ peak. Polarized IR absorption spectra of (100), (010), and (001) planes of the hydrous topaz were measured to examine IR active orientation of the 1165 cm⁻¹ OH related mode. Three pleochroic distributions of the absorption peak at 1165 cm⁻¹ on (100), (010), and (001) planes indicate an active orientation of the 1165 cm⁻¹ OH related mode. The IR active orientation of the 1165 cm⁻¹ OH related mode in topaz is normal to the OH dipole. The orthogonality and harmonic combination mode indicate that the 1165 cm⁻¹ peak is OH bending mode. The active orientation of OH bending mode is polarized in the plane normal to the OH dipole. The polarization suggests that anisotropic thermal vibration of protons on the hydroxyl is maximum along the IR active orientation. Received: August 16, 1996 / Revised, accepted: April 20, 1997     

The quantitative IR spectroscopic determination of structural OH groups in kyanites

Summary Kyanites from different occurrences show in the near IR two relatively strong absorption bands at 3 380 and 3 270 cm^–1 due to OH stretching frequencies. The integral molar extinction coefficient is 3201 · Mol^–1 · cm^–2. A quantitative IR spectroscopic microtechnique based on Beer's law allows to determine small amounts of structural OH groups in (100) cleavage plates of a few tenths mm in size proved to be free of inclusions and hydrous alteration products. There exists an obvious relation between the occurrence of the kyanites studied and their equivalent H₂O⁺ content ranging from < 0.005 to 0.180 wt.%.

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Die quantitative IR-spektroskopische Bestimmung von strukturell gebundenen OH Gruppen in Kyaniten

Zusammenfassung Kyanite verschiedener Vorkommen zeigen im nahen IR bei 3 380 und 3 270 cm^–1 zwei relativ starke Absorptionsbanden, die von OH-Streckfrequenzen herrühren. Der integrale molare Extinktionskoeffizient beträgt 320 1 · Mol^–1 · cm^–2. Eine auf dem Beerschen Gesetz beruhende quantitative IR-spektroskopische Mikromethode erlaubt kleine Mengen strukturell gebundener OH-Gruppen in (100) Spaltplättchen einiger Zehntelmillimeter Größe, die einschlußfrei und frei von Umwandlungsprodukten sind, zu bestimmen. Es besteht offensichtlich eine Beziehung zwischen dem Vorkommen der untersuchten Kyanite und ihrem äquivalenten H₂O⁺-Gehalt, der sich von < 0.005 bis 0.180 Gew.-% erstreckt.

     

The orientation of the OH− dipole in an optically anisotropie crystal: An application to the OH− dipole in topaz

For the purpose of determining the orientation of the OH^? dipole in an optically anisotropic crystal, distribution of polarized IR absorbance is formulated under Fourier transform microspectroscopy. The formulatd absorbance distribution suggests that the degree of pleochroism of absorbance depends on the angle between the orientation of the OH^? dipole and the principal orientation of the optically anisotropic crystal. As its application, the general orientation of the OH^? dipole in topaz is determined to be inclined 27.3° from the c-axis in (010).     

OH groups in nominally anhydrous framework structures: An infrared spectroscopic investigation of danburite and labradorite

The pleochroic behaviour of two nominally anhydrous structurally similar minerals, danburite and An59 labradorite, was investigated in the region of the OH stretching frequencies. Danburite shows a sharp absorption band at 3540 cm^?1, labradorite shows a broad band with an absorption maximum at 3230 cm^?1. On the basis of the pleochroic scheme of theinfrared (IR) absorption spectra it is proposed that the OH dipoles in danburite are located within the symmetry plane showing a distinct orientation parallel to [010]; the OH groups in labradorite are oriented approximately perpendicular to (001). The proposed models are in accordance with bond valence calculations showing that in both framework structures the most deficient oxygens, O5 in danburite and O _C m in labradorite, are partially replaced by OH.     

OH in natural orthopyroxene: an in situ FTIR investigation at varying temperatures

In situ unpolarized and polarized Fourier transform infrared spectra of a natural orthopyroxene at varying temperatures were obtained using a heating stage attached on an Infrared microscope. The three main bands (3,595, 3,520 and 3,410 cm⁻¹) at room temperature are ascribed to OH fundamental stretching bands. With increasing temperature from room temperature to 500 °C, the 3,595 cm⁻¹ band shifts 20 cm⁻¹ to lower frequency. The total integral absorbance decreases with increasing temperature. These changes are reversible. Excluding the influences of dehydration, proton migration, thermal expansion, and changes in OH dipole direction, the change of integral absorbance with temperature reflects the temperature dependence of absorption coefficient due to the anharmonicity of OH vibration. Based on the integral absorption coefficient at room temperature (14.84 ppm⁻¹ cm⁻²) from Bell et al. (Am Mineral 80:463–474, 1995), the integral absorption coefficients at other temperatures are calculated. The variation of integral absorption coefficient between room temperature and 500 °C obtained in this study is about 18.5 % and may be greater at higher temperature according to the proposed linear relationship.     

In-situ IR measurements of OH species in quartz at high temperatures

The nature of OH species in natural clear quartz was investigated by means of in-situ IR measurements over the temperature range –185 to 1000 °C. Reversible thermal behavior of OH species was examined for a sample pre-heated to 1000 °C for 1 hour. At room temperature, the IR spectrum of the quartz sample examined includes an intense absorption peak at 3379 cm^–1 which has been assigned to an OH stretching vibration associated with Al substituting for Si (OH(Al)). The major spectral changes of the OH(Al) bond involve a systematic shift of its peak position and a decrease in its integral absorbance with temperature. A quasi-linear increase of the peak position from –185 to 400 °C is interpreted to be due to the change in the vibrational frequency of OH(Al) with hydrogen bond (H bond) distance. At higher temperatures, the IR frequency shows only a slight change, indicating a small influence of the H bond. On the other hand, the gradual decrease of the integral absorbance of OH(Al) with temperature indicates a decrease of this defect’s molar absorptivity without any reduction in defect concentration. This is interpreted to result from a decrease in dipole moment of OH(Al) with temperature. A sudden shift of the vibrational frequency from 3396 to 3386 cm^–1 between 550 and 560 °C and a constant value of the integral absorbance from 535 to 570 °C were considered to be related to the change in H bond distance during the structural transformation of α-quartz to its β-form. The local environment of OH(Al) begins to change at temperatures below 570 °C, where the crystallographic α–β transition occurs. Received: 18 February 1998/ Accepted: 10 July 1998     

Raman spectroscopic investigation of the order parameter behaviour in hypersolvus alkali feldspar: Displacive phase transition and evidence for Na-K site ordering

Hard mode Raman spectroscopy (HMRS) on hypersolvus alkali feldspar shows a temperature dependence of the order parameter of the displacive \({{C2} \mathord{\left/ {\vphantom {{C2} {m{\text{ - }}C\bar 1}}} \right. \kern-0em} {m{\text{ - }}C\bar 1}}\) phase transition following mean-field behaviour: $$Q \sim \sqrt {T_c - T;} 300 {\text{K}} \lesssim T< T_c $$ At lower temperatures, a spontaneous saturation sets in, which is attributed to site-ordering effects of the alkali atoms even in hypersolvus anorthoclase. Fluctuational line broadening of Si-O viration bands is explained by strong lattice distortions around alkali positions and local deformation of the Al,Si,O network. The thermodynamic relevance of these distortions is discussed in relation to the possibility of an additional diffuse phase transition occurring atT _d =302 K. The experimental results of HMRS are compared with those on Al,Si ordered and disordered albite, where no fluctuation broadening occurs.     

Color centers in topaz: comparison between neutron and gamma irradiation

Neutron- and gamma irradiation-induced paramagnetic centers in natural colorless topaz from four different Brazilian localities were studied by electron paramagnetic resonance (EPR) and optical absorption as a function of irradiation dose and thermal treatment. Gamma irradiation doses were applied up to 1,000 kGy with a dose rate of 15 kGy h⁻¹. For the neutron irradiation experiments, a neutron flux of 4 × 10¹² cm⁻² s⁻¹ was used with an integrated flux of up to 1 × 10¹⁸ cm⁻². From the experiments, it is concluded that brownish colors are induced by gamma-rays and may be associated with a single broad isotropic EPR line with g = 2.015(2). Both the EPR line and the related optical absorption band at 460 nm (2.7 eV) are lost during thermal treatments between 150 and 200°C. Fast neutrons create the paramagnetic peroxyl radicals O₂ ⁻ and the paramagnetic O⁻ hole centers. The O⁻ centers have the same thermal stability as the optical absorption band at 620 nm (2.0 eV). It is confirmed that the absorption due to the O⁻ center is responsible for the blue color in topaz. Both color centers and their absorption bands are discussed in the context of O⁻ bound small polarons.     

The Quantitative IR Spectroscopic Determination of OH in Apatite Based on 1.4 μm

Water plays an important role in nearly every aspect of geological processes as well as in the evolution of planetary bodies. Chang E-3 NIR spectra appeared weak peak of OH in the vicinity of signal 1.4 μm, it may represent the presence of water. In order to quantitatively calculate the water content, apatite as the research object in the paper. Through analyzing and validating the infrared spectrum correlation between 1.4 μm and 2.8 μm of the structure water in the apatite, we obtained its molar absorption coefficient in the infrared spectrum of 1.4 μm. IR spectra were collected on oriented. When the light vector E is parallel to the c-axis of the apatite crystal, H₂O concentration in apatite can be related to measured IR absorbance as follows: C=ωA/ερd, which based on Beer-Lambert’s law. This result can provide reference for the interpretation of Chang E-3 near-infrared spectral data of water signal. This method can provide the basis for the quantitative calculation of structure water in the near infrared spectrum in other moon minerals.     

Distinct ruby suite at Sardapur, Orissa: A spectroscopic investigation

Orissa is an important area for gem variety of corundum deposits in India. Spectroscopic studies, such as ESR, OAS on samples from Sardapur, Orissa, were carried out to ascertain the colour cause of corundum. Electron spin resonance (ESR) spectroscopic study was carried out on the samples to detect the presence of paramagnetic ions i.e. Fe²⁺, Fe³⁺, Ti⁴⁺, Cr³⁺ and V³⁺ etc. The variable temperature experiment carried out to observe the effect of heating on peak valence state change in paramagnetic ions. Samples were cut and polished to obtain the optical absorption spectrum (OAS) to detect the colour causing transition ions/defect centres. The samples of gem variety were step heated up to 300°C for colour enhancement studies. EPMA analysis has revealed the low chromium concentration in the rubies. The varying hues of red in the corundum are due to the presence of bivalent and trivalent iron and charge transfer process along with Cr³⁺ absorption in the 550 nm region.     

A Raman spectroscopic investigation of Fe-rich sphalerite: effect of fe-substitution

A Raman spectroscopic study of Fe-rich sphalerite (Zn_{1 − x} Fe _x S) has been carried out for six samples with 0.10 ≤ x ≤ 0.24. Both the intensities and frequencies of the TO and LO modes of sphalerite are approximately independent of Fe concentration. However, the substitution of Zn by Fe results in five additional bands with frequencies between the TO (271 cm⁻¹) and LO (350 cm⁻¹) modes. Three of these bands are attributed to resonance modes (i.e. Y ₁, Y ₂ and Y ₃ modes). The fourth band (B mode) is assigned to a breathing mode of the nearest-neighbor sulfur atoms around the Fe atoms. The band at 337 cm⁻¹ is attributed to the presence of Fe³⁺. The excellent correlations between the normalized intensities of these five different modes and x _Fe show that these modes depend on Fe-content. Another extra mode at 287 cm⁻¹ is assigned to the presence of Cd in sphalerite.     

Magnetic and seismic refraction survey for site investigation of an urban expansion site in Abha District,Southwest Saudi Arabia

Arabian Journal of Geosciences - Ground magnetic and seismic refraction survey is carried out on an urban extension site in the southwest of Ahud Rufeidah town, southwest Saudi Arabia. The purpose...     

The relationship between foliation and strain: an experimental investigation

A multilayered salt/mica specimen with embedded strain markers was shortened to produce a fold and the distribution of strain was subsequently mapped out over the profile plane. On a fine scale the initial foliation, which is parallel to the undeformed layers, is folded by tight kinks to produce two new foliations; one is defined by the preferred orientation of kink boundaries and the other by the preferred orientation of (001) of mica. In the hinge region of the fold the first of these new foliations is parallel to the local λ₁λ₂-principal plane of strain whereas the preferred orientation of mica is bimodal and is symmetrical about the λ₁λ₂-plane. Elsewhere the two new foliations are not parallel to the principal plane of strain and angular divergencies of up to 30–35° are measured. If a March model with initial random mica orientation is assumed for the development of mica preferred orientation then the correct value of strain is predicted but the orientation of the principal plane of strain can be grossly in error. A theoretical analysis of the angular relationships to be expected between kink boundaries and the λ₁λ₂-plane of strain confirms that for the type of geometries experimentally developed, large divergences of up to 35° should be common. In rocks where the foliation has developed by processes similar to those recorded here, large angular divergencies between the foliation and the λ₁λ₂-principal plane of strain should be expected as the rule.     

Geoenvironmental site investigation using different techniques in a municipal solid waste disposal site in Brazil

Different geoenvironmental site investigation techniques to assess contamination from a municipal solid waste disposal site in Brazil are presented here. Superficial geophysical investigation (geoelectrical survey), resistivity piezocone penetration tests (RCPTU), soil samples collected with direct-push samplers and water samples collected from monitoring wells were applied in this study. The application of the geoelectrical method was indispensable to identify the presence and flow direction of contamination plumes (leachate) as well as to indicate the most suitable locations for RCPTU tests and soil and water sampling. Chemical analyses of groundwater samples contributed to a better understanding of the flow of the contaminated plume. The piezocone presented some limitations for tropical soils, since the groundwater level is sometimes deeper than the layer which is impenetrable to the cone, and the soil genesis and unsaturated conditions affect soil behavior. The combined interpretation of geoelectrical measurements and soil and water samplings underpinned the interpretation of RCPTU tests. The interpretation of all the test results indicates that the contamination plume has already overreached the landfill’s west-northwest borders. Geoenvironmental laboratory test results suggest that contamination from the solid waste disposal site has been developing gradually, indicating the need for continuous monitoring of the groundwater.     

The relationship between foliation and strain: an experimental investigation: discussion

The account of the relationship of foliation and strain in a salt-mica experiment by Hobbs, Means and Williams is criticized for two reasons. Firstly, the scales of the experimental material and the finite elements measured are considered inappropriate. Secondly, the strain data presented is actually the tectonic, not finite, strain. Both criticisms restrict the application of the experimental results to foliation and strain in rocks.     

The relationship between foliation and strain: an experimental investigation: reply

Contrary to the criticisms of our ideas by Treagus, we still believe that our experiments show that a secondary preferred orientation of micas or of small kink-like folds, closely resembling similar features in some cleaved rocks, can form at large angles to the λ₁λ₂ plane of strain, where the strain referred to is the strain coeval with development of these features.     

Phase relations of a F-enriched peraluminous granite: an experimental study of the Kymi topaz granite stock,southern Finland

Phase relations of F-rich Kymi equigranular topaz granite have been investigated experimentally at 100–500 MPa as a function of water activity and F content. Fluorite and topaz can crystallize as liquidus phases in F-rich peraluminous systems, but the F content of the melt should exceed 2.5–3.0 wt% for the crystallization of topaz. In peraluminous F-bearing melts containing more than 1 wt% F, topaz and muscovite are expected to be the first F-bearing phases to crystallize at high pressure, whereas fluorite and topaz should crystallize first at low pressure. Following reaction models the saturation of fluorite and topaz: CaAl₂Si₂O₈ (plagioclase) + 2[AlF₃]_melt = CaF₂ (fluorite) + 2Al₂SiO₄F₂ (topaz). The obtained partition coefficient for F between biotite and glass D(F)^Bt/glass ranges from 1.89 to 0.80 (average value 1.29) and can be used as an empirical fluormeter to determine the F content of coexisting melts. Combined petrological and experimental studies of the Kymi equigranular topaz granite indicate that plagioclase was the liquidus phase at nearly water-saturated (fluid-saturated) conditions and that the F content of the melt was at least 2 wt%. The mean F content of natural biotite (3.92 wt%) suggests that the late-stage crystallization of biotite occurred in melts containing about 3 wt% F. The early crystallization of biotite and the presence of muscovite in our experiments at 200 MPa contrasts with the late-stage crystallization of biotite and the absence of muscovite in the natural assemblage, indicating that crystallization pressure may have been lower than 200 MPa for the granite. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

The evolution of fluorine-rich felsic magmas: source dichotomy, magmatic convergence and the origins of topaz granite

Topaz granite is alkali-feldspar granite that contains essential albite, quartz, K-feldspar, lithium-mica, and topaz. As a group topaz granites are characterized by their extreme enrichment in F (up to 3 wt%) and a wide variety of lithophile elements. They can be subdivided into a 'low-P₂O₅ subtype' (P₂O₅ < 0.1 wt%, Al₂O₃ < 14.5 wt%, SiO₂ > 73 wt%) and a 'high-P₂O₅ subtype' (P₂O₅ > 0.4 wt%, Al₂O₃ > 14.5 wt%, SiO₂ < 73 wt%), the δ¹⁸O values of which indicate a dichotomy of source rock: the low-P₂O₅ subtype (δ¹⁸O < 10‰) having a meta-igneous protolith and the high-P₂O₅ subtype (δ¹⁸O > 10 ‰) a source with a significant component of pelitic material. The unusually high F contents enhance the efficacy of melt segregation and crystal-melt fractionation and so facilitate extreme differentiation in topaz granite magmas. Very low melt volumes restrict the bulk composition of the partial melts regardless of the nature of the source; and extreme fractionation forces them along a path of magmatic convergence, to produce a group of granitic rocks with near-minimum compositions so enriched in a variety of lithophile elements (Li, Nb, Ta, Sn) that economic mineralization often results.     

Development of a technique for IR spectroscopic determination of nitrogen content and aggregation degree in diamond crystals

A technique for IR spectroscopic determination of the total nitrogen content N _S in the form of A-and B ₁-defects is suggested. It provides for the computer processing and decomposition of IR spectra into constituent bands, calculation of the total absorption band area S _N and individual areas S _A and S _B1 and their normalization with respect to the total area of the diamond intrinsic absorption S ₀, with the normalization coefficients K _S , K _A , and K _B1 being calculated. Based on the analysis of the IR spectra of 60 octahedral diamond crystals from the Mir and Yubileinaya pipes (Sakha-Yakutiya), the empirical functions N _S = 911.85 K _S ^0.9919 ppm (R ² = 0.9859), N _A = 1185.6 K _A ^1.1511 ppm (R ² = 0.8703), and N _B1 = 911.85 K _S ^0.9919 ? 1185.6 K _A ^1.1511 ppm have been defined.