The OH site in topaz: an IR spectroscopic investigation

The OH site in topaz is investigated by IR spectroscopy depending on the OH concentration and temperature. The two OH bands that can be distinguished are due to the local ordering of F and OH in opposite sites of the crystal structure. The first typical sharp band stems from OH groups with fluorine in the opposite (=acceptor) site. The second band occurs as a shoulder on the low-energy wing and is related to two opposite OH groups. The degree of local OH–OH ordering depends on the OH concentration and, due to statistical F/OH distribution, can be predicted by probability calculations. The substitution of OH for F has a non-linear effect on the increase of the lattice parameters. An autocorrelation analysis of the IR spectra revealed two temperature-induced phase transitions. At −135°C, the local symmetry changes from P1 to Pbn2₁, although this change involves only the H atoms. The transition from Pbn2₁ to Pbnm at 160°C is caused by changes of the local F/OH ordering in the crystal structure.     

High temperature structural and thermoelastic behaviour of mantle orthopyroxene: an in situ neutron powder diffraction study

The temperature induced structural evolution and thermoelastic behaviour of a natural (Pbca) orthopyroxene (Opx), with chemical formula ^M2(Mg_0.856Ca_0.025Fe²⁺ _0.119) ^M1(Mg_0.957Fe²⁺ _0.011Fe³⁺ _0.016Cr_0.011Al_0.005)Al_0.032Si_1.968O₆, from a suite of high pressure ultramafic nodules of mantle origin, have been investigated by in-situ neutron powder diffraction at several temperatures starting from 1,200°C down to 150°C. Unit-cell parameter variations as a function of T show no phase transition within this temperature range. The volume thermal expansion coefficient, α = V ⁻¹(∂V/∂T) _P0, varies linearly with T. The axial thermal expansion coefficients, α_j = l _j⁻¹(∂l _j/∂T)_P0, increase non-linearly with T. The principal Lagrangian unit-strain coefficients (ɛ//a, ɛ//b, ɛ//c), increase continuously with T. However, the orientation of the unit-strain ellipsoid appears to change with T. With decreasing T, the values of the unit-strain coefficients along the b and c axes tend to converge. The orientation at ΔT = 1,080°C is maintained down to the lowest temperature (150°C). The two non-equivalent tetrahedral chains, TA _n OA_3n and TB _n OB_3n , are kinked differently. At room-T, the TB _n OB_3n chain is more strongly kinked by about 23° than the TA _n OA_3n chain. With increasing T, the difference decreases by 3° for the TB _n OB_3n chain. The intersite cation exchange reaction between M1 and M2 (Mg²⁺ and Fe²⁺) shows a slight residual order at 1,200°C followed by reordering with decreasing temperature although seemingly not with a definite progressive trend. At the lowest temperature reached (150°C), reordering has occurred with the same value of partitioning coefficient K _D as that before heating. The absence of the expected phase transition is most likely due to the presence of minor amounts of Fe³⁺, Al, Ca and Cr which must play a crucial role on the thermoelastic behaviour and phase stability fields in natural Opx, with consequent important petrologic and geological implications.     

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     

Spectroscopic investigation on the presence of OH in natural barrerite and in its collapsed phases

Barrerite, a zeolite with a stilbite-type framework, transforms on heating at 200–380° C and at 380–450° C into two new phases, called barrerite B and D respectively. After a few days barrerite B rehydrates to barrerite C. In the B and C heat-collapsed phases the aluminosilicate framework is interrupted by the statistical breaking of an oxygen bridge, giving rise to two partially occupied face-sharing tetrahedra. Near infrared (NIR) diffuse reflectance spectra show the absence of hydroxyls in natural barrerite and the presence of hydroxyls in its heat-collapsed phases. These results confirm the hypothesis that the fourth vertex of the tetrahedra generated from the breaking of the oxygen bridge is a hydroxyl. The presence of OH-bands in phase D suggests for this phase, as in the B and C phases, the presence of interrupted oxygen bridges.     

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.     

In situ Raman spectroscopy on kerogen at high temperatures and high pressures

Kerogen samples were treated at temperatures and pressures up to 25–600°C and ~9 GPa, respectively. In situ micro-Raman spectroscopy was used to measure the systematic changes in the first-order Raman spectral features during the process of temperature or pressure increment. Three Raman bands, D1, D2, and G bands, were examined to characterize the structural and chemical changes of kerogen at high temperatures and pressures. We found that the wavenumbers of D1, D2 and G bands showed a linear variation with both temperature and pressure. Therefore, a correlation between R1 and R2 and the peak temperature in regionally metamorphosed rocks cannot be applied to this work. This result implies that the G band may serve as a temperature or pressure indicator during the promotion of maturation of kerogen. Kerogen possesses reversible properties in contrast with the natural samples recovered from the field suffered from prolonged thermal history during regional metamorphism.     

Solubility of Ca and Al in orthopyroxene from spinel peridotite: an improved version of an empirical geothermometer

Geothermometric equations for spinel peridotites by Fujii (1976), Gasparik and Newton (1984), and Chatterjee, and Terhart (1985) based on the reaction enstatite (en)+spinel (sp)Mg–Tschermaks (mats)+forsterite (fo) were tested using a nearly isothermal suite of mantle xenoliths from the Eifel, West Germany. In spite of using activities of MgAl₂O₄, en, and mats to allow for the non-ideal solution behaviour of the constituent phases, temperatures calculated from these equations systematically change as a function of Cr/(Cr+AL+Fe³⁺) in spinel. We propose an improved version of the empirical geothermometer for spinel peridotites of Sachtleben and Seck (1981) derived from the evaluation of the solubilities of Ca and Al in orthopyroxene from more than 100 spinel peridotites from the Rhenish Volcanic Province. A least squares regression yielded a smooth correlation between

How natural hazards impact the social environment for vulnerable groups: an empirical investigation in Japan

Natural Hazards - Much research has demonstrated that vulnerable people fare more poorly than non-vulnerable ones in disasters and crises across a variety of outcomes—including mental and...     

Water in boninite glass and coexisting orthopyroxene: concentration and partitioning

 Spectroscopic measurements of water in glass inclusions in pyroxene from boninite samples from the Bonin Islands conclusively document the high (2.8–3.2 wt %) primary water contents of boninite magmas. Associated quenched glass from pillow lava rims have slightly lower (2.2–2.4 wt %) water contents, suggesting that minor amounts of degassing occurred between the time of melt entrapment in the orthopyroxenes and subsequent eruption on the sea floor. Some zonation of molecular water contents in pillow rim glasses was observed. OH contents of the host orthopyroxene phenocrysts were also measured, allowing for the calculation of partition coefficients for water between boninite melt and orthopyroxene. These values (0.003–0.004) for water partitioning between orthopyroxene and mafic melts may help constrain petrogenetic models of mantle-derived magmas. Received: 20 September 1993 / Accepted: 26 June 1994     

Ferric iron in orthopyroxene: a Mössbauer spectroscopic study

Ferric iron solid solution in synthetic orthopyroxene has been studied along the joins MgSiO₃-Al₂O₃ · Fe₂O₃ and MgSiO₃-Fe₂O₃. The partially reduced synthetic orthopyroxenes showed that major incorporation of ferric iron can only occur together with a concomitant incorporation of Al. Maximum solid solution of ferric iron along the join MgSiO₃-Fe₂O₃ was found to be only 0.63 wt% Fe₂O₃ at 1000°C and 2 kb total pressure. From the observed Mössbauer parameters octahedral ferric iron can be assigned to the MI position in orthopyroxene. Incorporation of Fe³⁺ and/or Al will increase the disorder of Fe²⁺ and Mg between the M1 and M2 sites, which is also observed in a ferric iron-containing aluminous orthopyroxene of metamorphic origin. In the assemblage orthopyroxene + sillimanite + quartz the ferric iron content of orthopyroxene is directly related to oxygen fugacity.     

Kinetic mechanism of oxygen isotope disequilibrium in precipitated witherite and aragonite at low temperatures: an experimental study

To study what dictates oxygen isotope equilibrium fractionation between inorganic carbonate and water during carbonate precipitation from aqueous solutions, a direct precipitation approach was used to synthesize witherite, and an overgrowth technique was used to synthesize aragonite. The experiments were conducted at 50 and 70°C by one- and two-step approaches, respectively, with a difference in the time of oxygen isotope exchange between dissolved carbonate and water before carbonate precipitation. The two-step approach involved sufficient time to achieve oxygen isotope equilibrium between dissolved carbonate and water, whereas the one-step approach did not. The measured witherite-water fractionations are systematically lower than the aragonite-water fractionations regardless of exchange time between dissolved carbonate and water, pointing to cation effect on oxygen isotope partitioning between the barium and calcium carbonates when precipitating them from the solutions. The two-step approach experiments provide the equilibrium fractionations between the precipitated carbonates and water, whereas the one-step experiments do not. The present experiments show that approaching equilibrium oxygen isotope fractionation between precipitated carbonate and water proceeds via the following two processes:

1.

Oxygen isotope exchange between [CO₃]²⁻ and H₂O:

(1)     

Antigorite equation of state and anomalous softening at 6 GPa: an in situ single-crystal X-ray diffraction study

The compressibility of antigorite has been determined up to 8.826(8) GPa, for the first time by single crystal X-ray diffraction in a diamond anvil cell, on a specimen from Cerro del Almirez. Fifteen pressure–volume data, up to 5.910(6) GPa, have been fit by a third-order Birch–Murnaghan equation of state, yielding V ₀ = 2,914.07(23) Å³, K _T0 = 62.9(4) GPa, with K′ = 6.1(2). The compression of antigorite is very anisotropic with axial compressibilities in the ratio 1.11:1.00:3.22 along a, b and c, respectively. The new equation of state leads to an estimation of the upper stability limit of antigorite that is intermediate with respect to existing values, and in better agreement with experiments. At pressures in excess of 6 GPa antigorite displays a significant volume softening that may be relevant for very cold subducting slabs.     

Nanoparticles in natural systems II: The natural oxide fraction at interaction with natural organic matter and phosphate

Information on the particle size and reactive surface area of natural samples and its interaction with natural organic matter (NOM) is essential for the understanding bioavailability, toxicity, and transport of elements in the natural environment. In part I of this series (Hiemstra et al., 2010), a method is presented that allows the determination of the effective reactive surface area (A, m²/g soil) of the oxide particles of natural samples which uses a native probe ion (phosphate) and a model oxide (goethite) as proxy. In soils, the natural oxide particles are generally embedded in a matrix of natural organic matter (NOM) and this will affect the ion binding properties of the oxide fraction. A remarkably high variation in the natural phosphate loading of the oxide surfaces (Γ, μmol/m²) is observed in our soils and the present paper shows that it is due to surface complexation of NOM, acting as a competitor via site competition and electrostatic interaction. The competitive interaction of NOM can be described with the charge distribution (CD) model by defining a ≡NOM surface species. The interfacial charge distribution of this ≡NOM surface species can be rationalized based on calculations done with an evolved surface complexation model, known as the ligand and charge distribution (LCD) model. An adequate choice is the presence of a charge of −1 v.u. at the 1-plane and −0.5 v.u. at the 2-plane of the electrical double layer used (Extended Stern layer model).The effective interfacial NOM adsorption can be quantified by comparing the experimental phosphate concentration, measured under standardized field conditions (e.g. 0.01 M CaCl₂), with a prediction that uses the experimentally derived surface area (A) and the reversibly bound phosphate loading (Γ, μmol/m²) of the sample (part I) as input in the CD model. Ignoring the competitive action of adsorbed NOM leads to a severe under-prediction of the phosphate concentration by a factor ∼10 to 1000. The calculated effective loading of NOM is low at a high phosphate loading (Γ) and vice versa, showing the mutual competition of both constituents. Both constituents in combination usually dominate the surface loading of natural oxide fraction of samples and form the backbone in modeling the fate of other (minor) ions in the natural environment.Empirically, the effective NOM adsorption is found to correlate well to the organic carbon content (OC) of the samples. The effective NOM adsorption can also be linked to DOC. For this, a Non-Ideal Competitive adsorption (NICA) model is used. DOC is found to be a major explaining factor for the interfacial loading of NOM as well as phosphate. The empirical NOM-OC relation or the parameterized NICA model can be used as an alternative for estimating the effective NOM adsorption to be implemented in the CD model for calculation of the surface complexation of field samples. The biogeochemical impact of the NOM-PO₄ interaction is discussed.     

Cr diffusion in orthopyroxene: Experimental determination, Mn-Cr thermochronology, and planetary applications

We have determined Cr diffusion coefficients (D) in orthopyroxene parallel to the a-, b-, and c-axial directions as a function temperature at f(O₂) corresponding to those of the wüstite-iron (WI) buffer. Diffusion is found to be significantly anisotropic with D(//c) > D(//b) > D(//a), conforming to an earlier theoretical prediction. Increase of f(O₂) from WI buffer conditions to 4.5 log unit above the buffer at 950 and 1050 °C leads to decrease of D(Cr) by a factor of two to three, possibly suggesting significant contribution from an interstitial diffusion mechanism. We have used the diffusion data to calculate the closure temperatures (T_c) of the Mn-Cr decay system in orthopyroxene as a function of initial temperature (T₀), grain size (a) and cooling rate for spherical and plane sheet geometries. We also present graphical relations that permit retrieval of cooling rates from knowledge of the resetting of Mn-Cr ages in orthopyroxene during cooling, T₀ and a. Application of these relations to the Mn-Cr age data of the cumulate eucrite Serra de Magé yields a T_c of 830-980 °C, and cooling rates of 2-27 °C/Myr at T_c and ∼1-13 °C/Myr at 500 °C. It is shown that the cooling of Serra de Magé to the closure temperature of the Mn-Cr system took place at its original site in the parent body, and thus implies a thickness for the eucrite crust in the commonly accepted HED parent body, Vesta, of greater than 30 km. This thickness of the eucrite crust is compatible only with a model of relatively olivine-poor bulk mineralogy in which olivine constitutes 19.7% of the total asteroidal mass.     

Neodymium diffusion in orthopyroxene: Experimental studies and applications to geological and planetary problems

We have determined the Nd³⁺ diffusion kinetics in natural enstatite crystals as a function of temperature, f(O₂) and crystallographic direction at 1 bar pressure and applied these data to several terrestrial and planetary problems. The diffusion is found to be anisotropic with the diffusion parallel to the c-axial direction being significantly greater than that parallel to a- and b-axis. Also, D(//a) is likely to be somewhat greater than D(//b). Diffusion experiments parallel to the b-axial direction as a function of f(O₂) do not show a significant dependence of D(Nd³⁺) on f(O₂) within the range defined by the IW buffer and 1.5 log unit above the WM buffer. The observed diffusion anisotropy and weak f(O₂) effect on D(Nd³⁺) may be understood by considering the crystal structure of enstatite and the likely diffusion pathways. Using the experimental data for D(Nd³⁺), we calculated the closure temperature of the Sm-Nd geochronological system in enstatite during cooling as a function of cooling rate, grain size and geometry, initial (peak) temperature and diffusion direction. We have also evaluated the approximate domain of validity of closure temperatures calculated on the basis of an infinite plane sheet model for finite plane sheets showing anisotropic diffusion. These results provide a quantitative framework for the interpretation of Sm-Nd mineral ages of orthopyroxene in planetary samples. We discuss the implications of our experimental data to the problems of melting and subsolidus cooling of mantle rocks, and the resetting of Sm-Nd mineral ages in mesosiderites. It is found that a cooling model proposed earlier [Ganguly J., Yang H., Ghose S., 1994. Thermal history of mesosiderites: Quantitative constraints from compositional zoning and Fe-Mg ordering in orthopyroxene. Geochim. Cosmochim. Acta 58, 2711-2723] could lead to the observed ∼90 Ma difference between the U-Pb age and Sm-Nd mineral age for mesosiderites, thus obviating the need for a model of resetting of the Sm-Nd mineral age by an “impulsive disturbance” [Prinzhoffer A, Papanastassiou D.A, Wasserburg G.J., 1992. Samarium-neodymium evolution of meteorites. Geochim. Cosmochim. Acta 56, 797-815].     

Correcting for crystal tilt in HRTEM images of minerals: the case of orthopyroxene

High-resolution transmission electron microscopy (HRTEM) is a powerful technique for crystal structure imaging and real structure analysis. It is theoretically possible to resolve inter-atomic distances with modern high resolution microscopes. In practice, however, the effects of sample and lens parameters such as crystal tilt and phase contrast transfer function (CTF) distort the images, reduce the resolution offered, and make image interpretation difficult. We have analyzed to what extent it is possible to reconstruct interpretable images of a tilted mineral by image processing.HRTEM images of orthopyroxene were simulated for a series of crystal tilts and thicknesses under Scherzer defocus condition using the parameters of a 400 kV microscope. The tilted images were reconstructed by crystallographic image processing. After correcting for crystal tilt, the images were as good as electron density maps calculated from X-ray diffraction structure factors.     

CO2 production in tar sand reservoirs under in situ steam temperatures: Reactive calcite dissolution

Recovery of highly viscous oil from some of the deeper oil sand deposits of northern Alberta, Canada, is made possible through injection of heat by steam or hot water flooding of the reservoirs. The rise in temperature lowers the viscosity of the bitumen allowing it to be produced. The increase in temperature accelerates the reactions between the matrix and pore minerals of the formation and can produce reaction products which can significantly alter the permeability of the reservoir. If carbonate minerals are present in the reservoir, inorganic CO₂ may also be a reaction product.

The Grand Rapids reservoir consists of relatively clean quartz sand containing 7 wt.% kaolinite, 1 wt.% calcite and a trace of smectite. Core floods of this sand by a neutral NaCl brine at 265°C, 8.2-MPa overburden pressure, 6.0-MPa fluid pressure and a flow velocity of 0.4 pore volumes per hour were used to determine the potential for hydrothermal reactions between clays and carbonate minerals in a natural reservoir sand. Reaction progress was followed by continuous sampling of the production fluids. The produced water was analyzed and the phase chemistry was calculated back to the run conditions using the computer code SOLMNEQF.

Mass-balance considerations on produced total inorganic carbon (TIC) show that calcite broke down very quickly, the maximum in CO₂ production occurring after only one pore volume of fluid had passed through the core. The Ca released from the breakdown of calcite was incorporated in the formation of smectite as was shown by post-run clay mineral analysis by the following unbalanced chemical reaction:

calcite+kaolinite+H₄Si04Ca-smectite+H₂0+CO₂

Silica was supplied by the dissolution of quartz. Silica concentrations analyzed in the production fluid were depressed from those predicted by previously published quartz rate equations because of the rapid rate of smectite synthesis.

These observations were used to formulate the following model for the passage of the first pore volume of NaCl brine through the core. Initially calcite is present throughout the core. As the brine enters the inlet of the core, it equilibrates with calcite. The brine remains in equilibrium with calcite throughout the core as quartz and kaolinite react to form smectite. This model was tested with the computer code PATH.UBC using CO₂ production as a measure of the progress variable ξ. A best fit was achieved to the produced fluid chemistry by varying relative dissolution rates of kaolinite and quatz and varying the suppression of precipitation of certain minerals.     

The Ni-in-garnet geothermometer: calibration at natural abundances

Experiments to study the partitioning of Ni between olivine and garnet at natural abundances were performed at 1200 °C – 3 GPa, 1300 °C – 3, 5 and 7 GPa and 1500 °C – 5 GPa using piston-cylinder and multi-anvil apparatus. The experiments were intended to provide a further test of the Ni-in-garnet geothermometer calibrated previously using enhanced Ni levels. The run products were analysed by electron microprobe using special operating conditions to enhance counting statistics. Ni-Mg and Fe-Mg exchange between olivine and garnet was tightly reversed. Results of the experiments suggest that Ni substitution in garnet behaves according to Henry's Law up to levels of ∼3000 ppm. The Ni-in-garnet geothermometer derived from reversed experiments in this study is consistent (within error) with that derived from previous experiments at enhanced levels of Ni; neither of these experimental calibrations is consistent with any empirically derived Ni-in-garnet geothermometer. Sources of the discrepancy between the empirical and experimental calibrations of the Ni-in-garnet geothermometer are examined in detail and it is concluded that the main reason for the differences involves errors in the calculation of temperatures in the empirical version. These errors are clearly demonstrated using a recently published data set for garnet peridotite xenoliths in which both Ni-in-garnet and more conventional multi-equilibrium thermobarometry was employed. Received: 25 August 1998 / Accepted: 10 March 1999