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.     

星际闪烁和BLO 0716＋71的快速射电变化

利用星际介质的折射闪烁理论解释在ＢＬＬａｃ天体０７１６＋７１中观测到的射电快速变化的结构函数，确定了对射电源结构和散射介质特性所提出的条件。为了解释这个源内观测到的射电变化的“快模式”和“慢模式”的转换，必须考虑时电源内致密结构的角径或运动状态的快速变化。射电变化和光学变化的相关性仍然是析射闪烁解释的一个难于克服的困难。     

Corrections to the luni-solar precession derived from a compilation catalogue of extragalactic radio sources

Observation catalogues of extragalactic radio sources obtained by Very long Baseline Interferometry during the last decade agree in the mean to a few milliarcseconds (mas). Within this range the position differences show constant, linear and periodic offsets. To reduce the influence of individual catalogue properties the construction of a compilation catalogue seems to be the appropriate procedure. In some detail the compilation method is described providing simultaneous adjustment of source positions and catalogue corrections. The compilation catalogue consists of 40 objects having positional errors of 0.2 mas in right ascension (RA) and 0.3 mas in declination (Dec). Comparing this catalogue with the IERS Celestial Reference Frame compiled by means of other precepts yields weighted root-mean-square differences of 0.7 mas in RA and 1.3 mas in Dec. Finally, the terms of general precession in RA and Dec are included in the adjustment process giving estimates of the correction to the luni-solar precession between –1 and –3 mas/yr, the latter figure applying when some early data are added.     

Phase transition and compression behavior of gibbsite under high-pressure

In situ high-pressure synchrotron X-ray diffraction and infrared absorption experiments for gibbsite were performed at room temperature up to 53 and 25 GPa, respectively. A phase transition was confirmed at about 2.5 GPa. The high-pressure phase is indexed as an orthorhombic structure, rather than a triclinic structure as reported in previous studies. The compressibility of gibbsite and its high-pressure polymorph were studied, and their bulk moduli K₀ were determined to be 49 and 75 GPa, respectively with K₀ as 4. The in situ high-pressure infrared absorption spectra revealed the gradual disordering of hydrogen substructure above 15 GPa in quasihydrostatic compression.     

Total OH Loss Rate Measurement

A new instrument has beendeveloped to measure the total decay rate of OH in ambient air. Theinstrument is based on the discharge flow technique in which OHgenerated within the instrument is reacted with ambient air pulled intothe flow tube. The OH decay is monitored by laser-induced fluorescence. Thistotal decay rate is compared to the sum of the individual decay rates ofOH with each trace species measured in the air to test for missing OHreactants. OH decay rates measured in an urban environment in thesummer of 1999 illustrates the promise of this technique.     

Three-Dimensional Calculation of Photolysis Frequencies in the Presence of Clouds and Impact on Photochemistry

For atmospheric photochemistry, clouds can significantly affect actinic flux distributions. In this paper, we examine the effects of convective clouds on the three-dimensional distribution of the spectral actinic flux and on photolysis frequencies for various chemical species. Three-dimensional solutions of the UV-VIS radiative transfer equation are produced using the Spherical Harmonic Discrete Ordinary Method solution technique. This solver uses as input the 3-D cloud characteristics simulated by a dynamical cloud model. The ultraviolet and visible spectra are divided into 5 intervals in order to explore the wavelength dependency of the cloud effect on the actinic flux. Results show that the distribution of the actinic flux over the cloud domain is far from homogeneous and depends primarily on the cloud extinction associated with the hydrometeors. Maximum actinic flux is found at the top edge of the cloud and is related to scattering by ice crystals. The actinic flux is enhanced by a factor of 2 to 5, compared to clear air values, above, at the top edge, and around the cloud. The 3-D actinic flux is used to calculate the photolysis rates for some chemical species (e.g. NO₂, O₃, and HCHO). Forcomputing photolysis rates, a discretized spectral representation of the absorption wavelengths is used in the model. The calculated photolysis rates are distributed inhomogeneously throughout the cloud, and maxima are found in regions where the actinic flux is enhancement is large. Temperature effects on absorption are found in the photolysis frequencies of some species. Finally, the potential importance of this photolysis enhancement on photochemistry is studied using box model simulations. Results show that enhanced OH concentrations are found in the upper troposphere (120–200%) overthe clouds and changes in ozone production rates (+15%) are obtained in quasi-steady state conditions.     

Highly Time Resolved Measurements of OH during POPCORN Using Laser-Induced Fluorescence Spectroscopy

Tropospheric hydroxyl radical (OH) concentrations were measured by laser-induced fluorescence (LIF) during the POPCORN field campaign in August 1994 at a rural site in the North East of Germany. Ambient air spectra were recorded by tuning the laser wavelength over a spectral region covering the Q11(3), Q21(3), and P11(1) rotational transitions of the (0-0) band in the A-X system of OH around 308 nm. The observed spectra clearly identify the OH radical in the atmosphere. Besides the OH absorption lines there was no sign of any other narrow-band spectral structure nearby demonstrating the high specificity of the method. For OH measurements with a typical time resolution of 60–100 seconds per data point the laser wavelength was tuned repetitively over small spectral intervals covering the peak position of the P11(1) OH-line and background positions. A total of 2300 measurements were recorded including diurnal cycles of OH with more than 300 data points. The OH as well as the LIF background signal data will be presented. In a first analysis the background signal will be characterized and the correlation between OH and the ozone photolysis frequency will be derived.     

表面活性剂影响Mg（OH）2吸附硼的研究

本文研究了表面活性剂对氢氧化镁吸附硼的影响,对不同类型的表面活性剂,不同的加入方式以及不同的加入量等进行了试验,并试验了在表面活性剂存在下,pH值对吸硼量的影响。阴离子表面活性剂——十二烷基硫酸钠的加入 可以减少Mg(OH)_2对硼的吸附;十二烷基硫酸钠加入的顺序对Mg(OH)_2吸硼没有影响,这表明Mg(OH)_2吸硼是可逆的;在十二烷基硫酸钠的存在下,最大吸硼量时的pH为10.3。     

Rate constant measurement for the reactions of OH and Cl with peroxyacetyl nitrate at 298 K

The gas phase reactions of peroxyacetyl nitrate (PAN) with OH and Cl have been studied using the discharge-flow EPR method. The rate constants are found to be k ₃=(7.5±1.4)×10^-14 and k ₄=(3.7±1.7)×10^-13 cm³ molecule^-1 s^-1 at 298 K, respectively. These results confirm that the OH+PAN reaction will be the dominant sink of PAN in the middle and upper troposphere, whereas the reaction Cl+PAN will be negligible in contrast with previous estimations.     

Crystal chemistry and OH defect concentrations in spodumene from different granitic pegmatites

Thirty spodumene samples of distinct paragenetic types (primary magmatic, secondary after petalite and hydrothermal) from variety of granitic pegmatites were characterized by electron microprobe, polarized FTIR spectroscopy and Mössbauer spectroscopy. The FTIR spectra of OH (weak sharp pleochroic bands at 3,425, 3,410, 3,395 cm⁻¹ and in the 3,500–3,470 spectral region) are strongly polarized with maximum absorption parallel to n_γ. The majority of OH dipoles are presumably generated by a partial replacement of O2 oxygen atoms with an orientation pointing above the Li vacancy site. The separation of the bands probably resulted from a replacement of the coordinating Al by Fe and Si by Al. Homogeneous spodumene mostly close to its ideal formula LiAlSi₂O₆ shows Fe (0.00–0.10 apfu as Fe³⁺; Fe³⁺ >> Fe²⁺) and Na (0.00–0.04 apfu) as the only minor cations and Fe³⁺Al₋₁ substitution up to 10 mol% of the LiFe³⁺Si₂O₆ component. Hydrogen concentrations (from 0.1 up to <5 ppm H₂O by weight) vary as a function of genetic type with the highest amounts in high-temperature magmatic spodumene. Differences among particular genetic types of spodumene are related to maximum solubility of OH in spodumene structure at given P–T conditions and at actual chemical composition of spodumene. OH defect concentrations in spodumene follow a trend, LT/LP pyroxenes containing lower hydrogen contents compared to HT/HP ones. The hydrogen contents in particular genetic types of spodumene and their decrease with decreasing T and P are consistent with petrologic models of the pegmatite (sub)types formations.