Location and quantitative analysis of OH in coesite

 The incorporation of hydrogen (deuterium) into the coesite structure was investigated at pressures from 3.1 to 7.5 GPa and temperatures of 700, 800, and 1100 °C. Hydrogen could only be incorporated into the coesite structure at pressures greater 5.0 GPa and 1100 °C . No correlation between the concentration of trace elements such as Al and B and the hydrogen content was observed based on ion probe analysis (1335 ± 16 H ppm and 17 ± 1 Al ppm at 7.5 GPa, 1100 °C). The FTIR spectra show three relatively intense bands at 3575, 3516, and 3459 cm⁻¹ (ν₁ to ν₃, respectively) and two very weak bands at 3296 and 3210 cm⁻¹ (ν₄ and ν₅, respectively). The band at 3516 cm⁻¹ is strongly asymmetric and can be resolved into two bands, 3528 (ν_2a) and 3508 (ν_2b) cm⁻¹, with nearly identical areas. Polarized infrared absorption spectra of coesite single-crystal slabs, cut parallel to (0 1 0) and (1 0 0), were collected to locate the OH dipoles in the structure and to calibrate the IR spectroscopy for quantitative analysis of OH in coesite (ɛ _{i ,tot}=190 000 ± 30 000 l mol⁻¹ _H2O cm⁻²). The polarized spectra revealed a strong pleochroism of the OH bands. High-pressure FTIR spectra at pressures up to 8 GPa were performed in a diamond-anvil cell to gain further insight into incorporation mechanism of OH in coesite. The peak positions of the ν₁, ν₂, and ν₃ bands decrease linearly with pressure. The mode Grüneisen parameters for ν₁, ν₂, and ν₃ are −0.074, −0.144 and −0.398, respectively. There is a linear increase of the pressure derivatives with band position which follows the trend proposed by Hofmeister et al. (1999). The full widths at half maximum (FWHM) of the ν₁, ν₂, and ν₃ bands increase from 35, 21, and 28 cm⁻¹ in the spectra at ambient conditions to 71, 68, and 105 in the 8 GPa spectra, respectively. On the basis of these results, a model for the incorporation of hydrogen in coesite was developed: the OH defects are introduced into the structure by the substitution Si^4+(Si2)+4O²⁻= ^[4]□^(Si2) + 4OH⁻, which gives rise to four vibrations, ν₁, ν_2a, ν_2b, and ν₃. Because the OH(D)-bearing samples do contain traces of Al and B, the bands ν₄ and ν₅ may be coupled to Al and/or B substitution. Received: 19 December 2000 / Accepted: 23 April 2001     

Characterisation of tobelite (NH4)Al2[AlSi3O10](OH)2 and ND4-tobelite (ND4)Al2[AlSi3O10](OD)2 using IR spectroscopy and Rietveld refinement of XRD spectra

Tobelite (NH₄) Al₂ [AlSi₃O₁₀] (OH)₂, the ammonium analogue of muscovite, and its deuterated form ND₄-tobelite (ND₄) Al₂ [AlSi₃O₁₀] (OD)₂ have been synthesised at 600?°C and 200 and 500 Mpa using a well homogenised, stoichiometric SiO₂-Al₂O₃ oxide mix with Al₂O₃ in excess of 5 mol% and a 25% NH₃ solution whose relative abundance was such that the amount of NH₄ ⁺ stoichiometrically available was in excess of 50%. Characterisation of both tobelite and ND₄-tobelite using IR-spectroscopy, Rietveld refinement of X-ray powder diffraction data, and electron microprobe analysis indicate that, similar to K⁺ in muscovite, the NH₄ ⁺ or ND₄ ⁺ molecule occupies the interlayer site. IR absorption bands caused by NH₄ ⁺ and ND₄ ⁺ can be explained, to a very good approximation, on the basis of T_d symmetry. Nevertheless, substantial line broadening and the occurrence of shoulders indicate a deviation from ideal T_d symmetry. However, even at 77?K, no discrete splitting of the degenerate states could be confirmed. The OH stretching frequencies observed for synthetic tobelite are quite similar to those for muscovite, indicating that the replacement of K⁺ by NH₄ ⁺ has no effect. The low FWHH of the OH bands indicate that the hydroxyl groups are well ordered within the structure. Rietveld refinement of tobelite and ND₄-tobelite indicates that all samples synthesised consist of the 3 different mica polytypes which are typical of muscovite – namely 1M (C2/m), 2M ₁ (C2/c) and 2M ₂ (C2/c). Tobelite and ND₄-tobelite synthesised at 500 Mpa principally contain the 1M polytype, whereas the principle polytype for ND₄-tobelite synthesised at 200 Mpa, is 2M ₂. Rietveld refinement of X-ray diffraction spectra for tobelite synthesised at 200 Mpa was problematic due to the very broad FWHH of the X-ray peaks indicating poor crystallinity. In comparision to synthetic muscovite, the cell dimensions observed for tobelite and its deuterated analogue are quite similar except for the lattice constant c. Due to the larger radius of NH₄ ⁺ or ND₄ ⁺ compared to K⁺ cation, the c-direction is expanded form 10.275 Å in muscovite to approximately 10.540 Å in tobelite and ND₄-tobelite.     

Application of short-wave infrared spectroscopy to define alteration zones associated with the Elura zinc–lead–silver deposit, NSW, Australia

Short-wave infrared reflectance spectra obtained from a Portable Infrared Mineral Analyser (PIMA) have been used to define alteration zones adjacent to base metal sulfide ore bodies at the Elura Mine, Cobar, Australia. The spectroscopic work identified white mica (sericite), chlorite and carbonates of hydrothermal origin in the alteration zones associated with the ore bodies. Weathering, alteration and ore zones can be discriminated by variations in the intensity and wavelength of relevant absorption features. Hydrothermal alteration is classified into four principal types, namely sericitic, silicic, chloritic and carbonate alteration. The first three types comprise overprinting hydrothermal assemblages of quartz, sericite, chlorite, ankerite, siderite, calcite and sulfides developed in strongly altered metasiltstone and slate of Early Devonian age, adjacent to the zinc–lead–silver mineralisation. An extensive zone of carbonate alteration, manifested as porphyroblasts of siderite in the host metasediments, is recognised beyond the zones of strong alteration. Spectral analysis is consistent with the mineralogical data obtained from XRD and XRF analyses and defines the limits of the alteration zones to distances of about 80 m around the ore bodies. The study demonstrates the potential for spectral analysis to assist with drill hole logging and the identification of alteration zones as part of mineral exploration and development programs.     

黄河上游的阶地与水系变迁

黄河上游于贵德盆地和共和盆地中有７级阶地，再往上游方向存在阶地级数递减的趋势。共和盆地中还有３级古黄河阶地，黄河上游水系是通过一级级河流袭夺相继贯通的，共和盆地与贵德盆地间的黄河古道始于中更新世末期，龙羊峡河段始于６０ｋａ Ｂ．Ｐ．前后，玛多与唐乃亥 间的峡谷河段是２０ｋａ Ｂ．Ｐ．才贯通的。     

岩石化探样中微量铀 钍的XRFA法测定

本文提出以粉末样品直接压饼法测定岩石化探样品中的微量U,Th,其方法简便、快速,适用于各类地质样品,尤其是岩石化探样品测量。     

Prediction method of sand-movement direction in water by geochemical elements

The analysis of sand samples by x-ray fluorescent spectroscopy (XRF) gives the ratio of the geochemical elements to construct the sand samples. The x-ray analysis therefore shows the geochemical characteristics of sand in the sampled area. In this study, sand is sampled on coasts and rivers of the Noto Peninsula to determine the geochemical elements and to show the geological characteristics that occur, especially iron and calcium. The experiments show the effect of rivers and Kotogahama beach on iron and calcium, respectively. Applying the method of ratio matching to the measured data of the geochemical elements, the direction of movement of sand on the coast is determined by considering the correlation matrix and the ratio of geochemical elements between sand samples at two locations. The predominant longshore direction movement of sand offshore in the study area is from south to north. Sand in rivers is not directly transported to adjacent beaches; however, offshore sand is transported to beaches. The estimated direction of movement of sand longshore near coastal structures agrees with observations. The proposed method to predict the direction of movement of sand gives the correct one in comparison with the observed data in rivers.     

成矿过程流体地球化学模拟及其矿床学意义：以江西银山矿床为例

本文将银山成矿体系为富含Ｈ２Ｓ，ＣＯ２的ＮａＣｌ体系，对Ｃｕ，Ｐｂ，Ｚｎ，Ａｇ和Ａｕ等金属元素在该体系降温过程中的地球化学行为和银山矿床的成矿过程进行计算机数字模拟，并与沸腾降温体系进行对比，证明了成矿体系地球化学演化对金属元素的迁移与沉淀具有得要影响。成矿硫体地球化学模拟在矿床成因，深部成矿预测和区域成矿规律研究中具有重要意义。     

且干布拉克蛭石的矿物学研究

本文对产于新疆且干布拉克的我国最大蛭石矿的组成、结构和谱学特征做了系统的阐述。研究表明:且干布拉克蛭石是由金云母风化而成。由于风化的不完全,该蛭石保留了许多金云母的特征。该蛭石不是个严格矿物学意义上的蛭石,它是由金云母、严格矿物学意义上的蛭石、以及两者组成的多种混层矿物的混合物。金云母风化过程中可能有杂质铁相生成。蛭石的颜色和多色性,可能起因于其中的O~(2-)→Fe~(2+23+)和Fe~(2+)→Fe~(3+)     

Intracrystalline fractionation of Fe in synthetic (Fe, Mg, Zn) - bearing staurolite: a Mössbauer spectroscopic study

⁵⁷Fe-Mössbauer spectra of eleven Fe-Mg-bearing staurolite samples, synthesized at 5, 20 and 25 kbar and 680°C, ranging in composition from x_Fe?=1.00 to x_Fe?=0.15, and of two Zn-Fe-bearing staurolite samples, synthesized at 20 kbar and 700°C with x_Fe?=0.10 and x_Fe?=0.32 were collected at room temperature. The spectra reveal that about 80% of Fe_tot (in case of Fe-Mg-bearing staurolite) and about 70% of Fe_tot (in case of Fe-Zn-bearing staurolite) are located as Fe²⁺ at the three subsites Fe1, Fe2 and Fe3 of the tetrahedral T2-site. The refinement of the spectra results in almost identical values for the isomer shift (IS) (±1.0 mm/s) but significantly different values for the quadropole splitting (QS) for the three subsites which is in accordance with the different distortions of these sites. About 8% of Fe_tot (in case of Fe-Mg-bearing staurolite) and 13% of Fe_tot (in case of Fe-Zn-bearing staurolite) are located as Fe²⁺ at the octahedral M4 site, while the remainder percents of Fe_tot indistinguishably occur as Fe²⁺ at the octahedral M1 and M2 sites of the kyanite-like part of the structure. Within the whole Fe-Mg-staurolite solid solution series the Mössbauer parameters QS of the sites M4 and (M1, M2) vary systematically with composition whereas IS remains constant. There is a high negative correlation of the total Mg-content with Fe-occupation of all the Fe-bearing sites indicating a continuous substitution of Fe²⁺ by Mg on all these sites. Synthetic Fe-staurolites show no increasing occupation of the octahedral sites by two-valent cations with pressure, as was assumed by several authors.     

Crystal chemistry of tremolite–tschermakite solid solutions

Tremolite–tschermakite solid solutions have been synthesized between 700 and 850 °C and 200 and 2000 MPa. The starting materials were oxide–hydroxide mixtures and an additional 0.1–1.8 molal CaBr₂ solution. The run products were characterized using SEM, HRTEM, EMP, XRD and FTIR. The synthesized Al tremolites formed needles and lath-shaped crystals of up to 300 × 20 μm. HRTEM investigations showed that the majority of the amphiboles were well ordered. The EMP analysis revealed that the Al tremolites were solid solutions in the ternary tremolite–tschermakite–cummingtonite. The highest observed Al content was close to the composition of magnesiohornblende (X_ts=0.54). Different cummingtonite concentrations (X_cum=0.00–0.18) were observed, which generally increased with Al content. Rietveld refinements of the lattice constants showed a linear decrease of the cell parameters a and b with increasing Al content, whereas c and β increased. Small deviations from the linear behaviour were caused by variable amounts of the cummingtonite component. For pure tschermakite lattice parameters of a=9.7438(11) Å, b=17.936(14) Å, c=5.2995(3) Å, β=105.68(9)° and V=891.7 ± 1.4 ų were extrapolated by least-squares regression. Using the a and β lattice parameters for tremolite, tschermakite and cummingtonite, it was possible to derive amphibole compositions using powder XRD. IR spectra of the Al tremolites showed a total of 12 individual bands. The FWHMs of all bands increased with increasing Al content. According to their FWHMs, these bands were grouped into three band systems at 3664–3676 cm^?1 (I), 3633–3664 cm^?1 (II) and 3526–3633 cm^?1 (III). Assuming ^[6]Al substitution at M2 and/or M3 and ^[4]Al at T1, three principal different configurational groups could be assigned as local environments for the proton. I: only Si⁴⁺ at T1 and one or two Al³⁺ at M2 and/or M3_far, II: one Al³⁺ at T1 and one to three Al³⁺ at M2 and/or at M3_far, III: either Al³⁺ on M3_near and/or two Al³⁺ on T1 and additional one to four Al³⁺ at M2. It is assumed that these three configurational groups correspond to the three groups of observed bands. This was quantitativly supported by Monte-Carlo simulations. A model with random distribution at M2 and M3 including Al avoidance at tetrahedral and octahedral sites yielded the best agreement with the spectroscopical results.