Schorlomite: a discussion of the crystal chemistry, formula, and inter-species boundaries

Examination of schorlomite from ijolite at Magnet Cove (USA) and silicocarbonatite at Afrikanda (Russia), using electron-microprobe and hydrogen analyses, X-ray diffraction and Mössbauer spectroscopy, shows the complexity of substitution mechanisms operating in Ti-rich garnets. These substitutions involve incorporation of Na in the eightfold-coordinated X site, Fe²⁺ and Mg in the octahedrally coordinated Y site, and Fe³⁺, Al and Fe²⁺ in the tetrahedrally coordinated Z site. Substitutions Ti⁴⁺Fe³⁺Fe³⁺_–1Si_–1 and Ti⁴⁺Al³⁺Fe³⁺_–1Si_–1 are of major significance to the crystal chemistry of schorlomite, whereas Fe²⁺ enters the Z site in relatively minor quantities (<3% Fe). There is no evidence (either structural or indirect, such as discrepancies between the measured and calculated Fe²⁺ contents) for the presence of ^[6]Ti³⁺ or ^[4]Ti⁴⁺ in schorlomite. The simplified general formula of schorlomite can be written as Ca₃Ti⁴⁺₂[Si_3-x(Fe³⁺,Al,Fe²⁺)_xO₁₂], keeping in mind that the notion of end-member composition is inapplicable to this mineral. In the published analyses of schorlomite with low to moderate Zr contents, x ranges from 0.6 to 1.0, i.e. Ti⁴⁺ in the Y site is <2 and accompanied by appreciable amounts of lower-charged cations (in particular, Fe³⁺, Fe²⁺ and Mg). For classification purposes, the mole percentage of schorlomite can be determined as the amount of ^[6]Ti⁴⁺, balanced by substitutions in the Z site, relative to the total occupancy in the Y site: (^[6]Ti⁴⁺–^[6]Fe²⁺–^[6]Mg²⁺– ^[8]Na⁺)/2. In addition to the predominant schorlomite component, the crystals examined in this work contain significant (>15 mol.%) proportions of andradite (Ca₃Fe³⁺₂Si₃O₁₂), morimotoite (Ca₃Fe²⁺TiSi₃O₁₂), and Ca₃MgTiSi₃O₁₂. The importance of accurate quantitative determination and assignment of Fe, Ti and other cations to the crystallographic sites for petrogenetic studies is discussed.

Synthesis, crystal structure and crystal chemistry of ferri-clinoholmquistite, ?Li 2Mg 3Fe 3+ 2Si 8O 22(OH) 2

This work reports the synthesis of ferri-clinoholmquistite, nominally _Li2(Mg₃Fe³⁺₂)Si₈O₂₂(OH)₂, at varying f_O2 conditions. Amphibole compositions were characterized by X-ray (powder and single-crystal) diffraction, microchemical (EMPA) and spectroscopic (FTIR, Mössbauer and Raman) techniques. Under reducing conditions ( NNO+1, where NNO = Nickel–Nickel oxide buffer), the amphibole yield is very high (>90%), but its composition, and in particular the FeO/Fe₂O₃ ratio, departs significantly from the nominal one. Under oxidizing conditions ( NNO+1.5), the amphibole yield is much lower (<60%, with Li-pyroxene abundant), but its composition is close to the ideal stoichiometry. The exchange vector of relevance for the studied system is ^M2(Mg,Fe²⁺) ^M4(Mg,Fe²⁺) ^M2Fe³⁺_–1 ^M4Li_–1, which is still rather unexplored in natural systems. Amphibole crystals of suitable size for structure refinement were obtained only at 800 °C, 0.4 GPa and NNO conditions (sample 152), and have C2/m symmetry. The X-ray powder patterns for all other samples were indexed in the same symmetry; the amphibole closest to ideal composition has a = 9.428(1) Å, b = 17.878(3) Å, c = 5.282(1) Å, = 102.06(2)°, V = 870.8(3) ų. Mössbauer spectra show that Fe³⁺ is strongly ordered at M2 in all samples, whereas Fe²⁺ is disordered over the B and C sites. FTIR analysis shows that the amount of ^CFe²⁺ increases for increasingly reducing conditions. FTIR data also provide strong evidence for slight but significant amounts of Li at the A sites.     

The crystal chemistry of lithium and Fe3+ in synthetic orthopyroxene

Lithian ferrian enstatite with Li₂O = 1.39 wt% and Fe₂O₃ 7.54 wt% was synthesised in the (MgO–Li₂O–FeO–SiO₂–H₂O) system at P = 0.3 GPa, T = 1,000°C, fO₂ = +2 Pbca, and a = 18.2113(7), b = 8.8172(3), c = 5.2050(2) Å, V = 835.79(9) Å³. The composition of the orthopyroxene was determined combining EMP, LA-ICP-MS and single-crystal XRD analysis, yielding the unit formula ^M2(Mg_0.59Fe _0.21 ²⁺ Li_0.20) ^M1(Mg_0.74Fe _0.20 ³⁺ Fe _0.06 ²⁺ ) Si₂O₆. Structure refinements done on crystals obtained from synthesis runs with variable Mg-content show that the orthopyroxene is virtually constant in composition and hence in structure, whereas coexisting clinopyroxenes occurring both as individual grains or thin rims around the orthopyroxene crystals have variable amounts of Li, Fe³⁺ and Mg contents. Structure refinement shows that Li is ordered at the M2 site and Fe³⁺ is ordered at the M1 site of the orthopyroxene, whereas Mg (and Fe²⁺) distributes over both octahedral sites. The main geometrical variations observed for Li-rich samples are actually due to the presence of Fe³⁺, which affects significantly the geometry of the M1 site; changes in the geometry of the M2 site due to the lower coordination of Li are likely to affect both the degree and the kinetics of the non-convergent Fe²⁺-Mg ordering process in octahedral sites.     

WHCORS的技术拓展与应用现状

介绍了武汉市连续运行卫星定位服务系统(WHCORS)的基本情况和发展现状;对基于WHCORS技术拓展研究的相关情况和WHCORS的应用推广进行了详述,针对具体的关键技术问题提出了较详细的解决方案,对用户有一定的参考和借鉴作用。     

精细化气象要素温度指导预报在山西区域的误差及特征

利用2009-2010年山西区域108站共730天精细化气象要素温度指导预报资料,对比日最高气温和日最低气温的预报误差,采用常规统计、EOF分析等方法研究指导预报误差的时间和空间分布特征,结果表明:山西区域的温度预报准确率比较稳定,但有明显的季节特点,夏季最高,秋季次之、冬春季相对偏低,日最高气温年平均正、负误差略高于日最低气温误差,春季大,冬秋次之,夏季小;正负误差值的空间分布与山西地形有一定的联系,日最高气温和日最低气温误差的分布特点具有明显的全区一致性.     

GPS-RTK用于矿山高精度沉陷监测的可行性研究

针对复杂地表条件下采用水准测量和导线测量等常规方式进行地表变形周期观测、任务量大甚至无法实施等问题,提出了建立研究区域的似大地水准面精化模型,同时采用GPS-RTK技术获取观测站三维空间信息,进而获得概率积分法预计参数。最后以内蒙古准格尔旗某煤矿的生产实践说明该技术的有效性和可行性,极大地提高了工作效率,为保护煤柱的留设提供了科学的依据。     

“移去-恢复法”在机场工程大比例尺测图控制网中的应用

对大地高、正高与正常高的关系进行阐述,对机场工程场址条件较为困难时使用区域似大地水准面精化的方式满足大比例尺测图的可能性进行叙述,对"移去-恢复法"的计算方法、误差来源与精度评定方法进行论述,在实际算例中使用不同的EGM模型、不同的残差拟合方法所得到的结果进行比对,提出适合于机场工程大比例尺测图用控制网点正常高值拟合的方法。     

An Adaptive Nonhydrostatic Atmospheric Dynamical Core Using a Multi-Moment Constrained Finite Volume Method

An adaptive 2 D nonhydrostatic dynamical core is proposed by using the multi-moment constrained finite-volume(MCV) scheme and the Berger-Oliger adaptive mesh refinement(AMR) algorithm. The MCV scheme takes several pointwise values within each computational cell as the predicted variables to build high-order schemes based on single-cell reconstruction. Two types of moments, such as the volume-integrated average(VIA) and point value(PV), are defined as constraint conditions to derive the updating formulations of the unknowns, and the constraint condition on VIA guarantees the rigorous conservation of the proposed model. In this study, the MCV scheme is implemented on a height-based, terrainfollowing grid with variable resolution to solve the nonhydrostatic governing equations of atmospheric dynamics. The AMR grid of Berger-Oliger consists of several groups of blocks with different resolutions, where the MCV model developed on a fixed structured mesh can be used directly. Numerical formulations are designed to implement the coarsefine interpolation and the flux correction for properly exchanging the solution information among different blocks. Widely used benchmark tests are carried out to evaluate the proposed model. The numerical experiments on uniform and AMR grids indicate that the adaptive model has promising potential for improving computational efficiency without losing accuracy.     

Dehydration experiments on natural omphacites: qualitative and quantitative characterization by various spectroscopic methods

A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe²⁺ at M1 as well as at M2, and in a first approach assigned Fe³⁺ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ε _i,tot = 65,000 ± 3,000 lmol_H2O ^?1 cm^?2. Using this new ε _i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H₂O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe³⁺ (<0.1 Fe³⁺ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm^?1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al³⁺ at the tetrahedral site (OH bands around 3,525 cm^?1, Koch-Müller et al., Am Mineral, 89:921–931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe³⁺-rich sample (0.2 Fe³⁺ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm^?1 plus shoulder at 3,450 cm^?1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe³⁺ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe²⁺ and combined with increase in Fe³⁺. That dehydration is correlated with oxidation of Fe²⁺ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH^? content and giving no indication of Fe²⁺-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe²⁺ at M2 and low-water concentrations, i.e., at a ratio of Fe^{2+ M2}/H > 10 dehydration occurs by iron oxidation of Fe²⁺ exclusively at the M2 site following the reaction: \( {\left[ {{\text{Fe}}^{{{\text{2 + [ M2]}}}}{\text{OH}}^{ - } } \right]} = {\left[ {{\text{Fe}}^{{{\text{3 + [ M2]}}}} {\text{O}}^{{{\text{2}} - }} } \right]} + {\text{1/2}}\;{\text{H}}_{{\text{2}}} \uparrow . \) In samples having relatively low concentration of Fe²⁺ at M2 but high-water concentrations, i.e., ratio of Fe^{2+ M2}/H < 5.0 dehydration occurs through oxidation of Fe²⁺ at M1.     

多源三维模型融合技术在三调城镇村内部细化调查中的应用研究

城镇村内部土地利用细化调查是第三次全国土调查中的重要组成部分,全面细化和完善的城镇村庄内部土地利用调查成果,有助于掌握翔实准确的全国国土利用现状和自然资源变化情况。本文基于多源三维模型融合技术,生成高精度高空地面、室内室外一体化三维模型,将其应用于城镇村内部土地利用细化调查工作中,修正城镇村内部土地利用现状图斑边界和地类属性等内容,最终形成准确的城镇村内部土地利用现状成果。利用融合后的三维模型上开展城镇村内部土地利用细化调查是一种有效的调查模式,可为三调高精度高效率调查工作提供技术支撑。