A Mössbauer and FTIR study of synthetic amphiboles along the magnesioriebeckite – ferri-clinoholmquistite join

A series of amphiboles along the magnesioriebeckite—Na₂Mg₃Fe³⁺ ₂Si₈O₂₂(OH)₂– ferri-clinoholmquistite—Li₂Mg₃Fe³⁺ ₂Si₈O₂₂(OH)2 - join, defined by the ^BLi^B Na_–1 exchange vector, were hydrothermally synthesized at 700°C, 0.4 GPa, NNO + 1 redox conditions. Powder XRD and SEM-EDAX showed a very high (> 90%) amphibole yield for all samples. X-ray patterns were indexed in the C2/m space group; refined cell-parameters show a linear decrease of a and as a function of chemistry. IR spectra in the OH-stretching region show four main and rather sharp bands; these are assigned to Mg and Fe²⁺ at M(1,3), and indicate that the obtained amphiboles depart from the nominal octahedral composition (^M1,3Mg₃). The IR spectra also show that there is an increasing filling-up of the A-site for increasing Na in the system (increasing solid-solution toward, arfvedsonite). Mössbauer spectra show four well-defined quadrupole doublets which are assigned to Fe³⁺ at M2 and to Fe²⁺ at M1, M3 and M4, respectively. The Fe³⁺/Fe²⁺ content derived from fitted peak areas show variable Fe³⁺ concentration along the series. Mössbauer spectra also show a distinct alteration of ⁵⁷Fe hyperfine parameters with changing Na–Li at M4. The most evident variation is observed for the quadrupole splitting of Fe³⁺ at M2, which increases by 50% from ferri-clinoholmquistite to magnesio-riebeckite; this suggest that the M2 octahedron in ferri-clinoholmquistite is much closer to the ideal geometry than the M2 octahedron in magnesio-riebeckite. Mössbauer spectra show also a well-defined increase in the Fe²⁺ quadrupole splitting of the M1 and M3 octahedra, which is attributed to the Na–Li distribution at the B-sites.     

Probing the magma plumbing of Erebus volcano,Antarctica, by open-path FTIR spectroscopy of gas emissions

Gas emissions from Erebus volcano, Antarctica, were measured by open-path Fourier transform infrared spectroscopy to understand degassing of its magmatic system. Two degassing phonolite lava lakes were present in the summit crater during observation in December 2004. We report analyses of H₂O, CO₂, CO, SO₂, HF, HCl and OCS, (in order of molar abundance) in the plumes. Variations in the proportions of these species strongly reflect the dynamics of degassing, and sourcing of gas from different depths in the magmatic network. The highest observed ratios of CO₂ and H₂O are consistent with gas extracted from the melt at a depth of up to ∼ 2 km below the lava lakes. Magma degassing above this depth contributes to a higher H₂O/CO₂ proportion in the airborne plume. The ratio therefore reflects the balance of deeper vs. shallower contributions of volatiles and, possibly, a combination of closed- and open-system degassing. We observe a strong contrast in HF content in emissions from the two lava lakes, which we attribute to differing levels of magma ascent and/or cooling and crystallization of the magma supply. Fluxes of all gas species were determined using independent SO₂ flux determinations and measured gas ratios. In the case of CO₂ and water, ∼ 1 and ∼ 0.4 m³ s^− 1, respectively, of parental basanite magma are required to sustain the calculated output. The discrepancy between the two figures is readily explained by sequestration of part of the magma supply at depth such that it only partially degasses its complement of water.     

黄绿色松脂岩玉的宝石学特征

近期,笔者在检测中见到一批黄绿色玉石原石样品,外观呈油脂光泽、黄绿色,可见白色斑点,外形似软玉。为查明其成分,经客户同意后对样品进行切磨抛光。利用宝石显微镜、X射线粉末衍射仪、红外光谱仪等仪器进行了测试分析以及岩石薄片分析。宝石显微镜、X射线粉末衍射仪、红外光谱仪的结果分析,很容易将结果误判为长石质玉,岩石薄片分析表明该样品基质由火山玻璃组成,含微斜长石以及石英斑晶,属于花岗岩类的松脂岩,根据国标应定名为松脂岩玉。     

Synthetic ANaB(Na x Li1 − x Mg1)CMg5Si8O22(OH)2 (with x = 0.6, 0.2 and 0) P21/m amphiboles at high pressure: a synchrotron infrared study

The high-pressure behavior of three synthetic amphiboles crystallized with space group P2₁/m at room conditions in the system Li₂O–Na₂O–MgO–SiO₂–H₂O has been studied by in situ synchrotron infrared absorption spectroscopy. The amphiboles have compositions ^ANa ^B(Na _x Li_1 − x Mg₁) ^CMg₅ Si₈ O₂₂(OH)₂ with x = 0.6, 0.2 and 0.0, respectively. The high-P experiments up to 32 GPa were carried out on the U2A beamline at Brookhaven National Laboratory (NY, USA) using a diamond anvil cell under non-hydrostatic or quasi-hydrostatic conditions. The two most intense absorption bands in the OH-stretching infrared spectra can be assigned to two non-equivalent O–H dipoles in the P2₁/m structure, bonded to the same local environment ^M1M3Mg₃–OH–^ANa, and pointing toward two differently kinked tetrahedral rings. In all samples these bands progressively merge to give a unique symmetrical absorption with increasing pressure, suggesting a change in symmetry from P2₁/m to C2/m. The pressure at which the transition occurs appears to be linearly correlated to the aggregate B-site dimension. The infrared spectra collected for amphibole ^B(Na_0.2Li_0.8Mg₁) in the frequency range 50 to 1,400 cm⁻¹ also show a series of changes with increasing pressure. The data reported here support the inference of Iezzi et al. (Am Miner 91:479–482, 2006a) regarding a new high-pressure amphibole polymorph.     

Characterization of Organic Contaminants in New York/New Jersey Harbor Sediments Using FTIR‐ATR and Synchrotron FTIR

Dredging and remediation of contaminated Harbor sediments requires characterization of organic pollutants. In this paper, we apply a combination of Fourier transform IR attenuated total reflectance (FTIR‐ATR) and synchrotron FTIR techniques to the investigation of sediments and related materials from New York/New Jersey Harbor and other locations. The FTIR techniques give information on the functional groups of the compounds found in the sediments and make possible measurements with a spatial resolution of about 0.015 mm. Comparisons of natural organic materials namely, river and groundwater humic substances, recent marine and lacustrine sediments, and ancient sedimentary kerogen show that contaminated NY/NJ Harbor sediments display a strong and distinct absorption in their IR spectra at 2850–2950 cm^?1 identified as a C? H stretching band, indicative of the presence of anthropogenic hydrocarbons. We suggest that the presence of this band could be used for rapid screening for the presence of contaminant organic compounds in sediments encountered in dredging operations and/or as an indicator for the efficacy of sediment decontamination technologies used for treatment of dredged material.     

高温高压处理钻石的谱学研究

对高温高压处理钻石进行了显微观察及红外光谱、低温紫外－可见－近红外吸收光谱和光致发光谱等谱学研究，认为钻石的去色是由于高温高压过程引起晶格结构的重组，从而得出天然褐色钻石的致色与位错附近的孤氮－空穴（N－V）的眯缺陷有关的结论。同时也提供了高温高压处理钻石的一些谱学特征，如红外光谱中较弱的3107cm^-1峰，紫外－可见吸收光谱中的325nm宽带，光致发光谱中的575nm与637nm峰。     

合成施威特曼石吸附Cu^2＋和Pb^2＋的实验研究

施威特曼石普遍存在于含大量SO42-的酸矿水中,其表面吸附的SO42-使得该矿物具有强吸附重金属离子的能力,可用于处理重金属离子污染。实验通过在不同浓度Cu2＋溶液中合成施威特曼石时发现,Cu2＋与施威特曼石的共沉淀量较低,FTIR分析表明Cu2＋与施威特曼石的羟基发生反应。开展施威特曼石吸附Pb2＋的实验,结果表明施威特曼石对Pb2＋的吸附符合Langmuir模型,施威特曼石吸附Cu2＋和Pb2＋后出现1545.4 cm-1和1435.0 cm-1（Cu2＋）两个吸收峰,可能是施威特曼石孔道表面形成了三元配合物。在241×10-6的初始浓度（与尾矿孔隙水的Pb2＋含量相近）下有61.4%的Pb2＋去除率,显示了较好的环境修复价值。     

固相萃取—热裂解—气相色谱—串联质谱法测定盐湖卤水中溶解性有机质

以青藏高原地区的大柴旦盐湖湖表卤水为研究对象,采用不同的固相萃取(Solid phase extraction,SPE)材料(HLB,PPL,ENVI-18,ENVI-Carb,XAD8和XAD4)对大柴旦盐湖湖表卤水中DOM进行了分离和富集,初步建立了从高盐体系盐湖卤水中高效分离富集出具有代表性的溶解性有机质(Dissolved organic matter,DOM)的方法,系统的考察了pH,上样体积,柱流速和洗脱溶剂对DOM回收率的影响。结合傅里叶变换红外光谱分析(Fourier transform infrared spectroscopy,FTIR)、热裂解—气相色谱—串联质谱分析(Pyrolysis-gas chromatography-mass spectrometry,Py-GC/MS)进一步对盐湖卤水分离物进行了谱学表征。研究结果表明,盐湖卤水在酸性条件下(pH=2),柱流速为0.5 mL/min时有助于吸附剂对DOM的吸附,而随着上样体积的增加,DOM的回收率逐渐下降,而甲醇是比较理想的洗脱剂。大柴旦盐湖湖表卤水中的DOM主要以芳香类,碳水化合物以及部分脂肪族化合物为主,而含氮类化合物含量较少。     

名义上无水矿物中"水"的原位变温红外光谱研究

名义上无水矿物(nominally anhydrous minerals, 简称NAMs, 如橄榄石、辉石、石榴石、长石等)中以缺陷形式存在的结构水的重要性已经被地球科学界广泛认同,并得到了越来越多的关注。由于对OH振动的高度敏感性,红外光谱方法被广泛用来测量NAMs中"水"的赋存状态、含量以及在晶体结构中的位置。随着傅立叶变换红外光谱仪的不断发展及分析技术的提高,以及红外附件的更新换代,出现了一些新的分析方法。原位变温红外光谱实验就是利用变温红外附件测量样品在不同温度下的红外光谱,通过研究不同温度下红外光谱图的峰形、峰位、峰数等参数的变化,了解温度改变过程中样品所发生的物理、化学变化,且具有实时监测的优点,因此广泛用于含水矿物和玻璃中OH和H₂O的研究。主要包括含水矿物和玻璃的脱水机理及脱水动力学研究,OH和H₂O的红外吸收系数的温度依赖性及不同温度下红外吸收系数的校正等方面。虽然原位变温红外光谱广泛应用于含水矿物和玻璃中水的研究,但是应用于名义上无水矿物还是刚刚起步。NAMs中的H是活动的,高温下H的赋存状态及其在晶体中的位置可能会不同于室温,而地质过程往往都在高温下进行,研究高温下NAMs中的水具有重要的地质学意义。因此,有必要利用原位变温红外光谱实时监测不同温度下NAMs中水的变化。有关NAMs中水的原位变温红外光谱实验早期工作只是观察不同温度下谱图参数的变化并给予一定的解释,以及用此法来确定NAMs中水的赋存状态。受含水矿物和玻璃的研究结果的启发,原位变温红外光谱实验目前也开始用来研究NAMs中水的脱水机理和扩散动力学。此外,利用原位变温红外光谱技术,通过研究不同温度下OH的积分吸收面积可探索NAMs中OH红外吸收系数温度依赖性;通过研究OH峰位随温度移动的幅度与某些化学成分的关系,可给出NAMs中OH的结合机理方面的有用信息。虽然近些年来已经开展了一些工作,取得了一些新的成果,但是总的说来还处在起步阶段,今后针对NAMs的研究重点应该集中在以下三个方面:(1)吸收系数温度依赖性的定量化,(2)脱水机理和动力学的扩展,(3) OH结合机理研究的深入。     

Study of Structural Disorder in Natural Tourmalines by Infrared Spectroscopy

Fourier Transformation Infrared (FTIR) spectroscopy in the range 2000-10000 cm^-1 was used to examine tourmalines from metarhyolites near Majjur within the Gadag Schist Belt and are compared with those from known compositions from quartz vein from gold mineralised area. FTIR spectra in this region are comprised of fundamental and combinational vibrational modes of hydroxyl ions delineating their structural environment. In these samples three fundamental vibrations observed at 3730-3720, 3637-3627 and 3550-3500 cm^-1 and combination modes at 4529, 4454, 4356 and 4238 cm^-1, and the Electron Probe analysis indicate that the tourmalines could be classified in to dravite-schrol series. However, additional shoulder mode observed around 3490 cm^-1 in tourmaline from Gadag Schist Belt, indicates structural disorder.