Heating duration of igneous rim formation on a chondrule in the Northwest Africa 3118 CV3oxA carbonaceous chondrite inferred from micro-scale migration of the oxygen isotopes

Due to their common occurrence in various types of chondrites, igneous rims formed on pre-existing chondrules throughout chondrule-forming regions of the solar nebula. Although the peak temperatures are thought to reach similar values to those achieved during chondrule formation events, the heating duration in chondrule rim formation has not been well defined. We determined the two-dimensional chemical and oxygen isotopic distributions in an igneous rim of a chondrule within the Northwest Africa 3118 CV3_oxA chondrite with sub-micrometer resolution using secondary ion mass spectrometry and scanning electron microscopy. The igneous rim experienced aqueous alteration on the CV parent body. The aqueous alteration resulted in precipitation of the secondary FeO-rich olivine (Fa_40–49) and slightly disturbed the Fe-Mg distribution in the MgO-rich olivine phenocrysts (Fa_11–22) at about a 1 μm scale. However, no oxygen isotopic disturbances were observed at a scale greater than 100 nm. The MgO-rich olivine, a primary phase of igneous rim formation, has δ¹⁷O = −6 ± 3‰ and δ¹⁸O = −1 ± 4‰, and some grains contain extreme ¹⁶O-rich areas (δ¹⁷O, δ¹⁸O = ∼−30‰) nearly 10 μm across. We detected oxygen isotopic migration of approximately 1 μm at the boundaries of the extreme ¹⁶O-rich areas. Using oxygen self-diffusivity in olivine, the heating time of the igneous rim formation could have continued from several hours to several days at near liquidus temperatures (∼2000 K) in the solar nebula suggesting that the rim formed by a similar flash heating event that formed the chondrules.     

硫酸型酸雨参与碳酸盐岩溶蚀的研究进展

碳酸盐岩的H2CO3溶蚀产生岩溶碳汇,占整个岩石风化碳汇的 94%。西南岩溶区硫酸型酸雨严重,硫酸型酸雨广泛参与碳酸盐岩的溶蚀。H2SO4参与的碳酸盐岩风化是一个大气CO2净释放过程,具有减汇作用巨大。另一方面,岩溶区石灰土壤和地下水具有较高的pH值及盐基饱和度,对H+有巨大的缓冲作用,大气酸沉降在碳酸盐岩地区可能并不会造成地下水的HCO3-和pH降低;相反,较高浓度的SO42-所产生的盐效应和SO2-4与各种阳离子形成的离子对会增大方解石、白云石溶解度,可增强H2CO3对碳酸盐的溶蚀,这可能会使岩溶作用产生更大的碳汇效应。因此,硫酸型酸雨参与碳酸盐岩风化的减汇效应不仅可能被高估,硫酸型酸雨还可能增强碳酸盐岩的H2CO3溶蚀,具有增加岩溶碳汇效应的作用。应结合石灰土壤对大气酸沉降的缓冲容量和阈值及大气酸沉降的H+与土壤中盐基离子的交换量,并综合考虑盐效应、离子对作用、同离子效应,客观评价硫酸型酸雨流经石灰土壤层后对碳酸盐岩溶蚀吸收大气/土壤CO2的影响      

‘Box‐Profile’ Ion Implants as Geochemical Reference Materials for Electron Probe Microanalysis and Secondary Ion Mass Spectrometry

Although electron probe microanalysis and secondary ion mass spectrometry are widely used analytical techniques for geochemical and mineralogical applications, metrologically rigorous quantification remains a major challenge for these methods. Secondary ion mass spectrometry (SIMS) in particular is a matrix‐sensitive method, and the use of matrix‐matched reference materials (RMs) is essential to avoid significant analytical bias. A major problem is that the number of available RMs for SIMS is extremely small compared with the needs of analysts. One approach for the production of matrix‐specific RMs is the use of high‐energy ion implantation that introduces a known amount of a selected isotope into a material. We chose the more elaborate way of implanting a so‐called ‘box‐profile’ to generate a quasi‐homogeneous concentration of the implanted isotope in three dimensions, which allows RMs not only to be used for ion beam analysis but also makes them suitable for EPMA. For proof of concept, we used the thoroughly studied mineralogically and chemically ‘simple’ SiO₂ system. We implanted either ⁴⁷Ti or ⁴⁸Ti into synthetic, ultra‐high‐purity silica glass. Several ‘box‐profiles’ with mass fractions between 10 and 1000 μg g^?1 Ti and maximum depths of homogeneous Ti distribution between 200 nm and 3 μm were produced at the Institute of Ion Beam Physics and Materials Research of Helmholtz‐Zentrum Dresden‐Rossendorf. Multiple implantation steps using varying ion energies and ion doses were simulated with Stopping and Range of Ions in Matter (SRIM) software, optimising for the target concentrations, implantation depths and technical limits of the implanter. We characterised several implant test samples having different concentrations and maximum implantation depths by means of SIMS and other analytical techniques. The results show that the implant samples are suitable for use as reference materials for SIMS measurements. The multi‐energy ion implantation technique also appears to be a promising procedure for the production of EPMA‐suitable reference materials.     

Li2SO4溶液中离子间的缔合相互作用:基于密度泛函理论和分子动力学模拟的研究

基于密度泛函理论,使用B3LYP/aVDZ方法对[Li_2SO_4(H_2O)_n]~0(n=0~10、18)水合团簇的结构和性质进行了系统地研究,并结合Car-Parrinello分子动力学(CPMD)模拟了不同浓度的Li_2SO_4溶液结构,目的在于理解在Li_2SO_4溶液中离子间缔合相互作用及可能存在的物种。研究发现,对于[Li_2SO_4(H_2O)_n]~0(n=0~10、18)水合团簇,双配位单齿螯合接触离子对结构比双配位双齿螯合接触离子对结构更稳定,溶剂共享离子对结构最不稳定。同时,CPMD模拟结果表明,在3.09和3.17 mol/kg的Li_2SO_4溶液中,双配位单齿螯合接触离子对结构仍然是主要物种。以上结果表明在饱和的Li_2SO_4溶液(3.16 mol/kg)中,Li~+和SO_4~(2-)离子间的相互缔合作用主要以双配位单齿螯合接触离子对结构的物种存在,而具有双配位双齿螯合离子对结构的物种占少数,溶剂共享离子对结构几乎不存在。     

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.     

一种建立在CPN基础上的分类方法在遥感影像分类中的应用研究

对偶神经网络利用了自组织映射近似函数的一种新的映射神经网络,其结构组合了Kohonen的自组织映射和Grossberg的外星(Outstar)结构,网络结构相对简单。本文以对偶神经网络分类方法原理为基础,研究了一种理想化的分类方法,并以MATLAB平台为基础对遥感影像进行分类处理,实验结果表明,其分类总精度为94.17%,分类精度较传统监督分类结果有所提高。     

南极洲伊丽莎白公主地区主要离子沉积方式及nssSO_4~(2-)气候效应研究

通过对１９９６／１９９７年中国首次南极内陆冰盖考察获得的南极洲伊丽莎白公主地区５０ｍ 雪芯样品主要阴、阳离子浓度、通量和积累率关系的研究,揭示以下规律：１）南极洲伊丽莎白公主地区大气中各主要离子浓度足够大,足以使本地区冰雪中主要离子浓度不随积累率的变化而变化,即离子浓度不受积累率的影响。２）各主要离子干、湿沉积所占比重的计算结果表明,本地区离子沉积方式以湿沉积为主。另外,ｎｓｓＳＯ２－４ 的研究结果表明火山爆发的中、短期气候效应在伊丽莎白公主地区反应不明显。     

柱撑粘土矿物的研究新进展——新矿物材料研究综述之一

柱撑粘土矿物作为一种大层间距的多酸型层柱微孔材料,是一种性能优异的催化剂和吸附剂,本文在较全面分析前人资料的基础上,结合笔者所做的工作,对柱撑粘土矿物的制备性能表征及其应用最新研究进展进行综述与展望。     

陶瓷釉矿物学特征的电子自旋共振(ESR)研究

早在６０年代初,Ｇｒｉｓｃｏｎ等人［１］就曾用ＥＳＲ方法对玻璃中的顺磁离子进行了研究。８０年代初Ｃａｎａｒａ等人［２］又用ＥＳＲ方法研究了硅酸玻璃、釉熔块和陶瓷色料的波谱特征,发现发色元素Ｃｒ、Ｆｅ、Ｃｏ等在釉料中的反应行为,石田等人［３］则研究了含铁高岭土和瓷胎中氧化铁的存在状态。８０年代末蔡秀成等人［４］应用ＥＳＲ方法探讨了景德镇传统“石灰碱釉”的油（煤）窑产品发黄机理。由此可见,用ＥＳＲ方法研究铁瓷釉及瓷胎中顺磁杂质离子的存在形式,对提高陶瓷质量和呈色机理的探讨有着广阔的应用前景。１　样…     

Negative ions in the auroral mesosphere during a PCA event around sunset

This is a study of the negative ion chemistry in the mesosphere above Tromsø using a number of EISCAT observations of high energy proton precipitation events during the last solar maximum, and in particular around sunset on 23 October, 1989. In these conditions it is possible to look at the relative importance of the various photodetachment and photodissociation processes controlling the concentration of negative ions. The data analysed are from several UHF GEN11 determinations of the ion-plasma ACF together with the pseudo zero-lag estimate of the ‘raw’ electron density, at heights between 55 km and 85 km, at less than 1 km resolution. The power profiles from the UHF are combined with the 55-ion Sodankylä model to obtain consistent estimates of the electron density, the negative ion concentrations, and the average ion mass with height. The neutral concentrations and ion temperature are given by the MSIS90 model. These parameters are then used to compare the calculated widths of the ion-line with the GEN11 determinations. The ion-line spectrum gives information on the effects of negative ions below 70 km where they are dominant; the spectral width is almost a direct measure of the relative abundance of negative ions.