57Fe− and 119Sn− Mössbauer study on stannite (Cu2FeSnS4)-kesterite (Cu2ZnSnS4) solid solution

A combined ⁵⁷Fe and ¹¹⁹Sn Mössbauer study is performed on the whole solid solution stannite-kesterite consisting of natural and synthetic samples. No discontinuous change of the Mössbauer parameters of ⁵⁷Fe as well as of ¹¹⁹Sn as function of the composition is observed, thus confirming the existence of a complete solid solution between both compounds.     

Nanoscale Chemical Imaging by Photo‐Induced Force Microscopy: Technical Aspects and Application to the Geosciences

Photo‐induced force microscopy (PiFM) is a new‐frontier technique that combines the advantages of atomic force microscopy with infrared spectroscopy and allows for the simultaneous acquisition of 3D topographic data with molecular chemical information at high spatial (~ 5 nm) and spectral (~ 1 cm^?1) resolution at the nanoscale. This non‐destructive technique is time efficient as it requires only conventional mirror‐polishing and has fast mapping rates on the order of a few minutes that allow the study of dynamic processes via time series. Here, we review the method’s historical development, working principle, data acquisition, and evaluation, and provide a comparison with traditional geochemical methods. We review PiFM studies in the areas of materials science, chemistry and biology. In addition, we provide the first applications for geochemical samples including the visualization of faint growth zonation in zircons, the identification of fluid speciation in high‐pressure experimental samples, and of nanoscale organic phases in biominerals. We demonstrate that PiFM analysis is a time‐ and cost‐efficient technique combining high‐resolution surface imaging with molecular chemical information at the nanoscale and, thus, complements and expands traditional geochemical methods.     

Tropical sea-surface temperatures during the last glacial period: a view based on alkenones in Indian Ocean sediments

The qualitification of tropical temperatures during the last glacial cycle (0-150 kyr BP) is a controversial issue since different proxies seem to provide conflicting informations. To obtain a complementary point of view, we use the alkenone method to estimate sea-surface temperatures and focus our work on deep-sea sediments recovered from the tropical Indian Ocean. We present alkenone data obtained in two cores which cover in detail the last deglaciation and in about twenty cores distributed between 20°S and 20°N that were chosen to evaluate the temperature contrast of the last glacial-interglacial transition. Our results indicate that Indian Ocean tropical temperatures remained an average within 1.5-2.5°C of their present values during the last glaciation. At 10°N the last deglaciation is characterized by two warming steps which is similar to the classical deglacial chronology observed in the North Atlantic area. At 20°S the deglacial warming occurred at ca. 15 cal kyr BP, lagging significantly (5-4 kyr) behind the Antarctic warming, but in phase with northern hemisphere time series.     

吉林蛇纹石玉特征初步研究

对产自吉林省白山市抚松县沿江乡的蛇纹石玉样品分别从地质背景、激光诱导离解光谱、X射线粉末衍射和红外吸收光谱等方面进行了研究,并与辽宁岫玉样品进行了对比。结果表明,吉林蛇纹石玉样品的主要颜色为深浅不一的绿色,主要含Si,Al,Cr,Fe,Mn,Mg,Ca,Sr和Na等元素,其中Ca与Mg的谱线较强,Al,Mn与Sr的质量分数少;X射线粉末衍射结果显示,样品的主要矿物组成为纤蛇纹石,红外光谱结果也显示了其具有纤蛇纹石峰值的特征。     

Balloon Intercomparison Campaigns: Results of remote sensing measurements of HCl

All of the techniques used to measure stratospheric HCl during the two BIC campaigns involved high resolution infrared spectroscopy. The balloon-borne instruments included five different spectrometers, three operating in the solar absorption mode and two in emission (at distinctly different wavelengths). Ground-based and aircraft correlative measurements were made close to the balloon locations, again by near-infrared spectroscopy.Within this set of results, comparisons between different techniques (absorption vs emission) viewing the same airmass (i.e., on the same gondola) were possible, as were comparisons between the same technique used on different gondolas spaced closely in time and location. The final results yield a mean profile of concentration of HC1 between 18 and 40 km altitude; an envelope of ±15% centered on this profile encompasses all of the results within one standard deviation of their individual mean values. The absolute accuracy of the final profile is estimated to be no worse than 10%. It is concluded also that the measurement techniques for HCl have reached a level of performance where a precision of 10% to 15% can be confidently expected.     

玻璃和熔体包裹体中水含量的拉曼光谱定量测定方面的进展评述

This paper is focused on the progress in the determination of water in glasses and melt inclusions with Raman spectroscopy. Using the presented ＂Comparator Technique＂ the water content of a sample is determined by siruple comparison with a known standard. A calibration curve is not necessary. Furthermore, with this technique the water concentration in silicate melt inclusions can be determined without exposing the inclusions for measurements. This is very important for extremely water-rich melt inclusions, which would loose H2O on exposure.     

Geological Applications of Laser‐Induced Breakdown Spectroscopy

Laser‐induced breakdown spectroscopy (LIBS) records light emitted from the decay of electrons to lower‐energy orbitals during cooling of laser‐induced ablation plasmas; the resultant spectra can be used in a variety of geoanalytical applications. Four aspects of LIBS analysis distinguish LIBS from traditional laboratory‐based analytical techniques: (i) the lack of necessary sample preparation, allowing rapid analysis of many samples, (ii) the ability to analyse both 20 to 100 μm‐diameter spots and whole rocks, (iii) the detailed chemical signature contained in a LIBS spectrum and (iv) the ability to take LIBS into the field in backpack portable instrumentation. Three case studies illustrate potential applications of LIBS in the geosciences. First, analysis of the Carrizozo basalt flow in New Mexico, USA, illustrated that LIBS spectra could discriminate between samples of similar composition within uncertainties typical of whole‐rock analysis by X‐ray fluorescence spectrometry. Second, spectra from four sets of rubies from Madagascar and Tanzania illustrate the use of LIBS and multivariate analysis to determine provenance with success rates of > 95%. This technique can also be applied to correlation of units. Finally, a chemical map of a copper ore from Butte, MT, USA, illustrates the use of spatially defined LIBS spectra to understand chemical variations within textural context.     

The effect of valence state and site geometry on Cr L3,2 electron energy-loss spectra of Cr-bearing oxidic compounds

Chromium L_3,2 energy loss near-edge structures (ELNES) of nine chromium compounds were measured in a transmission electron microscope to study the effect of valence state and site geometry of chromium on spectral features. The compounds studied represent a set of standards with given valence state and coordination. The chromium coordination is either octahedral or tetrahedral with different degree of distortion. The distortion of polyhedra results in a loss of the fine detail of spectral features in Cr L_3,2 ELNES spectra. The effect of valence state manifests in a systematic chemical shift of the ELNES spectra by about 2 eV per oxidation state for octahedrally coordinated Cr and 0.4–1.4 eV per oxidation state for tetrahedrally coordinated Cr. On the basis of collected Cr L_3,2 ELNES spectra we propose a simple quantification technique for the determination of chromium oxidation state in oxidic compounds which is independent of the coordination.     

Optical spectroscopy study of natural Fe, Ti-bearing calcic amphiboles

Over thirty samples of natural Ti-bearing amphiboles with Ti- and Fe-contents ranging from 0.111 to 0.729 atom per formula unit (a.p.f.u.) and from 0.479 to 2.045 a.p.f.u., respectively, were studied by means of optical absorption spectroscopy and microprobe analysis. Thirteen samples were also studied by Mössbauer spectroscopy. A strong pleochroic absorption edge, causing the dark brown colours of Ti-bearing amphiboles, is attributed to ligand-metal and metal-metal charge transfer transitions involving both iron and titanium ions (O^2?→ Fe³⁺, Fe²⁺, O^2?→ Ti⁴⁺ and Fe²⁺ + Ti⁴⁺→ Fe³⁺ + Ti³⁺). A broad intense Y-polarized band ～22?000?cm^?1 (ν_1/2?≈?3700?cm^?1) in spectra of two low iron amphiboles with a relatively low Fe³⁺/Fe_total ratio, both from eclogite-like rocks in kimberlite xenoliths, was attributed to electronic Fe²⁺(M3) + Ti⁴⁺(M2)→Fe³⁺(M3)+Ti³⁺(M2) IVCT transitions. The IVCT bands of other possible ion pairs, involving Ti⁴⁺ and Fe²⁺ in M2 and M1, M4 sites, respectively, are presumed to be at higher energies, being obscured by the absorption edge.     

Local structural heterogeneity,mixing behaviour and saturation effects in the grossular–spessartine solid solution

Local structural heterogeneities in crystals of the binary grossular–spessartine solid solution have been analyzed using powder IR absorption spectroscopy. Wavenumber shifts of the highest energy Si–O stretching mode in spectra collected at room temperature are consistent with variations in Si–O bond length from structural data. They show a smaller positive deviation from linearity across the join than is seen for the grossular–pyrope and grossular–almandine binaries. The effective line widths, corr, of three selected wavenumber regions all deviate positively from linear behaviour. An empirical calibration of this excess spectroscopic property, obtained by comparison with calorimetric enthalpy of mixing data, gives an estimate for the symmetric Margules parameter of W^H_spec = 14.4(7) kJ mol^–1 in H^mix = W^H_specX_GrX_Sp. W^H_spec values derived on the same basis for four aluminosilicate garnet solid solutions analyzed by IR spectroscopy vary with V², where V represents the difference in molar volume between the end members of each binary system. Measurements of lattice parameters and IR spectra were made over a range of temperatures for seven samples with different compositions. Positive excess molar volumes of mixing at low temperature (30 K) may be larger than the excess molar volumes at room temperature. The saturation temperatures of the molar volumes show no correlation with composition, however, in contrast with what had been expected on the basis of data for the grossular–pyrope binary. Saturation temperatures for spectroscopic parameters and lattice parameters of samples with compositions Gr15Sp85 and Gr60Sp40 seem to be outliers in all experiments. It is concluded that the data hint at systematic changes in saturation temperatures across the solid solution, with implications for both the excess entropy of mixing and the excess volume of mixing, but more precise data or further sample characterization are needed to prove that this composition dependence is real in garnet solid solutions.