Sulfur K-edge XANES study of local electronic structure in ternary monosulfide solid solution [(Fe, Co, Ni)0.923S]

 Synchrotron radiation S K-edge XANES spectra and unit-cell parameters are used to investigate the local electronic structure of non-stoichiometric binary and ternary Fe-Co-Ni monosulfide solid solution (mss; M_0.923S, M = Fe, Co, Ni) quenched from 800 °C and low pressure. The prominent absorption edge feature of the XANES spectra represents transition of S 1s core level electrons to unoccupied S 3p σ* antibonding orbitals hybridized with empty metal 3d(e_g) orbitals. There is a progressive increase in area of the edge peak from Fe_0.923S to Ni_0.923S and Co_0.923S, which correlates with progressive decrease in c and a parameters for the NiAs-type subcell and increase in metallic character, and reflects increase in the number and availability of empty e_g ^β orbitals and covalence of metal-S bonds. More generally, the area of the edge peak exhibits an inverse linear correlation with a, c and unit-cell volume of binary and ternary mss. This inverse linear correlation is attributed to progressive increase in covalence and M-S-M bonding interaction in the c-axis direction, through metal-S [M 3d(e_g) - S 3p (or 3d)] π bonding. However, the area of the edge peak does not correlate very well with the average number of 3d electrons per metal atom in these solid solutions, showing that the absorption of synchrotron radiation reflects the local electronic structure of individual absorber atoms (i.e. the SM₆ cluster), and is not a group (crystal energy band) effect. Received: 21 March 2000 / Accepted: 14 July 2000     

Comparison of COSPEC and two miniature ultraviolet spectrometer systems for SO2 measurements using scattered sunlight

The correlation spectrometer (COSPEC), the principal tool for remote measurements of volcanic SO₂, is rapidly being replaced by low-cost, miniature, ultraviolet (UV) spectrometers. We compared two of these new systems with a COSPEC by measuring SO₂ column amounts at Kīlauea Volcano, Hawaii. The two systems, one calibrated using in-situ SO₂ cells, and the other using a calibrated laboratory reference spectrum, employ similar spectrometer hardware, but different foreoptics and spectral retrieval algorithms. Accuracy, signal-to-noise, retrieval parameters, and precision were investigated for the two configurations of new miniature spectrometer. Measurements included traverses beneath the plumes from the summit and east rift zone of Kīlauea, and testing with calibration cells of known SO₂ concentration. The results obtained from the different methods were consistent with each other, with <8% difference in estimated SO₂ column amounts up to 800 ppm m. A further comparison between the COSPEC and one of the miniature spectrometer configurations, the ‘FLYSPEC’, spans an eight month period and showed agreement of measured emission rates to within 10% for SO₂ column amounts up to 1,600 ppm m. The topic of measuring high SO₂ burdens accurately is addressed for the Kīlauea measurements. In comparing the foreoptics, retrieval methods, and resultant implications for data quality, we aim to consolidate the various experiences to date, and improve the application and development of miniature spectrometer systems.     

Reaction overstepping and re-evaluation of peak P‒T conditions of the blueschist unit Sifnos,Greece: implications for the Cyclades subduction zone

ABSTRACT

Equilibrium thermodynamic modelling, quartz in garnet (QuiG) Raman geobarometry, and modelling of garnet nucleation at overstepped conditions were applied to three garnet-bearing blueschists from a 1.5 km-long transect across the eclogite-blueschist unit in Sifnos, Greece, in order to evaluate the accuracy of P?T conditions calculated via equilibrium thermodynamics. QuiG barometry uses the Raman shift of quartz inclusions in garnet to estimate the pressure of garnet nucleation and is independent of chemical equilibrium. Garnet nucleation temperatures were estimated by determining the stability field of the palaeo-assemblage inferred from garnet inclusion suites on mineral assemblage diagrams calculated in the MnNCKFMASH system and on temperatures obtained from Zr in rutile thermometry. These conditions were then compared to P?T conditions calculated at the equilibrium garnet isograd, and the method of intersecting isopleths. The P?T conditions calculated with intersecting garnet isopleths over- and underestimated the temperature of nucleation in samples SPH99-1a and SPH99-7, respectively, whereas they significantly underestimated nucleation pressure in SPH99-5. Nucleation of garnet in SPH99-1a at 12 kbar and ~484°C requires overstepping of ~6 kbar and a reaction affinity of 2.2 kJ mol^?1 O. SPH99-5 requires overstepping of ~8 kbar with garnet reaction affinities of at least 2.0 kJ mol^?1 O at 15 kbar and ~520°C. SPH99-7 requires overstepping of approximately 15 kbar and affinities of about 2.0–2.4 kJ mol^?1 O at ~23 kbar and ~530°C. The geotherms calculated from SPH99-7 (~6.7°C km^?1) and SPH99-5 (9.8°C km^?1) are in accordance with previous studies. The geotherm calculated from SPH99-1a, however, is warmer (11.3°C km^?1), and could reflect changes in the rate of subduction or differences in structural position within the down-going slab. The 10 kbar pressure difference between SPH99-7 and SPH99-1a can be explained by thrusting and accretion of thin slices of underplated wedge material facilitated by slab rollback and gravitational collapse.     

OH-bearing planar defects in olivine produced by the breakdown of Ti-rich humite minerals from Dabie Shan (China)

The partial breakdown of Ti-chondrodite and Ti-clinohumite during exhumation from ultra-high pressure to amphibolite facies conditions in garnet-pyroxenites from Dabie Shan (China) produces coronas of olivine coexisting with ilmenite blebs. Fourier transform infrared (FTIR) spectra of this newly formed olivine exhibit absorption bands in the hydroxyl-stretching region. Two intense peaks were observed at 3,564 and 3,394 cm⁻¹, identical in energy to peaks in Ti-clinohumite. Transmission electron microscopy (TEM) of the same olivine domains revealed the presence of a complex (001) planar intergrowth. These interlayers have a 1.35 nm repeat distance, which is characteristic of clinohumite. Such interlayers are also enriched in Ti with respect to the adjacent olivine as shown by energy dispersive spectrometry. The combined evidence from FTIR spectroscopy and TEM indicates that OH is incorporated along Ti-clinohumite planar defects. This study provides evidence that the nominally anhydrous phase olivine may contain OH as a humite-type defect beyond the breakdown of the hydrous humite minerals and confirms earlier suggestions that Ti plays a key role in OH incorporation in mantle olivine. We suggest that olivine containing Ti-clinohumite defects is an important phase for water transport in subduction zones and for the storage of water in cold subcontinental mantle. However, these defects are unlikely to be stable in hotter parts of the oceanic mantle such as where basaltic magmas are generated.     

A Reliable Method for Determining the Oxidation State of Manganese at the Microscale in Mn Oxides via Raman Spectroscopy

Manganese oxides are important geomaterials, widespread in terrestrial and Martian environments. Characterisation of the oxidation state of Mn is a central issue in science; this task has been addressed up to the present by X‐ray spectroscopy or diffraction techniques. The former, however, requires access to synchrotron facilities, while the latter does not provide crystal‐chemical information at the local scale. In this work, we compare a large set of Raman data from well‐characterised samples, already published by the same authors of this paper or as found in the literature. We show a clear correlation between the oxidation state of Mn and the wavenumber of peculiar bands; octahedrally co‐ordinated Mn²⁺ is recognised by a band around 530 cm^?1, Mn³⁺ by a band around 580 cm^?1 and Mn⁴⁺ by a band around 630 cm^?1, while tetrahedrally co‐ordinated Mn²⁺ is recognisable by a band around 650 cm^?1. Strongly distorted Mn³⁺ octahedra are indicated by the appearance of Jahn–Teller modes. Our method allows a reliable, easily accessible tool to characterise the oxidation states of Mn in oxides, also suitable for microscale mapping. It provides a robust analytical basis for the use of these minerals as redox indicators in geology/geochemistry, in exoplanetary research or for monitoring technological processes.     

磷灰石结构中[SO_4]、[SiO_4]四面体的喇曼谱学特点

磷灰石是重要的生物材料矿物。天然磷石晶体结构中［ＰＯ４］３－能广泛地被［ＳｉＯ４］、［ＳＯ４］类质同象取代,形成含硅硫磷灰石以至硅硫磷灰石［１］。据报道,在合成羟磷灰石中引入部分Ｓ、Ｓｉ离子将提高其抗蚀性能,因此［ＳｉＯ４］与［ＳＯ４］对［ＰＯ４］的四面体替换是磷灰石晶体化学研究的重要内容［２～４］。振动光谱（包括喇曼与红外光谱）是研究晶体结构络阴离子行为的主要手段之一。对磷灰石中磷氧四面体振动谱学特点的研究,无论是理论计算还是实验结果均已十分成熟［５,６］,但对其结构中硫氧、硅氧四面体的喇曼光…     

小西南岔富金铜矿床流体包裹体中子矿物特征及意义

运用显微镜和激光拉曼技术对小西南岔富金铜矿床北山矿段流体包裹体内的子晶矿物进行了鉴定。结果表明,其子晶矿物有硬石膏、石盐、钾盐以及黄铜矿等,这种特征反映该矿床的含矿流体为高盐、高氧化流体和还原流体,为进一步研究该矿床流体性质和矿床的成因提供了重要依据。     

Temperature dependence of the polarized electronic absorption spectra of olivines. Part II—Cobalt-containing olivines

Polarized electronic absorption spectra of single crystalline Co₂[SiO₄] and (Co_0.64Mg_0.36)₂[SiO₄] (E|| a (|| Z), E || b (|| X), E || c (|| Y)) have been studied in the temperature range 293 T/K 1273. The three polarized spectra show a total of 15 bands. Five bands are caused by spin-allowed transitions in Co²⁺ ions at M1 sites which appear in all polarization directions. Seven polarization-dependent bands can be ascribed to spin-allowed transitions in Co²⁺ ions at M2 sites and three bands may be assigned to spin-forbidden transitions. The assignment of bands due to Co²⁺ ions at M1 and M2 sites has been made on the basis of transition energies and intensity ratios. Further arguments have been derived from the comparison of spectra of crystals with different cobalt content, from the analysis of the polarization dependence of the spectra, and from the evolution of band intensities with temperature.     

Restoring Halite Fluid Inclusions as an Accurate Palaeothermometer: Brillouin Thermometry Versus Microthermometry

Halite traps inclusions of the mother fluid when precipitating. When unchanged, the density of these fluid inclusions (FIs) records the water temperature T_f at the time of crystal formation. As halite is ubiquitous on Earth and geological time, its FIs possess a high potential as temperature archives. However, the use of FIs in halite as an accurate palaeothermometer has been hampered due to limitations of microthermometry, the most commonly used analytical method. Here, we show how Brillouin spectroscopy in halite FIs bypasses these limitations and allows recovering T_f to within 1 °C or less. To demonstrate this, we measured samples synthesised at 24.6 ± 0.5 °C and 33 ± 1 °C, and obtained 24.8 ± 0.4 °C and 31.9 ± 0.4 °C, respectively. This novel approach thus provides an accurate palaeothermometer for lacustrine and marine environments. Moreover, Brillouin spectroscopy solves the long‐standing debate on damage of halite fluid inclusions through quantifying the acceptable temperature excursion for preserving elastic behaviour: [l/(1 µm)]^?0.64 × (90 °C), where l is the FI size. This threshold is lower for FIs close to the surface of the host crystal or to another FI. We also list ‘best practices’ for applying both microthermometry and Brillouin thermometry.