Preliminary Characterisation of New Glass Reference Materials (GSA-1G, GSC-1G, GSD-1G and GSE-1G) by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Using 193 nm, 213 nm and 266 nm Wavelengths

New glass reference materials GSA-1G, GSC-1G, GSD-1G and GSE-1G have been characterised using a prototype solid state laser ablation system capable of producing wavelengths of 193 nm, 213 nm and 266 nm. This system allowed comparison of the effects of different laser wavelengths under nearly identical ablation and ICP operating conditions. The wavelengths 213 nm and 266 nm were also used at higher energy densities to evaluate the influence of energy density on quantitative analysis. In addition, the glass reference materials were analysed using commercially available 266 nm Nd:YAG and 193 nm ArF excimer lasers. Laser ablation analysis was carried out using both single spot and scanning mode ablation. Using laser ablation ICP-MS, concentrations of fifty-eight elements were determined with external calibration to the NIST SRM 610 glass reference material. Instead of applying the more common internal standardisation procedure, the total concentration of all element oxide concentrations was normalised to 100%. Major element concentrations were compared with those determined by electron microprobe. In addition to NIST SRM 610 for external calibration, USGS BCR-2G was used as a more closely matrix-matched reference material in order to compare the effect of matrix-matched and non matrix-matched calibration on quantitative analysis. The results show that the various laser wavelengths and energy densities applied produced similar results, with the exception of scanning mode ablation at 266 nm without matrix-matched calibration where deviations up to 60% from the average were found. However, results acquired using a scanning mode with a matrix-matched calibration agreed with results obtained by spot analysis. The increased abundance of large particles produced when using a scanning ablation mode with NIST SRM 610, is responsible for elemental fractionation effects caused by incomplete vaporisation of large particles in the ICP.     

Did Paleogene North Atlantic rift-related eruptions drive early Eocene climate cooling?

The delivery of volcanogenic sulphur into the upper atmosphere by explosive eruptions is known to cause significant temporary climate cooling. Therefore, phreatomagmatic and phreatoplinian eruptions occurring during the final rifting stages of active flood basalt provinces provide a potent mechanism for triggering climate change.

During the early Eocene, the northeast Atlantic margin was subjected to repeated ashfall for 0.5 m.y. This was the result of extensive phreatomagmatic activity along 3000 km of the opening northeast Atlantic rift. These widespread, predominantly basaltic ashes are now preserved in marine sediments of the Balder Formation and its equivalents, and occur over an area extending from the Faroe Islands to Denmark and southern England. These ash-bearing sediments also contain pollen and spore floras derived from low diversity forests that grew in cooler, drier climates than were experienced either before or after these highly explosive eruptions. In addition, coeval plant macrofossil evidence from the Bighorn Basin, Wyoming, USA, also shows a comparable pattern of vegetation change. The coincidence of the ashes and cooler climate pollen and spore floras in northwest Europe identifies volcanism as the primary cause of climate cooling. Estimates show that whilst relatively few phreatomagmatic eruptive centres along the 3000 km opening rift system could readily generate 0.5–1 °C cooling, on an annual basis, only persistent or repeated volcanic phases would have been able to achieve the long-term cooling effect observed in the floral record. We propose that the cumulative effect of repeated Balder Formation eruptions initiated a biodiversity crisis in the northeast Atlantic margin forests. Only the decline of this persistent volcanic activity, and the subsequent climatic warming at the start of the Eocene Thermal Maximum allowed the growth of subtropical forests to develop across the region.     

SiO2-TiO2薄膜制备及其光催化性能研究

Sol-gel法制备SiO2-TiO2复合薄膜，进行甲醛的光催化降解实验，研究了SiO2掺杂量、薄膜焙烧温度、甲醛溶液pH值及初始浓度对光催化性能的影响。结果表明，500℃焙烧1h，掺杂质量SiO2：TiO2=12：100时，SiO2-TiO2薄膜的光催化活性最高，150min后甲醛降解率达76％，是单纯TiO2薄膜的1．3倍，该薄膜稳定性较好，经重复8次使用，最大降解率只下降4％。     

Sorption of carbon dioxide–methane mixtures

The paper reports the results of experiments concerning the sorption/desorption processes, observed under laboratory conditions, in two types of coal extracted from operational coal-mines in Poland, using CH₄ and CO₂ to observe their relative inter-reaction with the coal samples when introduced in varying proportions and conditions. Numerous studies concerning the sorption/desorption phenomena have described the operational mechanisms and the relationship of mine gases to the organically-created coal-body in mines. The differences in the behaviour of certain gases is twofold: firstly the essentially different characteristics of CO₂ and CH₄, and secondly the structure of the coal-bed itself: its degree of metamorphism and content of macerals. From the results yielded, it was observed that the divergence of the isotherms of sorption of CH₄ and other gases in comparison with the isotherms of sorption of CO₂ and a CO₂/CH₄ mixture differed and that the curve on the sorption isotherm was more clearly distinct after the introduction of CO₂ molecules to the system: coal with a higher degree of metamorphism—CH₄, which is closely related to the rigidity of the structure according to the level of metamorphism. Since coals with higher carbon content exhibit lower molecular bonding than low-carbonised coals, the characteristic feature of the bonds in the first case is their mobility. Knowledge of the physical and chemical properties of hard coals, as well as their interaction with mining gases, is of great use in solving problems concerned with the extraction of methane from mines or its storage in goafs.     

深直井旋转钻柱空转功率消耗的数学建模

通过对深井旋转钻柱空转功率消耗因素的分析，考虑空转时离心力作用在井壁上引起的摩擦力导致的功率消耗，并将钻井液视为牛顿液体，运用柱坐标系建立了旋转钻柱在深井作业条件下空转功率消耗的分析模型。综合考虑空转功率与钻柱旋转的角速度、钻柱与井眼结构参数、钻井液粘度系数等因素间的关系，即旋转钻柱运动过程中的离心力和钻井液作用在钻柱上的剪切应力对功率的影响，建立了更加符合实际工况的数学模型。     

High-T phase transition of synthetic ANaB(LiMg)CMg5Si8O22(OH)2 amphibole: an X-ray synchrotron powder diffraction and FTIR spectroscopic study

The synthetic amphibole Na_0.95(Li_0.95Mg_1.05)Mg₅Si₈O₂₂(OH)₂ was studied in situ at high-T, using IR OH-stretching spectroscopy and synchrotron X-ray powder diffraction. At room-T the sample has P2₁ /m symmetry, as shown by the FTIR spectrum. It shows in the OH region two well-defined and intense absorptions at 3,748 and 3,712 cm⁻¹, respectively, and two minor bands at 3,667 and 3,687 cm⁻¹. The main bands are assigned to the two independent O–H groups in the primitive structure. The two minor bands evidencing the presence of small amount of vacant A-site (^A□_0.05). With increasing T, these bands shift continuously and merge into a unique absorption at high temperature. A change as a function of increasing T is revealed by the evolution of the refined unit-cell parameters, whose trend shows a transition to C2/m at about 320–330°C. The spontaneous scalar strain, fitted with a tricritical 2–6 Landau potential, gives a T _c of 325(10)°C (β parameter = 0.27). Comparison with the second-order P2₁ /m ⇔ C2/m phase transition at 255°C for synthetic amphibole ^ANa_0.8^B(Na_0.8Mg_1.2)^CMg₅Si₈O₂₂(OH)₂ indicates that the substitution of Na with Li at the B-sites strongly affects the thermodynamic character and the T _c of the phase transition. The comparison of LNMSH amphiboles with cummingtonitic ones shows that the high-T thermodynamic behaviour is affected by A-site occupancy.     

Continuous Gradations among Primary Carbonatitic, Kimberlitic, Melilititic, Basaltic, Picritic, and Komatiitic Melts in Equilibrium with Garnet Lherzolite at 3-8 GPa

Multianvil melting experiments in the system CaO–MgO–Al₂O₃–SiO₂–CO₂(CMAS–CO₂) at 3–8 GPa, 1340–1800°C, involvingthe garnet lherzolite phase assemblage in equilibrium with CO₂-bearingmelts, yield continuous gradations in melt composition betweencarbonatite, kimberlite, melilitite, komatiite, picrite, andbasalt melts. The phase relations encompass a divariant surfacein P–T space. Comparison of the carbonatitic melts producedat the low-temperature side of this surface with naturally occurringcarbonatites indicates that natural magnesiocarbonatites couldbe generated over a wide range of pressures >2·5 GPa.Melts analogous to kimberlites form at higher temperatures alongthe divariant surface, which suggests that kimberlite genesisrequires more elevated geotherms. However, the amount of waterfound in some kimberlites has the potential to lower temperaturesfor the generation of kimberlitic melts by up to 150°C,provided no hydrous phases are present. Compositions resemblinggroup IB and IA kimberlites are produced at pressures around5–6 GPa and 10 GPa, respectively, whereas the compositionsof some other kimberlites suggest generation at higher pressuresstill. At pressures <4 GPa, an elevated geotherm producesmelilitite-like melt in the CMAS–CO₂ system rather thankimberlite. Even when a relatively CO₂-rich mantle compositioncontaining 0·15 wt % CO₂ is assumed, kimberlites andmelilitites are produced by <1% melting and carbonatitesare generated by even smaller degrees of melting of <0·5%. KEY WORDS: carbonatite; CO₂; kimberlite; melilitite; melt generation     

273.15K下LiCl-Li2B4O7-H2O体系热力学性质的等压研究

用等压法研究了273 15K下LiCl-Li2B4O7-H2O体系中纯盐水溶液(离子强度范围为LiCl0 2046～2 5055mol·kg-1,Li2B4O70 1295～0 3700mol·kg-1)以及混合盐水溶液(离子强度范围为0 0931～2 4911mol·kg-1)渗透系数和水活度;计算了LiCl-Li2B4O7-H2O体系的饱和蒸汽压,获得饱和蒸汽压、渗透系数随离子强度的变化规律。用实验数据以最小二乘法求取了LiCl和Li2B4O7纯盐参数及体系的混合盐参数,拟合的标准偏差分别为0 0077和0 026。用该模型计算的渗透系数值与实验结果取得合理的一致。同时研究结果与273 15K下LiCl-Li2SO4-H2O体系的渗透系数随离子强度变化的规律作了比较。本研究对完善低温下含锂、硼盐湖卤水体系的热力学模型和盐湖资源的综合开发利用具有重要意义。