水在硅酸盐熔体中的溶解度及研究意义

水是岩浆中主要的挥发份 ,而且其溶解作用强烈影响着熔体的物理和化学性质 ,因此对水在硅酸盐熔体中溶解度及溶解机制的研究是非常重要的。近年来研究表明 ,水在硅酸盐熔体中溶解度与压力、温度及熔体组分密切相关。具体而言 ,压力升高可使水的溶解度增大 ,而温度对溶解度的影响则与熔体组成有关。对于AbOrQ体系 ,在压力低于 4 0 0MPa时 ,溶解度与温度呈反相关 ;而在压力高于 50 0MPa时 ,则呈现出正相关。但是 ,温度对溶解度的影响要明显弱于压力的影响。至于水的溶解度与熔体组分的关系 ,通过对碱金属组分的研究表明水的溶解度按K ,Na ,Li的次序而增加。此外 ,根据碱金属组分对水在硅酸盐熔体中溶解度的影响对水的溶解机制进行了论述 ,这与Sykes等通过分子轨道计算和拉曼、红外光谱研究得出的水在铝硅酸盐熔体中的溶解机理是一致的。     

二连石——一种含铁和钒的硅酸盐新矿物

新矿物二连石(Erlianite)产于海相火山沉积硅质建造,经变质的铁矿层中的破碎带。矿物呈黑色,条痕褐色。晶体成纤维状、鳞片状,集合体为规则的板柱状。不透明,丝绢光泽。H_v=3.7kg/mm~2,D=3.11g/cm~3。解理(001)和(100)完全。斜方晶系。晶胞参数:a=23.20,b=9.20,c=13.18,Z=1,可能的空间群为Pmmn或Pm2_1n。二轴晶负光性,N_(?)=1.667,N_(?)=1.674,N_(?)=1.679,2V=56—59°。化学式为:(Fe~(2+)_(19·96)Fe~(3+)_(2·19)Mg_(1·33)Mn_(0·42))_(23·90)(Fe~(3+)_(11·32)V_((?)·68))_(12)(Si_(34·73)Ti_(0·26)Al_(0·20)Fe~(3+)_(0·81))_(36)O_(90)(OH,O)_(48)(单位晶胞氧原子总数O=138)。     

Boron and Oxygen Isotope Composition of Certified Reference Materials NIST SRM 610/612 and Reference Materials JB-2 and JR-2

We present data on the concentration, the isotope composition and the homogeneity of boron in NIST silicate glass reference materials SRM 610 and SRM 612, and in powders and glasses of geological reference materials JB-2 (basalt) and JR-2 (rhyolite). Our data are intended to serve as references for both microanalytical and wet-chemical techniques. The δ¹¹ B compositions determined by N-TIMS and P-TIMS agree within 0.5% and compare with SIMS data within 2.5%. SIMS profiles demonstrate boron isotope homogeneity to better than δ¹¹ B = 2% for both NIST glasses, however a slight boron depletion was detected towards the outermost 200 μm of the rim of each sample wafer. The boron isotope compositions of SRM 610 and SRM 612 were indistinguishable. Glasses produced in this study by fusing JB-2 and JR-2 powder also showed good boron isotope homogeneity, both within and between different glass fragments. Their major element abundance as well as boron isotope compositions and concentrations were identical to those of the starting composition. Hence, reference materials (glasses) for the in situ measurement of boron isotopes can be produced from already well-studied volcanic samples without significant isotope fractionation. Oxygen isotope ratios, both within and between wafers, of NIST reference glasses SRM 610 and SRM 612 are uniform. In contrast to boron, significant differences in oxygen isotope compositions were found between the two glasses, which may be due to the different amounts of trace element oxides added at ten-fold different concentration levels to the silicate matrix.     

Calibration of the New Certified Reference Materials ERM‐AE633 and ERM‐AE647 for Copper and IRMM‐3702 for Zinc Isotope Amount Ratio Determinations

The commonly used, but no longer available, reference materials NIST SRM 976 (Cu) and ‘JMC Lyon’ (Zn) were calibrated against the new reference materials ERM^®‐AE633, ERM^®‐AE647 (Cu) and IRMM‐3702 (Zn), certified for isotope amount ratios. This cross‐calibration of new with old reference materials provides a continuous and reliable comparability of already published with future Cu and Zn isotope data. The Cu isotope amount ratio of NIST SRM 976 yielded δ^65/63Cu values of ?0.01 ± 0.05‰ and ?0.21 ± 0.05‰ relative to ERM^®‐AE633 and ERM^®‐AE647, respectively, and a δ^66/64Zn_IRMM‐3702 value of ?0.29 ± 0.05‰ was determined for ‘JMC Lyon’. Furthermore, we separated Cu and Zn from five geological reference materials (BCR‐2, BHVO‐2, BIR‐1, AGV‐1 and G‐2) using a two‐step ion‐exchange chromatographic procedure. Possible isotope fractionation of Cu during chromatographic purification and introduction of resin‐ and/or matrix‐induced interferences were assessed by enriched ⁶⁵Cu isotope addition. Instrumental mass bias correction for the isotope ratio determinations by MC‐ICP‐MS was performed using calibrator‐sample bracketing with internal Ni doping for Cu and a double spike approach for Zn. Our results for the five geological reference materials were in very good agreement with literature data, confirming the accuracy and applicability of our analytical protocol.     

Usable Values of Nickel Ore and Nickel Concentrate Certified Reference Materials

The preparation and characterisation of three nickel ores and two nickel concentrate certified reference materials are described in this paper. The samples of nickel ore and nickel concentrate were collected from the Hongqiling nickel deposit in Jilin province. The raw materials were crushed and passed through a 2.0‐mm sieve. The rough samples were then ground for 48 hr in a high‐alumina ball mill to a final size of < 0.074 mm. Homogeneity of the samples was tested by X‐ray fluorescence spectrometry (WD‐XRF) and inductively coupled plasma‐atomic emission spectrometry (ICP‐AES). The relative standard deviations (RSD) of results on mass fraction measurements by WD‐XRF were < 1.0% m/m for eighteen components. F‐tests showed that all five samples were homogeneous. Nineteen laboratories contributed with measurement results (2127 in total) for the certification of mass fractions for twenty‐three elements and compounds. Twenty‐three components in the nickel ores and twenty components in the nickel concentrates were characterised as certified values, while the Ni mass fractions ranges from 0.1 to 9.02% m/m in these certified reference materials. These five samples were approved as national certified reference materials by the National Organisation of Reference Materials of China in 2012.     

Characterisation of Apatites as Potential Uranium Reference Materials for Fission‐track Dating by LA‐ICP‐MS

We report homogeneity tests on large natural apatite crystals to evaluate their potential as U reference materials for apatite fission‐track (AFT) thermochronology by laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS). The homogeneity tests include the measurements of major element concentrations by electron probe microanalysis (EPMA), whereas for U concentration, isotope dilution (ID) ICP‐MS and laser ablation (LA) ICP‐MS were employed. Two apatite crystals are potential reference materials for LA‐ICP‐MS analysis: a 1 cm³ fraction of a Durango crystal (7.5 μg g^?1 U) and a 1 cm³ Mud Tank crystal (6.9 μg g^?1 U). The relative standard deviation (1 RSD) of the U concentration determined by ID‐ICP‐MS of both apatite crystals was ≤ 1.5%, whereas 1 RSD for the LA‐ICP‐MS results was better than 4%, providing sufficient homogeneity for fission‐track dating. The results on the U homogeneity for two different apatite samples are an important step towards establishing in situ dating routines for AFT analysis by LA‐ICP‐MS.     

Utilization of Basic Oxygen Furnace (BOF) slag in the production of a hydraulic cement binder

Basic Oxygen Furnace (BOF) slag is a major waste product generated during the steelmaking process. In India and in most industrial countries, the use of BOF slag as a road ballast and land filler has had a very long history. This being a low end use, a study was conducted to examine the possibility of converting the slag into a hydraulic binder. This paper describes the effect of cooling rate on mineralogy and cementing characteristics of normal BOF slag as well as iron oxide-devoid BOF slag. Specifically, the mineralogy and compressive strengths of heat-treated slags were compared with a conventional ordinary Portland cement. It was found that the slowly cooled slags did not show any cementing properties. The iron oxide-devoid slag, on slow cooling, disintegrated into fine powder. The water-cured cubic specimens of quenched slag products were tested for their compressive strengths. The cementing properties of the quenched slag products were improved by formation of hydraulic phases and showed considerable strength after 28 days of water curing.     

Chemical Characterisation of Natural Ilmenite: A Possible New Reference Material

Seven ilmenite (FeTiO₃) megacrysts derived from alnöite pipes (Island of Malaita, Solomon Islands) were characterised for their major and trace element compositions in relation to their potential use as secondary reference materials for in situ microanalysis. Abundances of thirteen trace elements obtained by laser ablation ICP‐MS analyses (using the NIST SRM 610 glass reference material) were compared with those determined by solution‐mode ICP‐MS measurements, and these indicated good agreement for most elements. The accuracy of the LA‐ICP‐MS protocol employed here was also assessed by repeated analysis of MPI‐DING international glass reference materials ML3B‐G and KL2‐G. Several of the Malaitan ilmenite megacrysts exhibited discrepancies between laser ablation and solution‐mode ICP‐MS analyses, primarily attributed to the presence of a titano‐magnetite exsolution phase (at the grain boundaries), which were incorporated solely in the solution‐mode runs. Element abundances obtained by LA‐ICP‐MS for three of the ilmenite megacrysts (CRN63E, CRN63H and CRN63K) investigated here had RSD (2s) values of < 20% and therefore can be considered as working values for reference purposes during routine LA‐ICP‐MS analyses of ilmenite.     

含钾岩石微生物转化的分子机制及其碳汇效应

岩石矿物的微生物风化是地球表层系统最为活跃和普遍发生的地质营力之一。微生物对含钾岩石(以硅酸盐矿物为主)的风化能够释放其中的钾、硅和钙等元素,并在合适的环境条件下促进矿物元素的碳酸化沉淀,这是地表元素地球化学循环的重要环节之一。微生物对岩石的生物转化作用既涉及微生物的生长繁殖和代谢调控,也与元素的迁移转化和次生矿物的演化序列有关,具有重要研究价值。采用矿物学、微生物学和分子生物学等相结合的研究方法,有助于系统地研究微生物促进含钾硅酸盐矿物的风化并耦联碳酸化过程及其分子调控机制。研究证实,在纯培养条件下,微生物风化含钾矿物主要采用酸解、螯合、氧化还原等多种方式的协同作用,并可通过调控相关功能基因的表达来响应缺钾的环境以实现其对含钾矿物的有效风化,显然这有赖于微生物通过长期进化而形成的精细的分子调控机制。在土壤生态环境中,微生物对矿物风化的显著特征是该生态环境中微生物群落协同互作的群体作用效应。微生物碳酸酐酶参与的硅酸盐矿物风化伴随碳酸盐矿物的形成过程可能是个长期被忽视的地表碳增汇过程,对该问题的深入探索有助于进一步理解地质演化历史中微生物对碳素迁移转化的驱动机制。加入含钾硅酸盐矿粉的有机肥已经显示出其在土壤改良、作物生长和增加土壤碳汇等方面的正面应用效果,这为利用硅酸盐矿物的生物风化作用来延缓大气CO₂浓度的持续升高提供了新的思路。介绍了有关微生物对含钾岩石生物转化释放钾素的分子机理及其碳汇效应方面的研究进展,以期抛砖引玉,推动该领域研究的快速发展。     

大溶隙岩溶地层的有效钻孔堵漏方法

复杂地层钻探问题一直是地质勘探、工程勘察及工程施工钻进中的主要技术难题。分析了复杂地层钻探护壁堵漏的方法；结合宁夏六盘山区东北麓芒硝矿钻探工程，对于大溶隙岩溶地层钻探，提出采用水泥-水玻璃-布袋护壁堵漏方法。阐述了漏失通道的性质和位置的分析方法、护壁堵漏方案和原理、正确确定注浆压力及最大注浆量的方法。