硼及硼同位素地球化学在地质研究中的应用

总结了硼及硼同位素的地球化学特征：（１）硼是易溶元素,主要赋存在地球表层,尤其是海水、海相沉积物及海水交代岩石中。其同位素组成δ１１Ｂ值按顺序变化,封闭盐湖卤水（＞４０‰）＞海水（３９５‰）＞海相硼矿物（１８２‰～３１７３‰）＞海相沉积物（１３９‰～２５２‰）＞海水交代岩石（４５１‰～１０８５‰）。大陆水及陆相沉积物硼含量及硼同位素组成变化极大,并多以负值为主。海陆过渡构造带则具有过渡的硼丰度值和硼同位素组成。（２）１１Ｂ较１０Ｂ具有更活跃的地球化学性质,因此在水岩作用中具有明显的同位素交换。硅化交代作用中,岩石被硅化交代,释放硼,并优先释放重硼,同位素组成变轻;在脱硅反应中,岩石释放硅吸收硼,并优先吸收重硼,同位素组成变重。在封闭体系中,水溶液淋滤岩石中部分的硼,即可大量富集,并富集１１Ｂ;在开放体系中,岩石硼被大量淋滤流失,δ１１Ｂ值明显降低。由于水岩作用的结果,从新鲜海底玄武岩到正常海水,硼同位素值从－２９５‰到３９５‰逐渐升高。（３）变质脱水反应中硼被大量排出,并优先排出重硼同位素,进入流体相,因此随着变质程度由低到高,岩石中硼含量及同位素组成δ１１Ｂ值由高变低。（４）在成矿研究中?     

Si diffusion in zircon

Self-diffusion of Si under anhydrous conditions at 1 atm has been measured in natural zircon. The source of diffusant for experiments was a mixture of ZrO₂ and ³⁰Si-enriched SiO₂ in 1:1 molar proportions; experiments were run in crimped Pt capsules in 1-atm furnaces. ³⁰Si profiles were measured with both Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis with the resonant nuclear reaction ³⁰Si(p,γ)³¹P. For Si diffusion normal to c over the temperature range 1,350–1,550°C, we obtain an Arrhenius relation D = 5.8 exp(−702 ± 54 kJ mol⁻¹/RT) m² s⁻¹ for the NRA measurements, which agrees within uncertainty with an Arrhenius relation determined from the RBS measurements [62 exp(−738 ± 61 kJ mol⁻¹/RT) m² s⁻¹]. Diffusion of Si parallel to c appears slightly faster, but agrees within experimental uncertainty at most temperatures with diffusivities for Si normal to c. Diffusion of Si in zircon is similar to that of Ti, but about an order of magnitude faster than diffusion of Hf and two orders of magnitude faster than diffusion of U and Th. Si diffusion is, however, many orders of magnitude slower than oxygen diffusion under both dry and hydrothermal conditions, with the difference increasing with decreasing temperature because of the larger activation energy for Si diffusion. If we consider Hf as a proxy for Zr, given its similar charge and size, we can rank the diffusivities of the major constituents in zircon as follows: D _Zr < D _Si << D _{O, dry} < D _{O, ‘wet’}.     

高温高压下水岩界面反应与金的迁移富集

高温高压下水岩界面反应与金的迁移富集王玉荣阚小凤王志强（中国科学院广州地球化学研究所，广州５１０６４０）关键词水岩界面反应自发电池实验地球化学本实验以哈达门沟［１］及东坪金矿［２］为地质背景，研究钾长石岩中金矿化富集的物理化学条件。该区金矿既与早期变...     

Reactivity of micas and cap-rock in wet supercritical CO2 with SO2 and O2 at CO2 storage conditions

Seal or cap-rock integrity is a safety issue during geological carbon dioxide capture and storage (CCS). Industrial impurities such as SO₂, O₂, and NOx, may be present in CO₂ streams from coal combustion sources. SO₂ and O₂ have been shown recently to influence rock reactivity when dissolved in formation water. Buoyant water-saturated supercritical CO₂ fluid may also come into contact with the base of cap-rock after CO₂ injection. Supercritical fluid-rock reactions have the potential to result in corrosion of reactive minerals in rock, with impurity gases additionally present there is the potential for enhanced reactivity but also favourable mineral precipitation.The first observation of mineral dissolution and precipitation on phyllosilicates and CO₂ storage cap-rock (siliciclastic reservoir) core during water-saturated supercritical CO₂ reactions with industrial impurities SO₂ and O₂ at simulated reservoir conditions is presented. Phyllosilicates (biotite, phlogopite and muscovite) were reacted in contact with a water-saturated supercritical CO₂ containing SO₂, or SO₂ and O₂, and were also immersed in the gas-saturated bulk water. Secondary precipitated sulfate minerals were formed on mineral surfaces concentrated at sheet edges. SO₂ dissolution and oxidation resulted in solution pH decreasing to 0.74 through sulfuric acid formation. Phyllosilicate dissolution released elements to solution with ∼50% Fe mobilized. Geochemical modelling was in good agreement with experimental water chemistry. New minerals nontronite (smectite), hematite, jarosite and goethite were saturated in models. A cap-rock core siltstone sample from the Surat Basin, Australia, was also reacted in water-saturated supercritical CO₂ containing SO₂ or in pure supercritical CO₂. In the presence of SO₂, siderite and ankerite were corroded, and Fe-chlorite altered by the leaching of mainly Fe and Al. Corrosion of micas in the cap-rock was however not observed as the pH was buffered by carbonate dissolution. Ca-sulfate, and Fe-bearing precipitates were observed post SO₂-CO₂ reaction, mainly centered on surface cracks and an illite rich illite-smectite precipitate quantified. Water saturated impure supercritical CO₂ was observed to have reactivity to rock-forming biotite, muscovite and phlogopite mineral separates. In the cap-rock core however carbonates and chlorite were the main reacting minerals showing the importance of assessing actual whole core.     

Sulfur Isotopic Study of the Toyoha Deposit, Hokkaido, Japan Comparison between the Earlier-Stage and the Later-Stage Veins

Abstract: The sulfur isotopic ratios (δ³⁴S) of ore minerals from the Toyoha deposit, Hokkaido, one of the largest Pb–Zn–Ag polymetallic vein-type deposits in Japan, were studied. More than 90% of the δ³⁴S values of the studied sulfide minerals collected from the Toyoha deposit range from +5 to +9%, with an average of approximately +7% irrespective of the mineral species, veins, elevations, depth, mineralization stages and mineral assemblages. Relatively uniform δ³⁴S values obtained in this study suggest that the reduced aqueous sulfur species predominated over the oxidized sulfur in the ore solution throughout the mineralization stages. Thus, the source of sulfur for the ore sulfides is postulated to be magmatic.
The temperature obtained from the fluid inclusion study and the temperature of the sulfur isotopic geothermometer are not consistent. This suggests that each mineral precipitated under disequilibrated conditions with respect to the sulfur isotope.
The change in redox conditions presumably encountered between the mineralization stages did not account for the isotopic fluctuations since the isotopic exchanges between the oxidized and reduced aqueous sulfurs are much slower than the rate of oxidation of the ore solution.     

花岗岩研究的反思

花岗岩是地壳生长、发展以及再循环的地质见证,是地质科学中壳–幔相互作用研究的一个重要课题,同时也是流体与固体地球化学相互作用领域的研究前沿。近二百年来,有关花岗岩的研究经久不衰,大致可分为4个阶段。（1）混合花岗岩派与岩浆花岗岩派的论争,代表花岗岩成因研究开始进入理性认识阶段。一派以变质作用条件下地壳重熔的地质观察为基础,另一派以简单的玄武岩浆分异为依据,而展开论争。（2）地壳重熔实验阶段。以地壳岩石为源岩的热力学实验的开展,是花岗岩热力学研究的开始。（3）随着重熔实验的全面开展,包括了微量元素及同位素的研究,促使热力学熔融体系在花岗岩成因研究上进入全面应用阶段,使地质上的共生组合法则得以与热力学接轨。同时由于微量元素应用于花岗岩,它的多元机理（multiple stage mechanism）进一步确立,为动态研究的开展打下了一定的基础。（4）花岗岩成因与大地构造结合阶段,属于近代花岗岩研究的范畴,代表着花岗岩体系与动态地质演化过程的接轨,并开始建立一个地质实际的观察模式,为进一步向动力理论发展做好准备。为此,对花岗岩研究发展过程中出现的几个问题,如平衡热力学的应用,流体在花岗岩中的重要性,花岗岩成因与大地构造的结合以及热在长期的演化过程中的变化等问题进行了讨论。     

菱刈矿床矿脉群形成的构造环境

本文主要介绍菱刈矿床矿脉的赋存状态、裂隙体系分析、矿脉群赋存的构造环境。菱刈矿床属脉状浅成热液型金银矿床。矿床成因与裂隙系统的形成关系密切。矿脉群大致位于基底岩石(四万十层群)隆起的中央部位。     

Identification and Apportionment of Sources of Ozone‐forming Potential for Proper Reduction Strategies

In this study, results of source identification and apportionment for ambient volatile organic compounds (VOCs) from a previous work were used to estimate ozone‐forming potentials (OFPs) of effective sources for developing proper strategies for reduction of tropospheric ozone pollution. The source identification and apportionment of ambient VOC pollution within Yildiz Technical University's Davutpasa Campus (Istanbul, Turkey) was done by positive matrix factorization (PMF). The results suggested five effective source groups with the emissions related with paint use and solvent use having the highest contributions (36.8 and 28.2%). The results from PMF were used along with maximum incremental reactivities to estimate potentials of individual sources for ozone formation. It was found that biogenic emissions (3.78) and traffic related emissions (gasoline and diesel vehicle exhaust) (3.83 and 3.15, respectively) have the highest potential for ozone formation in terms of grams O₃/g VOC emitted. The results were used to suggest proper source‐based reduction strategies for OFP.     

昆明机场红土地层地下结构抗震模拟研究

昆明机场残积红土既是区域内重要的土地资源,更是各类工程建设的建筑地基,由于机场及临近区域内小江地震活动断裂带和普渡河断裂带地震活动频繁,使研究区处于较不稳定状态。本文采用MIDAS GTS有限元数值分析软件,利用动三轴试验所得出的结果,分别对昆明长水国际机场玄武岩残积红土、砂页岩残积红土地层下典型的地下结构进行了抗震模拟研究。所获得的研究成果,对红土分布区城市及村镇房屋建筑地基和地下空间结构抗震安全稳定性评价具有一定的指导意义和实用价值。     

多孔介质中含均相/非均相反应传质过程数值模拟

结合化学反应方程式,并应用多孔多相介质溶混污染物输运过程的数值模型,对多孔多相介质中含均相/非均相化学反应传质过程进行了数值模拟。化学反应主要包含均相快速/慢速和非均相快速/慢速等5种化学反应过程,溶质输运行为的控制机制主要考虑对流、扩散及降解、吸附等。基于原有的隐式特征线Galerkin离散化的有限元方法,求解模型控制方程的边值初值问题,求解过程中把均相化学反应物质中按照反应物和生成物分开,非均相反应物质按照固相和液相分开,对均相反应物及非均相液相物质浓度耦合求解,而均相生成物和非均相固相物质独立求解。使方程组按照其不同类型进行分类,同时可减少未知数的个数。对于含有非线性内状态变量的右端项进行迭代求解。数值例题结果验证了所提出的数值方法的有效性、计算精度和稳定性。