Solubility of silica polymorphs in electrolyte solutions, II. Activity of aqueous silica and solid silica polymorphs in deep solutions from the sedimentary Paris Basin

Activity coefficient for aqueous silica in saline waters and brines from the Paris Basin was calculated using Pitzer's specific interaction model. Quartz and chalcedony are the only reported authigenic silica minerals in the Dogger aquifer of the Paris Basin (France). However, the measured silica concentrations fall between those of these two phases. The silica concentrations measured in Dogger fluids seem to be controlled by a microcrystalline quartz phase with a grain size computed to be about 20 nm. Studies have shown that pressure can preserve small grain size for a long time at the geological scale. The effective mechanism of pressure action is probably linked to the fact that pressure simultaneously favours dissolution at the grain-contact inducing a quartz supersaturation and prohibits the increase in size of reprecipitated microcrystalline quartz grains. This hypothesis is supported by other studies reported in the literature. The proposed model, which incorporates silica mineralogy and a precise calculation of aqueous silica activity, allows us to explain measured silica concentrations in the deep sedimentary solutions of the Dogger aquifers. In the Keuper brines, silica solubility can in most cases be explained by an equilibrium with either chalcedony or quartz. Another application of the present work is shown by an example, where we examined the importance of precisely evaluating the activity coefficient in basin characterisation, as the goal of reservoir characterisation is to describe the spatial distribution of petrophysical parameters such as porosity, permeability, and saturations.     

测定硅灰石制得多孔SiO2粉体粒径的分散剂选择研究

考察了几种不同类型表面活性剂对一种气相白炭黑的分散效果。经比较研究发现：吐湿－80和六偏磷酸钠的分散效果较类似且较好，对此进行了讨论并选择六偏磷酸钠作为分散剂测试了由硅灰石制制得的多孔SiO2粉体的颗粒粒径。初步确定，该多孔SiO2粉体作为填料可用于反光塑料制品中。     

Solubility of silica polymorphs in electrolyte solutions, I. Activity coefficient of aqueous silica from 25° to 250°C, Pitzer''s parameterisation

Within the framework of Pitzer's specific interaction model, interaction parameters for aqueous silica in concentrated electrolyte solutions have been derived from Marshall and co-authors amorphous silica solubility measurements. The values, at 25°C, of the Pitzer interaction parameter (λ_SiO2(aq)−i) determined in this study are the following: 0.092 (i = Na⁺), 0.032 (K⁺), 0.165 (Li⁺), 0.292 (Ca²⁺, Mg²⁺), −0.139 (SO₄²⁻), and −0.009 (NO₃⁻). A set of polynomial equations has been derived which can be used to calculate λ_SiO2(aq)−i for these ions at any temperature up to 250°C. A linear relationship between the aqueous silica-ion interaction parameters (λ_SiO2(aq)−i) and the surface electrostatic field (Z_i/r_e,i) of ions was obtained. This empirical equation can be used to estimate, in first approximation, λ_SiO2(aq)−i if no measurements are available. From this parameterisation, the calculated activity coefficient of aqueous silica is 2.52 at 25°C and 1.45 at 250°C in 5 m NaCl solution. At lower concentrations, e.g. 2 m NaCl, the activity coefficient of silica is 1.45 at 25°C and 1.2 at 250°C. Hence, in practice, it is necessary to take into account the activity coefficient of aqueous silica (λ_SiO2(aq)≠1) in hydrothermal solutions and basinal brines where the ionic strength exceeds 1. A comparison of measured [Marshall, W.L., Chen, C.-T.A., 1982. Amorphous silica solubilities, V. Prediction of solubility behaviour in aqueous mixed electrolyte solutions to 300°C. Geochim. Cosmochim. Acta 46, 289–291.] and computed amorphous silica solubility, using this parameterisation, shows a good agreement. Because the effect of individual ions on silicate and silica polymorph solubilities are additive, the present study has permitted to derive Pitzer interaction parameters that allow a precise computation of γ_SiO2(aq) in the Na---K---Ca---Mg---Cl---SO₄---HCO₃---SiO₂---H₂O system, over a large range of salt concentrations and up to temperatures of 250°C.     

Excess silica in omphacite and the formation of free silica in eclogite

Silica lamellae in eclogitic clinopyroxene are widely interpreted as evidence of exsolution during decompression of eclogite. However, mechanisms other than exsolution might produce free silica, and the possible mechanisms depend in part on the nature and definition of excess silica. 'Excess' silica may occur in both stoichiometric and non-stoichiometric pyroxene. Although the issue has been debated, we show that all common definitions of excess silica in non-stoichiometric clinopyroxene are internally consistent, interchangeable, and therefore equivalent. The excess silica content of pyroxene is easily illustrated in a three-component, condensed composition space and may be plotted directly from a structural formula unit or recalculated end-members. In order to evaluate possible mechanisms for the formation of free silica in eclogite, we examined the net-transfer reactions in model eclogites using a Thompson reaction space. We show that there are at least three broad classes of reactions that release free silica in eclogite: (i) vacancy consumption in non-stoichiometric pyroxene; (ii) dissolution of Ti-phases in pyroxene or garnet; (iii) reactions between accessory phases and either pyroxene or garnet. We suggest that reliable interpretation of the significance of silica lamellae in natural clinopyroxene will require the evaluation not only of silica solubility, but also of titanium solubility, and the possible roles of accessory phases and inclusions on the balance of free silica.     

重量法测定岩石矿物中二氧化硅的几种凝聚剂

文章对十六烷基三甲基溴化铵、聚环氧乙烷、聚乙二醇（４００和６０００）、甲基纤维素和聚乙烯醇等６种凝聚剂在重量法测ＳｉＯ２过程中凝聚硅酸的效果进行了试验，这些操作较动物胶法方便、省时，测定标准样品结果与推荐值相符。     

天池天文峰全新世火山喷发物长石表面硅膜特征及意义

利用扫描电镜和能谱分析研究天池火山天文峰剖面全新世喷发物中长石表面硅膜的结构状态和化学组成,结果显示:天文峰剖面从顶部黑色浮岩向下到暗灰色浮岩中,长石表面发育有不同结构状态的硅膜.硅膜的结构特征有随火山喷发时代越早,长石颗粒表面硅膜越厚,结构越复杂;喷发时代越晚,长石颗粒表面硅膜越薄,其结构越简单的变化趋势,即长石表面...     

H_2O-CO_2体系融合二氧化硅毛细管样品原位显微激光拉曼光谱研究

使用配备Linkam冷热台的显微激光拉曼光谱仪,采用融合二氧化硅毛细管样品,在-120～31℃温度区间,1 200～1 500cm-1光谱区间上,原位采集H2O-CO2体系流体包裹体的拉曼光谱,并针对CO2特征拉曼光谱展开分析。结果表明,融合二氧化硅毛细管样品中的流体具有代表性。通过对毛细管样品进行拉曼光谱采集,该实验获得了流体包裹体中CO2气相、CO2液相、CO2固相、CO2水合物相和CO2水溶液相的特征光谱。光谱分析结果显示,在实验温度区间上,CO2固相和CO2水合物相特征峰的稳定性,有助于鉴别拉曼光谱;同时,CO2气相、CO2液相和CO2水溶液相费米共振峰峰位因CO2压力或密度影响而发生变化。此外,该实验在温度变化过程中,鉴定了不同相的拉曼特征光谱。结果表明,激光拉曼光谱结合显微测温技术能够有效鉴别包裹体中不同的流体相,获得相变过程,确定相变温度。     

纳克级铅同位素分析中硅胶-高铼酸发射剂体系的建立

核取证分析中需要实施纳克级（ng）铅的同位素全谱分析,质谱测量中要求铅的电离效率较高（大于10^-3）。传统硅胶-磷酸技术多用于微克级（μg）铅分析,电离效率一般为10^-4~10^-3;尽管后来发展的硅胶-硼酸技术可以得到10^-3以上的发射效率,但是由于铅在电离过程中存在离子流反复升高-衰减的过程,导致离子流发射不稳定,质谱测量条件难以掌握。本文改进了传统的硅胶发射剂,建立了一种新型硅胶加载体系——硅胶-高铼酸体系。与硅胶-硼酸技术相比,采用硅胶-高铼酸体系可显著提高铅的发射效率并获得稳定的离子流。对于1 ng铅的同位素质谱全谱测量,²⁰⁴Pb/²⁰⁶Pb、²⁰⁷Pb/²⁰⁶Pb、²⁰⁸Pb/²⁰⁶Pb的相对标准偏差分别为0.4%、0.2%和0.1%,测试精度优于采用其他硅胶技术。通过实验比较了硅胶-高铼酸体系与多种传统硅胶发射剂体系对铅离子流的发射效果,优化了硅胶试剂用量为0.5~3.0 μL,采用“夹心饼干”的涂样顺序,对1~100 ng铅样品的发射效率达到6.0×10^-3~4.6×10^-2,比传统硅胶-磷酸体系的发射效率（10^-4~10^-3）高了近10倍,与硅胶-硼酸技术的发射效率相当（10^-3~10^-2）,但铅离子发射更为稳定。本文建立的硅胶-高铼酸体系在测量精度上可满足核取证研究中铅作为地域指示剂的需求。     

南海南部17962柱状样生物硅沉积记录及其古海洋意义

生物硅沉积记录可以反映海洋表层水体的古生产力。南海南部１７９６２柱状样３万余年来的生物硅堆积速率曲线表明,南沙海区古生产力的升高与一系列变冷事件,如冰期中的Ｈｅｉｎｒｉｃｈ事件、冰消期新仙女木事件、中晚全新世变冷事件等有良好的对应关系。冬季风的强化及由此导致的海洋古生产力的升高可能是上述良好对应关系的内在原因。     

柴东欧南凹陷石炭系烃源岩有机质富集的影响因素

柴达木盆地东部地区欧南凹陷是石炭系油气运聚成藏的有利构造单元,具有一定勘探潜力,但对有机质富集机理认识不清导致对优质烃源岩分布的预测缺乏有效指导,制约了油气勘探进程。基于地球化学分析、XRD、SEM等分析测试,对石炭系烃源岩矿物组分、有机质丰度、干酪根类型、热演化程度、形成环境、TOC与主要矿物关系等进行了综合研究,明确了有机质富集的主要影响因素。结果表明：石炭系发育大量“差—中等”级别和少量“好”以上级别泥页岩和碳酸盐岩烃源岩,形成于咸水、干热、弱还原—弱氧化过渡带的海陆交互陆棚沉积环境;分散有机质由海相和陆相混源型生物有机质组成,整体处于“成熟—高成熟阶段”,烃源岩主要残留Ⅲ型干酪根,但抽提的氯仿沥青“A”主要来自于Ⅱ型干酪根;高丰度烃源岩TOC随石英矿物组分增大而升高,富含硅质微体生物化石,高硅烃源岩中硅质证实为生物成因,推测石炭纪硅质生物的参与引起海相生物有机质的富集并极大提高了沉积物初级生产力。研究认识为研究区石炭系优质烃源岩分布预测和下一步油气资源部署提供了依据。