莱河矿(Fe0.52+Fe1.03+SiO4)的超结构

莱河矿于1976年在中国辽宁省的磁铁矿床中首次被发现,许多人对它进行过研究。该矿物为黑色、不透明,化学式为Fe_0.58²⁺Fe_1.0³⁺Mg_0.03Si_0.96O₄,虽然它的晶体结构近似于橄榄石,但已确定为单斜晶系,空间群为P2₁/b。本文作者利用X射线、电子探针、高分解能透过电子显微镜对该矿物进行了系统的研究,发现它具有假双晶、超结构和显微条纹结构。     

吉林陨石原始捕获的40Ar/36Ar比值及其地质意义

地球大气圈中⁴⁰Ar/³⁶Ar的现代比值被公认为295.5,在利用K-Ar法测定地球物质年龄时,它是校正大气氩混染量的重要参数。陨石中原始捕获(trapped)的(⁴⁰Ar/³⁶Ar)_t比值是否和地球大气圈中氩同位素丰度相一致,这个问题不但在地质年龄测定中具有现实意义,而且对探索太阳系的形成和演化也有重要理论价值。近十几年,随着质谱分析技术的提高以及登月计划的实施,国外出现了一批有关月岩中氩同位素原始组分的资料,但至今对陨石中原始氩同位素丰度的报道很少。笔者采用⁴⁰Ar/³⁹Ar快中子活化技术和约克方程^[3,4],对吉林陨石雨2号标本进行了原始捕获的(⁴⁰Ar/³⁶Ar)_t比值进行了测定,并探讨了它的地质意义。     

玄武岩的 MnO-TiO2-P2O5判别图的修改与补充

近些年来,人们广泛地利用火山岩的主元素或微量元素的特征对火山岩进行地球化学、成因岩石学和构造岩石学的研究。Mullen(1983)利用玄武岩的 MnO、TiO₂和P₂O₅建立大洋型玄武岩的 MnO×10-TiO₂-P₂O₅×10的构造背景判别图(以下简称MTP图)和圈出了大陆拉斑玄武岩在 MTP 图中的分布范围。他选择了能反映玄武岩形成过程中的重要地球化学特征和成因机制的元素组作为该图的端元组分。     

一种改进的硫酸盐硫同位素制样方法

硫酸盐-氧化亚铜-石英砂直接热解法需要设置分离SO₂、H₂O和CO₂的冷阱。研究表明H₂O和CO₂主要来自试剂石英砂的气液包裹体。采取石英砂预处理措施能大大减少制样过程引入的H₂O和CO₂。改进后的制样系统简单、易操作,且与硫化物同位素样品制备兼容。     

硫酸盐矿物中制备质谱分析样方法的研究

硫酸盐类矿物特别是大洋水中的硫酸盐矿物的硫同位素分布及演化是硫同位素地质学研究的重要内容之一,海水硫酸盐参与海相沉积物中的氧化还原作用是海相沉积物中的硫化物以及矿床硫的主要来源,这也是研究层控矿床的重要依据之一。基于硫酸盐硫同位素的研究在地质上的重要性,国内外对硫酸盐制备SO_2的研究也很重视,在分析方法上趋于简便、高效率、准确性好。目前多数实验室从硫酸盐矿物中制备硫同位素分析样品(SO_2)的方法主要有两种:即     

重晶石、天青石硫同位素分析

在硫同位素地质研究工作中,经常遇到的研究对象是重晶石、天青石、石膏这一类硫酸盐矿物。如何从这类硫酸盐矿物中制备出适于质谱测定硫同位素组成的二氧化硫气体,国内外采取的方法不同。一、三酸还原法三酸还原法是利用强还原剂于强酸性溶液中持续加热,把SO_4离子中正六价硫还原成负二价硫(H_2S形式),然后变成硫化银,再按硫化物方法制备二氧化硫气体。     

锡铁山石的化学式再定义

利用电子探针能谱仪检查新矿物——锡铁山石的成分时,发现有相当含量的氯。因此,原来的化学式Fe³⁺(SO₄)(OH)·7H₂O应修改为Fe³⁺(SO₄)Cl·6H₂O。     

我国K-Ar法标准样40Ar-40K和40Ar-39Ar年龄测定及放射成因40Ar的析出特征

同位素地质年龄标准样的建立,是一项重要的基础工作,它在检查和比较各种实验流程,衡量各种定年方法的可信度,标定同位素稀释剂等方面,都是必不可少的。从1977年初开始,我国同位素地质标准样小组着手建立K-Ar法标准样。为了外检,笔者曾将ZBH-25黑云母、ZBJ角闪石带到澳大利亚国立大学地球科学院进行测定。这两个样品的K-Ar稀释法年龄、⁴⁰Ar/³⁹Ar坪年龄及⁴⁰Ar/³⁹Ar等时年龄的一致性表明,这些矿物结晶以后,未受过热的挠动,也不存在过剩氩,是作标准样的理想样品。本文还介绍样品中放射成因⁴⁰Ar的析出特征,并指出⁴⁰Ar可能有两种存在状态,它们各具不同的晶格能。     

AlPO4高温高压相变研究

利用配有电阻炉外加热装置的金刚石对顶砧及紧装式六面顶高压容器,在500—1700℃和常压至17.8GPa温压范围内,对AlPO₄进行了实验研究。常压下,磷铝石(石英型AlPO₄)向鳞石英型AlPO₄转变的温度约为778℃,鳞石英型向方英石型AlPO₄转变的温度约为1100℃,块磷铝石α-β相转变的温度为586℃。在5.4 GPa和1300℃以下,块磷铝石保持稳定,在5GPa和大于1700℃时,发现AlPO₄分解为Al₂O₃,(刚玉)和P₂O₅鳞石英型AlPO₄在6GPa及500℃转变成斜方晶系新相,新相在室温常压下的晶胞参数为:a=4.930Å,b=7.200Å和c=6.165Å,鳞石英型AlPO₄及块磷铝石在11GPa以上均变为NiSO₄型结构。文中讨论了AlPO₄与SiO₂的异同,并给出了一个AlPO₄可能的相图。     

氟对磷酸盐矿物形成影响的试验研究——Ca2+-HPO42--HCO31--F1--H2O体系

我們在前一篇文章里曾討論了Ca²⁺-HPO₄^2--F^1--H₂O体系中氟对磷酸盐矿物形成影响的若干方面。为了使該項模拟試驗工作更符合于表生作用条件,我們在叶連俊教授的指导下,在上述实驗体系中增加了一个組分--HCO₃^1-,进行了Ca²⁺-HPO₄^2--HCO₃^1-F^1--H₂O体系的試驗研究。其目的为进一步探索在合有HCO₃^1-組分的体系中氟对磷酸盐矿物形成的影响,以及CO₃^2-能否进入磷灰石晶格和磷酸盐矿物与碳酸盐矿物的沉积分异順序等問題。     

Determination of SO4β1 for yttrium and the rare earth elements at I = 0.66 m and t = 25°C—implications for YREE solution speciation in sulfate-rich waters

We present a complete set of stability constants (_SO4β₁) for the monosulfato-complexes of yttrium and the rare earth elements (YREE), except Pm, at I = 0.66 m and t = 25°C, where _SO4β₁ = [MSO₄⁺] × [M³⁺]⁻¹[SO₄²⁻]⁻¹ (M ≡ YREE and brackets indicate free ion concentrations on the molal scale). Stability constants were determined by investigating the solubility of BaSO₄ in concentrated aqueous solutions of MCl₃. This is the first complete set to be published in more than 30 years.The resulting _SO4β₁ pattern is very similar in shape to one reported by de Carvalho and Choppin (1967a) (I = 2 mol/L; t = 25°C) that has been largely ignored. Stability constants vary little between La and Sm, but display a weak maximum at Eu. Between Eu and Lu, _SO4β₁ decreases by 0.2 log units, substantially exceeding the ±0.02 log unit average analytical precision. The stability constant for Y is approximately equal to that for Er. Our _SO4β₁ pattern is consequently distinctly different from the consensus pattern, based on a single data set from 1954, which is essentially flat, with a range of only 0.07 log units between the lowest and highest _SO4β₁ values within the lanthanide series (excluding Y).Values of _SO4β₁ obtained in this work, in conjunction with the ion-pairing model of Millero and Schreiber (1982), allow prediction of _SO4β₁ between 0 and 1 m ionic strength. These results are used to assess both the absolute and relative extent of YREE sulfate complexation in acidic, sulfate-rich waters.     

Free energy of formation for green rust sodium sulphate (NaFe6Fe3(OH)18(SO4)2(s))

In a recent study, sulphate-bearing green rust (GR_SO4) was shown to incorporate Na⁺ in its structure (NaFe^II₆Fe^III₃(OH)₁₈(SO₄)_2(s); GR_Na,SO4). The compound was synthesised by aerial oxidation of Fe(OH)_2(s) in the presence of NaOH. This paper reports on its free energy of formation .Freshly synthesised GR_Na,SO4 was titrated with 0.5 M H₂SO₄ in an inert atmosphere at 25 °C, producing dissolved Fe²⁺ and magnetite or goethite. Solution concentrations, PHREEQC and the MINTEQ database were used to calculate reaction constants for the reactions:

     

清原树基沟英云闪长岩40Ar/39Ar年龄谱

清原太古代花岗-绿岩地体位于华北断块北缘,辽宁地块铁岭-靖宇古隆起中部,分布面积约8,000平方公里,花岗岩与绿岩出露面积比为2.5:1。绿岩地层自下而上分为石棚子组、红透山组和南天门组。石棚子组与红透山组整合接触,南天门组不整合于红透山组之上。     

Variation characteristics of CO2 in a newly-excavated soil profile,Chinese Loess Plateau: Excavation-induced ancient soil organic carbon decomposition

Soils of the Chinese Loess Plateau(CLP)contain substantial amounts of soil inorganic carbon(SIC),as well as recent and ancient soil organic carbon(SOC).With the advent of the Anthropocene,human perturbation,including excavation,has increased soil CO₂ emission from the huge loess carbon pool.This study aims to determine the potential of loess CO₂ emission induced by excavation.Soil CO₂ were continuously monitored for seven years on a newly-excavated profile in the central CLP and the stable C isotope compositions of soil CO₂ and SOC were used to identify their sources.The results showed that the soil CO₂ concentrations ranged from 830μL·L^-1 to 11190μL·L^-1 with an annually reducing trend after excavation,indicating that the human excavation can induce CO₂ production in loess profile.Theδ¹³ C of CO₂ ranged from–21.27‰to–19.22‰(mean:–20.11‰),with positive deviation from top to bottom.The range of δ¹³CSOC was–24.0‰to–21.1‰with an average of–23.1‰.Theδ¹³ C-CO₂ in this study has a positive relationship with the reversed CO₂ concentration,and it is calculated that 80.22%of the soil CO₂ in this profile is from the microbial decomposition of SOC and 19.78%from the degasification during carbonate precipitation.We conclude that the human excavation can significantly enhance the decomposition of the ancient OC in loess during the first two years after perturbation,producing and releasing soil CO₂ to atmosphere.     

新矿物中华铈矿Ba2Ce(CO3)3F

新近发现一种含钡和稀土的氟碳酸盐矿物,经电子探针、矿物化学、X-射线粉品、X-射线能谱、电子衍射、扫瞄电予显微镜和透射电子显微镜等分析,偏光显微镜和反光显微镜光性鉴定,差热分析以及显微硬度、比重和其他物理性质测定,确定是一种新矿物。     

硫酸盐化合物分子体积的加和性研究

自然界中已发现的硫酸盐矿物主要是表生作用和热液后期的产物,均是在低温、低压条件下形成的。因此,对于硫酸盐化合物来说,由于其结晶条件相似,那么,各种离子(或离子团)在不同的硫酸盐化合物中是否占有大致相同的体积。     

K-H3OFe3(SO4)2(OH)6铁矾的XRD研究

根据X射线衍射(XRD)分析发现: A Fe₃(SO₄)₂(OH)₆(A=K⁺、H₃O⁺)系列铁钒的XRD数据十分相近,难以用XRD区别,需通过能谱(EDS)辅助分析,才能区分此类铁矾。另外,此类铁矾的003和107面网间距d随K⁺含量增大而增大,且呈一元三次方程的关系;而033和220面网间距d随K⁺含量增大而减小,呈一元二次方程的关系。对该现象从铁矾晶体结构方面进行解释:K⁺、H₃O⁺离子位于较大空隙中,且沿着Z轴方向排列,当K⁺、H₃O⁺离子之间相互替换时,会导致该铁矾晶体结构在Z轴方向有较明显的变化。     

Determination of SrSO04 ion pair formation using conductimetric and ion exchange techniques

The dissociation constant for SrSO⁰₄ ion pair was determined at 25°C using conductance and ion-exchange techniques. Both approaches yield values for pK of SrSO⁰₄ at zero ionic strength in the range 2.28–2.31. Previously reported values range from 2.1 to 3.0. The refinement in the dissociation constant should allow more reliable appraisals of the extent of strontium mineral solubility controls on strontium concentrations in natural water systems.The Lee and Wheaton conductance model was used to interpret the results of the conductivity measurements in strontium sulphate solutions at 25°C. Because of the limitations imposed by the solubility of celestite, a sufficiently-wide concentration range to enable determination of all three of the parameters—dissociation constant, Λ₀, and the distance parameter could not be made. Instead, values are reported for the dissociation constant and Λ₀ using reasonable limiting values for the distance parameter.Dowex-50 was used in the ion-exchange technique to determine the dissociation constant for SrSO⁰₄. This method was used to determine values at other temperatures as well. Although there is considerable scatter in the temperature data, a standard enthalpy for the dissociation reaction: SrSO⁰₄→ Sr²⁺ + SO^2?₄ is computed to be 8.7 ± 2 kJmole^?1 at 25°C.     

N2-CH4（CO2）混合气体在线标样制备及其拉曼定量因子测定

利用混合气体的标准样品对激光拉曼探针进行标定,可以快速准确地对包裹体中的无机及有机气相组分进行定量分析。而常用的商用钢瓶装混合气体标样,存在费用高、气体组成单一固定等缺点。本文设计了一套在线标样制备装置,提出一种在线配置不同浓度和压力条件下混合气体标样的方法。利用高纯度(纯度99.999%)的N2、CH4以及CO2钢瓶气,经过在线混合增压,在5 MPa和10 MPa条件下制备了N2摩尔分数为30%、50%和70%的N2-CH4以及N2-CO2混合气体在线标样。该方法制备的标样与70%N2+30%CO2的商用钢瓶气标样对比表明,CO2与N2的拉曼相对峰高以及相对峰面积值的误差在4%以内,具有较高的准确度和重现性。通过不同压力和浓度条件下CH4以及CO2的拉曼相对定量因子测定表明,气体的相对定量因子在5~10 MPa压力条件下与压力及组成无关。地质样品应用结果表明,本方法可以方便、灵活、准确地按任意比例将两瓶及两瓶以上纯气体钢瓶样品进行混合及增压,为激光拉曼标定、气体组成原位测量等提供了一种新的技术思路。