X射线荧光光谱微区分析在铜矿物类质同象鉴定中的应用

铜矿物种类繁多,赋存状态各异,成分复杂,由于共生矿物和伴生矿物的存在,增加了传统岩矿鉴定工作的难度。特别是铜矿物间存在的类质同象现象(黝铜矿和砷黝铜矿)和铜矿物与其他矿物间(磁黄铁矿和方黄铜矿)存在镜下光学特征相似的现象,应用偏光或反光显微镜难以给铜矿物准确定名。本文应用具有微区分析功能的X射线荧光光谱仪扫描铜矿物标本谱图,通过选择测量条件、测量方式和干扰校正模型(谱线重叠和基体效应)建立了类质同象物相的鉴定方法。该方法具有较高的精密度和准确度,对黄铜矿标本进行12次测定,S、Fe、Cu的相对标准偏差(RSD)分别为0.74%、0.86%、0.18%;对铜矿物标准样品进行单次测定,待测元素的测量结果与推荐值的相对误差均小于6%。该方法可准确甄别出黝铜矿与含银砷黝铜矿、磁黄铁矿与方黄铜矿;测量效率高,能够提供主量元素和主要伴生元素的二维或三维图像,直观地呈现矿物的分布情况,为铜矿物的准确定名和矿物的综合利用提供了有价值的信息。     

粤北大宝山铜多金属矿区黄铁矿与磁黄铁矿EPMA和LA-ICP-MS原位微区组分特征及其对矿床成因机制约束

粤北大宝山铜多金属矿床一直存在燕山期岩浆热液成因和海西期火山喷流成因之争,争议的焦点在于块状、似层状硫化物矿体的成因。本文在全面开展矿区地质调查和钻探查证的基础上,对块状、似层状和脉状硫化物矿石中的黄铁矿和磁黄铁矿开展EPMA和LA-ICP-MS原位分析。测试结果表明,不同产状黄铁矿的平均分子式相似,分别为FeS_(1.98)、FeS_(1.99)和FeS_(1.98),似层状和脉状硫化物中磁黄铁矿的平均化学式为Fe_(0.886)S和Fe_(0.874)S,属形成温度相对较低单斜磁黄铁矿。与花岗岩岩浆热液标型黄铁矿相比,不同产状的黄铁矿和磁黄铁矿中Co、Ni、Mn、Se和Ge等元素以类质同象形式赋存,它们含量较低但稳定,Cu、Pb、Zn、Ag、Bi和Tl及Ga主要以微细矿物子晶形式存在,其含量丰富,但变化明显。从块状、似层状到脉状硫化物矿体,黄铁矿和磁黄铁矿中Co、Zn和Se的含量及Co/Ni值降低,而Cu、Pb、Ag、Bi等元素的含量明显升高。结合矿区次英安斑岩的产状和含矿性特征表明,大宝山矿床块状、似层状和脉状硫化物矿体都是次英安斑岩深部岩浆房产出的含矿流体在不同赋矿环境中的产物。     

Magnetic properties related to thermal treatment of pyrite

Detailed rock magnetic experiments were conducted on high-purity natural crystalline pyrite and its products of thermal treatments in both argon and air atmospheres. In argon atmosphere (reducing environment), the pyrite is altered by heating to magnetite and pyrrhotite; the latter is stable in argon atmosphere, and has coercive force and coercivity of remanence of ～20 and ～30 mT, respectively. Whereas in air, the pyrite is ultimately oxidized to hematite. First order reversal curve (FORC) diagram of the end product shows that the remanence coercivity of hematite is up to ～1400 mT. The corresponding thermal transformation process of pyrite in air can be simply summarized as pyrite→ pyrrhotite→magnetite→hematite. These results are helpful for understanding of sedimentary magnetism, secondary chemical remanence and meteorolite magnetic properties.     

Imprinting chemical remanent magnetization in claystones at 95 °C

Thermal effects related to burial and hydrothermal alteration leads to chemical remanent magnetization (CRM). We present an experimental study of CRM production by heating claystones at 95 °C. A vertical magnetic field of 2 mT was applied to the claystones during heating and the evolution of the remanence during heating in air is monitored intermittently for up to four months. Solid fragments (9 to 26 g) of claystones are included in a Teflon holder that is placed in the oven under a controlled atmosphere. Newly formed grains acquire a CRM and a thermoviscous magnetization (TVRM), both being parallel to the applied magnetic field. CRM is related to the amount of newly formed grains that pass the critical volume during the reaction. To measure the acquired remanence, the claystones are first cooled in a zero magnetic field and then measured using a 2G SQUID magnetometer.In the frame of the research programme on the feasibility of radioactive waste disposal in a deep geological formation, we investigate the magnetic transformation of Mont Terri Lower Dogger claystones (Switzerland) due to thermal imprinting at 95 °C. We simulate the dehydration that occurs in the walls of galleries after excavation when interstitial water evaporates and rehydration when the galleries are refilled allowing water to move towards dehydrated zones. During dehydration, the remanence gains one order of magnitude at the beginning of the experiment and then it follows a linear rate of 0.23 ± 0.07 mA m^− 1/day between 3 and 14 days. The magnetic susceptibility increases by a few percent. The increase of the remanence and of the magnetic susceptibility stops after 15 days. Mass monitoring indicates that interstitial water evaporates when remanence and magnetic susceptibility stabilizes. During rehydration, the remanence increases again whilst magnetic susceptibility drops by a few percent. After 20 days, the remanence during rehydration follows a rate of 0.42 ± 0.15 mA m^− 1/day. By contrast, when rehydration takes place later, after 66 days, the rate is much lower (0.09 ± 0.04 mA m^− 1/day). Low temperature investigation of magnetic properties indicates an initial magnetic assemblage of magnetite and pyrrhotite. Newly formed magnetite and hematite carry the remanence. We propose that magnetite is formed at the expense of pyrite. Hematite results from the progressive oxidation of newly formed magnetite. Our results suggest the possibility that any claystones that pass the oil window can be remagnetized due to the unique action of temperature.     

大水沟碲矿中楚碲铋矿显微文像结构：交代成因新证据

大水沟楚碲铋矿的产状及其文像矿物形态既有普遍的“交代”现象,也有明显的“出溶”特征。文像黄铁矿与伴生或残余的磁黄匠矿成分的相似性,以及文像矿物在分布和成分上与溶动力实验以及理论模式的差异,表明形成显微文像结构的根本原因富碲、铋流体交代早期磁黄铁矿。楚碲铋矿及其显微文像结构的特征取决于交代环境的“封闭”程度：强度弱、无铁带出的交代形成具明显“交代”特征的楚碲铋矿;当交代强度大、环境封闭时,交代残余矿     

胶东荣成榴辉岩中含铜磁黄铁矿出溶结构的磷灰石的发现及其意义

在苏鲁超高压变质带东北部胶东荣成地区的退变金红石榴辉岩中,我们发现了具含铜磁黄铁矿出溶结构的磷灰石。磷灰石在该榴辉岩中含量较高(≈5%),多为不规则形状,颗粒大小不一,粗大者可达1．2mm×0．6mm。样品中几乎所有的磷灰石均发育出溶结构,出溶棒可能分为相互垂直的两组,各自分别沿同一方向分布,出溶棒密度大,形状规则,宽度相似,长度最长可达0．1mm。在扫描电子显微镜下,利用X射线能谱仪测定出溶棒主要由Fe、Cu和S三种元素组成。由于很难准确确定三者的比例,暂将其定为含铜磁黄铁矿((Fe_(1-x)Cu_x)S)。报道的磷灰石含铜磁黄铁矿出溶结构,与江苏赣榆地区磷灰石的磁黄铁矿出溶结构,同产于苏鲁超高压变质带中,具有可对比性；磷灰石中Cu、Fe的溶解度可能是温压条件的函数；因此进一步精确研究磷灰石中这些出溶结构的成分和成因,将为深入探讨苏鲁超高压变质带不同地体变质条件、成因的差异及俯冲折返机制等问题提供重要线索。     

磁黄铁矿催化分解苯酚反应动力学及其产物特征

本文用批量实验法研究了天然磁黄铁矿在过氧化氢参与下催化分解苯酚的动力学反应。结果表明,在pH=3.81～5.88时,苯酚都可被有效的分解,分解速率k=4.0～212h-1(g/L)-1,高于氧化铁矿物类催化剂,可与Fenton试剂相比拟。同时它具有反应速率可控、催化剂与反应产物易于分离和回收等优点。对反应液中Fe(II)、Fe(Ⅲ)浓度和紫外光谱分析表明,反应过程与Fenton反应类似,苯酚先是被快速转化成多酚类化合物,接着被分解成羧酸类化合物。溶液pH不同,产物不同,总有机碳(TOC)矿化率也不同,一般可达50%～58%。     

紫硫镍矿交代镍黄铁矿的水热反应机理及动力学

本工作首次在实验室条件下对浅生区紫硫镍矿(Ni,Fe)3S4交代镍黄铁矿(Ni,Fe)9S8水热反应的机理及动力学进行了研究。起始反应矿物采用高纯自然镍黄铁矿,合成纯镍黄铁矿或合成镍黄铁矿-磁黄铁矿集合体。反应pH值采用0.2M醋酸-醋酸纳缓冲溶液控制在3～5的范围内。反应进程由X-射线衍射物相定量分析及扫描电镜观察进行跟踪。结果表明,当反应温度恒定在80℃时,交代20(4)%的镍黄铁矿需792h。相同条件下加入少量H2S可将反应速率提高一倍。当反应在125℃饱和蒸汽压水热环境下进行时,完全交代纯镍黄铁矿需约168h。此过程由于磁黄铁矿的存在而被催化,交代集合体中的镍黄铁矿仅需68h,进一步反应磁黄铁矿被交代成白铁矿。磁黄铁矿的催化作用可能源于溶解产生的微裂纹加速了流体的传质过程。当反应温度升高至145℃时,速率反而下降,不遵循Arrhenius经验规律。动力学分析得80℃速率常数介于5.8×10-8～3.0×10-7/s之间,125℃及145℃速率常数分别介于2.8×10-6～2.08×10-5/s及1×10-6～5.1×10-6/s之间,远高于同温度下固相扩散反应的速率常数,表明该反应在地质时标上为一快速反应。此外,用背散射电子显微技术对矿物表面形貌进行了分析,发现交代产物紫硫镍矿具有颗粒细小及存在微裂纹等特征,与自然界浅生矿床中的紫硫镍矿非常相似;电镜实验还表明该交代作用是一个典型的耦合溶解-再沉淀反应。其耦合机制的驱动力可能与反应界面处微空隙对流体饱和度的控制有关。     

四川里伍铜矿床磁黄铁矿成因矿物学研究

里伍铜矿床是产于江浪穹窿的中型富铜矿床,其磁黄铁矿的成分和结构对矿床成因有重要的指示意义。基于对矿床地质特征的认识,采用偏光显微镜、扫描电镜能谱分析、X射线衍射等方法,对主矿体内不同构造类型矿石中的磁黄铁矿的化学成分和结构进行了分析。结果表明,矿体内部只产出六方磁黄铁矿,Fe原子含量百分比为48.63%~47.99%,其成矿温度高于304℃;矿体边部同时存在六方和单斜磁黄铁矿,Fe原子百分比为45.97%~47.54%,成矿温度迅速降低至254℃以下。结合磁黄铁矿标型特征和矿床地质特征,推断里伍铜矿床是在原始矿胚发生变形变质活化的基础上,经历了燕山期中高温热液叠加改造而富集成矿。     

福建丁家山铅锌矿区磁黄铁矿成因矿物学特征研究

通过野外观察、光学显微镜、矿物场填图、X射线衍射、微区成分分析等手段,针对福建丁家山铅锌矿区磁黄铁矿的成因矿物学特征进行研究。结果表明,丁家山铅锌矿区磁黄铁矿具沿北东向断层串珠状排布,揭示明显的热液成矿特征;矿区内有4类产出形态各异的磁黄铁矿,多为单斜、六方混合相磁黄铁矿,其中单斜磁黄铁矿为六方磁黄铁矿的固溶体分离产物,指示矿区成矿为缓慢的降温过程;六方磁黄铁矿结晶温度在322℃～304℃之间,与同成矿期石英包裹体均一测温结果完全符合。六方磁黄铁矿-黄铁矿-闪锌矿成矿压力计计算结果集中在0.2GPa～0.3GPa之间,与该区燕山期花岗岩成岩压力完全一致。由此认为丁家山铅锌矿为燕山期花岗岩与中-新元古代马面山岩群龙北溪组上段经区域变质的富钙质岩发生接触交代作用而形成的矽卡岩型矿床。