利用X射线粉晶衍射和电感耦合等离子体质谱法研究江西西华山钨矿床中黑钨矿的矿物学特征及指示意义

目前针对江西大型黑钨矿石英脉型钨矿床西华山的黑钨矿矿物学特征及指示意义研究较少。本文利用X射线粉晶衍射分析和电感耦合等离子体质谱分析技术对黑钨矿晶体结构、化学成分特征及空间变化规律开展研究。获得黑钨矿晶胞参数为a0=0.477 nm,b0=0.573 nm,c0=0.498 nm,β=90°21',属于锰钨铁矿,与前人得出的黑钨矿晶胞参数略有不同,代表不同元素对铁锰的类质同象替代。主要化学成分WO3、Fe O、Mn O的含量在空间上具有一定的变化规律,反映了成矿物质的运移特征。微量元素Sc、Y、Nb、Ta在垂向含量变化大,说明矿液运移具有复杂性。稀土总量ΣREEs较高(397.16×10-6~1071.11×10-6),具有强烈的Eu负异常,具重稀土富集左倾的"躺椅式"球粒陨石标准化配分模式。将西华山、盘古山、淘锡坑、大吉山4个典型矿床的黑钨矿稀土元素特征进行对比,反映产在花岗岩内接触带的黑钨矿的稀土总量(ΣREEs)相对最高,分馏最明显;产在花岗岩内及其外接触带的黑钨矿的稀土总量(ΣREEs)相对较低,分馏程度最不明显;而产在花岗岩外接触带的黑钨矿的稀土总量(ΣREEs)有高有低,分馏程度有强有弱。因此,黑钨矿的化学成分变化特征,可以有效地指示成矿物质空间运移特征、物质来源和矿床成因。     

红土镍矿样品前处理方法和分析测定技术研究进展

随着常规镍来源的硫化镍矿资源的日益枯竭,可直接生产氧化镍、镍锍和镍铁等产品的红土镍矿倍受关注。对于红土镍矿中主量、次量、痕量元素的检测,相同的检测项目存在多种测试方法,且部分相同原理的测试方法存在细节上的差异,使得检测者选择合适的检测方法变得困难。本文综述了近年来红土镍矿中24种元素测定的样品前处理方式及分析技术研究进展。样品前处理方式依据目标元素及后续的分析方法进行选择,其中酸溶法和碱熔法用途最广。酸溶法引入的盐分少,操作简单,但是分解过程中易导致挥发元素As、Sb、Bi、Hg的损失,Cr易随高氯酸冒烟损失。碱熔法分解能力强,适合分析Cr、Si、全铁等项目,但会引入大量的盐类和因坩埚材料损耗而带入其他杂质,给后续分析带来困难。红土镍矿的分析技术依据实验室条件及目标元素的性质和浓度进行选择。电感耦合等离子体发射光谱法(ICP-AES)是主量、次量元素的主要分析方法,适合于分析含量为10-5~30%级别的金属元素;X射线荧光光谱法主要用于分析含量为10-3~1级别的元素,尤其适合于测定Al、Si、Ti、V和P,由于该方法的准确性依赖于一套高质量的标准样品,故更适合炉前检测或检测大批红土镍矿样品。电感耦合等离子体质谱法(ICP-MS)最适合于分析10-4含量以下的重元素,特别是稀土和贵金属元素。原子吸收光谱法(AAS)适合于分析10-4~10-2级别的Ca、Mg、Ni、Co、Zn、Cr、Mn等低沸点、易原子化元素。分光光度法主要用于分析Ni和P。原子荧光光谱法(AFS)主要用于分析As、Bi、Sb等易形成气态氢化物的元素。容量法主要用于分析Al、Fe、Mg和Si O2等主含量元素。尽管AAS、分光光度法、AFS法和容量法检测周期长,但所用仪器为实验室常规配置,可满足缺乏相应大型仪器实验室的日常检测。本文认为,针对各种检测方法的适用性及存在问题,应从开发微波消解法、固体进样直接测汞法、ICP-MS法以及Cr与其他元素同时分析的快速分析方法等方面开展研究,建立灵敏、准确的检测方法,从而更好地服务于红土镍矿的贸易、检验和综合利用。     

酸溶-电感耦合等离子发射光谱法测定密西西比型铅锌矿床矿石中的铅

密西西比型(MVT)铅锌矿床的主要矿物有方铅石、闪锌矿,常伴生有重晶石、萤石等矿物,使得MVT型矿石在酸处理过程中易生成不溶于水和酸的硫酸铅钡复盐,故而检测矿样中铅的含量偏低。本文建立了采用盐酸-硝酸-氢氟酸体系酸溶分解MVT型矿石,电感耦合等离子体发射光谱法(ICP-OES)测定铅含量的分析方法。实验比较了盐酸-硝酸-氢氟酸、盐酸-硝酸-氢氟酸-高氯酸、盐酸-硝酸-硫酸三种酸溶体系的溶样效果,并通过X射线衍射论证了方法的可行性。结果表明,盐酸-硝酸-氢氟酸体系克服了复盐硫酸铅钡和硫酸铅沉淀的生成,适量的氢氟酸促进了Pb SO4的溶解,X射线衍射表征也表明此种酸溶体系的沉淀中不含有Pb SO4,可更彻底地分解MVT型矿石。本方法精密度(RSD)为0.3%~0.6%,实际样品的加标回收率为96.0%~99.2%,铅的最佳检测范围为0.01%~20.0%。     

赣东北朱溪铜钨矿区花岗闪长斑岩LA-ICP-MS锆石U-Pb定年及地质意义

赣东北朱溪超大型铜钨矿位于江南古岛弧带塔前—赋春成矿带中段,该矿床的发现可进一步验证"南钨北扩"观点并对"南钨北铜"格局提出挑战,但前人对与朱溪铜钨矿成矿作用有关的花岗岩缺少精确的年代学研究,导致对其地球动力学背景理解不够深入。本研究通过详细的野外调查、岩心编录和岩矿鉴定,并利用激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)锆石U-Pb法对朱溪铜钨矿区侵入元古代双桥山岩群中的铜矿化花岗闪长斑岩进行测年,获得了锆石206Pb/238U加权平均年龄为847.2±9.4 Ma(MSWD=0.111),代表了其侵位结晶的年龄,属新元古代。分析认为:朱溪铜钨矿区铜矿化花岗闪长斑岩是新元古代早期华南古洋壳俯冲消减及扬子陆块与华夏陆块发生碰撞作用下的岩浆产物,这次岩浆活动与区域上塔前—赋春成矿带成矿作用关系密切,并为钦—杭成矿带提供了成矿物质基础。本次对其成岩年龄的限定,为研究朱溪超大型铜钨矿矿床提供了新证据。     

激光剥蚀电感耦合等离子体质谱元素微区分析标准物质研究进展

激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)是目前地球科学分析领域的重要技术手段,元素微区分析标准物质研制是该分析技术发展的重要方向。本文对当前LA-ICP-MS元素微区分析标准物质的种类、元素分布以及应用上的优缺点和标准物质的制备方法进行了评述。现有的有证标准物质数量不多、种类不齐全,部分元素浓度较低,定值不确定度较大,应用上受到较大的局限性;研制标准也不成熟,均匀性检验方面尚未有统一的方法。本文参照岩石粉末标准物质均匀性检验方法提出了两步均匀性检验法,同时指出在标准物质种类方面,铂族元素及Au元素浓度适当、Pb-S等不同硫化物基体标准物质,以及化学成分不同的碳酸岩和磷酸岩基体标准物质是当前的迫切需求;在标准物质研制技术方面,纳米岩石粉末压片技术的研发、原位微区分析标准物质(固体)均匀性检验判别标准研究是亟待解决的问题。     

电感耦合等离子体质谱-原子荧光光谱法研究上海口岸进口印度尼西亚煤炭微量元素的赋存形态特征

印度尼西亚是我国最大的煤炭进口国,本文应用电感耦合等离子体质谱、原子荧光光谱、直接测汞仪等技术分析了上海口岸31批进口印度尼西亚煤炭中的12种微量元素,结合数理统计方法研究该类煤炭中微量元素的赋存形态。结果表明,进口印尼煤炭中含有高汞煤、三级含砷煤,As、Hg的平均富集系数大于1,其迁移风险值得关注;Be、Cu、Mo、Cd、Sn、Pb含量均低于中国煤和世界煤炭的平均水平,体现出印尼煤炭低灰分的品质特征。12种微量元素和相关项目(灰分和全硫)可划分为3类:第一类归纳为黏土矿物吸附类,包括As、Be、Cr、Co、Ni、Cu、Mo、Cd、Sn、Pb、灰分;第二类归纳为硫铁矿类,包括Hg、全硫;第三类归纳为碳酸盐矿物类,包括Ba。本文研究结果对于指导进口煤炭开发、利用过程中的环境评价和洁净化处理具有一定的参考价值。     

激光拉曼光谱法在单个流体包裹体研究中的应用进展

激光拉曼光谱法以其非破坏性、高灵敏度和高分辨率等特性,一直以来都是研究流体包裹体的重要方法之一。近年来,围绕激光拉曼光谱在流体包裹体中的应用而展开的研究主要集中在半定量-定量测试方面,即在准确定性的基础上,采用高斯-洛仑兹去卷积分峰、低温原位等定量方法获取流体包裹体的成分和含量,从而克服了激光拉曼光谱法应用于溶液中阳离子的定量分析的灵敏度、准确度较低的问题,不仅能获得流体包裹体中一些常温下不具拉曼活性的盐类物质拉曼特征峰信息,还能根据特征峰与浓度、内压之间的线性关系,进一步对盐度和压力等性质进行测定,从而拓展了激光拉曼光谱法在流体包裹体中的应用范围。本文对激光拉曼光谱法应用于分析流体包裹体成分、盐度、同位素和压力所取得的最新进展进行了评述,并认为随着分析测试技术的不断进步,激光拉曼光谱法未来的分析方向也将继续围绕多元复杂体系及其定量方面的研究展开。     

戊基磷酸二戊酯萃取色层分离-电感耦合等离子体质谱法测定铀产品中9种杂质元素

铀产品中杂质元素的含量测定在核法证学溯源分析或燃料元件厂质量检验中具有重要应用价值,保证测量的准确度主要在于控制流程空白、提高杂质元素的回收率。本文建立了戊基磷酸二戊酯(UTEVA)树脂快速分离铀与杂质元素、电感耦合等离子体质谱法(ICP-MS)测定杂质元素含量的系统流程。结果表明,UTEVA树脂对铀的吸附能力强,铀样品取样量为16.43 mg时,全流程对铀的去污因子大于3×105,9种杂质元素(锰钼镍铜铬铝钛钒镉)的回收率为95.1%~105.1%,国家标准物质GBW04205中杂质元素的分析结果与参考值在不确定度(k=2)范围内一致。本工作建立的分离流程对铀的去污效果好,特别适用于样品量少的情况下铀中杂质元素的分析,为核法证分析最终的归因溯源或燃料质量检验提供了技术支持。     

Ore-forming Fluid Characteristics of the Saishitang Cu-polymetallic Deposit in Qinghai Province, China

Saishitang Cu-polymetallic deposit is located in the southeast section of Late Paleozoic arcfold in the southeastern margin of Qaidam platform. Accoring to the geological process of the deposit,four mineralization episodes were identified: melt/fluid coexisting period(O),skarn period(A),first sulfide period(B) and second sulfide period(C),and 10 stages were finally subdivided. Three types of inclusions were classified in seven stages,namely crystal bearing inclusions(type I),aqueous inclusions(type II) and pure liquid inclusions(type III). Type I and II inclusions were observed in stage O1,having homogenization temperature from 252 to 431°C,and salinities ranging from 24.3% to 48.0%. Type I inclusion was present in stage A1,having homogenization temperature from 506 to 548°C,and salinities ranging from 39.4% to 44.6%. In stage B1,type II and III inclusions were observed,with homogenization temperature concentrating between 300–400°C,and salinities from 0.4% to 4.3%. Type II inclusions were present in stage B2,with homogenization temperature varying from 403 to 550°C. In stage C1,type I and II inclusion commonly coexisted,and constituted a boiling inclusion group,having homogenization temperatures at 187–463°C,and salinities in a range of 29.4%–46.8% and 2.2%–11.0%. Type II and III inclusions were developed in stage C2,having homogenization temperature at 124–350°C,and salinities ranging between 1.6% and 15.4%. In stage C3,type II and III inclusions were presented,with a homogenization temperature range of 164–360°C,and salinities varying from 4.0% to 11.0%. The results of micro-thermal analysis show that fluids are characterized by high temperature and high salinity in stage O1 and A1,and experienced slight decrease in temperature and dramatic decrease in salinity in stage B1 and B2. In stage C1,the salinity of fluid increased greatly and a further decrease of temperature and salinity occurred in stage C2 and C3. Fluids boiled in stage C1. With calculated pressure of 22 MPa from the trapping temperature of 284–289°C,a mineralization depth of 2.2 km was inferred. Results of Laser Raman Spectroscopy show high density of H2 O,CH4 and CO2 were found as gas composition. H-O isotope study indicates the oreforming fluids were the mixture of magmatic water and meteoric water. Physicochemical parameters of fluids show oxygen and sulfur fugacity experienced a decrease,and redox state is weakly reducing. Along with fluid evolution,oxidation has increased slightly. Comprehensive analysis shows that melt exsolution occurred during the formation of quartz diorite and that metal elements existed and migrated in the form of chlorine complex. Immiscible fluid separation and boiling widely occurred after addition of new fluids,bringing about dissociation of chlorine-complex,resulting in a great deal of copper precipitation. In conclusion,Saishitang deposit,controlled by regional tectonics,is formed by metasomatism between highly fractionated mineralization rock body and wall rock,and belongs to banded skarn Cu-polymetallic deposit.     

Raman Micro-Spectroscopic Study of Sulfate Ion in the System Na2SO4 – H2O

This work aims to quantify sulfate ion concentrations in the system Na₂SO₄-H₂O using Raman micro-spectroscopy.Raman spectra of sodium sulfate solutions with known concentrations were collected at ambient temperature（293 K） and in the 500 cm^₁-4000 cm^-1 spectral region.The results indicate that the intensity of the SO₄^2- band increases with increasing concentrations of sulfate ion.A linear correlation was found between the concentration of SO₄^2-（c） and parameter I₁,which represents the ratio of the area of the SO₄^2- band to that of the O-H stretching band of water（A_s/A_w）:I₁=-0.00102+0.01538 c.Furthermore,we deconvoluted the O-H stretching band of water(2800 cm^-1-3800 cm^-1) at 3232 and 3430 cm^-1 into two sub-Gaussian bands,and then defined Raman intensity of the two sub-bands as A_Bi(3232 cm^-1) and A_B2(3430 cm^-1),defined the full width of half maximum（FWHM） of the two sub-bands as W_B1(3232 cm^-1) and W_B2(3430 cm^-1).A linear correlation between the concentration of SO₄^2-（c） and parameter I₂,which represents the ratio of Raman intensity of SO₄^2-（A_s）(in 981 cm^-1) to(A_B1+A_B2),was also established:I₂=-0.0111+0.3653 c.However,no correlations were found between concentration of SO₄^2-（c） and FWHM ratios,which includes the ratio of FWHM of SO₄^2-（W_s） to W_B1 W_B2 and W_B1+B2(the sum of W_B1 and W_B2),suggesting that FWHM is not suitable for quantitative studies of sulfate solutions with Raman spectroscopy.A comparison of Raman spectroscopic studies of mixed Na₂SO₄ and NaCI solutions with a constant SO₄^2- concentration and variable CI^- concentrations suggest that the I\ parameter is affected by CI^-,whereas the I₂ parameter was not.Therefore,even if the solution is not purely Na₂SO₄-H₂O,SO₄^2- concentrations can still be calculated from the Raman spectra if the H₂O band is deconvoluted into two sub-bands,making this method potentially applicable to analysis of natural fluid inclusions.