矿物药朱砂原生矿石显微结构及51种微量元素含量分析

Analysis on microstructure and 51 trace elements content of cinnabar primary ore

目的:对贵州省所产道地药材朱砂原生矿石的显微结构和微量元素含量进行研究,为贵州省朱砂原生矿石炮制及药用提供试验依据。方法:对贵州省贞丰县境内烂木厂铊汞矿及丹寨县四相厂汞矿所产的21个原生朱砂矿石样品用显微镜及电感耦合等离子体质谱(ICP-MS)技术进行显微结构及微量元素含量研究。通过显微镜获取朱砂的透射光及反射光结构照片。在朱砂粉末中加入溴化氢(HBr)、氢氟酸(HF)和硝酸(HNO3)消解样品后,再加入铑(Rh)内标溶液和去离子水定容后,配制成测试液上机测试其微量元素含量。ICP-MS以氩气为载气,通过高频震荡产生近7000℃的等离子体,用Rh元素作为内标元素监控测试漂移。结果:丹寨县及贞丰县2个典型朱砂产地所产朱砂一般呈现为粒状、团块状、脉状。朱砂通常与石英、方解石、黄铁矿、毒砂等矿物共生,且共生关系复杂,常呈包裹状、镶嵌状、侵染状结构。实验测试的21个朱砂样品中的51种微量元素含量差别较大,朱砂中铝(Al)、铁(Fe)、钡(Ba)等微量元素含量较高,含量变化范围为1.98~53278μg·g^(-1)。朱砂中大部分微量元素含量较低,其中,烂木厂铊汞矿朱砂中锂(Li)、钴(Co)、镍(Ni)、镓(Ga)、铷(Rb)、钇(Y)、铌(Nb)、钼(Mo)、银(Ag)、锑(Sb)、镨(Pr)、钐(Sm)、铕(Eu)、钆(Gd)、钍(Th)等元素含量为1μg·g^(-1)左右,四相厂朱砂中钒(V)、铬(Cr)、锗(Ge)、钇(Y)、镉(Cd)、铈(Ce)、铌(Nd)等元素含量为1μg·g^(-1)左右。结论:烂木厂铊汞矿及四相厂汞矿所产朱砂微量元素除了Al、Fe、Ba外,其余元素含量普遍较低,但朱砂原生矿石显微结构及矿物共生关系复杂,这两地所产朱砂原生矿石需剔除共生矿物杂质后方可考虑药用。

Objective:To study microscopic structure and trace element content of cinnabar primary ore produced in Guizhou Province in order to provide experimental basis for processing and medicinal use of cinnabar primaryore.Methods:The microstructures and contents of trace elements of 21 primary cinnabar ore samples from Thallium mercury mine in Lanmuchang,Zhenfeng County and Sixiang mercury mine in Danzhai County were studied by microscopic and inductively coupled plasma mass spectrometry(ICP-MS)technique.The transmitted light and reflected light structure pictures of cinnabar were obtained by microscope.The sample was digested by adding hydrogen bromide(HBr),hydrofluoric acid(HF)and nitric acid(HNO3)into cinnabar powder,and then rhodium(Rh)internal standard solution and deionized water at constant volume to prepare test solution for machine test.ICP-MS used argon as carrier gas to generate plasma at nearly 7000℃by high-frequency oscillation.Rhodium element was used as internal standard element to monitor test drift.Results:The cinnabar produced in Danzhai County and Zhenfeng County had a high degree of crystallization,and the cinnabar was generally granular,lumpiness and veined.Cinnabar was usually symbiotic with quartz,calcite,pyrite,arsenopyrite and other minerals,and the symbiotic relationship was complex,often in the form of inclusion,Mosaic,infection structure.The contents of 51 trace elements in 21 cinnabar samples were significantly different.The contents of aluminum(Al),iron(Fe),barium(Ba)and other trace elements in cinnabar were relatively high,ranging from 1.98μg·g^(-1)to 53278μg·g^(-1).The contents of most trace elements in cinnabar were low including lithium(Li),cobalt(Co),nickel(Ni),gallium(Ga),rubidium(Rb),yttrium(Y),niobium(Nb),molybdenum(Mo),silver(Ag),antimony(Sb),praseodymium(Pr),samarium(Sm),europium(Eu),gadolinium(Gd).The contents of thorium(Th)and other elements were about 1μg·g^(-1).The contents of vanadium(V),chromium(Cr),germanium(Ge),yttrium(Y),cadmium(Cd),cerium(Ce),niobium(Nd)in cinnabar from the Sixiangchang were about 1μg·g^(-1).Conclusion:Except for Al,Fe and Ba,the contents of trace elements in cinnabar produced by Thallium mercury mine in Langmuchang and Sixiangchang mercury mine are generally low.However,the microstructure and mineral symbiosis of cinnabar primary ores are complex.Therefore,it is necessary to remove the symbiosis mineral impurities before cinnabar primary ores can be considered for medicinal use.