连续提取-电感耦合等离子体质谱法测定离子型稀土矿中稀土元素总量及7种化学形态含量  

Determination of Total Amounts and 7 Chemical Species of Rare Earth Elements in Ionic-Adsorption Rare Earth Ore by Inductively Coupled Plasma Mass Spectrometry with Continuous Extraction

作　　者：施意华 李学彪 付伟[2] 唐碧玉 古行乾 邱丽 SHI Yihua;LI Xuebiao;FU Wei;TANG Biyu;GU Xingqian;QIU Li(China Nonferrous Metal(Guilin)Geology and Amining Co.,Ltd.,Guilin 541004,China;College of Earth Sciences,Guilin University of Technology,Guilin 541004,China)

机构地区：[1]中国有色桂林矿产地质研究院有限公司,桂林541004 [2]桂林理工大学地球科学学院,桂林541004

出　　处：《理化检验（化学分册）》2022年第12期1380-1388,共9页Physical Testing and Chemical Analysis(Part B:Chemical Analysis)

基　　金：国家自然科学基金重大研究计划培育项目(91962107);“十四五”国家重点研发计划(2021YFC2901702);广西自然科学基金面上项目(2019JJA150083、2020GXNSFAA159139);广西科学研究与技术开发计划项目(桂科能AD18126020、桂科AD20325011)。

摘　　要：采集某离子型稀土矿样品,经除杂、自然风干、研磨、过筛、混匀后,取样品1.000 g,依次经水、1 mol·L^(-1)氯化镁溶液、1 mol·L^(-1)乙酸钠溶液、0.1 mol·L^(-1)焦磷酸钠溶液、0.25 mol·L^(-1)盐酸羟胺-0.25 mol·L^(-1)盐酸的混合液、0.02 mol·L^(-1)硝酸-30%(体积分数)过氧化氢-1.6 mol·L^(-1)乙酸铵-1.6 mol·L^(-1)硝酸的混合液提取后,得到稀土元素的水溶态(F1)、离子交换态(F2)、碳酸盐结合态(F3)、腐殖酸结合态(F4)、铁锰氧化物结合态(F5)、强有机结合态(F6)和残渣态(F7),采用电感耦合等离子体质谱法(ICP-MS)测定样品中各稀土元素的7种化学形态的含量和15种稀土元素总量。利用基体匹配的混合标准溶液系列、稀释形态提取溶液20倍(F1稀释2倍)及103Rh-185Re双内标等,消除了各提取剂对稀土元素测定的影响。各稀土元素7种化学形态的检出限(3s)为0.0011~0.75 mg·kg^(-1),各稀土元素化学形态分析结果的相对标准偏差(n=5)为1.4%~11%,以GBW 07158为质控样,其测定值与认定值基本一致。方法用于实际离子型稀土矿样品分析,结果显示,该离子型稀土矿样品中稀土元素总量为691~2299 mg·kg^(-1),除铈外的钇、镧、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥等14种稀土元素的形态主要以F2存在,占稀土总量的47.6%~84.5%;而铈的形态主要以F2、F5、F6和F7存在。稀土元素各化学形态总和相对于稀土总量的回收率为95.7%~98.6%,表明所用的连续提取法适用于离子型稀土矿中稀土元素的化学形态分析。A sample of an ionic-adsorption rare earth ore was collected,which was removed from impurities,naturally air-dried,ground,sieved and mixed.1.000 g of the sample was taken,and the water-soluble state(F1),ion-exchange state(F2),carbonate-bound state(F3),humic acid-bound state(F4),iron-manganese oxide-bound state(F5),strong organic-bound state(F6)and residue state(F7)of rare earth elements in the sample were sequentially extracted with water,1 mol·L^(-1)magnesium chloride solution,1 mol·L^(-1)sodium acetate solution,0.1 mol·L^(-1)sodium pyrophosphate solution,a mixture of 0.25 mol·L^(-1)hydroxylamine hydrochloride-0.25 mol·L^(-1)hydrochloric acid,and a mixture of 0.02 mol·L^(-1)nitric acid-30%(volume fraction)hydrogen peroxide-1.6 mol·L^(-1)ammonium acetate-1.6 mol·L^(-1)nitric acid.7 species of each element and the total amounts of 15 rare earth elements in the sample were determined by inductively coupled plasma mass spectrometry(ICP-MS).Matrix matched mixed standard solution series,diluting the chemical specie extract solution 20 times(F1 twice)and103Rh-185Re double internal standards were used to eliminate the influence of various extractants on the determination of rare earth elements.Detection limits(3s)of the 7 chemical species of each rare earth element were in the range of 0.0011-0.75 mg·kg^(-1),and RSDs(n=5)of each rare earth element chemical specie analysis results were in the range of 1.4%-11%.GBW 07158 was the quality control sample,and its determined value was basically consistent with the certified value.This method was applied to the analysis of actual ionic-adsorption rare earth ore samples,and it was shown that the total amounts of rare earth elements in the samples of this ionic-adsorption rare earth ore were 691-2299 mg·kg^(-1).Except for cerium,speciation of 14 rare earth elements,including yttrium,lanthanum,praseodymium,neodymium,samarium,europium,gadolinium,terbium,dysprosium,holmium,erbium,thulium,ytterbium and lutetium,were mainly in F2,accounting for 47.6%to 84.5%of the total amou

关 键 词：电感耦合等离子体质谱法(ICP-MS) 离子型稀土矿 稀土元素 化学形态分析 

分 类 号：O657.3[理学—分析化学]