Determination of rare earth elements in shale by inductively coupledplasma mass spectrometry with perchloric acid-ammoniumbifluoride-nitric acid closed digestion
LIU Li-ping1, DONG Xue-lin2*,3, HE Hai-yang2, QIU Xiu-mei2, SONG Zhou2, ZHU Li-hua3
1. Hunan Province Geological Testing Institute, Changsha 410000, China; 2. Geological Experimental TestingCenter of Hubei Province, Key Laboratory of Rare Mineral, Ministry of Land and Resources, Wuhan 430034,China; 3.Huazhong University of Science and Technology, Wuhan 430074, China
Abstract：The discussion of content characteristic and distribution pattern of rare earth elements (REEs) in shale was helpful to understand the information of shale area such as the sedimentary environment characteristic and matter source. Therefore, it was necessary to establish the accurate and quantitative analysis method of REEs. The shale samples usually had complicated composition and high-content organic matters, so the complete digestion of sample was the foundation to accurately determine the content of REEs. The composition of sample was analyzed by X-ray diffraction. Based on the property that hydrofluoric acid could be produced during heating of ammonium bifluoride, the sample was digested in closed system by perchloric acid, ammonium bifluoride and nitric acid. Then the sample solution was determined by inductively coupled plasma mass spectrometry (ICP-MS). Consequently, the determination of REEs in shale were realized. The mixed standard solution series of REEs were determined under the optimized experimental conditions. The results showed that the linearity was good for each REEs with mass concentration in range of 1-100ng/mL. The linear correlation coefficients were all higher than 0.9996. The detection limits were between 0.002μg/g and 0.473μg/g. The proposed method was applied for the determination of REEs in certified reference material of shale. The results were consistent with the certified values, and the absolute values of relative errors were not than 6.77%. The shale actual sample was determined according to the experimental method, and the relative standard deviations (RSD, n=6) of determination results were all less than 10%. The experimental method was compared with ICP-MS after sample dissolution in closed high-temperature and high-pressure system. The determination results were consistent.
刘立平, 董学林, 何海洋, 仇秀梅, 宋洲, 朱丽华. 高氯酸-氟化氢铵-硝酸密闭消解电感耦合等离子体质谱法测定页岩中稀土元素[J]. 冶金分析, 2018, 38(12): 13-18.
LIU Li-ping, DONG Xue-lin, HE Hai-yang, QIU Xiu-mei, SONG Zhou, ZHU Li-hua. Determination of rare earth elements in shale by inductively coupledplasma mass spectrometry with perchloric acid-ammoniumbifluoride-nitric acid closed digestion. , 2018, 38(12): 13-18.
高桂梅,苏克,王文颖,等.吉林省桦甸油页岩中稀土元素和微量元素的研究[J]. 吉林大学学报:地球科学版,2006, 36(6):974-979.GAO Gui-mei,SU Ke,WANG Wen-ying,et al.Study on rare earth and trace elements in oil shale samples,Huadian,Jilin province[J].Journal of Jilin University:Earth Science Edition,2006,36(6):974-979.
[2]
柳蓉,刘招君,郭巍,等.巴格毛德油页岩中稀土元素特征研究及其地质意义[J]. 地球化学,2010,39(4):364-370.LIU Rong,LIU Zhao-jun,GUO Wei,et al.Rare earth element characteristics of Bagemaode oil shale,Inner Mongolia,China[J].Geochimica,2010,39(4):364-370.
[3]
柏静儒,王擎,魏艳珍,等.桦甸油页岩中稀土元素赋存状态研究[J].燃料化学学报,2011,39(7):489-494.BAI Jing-ru,WANG Qing,WEI Yan-zhen,et al.Geochemical occurrences of rare earth elements in oil shale from Huadian[J].Journal of Fuel Chemistry and Technology,2011,39(7):489-494.
[4]
谢尚克,杜佰伟,王剑.伦坡拉盆地丁青湖组油页岩稀土元素特征及其地质意义[J].地质科技情报,2015,34(2):57-62.XIE Shang-ke,DU Bai-wei,WANG Jian.Characteristics and geological implications of rare earth element of oil shale in Lunpola Basin,Tibet[J].Geological Science and Technology Information,2015,34(2):57-62.
[5]
张海全,王正和,王鹤,等.黔南地区早石炭世黑色岩系稀土元素地球化学特征及沉积-构造环境分析[J].沉积与特提斯地质,2016, 36(3):30-36.ZHANG Hai-quan,WANG Zheng-he,WANG He,et al.REE geochemistry and sedimentary-tectonic setting of the Early Carboniferous black rock series in southern Guizhou[J].Sedimentary Geology and Tethyan Geology,2016,36(3):30-36.
[6]
周建辉,白金峰.熔融玻璃片制样-X射线荧光光谱测定页岩中主量元素[J].岩矿测试,2009,28(2):179-181.ZHOU Jian-hui,BAI Jin-feng.Determination of major elements in shale samples by X-ray fluorescence spectrometry with fused glass disc sample preparation[J].Rock and Mineral Analysis,2009,28(2):179-181.
[7]
喻德科.X射线荧光光谱法直接测定油页岩中微量元素[J].光谱学与光谱分析,1992,12(5):111-114.YU De-ke.Direct determination of trace elements in oil shale by XRFA[J].Spectroscopy and Spectral Analysis,1992,12(5):111-114.
[8]
漆亮,胡静,邓海琳.等离子体质谱法测定黑色页岩中的稀有分散元素[J].广西化工,2000(s1):138-139.QI Liang,HU Jing,DENG Hai-lin.Determination of disperse elements in black shale by inductively coupled plasma mass spectrometry[J].Guangxi Chemical Industry,2000(s1):138-139.
[9]
李志伟,邰自安,任文岩,等.微波消解电感耦合等离子体质谱法测定黑色页岩中稀有稀土元素[J].岩矿测试,2010,29(3):259-262.LI Zhi-wei,TAI Zi-an,REN Wen-yan,et al.Determination of rare and rare earth elements in black shales by inductively coupled plasma-mass spectrometry with microwave digestion[J].Rock and Mineral Analysis,2010,29(3):259-262.
[10]
岳小金.电感耦合等离子体发射光谱法测定页岩微量元素[J].中国锰业,2017,35(1):113-115.YUE Xiao-jin.A determination of trace elements of shale by inductively coupled plasma atomic emission spectrometry[J].China′s Manganese Industry,2017,35(1):113-115.
[11]
孙友宝,马晓玲,李剑,等.封闭压力酸溶-盐酸提取-电感耦合等离子体原子发射光谱法(ICP-AES)测定页岩中的多种微量金属元素[J].中国无机分析化学,2014,4(2):29-31.SUN You-bao,MA Xiao-ling,LI Jian,et al.Determination of multiple trace metallic elements in shale by ICP-AES in conjunction with closed pressurized acid decomposition-hydrochloric acid extraction technique[J].Chinese Journal of Inorganic Analytical Chemistry,2014,4(2):29-31.
[12]
ZHANG Wen,HU Zhao-chu,LIU Yong-sheng,et al.Total rock dissolution using ammonium bifluoride (NH4HF2) in screw-top teflon vials:a new development in open-vessel digestion[J].Analytical Chemistry,2012,84(24):10686-10693.
[13]
李小涵,王朝辉.两种测定土壤有机碳方法的比较[J].分析仪器,2009(5):78-80.LI Xiao-han,WANG Zhao-hui.Comparison of two soil organic carbon determination methods[J].Analytical Instrumentation,2009(5):78-80.
[14]
刘晔,第五春荣,柳小明,等.密闭高温高压溶样ICP-MS测定56种国家地质标准物质中的36种痕量元素——对部分元素参考值修正和定值的探讨[J].岩矿测试,2013,32(2):221-228.LIU Ye,DIWU Chun-rong,LIU Xiao-ming,et al.Determination of 36 trace elements in 56 Chinese National standard reference materials by ICP-MS with pressurized acid-digestion[J].Rock and Mineral Analysis,2013,32(2):221-228.
