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1 第 47 卷第 6 期 Vol.47, No.6, 604~ 年 11 月 GEOCHIMICA Nov., 2018 MC-ICPMS 王樵珊 1,2, 马金龙 1*, 张乐 1, 韦刚健 1 (1., ; 2., ) 摘要 : (HFSEs: Ti, Nb, Ta, Zr, Hf W ) HF, AG1-X8 HF Ti Nb Ta Zr Hf W Ca Cr Mo V ; Ln Ti HFSEs, AG1-X8 HF Ti Ca Mg, Ti, 100% Ti Ti (MC-ICPMS) - - (SSB) Ti (NIST 3162a Ti solution), NIST 3162a (ε 49 Ti) BHVO-2 ε 49 Ti 0.5 ε,,,,,,, 关键词 : ; MC-ICPMS; ; 中图分类号 : P599; P597 文献标识码 : A 文章编号 : (2018) DOI: /j High-precision Ti isotope measurement of geological reference materials using MC-ICPMS WANG Qiao-shan 1,2, MA Jin-long 1*, ZHANG Le 1 and WEI Gang-jian 1 1. State Key Laboratory of Isotope Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou , China; 2. University of Chinese Academy of Sciences, Beijing , China Abstract: Here, we present a new three-stage Ti separation procedure using AG1-X8 and Ln resins. Ti isotopes of a number of geological reference materials were measured using MC-ICPMS calibrated by the standard-samplestandard bracketing method. Through the AG1-X8 resin, Ti and other high-field-strength elements (HFSEs), such as Nb, Ta, Zr, Hf, and W, could be effectively separated from matrix elements, such as Ca, V, Mo, Cr, and other major elements. Ti could be separated from other HFSEs by Ln resin. The Ti recovery rate was close to 100%, which was satisfactory to measure Ti isotopes using MC-ICPMS. The extra precision of ε 49 Ti for BHVO-2 (basalt reference materials) was 0.5ε for the past 12 months, which is close to that of the double-spike method. Ti isotopes of a number of geological reference materials were measured based on the above method. Basalts showed uniform Ti isotopes, whereas more evolved granites had higher Ti isotopes. The Ti isotopes of Fe-Mn nodules were between those of basalts and granites. The significant variation in Ti isotopes in different geological backgrounds provided a good proxy to trace the different geological processes. Key words: Ti isotope; MC-ICPMS; extra correction; geological standard materials 收稿日期 (Received): ; 改回日期 (Revised): ; 接受日期 (Accepted): 基金项目 : ( ); (29 [2015]93 ) 作者简介 : (1991 ),,, wangqiaoshan123@163.com * 通讯作者 (Corresponding author): MA Jin-long, jlma@gig.ac.cn; Tel:

2 第 6 期王樵珊等 : 利用 MC-ICPMS 高精度测定地质样品的钛同位素组成的方法研究 Ti,,,, [1] Ti, Ti 5, 46 Ti (8.25%) 47 Ti (7.44%) 48 Ti (73.72%) 49 Ti (5.41%) 50 Ti (5.18%), ( 49 Ti/ 47 Ti = ) [2] Ti ( 50 Ti 46 Ti), [2 17],, [18 21] Ti,,,,, Ti, Ti AG-1 [18] U-TEVA [19 21], TODGA [14,22,23] Ti, Ti, 46 Ca 46 Ti, 48 Ca 48 Ti 50 V 50 Cr 50 Ti AG-1 Zr [18,24], Zr, 92 Zr Ti, 94 Zr Ti AG-1 U-TEVA, Zr, Zr AG-1 TODGA Ti, (12 mol/l HNO 3 + 1% H 2 O 2 ),, 95% [14] Ti,,,, SSB Ti 100% Ti, (TIMS), TIMS Ti, [6,8] (MC-ICPMS) ( ),, : ( 49 Ti/ 47 Ti) [2,14], Ti (δ x Ti, ε x Ti),, ( ) (ε 46 Ti ε 50 Ti) [2 17] ; ( 47 Ti- 49 Ti), [22 23] ; - - (SSB) [19 21], AG1-X8 Ln (HDEHP) Ti, MC-ICPMS - - ( NIST Ti 3162a), : Milli-Pore 18.2 MΩ cm (Milli-Q ) HF: HF DST-1000 PFA 24 mol/l HF BVIII HF HF; HF Milli-Q HNO 3 : HNO 3 DST-1000 PFA 15 mol/l HNO 3

606 2018 年 HCl: HCl Milli-Q 9 mol/l HCl, DST-1000 PFA 9 mol/l HCl; HCl Milli-Q 1.2 20 mg PFA, 2 ml 24 mol/l HF 1 ml 7.

3 年 HCl: HCl Milli-Q 9 mol/l HCl, DST-1000 PFA 9 mol/l HCl; HCl Milli-Q mg PFA, 2 ml 24 mol/l HF 1 ml 7.5 mol/l HNO d,, 1 ml HNO 3, 1 ml HNO min, 1 ml 6 mol/l HCl,, 1 ml 2 mol/l HF, 1 ml 2 mol/l HF, 120 Ca Mg, ( CaF 2 MgF 2 ) 1.3 Ti Ti, 0.5 ml 200~400 ( 38~75 μm) AG1-X8 0.5 cm 4 cm Bio-rad, 6 mol/l HCl mol/l HF, Milli-Q 2 mol/l HF,, Ti 1, Ti 1( BHVO-2 ) Ti (Nb Ta Za Hf W) U-TEVA Ti Zr, TODGA HNO 3 Ti, Ti 表 1 AG1-X8 树脂分离 Ti 淋洗流程 Table 1 Ti separation on AG1-X8 resin (ml) 6 mol/l HCl mol/l HF 10 Milli-Q 4 2 mol/l HF 6 2 mol/l HF mol/l HF 10 V 0.2 mol/l HCl mol/l HF 10 Ti(Zr-Hf ) 6 mol/l HCl mol/l HF 6 Fig.1 1 AG1-X8 High-field-strength elements (HFSEs) separation from other elements on AG1-X8 resin

4 第 6 期王樵珊等 : 利用 MC-ICPMS 高精度测定地质样品的钛同位素组成的方法研究 607 Ln (HDEHP) Ti 1 ml HNO 3, 2~3 6 mol/l HCl,, Ti Ti, 2.5 mol/l HCl,, Ln Ti 1 ml 100~200 ( 75~150 μm) Ln, Ti Ti, 2, Ti 2,, Ca Mg,, Ti AG1-X8, Ca Mg, Ti 120, HNO 3 Ti HCl HNO 3 MC-ICPMS, 3, 0.5 ml 1% HNO % HF, 1.4 MC-ICPMS 表 2 Ln (HDEHP) 树脂分离 Ti 淋洗流程 Table 2 Ti separation on Ln (HDEHP) resin (ml) 6 mol/l HCl mol/l HF 10 Milli-Q mol/l HCl mol/l HCl 1 Ti 4 mol/l HCl + 0.1%H 2 O 2 5 HFSEs 2 mol/l HF 3 Neptune Plus MC-ICPMS 9, 48 Ti, 17%,, Ca V Cr Ti, 3, Ti ICP-MS Ca V ( 50 V V 0.25%) Cr, 50 Cr 50 Ti, ESI PFA 50 μl/ml Ti 10 μg/ml,, HF, Si, Si, 29 Si 18 O 47 Ti, 1% HNO % HF, 10, HF mol/l,, Si, 28 Si 0.2 V, HF (1% HNO % HF), Ti 0.6 mv, Ti, HF SiO +,, 400 ng/ml Ti, 48 Ti 8 V, Ti NIST 3162a 3, ε i Ti : ε i Ti = ( i Ti/ 47 Ti / i Ti/ 47 Ti 1) 10000; (i =46, 48, 49, 50) Ti 0.5 ng, Ti ng,, 0.6 mv, / 1000, 1.5 Ti Fig.2 2 Ln Ti Ti separation from other high-field-strength elements (HFSEs) on Ln resin - - Ti 100%, NIST3162a Ti

5 年表 3 MC-ICPMS 测试钛同位素时的主要工作参数 Table 3 The typical instrumental parameters during Ti isotope measurement with MC-ICPMS RF 1310 W ESI PFA 15 L/min X-pos mm 100 μl/min 0.45 L/min Y-pos mm L/min Z-pos mm s 3 s 10 kv Glass cyclonic Ca Al Mg Na Cr V Zr 1 ml, 10 μg/g,, Ti ICP-MS Ti (9.8±0.3) μg/g, Ti, NIST 3162a Ti (ε 49 Ti = 0.05±0.02), 2 2.1,, 46 Ca + 46 Ti +, 48 Ca + 48 Ti +, 50 (V Cr) + 50 Ti +,, 92 (Zr Mo) (Zr Mo) (Zr Mo) Ti + 47 Ti + 48 Ti +, 98 Mo Mo Ti + 50 Ti +,, AG1-X8, Mg Ca V Cr MC-ICPMS [19 21],, Zr Mo, Ln Zr Mo, Ti, Zr Mo, Zr Mo,, C H O Si,,, Ti 0.6 mv,, 2.2,, ( 3a 3b),,,, 46 Ca + 46 Ti +, 48 Ca + 48 Ti +, 50 (V Cr) + 50 Ti +,, Ti 47 Ti 49 Ti, ε 49 Ti, Millet et al. [22 23], 4 4,, Millet et al. [23] [23] OL-Ti,, 0 GSP-1, Millet et al. [22],, ( ) [22],,

6 第 6 期王樵珊等 : 利用 MC-ICPMS 高精度测定地质样品的钛同位素组成的方法研究 ( 2σ ) Fig.3 The mass-dependent fractionation line of Ti isotopes (error is 2σ) 表 4 地质标准物质的钛同位素组成 Table 4 Ti isotope compositions of geological standard materials ε 46 Ti 2σ * ε 48 Ti 2σ ε 49 Ti 2σ ε 50 Ti 2σ BIR BCR JB BHVO W SARM AGV GSP JSD GBW GBW : 2σ *, BHVO , 4 2, 2 Ti,,, Ti, Ti, Ti 3 Ti, 100% Ti, ; - - MC-ICPMS,

7 年 Fig.4 4 Ti isotope compositions of geological standard materials, ;, 中国科学院广州地球化学研究所刘颖高级工程师涂湘林高级工程师以及孙胜玲博士在本实验的流程标定以及元素测试工作中给予了诸多帮助, 特表示感谢本文的工作由国家自然科学基金 ( ) 和中国科学院关键技术人才基金项目 (29 科发人函字 [2015]93 号 ) 资助参考文献 (References): [1] Nesbitt H W, Young G M. Early Proterozoic climates and plate motions inferred from major element chemistry of lutites [J]. Nature, 1982, 299(5885): [2] Trinquier A, Bizzarro M. Origin of nucleosynthetic isotope heterogeneity in the solar protoplanetary disk [J]. Science, 2009, 324(5925): [3] Leya I, Schönbächler M, Wiechert U, Krähenbühl U, Halliday A N. Titanium isotopes and the radial heterogeneity of the solar system [J]. Earth Planet Sci Lett, 2008, 266(3/4): [4] Leya I, Schönbächler M, Krähenbühl U, Halliday A N. New titanium isotope data for Allende and Efremovka CAIs [J]. Astrophys J, 2009, 702(2): [5] Niederer F R, Papanastassiou D A, Wasserburg G J. Endemic isotopic anomalies in titanium [J]. 1980, 240(1): L73 L77. [6] Niederer F R, Papanastassiou D A, Wasserburg G J. The isotopic composition of titanium in the Allende and Leoville meteorites [J]. Geochim Cosmochim Acta, 1981, 45(7): [7] Niederer F R, Papanastassiou D A, Wasserburg G J. Absolute isotopic abundances of Ti in meteorites [J]. Geochim Cosmochim Acta, 1985, 49(3): [8] Niemeyer S, Lugmair G W. Ubiquitous isotopic anomalies in Ti from normal Allende inclusions [J]. Earth Planet Sci Lett, 1981, 53(2): [9] Niemeyer S, Lugmair G W. Titanium isotopic anomalies in meteorites [J]. Geochim Cosmochim Acta, 1984, 48(7): [10] Niemeyer S. Systematics of Ti isotopes in carbonaceous chondrite whole-rock samples [J]. Geophys Res Lett, 1985, 12(10): [11] Niemeyer S. Isotopic diversity in nebular dust: The distribution of Ti isotopic anomalies in carbonaceous chondrites [J]. Geochim Cosmochim Acta, 1988, 52(12): [12] Niemeyer S. Titanium isotopic anomalies in chondrules from carbonaceous chondrites [J]. Geochim Cosmochim Acta, 1988, 52(2): [13] Papanastassiou D A, Brigham C A. The identification of meteorite inclusions with isotope anomalies [J]. Astrophys J, 1989, 338(1): L37 L40. [14] Zhang J, Dauphas N, Davis A M, Pourmand A. A new method for MC-ICPMS measurement of titanium isotopic composition: Identification of correlated isotope anomalies in meteorites [J]. J Anal Atom Spect, 2011, 26(11): [15] Zhang J, Dauphas N, Davis A M, Leya I, Fedkin A. The proto- Earth as a significant source of lunar material [J]. Nature Geosci, 2012, 5(4): [16] Zhang J, Huang S, Davis A M, Dauphas N, Hashimoto A, Jacobsen S B. Calcium and titanium isotopic fractionations during evaporation [J]. Geochim Cosmochim Acta, 2014, 140: [17] Zinner E K, Fahey A J, Mckeegan K D, Goswami J N, Ireland T R. Large Ca-48 anomalies are associated with Ti-50 anomalies in Murchison and Murray hibonites [J]. Astrophys J, 1986, 311(2): L103 L107. [18] Leya I, Schönbächler M, Wiechert U, Krähenbühl U, Halliday A N. High precision titanium isotope measurements on geological samples by high resolution MC-ICPMS [J]. Int J Mass Spect, 2007, 262(3): [19] Zhu X K, Makishima A, Guo Y, Belshaw N S, O Nions R K. High precision measurement of titanium isotope ratios by plasma source mass spectrometry [J]. Int J Mass Spect, 2002, 220(1): [20] Makishima A, Zhu X K, Belshaw N S, O Nions R K. Separation of titanium from silicates for isotopic ratio determination using multiple collector ICP-MS [J]. J Anal Atom Spect, 2002, 17(10): [21],,,,. [J]., 2011, 39(12): Tang Suo-han, Zhu Xiang-kun, Zhao Xin-miao, Li Jin, Yan Bin. Ion exchange chromatography and multi collector induc-

8 第 6 期王樵珊等 : 利用 MC-ICPMS 高精度测定地质样品的钛同位素组成的方法研究 611 tively coupled plasma mass spectrometry for high precision isotopic measurements of titanium isotope ratio [J]. Chinese J Anal Chem, 2011, 39(12): (in Chinese with English abstract). [22] Millet M-A, Dauphas N. Ultra-precise titanium stable isotope measurements by double-spike high resolution MC-ICP-MS [J]. J Anal Atom Spect, 2014, 29(8): [23] Millet M-A, Dauphas N, Greber N D, Greber N D, Burton K W, Dale C W, Debret B, Macpherson C G, Nowell G M, Williams H M. Titanium stable isotope investigation of magmatic processes on the Earth and Moon [J]. Earth Planet Sci Lett, 2016, 449: [24] Schönbächler M, Rehkämper M, Lee D C, Halliday A N. Ion exchange chromatography and high precision isotopic measurements of zirconium by MC-ICP-MS [J]. Analyst, 2004, 129(1):

THE APPLICATION OF ISOTOPE RATIO ANALYSIS BY INDUCTIVELY COUPLED PLASMA MASS SPECTROMETER A Dissertation Presented By Chaoyong YANG Supervisor: Prof.D

10384 070302 9825042 UDC 2001.6. 2001.7. 20016 THE APPLICATION OF ISOTOPE RATIO ANALYSIS BY INDUCTIVELY COUPLED PLASMA MASS SPECTROMETER A Dissertation Presented By Chaoyong YANG Supervisor: Prof.Dr. Xiaoru