第 47 卷第 6 期 Vol.47, No.6, 604~611 2018 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., 510640; 2., 100049) 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 : 0379-1726(2018)06-0604-08 DOI: 10.19700/j.0379-1726.2018.06.002 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 510640, China; 2. University of Chinese Academy of Sciences, Beijing 100049, 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): 2017-05-04; 改回日期 (Revised): 2017-09-08; 接受日期 (Accepted): 2017-11-07 基金项目 : (41573003); (29 [2015]93 ) 作者简介 : (1991 ),,, E-mail: wangqiaoshan123@163.com * 通讯作者 (Corresponding author): MA Jin-long, E-mail: jlma@gig.ac.cn; Tel: +86-20-85290116
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 605 0 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 = 0.749766) [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 ++ 46 Ti, 94 Zr ++ 47 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) ( 10000 ),, : ( 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), 1 1.1 : 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 7.5 mol/l HNO 3 120 7 d,, 1 ml HNO 3, 1 ml HNO 3 120 4 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 + 0.5 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 + 0.5 mol/l HF 10 Milli-Q 4 2 mol/l HF 6 2 mol/l HF 0.9 2 mol/l HF 10 V 0.2 mol/l HCl + 0.5 mol/l HF 10 Ti(Zr-Hf ) 6 mol/l HCl + 0.5 mol/l HF 6 Fig.1 1 AG1-X8 High-field-strength elements (HFSEs) separation from other elements on AG1-X8 resin
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 3 + 0.01% 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 + 0.5 mol/l HF 10 Milli-Q 5 2.5 mol/l HCl 6 2.5 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 3 + 0.01% HF, 10, HF 0.0024 mol/l,, Si, 28 Si 0.2 V, HF (1% HNO 3 + 0.01% 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 10000 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
608 2018 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 3.310 mm 100 μl/min 0.45 L/min Y-pos 3.850 mm 0.938 L/min Z-pos 0.240 mm 4.194 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) ++ 94 (Zr Mo) ++ 96 (Zr Mo) ++ 46 Ti + 47 Ti + 48 Ti +, 98 Mo ++ 100 Mo ++ 49 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, 2014 2016 Millet et al. [22 23], 4 4,, Millet et al. [23] [23] OL-Ti,, 0 GSP-1, Millet et al. [22],, ( ) [22],,
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 609 3 ( 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 4.94 0.39 5.21 0.25 10.41 0.49 15.46 0.31 BCR-2 5.00 0.10 5.19 0.14 10.47 0.28 15.54 0.31 JB-3 5.09 0.61 5.15 0.32 10.30 0.65 15.55 0.75 BHVO-2 5.17 0.38 5.19 0.43 10.29 0.50 15.27 0.57 W-2 5.11 0.31 5.14 0.26 10.37 0.26 15.33 0.66 SARM-4 5.21 0.23 5.21 0.23 10.42 0.45 15.11 0.39 AGV-1 4.56 0.52 4.36 0.36 8.89 0.24 13.48 0.88 GSP-1 2.53 0.31 2.46 0.19 4.92 0.39 7.42 0.26 JSD-1 4.09 0.41 4.12 0.38 8.06 0.45 13.07 0.41 GBW07249 4.06 0.40 4.32 0.40 8.89 0.34 13.19 0.76 GBW07296 3.27 0.22 3.60 0.47 7.22 0.63 10.59 0.61 : 2σ *, BHVO-2 12 2, 4 2, 2 Ti,,, Ti, Ti, Ti 3 Ti, 100% Ti, ; - - MC-ICPMS,
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