Carbon and Oxygen Isotope Analysis of Trace Carbonate by Kiel Ⅳ-IRMS Using On-line Dual Technique
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摘要: 石笋能重建百年、十年的气候事件，为达到空间高分辨率，对微量碳酸盐的检测提出了更高要求，传统磷酸酸解法的样品用量大（约10 mg）已经无法满足微量样品的分析，而激光探针质谱分析方法需对检测结果进行校正。本文采用Kiel Ⅳ-IRMS双路在线分析技术对微量碳酸盐样品的碳、氧同位素进行检测研究其可行性，并以GBW 04405和NBS 19为例研究了不同样品量的碳酸盐标准样品在不同反应时间对同位素分馏的影响。结果表明，由于标准样品所需的反应时间不同，从而导致同位素分馏值的差异。对样品量为4~85 μg的标准样品GBW 04405进行检测，δ13C、δ18O测量值分别为0.574‰±0.027‰、-8.519‰±0.065‰，与推荐值0.57‰±0.03‰、-8.49‰±0.14‰基本一致，表明该方法能够满足微量碳酸盐测试的要求。将Kiel Ⅳ-IRMS双路在线分析技术与Gasbench Ⅱ-IRMS检测方法进行对比，对于标准样品GBW 04405，Kiel Ⅳ-IRMS所用样品量约为50 μg，δ13C、δ18O测量值分别为0.576‰±0.012‰、-8.501‰±0.050‰，Gasbench Ⅱ-IRMS所用样品量约为140 μg，δ13C、δ18O测量值分别为0.569‰±0.034‰、-8.590‰±0.099‰。表明Kiel Ⅳ-IRMS方法相比于GasbenchⅡ-IRMS方法所需样品量少，精度高，结果重现性好，该方法在碳酸盐样品的应用上能达到空间高分辨率。
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关键词:
- 微量碳酸盐 /
- 碳同位素 /
- 氧同位素 /
- Kiel Ⅳ-IRMS双路在线分析 /
- Gasbench Ⅱ-IRMS在线分析
Abstract: Stalagmites can rebuild the paleo-climate of decades and hundred years, which need more accurate detection of trace carbonates in order to achieve high spatial resolution. However, the traditional phosphate acid method with weight about 10 mg has been unable to meet analysis of trace samples, and the laser microprobe mass spectrometry method requires calibration for test results. Carbon and oxygen isotopes of trace carbonate samples have been detected by using Kiel Ⅳ-IRMS with on-line dual technique. Different carbonate standard reference materials of GBW 04405 and NBS 19 were detected under different reaction times and different weights, and the test results were compared with Gasbench Ⅱ-IRMS results. The results indicate that isotopic fractionation values of different carbonate standard reference materials are different, caused by different reaction times. 55 carbonate standard material of GBW 04405 with weight about 4-85 μg have been analyzed and mean values of δ13C and δ18O are 0.574‰±0.027‰ and -8.519‰±0.065‰ which are consistent with certified values of 0.57‰±0.03‰ and -8.49‰±0.14‰, respectively. 14 carbonate standard material of GBW 04405 have been analyzed by Kiel Ⅳ-IRMS and GasbenchⅡ-IRMS with weight respectively about 50 μg and 140 μg. The results of δ13C and δ18O are 0.576‰±0.012‰ and -8.501‰±0.050‰ detected by Kiel Ⅳ-IRMS, 0.569‰±0.034‰ and -8.590‰±0.099‰ detected by Gasbench Ⅱ-IRMS. The test result of the on-line dual technique consumed less sample, had better precision and were more reproducible than that by GasbenchⅡ-IRMS. The method of the on-line dual technique meets the requirements of trace carbonate detection and carbonate sample applications can be used to achieve high spatial resolution. -
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表 1 国家标准物质δ13C和δ18O分析结果
Table 1. Analytical results of δ13C and δ18O for national standard materials
标准样品 碳氧同位素值 推荐值 (‰) 测量值(‰) 标准偏差 (‰) 第1次 第2次 第3次 第4次 第5次 平均值 GBW 04405 δ13C 0.57±0.03 0.621 0.585 0.573 0.609 0.586 0.595 0.018 δ18O -8.49±0.14 -8.512 -8.396 -8.548 -8.492 -8.501 -8.490 0.050 GBW 04406 δ13C -10.85±0.05 -10.862 -10.885 -10.846 -10.823 -10.824 -10.848 0.026 δ18O -12.40±0.15 -12.265 -12.468 -12.333 -12.307 -12.357 -12.346 0.076 GBW 04416 δ13C 1.61±0.03 1.569 1.632 1.554 1.582 1.587 1.585 0.029 δ18O -11.59±0.11 -11.587 -11.469 -11.616 -11.500 -11.585 -11.551 0.063 
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表 2 应用Kiel Ⅳ-IRMS与Gasbench Ⅱ-IRMS检测GBW 04405的分析结果
Table 2. Analytical results of δ 13C and δ 18O for GBW 04405 by Kiel Ⅳ-IRMS and Gasbench Ⅱ-IRMS system
测量次数 δ13CVPDB(‰) δ18OVPDB(‰) Kiel Ⅳ-IRMS Gasbench Ⅱ-IRMS Kiel Ⅳ-IRMS Gasbench Ⅱ-IRMS 1 0.581 0.519 -8.543 -8.671 2 0.572 0.532 -8.576 -8.686 3 0.584 0.548 -8.524 -8.685 4 0.560 0.548 -8.482 -8.674 5 0.575 0.552 -8.55 -8.674 6 0.591 0.560 -8.497 -8.383 7 0.569 0.567 -8.577 -8.618 8 0.559 0.569 -8.565 -8.460 9 0.562 0.570 -8.494 -8.640 10 0.586 0.573 -8.567 -8.533 11 0.583 0.575 -8.569 -8.682 12 0.596 0.578 -8.405 -8.650 13 0.580 0.617 -8.525 -8.474 14 0.562 0.653 -8.481 -8.429 平均值 0.576 0.569 -8.501 -8.590 标准偏差 0.012 0.034 0.050 0.099
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