微量石笋碳酸盐碳氧同位素高精度双路进样质控方法及应用

Quality Control Method and Application of High-Precision Dual-Inlet Analysis for Trace Speleothem Carbonate Carbon and Oxygen Isotopes

  • 摘要: 石笋因具有高分辨率、可精确定年和陆地分布广泛等优势,已成为古气候研究的第四大支柱,中国科学家建立的69万年氧同位素集成序列更成为轨道与千年尺度研究的全球基准。然而,石笋氧同位素的指示意义仍存在争议,尤其在东亚季风区其气候解译面临挑战,准确测定石笋碳氧同位素是古气候重建的重要基础。当前,高精度双路进样同位素质谱测试仍面临微量样品分析稳定性不足、实验室间数据可比性缺乏统一标准等关键问题,且高精度双路进样同位素质谱测试尚缺乏系统性的质量控制体系研究,制约了高分辨率石笋序列的可靠性与国际可比性。为此,本文建立了超微量碳酸盐碳氧同位素双路进样测试的质控方法,从参考气稳定性、标准样品重复性等多维度系统评估了新一代双路进样质谱仪(Isoprime PrecisION)的可靠性与数据质量;并以陕西汉中地洞河溶洞编号为DDH-B15的石笋为对象,开展独立点对点重复性测试,同个石笋样品不同实验室的一致性测试结果确认了新建实验室分析方法的可靠性。本文进一步探讨了末次冰期20 ~ 17 ka BP (BP表示距1950之前)时段亚洲季风的显著增强现象,提出其驱动机制可能涉及冰期东部海岸线变迁与西太平洋海温异常所诱发的厄尔尼诺-南方涛动(ENSO)模态转变。本研究指出轨道尺度上中部地区氧同位素是东西部水汽氧同位素的混合状态,水汽来源对石笋氧同位素有重要影响,这对石笋氧同位素的解释提供了帮助。

     

    Abstract: Speleothems have become the fourth pillar of paleoclimate research due to their advantages of high resolution, precise chronology, and widespread terrestrial distribution. The 690,000-year oxygen isotope composite sequence established by Chinese scientists has further served as a global benchmark on the orbital and millennial time-scale studies. However, the climatic interpretation of speleothem oxygen isotopes remains controversial, especially in the East Asian monsoon region, where accurate measurement of speleothem carbon and oxygen isotopes forms a crucial basis for paleoclimate reconstruction. Currently, high-precision dual-inlet isotope ratio mass spectrometry faces several major challenges, including insufficient analytical stability for trace-mass samples and the lack of unified inter-laboratory standards for data comparability. In addition, systematic quality control protocols for dual-inlet techniques remain underdeveloped, constraining the reliability and international consistency of high-resolution speleothem isotope records. To address these issues, this study establishes a comprehensive quality-control framework for dual-inlet analysis of trace carbonate δ13C and δ18O. The performance and data quality of a new-generation dual-inlet mass spectrometer (Isoprime PrecisION) were evaluated from multiple dimensions, including reference gas stability and repeatability of standard samples. Independent point-by-point reproducibility tests conducted on stalagmite DDH-B15 from Didonghe Cave, as well as cross-laboratory consistency tests using identical sample batches, confirm the robustness of the newly developed laboratory methodology. Furthermore, this paper explores the significant intensification event of the Asian monsoon during 20–17 ka BP (ka = thousand years, BP = before 1950) in the Last Glacial Period. We propose that the driving mechanism may involve glacial coastline retreat in Eastern Asia and El Niño-Southern Oscillation (ENSO) mode shifts triggered by western Pacific SST anomalies. Our results demonstrate that orbital timescale oxygen isotopes in central China represent an average state of moisture isotopes from eastern and western sources, highlighting the important influence of moisture provenance on speleothem δ18O. These findings provide valuable insights into the interpretation of speleothem δ18O records.

     

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