热带海洋学报

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碳酸盐结合硫酸盐记录海水硫酸盐的δ34S和δ18O:来自南海南部礁碳酸盐岩的启示

邸鹏飞1,2,3, 李牛1,2,3,宫尚桂4 , Jörn Peckmann5 , 王淑红1,3 , 陈多福4 , 颜文1,3,*
  

  1. 1中国科学院南海海洋研究所 海洋与边缘海地质重点实验室,广东 广州 510301;

    2三亚海洋生态环境工程研究院,海南 三亚 572025;

    3中国科学院大学,北京 100049;

    4上海海洋大学 海洋科学学院 深渊科学与技术上海工程研究中心,上海 201306;

    5德国汉堡大学 地球系统研究与可持续性中心 地质研究所,汉堡 20146



  • 收稿日期:2025-12-17 修回日期:2026-02-15 接受日期:2026-03-26
  • 通讯作者: 颜文
  • 基金资助:

    国家重点研发计划项目(2021YFC3100600);海南省重点研发计划项目(ZDYF2021SHFZ060);中国科学院战略性先导科技专项(XDA13010102));

Carbonate-associated sulfate records seawater sulfate δ 34S and δ 18O: Insights from reef carbonate rocks in the southern South China Sea

DI Pengfei 1,2,3, LI Niu 1,2,3 , GONG Shanggui 4 , JÖRN Peckmann5, WANG Shuhong 1,3 , CHEN Duofu4, YAN Wen 1,3*    

  1. 1. Key Laboratory of Ocean and Marginal Sea Geology, South China Sea Institute of Oceanology, Chinese Academy of Sciences, Guangzhou, 510301, China

    2. Sanya Institute of Ocean Eco-Environmental Engineering, Sanya, 572025, China

    3. University of Chinese Academy of Sciences, Beijing 100049, China

    4. Shanghai Engineering Research Center of Hadal Science and Technology, College of Marine Sciences, Shanghai Ocean University, Shanghai 201306, China

    5. Institute for Geology, Center for Earth System Research and Sustainability, Universität Hamburg, 20146 Hamburg, Germany



  • Received:2025-12-17 Revised:2026-02-15 Accepted:2026-03-26
  • Supported by:
    National Key Research and Development Program of China(2021YFC3100600); the Key Research and Development Plan of Hainan Province(ZDYF2021SHFZ060); the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA13010102)

摘要: 碳酸盐结合硫酸盐(CAS)是重建古海水硫酸盐同位素演化与全球硫循环的重要代用指标,但其在经历复杂成岩作用的礁灰岩中原始信号的保真度尚存争议。本文对南海南部美济礁NK-1井连续礁灰岩岩芯开展系统CAS含量、δ34SCAS和δ18OCAS分析,以评估成岩作用对CAS记录的影响。结果表明,早期成岩作用显著降低CAS含量——原生文石–高镁方解石相含CAS高达5413 ppm,而经淡水或海水成岩改造后下降60%~80%,暴露面处因大气淋滤降至<200 ppm。尽管如此,δ34SCAS在整个岩芯中高度稳定(20.1‰–24.7‰,均值22.9‰),与同期海洋重晶石δ34S一致,表明硫同位素信号可有效抵抗再结晶与白云石化等成岩扰动。相反,δ18OCAS变化剧烈(7.1‰–15.0‰),仅5 Ma以来样品保留原始海水信号,更老样品明显受成岩流体氧同位素交换影响。本研究证实,礁灰岩中的CAS可可靠记录古海水δ34S,但δ18OCAS需谨慎用于古环境重建。这一发现为利用热带礁相沉积的高精度示踪硫循环历史提供了关键约束。

关键词: 与碳酸盐结合的硫酸盐(CAS), 硫氧同位素, 成岩作用, 礁灰岩, 南海

Abstract: Carbonate-associated sulfate (CAS) is a key proxy for reconstructing the isotopic evolution of seawater sulfate and tracing global sulfur cycling through geologic time. However, the fidelity of primary CAS isotopic signals in reef limestones subjected to complex diagenetic alteration remains uncertain. We present a systematic analysis of CAS abundance, sulfur isotopes (δ34SCAS), and oxygen isotopes (δ18OCAS) in a continuous reef limestone core (NK-1) from Meiji Atoll in the southern South China Sea to evaluate the impact of diagenesis on CAS records. Our results show that early diagenesis strongly controls CAS concentrations: primary aragonite-high-Mg calcite phases contain up to 5413 ppm CAS, whereas freshwater and marine diagenetic alteration reduces CAS by 60-80%, with values dropping below 200 ppm at subaerial exposure surfaces due to meteoric leaching. Despite this substantial loss of sulfate, δ 34SCAS remains remarkably stable throughout the core (20.1‰-24.7‰; mean = 22.9‰) and aligns closely with coeval marine barite δ34S, demonstrating that the original seawater sulfur isotope signature is robustly preserved even through intense recrystallization and dolomitization. In contrast, δ 18OCAS exhibits large variability (7.1‰-15.0‰), indicating high susceptibility to diagenetic overprint. Only samples younger than ~5 Ma retain primary seawater-like δ18OCAS values; older samples have been significantly modified by oxygen isotope exchange with diagenetic fluids. This study confirms that CAS in reef limestones provides a reliable archive of past seawater δ 34S, but cautions against the uncritical use of δ 18OCAS for paleoenvironmental reconstruction without rigorous diagenetic screening. These findings offer critical constraints for high-resolution reconstructions of tropical marine sulfur cycling using reefal carbonate successions.

Key words: Carbonate-associated sulfate, Sulfur and oxygen isotopes, Diagenesis, Reef limestone, South China Sea