中文摘要：

海洋沉积物孔隙水是研究海洋环境、地质与生物地球化学等问题的重要信息载体。高度还原的缺氧孔隙水普遍含有大量的溶解态硫化物（H2 S 和 HS-）。这些硫化物既是孔隙水调查的重要研究对象也关系到另一重要地化参数—pH 值。成分逸散、化学平衡破坏使传统非原位分析方法测定的海洋沉积物孔隙水硫化物浓度和 pH 值具有不确定性，难以反映原位地化信息。深海原位激光拉曼技术为解决这一问题提供了新的手段。孔隙水硫化物在拉曼光谱曲线上表现为位于2550～2620 cm－1的明显拉曼重叠峰，包括 H2 S 的 H-S 伸缩峰（2592 cm－1）和 HS－的 H-S 伸缩峰（2572 cm－1）。本研究在实验室条件下（25℃，0．1 MPa）对基于内标定法的 H2 S 与 HS－拉曼光谱定量分析进行了可行性研究，证实该技术可行且精度良好。H2 S 与 HS－作为一组共轭酸碱对，其浓度比与 pH 值呈函数关系。通过配制不同 pH 值的含硫化物溶液并进行拉曼光谱分析，发现这一关系在拉曼光谱上表现为特征拉曼重叠峰形态和 H2 S，HS－分峰强度的规律性变化，即硫化物拉曼光谱参数与溶液 pH 值之间存在一定的耦合关系。基于谱峰分解和相关分析，提出了一种全新的含硫化物孔隙水 pH 原位测定方法。可测定硫化物拉曼重叠峰可分辨情况下的孔隙水 pH，在本研究中为6．11～8．32，涵盖了已知的绝大多数孔隙水 pH 值范围。该研究为获取海洋沉积物孔隙水的高保真数据提供了新的技术参考。

英文摘要：

Marine sediment pore water is one of the important objects in the study of global environmental change,marine geology and biogeochemistry.Anoxic pore water in highly reducing deep-sea sediments com-monly contains a large amount of dissolved sulfide （H2 S and HS- ）.The sulfide species within sediment pore water are significant not only because the importance of themselves,but also because they exist as a function of pH which is another key parameter in pore water study.As degassing and chemical equilibrium altering are both inevitable,concentrations of sulfide species and pH value of marine sediment pore water acquired with traditional non-in situ technologies are of great uncertainty,and cannot represent the real geochemistry infor-mation.However,the recent deployment of an in situ laser Raman pore water sampler allows us to observe spectral sulfide signals of marine sediments in situ and in real time,which provide us a new technique to solve this problem.Sulfide species in water have a relatively strong Raman signal,which often appears in the form of a characteristic overlapping peak between 2 550 ~2 620 cm-1 and can be decomposed into HS- at 2 572 cm-1 and H2 S at 2 592 cm-1 .In the present paper,quantitative analysis of H2 S and HS- with Raman spec-troscopy is proved practicable and the accuracy is good.The pH of pore water is an important influencing fac-tor of the diagenetic processes.As H2 S and HS- are conjugate acid-base pairs,sulfide species within pore wa-ter exist as a function of pH and their concentration ratio depend on pH.This relationship is also shown in the Raman spectrum.To formulate the pore water pH calculation,sulfide solutions with pH range from 6.11 to 13.05 were prepared and their Raman spectra were observed.It is verified that the morphology of overlapping peaks change regularly with pH values.This phenomenon provides us the possibility of measuring the pH of pore water in situ via Raman spectroscopy.Based on peaks decomposition and correlativity analysis,we pro-pose here a novel in