Cold seep carbonates are important archives of pore water chemistry and ancient methane seepage activity. They also provide an important contribution to the global carbon sink. Seep carbonates at three sediment layers (3.0, 52.1, and 53.6 mbsf) were collected at site W08B in the Qiongdongnan Basin of the South China Sea. This study investigated the mineralogy, microstructure, stable carbon and oxygen isotopes, trace elements, and U-Th dates of these carbonates to identify the relationship between methane flux and authigenic carbonate precipitation. The results showed that the δ¹³C and δ¹⁸O values of all carbonates are similar, indicating that the carbon source for shallow carbonates and deep carbonates has remained constant over time and included biogenic and thermogenic methane. Although carbonates were found in three sediment layers, the two main stages of methane seepage events were discernible, which was likely caused by the dissociation of gas hydrates. The first methane seep took place at 131.1–136.3 ka BP. During a dramatic drop in the sea level, the seep carbonate at 52.1 mbsf formed at 136.3 ka BP through the anaerobic oxidation of methane (AOM). The carbonate at 53.6 mbsf resulted from the vertical downward movement of the sulfate-methane transition zone with decreasing methane flux at 131.1 ka BP. This is the reason for the age of carbonates at 52.1 mbsf being older than the age of carbonates at 53.6 mbsf. The second methane seep took place at 12.2 ka BP. Shallow carbonate formed at that time via AOM and is now located at 3 mbsf. Moreover, thin-section photomicrographs of deep carbonate mainly consisted of matrix micrite and biological debris and acicular aragonite occurred as vein cement filling the pore spaces between the matrix micrite. The acicular aragonite was mainly influenced by the timing of the carbonate precipitation of minerals. This research identified a long history of methane seep activity reflected by the vertical distribution of carbonates.

Sediments at marine cold seep areas provide potential archives of past fluid flow, which allow insights into the evolution of past methane seepage activities. However, signals for anaerobic oxidation of methane (AOM) might be obscured in bulk sediments in cold-seep settings due to several factors, especially flood and turbidite deposition. Comprehensive inorganic data were gathered in this study to explore the availability of related records at cold seeps and to provide insights into the evolution of past methane seepage activities. Sediments collected from the site 973-4 in the Taixinan Basin on the northern slope of the South China Sea were characterized in terms of total carbon and sulfur, δ¹³C values of total organic carbon (δ¹³C_TIC), δ³⁴S values of chromium reducible sulfur (δ³⁴S_CRS), and foraminiferal oxygen and carbon isotopes. The results confirmed a strong correlation between formation of authigenic minerals and AOM. Moreover, the ³⁴S enrichments and abundant chromium reducible sulfur (CRS) contents in the authigenic sulfides in the sulfate–methane transition zone (SMTZ) within 619–900 cm below seafloor (cmbsf) reflected past high methane fluxes supported by constant methane seepages. Lithological distribution and AMS (Accelerator Mass Spectra) ¹⁴C dating of planktonic foraminifera show that the turbidite (~35.14 ka) was related to a foraminifera-rich interval (Unit II: 440-619 cmbsf) and increased carbonate productivity during the last glacial maximum (LGM). Enrichment of Mo and U was observed accompanied by low contents of nutrient metals (Al, Ti, V, Ni, Fe, Mn, and Cu) in Unit II. The foraminifera-rich interval (Unit II) of cold seep sediments was probably linked to the phenomenon of inconsecutive sedimentary sequence due to the turbidites, which resulted in the lack of Fe, Mn, and Ba enrichment. There is no U enrichment but only Mo enrichment within Unit III, which might be related to H₂S produced by AOM during the methane seepages. Based on the above results, it can be speculated that this area has experienced multiple-episodes of methane seep events. Further exploration of AOM should focus on the risks of rapid deposition, especially the impact of turbidity current on sediments.