Description: Sulfate reduction could go through dissimilatory sulfate reduction and anaerobic methane oxidation couple with sulfate reduction (AOM-SR) with pyrite the end product. While AOM-SR is an important process in oxidizing methane and limiting methane entering the ocean, there is limited information available regarding pyrite formation and preservation under methane dominated environment. The purpose of this study is to report pyrite formation and preservation at a methane dominated environment, the YuanAn Ridge, where methane seeps have been observed, and to evaluate how would that differ from typical anoxic environment. Pore water methane, sulfate, dissolved sulfide, barium, and sediment pyrite, barium/Al ratio and organic carbon in sediments were analyzed from sediments collected by piston cores on board the R/V Ocean Researcher I (OR-I) from the study environment. The results showed methane flux is controlling pyrite formation in this methane dominated environment. Pyrite concentration is linearly correlated with methane flux with exceptions to shallower sulfate methane transition zone (SMTZ) sites where methane could have vent directly to the overlying water and contribute less to the pyrite formation. The more methane entering the SMTZ, the more pyrite formed and preserved in the sulfate methane transition zone sediments. Authigenic pyrite from dissimilatory sulfate reduction is a small fraction of the pyrite found in the methane dominant and low in organic carbon environment, with majority of pyrite derived from AOM-SR. Large spatial variations on rate of sulfate reduction, pyrite and methane concentrations were observed in the studied area sediments. Depth of sulfate methane transition zone varied between 1 and 14 m and is a log function of methane flux. Pore water sulfate profiles displayed three different types, linear, concave up and down, indicating methane flux have varied in time. Pyrite burial efficiency is high, approximately 50% of sulfate entering the SMTZ were preserved in sediments as pyrite. This efficiency of sulfate reduction through AOM-SR is much higher than pyrite formation from dissimilatory sulfate reduction in normal marine sediments. The AOM-SR and pyrite formation occurred at depth within the SMTZ favor a higher degree of pyrite preservation. Time require for the pyrite formation is about 4400 years in the YAR sediments, based on diffusion model calculation of barium sulfate precipitation.

Description: Geochemical data (CH4, SO42−, I−, Cl−, particulate organic carbon (POC), δ13C-CH4, and δ13C-CO2) are presented from the upper 30 m of marine sediment on a tectonic submarine accretionary wedge offshore southwest Taiwan. The sampling stations covered three ridges (Tai-Nan, Yung-An, and Good Weather), each characterized by bottom simulating reflectors, acoustic turbidity, and different types of faulting and anticlines. Sulfate and iodide concentrations varied little from seawater-like values in the upper 1–3 m of sediment at all stations; a feature that is consistent with irrigation of seawater by gas bubbles rising through the soft surface sediments. Below this depth, sulfate was rapidly consumed within 5–10 m by anaerobic oxidation of methane (AOM) at the sulfate-methane transition. Carbon isotopic data imply a mainly biogenic methane source. A numerical transport-reaction model was used to identify the supply pathways of methane and estimate depth-integrated turnover rates at the three ridges. Methane gas ascending from deep layers, facilitated by thrusts and faults, was by far the dominant term in the methane budget at all sites. Differences in the proximity of the sampling sites to the faults and anticlines mainly accounted for the variability in gas fluxes and depth-integrated AOM rates. By comparison, methane produced in situ by POC degradation within the modeled sediment column was unimportant. This study demonstrates that the geochemical trends in the continental margins offshore SW Taiwan are closely related to the different geological settings.

Description: With the discoveries of Bottom Simulating Reflectors (BSRs), large and dense chemosynthetic communities and rapid sulfate reductions in pore space sediments, gas hydrates may exist in offshore southwestern Taiwan. Methane concentrations in pore space sediments have been measured to investigate if fluids and gases are derived from dissociation of gas hydrates. Very high methane concentrations and very shallow depths of sulfate methane interface (SMI) imply the high methane flux underneath the seafloor. Linear sulfate gradients, low total organic carbon (TOC) have been combined to describe the process of anaerobic methane oxidation (AMO) and calculate the iffusive methane flux in Chuang et al. (2010). However, the appearance of concave (or non-linear) profiles of sulfate in some cores might indicate advective fluid flows. Hence, the methane flux may be much greater under advective conditions. In this study, numerical transport-reaction models were applied to calculate the methane flux including diffusion and advection of dissolved sulfate and methane and the anaerobic methane oxidation of methane. According to the modeled results of three giant piston cores (MD05-2911, MD05-2912 and MD05-2913) collected during the r/v Marion Dufresne cruise in 2005, gas bubbling or bioirrigation may occur in these site. Values of the methane flux ranging from 1.91 to 5.17 mmol m-2yr-1 and upward fluid flow velocities around 0.05-0.13 cm yr-1 are related to different geologic structures in the active continental margin. Site MD05-2912 is located on the Tainan Ridge where anticlines and blind thrusts are the dominate structures. Site MD052911 is on the Yung-An Ridge characterized by emergent and imbricate thrusts.

Description: The major processes that determine the distribution of methane (CH4) in anoxic marine sediments are methanogenesis and the anaerobic oxidation of methane (AOM), with organoclastic sulfate reduction exerting an important secondary control. However, the factors leading to the distribution of stable carbon isotopes (δ13C) of CH4 are currently poorly understood, in particular the commonly-observed minimum in δ13C-CH4 at the sulfate-methane transition (SMT) where AOM rates reach maximum values. Conventional isotope systematics predict 13C-enrichment of CH4 in the SMT due to preferential 12CH4 consumption by AOM. Two hypotheses put forward to explain this discrepancy are the addition of 12C-enriched CH4 to porewaters by methanogenesis in close proximity to AOM, and enzymatically-mediated carbon isotope equilibrium between forward and backward AOM at low concentrations of sulfate. To examine this in more detail, field data including δ13C of CH4 and dissolved inorganic carbon (DIC) from the continental margin offshore southwestern Taiwan were simulated with a reaction-transport model. Model simulations showed that the minima in δ13C-CH4 and δ13C-DIC in the SMT could only be simulated with carbon isotope equilibrium during AOM. The potential for carbon cycling between methanogenesis and AOM in and just below the SMT was insignificant due to very low rates of methanogenesis. Backward AOM also gives rise to a pronounced kink in the δ13C-DIC profile several meters below the SMT that has been observed in previous studies. We suggest that this kink marks the true base of the SMT where forward and backward AOM are operating at very low rates, possibly sustained by cryptic sulfur cycling or barite dissolution.