Description: Seafloormethane emission from the Quepos Slide on the submarine segment of the Costa Rica fore-arc margin was estimated by extrapolating flux measurements from individual seeps to the total area covered by bacterial mats. This approach is based on the combination of detailed mapping to determine the abundance of seeps and the application of a numerical model to estimate the amount of benthic methane fluxes. Model results suggest that the majority of the studied seeps transport rather limited amount of methane (on average: *177 lmol cm-2 a-1) into the water column due to moderate upward advection, allowing for intense anaerobic oxidation of methane (AOM; on average: 53 % of the methane flux is consumed). Depth-integrated AOM rates (56–1,538 lmol CH4 cm-2 a-1) are comparable with values reported from other active seep sites. The overall amount of dissolved methane released into the water column from the entire area covered by bacterial mats on the Quepos Slide is estimated to be about 0.28 9 106 mol a-1. This conservative estimate which relies on rather accurate determinations of seafloor methane fluxes emphasizes the potential importance of submarine slides as sites of natural methane seepage; however, at present the global extent of methane seepage from submarine slides is largely unknown.

Description: The Costa Rican forearc is characterized by active fluid venting related to mud diapirism and volcanism. The geochemical compositions of fluids obtained from dewatering sites indicate that mineral precipitation or dehydration is the major driver of fluid mobilization and upward migration. The peculiar situation at the latter sites is that Ca concentrations in the upward migrating fluids are well above seawater levels. In turn, these Ca-enriched fluids could offer a potential reason for widespread carbonate caps on top of the mounds. Here, a reactive-transport numerical model is applied to . . .

Description: The expulsion of liquids, gases and fluids at continental margins covers a wide range of processes including not only mud volcanism, mud diapirism and gas flares, but also continuously seeping methane-rich fluids leading to cold vent sites and even outbursts of over-pressured gases. Seepage of fluids frequently leads to precipitation of authigenic carbonates that modify sedimentary processes along the margin, and finally, the fluids constitute the energy source for a number of diverse and complex ecosystems. During the last two decades, researchers gained significant knowledge about the impact of fluid seepage on local ecosystems and the biogeochemical processes that result in carbonate formation via the anaerobic oxidation of methane (AOM). However, all the knowledge was gained in different areas and geological settings of the world ocean but left a regional gap in our knowledge about seeps at the continental margin offshore Costa Rica. Those processes including authigenic carbonate precipitation, quantification of the impact of fluid seepage and methane budgets are documented in the present thesis. Chapter II presents comprehensive results from five cold seep structures at the Costa Rican continental margin addressing the relationship between fluid advection, dissolved calcium concentrations in upward migrating fluids, and authigenic calcium carbonate precipitation. A numerical transport-reaction model was used to determine rates of AOM, CaCO3 precipitation, and benthic fluxes of solutes. Production of carbonate alkalinity and formation of authigenic carbonates is most intense at intermediate flow rates (3-40 cm a-1) and reduced under low and high flux conditions (0.1 and 200 cm a-1). Systematic model runs showed that high Ca concentrations in ascending fluids enhance the rate of authigenic carbonate production at moderate flow rates leading to an almost quantitative fixation of deeply derived Ca in authigenic carbonates. Hence, CaCO3 precipitation is not only controlled by Ca diffusing into the sediment from bottom water, but also by the Ca concentration in ascending fluids. Based on average precipitation rates deduced from the systematic model runs the global Ca-fixation at cold seeps (~2·1010 mol Ca a-1) suggesting that cold seeps are most likely not of key importance with respect to Ca cycling in the ocean. Chapter 3 comprises the quantitative estimates of dissolved methane discharge from wellstudied mud mounds (Mound 11 and Mound 12) at the submarine section of the Costa Rica fore-arc combining geochemical and geoacoustic data. The study is supported by 75 kHz sidescan sonar data, pore-water analysis and visual sea-floor observations by remotely operated vehicle (ROV). A numerical transport reaction model was applied to determine dissolved methane fluxes considering AOM and upward fluid flow. Model results reveal that a significant portion of methane from greater depth is discharged into the bottom water only at high fluid flow velocities that are not sufficiently moderate to allow for AOM. The overall amount of dissolved methane released from the entire mud mounds into the water column was moderate with a discharge of 0.36·106 mol a-1 at Mound 11 whereas it was calculated as 0.58·106 mol a-1 at Mound 12. Compared to other active cold seeps (mainly mud volcanoes), mud mounds at the submarine section of the Costa Rica fore arc do not represent a pathway for significant methane discharge from the seafloor. Sea floor methane emissions from bacterial mat sites of a submarine slide at the Costa Rica continental margin are presented in Chapter IV. The estimates of methane fluxes into the water column are based on (i) detailed mapping in order to determine the abundance of seeps, and thus the spatial validity of the flux measurements; and (ii) application of numerical model to estimate the amount of methane that is transported into the bottom water. Model results illustrate that the majority of the studied seeps transport rather limited amount of methane into the water column due to medium to low advection rates (average 10 cm a-1 ) allowing high methane consumption by AOM (average 45%) and limiting the methane discharge into the water column. Depth-integrated AOM rates (56-1538 μmol CH4 cm-2 a-1) are comparable with the values reported at other very active vents sites, suggesting that the Quepos Slide should be regarded as one of the most active sites at the seafloor. The overall amount of dissolved methane released from the entire bacterial mat sites into the water column is determined as 0.56·106 mol a-1. This conservative estimate, relying on rather accurate determinations of sea floor methane fluxes out of bacterial mats emphasizes the importance of submarine slides as sites of natural methane seepage.

Description: Five sediment cores from cold seeps at the forearc off Costa Rica were used to explore the relationship between fluid advection, dissolved Ca concentrations in upward migrating fluids, and authigenic CaCO3 precipitation. A numerical transport-reaction model was used to determine rates of anaerobic oxidation of methane (AOM), CaCO3 precipitation, and benthic fluxes of solutes. Production of carbonate alkalinity and formation of authigenic carbonates is most intense at intermediate flow rates (3–40 cm a−1) and reduced under low and high flux conditions (0.1 and 200 cm a−1). Dissolved Ca concentrations observed in the vent fluids off Costa Rica cover a wide range between 4 and 31 mM, clearly exceeding seawater concentrations at two locations. Systematic model runs showed that high Ca concentrations in ascending fluids enhance the rate of authigenic carbonate production at moderate flow rates leading to an almost quantitative fixation of deeply derived Ca in authigenic carbonates. Hence, CaCO3 precipitation is not only controlled by Ca diffusing into the sediment from bottom water, but also by the Ca concentration in ascending fluids. Thus, Ca enriched fluids offer a reason for enhanced subsurface CaCO3 precipitation and the occurrence of carbonate caps on dewatering structures in the Central American fore-arc. Based on average precipitation rates deduced from the systematic model runs it is possible to give a rough estimate of the global Ca-fixation at cold seeps (∼2·1010 mol Ca a−1), which suggests that cold seeps are most likely not of key importance with respect to Ca cycling in the ocean.