ALBERT

Description: In the oceans' high-nitrate-low-chlorophyll regions, such as the Peru/Humboldt Current system and the adjacent eastern equatorial Pacific, primary productivity is limited by the micronutrient iron. Within the Peruvian upwelling area, bioavailable iron is released from the reducing continental margin sediments. The magnitude of this seafloor source could change with fluctuations in the extension or intensity of the oxygen minimum zones. Here we show that measurements of molybdenum, uranium and iron concentrations can be used as a proxy for sedimentary iron release, and use this proxy to assess iron release from the sea floor beneath the Peru upwelling system during the past 140,000 years. We observe a coupling between levels of denitrification, as indicated by nitrogen isotopes, trace metal proxies for oxygenation, and sedimentary iron concentrations. Specifically, periods with poor upper ocean oxygenation are characterized by more efficient iron retention in the sediment and a diminished iron supply to the water column. We attribute efficient iron retention under more reducing conditions to widespread sulphidic conditions in the surface sediment and concomitant precipitation of iron sulphides. We argue that iron release from continental margin sediments is most effective in a narrow redox window where neither oxygen nor sulphide is present. We therefore suggest that future deoxygenation in the Peru upwelling area would be unlikely to result in increased iron availability, whereas in weaker oxygen minimum zones partial deoxygenation may enhance the iron supply. © 2014 Macmillan Publishers Limited.

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 surface sediments of two mud mounds (‘‘Mound 11’’ and ‘‘Mound 12’’) offshore southwest Costa Rica contain abundant authigenic carbonate concretions dominated by high-Mg calcite (14–20 mol-% MgCO3). Pore fluid geochemical profiles (sulfate, sulfide, methane, alkalinity, Ca and Mg) indicate recent carbonate precipitation within the zone of anaerobic oxidation of methane (AOM) at variable depths. The current location of the authigenic carbonate concretions is, however, not related to the present location of the AOM zone, suggesting mineral precipitation under past geochemical conditions as well as changes in the flow rates of upward migrating fluids. Stable oxygen and carbon isotope analysis of authigenic carbonate concretions yielded d18Ocarbonate values ranging between 34.0 and 37.7 % Vienna standard mean ocean water (VSMOW) and d13Ccarbonate values from -52.2 to -14.2 % Vienna Pee Dee belemnite (VPDB). Assuming that no temperature changes occurred during mineral formation, the authigenic carbonate concretions have been formed at in situ temperature of 4–5 °C. The d18Ocarbonate values suggest mineral formation from seawater-derived pore fluid (d18Oporefluid = 0 % VSMOW) for Mound 12 carbonate concretions but also the presence of an emanating diagenetic fluid (d18Oporefluid &5 %) in Mound 11. A positive correlation between d13Ccarbonate and d18Ocarbonate is observed, indicating the admixing of two different sources of dissolved carbon and oxygen in the sediments of the two mounds. The carbon of these sources are (1) marine bicarbonate (d13Cporefluid &0 %) and (2) bicarbonate which formed during the AOM (d13Cporefluid &-70 %). Furthermore, the d18Oporefluid composition, with values up to ?4.7 % Vienna standard mean ocean water (VSMOW), is interpreted to be affected by the presence of emanating, freshened and boronenriched fluids. Earlier, it has been shown that the origin of 18O-enriched fluids are deep diagenetic processes as it was indicated by the presence of methane with thermogenic signature (d13CCH4 = -38 %). A combination of present geochemical data with geophysical observations indicates that Mounds 11 and 12 represent a single fluid system interconnected by deep-seated fault(s).

Description: After more than a decade of multidisciplinary studies of the Central American subduction zone mainly in the framework of two large research programmes, the US MARGINS program and the German Collaborative Research Center SFB 574, we here review and interpret the data pertinent to quantify the cycling of mineral-bound volatiles (H2O, CO2, Cl, S) through this subduction system. For input-flux calculations, we divide the Middle America Trench into four segments differing in convergence rate and slab lithological profiles, use the latest evidence for mantle serpentinization of the Cocos slab approaching the trench, and for the first time explicitly include subduction erosion of forearc basement. Resulting input fluxes are 40–62 (53) Tg/Ma/m H2O, 7.8–11.4 (9.3) Tg/Ma/m CO2, 1.3–1.9 (1.6) Tg/Ma/m Cl, and 1.3–2.1 (1.6) Tg/Ma/m S (bracketed are mean values for entire trench length). Output by cold seeps on the forearc amounts to 0.625–1.25 Tg/Ma/m H2O partly derived from the slab sediments as determined by geochemical analyses of fluids and carbonates. The major volatile output occurs at the Central American volcanic arc that is divided into ten arc segments by dextral strike-slip tectonics. Based on volcanic edifice and widespread tephra volumes as well as calculated parental magma masses needed to form observed evolved compositions, we determine long-term (105 years) average magma and K2O fluxes for each of the ten segments as 32–242 (106) Tg/Ma/m magma and 0.28–2.91 (1.38) Tg/Ma/m K2O (bracketed are mean values for entire Central American volcanic arc length). Volatile/K2O concentration ratios derived from melt inclusion analyses and petrologic modelling then allow to calculate volatile fluxes as 1.02–14.3 (6.2) Tg/Ma/m H2O, 0.02–0.45 (0.17) Tg/Ma/m CO2, and 0.07–0.34 (0.22) Tg/Ma/m Cl. The same approach yields long-term sulfur fluxes of 0.12–1.08 (0.54) Tg/Ma/m while present-day open-vent SO2-flux monitoring yields 0.06–2.37 (0.83) Tg/Ma/m S. Input–output comparisons show that the arc water fluxes only account for up to 40 % of the input even if we include an “invisible” plutonic component constrained by crustal growth. With 20–30 % of the H2O input transferred into the deeper mantle as suggested by petrologic modeling, there remains a deficiency of, say, 30–40 % in the water budget. At least some of this water is transferred into two upper-plate regions of low seismic velocity and electrical resistivity whose sizes vary along arc: one region widely envelopes the melt ascent paths from slab top to arc and the other extends obliquely from the slab below the forearc to below the arc. Whether these reservoirs are transient or steady remains unknown.

Description: Due to their favorable P-T conditions and organic-rich deposits, sub-seafloor sediments in the northern Gulf of Mexico are known to have a large potential for gas hydrate accumulations. The presence of gas hydrates within sediments of the Green Canyon block has been proven by various methods, incl. seismic imaging, geochemical analysis, and drilling conducted mainly as a part of Joint Industry Project (JIP) Phase II. Gas hydrates reported therein usually occur as tens up to hundreds of meters thick sections with moderate to high concentrations within a range of 50 – 70 vol. % of pore space, and hence, seem to offer a considerable natural deposit of methane gas. The main focus of this study was to explore the complex effects of a set of control- parameters responsible for hydrocarbon migration and storage within the Gas Hydrate Stability Zone (GHSZ) on the accumulation of gas hydrates. To investigate the processes of basin formation and its subsidence history, source rock maturation, hydrocarbon migration and expulsion, and to quantify the gas hydrate accumulation potential, 3-D numerical study has been conducted using PetroMod. The area of interest extends over ~14 km x 33 km and covers the edge of the Sigsbee Escarpment representing the main salt mobility front in the region. The simulation contains full depositional history of the Green Canyon block, incl. salt deposition and re-mobilization as well as its further implications for temperature field, fluids migration and sedimentary layers distribution. Methane generation has been resolved by in-situ POC degradation and deep thermogenic mobilization from two distinct hydrocarbon sources. As a result, we present a number of likely scenarios of gas hydrate formation and accumulation in the study area that have been calibrated against available data.

Description: Cruise M86/5 aimed at collecting data from potential fluid dewatering sites located in the deep-sea region of the western part of the Gulf of Cadiz and the adjacent deep sea plain. Previous work on mud volcanoes (cruises SO175 and MSM1/3) located on the accretionary wedge in the Gulf of Cadiz showed that mud volcano fluids are typically sourced at several km depth below the seafloor. In addition, the geochemical composition of fluids from the deepest mud volcano in this area which is located on a west-east trending transform lineament (SWIM1) indicated that these fluids are typical for having been altered by the reaction with oceanic crust. This implies that there is active flow connecting the oceanic basement and the seafloor. To date, such kind of hydrothermal circulation is only known for relatively young oceanic crust (〈60 Ma). Hence, the existence of a hydrological connection between old, sedimented oceanic crust and the seafloor is a phenomenon, which essentially has not been investigated in the past, and may represent a (missing) link between hot vents at mid-ocean ridges and cold seeps at continental margins. On the cruise, we followed an interdisciplinary approach characterized by extensive geochemical sampling in the water column and the sediment, heat flow measurements, and detailed mapping with AUV and ship-based hydroacoustic systems. We mainly investigated selected sites with conspicuous backscatter anomalies recorded on previous cruises along the SWIM1 lineament: (i) within the transition between the accretionary prism and the Horseshoe Abyssal Plain and (ii) on seafloor highs within the Horseshoe Abyssal Plain itself. The geotectonic environment in both sections is completely different from the situation on the accretionary wedge, where numerous mud volcanoes were detected on previous cruises. Within the transition zone three new mud volcanoes were discovered and extensively sampled during M86/5. Typal chemoautotrophic organisms were found here together with conspicuous methane anomalies in der water column. Preliminary pore water analyses show that the fluids indicate a deep origin, but show distinctive differences to those found on the mud volcanoes on the wedge. Future analyses will show, if this phenomenon is - as hypothesized - due to decreasing sediment thickness with increasing westward distance from the wedge, and hence decreasing sediment-water interaction overprinting the original fluid composition. On the seafloor highs along the SWIM1 lineament in the Horseshoe Abyssal Plain no seeps or mud volcanoes were discovered. However, the lineament seems to be active in terms of fluid flow as indicated by pore water and heat flow anomalies as compared to values measured off the lineament. Overall, the major goal of the cruise could be fulfilled: fluid seeps related to active faults were discovered in a new geotectonic environment. The overall significance in terms of fluid transport in old oceanic crust and/or the role of deeply-rooted fault systems needs to be further addressed in subsequent studies.

Description: Highlights • We map out the 3D extent of gas hydrate stability beneath two methane seep sites. • Focused fluid flow has sustained large-scale gas hydrate instability. • The two seeps likely have the same deep fluid source, despite shallow differences. • Fault networks influenced the initiation of advective flow through the hydrate system. • Ongoing flow towards the seeps is likely sustained by networks of hydrofractures. Abstract Fluid flow through marine sediments drives a wide range of processes, from gas hydrate formation and dissociation, to seafloor methane seepage including the development of chemosynthetic ecosystems, and ocean acidification. Here, we present new seismic data that reveal the 3D nature of focused fluid flow beneath two mound structures on the seafloor offshore Costa Rica. These mounds have formed as a result of ongoing seepage of methane-rich fluids. We show the spatial impact of advective heat flow on gas hydrate stability due to the channelled ascent of warm fluids towards the seafloor. The base of gas hydrate stability (BGHS) imaged in the seismic data constrains peak heat flow values to View the MathML source∼60 mWm−2 and View the MathML source∼70 mWm−2 beneath two separate seep sites known as Mound 11 and Mound 12, respectively. The initiation of pronounced fluid flow towards these structures was likely controlled by fault networks that acted as efficient pathways for warm fluids ascending from depth. Through the gas hydrate stability zone, fluid flow has been focused through vertical conduits that we suggest developed as migrating fluids generated their own secondary permeability by fracturing strata as they forced their way upwards towards the seafloor. We show that Mound 11 and Mound 12 (about 1 km apart on the seafloor) are sustained by independent fluid flow systems through the hydrate system, and that fluid flow rates across the BGHS are probably similar beneath both mounds. 2D seismic data suggest that these two flow systems might merge at approximately 1 km depth, i.e. much deeper than the BGHS. This study provides a new level of detail and understanding of how channelled, anomalously-high fluid flow towards the seafloor influences gas hydrate stability. Thus, gas hydrate systems have good potential for quantifying the upward flow of subduction system fluids to seafloor seep sites, since the fluids have to interact with and leave their mark on the hydrate system before reaching the seafloor.