Methane discharge in sediments of the Dvurechenskii mud volcano

During the MARGASCH cruise M52/1 in 2001 with RV Meteor we sampled surface sediments from three stations in the crater of the Dvurechenskii mud volcano (DMV, located in the Sorokin Trough of the Black Sea) and one reference station situated 15 km to the northeast of the DMV. We analysed the pore water for sulphide, methane, alkalinity, sulphate, and chloride concentrations and determined the concentrations of particulate organic carbon, carbonate and sulphur in surface sediments. Rates of anaerobic oxidation of methane (AOM) were determined using a radiotracer (14CH4) incubation method. Numerical transport-reaction models were applied to derive the velocity of upward fluid flow through the quiescently dewatering DMV, to calculate rates of AOM in surface sediments, and to determine methane fluxes into the overlying water column. According to the model, AOM consumes 79% of the average methane flux from depth (8.9 x 10**+ 6 mol a**-1), such that the resulting dissolved methane emission from the volcano into the overlying bottom water can be determined as 1.9 x 10**+ 6 mol a**-1. If it is assumed that all submarine mud volcanoes (SMVs) in the Black Sea are at an activity level like the DMV, the resulting seepage represents less than 0.1% of the total methane flux into this anoxic marginal sea. The new data from the DMV and previously published studies indicate that an average SMV emits about 2.0 x 10**+ 6 mol a**-1 into the ocean via quiescent dewatering. The global flux of dissolved methane from SMVs into the ocean is estimated to fall into the order of 10**+10 mol a**-1. Additional methane fluxes arise during periods of active mud expulsion and gas bubbling occurring episodically at the DMV and other SMVs.

Pore water (SO4, CH4, alkalinity, HS-, Ca, Sr, Mg, Ba) and solid phase (Ca, Sr, Mg, Ba) data measured in pockmark sediments of the Northern Congo Fan

This study focuses on the vertical distribution of authigenic carbonates (aragonite and high Mg-calcite) in the form of finely disseminated precipitates as well as massive carbonate concretions present in and above gas hydrate bearing sediments of the Northern Congo Fan. Analyses of Ca, Mg, Sr and Ba in pore water, bulk sediments and authigenic carbonates were carried out on gravity cores taken from three pockmark structures (Hydrate Hole, Black Hole and Worm Hole). In addition, a background core was retrieved from an area not influenced by fluid seepage. Pore water Sr/Ca and Mg/Ca ratios are used to reveal the current depths of carbonate formation as well as the mineralogy of the authigenic precipitates. The Sr/Ca and Mg/Ca ratios of bulk sediments and massive carbonate concretions were applied to infer the presence and depth distribution of authigenic aragonite and high Mg-calcite, based on the approach presented by Bayon et al. [Bayon et al. (2007). Sr/Ca and Mg/Ca ratios in Niger Delta sediments: Implications for authigenic carbonate genesis in cold seep environments. Marine Geology 241(1-4), 93-109, doi:10.1016/j.margeo.2007.03.007]. We show that the approach developed by Bayon et al. (2007) for sediments of cold seeps of the Niger Delta is also suitable to identify the mineralogy of authigenic carbonates in pockmark sediments of the Congo Deep-Sea Fan. We expand this approach by combining interstitial with solid phase Sr/Ca and Mg/Ca ratios, which demonstrate that high Mg-calcite is the predominant authigenic carbonate that currently forms at the sulfate/methane reaction zone (SMRZ). This is the first study which investigates both solid phase and pore water signatures typical for either aragonite or high Mg-calcite precipitation for the same sediment cores and thus is able to identify active and fossil carbonate precipitation events. At all investigated pockmark sites fossil horizons of the SMRZ were deduced from high Mg-calcite located above and below the current depths of the SMRZ. Additionally, aragonite enrichments typical for high seepage rates were detected close to the sediment surface at these sites. However, active precipitation of aragonite as indicated by pore water characteristics only occurs at the Black Hole site. Dissolved and solid phase Ba concentrations were used to estimate the time the SMRZ was fixed at the current depths of the diagenetic barite fronts. The combined pore water and solid phase elemental ratios (Mg/Ca, Sr/Ca) and Ba concentrations allow the reconstruction of past changes in methane seepage at the investigated pockmark sites. At the Hydrate Hole and Worm Hole sites the time of high methane seepage was estimated to have ceased at least 600 yr BP. In contrast, a more recent change from a high flux to a more dormant stage must have occurred at the Black Hole site as evidenced by active aragonite precipitation at the sediment surface and a lack of diagenetic Ba enrichments.

Methane, helium isotope and hydrogen data from the Nibelungen hydrothermal area, Mid Atlantic Ridge

Hydrothermal emission of mantle helium appears to be directly related to magma production rate, but other processes can generate methane and hydrogen on mid-ocean ridges. In an on-going effort to characterize these processes in the South Atlantic, the flux and distribution of these gases were investigated in the vicinity of a powerful black smoker recently discovered at 8°17.9' S, 13°30.4' W. The vent lies on the shoulder of an oblique offset in the Mid-Atlantic Ridge and discharges high concentrations of methane and hydrogen. Measurements during expeditions in 2004 and 2006 show that the ratio of CH4 to 3He in the neutrally buoyant plume is quite high, 4 x 10**8. The CTD stations were accompanied by velocity measurements with lowered acoustic Doppler current profilers (LADCP), and from these data we estimate the methane transport to have been 0.5 mol/sec in a WSW-trending plume that seems to develop during the ebb tidal phase. This transport is an order of magnitude greater than the source of CH4 calculated from its concentration in the vent fluid and the rise height of the plume. From this range of methane fluxes, the source of 3He is estimated to be between 0.14 and 1.2 nmol/sec. In either case, the 3He source is significantly lower than expected from the spreading rate of the Mid-Atlantic Ridge. From the inventory of methane in the rift valley adjacent to the vent, it appears that the average specific rate of oxidation is 2.6 to 23/yr, corresponding to a turnover time between 140 and 16 days. Vertical profiles of methane in the surrounding region often exhibited Gaussian-like distributions, and the variances appear to increase with distance from the vent. Using a Gaussian plume model, we obtained a range of vertical eddy diffusivities between 0.009 and 0.08 m2m2/sec. These high values may be due to tidally driven internal waves across the promontory on which the vent is located.

Chemical composition of particulate matter and element fluxes in the eastern Norwegian Sea, NS Komsomolets wreck site area

This paper reports results of a geochemical study of suspended particulate matter and particle fluxes in the Norwegian Sea above the Bear Island slope. Concentrations of suspended particles and the main components of suspended matter were determined in the euphotic, intermediate (clean water), and bottom nepheloid layers. It was shown that biogenic components are predominant in water above the nepheloid layer, whereas suspended matter of the nepheloid layer is formed by resuspension of lithogenic components of bottom sediments. Chemical compositions of suspended matter and material collected in sediment traps are identical.

Downward particle fluxes at the oligotrophic and mesotrophic site of the EUMELI program

A two year record of downward particle flux was obtained with moored sediment traps at several depths of the water column in two regions characterized by different primary production levels (mesotrophic and oligotrophic) of the eastern subtropical North Atlantic Ocean in the framework of the EUMELI program. Settling particles were collected with multisample conical sediment-traps moored at 1000 and 2500 depths in the water column. Time-series samples were obtained between February 1991 and November 1992. During this time, sampling intervals varied from 8 to 10 d and were synchronized at all depths and also between the oligotrophic and mesotrophic moorings. Sediment-trap sampling procedures were consistent with JGOF and described elsewhere. The data shown here are mass, particulate organic carbon (POC), particulate inorganic carbon (PIC), coccolithophore, opal, and lithogenic downward fluxes obtained during the entire sediment-trap deployments at both sites.

Biogenic silica and silicic acid benthic fluxes of a North-eastern Atlantic Abyssal Locality

Within the framework of the EU-funded BENGAL programme, the effects of seasonality on biogenic silica early diagenesis have been studied at the Porcupine Abyssal Plain (PAP), an abyssal locality located in the northeast Atlantic Ocean. Nine cruises were carried out between August 1996 and August 1998. Silicic acid (DSi) increased downward from 46.2 to 213 µM (mean of 27 profiles). Biogenic silica (BSi) decreased from ca. 2% near the sediment-water interface to <1% at depth. Benthic silicic acid fluxes as measured from benthic chambers were close to those estimated from non-linear DSi porewater gradients. Some 90% of the dissolution occurred within the top 5.5 cm of the sediment column, rather than at the sediment-water interface and the annual DSi efflux was close to 0.057 mol Si/m**2/yr. Biogenic silica accumulation was close to 0.008 mol Si/m**2/yr and the annual opal delivery reconstructed from sedimentary fluxes, assuming steady state, was 0.065 mol Si/m**2/yr. This is in good agreement with the mean annual opal flux determined from sediment trap samples, averaged over the last decade (0.062 mol Si/m**2/yr). Thus ca. 12% of the opal flux delivered to the seafloor get preserved in the sediments. A simple comparison between the sedimentation rate and the dissolution rate in the uppermost 5.5 cm of the sediment column suggests that there should be no accumulation of opal in PAP sediments. However, by combining the BENGAL high sampling frequency with our experimental results on BSi dissolution, we conclude that non-steady state processes associated with the seasonal deposition of fresh biogenic particles may well play a fundamental role in the preservation of BSi in these sediments. This comes about though the way seasonal variability affects the quality of the biogenic matter reaching the seafloor. Hence it influences the intrinsic dissolution properties of the opal at the seafloor and also the part played by non-local mixing events by ensuring the rapid transport of BSi particles deep into the sediment to where saturation is reached.

Seawater carbonate chemistry and nutrient fluxes during experiments with brittlestar Amphiura filiformis, 2009

Rising levels of atmospheric carbon dioxide and the concomitant increased uptake of this by the oceans is resulting in hypercapnia-related reduction of ocean pH. Research focussed on the direct effects of these physicochemical changes on marine invertebrates has begun to improve our understanding of impacts at the level of individual physiologies. However, CO2-related impairment of organisms' contribution to ecological or ecosystem processes has barely been addressed. The burrowing ophiuroid Amphiura filiformis, which has a physiology that makes it susceptible to reduced pH, plays a key role in sediment nutrient cycling by mixing and irrigating the sediment, a process known as bioturbation. Here we investigate the role of A. filiformis in modifying nutrient flux rates across the sediment-water boundary and the impact of CO2- related acidification on this process. A 40 day exposure study was conducted under predicted pH scenarios from the years 2100 (pH 7.7) and 2300 (pH 7.3), plus an additional treatment of pH 6.8. This study demonstrated strong relationships between A. filiformis density and cycling of some nutrients; activity increases the sediment uptake of phosphate and the release of nitrite and nitrate. No relationship between A. filiformis density and the flux of ammonium or silicate were observed. Results also indicated that, within the timescale of this experiment, effects at the individual bioturbator level appear not to translate into reduced ecosystem influence. However, long term survival of key bioturbating species is far from assured and changes in both bioturbation and microbial processes could alter key biogeochemical processes in future, more acidic oceans.

Particle fluxes and in-situ particle properties measured with sediment traps and a moored camera system from 2008 - 2010 in region off Cape Blanc / NW-Africa

We compared particle data from a moored video camera system with sediment trap derived fluxes at ~1100 m depth in the highly dynamic coastal upwelling system off Cape Blanc, Mauritania. Between spring 2008 and winter 2010 the trap collected settling particles in 9-day intervals, while the camera recorded in-situ particle abundance and size-distribution every third day. Particle fluxes were highly variable (40-1200 mg m**-2 d**-1) and followed distinct seasonal patterns with peaks during spring, summer and fall. The particle flux patterns from the sediment traps correlated to the total particle volume captured by the video camera, which ranged from1 to 22 mm**3 l**-1. The measured increase in total particle volume during periods of high mass flux appeared to be better related to increases in the particle concentrations, rather than to increased average particle size. We observed events that had similar particle fluxes, but showed clear differences in particle abundance and size-distribution, and vice versa. Such observations can only be explained by shifts in the composition of the settling material, with changes both in particle density and chemical composition. For example, the input of wind-blown dust from the Sahara during September 2009 led to the formation of high numbers of comparably small particles in the water column. This suggests that, besides seasonal changes, the composition of marine particles in one region underlies episodical changes. The time between the appearance of high dust concentrations in the atmosphere and the increase lithogenic flux in the 1100 m deep trap suggested an average settling rate of 200 m d**-1, indicating a close and fast coupling between dust input and sedimentation of the material.