Porewater and particulate geochemistry during Maria S. Merian cruise MSM17/4

We present sedimentary geochemical data and in situ benthic flux measurements of dissolved inorganic nitrogen (DIN: NO3-, NO2-, NH4+) and oxygen (O2) from 7 sites with variable sand content along 18°N offshore Mauritania (NW Africa). Bottom water O2 concentrations at the shallowest station were hypoxic (42 µM) and increased to 125 µM at the deepest site (1113 m). Total oxygen uptake rates were highest on the shelf (-10.3 mmol O2 /m2 d) and decreased quasi-exponentially with water depth to -3.2 mmol O2 /m2 d. Average denitrification rates estimated from a flux balance decreased with water depth from 2.2 to 0.2 mmol N /m2 d. Overall, the sediments acted as net sink for DIN. Observed increases in delta 15NNO3 and delta 18ONO3 in the benthic chamber deployed on the shelf, characterized by muddy sand, were used to calculate apparent benthic nitrate fractionation factors of 8.0 pro mille (15epsilon app) and 14.1 pro mille (18epsilon app). Measurements of delta 15NNO2 further demonstrated that the sediments acted as a source of 15N depleted NO2-. These observations were analyzed using an isotope box model that considered denitrification and nitrification of NH4+ and NO2-. The principal findings were that (i) net benthic 14N/15N fractionation (epsilon DEN) was 12.9 ± 1.7pro mille, (ii) inverse fractionation during nitrite oxidation leads to an efflux of isotopically light NO2- (-22 ± 1.9 pro mille), and (iii) direct coupling between nitrification and denitrification in the sediment is negligible. Previously reported epsilon DEN for fine-grained sediments are much lower (4-8 pro mille). We speculate that high benthic nitrate fractionation is driven by a combination of enhanced porewater-seawater exchange in permeable sediments and the hypoxic, high productivity environment. Although not without uncertainties, the results presented could have important implications for understanding the current state of the marine N cycle.

Respiration and dissolution in sediments of the western Atlantic

We present in situ microelectrode measurements of sediment formation factor and porewater oxygen and pH from six stations in the North Atlantic varying in depth from 2159 to 5380 m. A numerical model of the oxygen data indicates that fluxes of oxygen to the sediments are as much as an order of magnitude higher than benthic chamber flux measurements previously reported in the same area. Model results require dissolution driven by metabolic CO2 production within the sediments to explain the pH data; even at the station with the most undersaturated bottom waters >60% of the calcite dissolution occurs in response to metabolic CO2. Aragonite dissolution alone cannot provide the observed buffering of porewater pH, even at the shallowest station. A sensitivity test of the model that accounts for uncertainties in the bottom water saturation state and the stoichiometry between oxygen consumption and CO2 production during respiration constrains the dissolution rate constant for calcite to between 3 and 30% day**-1, in agreement with earlier in situ determinations of the rate constant. Model results predict that over 35% of the calcium carbonate rain to these sediments dissolves at all stations, confirmed by sediment trap and CaCO3 accumulation data.

Methane fluxes and carbonate deposits at eastern Mediterranean cold seeps

High acoustic seafloor-backscatter signals characterize hundreds of patches of methane-derived authigenic carbonates and chemosynthetic communities associated with hydrocarbon seepage on the Nile Deep Sea Fan (NDSF) in the Eastern Mediterranean Sea. During a high-resolution ship-based multibeam survey covering a ~ 225 km**2 large seafloor area in the Central Province of the NDSF we identified 163 high-backscatter patches at water depths between 1500 and 1800 m, and investigated the source, composition, turnover, flux and fate of emitted hydrocarbons. Systematic Parasound single beam echosounder surveys of the water column showed hydroacoustic anomalies (flares), indicative of gas bubble streams, above 8% of the high-backscatter patches. In echosounder records flares disappeared in the water column close to the upper limit of the gas hydrate stability zone located at about 1350 m water depth due to decomposition of gas hydrate skins and subsequent gas dissolution. Visual inspection of three high-backscatter patches demonstrated that sediment cementation has led to the formation of continuous flat pavements of authigenic carbonates typically 100 to 300 m in diameter. Volume estimates, considering results from high-resolution autonomous underwater vehicle (AUV)-based multibeam mapping, were used to calculate the amount of carbonate-bound carbon stored in these slabs. Additionally, the flux of methane bubbles emitted at one high-backscatter patch was estimated (0.23 to 2.3 × 10**6 mol a**-1) by combined AUV flare mapping with visual observations by remotely operated vehicle (ROV). Another high-backscatter patch characterized by single carbonate pieces, which were widely distributed and interspaced with sediments inhabited by thiotrophic, chemosynthetic organisms, was investigated using in situ measurements with a benthic chamber and ex situ sediment core incubation and allowed for estimates of the methane consumption (0.1 to 1 × 10**6 mol a**-1) and dissolved methane flux (2 to 48 × 10**6 mol a**-1). Our comparison of dissolved and gaseous methane fluxes as well as methane-derived carbonate reservoirs demonstrates the need for quantitative assessment of these different methane escape routes and their interaction with the geo-, bio-, and hydrosphere at cold seeps.

Pore water chemistry of samples near the sediment-water interface

Rhizon samplers were originally designed as micro-tensiometers for soil science to sample seepage water in the unsaturated zone. This study shows applications of Rhizons for porewater sampling from sediments in aquatic systems and presents a newly developed Rhizon in situ sampler (RISS). With the inexpensive Rhizon sampling technique, porewater profiles can be sampled with minimum disturbance of both the sediment structure and possible flow fields. Field experiments, tracer studies, and numerical modeling were combined to assess the suitability of Rhizons for porewater sampling. It is shown that the low effort and simple application makes Rhizons a powerful tool for porewater sampling and an alternative to classical methods. Our investigations show that Rhizons are well suited for sampling porewater on board a ship, in a laboratory, and also for in situ sampling. The results revealed that horizontally aligned Rhizons can sample porewater with a vertical resolution of 1 cm. Combined with an in situ benthic chamber system, the RISS allows studies of benthic fluxes and porewater profiles at the same location on the seafloor with negligible effect on the incubated sediment water interface. Results derived by porewater sampling of sediment cores from the Southern Ocean (Atlantic sector) and by in situ sampling of tidal flat sediments of the Wadden Sea (Sahlenburg/Cuxhaven, Germany) are presented.

Benthic oxygen flixes on the Washington shelf and slope

Benthic oxygen fluxes calculated from in situ microelectrode profiles arc compared with benthic flux chamber O2 uptake measurements on a transect of eight stations across the continental shelf and three stations on the slope of Washington State. Station depths ranged from 40 to 630 m and bottom-water oxygen concentrations were 127-38 µM. The fluxes measured by the two methods were similar on the slope, but on the shelf, the chamber flux exceeded the microelectrode flux by as much as a factor of 3-4. We attribute this difference to pore-water irrigation, a process which apparently accounts for the oxidation of a significant amount of organic C in the continental shelf sediments. Combining our diffusive flux data with other data demonstrates clearly that the bottomwater oxygen concentration must play some significant role in determining the sedimentary oxygen consumption rate. Numerical simulation of the microelectrode 0, profiles suggests that roughly half the diffusive 0, flux must be consumed within - 1 mm of the sediment surface. If this conclusion is correct, then the magnitude of the diffusive flux depends both on the bottom-water oxygen concentration and on the supply rate of labile C to the sediment surf'ace.

Response of deep-sea benthic foraminifera to Late Quaternary climate changes, southeast Indian Ocean, offshore Western Australia

The Late Quaternary benthic foraminifera of four deep-sea cores off Western Australia (ODP 122-760A, ODP 122-762B, BMR96GC21 and RC9-150) have been examined for evidence of increased surface productivity to explain the anomalously low sea-surface paleotemperatures inferred by planktic foraminifera for the last and penultimate glaciations. The delta13C trends of Cibicidoides wuellerstorfi, and differences between the delta13C trends of planktics (Globigerinoides sacculifer) and benthics (C. wuellerstorfi) in the four cores indicate that during stage 6 bottom waters were significantly depleted in delta13C, and strong delta13C gradients were established in the water column, while during stage 2 and the Last Glacial Maximum, delta13C trends did not differ greatly from that of the Holocene. Two main assemblages of benthic foraminifera were identified by principal component analyses: one dominated by Uvigerina peregrina, another dominated by U. proboscidea. Abundance of these Uvigerinids, and of taxa preferring an infaunal microhabitat, and of Epistominella exigua and Bulimina aculeata indicate that episodes of high influx of particulate organic matter were established in most sites during glacial episodes, and particularly so during stage 6, while evidence for upwelling during the Last Glacial Maximum is less strong. The Penultimate Glaciation upwellings were established within the areas of low sea-surface paleotemperature indicated by planktic foraminifera. During the Last Interglacial Climax, upwelling appears to have been established in an isolated region offshore from a strengthened Leeuwin Current off North West Cape. Last Glacial Maximum delta13C values of C. wuellerstorfi at waterdepths of less than 2000 m show smaller than global mean glacial-interglacial changes suggesting the development of a deep hydrological front. A similar vertical stratification/bathyal front was also established during the Penultimate Glaciation.

Uppermost Jurassic to lower Cretaceous benthic foraminifera from ODP Hole 123-765C

Benthic foraminifers were studied in 99 samples collected from the lower 200 m of Hole 765C. The studied section ranges from the Tithonian to Aptian, and benthic foraminifers can be subdivided into five assemblages on the basis of faunal diversity and stratigraphic ranges of distinctive species. Compared with deep-water assemblages from Atlantic DSDP sites and Poland, assemblages from the Argo Abyssal Plain display a higher diversity of agglutinated forms, which comprise the autochthonous assemblages. Assemblages at the base of Hole 765C are wholly composed of agglutinated forms, reflecting deposition beneath the carbonate compensation depth (CCD). Most calcareous benthic species are found in turbidite layers, and the presence of an upper Valanginian Praedorothia praehauteriviana Assemblage may indicate deposition at or just below the CCD. The P. praehauteriviana Assemblage from Hole 765C is the temporal equivalent of similar assemblages from DSDP Holes 534A, 416A, 370, 105, and 101 in the Atlantic Ocean and Hole 306 in the Pacific Ocean. Stratigraphic ranges of cosmopolitan agglutinated species at Site 765 generally overlap with their reported ranges in the Atlantic and in the bathyal flysch sequences of the Carpathians; however, several species from Hole 765C have not been previously reported from Uppermost Jurassic to Lower Cretaceous abyssal sediments.

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.

pH and calcium change in the microenvironment of a benthic foraminifer (Ammonia sp.) and its size during experiments

Calcareous foraminifera are well known for their CaCO3 shells. Yet, CaCO3 precipitation acidifies the calcifying fluid. Calcification without pH regulation would therefore rapidly create a negative feedback for CaCO3 precipitation. In unicellular organisms, like foraminifera, an effective mechanism to counteract this acidification could be the externalization of H+ from the site of calcification. In this study we show that a benthic symbiont-free foraminifer Ammonia sp. actively decreases pH within its extracellular microenvironment only while precipitating calcite. During chamber formation events the strongest pH decreases occurred in the vicinity of a newly forming chamber (range of gradient about 100 µm) with a recorded minimum of 6.31 (< 10 µm from the shell) and a maximum duration of 7 h. The acidification was actively regulated by the foraminifera and correlated with shell diameters, indicating that the amount of protons removed during calcification is directly related to the volume of calcite precipitated. The here presented findings imply that H+ expulsion as a result of calcification may be a wider strategy for maintaining pH homeostasis in unicellular calcifying organisms.