Phosphate d18O pore-water profiles of sediment core GeoB11807-2 and GeoB11804-4

Phosphorus cycling in the ocean is influenced by biological and geochemical processes that are reflected in the oxygen isotope signature of dissolved inorganic phosphate (Pi). Extending the Pi oxygen isotope record from the water column into the seabed is difficult due to low Pi concentrations and small amounts of marine porewaters available for analysis. We obtained porewater profiles of Pi oxygen isotopes using a refined protocol based on the original micro-extraction designed by Colman (2002). This refined and customized method allows the conversion of ultra-low quantities (0.5 - 1 µmol) of porewater Pi to silver phosphate (Ag3PO4) for routine analysis by mass spectrometry. A combination of magnesium hydroxide co-precipitation with ion exchange resin treatment steps is used to remove dissolved organic matter, anions, and cations from the sample before precipitating Ag3PO4. Samples as low as 200 µg were analyzed in a continuous flow isotope ratio mass spectrometer setup. Tests with external and laboratory internal standards validated the preservation of the original phosphate oxygen isotope signature (d18OP) during micro extraction. Porewater data on d18OP has been obtained from two sediment cores of the Moroccan margin. The d18OP values are in a range of +19.49 to +27.30 per mill. We apply a simple isotope mass balance model to disentangle processes contributing to benthic P cycling and find evidence for Pi regeneration outbalancing microbial demand in the upper sediment layers. This highlights the great potential of using d18OP to study microbial processes in the subseafloor and at the sediment water interface.

Microbial community, biomarker concentrations and their isotopic signature in sediment of Gullfaks and Tommeliten methane seeps in the Northern North Sea

Gullfaks is one of the four major Norwegian oil and gas fields, located in the northeastern edge of the North Sea Plateau. Tommeliten lies in the greater Ekofisk area in the central North Sea. During the cruises HE 208 and AL 267 several seep locations of the North Sea were visited. At the Heincke seep at Gullfaks, sediments were sampled in May 2004 (HE 208) using a video-guided multiple corer system (MUC; Octopus, Kiel). The samples were recovered from an area densely covered with bacterial mats where gas ebullition was observed. The coarse sands limited MUC penetration depth to maximal 30 centimeters and the highly permeable sands did not allow for a high-resolution, vertical subsampling because of pore water loss. The gas flare mapping and videographic observation at Tommeliten indicated an area of gas emission with a few small patches of bacterial mats with diameters <50 cm from most of which a single stream of gas bubbles emerged. The patches were spaced apart by 10-100 m. Sampling of sediments covered by bacterial mats was only possible with 3 small push cores (3.8 cm diameter) mounted to ROV Cherokee. These cores were sampled in 3 cm intervals. Lipid biomarker extraction from 10 -17 g wet sediment was carried out as described in detail elsewhere (Elvert et al., 2003; doi:10.1080/01490450303894). Briefly, defined concentrations of cholestane, nonadecanol and nonadecanolic acid with known delta 13C-values were added to the sediments prior to extraction as internal standards for the hydrocarbon, alcohol and fatty acid fraction, respectively. Total lipid extracts were obtained from the sediment by ultrasonification with organic solvents of decreasing polarity. Esterified fatty acids (FAs) were cleaved from the glycerol head group by saponification with methanolic KOH solution. From this mixture, the neutral fraction was extracted with hexane. After subsequent acidification, FAs were extracted with hexane. For analysis, FAs were methylated using BF3 in methanol yielding fatty acid methyl esters (FAMES). The fixation for total cell counts and CARD-FISH were performed on-board directly after sampling. For both methods, sediments were fixed in formaldehyde solution. After two hours, aliquots for CARD-FISH staining were washed with 1* PBS (10mmol/l sodium phosphate solution, 130mmol/l NaCl, adjusted to a pH of 7.2) and finally stored in a 1:1 PBS:ethanol solution at -20°C until further processing. Samples for total cell counts were stored in formalin at 4°C until analysis. For sandy samples, the total cell count/CARD-FISH protocol was optimized to separate sand particles from the cells. Cells were dislodged from sediment grains and brought into solution with the supernatant by sonicating each sample onice for 2 minutes at 50W. This procedure was repeated four times and supernatants were combined. The sediment samples were brought to a final dilution of 1:2000 to 1:4000 and filtered onto 0.2µm GTTP filters (Millipore, Eschbonn, Germany).

A foraminiferal d18O record of sediment core GT90-3 covering the last 2,200 years

For many years the Torino Cosmogeophysics group has been studying sediment cores drilled from the Gallipoli Terrace in the Gulf of Taranto (Ionian Sea) and deposited in the last millennia. The gravity core GT90-3, in which the 18O series was measured, was drilled from the Gallipoli Terrace in the Gulf of Taranto (Ionian Sea) at 39°45'53''N, 17°53'33''E. It was extracted at a depth of 178 m and its length is 3.57 m. Thanks to its geographical location, the Gallipoli Terrace is a favourable site for climatic studies based on marine sediments, because of its closeness to the volcanically active Campanian area, a region that is unique in the world for its detailed historical documentation of volcanic eruptions. Tephra layers corresponding to historical eruptions were identified along the cores, thus allowing for accurate dating and determination of the sedimentation rate. The measurements performed in different cores from the same area showed that the sedimentation rate is uniform across the whole Gallipoli Terrace. We measured the oxygen isotope composition d18O of planktonic foraminifera. These measurements provided a high-resolution 2,200-year-long record. We sampled the core using a spacing of 2.5 mm corresponding to 3.87 years. Each sample of sediment (5 g) was soaked in 5% calgon solution overnight, then treated in 10% H2O2 to remove any residual organic material. Subsequently it was washed with a distilled-water jet through a sieve with a 150 µm mesh. The fraction > 150 µm was kept and oven-dried at 5°C. The planktonic foraminifera Globigerinoides ruber were picked out of the samples under a microscope. For each sample, 20-30 specimens were selected from the fraction comprised between 150 µm and 300 µm. The use of a relatively large number of specimens for each sample reduces the isotopic variability of individual organisms, giving a more representative d18O value. The stable isotope measurements were performed using a VG-PRISM mass spectrometer fitted with an automated ISO-CARB preparation device. Analytical precision based on internal standards was better than 0.1 per mil. Calibration of the mass spectrometer to VPDB scale was done using NBS19 and NBS18 carbonate standards. The strategic location of the drilling area makes this record a unique tool for climate and oceanographic studies of the Central Mediterranean.