Benthic anammox and dentrification rates measured in a slurry incubation experiments at four different stations in the Arabian Sea off Pakistan during the METEOR cruise M74/2 in 2007

Vertical distributions of benthic denitrification and anammox rates within the sediment were estimated from slurry incubation experiments. Rates were used to calculate the contribution of anammox and denitrification to the total N-loss. Briefly, MUC sediment cores were sliced in 2 cm intervals and the sediment was diluted and incubated with degassed bottom water in a gas tight bag. After pre-incubating the bags for 2 h, 15N-labeled substrates were injected into the bags and the slurries were thoroughly mixed. Incubations were performed in the dark at in situ temperatures. The N2 isotope ratio (28N2, 29N2, and 30N2) was determined by gas chromatography-isotopic ratio mass spectrometry (VG Optima, Micromass) and calculated according to Kuypers et al. (2005) and Holtappels et al. (2011), respectively.Furthermore, total organic carbon and nitrogen concentrations were measured of core sediment layers corresponding to those used for rate measurements. Concentrations of organic carbon and nitrogen were determined by combustion/gas chromatography (Carlo Erba NA-1500 CNS analyzer) of dried sediment samples after acidification. The same sediment layer were also used to extract nucleic acids. The concentrations of the DNA in the samples were measured spectrophotometrically with a NanoDrop instrument (Thermo Fisher Scientific Inc.). The biomarker functional gene nirS, encoding the cd1-containing nitrite reductase, for both denitrifiers and marine anammox bacteria were quantified with real-time PCR, using the primers cd3aF/R3cd (5'-GTSAACGTSAAGGARACSGG-3' (Michotey et al., 2000)/5'-GASTTCGGRTGSGTCTTGA-3'; Throback et al., 2004) and Scnir372F/Scnir845R (5'-TGTAGCCAGCATTGTAGCGT-3'/5'-TCAAGCCAGACCCATTTGCT-3'; Lam et al., 2009).

C4-C7 alkenones in deep sea sediments

It is believed that C4 to C7 hydrocarbons in petroleum are formed by the cracking of organic matter at depths generally exceeding 1,000 m at temperatures in excess of 50 °C (Cordel, 1972; Dow, 1974; Tissot et al., 1974)). Also, none of the alkanes in the butane-heptane range are formed biologically as far as is known at present. Consequently, it is thought that they do not occur in shallow, Recent sediments. In 1962, I analysed 22 samples of Recent sediments from 7 different environments and verified that these hydrocarbons were not present at the p.p.m. level (Dunton and Hunt, 1962) although traces of a few hydrocarbons such as butane, isobutane, isopentane and n-heptane have been found (Sokolov, 1957; Veber and Turkeltaub, 1958; Erdman et al., 1958; Emery and Hoggan, 1958). No identification of individual hexanes or heptanes has been reported except when there has been clear evidence of seepage from deeper source sediments (McIver, 1973).

Cholesterol and C30 of sediment profile MD90-963

In a deep-sea sediment core recovered from a site lying well above the local lysocline, several organic geochemical proxies, and two different calcite dissolution indicators, are compared in order to evaluate the relationship between calcite dissolution and paleoproductivity over the past three glacial-interglacial cycles. The degree of foraminiferal break-up, and the CaCO3 particle size distribution, both point to significant periods of dissolution every 22 kyr during glacial stages and substages. These dissolution events are concomitant with periods of enhanced primary productivity, as indicated by the abundance of several biomarkers (alkenones, cholesterol, brassicasterol, keto-ol), used here to indicate changes in paleoproductivity. Dissolution fluctuations are highly coherent and in phase with the estimated paleoproductivity variations providing strong evidence that the observed dissolution is due to organic matter remineralization within the sediments rather, than to changes in CO32? concentration in the overlying water column.

Long chain alkyl diol distribution in Arabian Sea surface sediments

Oxygen exposure has a large impact on lipid biomarker preservation in surface sediments and may affect the application of organic proxies used for reconstructing past environmental conditions. To determine its effect on long chain alkyl diol and keto-ol based proxies, the distributions of these lipids was studied in nine surface sediments from the Murray Ridge in the Arabian Sea obtained from varying water depths (900 to 3000 m) but in close lateral proximity and, therefore, likely receiving a similar particle flux. Due to substantial differences in bottom water oxygen concentration (<3 to 77 µmol/L) and sedimentation rate, substantial differences exist in the time the biomarker lipids are exposed to oxygen in the sediment. Long chain alkyl diol and keto-ol concentrations in the surface sediments (0-0.5 cm) decreased progressively with increasing oxygen exposure time, suggesting increased oxic degradation. The 1,15-keto-ol/diol ratio (DOXI) increased slightly with oxygen exposure time as diols had apparently slightly higher degradation rates than keto-ols. The ratio of 1,14- vs. 1,13- or 1,15-diols, used as upwelling proxies, did not show substantial changes. However, the C30 1,15-diol exhibited a slightly higher degradation rate than C28 and C30 1,13-diols, and thus the Long chain Diol Index (LDI), used as sea surface temperature proxy, showed a negative correlation with the maximum residence time in the oxic zone of the sediment, resulting in ca. 2-3.5 °C change, when translated to temperature. The UK'37 index did not show significant changes with increasing oxygen exposure. This suggests that oxic degradation may affect temperature reconstructions using the LDI in oxic settings and where oxygen concentrations have varied substantially over time.

(Table T1) N-alkane, n-alcohol and n-fatty acid concentrations in ODP Site 184-1147 and 184-1148 sediments

Lipid compositions of sediments recovered during Ocean Drilling Program Leg 184 in the South China Sea have been identified and quantified. The identified lipids can be ascribed to terrigenous and marine sources. Terrigenous lipids are mainly C27, C29, C31 n-alkanes, C26, C28, C30 n-fatty acids, and n-alcohols, which were derived from leaf waxes of higher land plants and transported to the sea by airborne dust or fresh water. Marine lipids, mainly C37 and C38 alkenones, C30 diol, and C30 and C32 keto-ols, were from microalgae, notably haptophytes and eustigmatophytes. Elevated concentrations and accumulation rates of both terrigenous and marine lipids in the interval 202-245 meters composite depth (mcd) and 0-166 mcd were postulated to be related to the development of the East Asian monsoon at 6-8 Ma and enhanced variations of the developed East Asian monsoon after 3.2 Ma, respectively. The pronounced late Oligocene input of terrigenous lipids reflects the paleoenvironment of a newly opened, narrow basin, with restricted ocean waters and the proximity of continental runoff.

Data on the biogeochemical cycle of methane in the ocean

Geological, mineralogical and microbiological aspects of the methane cycle in water and sediments of different areas in the oceans are under consideration in the monograph. Original and published estimations of formation- and oxidation rates of methane with use of radioisotope and isotopic methods are given. The role of aerobic and anaerobic microbial oxidation of methane in production of organic matter and in formation of authigenic carbonates is considered. Particular attention is paid to processes of methane transformation in areas of its intensive input to the water column from deep-sea hydrothermal sources, mud volcanoes, and cold methane seeps.

Organic-geochemical proxies (UK'37 and TEXH86) records in surface sediments of the tropical Eastern Indian Ocean

In this study we reconstruct sea surface temperatures (SSTs) using two lipid-based biomarker proxies (alkenone unsaturation index UK'37 and TEX86 index based on glycerol dibiphytanyl glycerol tetraethers) in 36 surface sediment samples from the Indonesian continental margin off west Sumatra and south of Java and the Lesser Sunda Islands. Comparison of measured temperatures (World Ocean Atlas 09) to reconstructed temperatures suggests that SST-UK'37 reflects the SE monsoon SST in the upwelling area south of Java and the Lesser Sunda Islands, whereas Temp-TEXH86 estimates are up to 2°C lower than SST-UK'37. This offset is possibly related to either one or a combination of two factors: i) the depth habitats of the source organisms; ii) different seasonal production and/ or seasonality of export associated with phytoplankton blooming triggered by primary productivity. In the non-upwelling area off west Sumatra, the alkenone-based SSTs are cooler than measured temperatures during the entire year, likely due to the reduced sensitivity of the UK'37 proxy beyond 28°C. However, reconstructed temperatures based on TEXH86 are consistent with mean annual SST, implying that the Temp-TEXH86 reflects the mean annual SST in the non-upwelling area of the tropical Eastern Indian Ocean.

Benthic foraminiferal abundances from eight sites of the Northwest Australian shelf

Foraminiferal analysis of Miocene to recent strata of the Northwest Shelf of Australia is used to chart West Pacific Warm Pool (WPWP) influence. The assemblage is typified by "larger" foraminifera with ingressions of the Indo-Pacific "smaller" taxa Asterorotalia and Pseudorotalia at around 4 Ma and from 1.6 to 0.8 Ma. A review of recent and fossil biogeography of these taxa suggests their stratigraphic distribution can be used to document WPWP evolution. From 10 to 4.4 Ma a lack of biogeographic connectivity between the Pacific and Indian Ocean suggests Indonesian Throughflow (ITF) restriction. During this period, the collision of Australia and Asia trapped warmer waters in the Pacific, creating a central WPWP biogeographic province from the equator to 26°N. By 3 Ma Indo-Pacific species migrated to Japan with the initiation of the "modern" Kuroshio Current coinciding with the intensification of the North Pacific Gyre and Northern Hemisphere ice sheet expansion. Indo-Pacific taxa migrated to the northwest Australia from 4.4 to 4 Ma possibly because of limited ITF. The absence of Indo-Pacific taxa in northwest Australia indicates possible ITF restriction from 4 to 1.6 Ma. Full northwest Australian biogeographic connectivity with the WPWP from 1.6 to 0.8 Ma suggests an unrestricted stronger ITF (compared to today) and the initiation of the modern Leeuwin Current. The extinction of some Indo-Pacific species in northwest Australia after 0.8 Ma may be related to the effects of large glacial/interglacial oscillations and uplift of the Indonesian Archipelago causing Indonesian seaway restriction.

(Table 1) Low molecular weight hydrocarbon concentrations and organic carbon contents at DSDP Hole 71-511

C2-C8 hydrocarbons (36 compounds identified) from 56 shipboard sealed, deep-frozen core samples of DSDP Leg 71, Site 511, Falkland Plateau, South Atlantic, were analyzed by a combined hydrogen stripping-thermovaporization method. Concentrations, which represent hydrocarbons dissolved in the pore water and adsorbed to the mineral surfaces of the sediment, vary from 24 ng/g of dry weight sediment in Lithologic Unit 4 to 17,400 ng/g in Lithologic Unit 6 ("black shale" unit). Likewise, the organic carbon normalized C2-C8 hydrocarbon concentrations range from 104 to 3.5 x 105 ng/g Corg. The latter value is more than one order of magnitude lower than expected for petroleum source beds in the main phase of oil generation. The low maturity at 600 meters depth is further supported by light hydrocarbon concentration ratios. The change of the kerogen type from Lithologic Unit 5 (Type III) to 6 (Type II) is evidenced by changes in the C6 and C7 hydrocarbon composition. Redistribution phenomena are observed close to the Tertiary-Cretaceous unconformity and at the contact between the "black shale" unit and the overlying Cretaceous chalks and claystones. Otherwise, the low molecular weight hydrocarbons in Hole 511 are formed in situ and remain at their place of formation. The core samples turned out to be contaminated by large quantities of acetone, which is routinely used as a solvent during sampling procedures onboard Glomar Challenger.

Decadal-to-centennial scale variations during the Holocene reconstructed from sediment core D13902

Sea surface temperature (SST), marine productivity, and fluvial input have been reconstructed for the last 11.5 calendar (cal) ka B.P. using a high-resolution study of C37 alkenones, coccolithophores, iron content, and higher plant n-alkanes and n-alkan-1-ols in sedimentary sequences from the inner shelf off the Tagus River Estuary in the Portuguese Margin. The SST record is marked by a continuous decrease from 19C, at 10.5 and 7 ka, to 15C at present. This trend is interrupted by a fall from 18C during the Roman and Medieval Warm Periods to 16C in the Little Ice Age. River input was very low in the early Holocene but increased in the last 3 cal ka B.P. in association with an intensification of agriculture and deforestation and possibly the onset of the North Atlantic Oscillation/Atlantic Multidecadal Oscillation modes of variability. River influence must have reinforced the marine cooling trend relative to the lower amplitude in similar latitude sites of the eastern Atlantic. The total concentration of alkenones reflects river-induced productivity, being low in the early Holocene but increasing as river input became more important. Rapid cooling, of 1-2C occurring in 250 years, is observed at 11.1, 10.6, 8.2, 6.9, and 5.4 cal ka B.P. The estimated age of these events matches the ages of equivalent episodes common in the NE Atlantic- Mediterranean region. This synchronicity reveals a common widespread climate feature, which considering the twentieth century analog between colder SSTs and negative North Atlantic Oscillation (NAO), is likely to reflect periods of strong negative NAO.

Palynomorphs from the Lateglacial and Holocene of the Mt-Athos Basin, Aegean Sea

To unravel the climatic and environmental dynamics in the borderlands of the Aegean Sea during the early and middle Holocene, and notably for the interval of sapropel S1 (S1) formation, we have analysed terrestrial palynomorphs from a marine core in the northern Aegean Sea. The qualitative results were complemented by quantitative pollen-based climate reconstructions. A land-sea correlation was established based on pollen data and sediment lightness measurements from the same core, and previously published benthic foraminifer data from a nearby core. The borderlands of the Aegean Sea underwent a transition from an open vegetation to oak-dominated woodlands between ~10.4 and ~9.5 ka cal BP. A coeval increase in winter precipitation suggests that moisture availability was the main factor controlling Holocene reforestation. The ~50% higher winter precipitation during S1 formation relative to "pre-sapropelic" conditions suggests a strong contribution from the borderlands of the Aegean Sea to the freshwater surplus during S1 formation. The humid and mild winter conditions during S1 formation were repeatedly punctuated by short-term climatic events that caused a partial deforestation and a reorganisation within the broad-leaved arboreal vegetation. In the marine realm, these events are documented by improved benthic oxygenation. The strongest event represents the regional expression of the 8.2 ka cold event and led to an interruption in S1 formation. Except for the interval of S1 formation, the pollen-derived winter temperatures correlate with the smoothed GISP2 K+ series. They support the previously published, marine-based concept that the intensity of the Siberian High strongly controlled the winter climate in the Aegean region. During S1 formation in the Aegean Sea, however, climate conditions in the borderlands were more strongly affected by the monsoonally influenced climate system of the lower latitudes.