Molecular dissolved organic matter composition and environmental parameters from a laboratory incubation study

Dissolved organic matter (DOM) in the oceans constitutes a major carbon pool involved in global biogeochemical cycles. More than 96% of the marine DOM resists microbial degradation for thousands of years. The composition of this refractory DOM (RDOM) exhibits a molecular signature which is ubiquitously detected in the deep oceans. Surprisingly efficient microbial transformation of labile into RDOM was shown experimentally, implying that microorganisms produce far more RDOM than needed to sustain the global pool. By assessing the microbial formation and transformation of DOM in unprecedented molecular detail for 3 years, we show that most of the newly formed RDOM is molecularly different from deep sea RDOM. Only <0.4% of the net community production was channeled into RDOM molecularly undistinguishable from deep sea DOM. Our study provides novel experimentally derived molecular evidence and data for global models on the production, turnover and accumulation of marine DOM.

Sedimentology and stable oxygen isotope ratios of foraminifera from cores of the Porcupine Seabight, Northeast Atlantic

Large carbonate mound structures have been discovered in the northern Porcupine Seabight (Northeast Atlantic) at depths between 600 and 1000 m. These mounds are associated with the growth of deep-sea corals Lophelia pertusa and Madrepra oculata. In this study, three sediment cores have been analysed. They are from locations close to Propeller Mound, a 150 m high ridge-like feature covered with a cold-water coral ecosystem at its upper flanks. The investigations are concentrated on grain-size analyses, carbon measurements and on the visual description of the cores and computer tomographic images, to evaluate sediment content and structure. The cores portray the depositional history of the past ~31 kyr BP, mainly controlled by sea-level fluctuations and the climate regime with the advance and retreat of the Irish Ice Sheet onto the Irish Mainland Shelf. A first advance of glaciers is indicated by a turbiditic release slightly older than 31 kyr BP, coherent with Heinrich event 3 deposition. During Late Marine Isotope Stage 3 (MIS 3) and MIS 2 shelf erosion prevailed with abundant gravity flows and turbidity currents. A change from glaciomarine to hemipelagic contourite sedimentation during the onset of the Holocene indicates the establishment of the strong, present-day hydrodynamic regime at intermediate depths. The general decrease in accumulation of sediments with decreasing distance towards Propeller Mound suggests that currents (turbidity currents, gravity flows, bottom currents) had a generally stronger impact on the sediment accumulation at the mound base for the past ~31 kyr BP, respectively.

Petrography and geochemistry of organic matter at DSDP Holes 80-549 and 80-550B

Three lower Barremian to middle/upper Cenomanian samples from DSDP Hole 549 and three lower Cenomanian to lower Maestrichtian samples from DSDP Hole 550B were investigated by organic geochemical and organic petrographic methods. The samples came from wells drilled in the area of the Goban Spur in the northeastern Atlantic; they represent gray to greenish gray carbonaceous mud or siltstones from the deeper parts of the Cretaceous sequences penetrated and light-colored chalks from the shallower ones. The total amount of organic carbon is below 1% in all samples; it is especially low in the Cenomanian to Maestrichtian chalks. Terrigenous organic matter predominates; only the Barremian sample shows a moderate number of marine phytoclasts. As indicated by several parameters, the maturity of the organic matter is low, corresponding to about 0.4% vitrinite reflectance.

Accumulation rates of bulk sediment and total organic carbon for Ontong Java Plateau sediments

Organic geochemical investigations were performed on sediments of Leg 130 to reconstruct the depositional environment of the Ontong Java Plateau. The Miocene to Quaternary sediments collected during the drilling campaign are characterized by extremely low organic carbon contents. As indicated by C/N ratios and Rock-Eval data, most of the organic matter is probably of marine origin. Based on mass-accumulation rates of organic carbon, the paleoproductivity for the Miocene-Pliocene and the late Pliocene-Pleistocene time intervals as well as the modern surface-water production were estimated. The productivity values of the surface sediments (25-59 gC/m2/yr) reflect the various influences of the equatorial upwelling cell on the different sites. The accumulation rates of organic carbon are generally low; however, they show a distinct increase at 8 Ma and a decrease at 2 Ma.

Diagenetic alteration of organic matter in DSDP Leg 57 Holes

I analyzed Leg 57 sediments organogeochemically and spectroscopically. Organic carbon and extractable organic matter prevail from the Pliocene to the Miocene. Humic acids occur widely from the Pleistocene to the lower Miocene and one portion of the Oligocene. The absence of humic acids in Oligocene and Cretaceous samples suggests that humic acids had changed to kerogen. Visible spectroscopic data reveal that humic acids in this study have a low degree of condensed aromatic-ring system, which is a feature of anaerobic conditions during deposition, and that chlorophyll derivatives that had at first combined with humic acids moved to the solvent- soluble fraction during diagenesis. The elemental compositions of humic acids show high H/C and O/C ratios, which seem appropriate to a stage before transformation to kerogen. The relation between the linewidths and g-values on the electron spin resonance data indicates that the free radicals in humic acids are quite different from those in kerogen. The low spin concentrations of kerogen and the yields of humic acids up to the lower Miocene demonstrate that organic matter in these sediments is immature. The foregoing indicate the necessity to isolate humic acids even in ancient rocks in the study of kerogen.

(Table 2) Chemistry of the organic matter at DSDP Leg 62 Holes

The wide distribution of sapropelic deposits in the sedimentary cover of the oceans, their Cretaceous age, and their possible oil- and gas-generating characteristics allow us to regard these deposits as a regular global stage in the history of oceanic sedimentation. So, Cretaceous sapropelic deposits are a unique object for study. Cretaceous sapropelic deposits of DSDP Sites 463, 465, and 466, as well as similar sediments of the Atlantic and Indian Oceans, are characterized by enrichment in organic matter, which sometimes reaches 33% (Cape Verde Basin, DSDP Sites 367 and 368). The objective of this study is the elucidation of genesis, paleogeographic environment of sedimentation, and oil-generating potential of Cretaceous sapropelic deposits at these sites. Attention is given to petrographic composition and distribution of the organic matter.

Organic geochemistry, visual composition, atomic ratios, and reflectance at DSDP Site 87-582, 87-583 and 87-584

Geochemical analyses of organic matter were carried out on Quaternary sediments from Sites 582 and 583 (Nankai Trough) and on Pliocene to Miocene sediments from Site 584 (Japan Trench), DSDP Leg 87, to evaluate petroleum-generating potential and to characterize the organic matter. The vitrinite-huminite reflectances of indigenous materials for these sites are less than 0.3% indicating the immature nature of the sediments. The sediments, however, contain remarkable amounts of recycled organic materials. The Quaternary sediments from Sites 582 and 583 contain small amounts of amorphous organic matter (less than 0.75 wt.% organic carbon and 66-90% amorphous debris), which is composed of predominantly recycled, oxidized, and over-matured (or matured) Type III material. The amount of hydrocarbon yield indicates that those sediments have lean-source potential for commercial hydrocarbon generation. The Pliocene to Miocene sediments from Site 584 contain organic matter (0.3-1.09 wt.% organic carbon) of predominantly amorphous debris (68-96%) that originated in two sources, an indigenous Type II material and a recycled, over-matured material. Pyrolysis shows an upward increase in the section of hydrocarbon yield and the same trend is also observed in organic-carbon content. The amount of the yield indicates that the Miocene sediments have lean-to-fair source potential and the Pliocene sediments have fair-to-good source potential.

Distribution of organic carbon in surface sediments covered during SONNE cruise SO184

Sediments were sampled and oxygen profiles of the water column were determined in the Indian Ocean off west and south Indonesia in order to obtain information on the production, transformation, and accumulation of organic matter (OM). The stable carbon isotope composition (d13Corg) in combination with C/N ratios depicts the almost exclusively marine origin of sedimentary organic matter in the entire study area. Maximum concentrations of organic carbon (Corg) and nitrogen (N) of 3.0% and 0.31%, respectively, were observed in the northern Mentawai Basin and in the Savu and Lombok basins. Minimum d15N values of 3.7 per mil were measured in the northern Mentawai Basin, whereas they varied around 5.4 per mil at stations outside this region. Minimum bottom water oxygen concentrations of 1.1 mL L**1, corresponding to an oxygen saturation of 16.1%, indicate reduced ventilation of bottom water in the northern Mentawai Basin. This low bottom water oxygen reduces organic matter decomposition, which is demonstrated by the almost unaltered isotopic composition of nitrogen during early diagenesis. Maximum Corg accumulation rates (CARs) were measured in the Lombok (10.4 g C m**-2 yr**-1) and northern Mentawai basins (5.2 g C m**-2 yr**-1). Upwelling-induced high productivity is responsible for the high CAR off East Java, Lombok, and Savu Basins, while a better OM preservation caused by reduced ventilation contributes to the high CAR observed in the northern Mentawai Basin. The interplay between primary production, remineralisation, and organic carbon burial determines the regional heterogeneity. CAR in the Indian Ocean upwelling region off Indonesia is lower than in the Peru and Chile upwellings, but in the same order of magnitude as in the Arabian Sea, the Benguela, and Gulf of California upwellings, and corresponds to 0.1-7.1% of the global ocean carbon burial. This demonstrates the relevance of the Indian Ocean margin off Indonesia for the global OM burial.

Carbon and oxygen isotope data for carbonates and benthic foraminifers from ODP Hole 113-689B

At Ocean Drilling Program Site 689 (Maud Rise, Southern Ocean), d18O records of fine-fraction bulk carbonate and benthic foraminifers indicate that accelerated climate cooling took place following at least two closely spaced early late Eocene extraterrestrial impact events. A simultaneous surface-water productivity increase, as interpreted from d13C data, is explained by enhanced water-column mixing due to increased latitudinal temperature gradients. These isotope data appear to be in concert with organic-walled dinoflagellate-cyst records across the same microkrystite-bearing impact-ejecta layer in the mid-latitude Massignano section (central Italy). In particular, the strong abundance increase of Thalassiphora pelagica is interpreted to indicate cooling or increased productivity at Massignano. Because impact-induced cooling processes are active on time scales of a few years at most, the estimated 100 k.y. duration of the cooling event appears to be too long to be explained by impact scenarios alone. This implies that a feedback mechanism, such as a global albedo increase due to extended snow and ice cover, may have sustained impact-induced cooling for a longer time after the impacts.

Stable oxygen isotopes of Globigerinoides ruber and biostratigraphic datums at ODP Site 165-1002

Ocean Drilling Program Site 1002 in the Cariaco Basin was drilled in the final two days of Leg 165 with only a short transit remaining to the final port of San Juan, Puerto Rico. Because of severe time constraints, cores from only the first of the three long replicate holes (Hole 1002C) were opened at sea for visual description, and the shipboard sampling was restricted to the biostratigraphic examination of core catchers. The limited sampling and general scarcity of biostratigraphic datums within the late Quaternary interval covered by this greatly expanded hemipelagic sequence resulted in a very poorly defined age model for Site 1002 as reported in the Leg 165 Initial Reports volume of the Proceedings of the Ocean Drilling Program. Here, we present for the first time a new integrated stratigraphy for Site 1002 based on the standard of late Quaternary oxygen-isotope variations linked to a suite of refined biostratigraphic datums. These new data show that the sediment sequence recovered by Leg 165 in the Cariaco Basin is continuous and spans the time interval from 0 to ~580 ka, with a basal age roughly twice as old as initially suspected from the tentative shipboard identification of a single biostratigraphic datum. Lithologic subunits recognized at Site 1002 are here tied into this new stratigraphic framework, and temporal variations in major sediment components are reported. The biogenic carbonate, opal, and organic carbon contents of sediments in the Cariaco Basin tend to be high during interglacials, whereas the terrigenous contents of the sediments increase during glacials. Glacioeustatic variations in sea level are likely to exert a dominant control on these first-order variations in lithology, with glacial surface productivity and the nutrient content of waters in the Cariaco Basin affected by shoaling glacial sill depths, and glacial terrigenous inputs affected by narrowing of the inner shelf and increased proximity of direct riverine sources during sea-level lowstands.

Stable oxygen and carbon isotope ratios of Pliocene benthic foraminifera in the Atlantic Ocean

Large changes in benthic foraminiferal delta180 and delta13C occurred during the Pliocene (between 3.0 and 2.0 Ma) at Hole 665A. Oxygen isotopic compositions increased to maximum values at 2.4 Ma, correlating with an 18O enrichment observed at Hole 552A and other locations (Shackleton et al., 1984). As at Hole 606 (Keigwin, 1986), however, maximum delta180 values at 2.4 Ma were not as great as at Hole 552A, and enrichments in delta180 also occurred before 2.4 Ma. We believe that the section representing sediments from 2.5 to 2.7 or 2.8 Ma is missing at Hole 552A because of incomplete core recovery. Consequently, the older delta180 increases are not found at Hole 552A. Benthic foraminiferal delta13C values are much lower at Hole 665A than at Hole 552A, approaching the low values observed in the Pliocene Pacific Ocean. This geographic distribution of delta13C suggests that, like late Quaternary glaciations, the equatorial Atlantic Ocean was dominated during the Pliocene by deep water that originated in the Southern Ocean and had chemical characteristics very similar to the Pacific Ocean. Reduced O2 values were probably associated with low delta13C values and contributed to increased preservation of organic carbon during enriched 180 intervals of the Pliocene equatorial Atlantic.

Analysis of Recent benthic foraminiferal assemblages from the oxygen minimum zone of the Pakistan continental margin

Live (Rose Bengal stained) and dead benthic foraminiferal communities (hard-shelled species only) from the Pakistan continental margin oxygen minimum zone (OMZ) have been studied in order to determine the relation between faunal composition and the oxygenation of bottom waters. During R.R.S. Charles Darwin Cruises 145 and 146 (12 March to May 28 2003), 11 multicores were taken on the continental margin off Karachi, Pakistan. Two transects were sampled, constituting a composite bathymetric profile from 136 m (above the OMZ in spring 2003) down to 1870 m water depth. Cores (surface area 25.5 cm2) were processed as follows: for stations situated above, and in the upper part of the OMZ, sediment slices were taken for the 0-0.5 and 0.5-1 cm intervals, and then in 1 cm intervals down to 10 cm. For the lower part of the OMZ, the second centimetre was also sliced in half-centimetre intervals. Each sample was stored in 10 % borax-buffered formalin for further processing. Onshore, the samples were wet sieved over 63 µm, 150 µm and 300 µm sieves and the residues were stained for one week in ethanol with Rose Bengal. After staining, the residue was washed again. The stained faunas were picked wet in three granulometric fractions (63-150 µm, 150-300 µm and >300 µm), down to 10 cm depth. To gain more insight into the population dynamics we investigated the dead (unstained) foraminifera in the 2-3 cm level for the fractions 150-300 µm and >300 µm. The fractions >300 µm and 150-300 µm show nearly the same faunal distribution and therefore the results are presented here for both fractions combined (i.e. the >150 µm fraction). Live foraminiferal densities show a clear maximum in the first half centimetre of the sediment; only few specimens are found down to 4 cm depth. The faunas exhibit a clear zonation across the Pakistan margin OMZ. Down to 500 m water depth, Uvigerina ex gr. U. semiornata and Bolivina aff. B. dilatata dominate the assemblages. These taxa are largely restricted to the upper cm of the sediment. They are adapted to the very low bottom-water oxygen values (ab. 0.1 ml/l in the OMZ core) and the extremely high input of organic carbon on the upper continental slope. The lower part of the OMZ is characterized by cosmopolitan faunas, containing also some taxa that in other areas have been described in deep infaunal microhabitats.

Surface sediment samples from several fore-arc basins west and southwest of the Indonesian Archipelago, analyzed by planktonic foraminifera, stable oxygen and carbon isotopic signals and opal and CaCO3 contents in bulk sediment

A total of 69 surface sediment samples from several fore-arc basins located west and southwest of the Indonesian Archipelago was analyzed with respect to the faunal composition of planktonic foraminifera, the stable oxygen and carbon isotopic signal of a surface-dwelling (Globigerinoides ruber) and a thermocline-dwelling (Neogloboquadrina dutertrei) species, and the opal and CaCO3 contents in bulk sediment. Our results show that the distribution pattern of opal in surface sediments corresponds well to the upwelling-induced chlorophyll concentration in the upper water column and thus, represents a reliable proxy for marine productivity in the coastal upwelling area off S and SW Indonesia. Present-day oceanography and marine productivity are also reflected in the tropical to subtropical and upwelling assemblages of planktonic foraminifera in the surface sediments, which in part differ from previous studies in this region probably due to different coring methods and dissolution effects. The average stable oxygen isotopic values (d18O) of G. ruber in surface sediments vary between 2.9 per mill and 3.2 per mill from basin to basin and correspond to the oceanographic settings during the SE monsoon (July-October) off west Sumatra, whereas off southern Indonesia, they reflect the NW monsoon (December-March) or annual average conditions. The d18O values of N. dutertrei show a stronger interbasinal variation between 1.6 per mill and 2.2 per mill and correspond to the upper thermocline hydrology in July-October. In addition, the difference between the shell carbon isotopic values (d13C) of G. ruber and N. dutertrei (Delta d13C) appears to be an appropriate productivity recorder only in the non-upwelling areas off west Sumatra. Consequently, joint interpretation of the isotopic values of these species is distinctive for different fore-arc basins W and SW of Indonesia and should be considered in paleoceanographic studies.

Organic geochemistry of sediment cores from the Arbian Sea

Two deep-sea sediment cores from the northeastern and the southeastern Arabian Sea were studied in order to reconstruct the palaeoenvironments of the past glacial cycles. Core 136KL was recovered from the high-productivity area off Pakistan within the modern oxygen-minimum zone (OMZ). By contrast, modern primary productivity at the site of MD900963 close to Maldives is moderate and bottom waters are today well oxygenated. For both cores, we reconstructed the changes in palaeoproductivity using a set of biomarkers (alkenones, dinosterol and brassicasterol); the main result is that primary productivity is enhanced during glacial stages and lowered during interstadials. The proxies associated with productivity show a 23 kyr cyclicity corresponding to the precession-related insolation cycle. Palaeoredox conditions were studied in both cores using a new organic geochemical parameter (C35/C31-n-alkane ratio) developed by analysing surface sediments from a transect across the OMZ off Pakistan. The value of this ratio in core 136KL shows many variations during the last 65 kyr, indicating that the OMZ was not stable during this time: it disappeared completely during Heinrich- and the Younger Dryas events, pointing to a connection between global oceanic circulation and the stability of the OMZ. The C35/C31 ratio determined in sediments of core MD900963 shows that bottom waters remained rather well oxygenated over the last 330 kyr, which is confirmed by comparison with authigenic metal concentrations in the same sediments. A zonally averaged, circulation-biogeochemical ocean model was used to explore how the intermediate Indian Ocean responds to a freshwater flux anomaly at the surface of the North Atlantic. As suggested by the geochemical time series, both the abundance of Southern Ocean Water and the oxygen concentration are significantly increased in response to this freshwater perturbation.

Sedimentology and geochemistry of Oxygen Isotope Stage 3 and Holocene sediments from Laguna Potrok Aike, Patagonia

Seismic reflection studies in the maar lake Laguna Potrok Aike (51°58? S, 70°23? W) revealed an erosional unconformity associated with a sub-aquatic lake-level terrace at a water depth of 30m. Radiocarbon-dated, multi-proxy sediment studies of a piston core from this location indicate that the sediment below this discontinuity has an age of 45kyr BP (Oxygen Isotope Stage 3), and was deposited during an interval of high lake level. In comparison to the Holocene section, geochemical indicators of this older part of the record either point towards a different sediment source or to a different transport mechanism for Oxygen Isotope Stage 3 sediments. Holocene sedimentation started again before 6790cal. yr BP, providing a sediment record of hydrological variability until the present. Geochemical and isotopic data indicate a fluctuating lake level until 5310cal. yr BP. During the late Holocene the lake level shows a receding tendency. Nevertheless, the lake level did not drop below the 30m terrace to create another unconformity. The geochemical characterization of volcanic ashes reveals evidence for previously unknown explosive activity of the Reclús and Mt. Burney volcanoes during Oxygen Isotope Stage 3.