Organic geochemistry of Upper Albian sediments from the Kirchrode I borehole

In the framework of a multidisciplinary research program, an organic geochemical study was carried out on a drill core which comprises a 245 m thick sequence of light-colored, Upper Albian marlstones that were deposited in the central part of the Lower Saxony basin (northern Germany). For part of the Upper Albian sequence, high-resolution measurements of carbonate contents reveal cycles which can be related to earth orbital forcing. Based on these data, sediment accumulation rates were calculated to be in the order of 15 g/m**2/yr. These high accumulation rates contrast with very low organic carbon contents and an extremely poor preservation of the autochthonous organic matter. Most of the sedimentary organic matter is of terrigenous origin and mainly derived from the erosion of older sedimentary rocks. Organic petrography reveals only a very small fraction of marine organic particles. Carbon/sulphur ratios, pristane/phytane ratios as well as the predominance of resedimented organic particles over autochthonous organic particles suggest that aerobic degradation processes rather than anaerobic processes (sulphate reduction) were responsible for the degradation of the organic matter. Furthermore, the scarcity of terrigenous organic particles (vitrinite) indicates that there was little vegetation on nearby land areas. To explain these analytical results, a depositional model was developed which could explain the scarcity of organic matter in the Upper Albian sediments. This model is based on downwelling of oxygen-rich, saline waters of Tethyan origin, which reduces the nutrient content of surface waters and thus primary bioproductivity while degradation of primary organic matter in the water column is enhanced at the same time. These conditions contrast to those which existed in Barremian and early Aptian times in this basin, when limited water exchange with adjacent oceans caused oxygen deficiency and the deposition of numerous organic carbon-rich black shales. The thick, organic matter-poor Upper Albian sequence of northern Germany also contrasts with comparatively thin, time-equivalent, deep-sea black shales from Italy. This discrepancy indicates that local and regional oceanographic factors (at least in this case) have a greater influence on organic matter deposition than global events.

Geochemistry of sediments from the Eastern Cape Basin

Sediment cores retrieved in the Benguela coastal upwelling system off Namibia show very distinct enrichments of solid phase barium at the sulfate/methane transition (SMT). These barium peaks represent diagenetic barite (BaSO4) fronts which form by the reaction of upwardly diffusing barium with interstitial sulfate. Calculated times needed to produce these barium enrichments indicate a formation time of about 14,000 yr. Barium spikes a few meters below the SMT were observed at one of the investigated sites (GeoB 8455). Although this sulfate-depleted zone is undersaturated with respect to barite, the dominant mineral phase of these buried barium enrichments was identified as barite by scanning electron microscopy (SEM). This is the first study which reports the occurrence/preservation of pronounced barite enrichments in sulfate-depleted sediments buried a few meters below the SMT. At site GeoB 8455 high concentrations of dissolved barium in pore water as well as barium in the solid phase were observed. Modeling the measured barium concentrations at site GeoB 8455 applying the numerical model CoTReM reveals that the dissolution rate of barite directly below the SMT is about one order of magnitude higher than at the barium enrichments deeper in the sediment core. This indicates that the dissolution of barite at these deeper buried fronts must be retarded. Thus, the occurrence of the enrichments in solid phase barium at site GeoB 8455 could be explained by decreased dissolution rates of barite due to the changes in the concentration of barite in the sediment, as well as changes in the saturation state of fluids. Furthermore, the alteration of barite into witherite (BaCO3) via the transient phase barium sulfide could lead to the preservation of a former barite front as BaCO3. The calculations and modeling indicate that a relocation of the barite front to a shallower depth occurred between the last glacial maxium (LGM) and the Pleistocene/Holocene transition. We suggest that an upward shift of the SMT occurred at that time, most likely as a result of an increase in the methanogenesis rates due to the burial of high amounts of organic matter below the SMT.

Sedimentology of ODP sites in the Cape Basin, southeast Atlantic Ocean

Middle/late Miocene to early Pliocene sedimentary sequences along the continental margin of southwest Africa have changes that correspond to the carbonate crash (12-9 Ma) and biogenic bloom events (~7-4 Ma) described in the equatorial Pacific by Farrell et al. (1995, doi:10.2973/odp.proc.sr.138.143.1995). To explore the origins of these changes, we analyzed the carbon and coarse fraction contents of sediments from ODP Sites 1085, 1086, and 1087 at a time resolution of 5 to 30 kyr. Several major drops in CaCO3 concentration between 12 and 9 Ma are caused by dilution from major increases in clastic input from the Oranje River during global sea level regressions. Abundant pyrite crystals and good preservation of fish debris reflect low oxygenation of bottom/pore waters. Regional productivity was enhanced during the time equivalent to the carbonate crash period. Higher benthic/planktic foraminiferal ratios indicate that CaCO3 dissolution at Site 1085 peaked between 9 to 7 Ma, which was after the global carbonate crash. This period of enhanced dissolution suggests that Site 1085 was located within a low-oxygen water mass that dissolved CaCO3 more easily than North Atlantic Deep Water, which began to bathe this site at 7 Ma. At 7 to 6 Ma, the onset of the biogenic bloom, increases and variations in total organic carbon and benthic foraminiferal accumulation rates show that paleoproductivity increased significantly above values observed during the carbonate crash period and fluctuated widely. We attribute the late Miocene paleoproductivity increase off southwest Africa to ocean-wide increases in nutrient supply and delivery.

Siliceous microplankton in surface sediments and the water column of the Red Sea

We studied the siliceous microplankton assemblages (mainly diatoms) from plankton tows (mesh size 20 µm) and surface sediment samples collected along a N-S transect in the northern Red Sea (28-21°N). In addition, we analyzed differences/similarities between plankton and sediment assemblages within a brine-filled basin (the southern basin) of the Shaban Deep and compared these assemblages with those from outside the brine. Plankton samples revealed the overwhelming dominance of diatoms over other siliceous groups. Diatoms accounted for ca. 97% of all biosiliceous particles at 120-20 m (vs. 2.9% silicoflagellates and 0.4% radiolarians), and ca. 94% at 200-120 m (vs. 4.5% silicoflagellates and 1.6% radiolarians). In general, a marine, warm-water (tropical/subtropical) diatom assemblage characterizes the plankton samples. Representatives of the Nitzschia bicapitata group are by far the most abundant contributors at both depth intervals (average=43%), ranging from ca. 30% in the North to ca. 60% in the South. Biogenic opal content in non-brine surface sediments is very low, (below 0.2 wt.% SiO2); and concentration of siliceous microorganisms is also low and of the order of 5*10**3-10**4 microorganisms/g dry sediment. Diatoms are the main contributors to the opal signal in the 20-40 µm fraction, while they share dominance with radiolarians in the >40 µm fraction. Total diatom concentrations average 1.2*10**4 valves/g in the 20-40 µm fraction and 4*10**3 valves/g in the >40 µm fraction. Robust taxa of warm water affinity (Alveus marinus, Azpeitia neocrenulata, Azpeitia nodulifera and Roperia tesselata) characterize the surface sediments. In contrast, biogenic opal content in brine surface sediment samples is much higher than in the non-brine samples, ranging from 2.8 to 3.8 wt.% SiO2, and concentration of siliceous microorganisms is 3-4 orders of magnitude higher. In addition here, diatoms dominate the opal signal. The taxa found in these samples are a mixture of non-brine and plankton samples, and fragile forms (e.g., N. bicapitata group, Neodelphineis indica) are well preserved in these sediments. Thus, brine sediments in this region seem to offer a great potential for palaeoenvironmental studies.

Geochemical analysis of sediments from three coring sites in the Mediterranean

In a gravity core from the eastern Mediterranean Sea, a chemically and mineralogically distinct, 5.5-cm-thick layer is present above sapropel S-1 and overlain by hemipelagic marls. Calcite is completely absent in this exotic layer, dolomite is present only in small amounts, and the Cr concentrations are significantly enhanced. The layer was deposited primarily under reducing conditions, but the distributions of redox-sensitive elements show that a large part of the exotic layer is now oxidised by a downward-progressing oxidation front. Sediments from within the nearby anoxic, hypersaline Urania Basin are similar to those from the exotic layer, in particular in S-, C-, and O-isotope distributions of pyrite and dolomite, as well as increased Cr concentrations. Mud expulsion due to expansion of gas-rich mud is proposed to explain the presence of the exotic layer outside the Urania Basin. The deposition of an anoxic layer above S-1 shielded the sapropel from oxidation which resulted in the rare occurrence of a complete preservation of S-1 and provides the first minimum age for the start of anoxic mud accumulation in the Urania Basin.

Low-temperature experiments of sediment core GeoB6229-6 at the South American continental margin off the Rio de la Plata estuary

With various low-temperature experiments performed on magnetic mineral extracts of marine sedimentary deposits from the Argentine continental slope near the Rio de la Plata estuary, a so far unreported style of partial magnetic self-reversal has been detected. In these sediments the sulphate-methane transition (SMT) zone is situated at depths between 4 and 8 m, where reductive diagenesis severely alters the magnetic mineral assemblage. Throughout the sediment column magnetite and ilmenite are present together with titanomagnetite and titanohematite of varying compositions. In the SMT zone (titano-)magnetite only occurs as inclusions in a siliceous matrix and as intergrowths with lamellar ilmenite and titanium-rich titanohematite, originating from high temperature deuteric oxidation within the volcanic host rocks. These abundant structures were visualized by scanning electron microscopy and analysed by energy dispersive spectroscopy. Warming of field-cooled and zero-field-cooled low-temperature saturation remanence displays magnetic phase transitions of titanium-rich titanohematite below 50 K and the Verwey transition of magnetite. A prominent irreversible decline characterizes zero-field cooling of room temperature saturation remanence. It typically sets out at ~210 K and is most clearly developed in the lower part of the SMT zone, where low-temperature hysteresis measurements identified ~210 K as the blocking temperature range of a titanohematite phase with a Curie temperature of around 240 K. The mechanism responsible for the marked loss of remanence is, therefore, sought in partial magnetic self-reversal by magnetostatic interaction of (titano-)magnetite and titanohematite. When titanohematite becomes ferrimagnetic upon cooling, its spontaneous magnetic moments order antiparallel to the (titano-)magnetite remanence causing an drastic initial decrease of global magnetization. The loss of remanence during subsequent further cooling appears to result from two combined effects (1) magnetic interaction between the two phases by which the (titano-)magnetite domain structure is substantially modified and (2) low-temperature demagnetization of (titano-)magnetite due to decreasing magnetocrystalline anisotropy. The depletion of titanomagnetite and superior preservation of titanohematite is characteristic for strongly reducing sedimentary environments. Typical residuals of magnetic mineral assemblages derived from basaltic volcanics will be intergrowths of titanohematite lamellae with titanomagnetite relics. Low-temperature remanence cycling is, therefore, proposed as a diagnostic method to magnetically characterize such alteration (palaeo-)environments.

(Table 2) Taxonomic composition of diatoms in dredged samples from the island-side slope of the Kuril-Kamchatka Trench

Studies of diatoms from dredge samples collected on the island slope of the Kuril-Kamchatka Trench have allowed to recognize well-preserved marine diatom assemblages corresponding to assemblages of the followed Oligocene zones: Rhizosolenia oligocaenica (subzone ''a'', 33.6-31 Ma), Cavitatus rectus (29.6-28.2 Ma), and Rocella gelida (28.2-24.0 Ma) as identified in the North Pacific zonal scale. Description of these assemblages and their complete taxonomic composition are presented. Diversity of species together with abundance and degree of preservation of diatoms and accompanying siliceous microorganisms suggests their autochtonous origin and favorable conditions of their development. Assemblages of the Early Oligocene zones Rhizosolenia oligocaenica and Cavitatus rectus recognized in sediments of the outer zone of the Lesser Kuril Ridge (submarine slope of the Shikotan Island) and on the Vityaz' submarine ridge were most probably formed under conditions of a vast shelf, while assemblage of the Late Oligocene zone Rocella gelida encountered only in the region of the Lesser Kuril Ridge formed under more deep-water conditions, presumably, over an island slope. Deepening of the basin in the region of the outer zone of the Lesser Kuril Ridge in Late Oligocene probably reflects one of stages of evolution of the Kuril-Kamchatka Trench.

Benthic foraminifers in Mesozoic and Cenozoic sediments of the southwestern Atlantic

Benthic foraminiferal assemblages in Mesozoic and Cenozoic sediments were studied at Sites 511, 512, 513, and 514 drilled during Leg 71 in the southwestern Atlantic on the Maurice Ewing Bank and in the Argentine Basin. Benthic foraminifers in almost all stratigraphic subdivisions of Sites 511 and 512 reflect the gradual subsidence of the Falkland Plateau from shelf depths in the Barremian-Albian, when a semiclosed basin with restricted circulation of water masses and anaerobic conditions existed, to lower bathyal depths in the Late Cretaceous and Cenozoic, with an abrupt acceleration at the boundary of Lower and Upper Cretaceous. The composition, distribution, and preservation of Late Cretaceous assemblages of benthic foraminifers suggest considerable fluctuations of the foraminiferal lysocline and the CCD. This is evidenced by dissolution facies and foraminiferal assemblages in which agglutinated and resistant calcareous forms predominated during high stands of the CCD and by calcareous facies in which rich assemblages of calcareous species predominated during low stands. The highest position of the CCD on the Plateau (less than 1500-2000 m) was in the late Cenomanian, Turonian, and Coniacian. In the Santonian and Campanian the CCD was at depths below 1500-2000 meters. At the end of the Campanian the CCD shifted again to depths comparable with those of Cenomanian and Turonian time. In the latest Campanian and the Maestrichtian the CCD was low and nanno-foraminiferal oozes with a rich assemblage of benthic foraminifers accumulated. Foraminiferal assemblages at Sites 513 and 514 in the Argentine Basin also testify to oceanic subsidence from lower bathyal depths in the Oligocene to abyssal ones at present. This process was complicated by the influence of geographical migrations of the Polar Front caused by extensions of the ice sheet in the Antarctic after the opening of the Drake Passage during the Oligocene. In Mesozoic and Cenozoic deposits of the Falkland Plateau and the Argentine Basin seven assemblages of benthic foraminifers were distinguished by age: early-middle Albian, middle-late Albian, Late Cretaceous (including four groups), middle Eocene, late Eocene-early Miocene, middle-late Miocene, and Pliocene-Quaternary. The Albian assemblages contain many species common to the foraminiferal fauna of the Austral Biogeographical Province. The Late Cretaceous assemblage contains, along with Austral species, species common to foraminifers of North America, Western Europe, the Russian platform, and the south of the U.S.S.R. Deep-sea cosmopolitan species prevail in Cenozoic assemblages.

Silt grain-size analysis of ODP holes from the western equatorial Atlantic

Grain-size records of the terrigenous and calcareous silt fraction, preservation of planktic foraminifera, and benthic foraminiferal stable-isotope data (delta13C, delta18O values of C. wuellerstorfi) at ODP Site 927 on the Ceará Rise (5°27.7'N, 44°28.8'W), are used to reconstruct variations in the history of bottom current strength, ventilation, and carbonate corrosiveness of deep waters during the time interval from 0.8 to 0.3 Ma. Glacial periods are characterized by generally smaller mean sizes of the terrigenous sortable silt fraction (mean(SS)), lower delta13C values, and poorer preservation of planktic foraminifera compared to interglacials. This indicates lower bottom current speeds, larger nutrient contents and more corrosive deep water. By contrast, larger mean(SS) sizes, higher delta13C values, and well preserved planktic foraminifera indicate strong circulation and a well ventilated deep-water mass during interglacials. The observed changes are most likely related to the weakening and strengthening of circulation of Lower North Atlantic Deep Water (LNADW). Cross-spectral analysis between the mean(SS) and benthic delta18O records reveals that minima in mean(SS) occur about 7.6 k.y. after the maximum in ice volume. This indicates a considerable lag time between ice-shield induced changes in LNADW production and subsequent changes in the velocity of LNADW flow in the western equatorial Atlantic. Striking changes in bottom current speed occur regularly during glacial to interglacial transitions. Extremely fine mean(SS) minima point to an almost complete shutdown of bottom current vigor in response to a cessation of LNADW production caused by an enhanced melt water release during the initial phases of deglaciation. However, each of the fine minima extremes is followed by a rapid shift to very high mean(SS) values that indicate strong bottom currents, and hence, vigorous LNADW flow during the early interglacials. After the onset of glacial Stage 12, generally poorer carbonate preservation and higher variability is registered. This coincides with a global decrease in carbonate preservation during the mid-Brunhes (mid-Brunhes dissolution event). Detailed grain-size analysis of the calcareous fine fraction (<63 µm) revealed a considerable reduction of particles in the fraction from 7 to 63 µm during periods of enhanced dissolution. This indicates a preferential dissolution of larger planktic foraminiferal fragments which leads to an enrichment of coccoliths in the calcareous fine fraction.

Radiolarians of the Celebes Sea

Two sites were drilled in the Celebes Sea as part of Ocean Drilling Program Leg 124; Site 767 and Site 770. Radiolarians are preserved in Paleogene pelagic claystones with minor occurrences in certain Neogene successions. The brown clays that immediately overlie basalt at both sites contain radiolarians of the late middle Eocene Podocyrtis chalara Zone. Late Eocene radiolarians are not found, due to dissolution and probable hiatus. The Oligocene is represented by the Theocyrtis tuberosa and Dorcadospyris ateuchus Zones. Oligocene sediments are strongly dominated by abundant and diverse radiolarians of the TristylospyrislDorcadospyris lineage. Preservation of Paleogene radiolarian assemblages ranges from good to very poor. Late Miocene radiolarians of the Didymocyrtis antepenultima Zone are found only in Site 770. Other Neogene sediments are barren of radiolarian remains, with the exception of latest Pleistocene and Holocene sediments.

Viral decay and production in sediments of the Mediterranean Sea

Here, for the first time, we have carried out synoptic measurements of viral production and decay rates in continental-shelf and deep-sea sediments of the Mediterranean Sea to explore the viral balance. The net viral production and decay rates were significantly correlated, and were also related to prokaryotic heterotrophic production. The addition of enzymes increased the decay rates in the surface sediments, but not in the subsurface sediments. Both the viral production and the decay rates decreased significantly in the deeper sediment layers, while the virus-to-prokaryote abundance ratio increased, suggesting a high preservation of viruses in the subsurface sediments. Viral decay did not balance viral production at any of the sites investigated, accounting on average for c. 32% of the gross viral production in the marine sediments. We estimate that the carbon (C) released by viral decay contributed 6-23% to the total C released by the viral shunt. Because only ca. 2% of the viruses produced can infect other prokaryotes, the majority is not subjected to direct lysis and potentially remains as a food source for benthic consumers. The results reported here suggest that viral decay can play an important role in biogeochemical cycles and benthic trophodynamics.