Rare earth and other element contents in surface layer bottom sediments and ferromanganese nodules along the Transatlantic profile

Behavior of rare earth elements (REE) and Th is studied along the Transatlantic transect at 22°N. It is shown that both REE and Th contents relative to Al (the most lithogenic element) increase toward the pelagic region. The increasing trend becomes more complicated due to variations in content of biogenic calcium carbonate that acts as a diluting component in sediments. REE composition varies symmetrically relative to the Mid-Atlantic Ridge (MAR) emphasizing weak hydrothermal influence on sediments of the ridge axis, although the well-known criteria for hydrothermal contribution, such as Al/(Al+Mn+Fe) and (Fe+Mn)/Ti, do not reach critical values. Variations in REE content and composition allowed to distinguish the following five sediment zones in the transect: (I) terrigenous sediments of the Nares abyssal plain; (II) pelagic sediments of the North American Basin; (III) carbonate ooze of the MAR axis; (IV) pelagic sediments of the Canary Basin; and (V) terrigenous clay and calcareous mud of the African continental slope and slope base. Ferromanganese nodules of the hydrogenous type with extremely high Ce (up to 1801 ppm) and Th (up to 138 ppm) contents occur in pelagic sediments. It is ascertained that P, REE, and Th contents depend on Fe content in Atlantic sediments. Therefore, one can suggest that only minor amount of phosphorus is bound with bone debris. Low concentration of bone debris phosphorus is a result of relatively high sedimentation rates in the Atlantic Ocean, as compared with those in pelagic regions of the Pacific Ocean.

Ba, Al and SO4 concentrations in sediments and pore fluid of ODP Leg 127/128 samples

The barium distribution in sediments and pore fluids from five sites drilled in the Japan Sea have been used to illustrate the geochemical behavior of this element as it pertains paleoproductivity reconstructions, diagenetic remobilization, and barite precipitation in authigenic fronts. Sites where sulfate is depleted in the pore fluids also show high concentrations of dissolved barium, reflecting dissolution of biogenic barite. The high rate of sedimentation at Sites 798 and 799 results in a rapid sulfate depletion, which in turn leads to barite dissolution and reprecipitation in diagenetic fronts. The dissolved barium distribution at these sites has been used to quantify the rate of barite dissolution; we estimate a first-order rate constant for barite dissolution to be 2*10**-6/s at Site 799 and 2*10**-7/s at Site 798. Authigenic barite has been documented in sediments from Site 799 at 323 meters below seafloor by scanning electron microscopy and X-ray fluorescence analysis. These results indicate barite precipitation in a diagenetic front near the zone of sulfate depletion by upward migration of dissolved barium and downward diffusion of sulfate. Barite precipitation has also been inferred at Sites 796 and 798 based on sedimentary and dissolved barium distributions. Sulfate is not depleted in the pore fluids of Site 794. The lack of diagenetic remobilization of biogenic barium at this site preserves the high barium signal associated with the high-productivity sequences deposited during the late Miocene to Pliocene. Significantly, the organic carbon distribution does not indicate high accumulation rates during the periods of high opal and barium deposition. Instead, higher organic carbon accumulations are recorded in the Quaternary and middle Miocene sequences; intervals that are also characterized by deposition of siliciclastic turbidites. The presence of a terrestrial component in the organic carbon record renders barium a more useful indicator than organic carbon for paleoproductivity reconstructions in this marginal sea.

Age and strontium isotope composition for Cretaceous in DSDP Hole 74-525

Firm stratigraphic correlations are needed to evaluate the global significance of unconformity bounded units (sequences). We correlate the well-developed uppermost Campanian and Maestrichtian sequences of the New Jersey Coastal Plain to the geomagnetic polarity time scale (GPTS) by integrating Sr-isotopic stratigraphy and biostratigraphy. To do this, we developed a Maestrichtian (ca. 73-65 Ma) Sr-isotopic reference section at Deep Sea Drilling Project Hole 525A in the southeastern Atlantic Ocean. Maestrichtian strata can then be dated by measuring their 87Sr/86Sr composition, calibrating to the GPTS of S. C. Cande and D. V. Kent (1993, personal commun.), and using the equation Age (Ma) = 37326.894-52639.89 (87Sr/86Sr). Sr-stratigraphic resolution for the Maestrichtian is estimated as +-1.2 to +-2 m.y. At least two unconformity-bounded units comprise the uppermost Campanian to Maestrichtian strata in New Jersey. The lower one, the Marshalltown sequence, is assigned to calcareous nannofossil Zones CC20/21 (~NC19) and CC22b (~NC20). It ranges in age from ~74.1 to 69.9 Ma based on Sr-isotope age estimates. The overlying Navesink sequence is assigned to calcareous nannoplankton Zones CC25-26 (~NC21-23); it ranges in age from 69.3 to 65 Ma based on Sr-isotope age estimates. The upper part of this sequence, the Tinton Formation, has no calcareous planktonic control; Sr-isotopes provide an age estimate of 66 +- 1.2 Ma (latest Maestrichtian). Sequence boundaries at the base and the top of the Marshalltown sequence match boundaries elsewhere in the Atlantic Coastal Plain (Owens and Gohn, 1985) and the inferred global sea-level record of Haq et al. (1987); they support eustatic changes as the mechanism controlling depositional history of this sequence. However, the latest Maestrichtian record in New Jersey does not agree with Haq et al. (1987); we attribute this to correlation and time-scale differences near the Cretaceous/Paleogene boundary. High sedimentation rates in the latest Maestrichtian of New Jersey (Shrewsbury Member of the Red Bank Formation and the Tinton Formation) suggest tectonic uplift and/or rapid progradation during deposition of the highstand systems tract.

Benthic foraminifera of surface sediments from the continental slope off Sierra Leone, North-West Africa

On "Meteor" cruise 30 (1973) 22 piston-cores were collected off Sierra Leone from water-depths between about 5000 m (Sierra Leone Basin) and 500 m (upper continental slope) with the objective to study the sediment composition and age as well as processes of sedimentation on the continental slope in a tropical humid region. Granulometric analysis and determinations of the carbonate contents of the sediment samples were carried out, as well as qualitative and quantitative analysis of the components of the grain size fractions > 63 µm and of the planktonic and benthonic foraminifera > 160 µm. Presently, the cold Canary Current influences the composition of the planktonic foraminifera within the northwestern area of investigation (profile A), whereas the planktonic fauna of the eastern area (profile C) seems to be truly tropical. In all Quaternary sediments from the continental slope off Sierra Leone, species of Globorotalia are less abundant than in truly pelagic sediments. For that reason, the zonation of the Pleistocene sediments based on the presence or absence of Globorotalia cultrata does not always agree with the climatic changes reflected in the sediments. Concerning past climates better results can be obtained by using the changes in percentage abundances of Globigerina sp. sp. and Globigerinoides sp. sp. as indicators for cool and warm temperatures. The Tertiary sediments contain a pelagic foraminiferal assemblage. In the Holocene sediments the benthonic foraminifera do not only serve as good paleodepth indicators, but their communities are also restricted to defined water masses, which change their positions in accordance with climatic changes. Thus, Cassidulina carinata in the area of investigation is an excellent indicator for sediments deposited during times, which were cooler than today; this is true for all cores from the continental slope off Sierra Leone independent of water-depth although this species presently abounds at water-depths around 600 m. The cores from the continental rise and from the Sierra Leone Basin (M30-261, M30-146, M30-147) were deposited below the calcium carbonate compensation depth. Only small sections of the cores consist of the original carbonate-free sediments, whereas the main part of the sediment column is redeposited material, rich in foraminifera, which normally live on the upper continental slope, or even on the shelf. From these cores only M30-261 can be subdivided into biostratigraphic zones ranging from zone V to zone Y. In all cores from the middle and upper continental slope of the eastern area of investigation (profile C; KL 230, 209-204) and in cores KL 183 and KL 184 from the northwestern area (profile A) we observed an undisturbed succession of sediments from the biostratigraphic zones X (partly), Y and Z. All cores from the central area (M30-181, M30-182, M30-262 to 264) and M30-187 from the upper slope of profile A show variable hiatuses in the sedimentary record. Locally, high velocity bottom currents were probably responsible for erosion, nondeposition or minimal sedimentation rates. These currents might have been initiated partly by the somewhat exposed position of this part of the continental slope, where the shelf edge bends from a northwest towards an eastern direction, and partly by very young tectonic movements. Fracture zones with vertically displaced fault blocs are frequent at Sierra Leone continental margin. According to seismic measurements by McMaster et al. (1975) the sites of the central area are located on an uplifted fault bloc explaining the reduced sediment rates or erosion. Unlike the central area, the eastern area (profile C) is situated on a downfaulted bloc with high sediment rates. The sediments from the cores of profile B as well as the turbiditic deep-sea sediments were deposited under a higher flow regime; therefore they are coarser than the extremely fine-grained sediments of the cores from profile C. Since the sand fraction (> 63 µm) is mainly composed of foraminifera, besides pteropods and light-colored fecal pellets, the carbonate content increases with the increasing percentage of the coarse grain fraction. Higher concentrations of quartz were only observed in core sections with considerable carbonate dissolution (mainly in the X-Zone), and, in general, in all sediments from the eastern area with higher terrigenous input including larger concentration of mica. Especially during times transitional between glacials and interglacials (or interstadials) the bottom currents were intensified. The percentages of coarse fraction and carbonate increase with increasing current velocities. Calcium carbonate dissolution becomes important in water depths > 3500 m. During cooler times the lysokline is depressed. Light-colored fecal pellets were redeposited from Late Neogene sediments (M30-187, M30-181). In the area of investigation they occur in the Holocene and mainly the Pleistocene sediments of the cores from the northwestern and central area because only here Tertiary sediments have been eroded at the uppermost continental slope. In the central area there are at least two periods of non-sedimentation and/or erosion which can be confined as being (1) not older than middle Pliocene and not younger than zone V and (2) younger than zone W. The local character of the erosion is documented by the fact that a complete Late Quaternary section is present in the cores of the northwestern and eastern area, each within less than 100 km from incomplete cores from the central area.

Geochemical composition of surface sediments in the Trondheimsfjord, central Norway

High sedimentation rates in fjords provide excellent possibilities for high resolution sedimentary and geochemical records over the Holocene. As a baseline for an improved interpretation of geochemical data from fjord sediment cores, this study aims to investigate the inorganic/organic geochemistry of surface sediments and to identify geochemical proxies for terrestrial input and river discharge in the Trondheimsfjord, central Norway. Sixty evenly distributed surface sediment samples were analysed for their elemental composition, total organic carbon (Corg), nitrogen (Norg) and organic carbon stable isotopes (d13Corg), bulk mineral composition and grain size distribution. Our results indicate carbonate marine productivity to be the main CaCO3 source. Also, a strong decreasing gradient of marine-derived organic matter from the entrance towards the fjord inner part is consistent with modern primary production data. We show that the origin of the organic matter as well as the distribution of CaCO3 in Trondheimsfjord sediments can be used as a proxy for the variable inflow of Atlantic water and changes in river runoff. Furthermore, the comparison of grain size independent Al-based trace element ratios with geochemical analysis from terrigenous sediments and bedrocks provides evidence that the distribution of K/Al, Ni/Al and K/Ni in the fjord sediments reflect regional sources of K and Ni in the northern and southern drainage basin of the Trondheimsfjord. Applying these findings to temporally well-constrained sediment records will provide important insights into both the palaeoenvironmental changes of the hinterland and the palaeoceanographic modifications in the Norwegian Sea as response to rapid climate changes and associated feedback mechanisms.

Miocene strontium isotope record of DSDP Hole 30-289

A composite strontium isotopic seawater curve was constructed for the Miocene between 24 and 6 Ma by combining 87Sr/86Sr measurements of planktonic foraminifera from Deep Sea Drilling Project sites 289 and 588. Site 289, with its virtually continuous sedimentary record and high sedimentation rates (26 m/m.y.), was used for constructing the Oligocene to mid-Miocene part of the record, which included the calibration of 63 biostratigraphic datums to the Sr seawater curve using the timescale of Cande and Kent (1992 doi:10.1029/92JB01202). Across the Oligocene/Miocene boundary, a brief plateau occurred in the Sr seawater curve (87Sr/86Sr values averaged 0.70824) which is coincident with a carbon isotopic maximum (CM-O/M) from 24.3 to 22.6 Ma. During the early Miocene, the strontium isotopic curve was marked by a steep rise in 87Sr/86Sr that included a break in slope near 19 Ma. The rate of growth was about 60 ppm/m.y. between 22.5 and 19.0 Ma and increased to over 80 ppm/m.y. between 19.0 and 16 Ma. Beginning at ~16 Ma (between carbon isotopic maxima CM3 and CM4 of Woodruff and Savin (1991 doi:10.1029/91PA02561)), the rate of 87Sr/86Sr growth slowed and 87Sr/86Sr values were near constant from 15 to 13 Ma. After 13 Ma, growth in 87Sr/86Sr resumed and continued until ~9 Ma, when the rate of 87Sr/86Sr growth decreased to zero once again. The entire Miocene seawater curve can be described by a high-order function, and the first derivative (d87Sr/86Sr/dt) of this function reveals two periods of increased slope. The greatest rate of 87Sr/86Sr change occurred during the early Miocene between ~20 and 16 Ma, and a smaller, but distinct, period of increased slope also occurred during the late Miocene between ~12 and 9 Ma. These periods of steepened slope coincide with major phases of uplift and denudation of the Himalayan-Tibetan Plateau region, supporting previous interpretations that the primary control on seawater 87Sr/86Sr during the Miocene was related to the collision of India and Asia. The rapid increase in 87Sr/86Sr values during the early Miocene from 20 to 16 Ma imply high rates of chemical weathering and dissolved riverine fluxes to the oceans. In the absence of another source of CO2, these high rates of chemical weathering should have quickly resulted in a drawdown of atmospheric CO2 and climatic cooling through a reversed greenhouse effect. The paleoclimatic record, however, indicates a warming trend during the early Miocene, culminating in a climatic optimum between 17 and 14.5 Ma. We suggest that the high rates of chemical erosion and warm temperatures during the climatic optimum were caused by an increase in the contribution of volcanic CO2 from the eruption of the Columbia River Flood Basalts (CRFB) between 17 and 15 Ma. The decrease in the rate of CRFB eruptions at 15 Ma and the removal of atmospheric carbon dioxide by increased organic carbon burial in Monterey deposits eventually led to cooling and increased glaciation between ~14.5 and 13 Ma. The CRFB hypothesis helps to explain the significant time lag between the onset of increased rates of organic carbon burial in the Monterey at 17.5 Ma (as marked by increased delta13C values) and the climatic cooling and glaciation during the middle Miocene (as marked by the increase in delta18O values), which did not begin until ~14.5 Ma.

Sedimentation patters in the eastern equatorial Pacific Ocean

The post-middle Miocene evolution of sedimentary patterns in the eastern equatorial Pacific Ocean has been deduced from a compilation and synthesis of CaCO3, opal, and nannofossil assemblage data from 11 sites drilled during Leg 138. Improvements in stratigraphic correlation and time scale development enabled the construction of lithostratigraphic and chronostratigraphic frameworks of exceptional quality. These frameworks, and the high sedimentation rates (often exceeding 4 cm/k.y.) provided a detailed and synoptic paleoceanographic view of a large and highly productive region. The three highlights that emerge are: (1) a middle late Miocene "carbonate crash" (Lyle et al., this volume); (2) a late Miocene-early Pliocene "biogenic bloom"; and (3) an early Pliocene "opal shift". During the carbonate crash, an interval of dissolution extending from -11.2 to 7.5 Ma, CaCO3 accumulation rates declined to near zero over much of the eastern equatorial Pacific, whereas opal accumulation rates remained substantially unchanged. The crash nadir, near 9.5 Ma, was marked by a brief shoaling of the regional carbonate compensation depth by more than 1400 m. The carbonate crash has been correlated over the entire tropical Pacific Ocean, and has been attributed to tectonically-induced changes in abyssal flow through the Panamanian seaway. The biogenic bloom extended from 6.7 to 4.5 Ma, and was characterized by an overall increase in biogenic accumulation and by a steepening of the latitudinal accumulation gradient toward the equator. The bloom has been observed over a large portion of the global ocean and has been linked to increased productivity. The final highlight, is a distinct and permanent shift in the locus of maximum opal mass accumulation rate at 4.4 Ma. This shift was temporally, and perhaps causally, linked to the final closure of the Panamanian seaway. Before 4.4 Ma, opal accumulation was greatest in the eastern equatorial Pacific Basin (near 0°N, 107°W). Since then, the highest opal fluxes in the equatorial Pacific have occurred in the Galapagos region (near 3°S, 92°W).

Calcareous nannofossils of ODP sites 177-1088 and 177-1090

During ODP Leg 177, a Miocene to Pliocene calcareous nannofossil record was recovered at Sites 1088 and 1090. Site 1088, located at 41°8'S, shows a continuous middle-upper Miocene to Pliocene carbonate sequence that was deposited at relatively high sedimentation rates (Shipboard Scientific Party, 1999a, doi:10.2973/odp.proc.ir.177.103.1999). Moreover, Site 1088 proved suitable for calcareous nannofossil analysis as a means to improve the biostratigraphy at this southern latitude. Site 1090 was drilled at 42°54'S; a tephra layer marks a significant disconformity at the Miocene/Pliocene boundary of this sequence (Shipboard Scientific Party, 1999b, doi:10.2973/odp.proc.ir.177.105.1999). Although nannofossil assemblages are poorly preserved at this site (Shipboard Scientific Party, 1999b), they may help in determining the age of the disconformity and its paleoceanographic significance.

Depth and ages of calcareous nannofossil events from ODP Leg 184 sites, South China Sea

Sites 1146 and 1148 of Ocean Drilling Program Leg 184, in the South China Sea (SCS), comprise long sediment sections with a time span from the early Oligocene to the Pleistocene. Calcareous nannofossils from these two sites were biostratigraphically studied. We recognized 53 early Oligocene to Pleistocene events that are commonly found in open sea areas and can therefore be correlated within a large geographic range. This study also revealed that a few conventionally used nannofossil events are not suitable for the SCS, and further evaluation is needed. The lower Oligocene to Pleistocene sequences recovered at Sites 1146 and 1148 were subdivided into the 4 Paleogene zones and 21 Neogene to Quaternary zones of Martini, in correlation with the Paleogene to Quaternary zones of Okada and Bukry. This provided a lower Oligocene through Pleistocene nannofossil biostratigraphic framework. A significant unconformity was recognized in the Oligocene-Miocene transition, in which the upper part of Oligocene Zone NP25 and lower part of Miocene Zone NN1 were missing. The time span of the unconformity was estimated to be ~1 m.y. Very high sedimentation rates were seen in the Oligocene, relative low values were seen in the Miocene, and the highest values were seen in the Pleistocene, which was believed to be the result of tectonic and sedimentation history of the SCS.

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.

Barium intensities and tie points between holes of Leg 208

The Paleocene - Eocene thermal maximum (PETM) is one of the best known examples of a transient climate perturbation, associated with a brief, but intense, interval of global warming and a massive perturbation of the global carbon cycle from injection of isotopically light carbon into the ocean-atmosphere system. One key to quantifying the mass of carbon released, identifying the source(s), and understanding the ultimate fate of this carbon is to develop high-resolution age models. Two independent strategies have been employed, cycle stratigraphy and analysis of extraterrestrial Helium (HeET), both of which were first tested on Ocean Drilling Program (ODP) Site 690. Both methods are in agreement for the onset of the PETM and initial recovery, or the clay layer ("main body"), but seem to differ in the final recovery phase of the event above the clay layer, where the carbonate contents rise and carbon isotope values return toward background values. Here we present a state-of-the-art age model for the PETM derived from a new orbital chronology developed with cycle stratigraphic records from sites drilled during ODP Leg 208 (Walvis Ridge, Southeastern Atlantic) integrated with published records from Site 690 (Weddell Sea, Southern Ocean, ODP Leg 113). During Leg 208, five Paleocene - Eocene (P-E) boundary sections (Sites 1262 to 1267) were recovered in multiple holes over a depth transect of more than 2200 m at the Walvis Ridge yielding the first stratigraphically complete P-E deep-sea sequence with moderate to relatively high sedimentation rates (1 to 3 cm/kyr). A detailed chronology was developed with non-destructive X-ray fluorescence (XRF) core scanning records on the scale of precession cycles, with a total duration of the PETM now estimated to be ~ 170 kyr. The revised cycle stratigraphic record confirms original estimates for the duration of the onset and initial recovery, but suggests a new duration for the final recovery that is intermediate to the previous estimates by cycle stratigraphy and HeET.

Age model and sediment description of DSDP Hole 90-594, Chatham Ridge east of New Zealand

Detailed sedimentological investigations were performed on sediments from DSDP-Site 594 (Chatham Rise, east of New Zealand) in order to reconstruct the evolution of paleoclimate and paleoceanographic conditions in the Southwest Pacific during the last 6 million years. The results can be summarized as follows: (1) High accumulation rates of biogenic opal and carbonate and the dominance of smectites in the clay fraction suggest increased oceanic productivity and an equable dominantly humid climate during the late Miocene. (2) During Pliocene times, decreasing contents of smectites and increasing feldspar/quartz ratios point to an aridification in the source area of the terrigenous sediments, culmunating near 2.5 Ma. At that time, accumulation rates of terrigenous components distinctly increased probably caused by increased sediment supply due to intensified atmospheric and oceanic circulation, lowered sea level, and decreased vegetation cover. (3) A hiatus (1.45 to 0.73 Ma) suggests intensified intermediate-water circulation. (4) Major glacial/interglacial cycles characterize the upper 0.73 Ma. During glacial times, oceanic productivity and terrigenous sediment supply was distinctly increased because of intensified atmospheric and oceanic circulations and lowered sea level, whereas during interglacials productivity and terrigenous sediment supply were reduced. (5) An increased content of amphibols in the sediments of Site 594 indicates increased volcanic activities during the last 4.25 Ma.

Pleistocene and upper Pliocene sapropels in the Tyrrhenian Sea, Mediterranean Sea

A most significant finding of the ODP Leg 107 drilling campaign was the recovery of at least 56 distinct sapropel intervals in upper Pliocene to Pleistocene sediments of six sites drilled in the Tyrrhenian Sea. Except for 3 repots of disturbed organic-rich sediments - recovered in Core 201 of the Swedish Deep-Sea Expedition, in Core 2R-1,107 cm of Site 373 (Leg 13 DSDP) and at Site 373, Core 1-2,O-5 cm of DSDP Leg 42A - sapropels had previously only been described from the eastern Mediterranean and the Black Sea. Scientific deep-sea drilling in the Tyrrhenian Sea during DSDP Legs 13 and 42A apparently missed most of these deposits due to spot coring and rotary drilling techniques; high sedimentation rates may have precluded recovery by conventional gravity coring devices. The recovery of multiple layers of sapropels and sapropelic sediments in the Tyrrhenian Sea demonstrates that oceanographic conditions conducive to sapropel formation were not confined to the Black Sea and eastern Mediterranean, but occurred sporadically and possibly simultaneously in the entire Mediterranean during the Pliocene and Pleistocene. In the light of this finding, previous models of sapropel genesis may need reconsideration. In this paper, we present some initial data on the Tyrrhenian sapropels and suggest some implications of their massive occurrence in the western Mediterranean realm. We end by outlining possible causes for deposition of sapropels in an attempt to revive the interest in sapropels and their paleoceanographic significance.

Geochemistry of middle Eocene-lower Oligocene pelagic sediments of ODP Hole 105-647A

Geochemical analyses of the middle Eocene through lower Oligocene lithologic Unit IIIC (260-518 meters below seafloor [mbsf]) indicate a relatively constant geochemical composition of the detrital fraction throughout this depositional interval at Ocean Drilling Program (ODP) Site 647 in the southern Labrador Sea. The main variability occurs in redox-sensitive elements (e.g., iron, manganese, and phosphorus), which may be related to early diagenetic mobility in anaerobic pore waters during bacterial decomposition of organic matter. Initial preservation of organic matter was mediated by high sedimentation rates (36 m/m.y.). High iron (Fe) and manganese (Mn) contents are associated with carbonate concretions of siderite, manganosiderite, and rhodochrosite. These concretions probably formed in response to elevated pore-water alkalinity and total dissolved carbon dioxide (CO2) concentrations resulting from bacterial sulfate reduction, as indicated by nodule stable-isotope compositions and pore-water geochemistry. These nodules differ from those found in upper Cenozoic hemipelagic sequences in that they are not associated with methanogenesis. Phosphate minerals (carbonate-fluorapatite) precipitated in some intervals, probably as the result of desorption of phosphorus from iron and manganese during reduction. The bulk chemical composition of the sediments differs little from that of North Atlantic Quaternary abyssal red clays, but may contain a minor hydrothermal component. The silicon/ aluminum (Si/Al) ratio, however, is high and variable and probably reflects original variations in biogenic opal, much of which is now altered to smectite and/or opal CT. An increase in the sodium/potassium (Na/K) ratio in the upper Eocene corresponds to the beginning of coarsergrained feldspar flux to the site, possibly marking the onset of more vigorous deep currents. Although the Site 647 cores provide a nearly complete high-resolution, high-latitude Eocene-Oligocene record, the high sedimentation rate and somewhat unusual diagenetic conditions have led to variable alteration of benthic foraminifers and fine-fraction carbonate and have overprinted the original stable-isotope records. Planktonic foraminifers are less altered, but on the whole, there is little chance of sorting out the nature and timing of environmental change on the basis of our stable-isotope analyses.

Facies and diagenesis of organic matter in sediments at DSDP Leg 87

A series of upper Pliocene to Pleistocene sediment samples from DSDP Sites 582 and 583 (Nankai Trough, active margin off Japan) were investigated by organic geochemical methods including organic carbon determination, Rock- Eval pyrolysis, gas chromatography of extractable hydrocarbons, and kerogen microscopy. The organic carbon content is fairly uniform and moderately low (0.35 to 0.77%) at both sites, although accompanied by high sedimentation rates. The low organic matter concentrations are the result of the combined effect of several factors: low bioproductivity, oxic depositional environment, and dilution with lithogenic material. Organic petrography revealed a mixture of three maceral types: (1) fresh, green fluorescent alginites of aquatic origin probably transported by turbidites from the shelf edge, (2) gelified huminites and paniculate liptinites derived from the erosion of unconsolidated peat, and (3) highly reflecting inertinites derived from continental erosion. By a combination of organic petrography and Rock-Eval pyrolysis results, the organic matter is characterized as mainly type III kerogen with a slight tendency to a mixed type II-III. During Rock-Eval pyrolysis, a mineral matrix effect on the generated hydrocarbons was observed. The organic matter in all sediments has a low level of maturity (below 0.45% Rm) and has not yet reached the onset of thermal hydrocarbon generation according to several geochemical maturation parameters. This low maturity is in contrast to anomalously high extract yields at both sites and large hydrocarbon proportions in the extracts at Site 583. This contrast may be due to early generation of polar compounds and perhaps redistribution of hydrocarbons caused by subduction tectonics. Carbon isotope data of the interstitial hydrocarbon gases indicate their origin from bacterial degradation of organic matter, although only very few bacterially degraded maceral components were detected.