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.

Benthic foraminiferal stable isotope stratigraphy of ODP Site 138-846 in the tropical Pacific Ocean

A stable-isotope stratigraphy at Site 846 (tropical Pacific, 3°06'S, 90°49'W, 3307 m water depth), based on the benthic foraminifers Cibicides wuellerstorfi and Uvigerina peregrina, yields a high-resolution record of deep-sea delta18O and delta13C over the past 1.8 Ma, with an average sampling interval of 3 k.y. Variance in the delta18O and delta13C records is concentrated in the well-known orbital periods of 100, 41, and 23 k.y. In the 100-k.y. band, both isotopic signals grow from relatively low amplitudes prior to 1.2 Ma, to high amplitudes in the late Quaternary since 0.7 Ma. The amplitude of delta18O and especially of delta13C decreases in the 41-k.y. band as it grows in the 100-k.y. band, consistent with a transfer of energy into an orbitally-paced internal oscillation. A weak 30-k.y. rhythm, present in both delta18O and delta13C, may reflect nonlinear interaction between the 41-k.y. and 100-k.y. bands in the evolving climate system. In the 23-k.y. and 19-k.y. bands associated with orbital precession, delta18O and delta13C are not coherent with each other on long time scales, and do not evolve like the 100-k.y. and 41-k.y. bands. This suggests that the source of the growing 100-k.y. oscillation is not a nonlinear response to precession, in contrast to predictions of some climate models. Sedimentation rates at this site also vary with a strong 100-k.y. cycle. Unlike the isotope records, the amplitude of 100-k.y. variations in sedimentation rate is relatively constant over the past 1.8 Ma, ranging from about 15 to 70 m/m.y. Prior to 0.9 Ma, sedimentation rates co-vary with orbital eccentricity, rather than with global climate as reflected by delta18O or delta13C. A source of this 100-k.y. cycle of sedimentation rate in the absence of similar ice volume fluctuations may be precessional heating of equatorial land masses, which in an energy balance climate model drives variations of monsoonal climates with a 100-k.y. rhythm. For the interval younger than 0.9 Ma, high sedimentation rates in the 100-k.y. band are consistently associated with glacial stages. This change of pattern suggests that when the amplitude of glacial cycles become large enough, their global effects overpower a local monsoon-driven variation in sedimentation rate at Site 846.

High-resolution isotope stratigraphy of ODP Site 184-1144

Narrow-spaced oxygen and carbon stable isotope records of the planktonic foraminifer Globigerinoides ruber (white) were obtained at Ocean Drilling Program Leg 184 Site 1144 to establish a first record of high-resolution Pleistocene monsoon variability on orbital to centennial timescales in the northern South China Sea. The new records extend from the Holocene back to marine isotope Stage (MIS) 34 (1.1 Ma). Sedimentation rates average 0.56 m/k.y. for the upper Matuyama and Brunhes Chrons and increase to 1.8 m/k.y. over the last 100 k.y. Stable isotope records thus reach an average time resolution of 270-500 yr for the last 375 k.y. and 570 yr further back to 700 ka. On the other hand, major stratigraphic gaps were identified for peak warm Stages 5.5, 7.5 (down to 8.4), 11.3, and 15.5. These gaps probably resulted from short-lasting events of contour current erosion induced by short-term enhanced incursions of Upper Pacific Deep Water near the end of glacial terminations. A further major hiatus extends from MIS 34 to MIS 73(?). The long-term variations in monsoon climate were largely dominated by the 100-k.y. eccentricity cycle. Planktonic delta13C values culminated near 30, 480, and 1035 ka and reflect an overlying 450-k.y. eccentricity cycle of minimum nutrient concentrations in the surface ocean. Superimposed on the orbital variations, millennial-scale cycles were prominent throughout the last 700 k.y., mainly controlled by short-term changes in monsoon-driven precipitation and freshwater input from mainland China. During the last 110 k.y. these short-lasting oscillations closely match the record of 1500-yr Dansgaard-Oeschger climate cycles in the Greenland ice core record.

Age determination and planktonic foraminifera og ODP Site 159-958

Site 958 was drilled to monitor the late Neogene history of both continental aridity in northwestern Africa and the Canary Current distant from nearshore upwelling. Based on magnetostratigraphy, biostratigraphic datums, variations in carbonate, coarse fraction components, and the species composition of planktonic foraminifers, as well as using the d18O records of Globigerinoides ruber (white), we established a splice between Holes 958A and 958B and a stratigraphic age scale deciphering Milankovitch cycles. Over the last 630 k.y., sedimentation rates amount to 2.9 cm/k.y., and to 2.05-2.53 cm/k.y. back to the base of the Pleistocene. Extremely low rates of 0.4 cm/k.y. and a reworking of fossils mark the late Pliocene. The first continuous, long, sea-surface temperature (SST) record from the center of the Canary Current, which is based on foraminifer species census data, depicts a general temperature decrease in the late Pliocene, lower SST and high seasonalities of up to 6°C ~2.0-1.6 Ma, a warmer interval from 1.6 Ma to ~0.85 Ma, again lower SST and higher seasonalities until 0.33 or 0.26 Ma, and a final warmer interval, lasting until at least 50 ka, possibly reflecting the attenuated dynamics of the Canary Current. Especially over the last 400 k.y., since Stage 11, glacial stages are hardly reflected by cold SST cycles, except for various abrupt and extremely short cooling events amounting to D6°C, which possibly result from North Atlantic Heinrich events. Similar, but not necessarily synchronous, events of short-term, extremely high values occur in the paleoproductivity and (d13Cbased) paleonutrient records, which indicate a generally low primary production averaging to 180 g C m**-2 yr**-1 at 50-330 ka and about 300 g C m**-2 yr**-1 back to the base of the Pleistocene. Near 1.2-1.6 Ma, the grain-size and magnetic susceptibility records document a significant increase in the discharge of south Saharan/Sahelian dust, possibly linked to increasing aridity.

Sedimentary records of ODP Site 198-1209 on Shatsky Rise

The accumulation of wind blown (eolian) dust in deep-sea sediments reflects the aridity/humidity conditions of the continental region supplying the dust, as well as the "gustiness" of the climate system. Detailed studies of Pleistocene glacial-interglacial dust fluxes suggest changes in accumulation rates corresponding to orbital variations in solar insolation (Milankovitch cycles). While the orbital cycles found in sedimentary archives of the Pleistocene are intricately related to glacial growth and decay, similar global orbital signals recognized in deep-sea sediments of early Paleogene age, the last major greenhouse interval ~65-45 million years ago, could not have been linked to the waxing and waning of large ice sheets. Thus orbital signals recorded in early Paleogene sediments must reflect some other climate response to changes in solar insolation. To explore the potential connection between orbital forcing and the climate processes that control dust accumulation, we generated a high-resolution dust record for ~58 Myr old sediments from Shatsky Rise (ODP Site 1209, paleolatitude ~15°N-20°N). The dust accumulation data provide the first evidence of a correlation between dust flux to the deep sea and orbital cyclicity during the early Paleogene, indicating dust supply responded to insolation forcing during the last major interval of greenhouse climate. Furthermore, the relative amplitude of the dust flux response during the early Paleogene greenhouse was comparable to that during icehouse climates. Thus, subtle variations in solar insolation driven by changes in Earth's orbit about the Sun may have had a similar impact on climate during intervals of overall warmth as they did during glacial-interglacial states.

Sulfur concentrations and isotope ratios in sediments from Kiel Bay, western Baltic Sea

The isotope-ratios of sulfur-components in several sedimentologically different cores of recent marine sediments from Kiel Bay (Baltic Sea) were investigated. In addition, quantitative determinations were made on total sulfur, sulfate, sulfide, chloride, organic carbon, iron and watercontent in the sediment or in the pore-water solution. The investigations gave the following results: 1. The sulfur in the sediment (about 0.3 -2 % of the dry sample) was for the most part introduced into the sediment after sedimentation. This confirms the results of Kaplan et al. (1963, doi:10.1016/0016-7037(63)90074-7). The yield of Sulfur from organic material is very small (in our samples about 5-10% of the total sulfur in the sediment). 2. The sulfur bound in the sediment is taken from the sulfate of the interstitial water. During normal sedimentation, the exchange of sulfate by diffusion significant for changes in the sulfur-content goes down to a sediment depth of 4-6 cm. In this way the sulfate consumed by reduction and formation of sulfide or pyrite is mostly replaced. The uppermost layer of the sediment is an partly open system for the sulfur. The diagenesis of the sulfur is allochemical. 3. The isotope-values of the sediment-sulfur are largely influenced by the sulfur coming into the sediment by diffusion and being bound by bacteriological reduction. Due to the prevailing reduction of 32S and reverse-diffusion of sulfate into the open sea-water, an 32S enrichment takes place in the uppermost layer of the sediment. delta34S-values in the sediment range between -15 and -35 ? while seawater-sulfate has +20 ?. No relationship could be established between sedimentological or chemical changes and isotope-ratios. In the cores, successive sandy and clayly layers showed no change in the delta-values. The sedimentation rate, however, seems to influence isotope-ratios. In one core with low sedimentationrates the delta34S-values varied between -29 and -33 ?, while cores with higher sedimentationrates showed values between -17 and -24 ?. 4. As sediment depth increases, the pore-water sulfate shows decreasing concentrations (in a depth of 30-40 cm we found between 20 and 70 % of the seawater-values), and increasing delta 34S-values (in one case reaching more than +60 ?). The concentration of sulfide in the pore-water increases with sediment-depth (reaching 80 mg S/l in one case). The (delta34S-values of the pore-water-sulfide in all cores show increases paralleling the sulfate sulfur, with a nearly constant delta-distance of 50-60 ? in all cores. This seems to confirm the genetic relationship between the two components.

Palynology of ODP Site 108-658

Ocean Drilling Program Site 658 at 21°N off northwest Africa has a high sedimentation rate and a high concentration of pollen grains and is thus very suitable for detailed pollen analysis. The time scale for the upper 100 m (the last 670 k.y.) of Site 658 is based on biostratigraphic data and isotope stratigraphy. The pollen record has been divided into 34 zones. These are classified into 7 zone types covering a range from very arid to rather humid conditions. The sequence shows a long-term climatic decline: strong glacial stages were found only after 480 k.y. and strong interglacial stages only before 280 k.y. The Site 658 record correlates well with a terrestrial sequence from northern Greece, although both records differ in their response to global climatic change. Spectral analysis shows a 100- and a 42-k.y. period in the curves of pollen brought in by the northwest trade winds and only a 42-k.y. period in the curves of pollen mostly transported by the African Easterly Jet. A 31-k.y. period is found in the curves for Ephedra and Chenopodiaceae-Amaranthaceae. In addition, Ephedra shows a 54-k.y. period.

Sedimentology and Th, Pa, U, and N isotopic composition of core MD84-527

High-resolution records of opal, carbonate, and terrigenous fluxes have been obtained from a high-sedimentation rate core (MD84-527: 43°50'S; 51°19'E; 3269 m) by normalization to 230Th. This method estimates paleofluxes to the seafloor on a point-by-point basis and distinguishes changes in sediment accumulation due to variations in vertical rain rates from those due to changes in syndepositional sediment redistribution by bottom currents. We also measured sediment delta15N to evaluate the changes in nitrate utilization in the overlying surface waters associated with paleoflux variations. Our results show that opal accumulation rates on the seafloor during the Holocene and stage 3, based on 14C dating, were respectively tenfold and fivefold higher than the vertical rain rates, At this particular location, changes in opal accumulation on the seafloor appear to be mainly controlled by sediment redistribution by bottom currents rather than variations in opal fluxes from the overlying water column. Correction for syndepositional sediment redistribution and the improved time resolution that can be achieved by normalization to 230Th disclose important variations in opal rain rates. We found relatively high but variable opal paleoflux during stage 3, with two maxima centered at 36 and 30 kyr B.P., low opal paleoflux during stage 2 and deglaciation and a pronounced maximum during the early Holocene, We interpret this record as reflecting variations in opal production rates associated with climate-induced latitudinal migration of the southern ocean frontal system. Sediments deposited during periods of high opal paleoflux also have high authigenic U concentrations, suggesting more reducing conditions in the sediment, and high Pa-231/Th-230 ratios, suggesting increased scavenging from the water column. Sediment delta15N is circa 1.5 per mil higher during isotopic stage 2 and deglaciation. The low opal rain rates recorded during that period appear to have been associated with increased nitrate depletion. This suggests that opal paleofluxes do not simply reflect latitudinal migration of the frontal system but also changes in the structure of the upper water column. Increased stratification during isotopic stage 2 and deglaciation could have been produced by a meltwater lid, leading to lower nitrate supply rates to surface waters.

(Table 1) Positions of the Mesocena elliptica zone in sediment cores from the Pacific and Indian Oceans

The Mesocena elliptica Ehr. zone in deep-sea sediments of the Pacific Ocean is characterized by a short vertical range at the base of the Pleistocene section. Depending on sedimentation rate this zone lies at various depths below the ocean bottom. M. elliptica is unknown in recent oceanic plankton. In fossil state known species indicate that sediments containing them are of Oligocene-Miocene age. New data obtained in early 1960's show that within a short interval, evidently in Early Pleistocene, M. elliptica was abundant in plankton, primarily in tropical regions. Correlation of paleomagnetic data with results of diatom analysis shows that the Mesocena elliptica zone always lies above the Pliocene-Pleistocene boundary, and that maximum contents of M. elliptica coincide with the Jaramillo event (0.85-0.95 million years ago).

Accumulation rates, grain-size fractions and calcium carbonate at DSDP Sites 89-586 and 90-591

Carbonate oozes recovered by hydraulic piston coring at DSDP Site 586 on Ontong-Java Plateau and Site 591 on Lord Howe Rise have carbonate contents that are consistently higher than 90% with only minor variations. Consequently, paleoceanographic signals were not recorded in detail in the carbonate contents. However, mass accumulation rates of carbonate increased in the late Miocene to mid-Pliocene, reflecting an increase in productivity, then abruptly decreased from mid-Pliocene to the present. Variations in relative abundances of coarse material (foraminifers) and fine material (mostly calcareous nannofossils) do reflect histories of current winnowing and biogenic productivity at the two sites. The late Miocene from 10.5 to 6.5 m.y. ago was a time of relatively constant, quiet, pelagic sedimentation with typical southwest Pacific sedimentation rates of 20-25 m/m.y. The average coarse-fraction abundances are always higher at Site 586 than at Site 591, which reflects winnowing at Site 586. These conditions were interrupted between 6.5 to 4.0 m.y. ago when increased upwelling at the Subtropical Divergence and the Equatorial Divergence produced greater productivity of calcareous planktonic organisms. The increased productivity is suggested by large increases in both fineand coarse-fraction material and constant ratios of foraminifers to nannofossils. The maximum of productivity was about 4.0 m.y. ago. This period of increased upwelling is coincident with the inferred development of the West Antarctic ice sheet. The high productivity was followed by an abrupt increase in winnowing about 2.5 m.y. ago at Site 591, but not until about 2.0 m.y. ago at Site 586. By 2.0 m.y. ago in the late Pliocene, quiet, pelagic sedimentation conditions prevailed, similar to those of the late Miocene. The last 0.7 m.y. has been a period of relatively intense winnowing on Lord Howe Rise but not on Ontong-Java Plateau. The coarse-fraction data have both long- and short-period fluctuations. Long-period fluctuations at Site 591 average about 850 *10**3 yr./cycle and those at Site 586 average 430*10**3 yr./cycle. The highest amplitudes are found in the Pliocene and Quaternary sections. The short-period fluctuations range from 100 to 48*10**3 yr./cycle at Site 586 and from 250 to 33 *10**3 yr./cycle at Site 591. The effects of local fluctuations of productivity and winnowing have modified the primary orbital forcing signals at these two sites to yield complex paleoceanographic records.

(Table 1) Positions of the Mesocena elliptica zone in sediment cores from the Pacific and Indian Oceans

The Mesocena elliptica Ehr. zone in deep-sea sediments of the Pacific Ocean is characterized by a short vertical range at the base of the Pleistocene section. Depending on sedimentation rate this zone lies at various depths below the ocean bottom. M. elliptica is unknown in recent oceanic plankton. In fossil state known species indicate that sediments containing them are of Oligocene-Miocene age. New data obtained in early 1960's show that within a short interval, evidently in Early Pleistocene, M. elliptica was abundant in plankton, primarily in tropical regions. Correlation of paleomagnetic data with results of diatom analysis shows that the Mesocena elliptica zone always lies above the Pliocene-Pleistocene boundary, and that maximum contents of M. elliptica coincide with the Jaramillo event (0.85-0.95 million years ago).

Geochemistry at DSDP Leg 70 Holes

The hydrothermal mounds on the southern flank of the Galapagos Spreading Center are characterized by the following main features: 1) They are located over a young basement (0.5 to 0.85 m.y. of age) in a region known for its high sedimentation rate (about 5 cm/10**3 y.) because it is part of the equatorial high biological productivity zone. 2) They are located in a region with generally high heat flow (8 to 10 HFU). The highest heat-flow measurements (up to 10**3 HFU) correspond to mound peaks (Williams et al., 1979), where temperatures up to 15°C were measured during a dive of the submersible Alvin (Corliss et al., 1978). 3) They are often located on small vertical faults which displace the basement by a few meters (Lonsdale, 1977) and affect the 25- to 50-meter-thick sediment cover. Most of these characteristics have also been observed in the other three known cases of hydrothermal deposits with mineral parageneses similar to that of the Galapagos mounds. However, the case of the hydrothermal mounds south of the Galapagos Spreading Center is unique because of the unusual thickness of the hydrothermal deposits present. The mounds are composed of several, up to 4.5-meter-thick, layers of green clays which, in one case (Hole 509B), are overlain by about 1.4 meters of Mn-oxide crust. We suspect that such a large accumulation of hydrothermal products results from the "funnelling" of the hydrothermal solutions exiting from a highly permeable basement along the faults. This chapter reports a preliminary study of those green clays collected by hydraulic piston coring of the Galapagos mounds during Deep Sea Drilling Project (DSDP) Leg 70 of the D/V Glomar Challenger. Green clays have also been reported from three presently or recently active hydrothermal areas in or close to spreading centers.

Geotechnical properties of sediments at DSDP Site 75-532

During Leg 75 of the Deep Sea Drilling Project (DSDP) from the D/V Glomar Challenger, a 200-m deep hole was drilled at Hole 532A on the eastern side of Walvis Ridge at a water depth of 1331 m. Sediment cores were obtained by means of a hydraulic piston corer. All of the cores from this boring were designated for geotechnical studies and were distributed among eight institutions. The results of laboratory studies on these sediment cores were compiled and analyzed. Sediment properties, including physical characteristics, strength, consolidation, and permeability were studied to evaluate changes as a function of depth of burial. It was concluded that the sediment profile to the explored depth of 200 m at Walvis Ridge consists of approximately 50 m of foram-nannofossil marl (Subunit 1a) over 64 m of diatom-nannofossil marl (Subunit 1b) over nannofossil marl (Subunit 1c) to the depth explored. All three sediment units appear to be normally consolidated, although some anomalies seem to exist to a depth of 120 m. No distinct differences were found among the sediment properties of the three subunits (1a, 1b, and 1c) identified at this site.

Geochemistry of pore water and sediments offshore Nicaragua and Costa Rica

Four volcanic ash-bearing marine sediment cores and one ash-free reference core were examined during research cruise RV Meteor 54/2 offshore Nicaragua and Costa Rica to investigate the chemical composition of pore waters related to volcanic ash alteration. Sediments were composed of terrigenous matter derived from the adjacent continent and contained several distinct ash layers. Biogenic opal and carbonate were only minor components. The terrigenous fraction was mainly composed of smectite and other clay minerals while the pore water composition was strongly affected by the anaerobic degradation of particulate organic matter via microbial sulphate reduction. The alteration of volcanic matter showed only a minor effect on major element concentrations in pore waters. This is in contrast to prior studies based on long sediment cores taken during the DSDP, where deep sediments always showed distinct signs of volcanic ash alteration. The missing signal of ash alteration is probably caused by low reaction rates and the high background concentration of major dissolved ions in the seawater-derived pore fluids. Dissolved silica concentrations were, however, significantly enriched in ash-bearing cores and showed no relation to the low but variable contents of biogenic opal. Hence, the data suggest that silica concentrations were enhanced by ash dissolution. Thus, the dissolved silica profile measured in one of the sediment cores was used to derive the in-situ dissolution rate of volcanic glass particles in marine sediments. A non-steady state model was run over a period of 43 kyr applying a constant pH of 7.30 and a dissolved Al concentration of 0.05 ?M. The kinetic constant (AA) was varied systematically to fit the model to the measured dissolved silica-depth profile. The best fit to the data was obtained applying AA = 1.3 * 10**-U9 mol of Si/cm**2/ s. This in-situ rate of ash dissolution at the seafloor is three orders of magnitude smaller than the rate of ash dissolution determined in previous laboratory experiments. Our results therefore imply that field investigations are necessary to accurately predict natural dissolution rates of volcanic glasses in marine sediments.

Thorium and uranium isotopes in upper Pleistocene sediments of the Baffin Bay

Concentrations and activity ratios of uranium and thorium isotopes (234U/238U, 230Th/232Th) were determined at about 5-m intervals through the composite top 22-m sequence of Ocean Drilling Program (ODP) Hole 645 in Baffin Bay and, in the Labrador Sea, at 1-m intervals through the top 11 m of Core 84-030-003 (TWC and P) collected by the Hudson during a preliminary survey of Site 647, and also at about 2-m intervals through the composite top 22-m sequence of Hole 646. In the Labrador Sea, surficial sediments show unsupported 230Th having a 230Th/234U activity ratio of about 3. At Site 647, a regular decrease in the 230Th/232Th activity ratio was observed downcore from about 1.2 (at 1 mbsf) to about 0.4 (at ~8 mbsf), through a sequence spanning over 18O stages 2 through 8. The correlative thorium/uranium chronology and 18O stratigraphy indicate relatively constant sedimentation rates throughout the sequence. At Site 646, down Greenland slope, and at Site 645, in Baffin Bay, highly variable uranium and thorium concentrations and isotopic ratios were observed in relation to highly variable sedimentation rates. As a whole, the lower-excess observed in Baffin Bay records is indicative of very high absolute sedimentation rates in comparison with those of the Labrador Sea. These rates are confirmed by the 18O-stratigraphy and a few AMS 14C controls on handpicked foraminifers. At both Labrador Sea sites, a clear indication of an initial 230Th-excess (over the 230Th-rain from the water column) was found.