Total organic carbon content and isorenieratene concentrations from three holes of ODP Leg 160

Carotenoids were analysed in ca. 1-cm thick subsamples of three laterally time-equivalent sapropels from a west-east transect of the eastern Mediterranean Basin to study euxinic periods during Pliocene sapropel formation. The amount of intact isorenieratene (summed all-trans and cis isomers), ranged from non-detectable at the base and top of a sapropel up to 140 µg/g sediment in the central parts. Isorenieratene accumulation rates at the central and western site are remarkably similar and increase sharply to levels of up to 3.0 mg/m**2/ yr in the central part of the sapropel and then drop to low levels. This pattern indicates an expansion of euxinic conditions reaching into the photic zone, followed by deepening of the chemocline during deposition of this Pliocene sapropel. The sapropel from the easternmost site of the basin, which contains less organic carbon, shows much lower isorenieratene accumulation rates and even absence of isorenieratene in the central part of the sapropel. Ba/Al ratios indicate enhanced palaeoproductivity during sapropel formation, supporting previously proposed models, according to which increased productivity is the driving force for the generation of euxinic conditions.

Interstitial-water geochemistry of Kerguelen Plateau sediments

This report synthesizes all of the interstitial-water chemistry studies associated with the Kerguelen Plateau phase of ODP Leg 119. Sediments were cored at six sites (49°24'S to 59°36'S) in water depths ranging from 564 to 4082 m. A total of 77 interstitial-water samples was recovered as part of the routine sampling protocol. In addition, a novel, highresolution pore-water sampling program was tested during Leg 119 that enabled us to pinpoint reaction zones and extend our data base to deeper, drier levels that were heretofore inaccessible. Data collected include interstitial-water sodium, potassium, calcium, magnesium, pH, alkalinity, sulfate, ammonia, phosphate, aqueous silica, salinity, chloride, oxidation-reduction potentials, and sediment chemistry. The northern sector (Sites 736 and 737) is characterized by the highest sedimentation rates (up to 140 m/m.y.) and thermal gradients (70°-98°C/km) encountered on the Kerguelen Plateau during Leg 119. Site 737 represents the most reactive sediment column cored on the Kerguelen Plateau. Major cation fluxes at Site 737 are the strongest measured during Leg 119. High dissolved calcium concentrations (141.5 mM) were encountered near the bottom of Hole 737B. Elevated temperatures promote silica diagenesis and the alteration of volcanic material below 300 mbsf, and a diagenetic front was discovered near 370 mbsf at Site 737. The southern portion of the Kerguelen Plateau (Sites 738 and 744) records the lowest sedimentation rates (less than 5 m/m.y.) and thermal gradients (43°C/km) of the three study areas. Major cation fluxes at the southern sites are the lowest that we measured on the Kerguelen Plateau. High-resolution sampling provided evidence for significant silica release to the pore waters during the weathering of basement basalt. The relatively low thermal gradient does not appear to be sufficient for the formation of the opal-CT and quartz chert beds and nodules that were encountered below 120 mbsf at Site 738. Sediment-accumulation rates on the Eastern Kerguelen Sediment Ridge (Sites 745 and 746) are intermediate to those of the northern and southern sites. Deposition below the regional CCD accounts for the nearly carbonate-free, siliceous sediments. Despite their low organic carbon contents (mean = 0.15%), sediments on the Eastern Kerguelen Sediment Ridge exhibit the highest pore-water alkalinity (6.77 mM), ammonium (0.50 mM), and phosphate (23 µM) concentrations measured on the Kerguelen Plateau. Major cation fluxes are intermediate to those calculated for the northern and southern sites. The Eastern Kerguelen Sediment Ridge interstitial waters are unusual, however, in that the downward flux of magnesium is greater than the upward flux of calcium.

Thorium and radiocarbon measurements on sediment cores from the Northseast Atlantic

Radiocarbon and 230Thexcess data from six NE Atlantic box cores are considered. The cores form a transect from the Porcupine Abyssal Plain over the East Thulean Rise to the southern end of Feni Drift. The chronology for the cores is established from bulk sediment carbonate radiocarbon data and reveals that sections exhibiting constant accumulation rates can be identified in all the cores, with rates of 3.0-3.5 cm/kyr on the plain through the Holocene and late Holocene rates of 4.3-6.6 cm/kyr elsewhere. Five out of the six cores show accumulations of more 230Thexcess than is produced in the overlying water column, with the greatest inventories (up to 225% of production) in the cores from the rise and drift. A size fraction comparison between two cores from the plain and rise reveals that the higher overall accumulation rates and 230Thexcess inventories in the off-plain cores are due to an increased fine (<5 µm) component fraction, whereas the flux of coarser material is similar to that received on the plain. This suggests that the higher fluxes of materials observed are physically (rather than biogeochemically) driven and also that drift formation has been continuously active in the late Holocene. Sections of all the cores where regular accumulation is defined by the radiocarbon data are modeled first by a linear radiocarbon age/depth model and second by a constant rain (230Thexcess)0 model prorated for the observed core inventories. These modeling approaches yield historical mass accumulation rate estimates which are generally in reasonable agreement (±30%), but the differences observed appear to be well organized in time rather than random.

Sedimentological and benthic foraminiferal data pertaining to ODP Holes 208-1262A and 208-1263C

Eocene Thermal Maximum 2 (ETM2) occurred ~1.8 Myr after the Paleocene Eocene Thermal Maximum (PETM) and, like the PETM, was characterized by a negative carbon isotope excursion coupled with warming. We combined benthic foraminiferal and sedimentological records for Southeast Atlantic Sites 1263 (1500 m paleodepth) and 1262 (3600 m paleodepth) to show that benthic foraminiferal diversity and accumulation rates declined more precipitously and severely at the shallower site during peak ETM2. The sites are in close proximity, so differences in surface productivity cannot have caused this differential effect. Instead, on the basis of an analysis of climate modelling experiments, we infer that changes in ocean circulation pattern across ETM2 may have resulted in more pronounced warming at intermediate depths (Site 1263). The effects of more pronounced warming include increased metabolic rates, leading to a decrease in effective food supply and increased deoxygenation, thus potentially explaining the more severe benthic impacts at Site 1263. In response to more severe benthic disturbance, bioturbation may have decreased at Site 1263 as compared to Site 1262, hence differentially affecting the bulk carbonate record. We use a sediment-enabled Earth system model to test whether a reduction in bioturbation and/or the likely reduced carbonate saturation of more poorly ventilated waters can explain the more extreme excursion in bulk d13C and sharper transition in wt% CaCO3 at Site 1263. We find that both enhanced acidification and reduced bioturbation during peak ELMO conditions are needed to account for the observed features. Our combined ecological and modelling analysis illustrates the potential role of ocean circulation changes in amplifying local environmental changes and driving temporary, but drastic, loss of benthic biodiversity and abundance.

Radioisotope stratigraphy, sedimentology and geochemistry of Late Quaternary sediments from the Eastern Arctic Ocean

To reconstruct Recent and past sedimentary environments, marine sediments of Upper Pleistocene and Holocene ages from the eastern Arctic Ocean and especially from the Nansen-Gakkel Ridge (NGR) were investigated by means of radioisotopic, geochemical and sedimentological methods. In combination with mass physical property data and lithological analysis these investigations allow clearly to characterize the depositional environments. Age dating by using the radioisotope 230Th gives evidence that the investigated sediments from the NGR are younger than 250,000 years. Identical lithological sediment sequences within and between sediment cores from the NGR can be related to sedimentary processes which are clearly controlled by palaeoclimate. The sediments consist predominantly of siliciclastic, terrigenous ice-rafted detritus (IRD) deriving from assorted and redeposited sediments from the Siberian shelfs. By their geochemical composition the sediments are similar to mudstone, graywacke and arcose. Sea-ice as well as icebergs play a major roll in marine arctic sedimentation. In the NGR area rapid change in sedimentary conditions can be detected 128,000 years ago. This was due to drastic change in the kind of ice cover, resulting from rapid climatic change within only hundreds of years. So icebergs, deriving mostly from Siberian shelfs, vanished and sea-ice became dominant in the eastern Arctic Ocean. At least three short-period retreats of the shelf ice between 186,000 and 128,000 years are responsible for the change of coarse to fine-grained sediments in the NGR area. These warmer stages lasted between 1,000 and 3,000 years. By monitoring and comparing the distribution patterns of sedimentologic, mass physical and geochemical properties with 230Th ex activity distribution patterns in the sediment cores from the NGR, there is clear evidence that sediment dilution is responsible for high 230Th ex activity variations. Thus sedimentation rate is the controlling factor of 230Th ex activity variations. The 230Th flux density in sediments from the NGR seems to be highly dependent On topographic Position. The distribution patterns of chemical elements in sediment cores are in general governed by lithology. The derivation of a method for dry bulk density determination gave the opportunity to establish a high resolution stratigraphy on sediment cores from the eastern Arctic Ocean, based on 230Thex activity analyses. For the first time sedimentation and accumulation rates were determined for recent sediments in the eastern Arctic Ocean by 230Th ex analyses. Bulk accumulation rates are highly variable in space and time, ranging between 0.2 and 30 g/cm**2/ka. In the sediments from the NGR highly variable accumulation rates are related to the kind of ice cover. There is evidence for hydrothermal input into the sediments of the NGR. Hydrothermal activity probably also influences surficial sediments in the Sofia Basin. High contents of As are typical for surficial sediments from the NGR. In particular SL 370-20 from the bottom of the rift valley has As contents exceeding in parts 300 ppm. Hydrothermal activity can be traced back to at least 130,000 years. Recent to subrecent tectonic activity is documented by the rock debris in KAL 370 from the NGR. In four other sediment cores from the NGR rift valley area tectonically induced movements can be dated to about 130,000 years ago, related most probably to the rapid climate change. Processes of early diagenesis in sediments from the NGR caused the aobilization and redeposition of Fe, Mn and Mo. These diagenetic processes probably took place during the last 130,000 years. In sediment cores from the NGR high amounts of kaolinite are related to coarse grained siliciclastic material, probably indicating reworking and redeposition of siberian sandstones with kaolinitic binding material. In contrast to kaolinite, illite is correlated to total clay and 232Th contents. Aragonite, associated with serpentinites in the rift valley area of the NGR, was precipitated under cold bottom-water conditions. Preliminary data result in a time of formation about 60 - 80 ka ago. Manganese precipitates with high Ni contents, which can be related to the ultrabasic rocks, are of similar age.

Radiocarbon dates and dinoflagellate cysts of sediment core DP30PC

To obtain insight into character and potential forcing of short-term climatic and oceanographic variability in the southern Italian region during the "Roman Classical Period" (60 BC-AD 200), climatic and environmental reconstructions based on a dinoflagelate cyst record from a well dated site in the Gulf of Taranto located at the distal end of the Po-river discharge plume have been established with high temporal resolution. Short-term fluctuations in accumulation rates of the Adriatic Surface Water species Lingulodinium machaerophorum, the freshwater algae Concentricystes and species resistant to aerobic degradation indicate that fluctuations in the trophic state of the upper waters are related to river discharge of northern and eastern Italian rivers which in turn are strongly related to precipitation in Italy. The dinoflagellate cyst association indicates that local sea surface temperatures which in this region are strongly linked to local air temperatures were slightly higher than today. We reconstruct that sea surface temperatures have been relatively high and stable between 60 BC-AD 90 and show a decreasing trend after AD 90. Fluctuations in temperature and river discharge rates have a strong cyclic character with main cyclicities of 7-8 and 11 years. We argue that these cycles are related to variations of the North Atlantic Oscillation climate mode. A strong correlation is observed with global variation in Delta14C anomalies suggesting that solar variability might be one of the major forcings of the regional climate. Apart from cyclic climate variability we observed a good correlation between non-cyclic temperature drops and global volcanic activity indicating that the latter forms an additional major forcing factor of the southern Italian climate during the Roman Classical Period.

Radiolarian faunal turnover across the Oligocene/Miocene boundary in the equatorial Pacific Ocean

The global warming trend of the latest Oligocene was interrupted by several cooling events associated with Antarctic glaciations. These cooling events affected surface water productivity and plankton assemblages. Well-preserved radiolarians were obtained from upper Oligocene to lower Miocene sediments at Ocean Drilling Program (ODP) Leg 199 Sites 1218 and 1219 in the equatorial Pacific, and 110 radiolarian species were identified. Four episodes of significant radiolarian faunal changes were identified: middle late Oligocene (27.5 to 27.3 Ma), latest Oligocene (24.4 Ma), earliest Miocene (23.3 Ma), and middle early Miocene (21.6 Ma). These four episodes approximately coincide with increases and decreases of biogenic silica accumulation rates and increases in delta18O values coded as "Oi" and "Mi" events. These data indicate that Antarctic glaciations were associated with change of siliceous sedimentation patterns and faunal changes in the equatorial Pacific. Radiolarian fauna was divided into three assemblages based on variations in radiolarian productivity, species richness and the composition of dominant species: a late Oligocene assemblage (27.6 to 24.4 Ma), a transitional assemblage (24.4 to 23.3 Ma) and an early Miocene assemblage (23.3 to 21.2 Ma). The late Oligocene assemblage is characterized by relatively high productivity, low species richness and four dominant species of Tholospyris anthophora, Stichocorys subligata, Lophocyrtis nomas and Lithelius spp. The transitional assemblage represents relatively low values of productivity and species richness, and consists of three dominant species of T. anthophora, S. subligata and L. nomas. The characteristics of the early Miocene assemblage are relatively low productivity, but high species richness. The two dominant species present in this assemblage are T. anthophora and Cyrtocapsella tetrapera. The most significant faunal turnover of radiolarians is marked at the boundary between the transitional/early Miocene assemblages.

Multi-proxy analyses of sediment cores from the Pakistan continental margin

Late Holocene laminated sediments from a core transect centred in the oxygen minimum zone (OMZ) impinging at the continental slope off Pakistan indicate stable oxygen minimum conditions for the past 7000 calendar years. High SW-monsoon-controlled biological productivity and enhanced organic matter preservation during this period is reflected in high contents of total organic carbon (TOC) and redox-sensitive elements (Ni, V), as well as by a low-diversity, high-abundance benthic foraminiferal Buliminacea association and high abundance of the planktonic species Globigerina bulloides indicative of upwelling conditions. Surface-water productivity was strongest during SW monsoon maxima. Stable OMZ conditions (reflected by laminated sediments) were found also during warm interstadial events (Preboreal, Bølling-Allerød, and Dansgaard-Oeschger events), as well as during peak glacial times (17-22.5 ka, all ages in calendar years). Sediment mass accumulation rates were at a maximum during the Preboreal and Younger Dryas periods due to strong riverine input and mobilisation of fine-grained sediment coinciding with rapid deglacial sea-level rise, whereas eolian input generally decreased from glacial to interglacial times. In contrast, the occurrence of bioturbated intervals from 7 to 10.5 ka (early Holocene), in the Younger Dryas (11.7-13 ka), from 15 to 17 ka (Heinrich event 1) and from 22.5 to 25 ka (Heinrich event 2) suggests completely different conditions of oxygen-rich bottom waters, extremely low mass and organic carbon accumulation rates, a high-diversity benthic fauna, all indicating lowered surface-water productivity. During these intervals the OMZ was very poorly developed or absent and a sharp fall of the aragonite compensation depth favoured the preservation of pteropods. The abundance of lithogenic proxies suggests aridity and wind transport by northwesterly or northeasterly winds during these periods coinciding with the North Atlantic Heinrich events and dust peaks in the Tibetan Loess records. The correlation of the monsoon-driven OMZ variability in the Arabian Sea with the rapid climatic fluctuations in the high northern latitudes suggests a close coupling between the climates of the high and low latitudes at a global scale.

Age model and color measurements of sediment cores from the eastern equatorial Pacific

High-resolution records of glacial-interglacial variations in biogenic carbonate, opal, and detritus (derived from non-destructive core log measurements of density, P-wave velocity and color; r >= 0.9) from 15 sediment sites in the eastern equatorial (sampling resolution is ~1 kyr) clear response to eccentricity and precession forcing. For the Peru Basin, we generate a high-resolution (21 kyr increment) orbitally-based chronology for the last 1.3 Ma. Spectral analysis indicates that the 100 kyr cycle became dominant at roughly 1.2 Ma, 200-300 kyr earlier than reported for other paleoclimatic records. The response to orbital forcing is weaker since the Mid-Brunhes Dissolution Event (at 400 ka). A west-east reconstruction of biogenic sedimentation in the Peru Basin (four cores; 91-85°W) distinguishes equatorial and coastal upwelling systems in the western and eastern sites, respectively. A north-south reconstruction perpendicular to the equatorial upwelling system (11 cores, 11°N-°3S) shows high carbonate contents (>= 50%) between 6°N and 4°S and highly variable opal contents between 2°N and 4°S. Carbonate cycles B-6, B-8, B-10, B-12, B-14, M-2, and M-6 are well developed with B-10 (430 ka) as the most prominent cycle. Carbonate highs during glacials and glacial-interglacial transitions extended up to 400 km north and south compared to interglacial or interglacial^glacial carbonate lows. Our reconstruction thus favors glacial-interglacial expansion and contraction of the equatorial upwelling system rather than shifting north or south. Elevated accumulation rates are documented near the equator from 6°N to 4°S and from 2°N to 4°S for carbonate and opal, respectively. Accumulation rates are higher during glacials and glacial-interglacial transitions in all cores, whereas increased dissolution is concentrated on Peru Basin sediments close to the carbonate compensation depth and occurred during interglacials or interglacial-glacial transitions.

Sedimentology on cores from the Peru Basin

We investigated surficial sediments for physico-chemical composition from numerous sites of seven study areas in the manganese nodule field of the northern Peru Basin as part of a deep-sea environmental study. Major results from this study are strong variability with respect to water depth, productivity in surface waters, locality, bottom water flow, and seafloor topography. Sediment sites are located mostly in 3900 to 4300 m water depth between the lysocline and the carbonate compensation depth (CCD). Large fluctuations in carbonate content (0% to 80%) determine sediment density and compressional-wave velocity, and, by dilution, contents of opal and non-biogenic material. Mass accumulation rates of biogenic components as well as geochemical proxies (barium and phosphorus) distinguish areas of higher productivity in the northwest near equatorial upwelling and in the northeast close to coastal upwelling, from areas of lower productivity in the west and south. Comparisons between the central Peru Basin area (Discol) and western Peru Basin area (Sediperu) reveals, for the Sediperu area, a shallower CCD, more carbonate but less opal, organic carbon, and non-biogenic material in sediments at the same water depth as well as larger down-core fluctuations of organic carbon and MnO2. Bottom water flow in the abyssal hill topography causes winnowing of material from summits of seamounts and ridges, where organic carbon preservation is poor, to basins where organic carbon preservation is better. Down-core measurements in box cores indicate a three-fold division in the upper 50 cm of the sediment column. An uppermost semi-liquid top layer is dark brown, 5-15 cm thick and contains most of the ferro-manganese nodules. A 5-15 cm thick transition zone of light sediment color has increasing shear strength, lowest opal contents and compressional-wave velocities, but highest carbonate contents and sediment densities. The lowermost layer contains stiffer light gray sediments.

Late Neogene carbonate sedimentation and stable isotope record of ODP Site 121-758

The evolution of oceanic and climatic conditions the northeast Indian Ocean during the last 7 m.y. is revealed in the sediments from Site 758. We present detailed and continuous records of d18O and d13C from planktonic foraminifers, weight percent calcium carbonate, weight percent coarse fraction, magnetic susceptibility, and geomagnetic reversals. Sample spacing of the records ranges from 3 to 10 cm and is equivalent to an average time interval of 2000 to 6000 yr. Despite the fact that core recovery ranged between 100% and 105%, recovery gaps as large as 2.7 m occurred at nearly every break between advanced hydraulic piston cores. Approximately 12% of the late Neogene sequence was not recovered in each of the two holes drilled at Site 758. To circumvent the discontinuity introduced by the gaps, a composite depth section was constructed from multiple cores taken from offset holes at Site 758. The resulting composite depth section extends continuously from 0 to 116 mbsf, from the Holocene to the upper Miocene. A detailed chronostratigraphy is based on geomagnetic reversals which extend from the Brunhes Chron to Chron 6, and on d18O stages 1 through 105, which span from 0 to 2.5 Ma. The d18O record is dominated by a ~40-k.y. cycle in the late Pliocene and early Pleistocene, and is followed by a change to a ~100-k.y. cycle in the late Pleistocene. The mid-Pleistocene transition between these two modes of variability occurs between d18O stages 25 and 22 (between 860 and 800 Ka). Thirteen major volcanic ash horizons from the Indonesian arc are observed throughout the sedimentary section and are dated by their relative position within the geomagnetic reversals and the d18O chronostratigraphy. Since 5 Ma, there has been a long-term decline in weight percent CaCO3 and CaCO3 mass accumulation rates, and an associated rise in non-CaCO3 mass accumulation rates. We attribute these changes to a decrease in CaCO3 productivity and an increase in terrigenous sedimentation through enhanced riverine input. Such input may be linked to rapid tectonic uplift of the Himalayas and the Tibetan Plateau via mechanisms such as the intensification of the monsoonal rains, increased fluvial erosion, and regional glaciation. The long-term increase in percent coarse fraction since 5 Ma suggests a gradual increase in CaCO3 preservation. Higher frequency fluctuations in CaCO3 preservation are superimposed on the long-term trend and are related to climate fluctuations. The abrupt drop (-50%) in CaCO3 accumulation at 3.4 Ma signals a dramatic decrease in CaCO3 production that occurred over much of the Indian Ocean.

Lithium and strontium isotopic compositions of sediments and pore waters at ODP Sites 152-918 and 152-919

The distribution of Li isotopes in pore waters to a depth of 1157 m below seafloor is presented for ODP Sites 918 and 919 in the Irminger Basin, offshore Greenland. Lithium isotope data are accompanied by strontium isotope ratios to decipher diagenetic reactions in the sediments which are characterized by the pervasive presence of volcanic material, as well as by very high accumulation rates in the upper section. The lowering of the 87Sr/86Sr ratio below contemporaneous seawater values indicates several zones of volcanic material alteration. The Li isotope profiles are complex suggesting a variety of exchange reactions with the solid phases. These include cation exchange with NH4+ and mobilization from sediments at depth, in addition to the alteration of volcanic matter. Lithium isotopes are, therefore, a sensitive indicator of sediment-water interaction. d6Li values of pore waters at these two sites vary between -42 and -25?. At shallow depths (<100 mbsf), rapid decreases in the Li concentration, accompanied by a shift to heavier isotopic compositions, indicate uptake of Li into alteration products. A positive anomaly of d6Li observed at both sites is coincident with the NH4+ maximum produced by organic matter decomposition and may be related to ion exchange of Li from the sediments by NH4+. In the lower sediment column at Site 918, dissolved Li increases with depth and is characterized by enrichment of 6Li. The Li isotopic compositions of both the waters and the solid phase suggest that the enrichment of Li in deep interstitial waters is a result of release from pelagic sediments. The significance of sediment diagenesis and adsorption as sinks of oceanic Li is evaluated. The maximum diffusive flux into the sediment due to volcanic matter alteration can be no more than 5% of the combined inputs from rivers and submarine hydrothermal solutions. Adsorption on to sediments can only account for 5-10% of the total inputs from rivers and submarine hot springs.