(Table 1) Sapropel analysis from ODP Sites 160-964, 160-966, 160-967 and 160-969

Seventeen eastern Mediterranean Pliocene sapropels from ODP Sites 964, 966, 967 and 969, some of which are coeval, have been analysed for their geochemistry. The sapropels are characterized by very high organic carbon contents (up to 30%) which are reported to be the result of both increased productivity and improved preservation. Although the organic matter in the sapropels is mainly of marine origin, the d13Corg values and C/N ratios appear "terrestrial". This is the result of anaerobic organic matter degradation which preferentially removed nitrogen- and 13C-rich organic components. A comparison with Ti/Al profiles, which mimic the precession index, and a calculation of organic carbon accumulation rates indicate that sedimentation rates were at most 30% lower or at most 50% higher during sapropel formation. Thus, sapropel formation lasted from between 2000 and 10,000 years at Site 964 to between 4500 and 12,000 years at Site 967. A synthesis of new data and a comparison with existing models indicates that productivity, which increased due to extra nutrients supplied as a result of winter mixing and as a result of enhanced input by the Nile, was the driving mechanism behind sapropel formation. The resulting sapropel formation was simultaneous at different depths, but lasted longer in the part of the basin closest to the Nile.

Methane concentrations in sediments of ODP sites 186-1150 and 186-1151

Substantial amounts of adsorbed methane were detected in authigenic carbonate concretions recovered from sedimentary layers from depths between 245 and 1,108 m below seafloor during Ocean Drilling Program Leg 186 to ODP sites 1150 and 1151 on the deep-sea terrace of the Japan Trench. Methane contents were almost two orders of magnitude higher in the concretions (291-4,528 nmol/g wet wt) than in the surrounding bulk sediments (5-93 nmol/g wet wt), whereas methane/ethane ratios and stable carbon isotopic compositions were very similar. Carbonate content of surrounding bulk sediments (0.02-3.2 wet wt%) and methane content of the surrounding bulk sediments correlated positively. Extrapolation of the carbonate contents of bulk sediments suggests that 100 wt% carbonate would correspond to 1,886±732 nmol methane per g bulk sediment, which is similar to the average value observed in the carbonate concretions (1,321±1,067 nmol/g wet wt, n = 13). These data support the hypothesis that, in sediments, adsorbed hydrocarbon gases are strongly associated with authigenic carbonates.

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.

Argon composition and new combined chronologies of ODP Sites 185-1149 and 191-1179

Despite the different scientific objectives of Legs 185 and 191, the sedimentary sections recovered from Sites 1149 and 1179 are the two most complete sections recovered from the northwestern Pacific Basin by either the Deep Sea Drilling Project (DSDP) (i.e., Legs 6, 20, 32, and 86) or ODP (i.e., Legs 185 and 191). During Leg 185, a complete sedimentary section (410 m) and an additional 133 m of highly altered volcanic basement were recovered. The Miocene to Pleistocene section (i.e., upper ~150 m) recovered from Site 1149 includes lithostratigraphic Unit I (0-118.2 meters below sea floor [mbsf]) and Subunit IIA (118.2-149.5 mbsf) of Plank, Ludden, Escutia, et al. (2000, doi:10.2973/odp.proc.ir.185.2000) and consists of ash- and biogenic silica- bearing clay, radiolarian-bearing clay, silt-bearing clay, ash-bearing siliceous ooze, and diatomaceous clay, with numerous discrete volcanic ash layers (Plank, Ludden, Escutia, et al., 2000, doi:10.2973/odp.proc.ir.185.2000). During Leg 191, a near-continuous 375-m-thick sedimentary section was recovered in addition to 100 m of basaltic basement. The upper 221.5 m of the sedimentary section at Site 1179 (i.e., within lithostratigraphic Unit I of Kanazawa, Sager, Escutia et al. [2001, doi:10.2973/odp.proc.ir.191.2001]) consists of upper Miocene to Pleistocene clay- and radiolarian-bearing diatom ooze containing numerous discrete ash layers. The presence of discrete ash layers within the Miocene to Pleistocene sedimentary section at both Site 1149 and 1179 provides a unique opportunity to conduct 40Ar/39Ar ash chronology to refine the excellent magnetostratigraphic records (based on the scale of Berggren et al., 1995) obtained shipboard from both sites (Plank, Ludden, Escutia, et al., 2000, doi:10.2973/odp.proc.ir.185.2000; Kanazawa, Sager, Escutia, et al., 2001, doi:10.2973/odp.proc.ir.191.2001).In this data report we present the analytical results from the 40Ar/39Ar incrementally heated analyses and provide a new combined late Miocene to Pleistocene 40Ar/39Ar and magnetostratigraphic chronology for the northwestern Pacific.

Carbon and deuterium isotopes and C ratios in gas hydrates of ODP Leg 204 sites

Sediments at the southern summit of Hydrate Ridge display two distinct modes of gas hydrate occurrence. The dominant mode is associated with active venting of gas exsolved from the accretionary prism and leads to high concentrations (15%-40% of pore space) of gas hydrate in seafloor or near-surface sediments at and around the topographic summit of southern Hydrate Ridge. These near-surface gas hydrates are mainly composed of previously buried microbial methane but also contain a significant (10%-15%) component of thermogenic hydrocarbons and are overprinted with microbial methane currently being generated in shallow sediments. Focused migration pathways with high gas saturation (>65%) abutting the base of gas hydrate stability create phase equilibrium conditions that permit the flow of a gas phase through the gas hydrate stability zone. Gas seepage at the summit supports rapid growth of gas hydrates and vigorous anaerobic methane oxidation. The other mode of gas hydrate occurs in slope basins and on the saddle north of the southern summit and consists of lower average concentrations (0.5%-5%) at greater depths (30-200 meters below seafloor [mbsf]) resulting from the buildup of in situ-generated dissolved microbial methane that reaches saturation levels with respect to gas hydrate stability at 30-50 mbsf. Net rates of sulfate reduction in the slope basin and ridge saddle sites estimated from curve fitting of concentration gradients are 2-4 mmol/m**3/yr, and integrated net rates are 20-50 mmol/m**2/yr. Modeled microbial methane production rates are initially 1.5 mmol/m**3/yr in sediments just beneath the sulfate reduction zone but rapidly decrease to rates of <0.1 mmol/m**3/yr at depths >100 mbsf. Integrated net rates of methane production in sediments away from the southern summit of Hydrate Ridge are 25-80 mmol/m**2/yr. Anaerobic methane oxidation is minor or absent in cored sediments away from the summit of southern Hydrate Ridge. Ethane-enriched Structure I gas hydrate solids are buried more rapidly than ethane-depleted dissolved gas in the pore water because of advection from compaction. With subsidence beneath the gas hydrate stability zone, the ethane (mainly of low-temperature thermogenic origin) is released back to the dissolved gas-free gas phases and produces a discontinuous decrease in the C1/C2 vs. depth trend. These ethane fractionation effects may be useful to recognize and estimate levels of gas hydrate occurrence in marine sediments.

(Table T1) Nd and Sr isotopic compositions, and Nd and Sm concentrations of glasses from ODP Leg 187 sites

The principal objective of Leg 187 was to locate the Indian/Pacific mantle boundary by sampling and analyzing 8- to 28-Ma seafloor basalts to the north of the Australian Antarctic Discordance (AAD). In this paper we present Sr and Nd isotopic data from basaltic glasses recovered from the 13 sites drilled during Leg 187. Our data show that the boundary region is characterized by a gradual east-west increase in 87Sr/86Sr, with a corresponding decrease in 143Nd/144Nd across a 150-km-wide zone located east and west of the 127°E Fracture Zone. The Sr-Nd isotopic composition of glasses therefore confirms the general conclusions derived by the Leg 187 shipboard scientific party in that the mantle boundary follows a west-pointing, V-shaped depth anomaly that stretches across the ocean floor from the Australian to the Antarctic continental margins. We document that two systematic trends of covariation between 87Sr/86Sr and 143Nd/144Nd can be distinguished, suggesting that the basalts sampled during Leg 187 formed through the interaction of three contrasting source components: (1) a component that lies within the broad spectrum of Indian-type mantle compositions, (2) a boundary component, and (3) a Pacific-type mantle component. The variations in elemental and isotopic compositions indicate that the boundary component represents a distinct mantle region that is associated with the boundary between the Pacific and the Indian mid-ocean-ridge basalt (MORB) sources rather than a dispersed mantle heterogeneity that was preferentially extracted in the boundary region. However, the origin of the boundary component remains an open question. The three components are not randomly intermixed. The Indian and the Pacific mantle sources both interacted with the boundary component, but they seem not to have interacted directly with each other. Large local variability in isotopic compositions of lavas from the mantle boundary region demonstrates that magma extraction processes were unable to homogenize the isotopic contrasts present in the mantle source in this region. Systematic variations in rare earth element (REE) concentrations across the depth anomaly cannot be explained solely by variations in source composition. The observed variations may be explained by an eastward increase and westward decrease in the degree of melting toward the mantle boundary region, compatible with a cooling of the Pacific mantle and a heating of the Indian mantle toward the mantle boundary.

Susceptibility, magnetization and S-ratio of ODP Sites 201-1225 and 201-1227

Samples were collected at Sites 1225 and 1227 to investigate the occurrence of fine-grained, biogenic magnetic particles (magnetosomes). Several magnetic methods, including anhysteretic remanent magnetization and isothermal remanent magnetization, were used to characterize the main magnetic carriers in the samples. Extracts were made to isolate the fine-grained fraction, which was then examined under a transmission electron microscope. Grains with the unique characteristics of magnetosomes were found in samples from regions in the core with both high and low concentrations of magnetic minerals. This suggests they have the potential to be a persistent proxy of paleoredox conditions.

Amino acids in interstitial waters from ODP Sites 126-790 and 126-791

Sites 790 and 791 lie in the eastern half graben of the Sumisu Rift, a backarc graben west of the active Izu-Bonin arc volcanoes Sumisu Jima and Tori Shima, at 30°54.96'N, 139°50.66'E, in 2223 m water depth and 30°54.97'N, 139°52.20'E, in 2268 m water depth, respectively. A small decrease in the sulfate concentration in the interstitial waters from these sites suggests fairly low microbial activity by sulfate-reducing bacteria. The values of the dissolved free amino acids (DFAA) in the interstitial waters from both sites range from 1.26 to 6.82 µmol/L, with an average of 3.81 µmol/L. The acidic, basic, neutral, aromatic, and sulfur-containing amino acids have average values of 0.32, 0.50, 2.71, 0.15, and 0.09 µmol/L, respectively. The relative abundances of the acidic, basic, neutral, aromatic, and sulfur-containing amino acids average 8, 13,72, 4, and 1 mol%, respectively. Glycine, serine, alanine, ornithine, and aspartic acid are major constituent amino acids. The dissolved combined amino acids (DCAA) values range between 1.25 and 44.35 µmol/L, with an average of 10.36 µmol/L. The mean concentrations and relative abundances of the acidic, basic, neutral, aromatic, and sulfur-containing amino acids are 2.29 (22 mol%), 0.60 (6 mol%), 6.70 (65 mol%), 0.09 (1 mol%), and 0.00 µmol/L (0 mol%), respectively. Glycine is the most abundant amino acid residue, followed by glutamic acid, serine, and alanine. The predominance of DCAA over DFAA present in the interstitial waters from Sites 790 and 791 is consistent with previous results from interstitial-water and seawater analyses. The most plausible source for the DCAA is biogenic calcareous debris. A much greater depletion of aspartic acid and the basic fraction, except for ornithine, is found in the DCAA. The decomposition of the basic amino acid fraction or its incorporation to clay minerals would result in a decrease in its relative abundance, whereas ornithine is produced during early diagenesis. The characteristics of the amino acids in the interstitial waters are (1) a greater depletion of the acidic amino acid fraction in the DFAA than in the DCAA and (2) the enrichment of glycine and serine in both. The adsorption or reaction of the amino acids in interstitial waters with biogenic carbonates would be responsible for the lower relative abundance of the acidic fraction of the DFAA. The production of glycine during early diagenesis and its stability in solution would raise its relative abundance in the interstitial waters.

The Paleocene-Eocene boundary in ODP Leg 208 sites

The Paleocene-Eocene thermal maximum (PETM) has been attributed to the rapid release of ~2000 * 10**9 metric tons of carbon in the form of methane. In theory, oxidation and ocean absorption of this carbon should have lowerd deep-sea pH, thereby triggering a rapid (<10,000-year) shoaling of the calcite compensation depth (CCD), followed by gradual recovery. Here we present geochemical data from five new South Atlantic deep-sea sections that constrain the timing and extent of massive sea-floor carbonate dissolution coincident with the PETM. The sections, from between 2.7 and 4.8 kilometers water depth, are marked by a prominent clay layer, the character of which indicates that the CCD shoaled rapidly (<10,000 years) by more than 2 kilometers and recovered gradually (>100,000 years). These findings indicate that a large mass of carbon (>>2000 * 10**9 metric tons of carbon) dissolved in the ocean at the Paleocene-Eocene boundary and that permanent sequestration of this carbon occurred through silicate weathering feedback.

Median grain size in ODP Sites 184-1143 and 184-1144

Monsoon climate is an important component of the global climatic system. A comprehensive understanding of its variability over glacial-interglacial time scales as well as of its effects on the continent and in the ocean is required to decipher links between climate, continental weathering and productivity. A detailed multiproxy study, including bulk and clay mineralogy, grain-size analysis, phosphorus geochemistry (SEDEX extraction), organic matter characterization, and nitrogen stable isotopes, was carried out on samples from ODP Sites 1143 and 1144 (Leg 184, South China Sea), covering the past 140 000 years. We tentatively reconstruct the complex sedimentation and climatic history of the region during the last glacial-interglacial cycle, when sea-level variations, linked to the growth and melting of ice caps, interact with monsoon variability. During interglacial periods of high sea level, summer monsoon was strong, and humid and warm climate characterized the adjacent continent and islands. Clay minerals bear signals of chemical weathering during these intervals. High calcite and reactive phosphorus mass accumulation rates (MARs) indicate high productivity, especially in the southern region of the basin. During glacial intervals, strong winter monsoon provided enhanced detrital input from the continent, as indicated by high detrital MAR. Glacial low sea level resulted in erosion of sediments from the exposed Sunda shelf to the south, and clay mineral variations indicate that warm and humid conditions still prevailed in the southern tropical areas. Enhanced supply of nutrients from the continent, both by river and eolian input, maintained high primary productivity. Reduced circulation during these periods possibly induced active remobilization of nutrients, such as phosphorus, from the sediments. Intense and short cold periods recorded during glacial and interglacial stages correlate with loess records in China and marine climatic records in the North Atlantic, confirming a teleconnection between low- and high-latitude climate variability.

40Ar-39Ar investigation of volcanic clasts in glaciogenic sediments at ODP Sites 1097 and 1103

Three selected diamictite samples recovered within sequence group S3 at Sites 1097 (Sample 178-1097A-27R-1, 35-58 cm) and 1103 (Samples 178-1103A-31R-2, 0-4 cm, and 36R-3, 4-8 cm) of Ocean Drilling Program Leg 178 have been investigated by scanning electron microscope, electron microprobe, and 40Ar-39Ar laser-heating techniques. They contain variable proportions of fragments of volcanic rock groundmass (mostly in the range of 100-150 µm) with textures ranging from microcrystalline to ipocrystalline. Their rounded shapes indicate mechanical reworking. Fresh groundmass glasses, recognized only in grains from samples of Site 1103, show mainly a subalkaline affinity on the basis of total alkali-silica variations. However, they are characterized by relatively high TiO2 and P2O5 contents (1.4-2.8 and 0.1-0.9 wt%, respectively). Because of the small size of homogeneous grains (100-150 µm), they were not suitable for single-grain total fusion 40Ar-39Ar analyses. The incremental laser-heating technique was applied to milligram-sized samples (only for Samples 178-1097A-27R-1, 35-58 cm, and 178-1103A-36R-3, 4-8 cm) and to various small fractions (each consisting of 10 grains for the sample from Site 1097 and 30 grains for samples from Site 1103). The latter approach resulted in more effective resolution of sample heterogeneity. Argon ages from the small fractions show significantly different ranges in the three samples: 75-173 Ma for Sample 178-1097A-27R-1, 35-58 cm, 18-57 Ma for Sample 178-1103A-31R-2, 0-4 cm, and 7.6-50 Ma for Sample 178-1103A-36R-3, 4-8 cm. Ca/K ratios derived from argon isotopes at Site 1103 suggest that the data mainly refer to outgassing of groundmass glass. At Site 1103, we observe an overall apparent age increase with decreasing sample depth. This is compatible with glacial erosion that affected with time deeper levels of a volcanic sequence previously deposited on the continent. The youngest apparent age of 7.6 ± 0.7 Ma detected close to the bottom of Hole 1103A (340 meters below seafloor [mbsf]) is compatible with the age range of the diatom Actinocyclus ingens v. ovalis Zone (6.3-8.0 Ma) determined for the interval 320-355 mbsf and with the maximum ages derived from strontium isotope composition of barnacle fragments obtained at 262-263 mbsf at the same site. Nevertheless, this age cannot be taken as the maximum youngest age of the volcanic sequence sampled by glacial erosion or as the maximum age for the deposition of the Sequence S3 at 340 mbsf unless validated by further research.