(Table A1) Chemical composition of abyssal peridotites from ODP Hole 153-920

The compatibility of vanadium (V) during mantle melting is a function of oxygen fugacity (fO2): at high fO2's, V becomes more incompatible. The prospects and limitations of using the V content of peridotites as a proxy for paleo-fO2 at the time of melt extraction were investigated here by assessing the uncertainties in V measurements and the sensitivity of V as a function of degree of melt extracted and fO2. V-MgO and V-Al2O3 systematics were found to be sensitive to fO2 variations, but consideration of the uncertainties in measurements and model parameters indicates that V is sensitive only to relative fO2 differences greater than ~2 log units. Post-Archean oceanic mantle peridotites, as represented by abyssal peridotites and obducted massif peridotites, have V-MgO and -Al2O3 systematics that can be modeled by 1.5 GPa melting between FMQ - 3 and FMQ - 1. This is consistent with fO2's of the mantle source for mid-ocean ridge basalts (MORBs) as determined by the Fe3+ activity of peridotitic minerals and basaltic glasses. Some arc-related peridotites have slightly lower V for a given degree of melting than oceanic mantle peridotites, and can be modeled by 1.5 GPa melting at fO2's as high as FMQ. However, the majority of arc-related peridotites have V-MgO systematics overlapping that of oceanic mantle peridotites, suggesting that although some arc mantle may melt under slightly oxidizing conditions, most arc mantle does not. The fact that thermobarometrically determined fO2's in arc peridotites and lavas can be significantly higher than that inferred from V systematics, suggests that V retains a record of the fO2 during partial melting, whereas the activity of Fe3+ in arc peridotitic minerals and lavas reflect subsequent metasomatic overprints and magmatic differentiation/emplacement processes, respectively. Peridotites associated with middle to late Archean cratonic mantle are characterized by highly variable V-MgO systematics. Tanzanian cratonic peridotites have V systematics indistinguishable from post-Archean oceanic mantle and can be modeled by 3 GPa partial melting at ~FMQ - 3. In contrast, many South African and Siberian cratonic peridotites have much lower V contents for a given degree of melting, suggesting at first glance that partial melting occurred at high fO2's. More likely, however, their unusually low V contents for a given degree of melting may be artifacts of excess orthopyroxene, a feature that pervades many South African and Siberian peridotites but not the Tanzanian peridotites. This is indicated by the fact that the V contents of South African and Siberian peridotites are correlated with increases in SiO2 content, generating data arrays that cannot be modeled by partial melting but can instead be generated by the addition of orthopyroxene through processes unrelated to primary melt depletion. Correction for orthopyroxene addition suggests that the South African and Siberian peridotites have V-MgO systematics similar to those of Tanzanian peridotites. Thus, if the Tanzanian peridotites represent the original partial melting residues, and if the South African and Siberian peridotites have been modified by orthopyroxene addition, then there is no indication that Archean cratonic mantle formed under fO2's significantly greater than that of modern oceanic mantle. Instead, the fO2's inferred from the V systematics in these three cratonic peridotite suites are within range of modern oceanic mantle. This also suggests that the transition from a highly reducing mantle in equilibrium with a metallic core to the present oxidized state must have occurred by late Archean times.

Organic geochemistry of DSDP Site 467

Results of the analyses of twenty-three samples from the Middle Miocene to Lower Pliocene strata from DSDP Site 467, offshore California, are presented. The analyses were performed with the aim of determining the origin of the organic matter, the stratigraphic section's hydrocarbon generation potential and extent of organic diagenesis. Organic carbon contents are an order of magnitude greater than those typically found in deep sea sediments, suggesting an anoxic depositional environment and elevated levels of primary productivity. Hydrocarbon generation potentials are above average for most samples. The results of elemental analyses indicate that the kerogens are primarily composed of type II organic matter and are thermally immature. Analysis of the bitumen fractions confirms that the samples are immature. In cores from 541 to 614 meters, the gas chromatograms of the C15+ non-aromatic hydrocarbon fractions are dominated by a single peak which was identified as 17*(H), 18*(H), 21beta(H)-28, 30-bisnorhopane. This interval is the same area in which the highest degrees of anoxia are observed as reflected by the lowest pristane/phytane ratios. This correlation may have some implications with regard to the origin of the bisnorhopane and its possible use as an indicator of anoxic depositional conditions within thermally immature sediments.

Strontium and neodymium isotope data for barite separates and pore waters, and isotope and concentration data for foraminifera and fish teeth from DSDP Leg 85 sediments

Strontium and neodymium isotopic data are reported for barite samples chemically separated from Late Miocene to Pliocene sediments from the eastern equatorial Pacific. At a site within a region of very high productivity close to the equator, 87Sr/86Sr ratios in the barite separates are indistinguishable from those of foraminifera and fish teeth from the same samples. However, at two sites north of the productivity maximum barite separates have slightly, but consistently lower (averaging 0.000062) ratios than the coexisting phases, although values still fall within the total range of published values for the contemporaneous seawater strontium isotope curve. We examine possible causes for this offset including recrystallization of the foraminifera, fish teeth or barite, the presence of non-barite contaminants, or incorporation of older, reworked deep-sea barite; the inclusion of a small amount of hydrothermal barite in the sediments seems most consistent with our data, although there are difficulties associated with adequate production and transportation of this phase. Barite is unlikely to replace calcite as a preferred tracer of seawater strontium isotopes in carbonate-rich sediments, but may prove a useful substitute in cases where calcite is rare or strongly affected by diagenesis. In contrast to the case for strontium, neodymium isotopic ratios in the barite separates are far from expected values for contemporary seawater, and appear to be dominated by an (unobserved) eolian component with high neodymium concentration and low 143Nd/144Nd. These results suggest that the true potential of barite as an indicator of paleocean neodymium isotopic ratios and REE patterns will be realized only when a more selective separation procedure is developed.

South Pacific dissolved Nd isotope compositions, rare earth element and nutrient concentrations from SONNE cruise SO213

Despite its enormous extent and importance for global climate, the South Pacific has been poorly investigated in comparison to other regions with respect to chemical oceanography. Here we present the first detailed analysis of dissolved radiogenic Nd isotopes (epsilon-Nd) and rare earth elements (REEs) in intermediate and deep waters of the mid-latitude (~40°S) South Pacific along a meridional transect between South America and New Zealand. The goal of our study is to gain better insight into the distribution and mixing of water masses in the South Pacific and to evaluate the validity of Nd isotopes as a water mass tracer in this remote region of the ocean. The results demonstrate that biogeochemical cycling (scavenging processes in the Eastern Equatorial Pacific) and release of LREEs from the sediment clearly influence the distribution of the dissolved REE concentrations at certain locations. Nevertheless, the Nd isotope signatures clearly trace water masses including AAIW (Antarctic Intermediate Water) (average epsilon-Nd = -8.2 ± 0.3), LCDW (Lower Circumpolar Deep Water) (average epsilon-Nd = -8.3 ± 0.3), NPDW (North Pacific Deep Water) (average epsilon-Nd = -5.9 ± 0.3), and the remnants of NADW (North Atlantic Deep Water) (average epsilon-Nd = -9.7 ± 0.3). Filtered water samples taken from the sediment-water interface under the deep western boundary current off New Zealand suggest that boundary exchange processes are limited at this location and highlight the spatial and temporal variability of this process. These data will serve as a basis for the paleoceanographic application of Nd isotopes in the South Pacific.

Geochemistry of volcanic rocks from the Hikurangi and Manihiki Plateaus

Here we present the first radiometric age data and a comprehensive geochemical data set (including major and trace element and Sr-Nd-Pb-Hf isotope ratios) for samples from the Hikurangi Plateau basement and seamounts on and adjacent to the plateau obtained during the R/V Sonne 168 cruise, in addition to age and geochemical data from DSDP Site 317 on the Manihiki Plateau. The 40Ar/39Ar age and geochemical data show that the Hikurangi basement lavas (118-96 Ma) have surprisingly similar major and trace element and isotopic characteristics to the Ontong Java Plateau lavas (ca. 120 and 90 Ma), primarily the Kwaimbaita-type composition, whereas the Manihiki DSDP Site 317 lavas (117 Ma) have similar compositions to the Singgalo lavas on the Ontong Java Plateau. Alkalic, incompatible-element-enriched seamount lavas (99-87 Ma and 67 Ma) on the Hikurangi Plateau and adjacent to it (Kiore Seamount), however, were derived from a distinct high time-integrated U/Pb (HIMU)-type mantle source. The seamount lavas are similar in composition to similar-aged alkalic volcanism on New Zealand, indicating a second wide-spread event from a distinct source beginning ca. 20 Ma after the plateau-forming event. Tholeiitic lavas from two Osbourn seamounts on the abyssal plain adjacent to the northeast Hikurangi Plateau margin have extremely depleted incompatible element compositions, but incompatible element characteristics similar to the Hikurangi and Ontong Java Plateau lavas and enriched isotopic compositions intermediate between normal mid-ocean-ridge basalt (N-MORB) and the plateau basement. These younger (~52 Ma) seamounts may have formed through remelting of mafic cumulate rocks associated with the plateau formation. The similarity in age and geochemistry of the Hikurangi, Ontong Java and Manihiki Plateaus suggest derivation from a common mantle source. We propose that the Greater Ontong Java Event, during which ?1% of the Earth's surface was covered with volcanism, resulted from a thermo-chemical superplume/dome that stalled at the transition zone, similar to but larger than the structure imaged presently beneath the South Pacific superswell. The later alkalic volcanism on the Hikurangi Plateau and the Zealandia micro-continent may have been part of a second large-scale volcanic event that may have also triggered the final breakup stage of Gondwana, which resulted in the separation of Zealandia fragments from West Antarctica.

Geochemical and rock magnetic investigation of sediment cores of the western South Atlantic

Geochemical and rock magnetic investigations of sediments from three sites on the continental margin off Argentina and Uruguay were carried out to study diagenetic alteration of iron minerals driven by anaerobic oxidation of methane (AOM). The western Argentine Basin represents a suitable sedimentary environment to study nonsteady-state processes because it is characterized by highly dynamic depositional conditions. Mineralogic and bulk solid phase data document that the sediment mainly consists of terrigenous material with high contents of iron minerals. As a typical feature of these deposits, distinct minima in magnetic susceptibility (k) are observed. Pore water data reveal that these minima in susceptibility coincide with the current depth of the sulfate/methane transition (SMT) where HS- is generated by the process of AOM. The released HS- reacts with the abundant iron (oxyhydr)oxides resulting in the precipitation of iron sulfides accompanied by a nearly complete loss of magnetic susceptibility. Modeling of geochemical data suggest that the magnetic record in this area is highly influenced by a drastic change in mean sedimentation rate (SR) which occurred during the Pleistocene/Holocene transition. We assume that the strong decrease in mean SR encountered during this glacial/interglacial transition induced a fixation of the SMT at a specific depth. The stagnation has obviously enhanced diagenetic dissolution of iron (oxyhydr)oxides within a distinct sediment interval. This assumption was further substantiated by numerical modeling in which the mean SR was decreased from 100 cm/kyr during glacial times to 5 cm/kyr in the Holocene and the methane flux from below was fixed to a constant value. To obtain the observed geochemical and magnetic patterns, the SMT must remain at a fixed position for ~9000 yrs. This calculated value closely correlates to the timing of the Pleistocene/Holocene transition. The results of the model show additionally that a constant high mean SR would cause a concave-up profile of pore water sulfate under steady state conditions.

Bromine and iodine concentrations in sediments and pore fluids of ODP Leg 112

At the Peruvian convergent margin, two distinct pore fluid regimes are recognized from differences in their Cl- concentrations. The slope pore fluids are characterized by low Cl- concentrations, but elevated Br- and I- concentrations due to biogenic production. The shelf pore fluids exhibit elevated Cl- and Br- concentrations due to diffusive mixing with an evaporitic brine. In the slope pore fluids, the Br-, I-, and NH4+ concentrations are elevated following bacterial decomposition of organic matter, but the I- concentrations are in excess of those expected based on mass balance calculations using NH4+ and Br- concentrations. The slope sediment organic matter, which is enriched in iodine from oxidationreduction processes at the oxygenated sediment-water interface, is responsible for this enrichment. The increases in dissolved I- and the I- enrichments relative to NH4+ and Br- correlate well with sedimentation rates because of differential trapping following regeneration. The pore-fluid I-/Br- ratios suggest that membrane ion fiitration is not a major cause of the decreases in Cl- concentrations. Other possible sources for low Cl- water, including meteoric water, clathrate dissociation, and/or mineral dehydration reactions, imply that the diluting component of the slope low-Cl- fluids has flowed at least 1 km through the sediment. The low bottom-water oxygenation in the shelf is responsible for the low (if any) enrichment of iodine in the shelf sediments. Fluctuations in bottom-water oxygen concentrations in the past, however, may be responsible for the observed variations in the sediment I/Br ratios. Comparison of Na+/Cl- and Br-/Cl- molar ratios in the pore fluids shows that the shelf high-Cl- fluid formed from mixing with a brine that formed from seawater concentrated by twelve to nineteen times and probably was modified by halite dissolution. This dense brine, located below the sediment sections drilled, appears to have flowed a distance >500 km through the sediment.

Chemical and mineral compositions of basalts and volcanic glasses from DSDP Sites 65-483 and 65-485

Major and rare earth element (REE) data for basalts from Holes 483, 483B, and 485A of DSDP Leg 65, East Pacific Rise, mouth of the Gulf of California, support a simple fractional crystallization model for the genesis of rocks from this suite. The petrography and mineral chemistry (presented in detail elsewhere) provide no evidence for magma mixing, but rather a simple multistage cooling process. Based on its lowest TiO2 content (0.88%), FeO*/MgO ratio (0.95 with total Fe as FeO), and Mg# (100 Mg/Mg + Fe" = 70), sample 483-17-2-(78-83) has been selected as the most primitive primary magma of the samples analyzed. This is supported by the REE data which show this sample has the lowest total REE content, a La/Sm_cn (chondrite-normalized) = 0.36, and Eu/Sm_cn = 1.05. Because other samples analyzed have higher SiO2, lower Mg#, and a negative Eu anomaly (Eu/Sm_cn as low as 0.89), they are most likely derivative magmas. Wright-Doherty and trace element modelling support fractional crystallization of 14.1% plagioclase (An88), 6.7% olivine (Fo86), and 4.7% clinopyroxene (Wo41En49Fs10) from 483-17-2-(78-83) to form the least differentiated sample with Mg# = 63. The La/Sm_cn of this derivative magma is almost identical to the parent magma (0.35 to 0.36), but the other samples have higher La/Sm_cn (0.45 to 0.51), more total REE, and lower Mg# (60 to 56). Both Wright-Doherty and trace element modelling indicate that the primary magma chosen cannot produce these more evolved samples. For the major elements, the TiO2 and P2O5 are too low in the calculated versus the observed (1.38 to 1.90; 0.11 to 0.17, respectively, for example). Rayleigh fractionation calculates a lower La/Sm_cn and requires about 60% crystal removal versus 40% for the Wright-Doherty. These more evolved samples must be derived from a parent magma different from the one selected here and, unfortunately, not sampled in this study. A magma formed by a smaller degree of partial melting with slightly more residual clinopyroxene left in the mantle than for sample 483-17-2-(78-83) is required.