(Table 1) Lead isotopic composition and concentration at DSDP Leg 82 Holes

The aim of DSDP Leg 82 was to decipher the temporal and spatial evolution of Azores Plume. The Pb-isotopic results of this leg are rather complex, and can be summarized as follows: 1. At a given site (561, 558), variations of Pb isotopic compositions are generally accompanied by major changes in trace-element ratios, indicating significant heterogeneity of the source region. There is a correlation between Pb isotopes and trace elements. 2. In contrast, if all the data (i.e., all studied sites) of Leg 82 are considered together, no correlation can be discerned between Pb isotopes and trace elements. Site 556, especially, shows abnormal behavior. 3. Leg 82 samples not only cover the entire range of Pb isotopic composition previously established for the Atlantic Ocean, but extend this field to more radiogenic values. 4. The data are compatible with the hot-spot model proposed by Schilling (1975), if one considers that the Azores Plume itself is isotopically heterogeneous, and that it has been progressively contaminated to various degrees by upper mantle material.

(Table 1) Sulfur content and sulfur-isotope ratios at DSDP Leg 82 Holes basalts

The sulfur contents of 21 basalt samples from four DSDP Leg 82 holes were determined and the isotopic compositions of sulfur were measured on 15 of them. Most of the basalts are altered and have sulfur contents of about 100 ppm. Isotopic ratios for sulfate and total sulfur range from +0.7 to +10.5 per mil, indicating almost complete leaching of the igneous sulfide in low-sulfur samples by alteration. Total sulfur content of some samples ranges between 960 and 1170 ppm, somewhat higher than expected for tholeiitic basalts. The isotope ratios of total sulfur in these samples are slightly shifted to values heavier than the generally assumed mantle ratio of zero, and this shift is thought to result from a secondary source of sulfur.

Grain-size and bulk and clay mineralogy of ODP Leg 204 sediments

We present grain size, granulometric statistical parameters, and calcium carbonate content of sediment samples from the summit and east and west flanks of southern Hydrate Ridge (Sites 1244-1250). These data are compared with magnetic susceptibility measurements from the same intervals. Bulk and clay mineralogy from Sites 1244 (east flank), 1247 (west flank), and 1250 (summit) are also presented. The integration of these data allows us to characterize the main sedimentary facies and composition of the Quaternary age sediments from southern Hydrate Ridge.

Interstitial water chemistry, Deep Sea Drilling Project, Leg 96

On Leg 96 of the Deep Sea Drilling Project (DSDP), holes were drilled in Orca and Pigmy basins on the northern Gulf of Mexico continental slope and on the Mississippi Fan. The holes on the fan encountered interbedded sand, silt, and mud deposited extremely rapidly, most during late Wisconsin glacial time. Pore-water chemistry in these holes is variable, but does not follow lithologic changes in any simple way. Both Ca and SO4 are enriched in the pore water of many samples from the fan. Two sites drilled in the prominent central channel of the middle fan show rapid SO4 reduction with depth, whereas two nearby sites in overbank deposits show no sulfate reduction for 300 m. Calcium concentration decreases as SO4 is depleted and Li follows the same pattern. Strontium, which like Li, is enriched in samples enriched in Ca, does not decrease with SO4 and Ca. Potassium in the pore water decreases with depth at almost all sites. Sulfate reduction was active at the two basin sites and, as on the fan, this resulted in calcium carbonate precipitation and a lowering of pore water Ca, Mg, and Li. The Orca Basin site was drilled through a brine pool of 258? salinity. Pore-water salinity decreases smoothly with depth to 50 m and remains well above normal seawater values to the bottom of the hole at about 90 m. This suggests constant sedimentation under anoxic hypersaline conditions for at least the last 50,000 yr.

Mineral composition and geochemistry of sediments from ODP Leg 127 sites

The lithostratigraphy of Neogene hemipelagic sediments recovered from the Japan Sea during Leg 127 was revised to improve intersite consistency and to remove confusion stemming from diagenetic modification of the lithology through the opal-A to opal-CT transformation. Special emphasis was put on the presence and nature of dark-light cycles in revising the lithostratigraphy. Mineral composition analysis was conducted for samples from Sites 794, 795, and 797. In addition, major element chemical composition analysis was conducted for these same sample sets from Site 794. The result of mineral composition analysis suggests that the detrital component, which consists of such minerals as quartz, plagioclase, illite, and kaolinite plus chlorite, is diluted to various degrees by biogenic silica (opal-A) and its diagenetic equivalents (opal-CT and quartz). Smectite, on the other hand, may be a diagenetic or hydrothermal alteration product of volcanic material, although more study is necessary to confirm its origin. As a whole, vertical variation in the sediment composition is consistent with the revised lithostratigraphy and helps to characterize the redefined lithologic units quantitatively.

(Table S1) Stable oxygen isotope record of barite from DSDP Leg 85 sites

Oxygen isotopes in marine sulfate (d18O SO4) measured in marine barite show variability over the past 10 million years, including a 5per mil decrease during the Plio-Pleistocene, with near-constant values during the Miocene that are slightly enriched over the modern ocean. A numerical model suggests that sea level fluctuations during Plio-Pleistocene glacial cycles affected the sulfur cycle by reducing the area of continental shelves and increasing the oxidative weathering of pyrite. The data also require that sulfate concentrations were 10 to 20% lower in the late Miocene than today.

Iron and phosphorus speciations in DSDP Leg 92 sediments

We present a detailed study of the co-diagenesis of Fe and P in hydrothermal plume fallout sediments from ~19°S on the southern East Pacific Rise. Three distal sediment cores from 340-1130 km from the ridge crest, collected during DSDP Leg 92, were analysed for solid phase Fe and P associations using sequential chemical extraction techniques. The sediments at all sites are enriched in hydrothermal Fe (oxyhydr)oxides, but during diagenesis a large proportion of the primary ferrihydrite precipitates are transformed to the more stable mineral form of goethite and to a lesser extent to clay minerals, resulting in the release to solution of scavenged P. However, a significant proportion of this P is retained within the sediment, by incorporation into secondary goethite, by precipitation as authigenic apatite, and by readsorption to Fe (oxyhydr)oxides. Molar P/Fe ratios for these sediments are significantly lower than those measured in plume particles from more northern localities along the southern East Pacific Rise, and show a distinct downcore decrease to a depth of ~12 m. Molar P/Fe ratios are then relatively constant to a depth of ~35 m. The Fe and P speciation data indicate that diagenetic modification of the sediments is largely complete by a depth of 2.5 m, and thus depth trends in molar P/Fe ratios can not solely be explained by losses of P from the sediment by diffusion to the overlying water column during early diagenesis. Instead, these sediments are likely recording changes in dissolved P concentrations off the SEPR, possibly as a result of redistribution of nutrients in response to changes in oceanic circulation over the last 10 million years. Furthermore, the relatively low molar P/Fe ratios observed throughout these sediments are not necessarily solely due to losses of scavenged P by diffusion to the overlying water column during diagenesis, but may also reflect post-depositional oxidation of pyrite originating from the volatile-rich vents of the southern East Pacific Rise. This study suggests that the molar P/Fe ratio of oxic Fe-rich sediments may serve as a proxy of relative changes in paleoseawater phosphate concentrations, particularly if Fe sulfide minerals are not an important component during transport and deposition.

Nature, origin, and petroleum source potential of organic matter at DSDP Leg 56-57 Holes

As part of a continuing program of organic-geochemistry studies of sediments recovered by the Deep Sea Drilling Project, we have analyzed the types, amounts, and thermal-alteration indices of organic matter in samples collected from the landward wall of the Japan Trench on Legs 56 and 57. The samples were canned aboard ship, enabling us to measure also their gas contents. In addition, we analyzed the heavy C15+ hydrocarbons, NSO compounds, and asphaltenes extracted from selected samples. Our samples form a transect down the trench wall, from Holes 438 and 438A (water depth 1558 m), through Holes 435 and 435A (water depth 3401 m), and 440 (water depth 4507 m), to Holes 434 and 434B (water depth 5986 m). The trench wall is the continental slope of Japan. Its sediments are Cenozoic hemipelagic diatomaceous muds that were deposited where they are found or have slumped from farther up the slope. Their terrigenous components probably were deposited from near-bottom nepheloid layers transported by bottom currents or in low density flows (Arthur et al., 1978). Our objective was to find out what types of organic matter exist in the sediment and to estimate their potential for generation of hydrocarbons.

Petrology, mineralogy, and chemistry of basaltic rocks at DSDP Leg 81 Holes

We detail the petrography and mineralogy of 145 basaltic rocks from the top, middle, and base of flow units identified on shipboard along with associated pyroclastic samples. Our account includes representative electron microprobe analyses of primary and secondary minerals; 28 whole-rock major-oxide analyses; 135 whole-rock analyses each for 21 trace elements; 7 whole-rock rare-earth analyses; and 77 whole-rock X-ray-diffraction analyses. These data show generally similar petrography, mineralogy, and chemistry for the basalts from all four sites; they are typically subalkaline and consanguineous with limited evolution along the tholeiite trend. Limited fractionation is indicated by immobile trace elements; some xenocrystic incorporation from more basic material also occurred. Secondary alteration products indicate early subaerial weathering followed by prolonged interaction with seawater, most likely below 150°C at Holes 552, 553A, and 554A. At Hole 555, greenschist alteration affected the deepest rocks (olivine-dolerite) penetrated, at 250-300°C.