Isotopic composition of rocks from the Lau/Tonga back-arc basin, data of DSDP Leg 21 and ODP Legs 91 an 135

New trace element, Sr-, Nd-, Pb- and Hf isotope data provide insights into the evolution of the Tonga-Lau Basin subduction system. The involvement of two separate mantle domains, namely Pacific MORB mantle in the pre-rift and early stages of back-arc basin formation, and Indian MORB mantle in the later stages, is confirmed by these results. Contrary to models proposed in recent studies on the basis of Pb isotope and other compositional data, this change in mantle wedge character best explains the shift in the isotopic composition, particularly 143Nd/144Nd ratios, of modern Tofua Arc magmas relative to all other arc products from this region. Nevertheless, significant changes in the slab-derived flux during the evolution of the arc system are also required to explain second order variations in magma chemistry. In this region, the slab-derived flux is dominated by fluid; however, these fluids carry Pb with sediment-influenced isotopic signatures, indicating that their source is not restricted to the subducting altered mafic oceanic crust. This has been the case from the earliest magmatic activity in the arc (Eocene) until the present time, with the exception of two periods of magmatic activity recorded in samples from the Lau Islands. Both the Lau Volcanic Group, and Korobasaga Volcanic Group lavas preserve trace element and isotope evidence for a contribution from subducted sediment that was not transported as a fluid, but possibly in the form of a melt. This component shares similarities with that influencing the chemistry of the northern Tofua Arc magmas, suggesting some caution may be required in the adoption of constraints for the latter dependent upon the involvement of sediments from the Louisville Ridge. A key outcome of this study is to demonstrate that the models proposed to explain subduction zone magmatism cannot afford to ignore the small but important contributions made by the mantle wedge to the incompatible trace element inventory of arc magmas.

Sediment texture, carbonate content, and carbonate mineralogy of ODP Holes 182-1130A and 182-1132B

At Sites 1130 and 1132 of Ocean Drilling Program Leg 182 in the Great Australian Bight, we recovered an expanded Pleistocene section dominated by packstone and wackestone, deposited at unusually high rates of >20 cm/k.y. Shipboard observations detected an intermittent meter-scale alternation of light gray intervals with olive-gray intervals. Meter-scale samples were collected from the upper 250 m at both sites and decimeter-scale samples from four selected 2.5- to 4.0-m intervals in order to determine the texture and composition of sediments deposited along the upper slope throughout the Quaternary. Detailed textural and compositional data are presented from a total of 540 samples collected from both sites. Results indicate a general coarsening upward at both sites, with an accompanying upcore increase in high-Mg calcite (HMC) and aragonite and a decrease in low-Mg calcite (LMC). Samples collected at decimeter-scale intervals substantiate that the alternating light gray and olive-gray units detected on board ship are lithologically distinct. Light gray units consist of an LMC-rich silt, whereas olive-gray units consist of an aragonite and HMC-rich sand and silt. Sediment sources as well as timing and controls of this cyclic depositional pattern will be the subject of further investigations.

Stable isotopes, sedimentology and geochemical analyses of Middle Eocene to early Miocene sediments of ODP Site 177-1090

During Leg 177 of the Ocean Drilling Program (ODP), a well-preserved middle Eocene to lower Miocene sediment record was recovered at Site 1090 on the Agulhas Ridge in the Atlantic sector of the Southern Ocean. This new sediment record shows evidence of a hitherto unknown late Eocene opal pulse. Lithological variations, compositional data, mass-accumulation rates of biogenic and lithogenic sediment constituents, grain-size distributions, geochemistry, and clay mineralogy are used to gain insights into mid-Cenozoic environmental changes and to explore the circumstances of the late Eocene opal pulse in terms of reorganizations in ocean circulation. The base of the section is composed of middle Eocene nannofossil oozes mixed with red clays enriched in authigenic clinoptilolite and smectite, deposited at low sedimentation rates (LE 2 cm/ka). It indicates reduced terrigenous sediment input and moderate biological productivity during this preglacial warm climatic stage. The basal strata are overlain by an extended succession (100 m, 4 cm/ka) of biosiliceous oozes and muds, comprising the upper middle Eocene, the entire late Eocene, and the lowermost early Oligocene. The opal pulse occurred between 37.5 and 33.5 Ma and documents the development of upwelling cells along topographic highs, and the utilization of a marine nutrient- and silica reservoir established during the pre-late Eocene through enhanced submarine hydrothermal activity and the introduction of terrigenous solutions from chemical weathering on adjacent continents. This palaeoceanographic overturn probably was initiated through the onset of increased meridional ocean circulation, caused by the diversion of the Indian equatorial current to the south. The opal pulse was accompanied by increased influxes of terrigenous detritus from southern African sources (illite), mediated by enhanced ocean particle advection in response to modified ocean circulation. The opal pulse ended because of frontal shifts to the south around the Eocene/Oligocene boundary, possibly in response to the opening of the Drake Passage and the incipient establishment of the Antarctic Circumpolar Current. Condensed sediments and a hiatus within the early Oligocene part of the section possibly point to an invigoration of the deep-reaching Antarctic Circumpolar Current. The mid-Oligocene to lower Miocene section on long time scale exhibits less pronounced lithological variations than the older section and points to relatively stable palaeoceanographic conditions after the dramatic changes in the late Eocene to early Oligocene.

Fe-Mn nodules and host sediments from the Gulf of Finland

Distributions of major and trace elements in ferromanganese nodules, which are buried or exposed on the sea floor and in host sediments, were studied in ten concretion/sediment pairs by various physical and chemical methods. It was established that, in addition to Fe and Mn, a limited number of major and trace elements (P, Ca, Sr, Ba, Mo, Co, Zn, Ni, As, Pb, Sb, Tl, U, W, Y, and Ga) is accumulated with variable degree of intensity (relative to sediments) in the nodules. The maximal content of Mn in the nodules is 100 times higher than in the host sediments, whereas for all other elements listed above these ratios vary from more than one to 10-20. Manganese and, to a lesser extent, Ba and Sr are concentrated in the buried concretions. Other elements are primarily concentrated in concretions exposed on the sea floor. The occurrence mode of the concretions and compositional data on interstitial water suggest that metals in the concretions derive from seawater and suspended particulates, in addition to sediments. Burial of concretions in the sediment pile is accompanied by alteration of their composition, accumulation of Mn (relative to Fe), and loss of several associated metals.

Chemistry of magmatic samples of ODP Holes 134-832B and 134-833B

New petrographic and compositional data were reported for 143 samples of core recovered from Sites 832 and 833 during Ocean Drilling Program (ODP) Leg 134. Site 832 is located in the center and Site 833 is on the eastern edge of the North Aoba Basin, in the central part of the New Hebrides Island Arc. This basin is bounded on the east (Espiritu Santo and Malakula islands) and west (Pentecost and Maewo islands) by uplifted volcano-sedimentary ridges associated with collision of the d'Entrecasteaux Zone west of the arc. The currently active Central Belt volcanic front extends through the center of this basin and includes the shield volcanoes of Aoba, Ambrym, and Santa Maria islands. The oldest rocks recovered by drilling are the lithostratigraphic Unit VII Middle Miocene volcanic breccias in Hole 832B. Lava clasts are basaltic to andesitic, and the dominant phenocryst assemblage is plagioclase + augite + orthopyroxene + olivine. These clasts characteristically contain orthopyroxene, and show a low to medium K calc-alkaline differentiation trend. They are tentatively correlated with poorly documented Miocene calc-alkaline lavas and intrusives on adjacent Espiritu Santo Island, although this correlation demands that the measured K-Ar of 5.66 Ma for one clast is too young, due to alteration and Ar loss. Lava clasts in the Hole 832B Pliocene-Pleistocene sequence are mainly ankaramite or augite-rich basalt and basaltic andesite; two of the most evolved andesites have hornblende phenocrysts. These lavas vary from medium- to high-K compositions and are derived from a spectrum of parental magmas for which their LILE and HFSE contents show a broad inverse correlation with SiO2 contents. We hypothesize that this spectrum results from partial melting of an essentially similar mantle source, with the low-SiO2 high HFSE melts derived by lower degrees of partial melting probably at higher pressures than the high SiO2, low HFSE magmas. This same spectrum of compositions occurs on the adjacent Central Chain volcanoes of Aoba and Santa Maria, although the relatively high-HFSE series is known only from Aoba. Late Pliocene to Pleistocene lava breccias in Hole 833B contain volcanic clasts including ankaramite and augite + olivine + plagioclase-phyric basalt and rare hornblende andesite. These clasts are low-K compositions with flat REE patterns and have geochemical affinities quite different from those recovered from the central part of the basin (Hole 832B). Compositionally very similar lavas occur on Merelava volcano, 80 km north of Site 833, which sits on the edge of the juvenile Northern (Jean Charcot) Trough backarc basin that has been rifting the northern part of the New Hebrides Island Arc since 2-3 Ma. The basal sedimentary rocks in Hole 833B are intruded by a series of Middle Pliocene plagioclase + augite +/- olivine-phyric sills with characteristically high-K evolved basalt to andesite compositions, transitional to shoshonite. These are compositionally correlated with, though ~3 m.y. older than, the high-HFSE series described from Aoba. The calc-alkaline clasts in Unit VII of Hole 832B, correlated with similar lavas of Espiritu Santo Island further west, presumably were erupted before subduction polarity reversal perhaps 6-10 Ma. All other samples are younger than subduction reversal and were generated above the currently subduction slab. The preponderance in the North Aoba Basin and adjacent Central Chain islands of relatively high-K basaltic samples, some with transitional alkaline compositions, may reflect a response to collision of the d'Entrecasteaux Zone with the arc some 2-4 Ma. This may have modified the thermal structure of the subduction zone, driving magma generation processes to deeper levels than are present normally along the reminder of the New Hebrides Island Arc.

Geochemistry of ocean floor and forearc serpentinites

We provide new insights into the geochemistry of serpentinites from mid-ocean ridges (Mid-Atlantic Ridge and Hess Deep), passive margins (Iberia Abyssal Plain and Newfoundland) and fore-arcs (Mariana and Guatemala) based on bulk-rock and in situ mineral major and trace element compositional data collected on drill cores from the Deep Sea Drilling Project and Ocean Drilling Program. These data are important for constraining the serpentinite-hosted trace element inventory of subduction zones. Bulk serpentinites show up to several orders of magnitude enrichments in Cl, B, Sr, U, Sb, Pb, Rb, Cs and Li relative to elements of similar compatibility during mantle melting, which correspond to the highest primitive mantle-normalized B/Nb, B/Th, U/Th, Sb/Ce, Sr/Nd and Li/Y among subducted lithologies of the oceanic lithosphere (serpentinites, sediments and altered igneous oceanic crust). Among the elements showing relative enrichment, Cl and B are by far the most abundant with bulk concentrations mostly above 1000 µg/g and 30 µg/g, respectively. All other trace elements showing relative enrichments are generally present in low concentrations (µg/g level), except Sr in carbonate-bearing serpentinites (thousands of µg/g). In situ data indicate that concentrations of Cl, B, Sr, U, Sb, Rb and Cs are, and that of Li can be, increased by serpentinization. These elements are largely hosted in serpentine (lizardite and chrysotile, but not antigorite). Aragonite precipitation leads to significant enrichments in Sr, U and B, whereas calcite is important only as an Sr host. Commonly observed brucite is trace element-poor. The overall enrichment patterns are comparable among serpentinites from mid-ocean ridges, passive margins and fore-arcs, whereas the extents of enrichments are often specific to the geodynamic setting. Variability in relative trace element enrichments within a specific setting (and locality) can be several orders of magnitude. Mid-ocean ridge serpentinites often show pronounced bulk-rock U enrichment in addition to ubiquitous Cl, B and Sr enrichment. They also exhibit positive Eu anomalies on chondrite-normalized rare earth element plots. Passive margin serpentinites tend to have higher overall incompatible trace element contents than mid-ocean ridge and fore-arc serpentinites and show the highest B enrichment among all the studied serpentinites. Fore-arc serpentinites are characterized by low overall trace element contents and show the lowest Cl, but the highest Rb, Cs and Sr enrichments. Based on our data, subducted dehydrating serpentinites are likely to release fluids with high B/Nb, B/Th, U/Th, Sb/Ce and Sr/Nd, rendering them one of the potential sources of some of the characteristic trace element fingerprints of arc magmas (e.g. high B/Nb, high Sr/Nd, high Sb/Ce). However, although serpentinites are a substantial part of global subduction zone chemical cycling, owing to their low overall trace element contents (except for B and Cl) their geochemical imprint on arc magma sources (apart from addition of H2O, B and Cl) can be masked considerably by the trace element signal from subducted crustal components.

Petrology of basalts from DSDP Hole 83-504B

Basalts from Hole 504B, Leg 83, exhibit remarkable uniformity in major and trace element composition throughout the 1075.5 m of basement drilled. The majority of the basalts, Group D', have unusual compositions relative to normal (Type I) mid-ocean ridge basalts (MORB). These basalts have relatively high mg values (0.60-0.70) and CaO abundances (11.7-13.7%; Ca/Al = 0.78-0.89), but exhibit a marked depletion in compatible trace elements (Cr and Ni); moderately incompatible trace elements (Zr, Y, Ti, etc.); and highly incompatible trace elements (Nb, LREE, etc.). Petrographic and compositional data indicate that most of these basalts are evolved, having fractionated significant amounts of plagioclase, olivine, and clinopyroxene. Melting experiments on similar basalt compositions from the upper portion of Hole 504B (Leg 70; Autio and Rhodes, 1983) indicate that the basalts are co-saturated with olivine and plagioclase and often clinopyroxene on the 1-atm. liquidus. Two rarely occurring groups, M' and T, are compositionally distinct from Group D' basalts. Group T is strongly depleted in all magmaphile elements except the highly incompatible ones (Nb, La, etc.), while Group M' has moderate concentrations of both moderately and highly incompatible trace elements and is similar to Type I MORB. Groups M' and T cannot be related to Group D' nor to each other by crystal fractionation, crystal accumulation, or magma mixing. The large differences in magmaphile element ratios (Zr/Nb, La/Yb) among these three chemical groups may be accounted for by complex melting models and/or local heterogeneity of the mantle beneath the Costa Rica Ridge. Xenocrysts and xenoliths of plagioclase and clinopyroxene similar in texture and mineral composition to crystals in coarse-grained basalts from the lower portion of the hole are common in Hole 504B basalts. These suggest that addition of solid components either from conduit or magma chamber walls has occurred and may be a common source of disequilibrium crystals in these basalts. However, mixing of plagioclase-laden depleted melts (similar to the Costa Rica Ridge Zone basalts) with normal MORB magmas could provide an alternate source for some refractory plagioclase crystals found out of equilibrium in many phyric MORB. The uniformity of major element compositions in Hole 504B basalts affords an ideal situation for investigating the effects of alteration on some major and trace elements in oceanic basalts. Alteration observed in whole-rock samples records primarily two events - a high-temperature and a low-temperature phase. High-temperature phases include: chlorite, talc, albite, actinolite, sphene, quartz, and pyrite. The low-temperature phases include smectite (saponite), epistilbite or laumontite, and minor calcite. Laumontite may actually straddle the gap between the low- and high-temperature mineral assemblages. Alteration is restricted primarily to partial replacement of primary phases. Metamorphic grade, in general, increases from the top to the bottom of Hole 504B (Legs 69, 70, and 83) as seen in the change from a smectiteto- chlorite-dominated secondary mineral assemblage. However, a systematic progression for the interval recovered during Leg 83 is not apparent. Rather, the extent of alteration appears to be a function of the initial texture and fracture density. Variations in whole-rock major and trace element concentrations cannot be attributed convincingly to any differences in alteration observed. Compositional characteristics of the secondary minerals indicated that extensive remobilization of elements has not occurred; local redistribution is suggested in most cases. Thus, the major and trace element signature of these basalts remains effectively the same as the original composition prior to alteration.

(Table 1) Grain size results, statistical parameters and magnetic susceptibility values of disturbed sediments from ODP holes 204-1249C and 204-1245B

Soupy and mousse-like fabrics are disturbance sedimentary features that result from the dissociation of gas hydrate, a process that releases water. During the core retrieval process, soupy and mousse-like fabrics are produced in the gas hydrate-bearing sediments due to changes in pressure and temperature conditions. Therefore, the identification of soupy and mousse-like fabrics can be used as a proxy for the presence of gas hydrate in addition to other evidence, such as pore water freshening or anomalously cool temperature. We present here grain-size results, mineralogical composition and magnetic susceptibility data of soupy and mousse-like samples from the southern Hydrate Ridge (Cascadia accretionary complex) acquired during Leg 204 of the Ocean Drilling Program. In order to study the relationship between sedimentary texture and the presence of gas hydrates, we have compared these results with the main textural and compositional data available from the same area. Most of the disturbed analyzed samples from the summit and the western flank of southern Hydrate Ridge show a mean grain size coarser than the average mean grain size of the hemipelagic samples from the same area. The depositional features of the sediments are not recognised due to disturbance. However, their granulometric statistical parameters and distribution curves, and magnetic susceptibility logs indicate that they correspond to a turbidite facies. These results suggest that gas hydrates in the southern Hydrate Ridge could form preferentially in coarser grain-size layers that could act as conduits feeding gas from below the BSR. Two samples from the uppermost metres near the seafloor at the summit of the southern Hydrate Ridge show a finer mean grain-size value than the average of hemipelagic samples. They were located where the highest amount of gas hydrates was detected, suggesting that in this area the availability of methane gas was high enough to generate gas hydrates, even within low-permeability layers. The mineralogical composition of the soupy and mousse-like sediments does not show any specific characteristic with respect to the other samples from the southern Hydrate Ridge.

Sea-surface temperature and salinity reconstruction for sediment core GeoB5844-2

We present high-resolution paleoceanographic records of surface and deep water conditions within the northern Red Sea covering the last glacial maximum and termination I using alkenone paleothermometry, stable oxygen isotopes, and sediment compositional data. Paleoceanographic records in the restricted desert-surrounded northern Red Sea are strongly affected by the stepwise sea level rise and appear to record and amplify well-known millennial-scale climate events from the North Atlantic realm. During the last glacial maximum (LGM), sea surface temperatures were about 4°C cooler than the late Holocene. Pronounced coolings associated with Heinrich event 1 (~2°C below the LGM level) and the Younger Dryas imply strong atmospheric teleconnections to the North Atlantic. Owing to the restricted exchange with the Indian Ocean, Red Sea salinity is particularly sensitive to changes in global sea level. Paleosalinities exceeded 50 psu during the LGM. A pronounced freshening of the surface waters is associated with the meltwater peaks MWP1a and MWP1b owing to an increased surface-near inflow of "normal" saline water from the Indian Ocean. Vertical delta18O gradients are also increased during these phases, indicating stronger surface water stratification. The combined effect of deglacial changes in sea surface temperature and salinity on water column stratification initiated the formation of two sapropel layers, which were deposited under almost anoxic condition in a stagnant water body.

(Table 3, page 280) Chemical composition of micronodules from a series of stations and sediment depths from Areas C, F, G and K in the Pacific Ocean from R/V Sonne Cruise SO06

Compositional data for coexisting manganese nodules, micronodules, sediments and pore waters from five areas in the equatorial and S.W. Pacific have been obtained. This represents the largest study of its type ever undertaken to establish the distribution of elements between the various phases within the sediment column. The composition of manganese nodules, micronodules and sediments (on a carbonate-free basis) shows marked differences between the equatorial high productivity zone and the low productivity region of the S.W. Pacific. In the case of the nodules, th is reflects an increased supply of transition elements (notably Ni, Cu and Zn) to the nodules as a result of the in situ dissolution of siliceous tests within the sediment column in the equatorial Pacific high productivity zone. Micronodules display similar, but somewhat different, compositions to those of the associated nodules in each area. Micronodule composition is therefore influenced by the same basic factors that control nodule composition, but is modified by dissolution of the micronodules in situ within the sediment column. Locally, as in the area immediately south of the Marquesas Fracture Zone, the micronodule population is contaminated by small, angular volcanic rock fragments; this leads to apparently anomalous micronodule compositions. Micronodules appear to be a transient feature in the sediment column, especially in the equatorial Pacific. Dissolution of micronodules in the sediment column therefore represents an important source of elements for the growth of manganese nodules in the equatorial Pacific. Sediment composition is markedly influenced by the carbonate content. On a carbonate-free basis, the sediments from the equatorial high productivity zone are quite distinct in composition from those in the S.W. Pacific. This reflects differences in the lithology of the sediments. In the Aitutaki Passage, the local influence of volcanoclastic material in sediment composition has been established. The major cations and anions in pore waters measured here show no major differences between equatorial and S.W. Pacific sediments. Silica is, however, higher in equatorial Pacific pore waters reflecting the dissolution of siliceous tests in these sediments.

Compositional and isotopic data on core MD84641

The organic carbon isotopic record of the sapropels(S1 and S3-S10) and intercalated marl oozes has been determined in a 12-m piston core from the eastern Mediterranean. The d13C_organic values are systematically lighter (mean=-21.0±0.82 per mil) in all sapropels and heavier (mean=-18.8±1.07 per mil) in the marl oozes. These differences are not due to variable marine and terrestrial organic matter mixtures because all values are heavier than modern plankton in the Mediterranean, there is no relationship between the C_organic/N ratios and the isotopic values, and published information on the abundance and distribution of organic biomarkers shows that terrestrial material constitutes a minor fraction of the total organic matter. Temperature effects on isotope fractionation are also discounted because the change in d13C_organic values between glacial and interglacial horizons is in the opposite sense. Diagenesis, which can produce relatively small changes in the carbon isotopic composition of sedimentary organic matter under certain circumstances, is unlikely to have caused the observed differences because this mechanism would cause an enrichmet in 12C, implying that all values were even heavier originally, and there is no secular trend in the d13C_organic record. The observed differences in d13C_organic between the two lithologies are probably produced by changes in the isotopic composition and the concentration of dissolved CO2. First, freshwater flooding during the formation of the sapropels caused the isotopic composition of the dissolved inorganic carbon in the surface waters of the Mediterranean to become lighter because of the 13C deficiency in fresh waters. Hence photosynthesis would have produced isotopically lighter organic material. Second, changes in atmospheric pCO2 between glacial and interglacial periods, as shown by the Vostok ice core, caused marked changes in the concentration of free dissolved CO2 in the mixed layer; lower values during glacial maxima caused a smaller fractionation of the carbon isotopes by phytoplankton, whereas levels were less limiting during the interglacials. Concentrations of dissolved CO2 could also have been much higher during the deposition of the sapropels because of the supply of regenerated CO2 to the mixed layer by upwelling, and this could have further lightened the d13C_organic values in the sapropels themselves. Carbon isotope records may provide an alternative method for estimating atmospheric pCO2 levels over longer time periods than can be obtained from ice cores.