Geochemistry of boninite and harzburgite of ODP Leg 125 basement samples

Holes drilled into the volcanic and ultrabasic basement of the Izu-Ogasawara and Mariana forearc terranes during Leg 125 provide data on some of the earliest lithosphere created after the start of Eocene subduction in the Western Pacific. The volcanic basement contains three boninite series and one tholeiite series. (1) Eocene low-Ca boninite and low-Ca bronzite andesite pillow lavas and dikes dominate the lowermost part of the deep crustal section through the outer-arc high at Site 786. (2) Eocene intermediate-Ca boninite and its fractionation products (bronzite andesite, andesite, dacite, and rhyolite) make up the main part of the boninitic edifice at Site 786. (3) Early Oligocene intermediate-Ca to high-Ca boninite sills or dikes intrude the edifice and perhaps feed an uppermost breccia unit at Site 786. (4) Eocene or Early Oligocene tholeiitic andesite, dacite, and rhyolite form the uppermost part of the outer-arc high at Site 782. All four groups can be explained by remelting above a subduction zone of oceanic mantle lithosphere that has been depleted by its previous episode of partial melting at an ocean ridge. We estimate that the average boninite source had lost 10-15 wt% of melt at the ridge before undergoing further melting (5-10%) shortly after subduction started. The composition of the harzburgite (<2% clinopyroxene, Fo content of about 92%) indicates that it underwent a total of about 25% melting with respect to a fertile MORB mantle. The low concentration of Nb in the boninite indicates that the oceanic lithosphere prior to subduction was not enriched by any asthenospheric (OIB) component. The subduction component is characterized by (1) high Zr and Hf contents relative to Sm, Ti, Y, and middle-heavy REE, (2) light REE-enrichment, (3) low contents of Nb and Ta relative to Th, Rb, or La, (4) high contents of Na and Al, and (5) Pb isotopes on the Northern Hemisphere Reference Line. This component is unlike any subduction component from active arc volcanoes in the Izu-Mariana region or elsewhere. Modeling suggests that these characteristics fit a trondhjemitic melt from slab fusion in amphibolite facies. The resulting metasomatized mantle may have contained about 0.15 wt% water. The overall melting regime is constrained by experimental data to shallow depths and high temperatures (1250? C and 1.5 kb for an average boninite) of boninite segregation. We thus envisage that boninites were generated by decompression melting of a diapir of metasomatized residual MORB mantle leaving the harzburgites as the uppermost, most depleted residue from this second stage of melting. Thermal constraints require that both subducted lithosphere and overlying oceanic lithosphere of the mantle wedge be very young at the time of boninite genesis. This conclusion is consistent with models in which an active transform fault offsetting two ridge axes is placed under compression or transpression following the Eocene plate reorganization in the Pacific. Comparison between Leg 125 boninites and boninites and related rocks elsewhere in the Western Pacific highlights large regional differences in petrogenesis in terms of mantle mineralogy, degree of partial melting, composition of subduction components, and the nature of pre-subduction lithosphere. It is likely that, on a regional scale, the initiation of subduction involved subducted crust and lithospheric mantle wedge of a range of ages and compositions, as might be expected in this type of tectonic setting.

Gravity mapping in the southern Weddell Sea region, Antarctica (Scale 1:2 000 000)

New maps of free-air and the Bouguer gravity anomalies on the Weddell Sea sector (70-81° S, 6-75° W) of Antarctica are presented. These maps are based on the first computer compilation of available gravity data collected by ''Sevmorgeologia'' in 1976-89 in the southern Weddell Sea and adjacent coasts of western Dronning Maud Land (WDML) and Coats Land. The accomplished gravity studies comprise airborne observations with a line spacing of about 20 km and conventional measurements at over-the-ice points, which were spaced at 10-30 km and supplemented by seismic soundings. Hence, anomalies on the maps represent mainly large-scale and deep crustal features. The dominant feature in free-air gravity map is a large dipolar gravity anomaly stretching along the continental margin. Following the major grain of seabed morphology this shelf-edge/slope anomaly (SESA) is clearly divided into three segments characterized by diverse anomaly amplitudes, wavelengths and trends. They are associated with continental margins of different geotectonic provinces of Antarctica surrounding the Weddell Sea. Apparent distinctions in the SESA signatures are interpreted as the gravity expression of tectonic, deep crustal structure segmentation of the continental margin. The prominent gravity highs (100-140 mGal) of the shelf edge anomaly mapped along WDML are assumed to represent high-density mantle injections intruded into the middle/lower crust during initial rifting of continental breakup. Enlarged wavelengths and diminished amplitudes of the gravity anomaly westwards, along the Weddell Sea embayment (WSE) margin, reflect a widening of the continental slope and a significant increase in thickness of underlying sediment strata. Low amplitude, negative free-air anomalies in the Filchner-Ronne Ice Shelves (FRIS) contrast sharply with the dominating positive anomalies offshore. This indicates a greater sedimentary thickness of the basin in this area. Crustal response to the enlarged sediment load is impressed in mostly positive features of the Bouguer gravity field observed here. Two pronounced positive Bouguer anomalies of 50-70 mGal and an average widths of 200 km dominate the Weddell Sea embayment margins towards the Antarctic Peninsula and the East Antarctic craton. They correlate well with very deep seabed troughs (> 1000 m below sea level). The gravity highs are most likely caused by a shallow upper mantle underneath graben-rift structures evolved at the margins of the WSE basin. A regional zone (> 100 km in width) of the prominent Bouguer and free-air negative anomalies (-40 to -60 mGal) adjacent Coats Land to the north of the ice shelf edge may indicate the presence of the thick old cratonic crust far offshore beneath the Weddell Sea Embayment.

Basalt density, basement age, and intrusive/extrusive relations from DSDP Legs 2 through 7, 9, and 14

Densities of layer 2 basalt recovered during the Deep Sea Drilling Project have been found to decrease steadily with age, a finding ascribed to progressive submarine weathering in the context of sea-floor spreading. The least-squares solution for 52 density measurements gives a rate of decrease in density of (Delta p)/(Delta t) = -0.0046 g per ccm m.y. = -16 percent per 100 m.y., which is in excellent agreement with earlier estimates based on observed chemical depletion rates of dredged oceanic basalt. Weathering of sea-floor basalt, should it penetrate to any considerable depth in layer 2, will decrease layer 2 seismic refraction velocities, act as a source of geothermal heat, and substantially influence the chemistry of sea water and the overlying column of sediment.

AMS 14C ages and isotopic compositions of samples from the Derugin Basin, Sea of Okhotsk

An area of massive barite precipitations was studied at a tectonic horst in 1500 m water depth in the Derugin Basin, Sea of Okhotsk. Seafloor observations and dredge samples showed irregular, block- to column-shaped barite build-ups up to 10 m high which were scattered over the seafloor along an observation track 3.5 km long. High methane concentrations in the water column show that methane expulsion and probably carbonate precipitation is a recently active process. Small fields of chemoautotrophic clams (Calyptogena sp., Acharax sp.) at the seafloor provide additional evidence for active fluid venting. The white to yellow barites show a very porous and often layered internal fabric, and are typically covered by dark-brown Mn-rich sediment; electron microprobe spectroscopy measurements of barite sub-samples show a Ba substitution of up to 10.5 mol% of Sr. Rare idiomorphic pyrite crystals (~1%) in the barite fabric imply the presence of H2S. This was confirmed by clusters of living chemoautotrophic tube worms (1 mm in diameter) found in pores and channels within the barite. Microscopic examination showed that micritic aragonite and Mg-calcite aggregates or crusts are common authigenic precipitations within the barite fabric. Equivalent micritic carbonates and barite carbonate cemented worm tubes were recovered from sediment cores taken in the vicinity of the barite build-up area. Negative d13C values of these carbonates (>-43.5 per mill PDB) indicate methane as major carbon source; d18O values between 4.04 and 5.88 per mill PDB correspond to formation temperatures, which are certainly below 5°C. One core also contained shells of Calyptogena sp. at different core depths with 14C-ages ranging from 20 680 to >49 080 yr. Pore water analyses revealed that fluids also contain high amounts of Ba; they also show decreasing SO4**2- concentrations and a parallel increase of H2S with depth. Additionally, S and O isotope data of barite sulfate (d34S: 21.0-38.6 per mill CDT; d18O: 9.0-17.6 per mill SMOW) strongly point to biological sulfate reduction processes. The isotope ranges of both S and O can be exclusively explained as the result of a mixture of residual sulfate after a biological sulfate reduction and isotopic fractionation with 'normal' seawater sulfate. While massive barite deposits are commonly assumed to be of hydrothermal origin, the assemblage of cheomautotrophic clams, methane-derived carbonates, and non-thermally equilibrated barite sulfate strongly implies that these barites have formed at ambient bottom water temperatures and form the features of a Giant Cold Seep setting that has been active for at least 49 000 yr.

(Table 1) Light minerals in sand at DSDP Leg 84 holes

The Middle America active continental margin is the best-sampled active plate margin to date, having been drilled during Legs 84, 67, and 66. With nine sites drilled on the continental slope of Guatemala and an additional site drilled on the Costa Rican slope, a summary of slope sediments and sedimentary processes can be made. Sediments are easily subdivided into a thick apron of Neogene and Quaternary volcanically derived hemipelagic and turbidite mud and mudstone and a thinner, more varied assemblage of mostly Paleogene mudstone, radiolarian mudstone, and limestone. This latter assemblage may contain hiatuses or be completely lacking between slope deposits and basement. Cores from the foot of the continental slope (Core 567A-19) consist of Campanian micrite. The pre-Neogene section is much thicker and of more terrigenous provenance beneath the forearc basin landward of the forearc structural high than on the continental slope. Sedimentary processes of the Neogene and Quaternary slope sediments include reworking of hemipelagic and turbidite deposits. Redeposition by slumping, plastic flow, and turbidity current-documentable through benthic foraminiferal analysis-occurs in intracanyon and canyon settings. Erosion by slumping and by turbidity current and deposition of mud or sand in canyons and in local depressions on the continental slope and different rates of sediment accumulation result in dramatic thickness variations of lithologic units over small distances in localized pockets of sand in small filled canyons on the slope or in sediment ponds, and in high-relief basement topography. The age of sediment overlying igneous basement ranges from Cretaceous to Quaternary. Gas hydrate was visible or inferred present at every site drilled during Leg 84. Nevertheless, except for a small amount in the last core, it was not recovered in sufficient quantities to be visible at Site 568, a site specifically chosen for the study of hydrate and located near Site 496, which was abandoned during Leg 67 because of the dangerous abundance of hydrates. The association of hydrate with porous, coarser sediment results in a distribution as localized and unpredictable as the slope sands off Guatemala, which do not occur in beds coherent enough to produce acoustic reflection. Although the normal lithologic section at Sites 567 and 496 limits the volume of sediment that could be part of an accretionary prism offshore Guatemala and the volume of sediment in the Trench axis is not sufficient to argue for significant accumulation of Cocos Plate sediments, the varied lithology and attenuated thickness of pre-Neogene sediment seaward of the forearc structural high do not exclude earlier accretion from the history of the Guatemalan continental margin.

Chemical and isotopic compositions of sediments and some minerals from the Derugin Basin, Sea of Okhotsk

The paper reports specific mineralogical and geochemical characteristics of deposits from local depressions of the Derugin Basin. They were formed in an environment with periodic changes from oxic to anoxic conditions and show evidence for presence of hydrogen sulfide in bottom waters. Deposits of this type can be considered as a modern model for ancient ore-bearing black shale associations. Compared with typical metalliferous black shale sequences, which are characterized by high contents of organic matter, the sediments described here are depleted in elements of the organophilic association (Mo, Ni, Cu, Zn, V, and U), but have higher Mn contents.

Geochemistry of sediments from the Eastern Cape Basin

Sediment cores retrieved in the Benguela coastal upwelling system off Namibia show very distinct enrichments of solid phase barium at the sulfate/methane transition (SMT). These barium peaks represent diagenetic barite (BaSO4) fronts which form by the reaction of upwardly diffusing barium with interstitial sulfate. Calculated times needed to produce these barium enrichments indicate a formation time of about 14,000 yr. Barium spikes a few meters below the SMT were observed at one of the investigated sites (GeoB 8455). Although this sulfate-depleted zone is undersaturated with respect to barite, the dominant mineral phase of these buried barium enrichments was identified as barite by scanning electron microscopy (SEM). This is the first study which reports the occurrence/preservation of pronounced barite enrichments in sulfate-depleted sediments buried a few meters below the SMT. At site GeoB 8455 high concentrations of dissolved barium in pore water as well as barium in the solid phase were observed. Modeling the measured barium concentrations at site GeoB 8455 applying the numerical model CoTReM reveals that the dissolution rate of barite directly below the SMT is about one order of magnitude higher than at the barium enrichments deeper in the sediment core. This indicates that the dissolution of barite at these deeper buried fronts must be retarded. Thus, the occurrence of the enrichments in solid phase barium at site GeoB 8455 could be explained by decreased dissolution rates of barite due to the changes in the concentration of barite in the sediment, as well as changes in the saturation state of fluids. Furthermore, the alteration of barite into witherite (BaCO3) via the transient phase barium sulfide could lead to the preservation of a former barite front as BaCO3. The calculations and modeling indicate that a relocation of the barite front to a shallower depth occurred between the last glacial maxium (LGM) and the Pleistocene/Holocene transition. We suggest that an upward shift of the SMT occurred at that time, most likely as a result of an increase in the methanogenesis rates due to the burial of high amounts of organic matter below the SMT.

Abundance and chemical and mineral compositions of nodules from the Pacific Ocean

The monograph highlights extensive materials collected during expeditions of P.P. Shirshov Institute of Oceanology. We consider facial conditions of nodule formation, regularities of their distribution, stratigraphic position, petrography, mineral composition, textures, geochemistry of nodules and hosting sediments. Origin of iron-manganese nodules in the Pacific Ocean is considered as well.

Age models, organic analyses and major-element analyses of sediment cores on a transect of the tropical African rainbelt

The distribution of rainfall in tropical Africa is controlled by the African rainbelt**1, which oscillates on a seasonal basis. The rainbelt has varied on centennial to millennial timescales along with changes in Northern Hemisphere high-latitude climate**2, 3, 4, 5, the Atlantic meridional overturning circulation**6 and low-latitude insolation**7 over the past glacial-interglacial cycle. However, the overall dynamics of the African rainbelt remain poorly constrained and are not always consistent with a latitudinal migration**2, 4, 5, 6, as has been proposed for other regions**8, 9. Here we use terrestrially derived organic and sedimentary markers from marine sediment cores to reconstruct the distribution of vegetation, and hence rainfall, in tropical Africa during extreme climate states over the past 23,000 years. Our data indicate that rather than migrating latitudinally, the rainbelt contracted and expanded symmetrically in both hemispheres in response to changes in climate. During the Last Glacial Maximum and Heinrich Stadial 1, the rainbelt contracted relative to the late Holocene, which we attribute to a latitudinal compression of atmospheric circulation associated with lower global mean temperatures**10. Conversely, during the mid-Holocene climatic optimum, the rainbelt expanded across tropical Africa. In light of our findings, it is not clear whether the tropical rainbelt has migrated latitudinally on a global scale, as has been suggested**8,9.

Geochemistry of Miocene Alborán Basin volcanism

We present new major and trace element and O-Sr-Nd-isotope data for igneous rocks from the western Mediterranean Alborán Sea, collected during the METEOR 51/1 cruise, and for high-grade schists and gneisses from the continental Alborán basement, drilled during the Ocean Drilling Programme (ODP Leg 161, Site 976). The geochemical data allow a detailed examination of crustal and mantle processes involved in the petrogenesis of the lavas and for the first time reveal a zonation of the Miocene Alborán Sea volcanism: (1) a keel-shaped area of LREE-depleted (mainly tholeiitic series) lavas in the central Alborán Sea, generated by high degrees of partial melting of a depleted mantle source and involving hydrous fluids from subducted marine sediments, that is surrounded by (2) a horseshoe-shaped zone with LREE-enriched (mainly calc-alkaline series) lavas subparallel to the arcuate Betic-Gibraltar-Rif mountain belt. We propose that the geochemical zonation of the Miocene Alborán Basin volcanism results from eastward subduction of Tethys oceanic lithosphere coupled with increasing lithospheric thickness between the central Alborán Sea and the continental margins of Iberia and Africa.

Geochemistry of bulk sediment from the Cape Basin

A technique for onsite application of X-ray fluorescence (XRF) spectrometry to samples from sediment cores aboard a research vessel was developed and tested. The method is sufficiently simple, precise, and fast to be used routinely for high-resolution analyses of depth profiles as well as surface samples. Analyses were performed with the compact high-performance energy-dispersive polarisation X-ray fluorescence (EDPXRF) analyser Spectro Xepos. Contents of the elements Si, Ti, Al, Fe, Mn, Mg, Ca, K, Sr, Ba, Rb, Cu, Ni, Zn, P, S, Cl and Br were simultaneously determined on 200-225 samples of each core within 24 h of recovery. This study presents a description of the employed shipboard preparation and analysis technique, along with some example data. We show land-based datasets that support our decisions to use powder samples and to reduce the original measuring time for onboard analyses. We demonstrate how well the results from shipboard measurements for the various elements compare with the land-based findings. The onboard geochemical data enabled us to establish an element stratigraphy already during the cruise. Correlation of iron, calcium and silicon enrichment trends with an older reference core provided an age model for the newly retrieved cores. The Spectro Xepos instrument performed without any analytical and technical difficulties which could have been caused by rougher weather conditions or continuous movement and vibration of the research vessel. By now, this XRF technique has been applied during three RV Meteor cruises to approximately 5,000 Late Quaternary sediment samples from altogether 23 gravity cores, 25 multicorer cores and two box cores from the eastern South Atlantic off South Africa/Namibia and the eastern Atlantic off NW Africa.