Neodymium isotopic data, radiocarbon dates and calibrated ages of sediment samples off the La Plata Estuary, southeastern South America

The continental margin off the La Plata Estuary (SE South America) is characterized by high fluvial sediment supply and strong ocean currents. High-resolution sediment-acoustic data combined with sedimentary facies analysis, AMS-14C ages, and neodymium isotopic data allowed us to reconstruct late Quaternary sedimentary dynamics in relation to the two major sediment sources, the La Plata Estuary and the Argentine margin. Sediments from these two provinces show completely different dispersal patterns. We show that the northward-trending La Plata paleo-valley was the sole transit path for the huge volumes of fluvial material during lower sea levels. In contrast, material from the Argentine margin sector was transported northwards by the strong current system. Despite the large sediment volumes supplied by both sources, wide parts of the shelf were characterized by either persistent non-deposition or local short-term depocenter formation. The location and formation history of these depocenters were primarily controlled by the interplay of sea level with current strength and local morphology. The high sediment supply was of secondary importance to the stratigraphic construction, though locally resulting in high sedimentation rates. Thus, the shelf system off the La Plata Estuary can be considered as a hydrodynamic-controlled end-member.

Silicoflagellate abundances in sediments of ODP Leg 207 sites

The Ocean Drilling Program (ODP) drilled at five sites in the western Atlantic Ocean during Leg 207. The objective of the drilling was to recover samples from the shallow buried Cretaceous and Paleocene sediments on the Demerara Rise off Suriname, South America. These sediments are being studied for a number of paleoceanographic studies of the low-latitude Atlantic off the coast of Suriname (this volume). For this report two sites, Sites 1257 and 1258, were selected for silicoflagellate study because shipboard results suggested these two sites as the only ones with siliceous microfossils of Paleocene-Eocene age. The Demarara Rise is a predominant submarine plateau located off the coast of Suriname and French Guyana. This plateau stretches 380 km along the coast and is 220 km wide. The depth to seafloor along the depth transect drilled during ODP Leg 207 ranges from 1000 to 4500 m, but most of the remainder of the plateau lies in shallow water of 700 m. Much of this area is covered with 2-3 km of sediments. The Demerara Rise is built on rifted Precambrian continental crust. The plateau was one of the last places to be in contact with West Africa during the opening of the Atlantic Ocean (see Shipboard Scientific Party, 2004). Site 1257 (9°27'N, 54°20'W; water depth = 2951 m) is located on a terrace on the northwestern Demerara Rise ~400 km from Suriname. This is the second deepest water depth location drilled during Leg 207. Sediments from this area range in age from Miocene to Albian. This area is part of the transform fault that separated from Central America and western Africa. Three holes were drilled at Site 1257. Site 1258 (9°26'N, 54°43'W; water depth = 3192 m) is located on the western slope of the Demerara Rise ~380 km north of Suriname. This site is the distal and deepest site of the paleoceanographic depth transect drilled across Demerara Rise during Leg 207. The area is located on a ridge of Paleocene sediments cropping out on the seafloor. Three holes were drilled at Site 1258, but only one is studied.

Chemical composition of minerals and rocks from the Sierra Leone segment of the Mid-Atlantic Ridge and from the Markov depression, Central Atlantic

Silicic Fe-Ti-oxide magmatic series was the first recognized in the Sierra Leone axial segment of the Mid-Atlantic Ridge near 6°N. The series consists of intrusive rocks (harzburgites, lherzolites, bronzitites, norites, gabbronorites, hornblende Fe-Ti-oxide gabbronorites and gabbronorite-diorites, quartz diorites, and trondhjemites) and their subvolcanic (ilmenite-hornblende dolerites) and, possibly, volcanic analogues (ilmenite-bearing basalts). Deficit of most incompatible elements in the rocks of the series suggests that parental melts derived from a source that had already been melted. Correspondingly, these melts could not be MORB derivatives. Origin of the series is thought to be related to melting of the hydrated oceanic lithosphere during emplacement of an asthenospheric plume (protuberance on the surface of large asthenospheric lens beneath MAR). Genesis of different melts was supposedly controlled by ascent of a chamber of hot mantle magmas thought this lithosphere in compliance with the zone melting mechanism. Melt acquired fluid components from heated rocks at peripheries of the plume and became enriched in Fe, Ti, Pb, Cu, Zn, and other components mobile in fluids.

Pollen and spores record, and paleotemperature reconstructions for mid-Holocene sediments of the Northwest Pacific

Sannai-Maruyama is one of the most famous and best-researched mid-Holocene (mid-Jomon) archaeological sites in Japan, because of a large community of people for a long period. Archaeological studies have shown that the Jomon people inhabited the Sannai-Maruyama site from 5.9-4.2 +/- 0.1 cal. kyr B.P. However, a continuous record of the terrestrial and marine environments around the site has not been available. Core KT05-7 PC-02, was recovered from Mutsu Bay, only 20 km from the site, for the reconstruction of high-resolution time series of environmental records, including sea surface temperature (SST). C37 alkenone SSTs showed clear fluctuations, with four periods of high (8.4-7.9, 7.0-5.9, 5.1-4.1, and 2.3-1.4 cal. kyr B.P.) and four of low (-8.4, 7.9-7.0, 5.9-5.1, and 4.1-2.3 cal. kyr B.P.) SST. Thus, each SST cycle lasted 1.0-2.0 kyr, and the amplitude of fluctuation was about 1.5-2.0 °C. Total organic carbon (TOC) and C37 alkenone contents, and the TOC/total nitrogen ratio indicate that marine biogenic production was low before 7.0 cal. kyr B.P., but was clearly increased between 5.9 and 4.0 cal. kyr B.P., because of stronger vertical mixing. During the period when the community at the site prospered (between 5.9 and 4.2 +/- 0.1 cal. kyr B.P.), the terrestrial climate was relatively warm. The high relative abundance of pollen of both Castanea and Quercus subgen. Cyclobalanopsis supports the interpretation that the local climate was optimal for human habitation. Between 5.9 and 5.1 cal. kyr B.P., in spite of warm terrestrial climates, the C37 alkenone SST was low; this apparent discrepancy may be attributed to the water column structure in the Tsugaru Strait, which differed from the modern condition. The evidence suggests that at about 5.9 cal. kyr B.P, high productivity of marine resources such as fish and shellfish and a warm terrestrial climate led to the establishment of a human community at the Sannai-Maruyama site. Then, at about 4.1 +/- 0.1 cal. kyr B.P., abrupt marine and terrestrial cooling, indicated by a decrease of about 2 °C in the C37 alkenone SST and an increase in pollen of taxa of cooler climates, led to a reduced terrestrial food supply, causing the people to abandon the site. The timing of the abandonment is consistent with the timing (around 4.0-4.3 cal. kyr B.P.) of the decline of civilizations in north Mesopotamia and along the Yangtze River. These findings suggest that a temperature rise of ~2 °C in this century as a result of global warming could have a great impact on the human community and especially on agriculture, despite the advances of contemporary society.

Major element oxides and 40Ar/39Ar plateau and isochron ages of ODP Hole 165-1001A

40Ar-39Ar incremental heating experiments and electron microprobe analyses were performed on basaltic rocks recovered from Site 1001 during Ocean Drilling Program Leg 165. The lower Nicaraguan Rise, on which Site 1001 lies, appears to be part of a larger Caribbean oceanic plateau that makes up the core of the Caribbean plate. Our results indicate an eruption age of 81 ± 1 Ma. A single flow-rim glass is tholeiitic and almost identical to the shipboard X-ray fluorescence analyses of the whole rock. The slightly porphyritic basalts have at least two populations of plagioclase, groundmass, and glomerocrystic plagioclase laths that appear to be in equilibrium with the surrounding melt and corroded tabular phenocrysts that have a higher An content (An84-86).

The magnesium isotope composition of diagenetic dolomites from ODP Hole 112-685A and 201-1230A of the Peru Margin

The magnesium isotope composition of diagenetic dolomites and their adjacent pore fluids were studied in a 250 m thick sedimentary section drilled into the Peru Margin during Ocean Drilling Program (ODP) Leg 201 (Site 1230) and Leg 112 (Site 685). Previous studies revealed the presence of two types of dolomite: type I dolomite forms at ~ 6 m below seafloor (mbsf) due to an increase in alkalinity associated with anaerobic methane oxidation, and type II dolomite forms at focused sites below ~ 230 mbsf due to episodic inflow of deep-sourced fluids into an intense methanogenesis zone. The pore fluid delta 26Mg composition becomes progressively enriched in 26Mg with depth from values similar to seawater (i.e. -0.8 per mil, relative to DSM3 Mg reference material) in the top few meters below seafloor (mbsf) to 0.8 ± 0.2 per mil within the sediments located below 100 mbsf. Type I dolomites have a delta 26Mg of -3.5 per mil, and exhibit apparent dolomite-pore fluid fractionation factors of about -2.6 per mil consistent with previous studies of dolomite precipitation from seawater. In contrast, type II dolomites have delta 26Mg values ranging from -2.5 to -3.0 per mil and are up to -3.6 per mil lighter than the modern pore fluid Mg isotope composition. The enrichment of pore fluids in 26Mg and depletion in total Mg concentration below ~ 200 mbsf is likely the result of Mg isotope fractionation during dolomite formation, The 26Mg enrichment of pore fluids in the upper ~ 200 mbsf of the sediment sequence can be attributed to desorption of Mg from clay mineral surfaces. The obtained results indicate that Mg isotopes recorded in the diagenetic carbonate record can distinguish near surface versus deep formed dolomite demonstrating their usefulness as a paleo-diagenetic proxy.

Neodymium isotope composition of planktonic foraminifera from ODP Hole 121-758A

This study presents neodymium isotope and elemental data for cleaned planktonic foraminifera from ODP site 758 in the southernmost reaches of the Bay of Bengal in the north-east Indian Ocean. Cleaning experiments using oxidative-reductive techniques suggest that diagenetic Fe-Mn oxyhydroxide coatings can be effectively removed, and that the measured Nd isotope composition reflects the composition of seawater from which the foraminiferal calcium carbonate was precipitated. Modern core-top Pulleniatina obliquiloculata and Globorotalia menardii give epsilon-Nd values of 310.12 +/- 0.16 and 310.28 +/- 0.16, respectively, indistinguishable from recent direct measurements of surface seawater in this area. A high-resolution Nd isotope record obtained from G. menardii for the past 150 kyr shows systematic variations (Delta epsilon-Nd = 3) on glacial-interglacial timescales. The timing of those variations shows a remarkable correspondence with the global oxygen isotope record, which suggests a process controlling the Nd isotope composition that responds in phase with global climate cycles. Palaeoclimate reconstruction indicates that during the last glacial maximum changes in monsoon circulation resulted in a reduction in rainfall over the Indian subcontinent, and a decrease in the flux of river water delivered to the Bay of Bengal. Thus, changes in the riverine input of Nd, a change in either flux or composition, most likely caused the isotope variations, although changes in dust source or local ocean circulation may have also played a role. These results clearly establish a link between climate change and variations in radiogenic isotopes in the oceans, and illustrate the potential of Nd isotopes in foraminifera for highresolution palaeoceanographic reconstruction.

Chemical and germanium isotopic compositions of sediments and sedimentary rocks from ODP Sites 129-801 and 185-1149

A new technique for the precise and accurate determination of Ge stable isotope compositions has been developed and applied to silicate rocks and biogenic opal. The analyses were performed using a continuous flow hydride generation system coupled to a MC-ICP-MS. Samples have been purified through anion- and cation-exchange resins to separate Ge from matrix elements and eliminate potential isobaric interferences. Variations of 74Ge/70Ge ratios are expressed as d74Ge values relative to our internal standard and the long-term external reproducibility of the data is better than 0.2? for sample size as low as 15 ng of Ge. Data are presented for igneous and sedimentary rocks, and the overall variation is 2.4? in d74Ge, representing 12 times the uncertainty of the measurements and demonstrating that the terrestrial isotopic composition of Ge is not unique. Co-variations of 74Ge/70Ge, 73Ge/70Ge and 72Ge/70Ge ratios follow a mass-dependent behaviour and imply natural isotopic fractionation of Ge by physicochemical processes. The range of d74Ge in igneous rocks is only 0.25? without systematic differences among continental crust, oceanic crust or mantle material. On this basis, a Bulk Silicate Earth reservoir with a d74Ge of 1.3+/-0.2? can be defined. In contrast, modern biogenic opal such as marine sponges and authigenic glauconite displayed higher d74Ge values between 2.0? and 3.0?. This suggests that biogenic opal may be significantly enriched in light isotopes with respect to seawater and places a lower bound on the d74Ge of the seawater to +3.0?.This suggests that seawater is isotopically heavy relative to Bulk Silicate Earth and that biogenic opal may be significantly fractionated with respect to seawater. Deep-sea sediments are within the range of the Bulk Silicate Earth while Mesozoic deep-sea cherts (opal and quartz) have d74Ge values ranging from 0.7? to 2.0?. The variable values of the cherts cannot be explained by binary mixing between a biogenic component and a detrital component and are suggestive of enrichment in the light isotope of diagenetic quartz. Further work is now required to determine Ge isotope fractionation by siliceous organisms and to investigate the effect of diagenetic processes during chert lithification.

Chemical and boron isotopic compositions of volcanics from ODP Sites 135-834 to 135-840

The influence of fluid flux on petrogenesis in the Tonga-Kermadec Arc was investigated using ion microprobe measurements of B/Be and boron isotope ratios (11B/10B) to document the source and relative volumes of the fluids released from the subducting oceanic plate. We analyzed young lavas from eight different islands along the Tonga-Kermadec Arc, as well as glass shards in volcanic sediments from Ocean Drilling Program (ODP) Site 840, which record the variations in the chemistry of Tonga magmatism since 7 Ma. B/Be is variable (5.8-122), in young Tonga-Kermadec Arc lavas. In contrast, glass shards from around 3 to 4 Ma old volcanic sediments at Site 840 have the highest B/Be values yet reported for arc lavas (18-607). These values are too high to be related simply to a sediment influence on petrogenesis. Together with very high d11B values (-11.6 to +37.5) for the same shards and lavas these data indicate that most of the B is derived from fluid escaped from the subducting altered Pacific oceanic crust, rather than from sediment. High d11B values also reflect large degrees of isotopic fractionation in this cold fast subduction zone. Lower d11B values noted in the Kermadec Arc (17 to -4.4) are related to the influence of sediment eroded from New Zealand and slower convergence. High fluid flux (B/Be) is synchronous in Tonga and the Marianas at 3 to 4 Ma and may be related to acceleration of the Pacific Plate just prior to this time. The timing of maximum B/Be at 3 to 4 Ma correlates with maximum light rare earth (LREE) and high field strength element depletion. This suggests maximum degrees of partial melting at this time. Although thinning of the arc lithosphere during rifting to form the Lau Basin is expected to influence the arc geochemistry, variable aqueous fluid flux from the subducting plate alone appears capable of explaining boron and other trace element systematics in the Tonga-Kermadec Arc with no indication of slab melting.

Geochemistry of Indian Ocean tephra and Afro-Arabian lavas

Widespread silicic pyroclastic eruptions of the Oligocene Afro-Arabian flood volcanic province (ignimbrites and airfall tuffs) produced up to 20% of the total flood volcanic stratigraphy (>6*10**4 km**3). Volumes of individual ignimbrites and tuffs exposed on land range from ~150 to >2000 km**3 and eight major units (15-100 m thick) were erupted in <2 Myr, placing these amongst the largest-magnitude silicic pyroclastic eruptions on Earth. They are compositionally distinctive time-stratigraphic markers which were deposited as co-ignimbrite ashfall deposits on a near-global scale around the time of the Oi2 cooling anomaly at ~30 Ma. Two ignimbrites from the lower part of the flood volcanic succession in Yemen have been correlated to: (a) the conjugate rifted margin of Ethiopia (>500 km distant); and (b) to two deep sea ash layers sampled by ODP Leg 115 in the Indian Ocean ~2700 km to the southeast. This correlation is based on whole rock analyses of silicic units for isotope ratios (Pb, Nd) and rare earth element compositions, in conjunction with novel in situ Pb isotope laser ablation multicollector inductively coupled plasma mass spectroscopy analysis of groundmass and glass shards. Compositional diversity preserved on the scale of individual ash shards in these deep sea tephra layers record chemical heterogeneity present in the silicic magma chambers that is not evident in the welded on-land deposits. Ages of the ash layers can be established by correlation to precisely dated on-land ignimbrites, and current evidence suggests that while these eruptions may have exacerbated already changing climatic conditions, they both marginally post-date the Oi2 global cooling anomaly.

Late Miocene to Pleistocene paleoceanographic records from the Feni and Gardar Drifts: Pliocene reduction in abyssal flow

Magnetic fabric analyses from two North Atlantic drift deposits provide proxies for determining relative variations in the strength of abyssal flow over the last 10 my. The data show a cessation of current-controlled sedimentation at the shallower Feni Drift (2417 m) at the time of onset of Northern Hemisphere glaciation (2.6 Ma). Drift formation ended nearly 2 my earlier (4.2 Ma) at the deeper Gardar Drift (3220 m), implying stepwise reduction in deep-water flow. Relatively light delta18O values at the deeper Gardar Drift indicate a warmer, thus also more salty, water mass site prior to 6 Ma. We interpret this as representing Mediterranean Sea water, which flowed north at depths greater than that of the Feni Drift Site. The supply of Mediterranean Water to the North Atlantic was shut off as the Gibraltar Straits closed, causing the Messinian salinity crisis, and never returned to that position in the water column after the Mediterranean opened again.

Mineral composition and 40Ar-39Ar data of samples from Garnet Point, Aurora Peak, Correll Nunatak, Penguin Point and Horn Bluffs, East Antarctica

George V Land (Antarctica) includes the boundary between Late Archean-Paleoproterozoic metamorphic terrains of the East Antarctic craton and the intrusive and metasedimentary rocks of the Early Paleozoic Ross-Delamerian Orogen. This therefore represents a key region for understanding the tectono-metamorphic evolution of the East Antarctic Craton and the Ross Orogen and for defining their structural relationship in East Antarctica, with potential implications for Gondwana reconstructions. In the East Antarctic Craton the outcrops closest to the Ross orogenic belt form the Mertz Shear Zone, a prominent ductile shear zone up to 5 km wide. Its deformation fabric includes a series of progressive, overprinting shear structures developed under different metamorphic conditions: from an early medium-P granulite-facies metamorphism, through amphibolite-facies to late greenschist-facies conditions. 40Ar-39Ar laserprobe data on biotite in mylonitic rocks from the Mertz Shear Zone indicate that the minimum age for ductile deformation under greenschist-facies conditions is 1502 ± 9 Ma and reveal no evidence of reactivation processes linked to the Ross Orogeny. 40Ar-39Ar laserprobe data on amphibole, although plagued by excess argon, suggest the presence of a ~1.7 Ga old phase of regional-scale retrogression under amphibolite-facies conditions. Results support the correlation between the East Antarctic Craton in the Mertz Glacier area and the Sleaford Complex of the Gawler Craton in southern Australia, and suggest that the Mertz Shear Zone may be considered a correlative of the Kalinjala Shear Zone. An erratic immature metasandstone collected east of Ninnis Glacier (~180 km east of the Mertz Glacier) and petrographically similar to metasedimentary rocks enclosed as xenoliths in Cambro-Ordovician granites cropping out along the western side of Ninnis Glacier, yielded detrital white-mica 40Ar-39Ar ages from ~530 to 640 Ma and a minimum age of 518 ± 5 Ma. This pattern compares remarkably well with those previously obtained for the Kanmantoo Group from the Adelaide Rift Complex of southern Australia, thereby suggesting that the segment of the Ross Orogen exposed east of the Mertz Glacier may represent a continuation of the eastern part of the Delamerian Orogen.

Geochemistry and isotopic composition of volcanic rocks of ODP Hole 128-794D

The Yamato Basin basement in the Sea of Japan was drilled below the sediment pile during Legs 127 and 128. Two superposed volcanic complexes are distinguished. The upper complex consists of continental tholeiite sills dated around 20-18 Ma and attributed to the rifting stage of the backarc basin. The lower complex consists of backarc basin basalts probably intruded below the upper complex during the spreading stage. Trace-element compositions and Sr and Nd isotopic signatures may be explained by mixing of at least two end members with a very small addition of crustal and subducted sediment component. Thus, upwelling of mantle diapir occurred during the rifting stage. Contribution of the depleted mantle increased in the spreading stage. The Neogene magmatic history of the Japan Sea is reviewed in the light of the ODP new data.

Geochemistry of Pliocene-Pleistocene volcanic rocks from the Izu Arc

The igneous geochemistry of lavas and breccias from the basement of Sites 790 and 791, and pumice clasts from the Pliocene-Pleistocene sedimentary section of Sites 788, 790, 791, and 793 were studied. Arc volcanism became silicic about 1.5 m.y. before the inception of rifting in the Sumisu Rift at 2 Ma, but eruption of these silicic magmas reflects changes in stress regime, especially during the last 130,000 yr, rather than crustal anatexis. Arc magmas have had a larger proportion of slab-derived components since the inception of rifting than before, but are otherwise similar. Rift basalts and rhyolites are derived from a different source than are arc andesites to rhyolites. The rift source has less slab-derived material and is an E-MORB-like source, in contrast to an N-MORB-type source overprinted with more slab-derived material beneath the arc. Rift magma types, in the form of rare pumice and lithic clasts, preceded the rift, and the earliest magmas that erupted in the rift already differed from those of the arc. The earliest large rift eruption produced an exotic explosion breccia ("mousse") despite eruption at >1800 mbsl. Although this rock type is attributed primarily to high magmatic water content, the clasts are more MORB-like in trace element and isotopic composition than are modern Mariana Trough basalts. After rifting began, arc volcanism continued to be predominantly silicic, with individual pumice deposits containing clasts that vary in composition by about 5 wt% SiO2, or about as much as in historical eruptions of submarine Izu Arc volcanoes. The overall variations in magma composition with time during the inception of arc rifting are broadly similar in the Sumisu Rift and Lau Basin, though newly tapped OIB-type mantle seems to be present earlier during basin formation in the Sumisu than Lau case.

Zircon U-Pb and Hf-O analysis of porphyries from the Duolong porphyry Cu-Au deposit in the Bangongco copper belt, central Tibet

The Duolong porphyry Cu-Au deposit (5.4 Mt at 0.72% Cu, 41 t at 0.23 g/t Au), which is related to the granodiorite porphyry and the quartz-diorite porphyry from the Bangongco copper belt in central Tibet, formed in a continental arc setting. Here, we present the zircon U-Pb ages, geochemical whole-rock, Sr-Nd whole-rock and zircon in-situ Hf-O isotopic data for the Duolong porphyries. Secondary ion mass spectrometry (SIMS) zircon U-Pb analyses for six samples yielded consistent ages of ~118 Ma, indicating a Cretaceous formation age. The Duolong porphyries (SiO2 of 58.81-68.81 wt.%, K2O of 2.90-5.17 wt.%) belong to the high-K calc-alkaline series. They show light rare earth element (LREE)-enriched distribution patterns with (La/Yb)N = 6.1-11.7, enrichment in large ion lithophile elements (e.g., Cs, Rb, and Ba) and depletion of high field strength elements (e.g., Nb), with negative Ti anomalies. All zircons from the Duolong porphyries share relatively similar Hf-O isotopic compositions (d18O=5.88-7.27 per mil; eHf(t)=3.6-7.3), indicating that they crystallized from a series of cogenetic melts with various degrees of fractional crystallization. This, along with the general absence of older inherited zircons, rules out significant crustal contamination during zircon growth. The zircons are mostly enriched in d18O relative to mantle values, indicating the involvement of an 18O-enriched crustal source in the generation of the Duolong porphyries. Together with the presence of syn-mineralization basaltic andesite, the mixing between silicic melts derived from the lower crust and evolved H2O-rich mafic melts derived from the metsomatizied mantle wedge, followed by subsequent fractional crystallization (FC) and minor crustal contamination in the shallow crust, could well explain the petrogenesis of the Duolong porphyries. Significantly, the hybrid melts possibly inherited the arc magma characteristics of abundant F, Cl, Cu, and Au elements and high oxidation state, which contributed to the formation of the Duolong porphyry Cu-Au deposit.