Holocene corals from the South China Sea

The South China Sea (SCS) is well connected with the western Pacific and influenced by the East Asian monsoon. We have examined temporal variations in radiocarbon marine reservoir ages (R) and regional marine reservoir corrections (DeltaR) of the SCS during the Holocene using paired measurements of AMS 14C and TIMS 230Th on 20 pristine corals. The results show large fluctuations in both R and DeltaR values over the past 7500 years (yrs) with two distinct plateaus during 7.5-5.6 and 3.5-2.5 thousand calendar years before present (cal ka BP). The respective weighted mean DeltaR values of these plateaus are 151 ± 85 and 89 ± 59 yrs, which are significantly higher than its modern value of -23 ± 52 yrs. This suggests that using a constant modern DeltaR value to calibrate 14C dates of the SCS marine samples will introduce additional errors to the calibrated ages. Our results provide the first database for the Holocene R and DeltaR values of the SCS for improved radiocarbon calibration of marine samples. We interpret the two DeltaR plateaus as being related to two intervals with weakened El Niño - Southern Oscillation (ENSO) and intensified East Asian summer monsoon (EASM). This is because the 14C content of the SCS surface water is controlled by both the 14C concentration of the Pacific North Equatorial Current (NEC) which is in turn influenced by ENSO-induced upwelling along the Pacific equator and vertical upwelling within the SCS as a result of moisture transportation to midlatitude region to supply the EASM rainfall.

Contents of 230Th, Fe2O3, MnO and P2O5 in bottom sediments from the Tropical Pacific

Shape of the 230Th vertical distribution curve ideally close to exponential is studied to determine isotopic age of deep-sea sediments. In practice such ideal 230Th vertical distribution curve is rarely occur; secondary maxima and minima often appear on it. It has been shown that oxyhydroxides of Fe, Mn, and also Corg and P are of prime importance for 230Th concentration. A method is offered for normalizing the vertical distribution curve of 230Th based on taking into account content of these elements in sediment.

Biogenic sedimentation of DSDP Site 85-574

The equatorial Pacific is an important part of the global carbon cycle and has been affected by climate change through the Cenozoic (65 Ma to present). We present a Miocene (12-24 Ma) biogenic sediment record from Deep Sea Drilling Project (DSDP) Site 574 and show that a CaCO3 minimum at 17 Ma was caused by elevated CaCO3 dissolution. When Pacific Plate motion carried Site 574 under the equator at about 16.2 Ma, there is a minor increase in biogenic deposition associated with passing under the equatorial upwelling zone. The burial rates of the primary productivity proxies biogenic silica (bio-SiO2) and biogenic barium (bio-Ba) increase, but biogenic CaCO3 decreases. The carbonate minimum is at ~17 Ma coincident with the beginning of the Miocene climate optimum; the transient lasts from 18 to 15 Ma. Bio-SiO2 and bio-Ba are positively correlated and increase as the equator was approached. Corg is poorly preserved, and is strongly affected by changing carbonate burial. Terrestrial 232Th deposition, a proxy for aeolian dust, increases only after the Site 574 equator crossing. Since surface production of bio-SiO2, bio-Ba, and CaCO3 correlate in the modern equatorial Pacific, the decreased CaCO3 burial rate during the Site 574 equator crossing is driven by elevated CaCO3 dissolution, representing elevated ocean carbon storage and elevated atmospheric CO2. The length of the 17 Ma CaCO3 dissolution transient requires interaction with a 'slow' part of the carbon cycle, perhaps elevated mantle degassing associated with the early stages of Columbia River Basalt emplacement.

Trace element geochemistry of zircons frim in situ ocean lithoshere

We characterize the textural and geochemical features of ocean crustal zircon recovered from plagiogranite, evolved gabbro, and metamorphosed ultramafic host-rocks collected along present-day slow and ultraslow spreading mid-ocean ridges (MORs). The geochemistry of 267 zircon grains was measured by sensitive high-resolution ion microprobe-reverse geometry at the USGS-Stanford Ion Microprobe facility. Three types of zircon are recognized based on texture and geochemistry. Most ocean crustal zircons resemble young magmatic zircon from other crustal settings, occurring as pristine, colorless euhedral (Type 1) or subhedral to anhedral (Type 2) grains. In these grains, Hf and most trace elements vary systematically with Ti, typically becoming enriched with falling Ti-in-zircon temperature. Ti-in-zircon temperatures range from 1,040 to 660°C (corrected for a TiO2 ~ 0.7, a SiO2 ~ 1.0, pressure ~ 2 kbar); intra-sample variation is typically ~60-15°C. Decreasing Ti correlates with enrichment in Hf to ~2 wt%, while additional Hf-enrichment occurs at relatively constant temperature. Trends between Ti and U, Y, REE, and Eu/Eu* exhibit a similar inflection, which may denote the onset of eutectic crystallization; the inflection is well-defined by zircons from plagiogranite and implies solidus temperatures of ~680-740°C. A third type of zircon is defined as being porous and colored with chaotic CL zoning, and occurs in ~25% of rock samples studied. These features, along with high measured La, Cl, S, Ca, and Fe, and low (Sm/La)N ratios are suggestive of interaction with aqueous fluids. Non-porous, luminescent CL overgrowth rims on porous grains record uniform temperatures averaging 615 ± 26°C (2SD, n = 7), implying zircon formation below the wet-granite solidus and under water-saturated conditions. Zircon geochemistry reflects, in part, source region; elevated HREE coupled with low U concentrations allow effective discrimination of ~80% of zircon formed at modern MORs from zircon in continental crust. The geochemistry and textural observations reported here serve as an important database for comparison with detrital, xenocrystic, and metamorphosed mafic rock-hosted zircon populations to evaluate provenance.

Composition of rocks, minerals, water, and gases from uplift areas of the Central Atlantic

Original geological, geophysical, lithological, mineralogical data on uplifts of the Central Atlantic are given in the book based on materials of Cruise 1 of the R/V Akademik Nikolaj Strakhov. Geological and geophysical studies include description of the obtained material and analysis of structural and morphological elements of the ocean floor. Results of lithological, petrochemical and geochemical studies were extremely innovative and develop a conceptual model. The latter include studies of petrochemical evolution of tholeiitic alkaline plate volcanism, large-scale hydrothermal transformation of basement rocks - palygorskitization, phosphatization and ferromanganese mineralization. Showing imposition Superposition of hydrogenic alteration on hydrothermally altered rocks and its role in Cenozoic history of sedimentation is shown.

Thallium isotope composition in pyrites

This paper presents the first study of Tl isotopes in early diagenetic pyrite. Measurements from two sections deposited during the Toarcian Ocean Anoxic Event (T-OAE, ~183 Ma) are compared with data from Late Neogene (<10 Ma) pyrite samples from ODP legs 165 and 167 that were deposited in relatively oxic marine environments. The Tl isotope compositions of Late Neogene pyrites are all significantly heavier than seawater, which most likely indicates that Tl in diagenetic pyrite is partially sourced from ferromanganese oxy-hydroxides that are known to display relatively heavy Tl isotope signatures. One of the T-OAE sections from Peniche in Portugal displays pyrite thallium isotope compositions indistinguishable from Late Neogene samples, whereas samples from Yorkshire in the UK are depleted in the heavy isotope of Tl. These lighter compositions are best explained by the lack of ferromanganese precipitation at the sediment-water interface due to the sulfidic (euxinic) conditions thought to be prevalent in the Cleveland Basin where the Yorkshire section was deposited. The heavier signatures in the Peniche samples appear to result from an oxic water column that enabled precipitation of ferromanganese oxy-hydroxides at the sediment-water interface. The Tl isotope profile from Yorkshire is also compared with previously published molybdenum isotope ratios determined on the same sedimentary succession. There is a suggestion of an anti-correlation between these two isotope systems, which is consistent with the expected isotope shifts that occur in seawater when marine oxic (ferromanganese minerals) fluxes fluctuate. The results outlined here represent the first evidence that Tl isotopes in early diagenetic pyrite have potential to reveal variations in past ocean oxygenation on a local scale and potentially also for global oceans. However, much more information about Tl isotopes in different marine environments, especially in anoxic/euxinic basins, is needed before Tl isotopes can be confidently utilized as a paleo-redox tracer.

Isotopic and chemical compositions of lower crust rocks and minerals from ODP Hole 176-735B

The composition of gabbroic rocks from the drill core of Hole 735B (ODP Leg 176) at the 11 Ma Atlantis II bank close to the slow spreading Southwest Indian Ridge (SWIR) has been analyzed for major and trace elements and Sr, Nd and Pb isotopic composition. The samples are thought to represent much of the mineralogical and geochemical variation in a vertical 1-km section (500-1500 m below the sea floor) of the lower ocean crust. Primitive troctolitic gabbros, olivine gabbros and gabbros that have Mg#=84-70, Ca#>61 and low Na# (Na/(Na+Al)) (8-17) are intruded by patches or veins of more evolved FeTi-oxide rich gabbroic and dioritic rocks with Mg# to 20, Ca# to 32, Na#=14-23, TiO2<7 wt.% and FeOtotal<18 wt.%. All rocks are acdcumulates, and incompatible element concentrations are low, e.g. Pb=0.1-0.7 ppm and U

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.

Rare and trace element analyses from DSDP Holes 31-291 and 31-294 from the Philippine Sea

Metal-rich sediments were found in the West Philippine Basin at DSDP sites 291 (located about 500 km SW of the Philippine Ridge or Central Basin Fault) and 294/295 (located about 580 km NE of the Philippine Ridge). In both cases the metalliferous deposits constitute a layer, probably Eocene in age, resting directly above the basaltic basement at the bottom of the sediment column. The chemistry of the major (including Fe and Mn) and trace elements (including trace metals, rare earth elements, U and Th) suggest a strong similarity of these deposits to metalliferous deposits produced by hydrothermal activity at oceanic spreading centers. Well-crystallized hematite is a major component of the metal-rich deposits at site 294/295. We infer that the Philippine Sea deposits were formed at some spreading center by hydrothermal processes of metallogenesis, similar to processes occurring at oceanic spreading centers. A locus for their formation might have been the Philippine Ridge (Central Basin Fault), probably an extinct spreading center. We conclude that metallogenesis of the type occurring at oceanic spreading centers can take place also in marginal basins. This has implications for the origin of metal deposits found in some ophiolite complexes, such as those in Luzon (Philippines), which may represent fragments of former marginal basins rather than of oceanic lithosphere.

Pb-, Sr-, and Nd-isotopic composition of basaltic rocks from the Lau Basin

New Pb, Sr, and Nd isotope data are presented for 64 samples from the six backarc sites drilled during Leg 135. Systematic changes in Pb and Sr compositions illustrate significant isotopic variations between and within sites as well as provide two key pieces of information. First, a recent influx of asthenosphere with Indian Ocean mantle affinities has occurred and has successfully displaced older "Pacific" asthenosphere from the mantle underlying the backarc region. Second, clear evidence exists for mixing between these two asthenospheric end-members and at least one "arc-like" component. The latter was not the same as most material currently erupting in the Tofua Arc, but it must have had a more radiogenic Pb-isotope signature, perhaps similar to rocks analyzed from the islands of Tafahi, and Niuatoputapu. A comparison between the isotopic variations and the tectonic setting of the drill sites reveals consistent and important information regarding the mantle dynamics beneath the evolving backarc basin. We propose a model in which the source of upwelling magmas changes from Pacific to Indian Ocean asthenosphere with the propagation of seafloor spreading, a model with important implications for the rate of mantle influx into this region. Although the chemistries of backarc magmas have been profoundly influenced by this process, an additional consequence is the advection of Indian Ocean asthenosphere into the sub-arc mantle source. The isotopic compositions of arc rocks from the vicinity have been reevaluated on the basis of the proposed mantle advection model. We suggest that the slab-derived flux of trace elements into the arc wedge has remained relatively uniform with time (i.e., ~40 Ma), so that the change in arc chemistry results from mantle source substitution, rather than from differences in the composition of the downgoing plate.

Geochemistry of ODP Site 145-882

Measurements of benthic foraminiferal cadmium:calcium (Cd/Ca) have indicated that the glacial-interglacial change in deep North Pacific phosphate (PO4) concentration was minimal, which has been taken by some workers as a sign that the biological pump did not store more carbon in the deep glacial ocean. Here we present sedimentary redox-sensitive trace metal records from Ocean Drilling Program (ODP) Site 882 (NW subarctic Pacific, water depth 3244 m) to make inferences about changes in deep North Pacific oxygenation - and thus respired carbon storage - over the past 150,000 yr. These observations are complemented with biogenic barium and opal measurements as indicators for past organic carbon export to separate the influences of deep-water oxygen concentration and sedimentary organic carbon respiration on the redox state of the sediment. Our results suggest that the deep subarctic Pacific water mass was depleted in oxygen during glacial maxima, though it was not anoxic. We reconcile our results with the existing benthic foraminiferal Cd/Ca by invoking a decrease in the fraction of the deep ocean nutrient inventory that was preformed, rather than remineralized. This change would have corresponded to an increase in the deep Pacific storage of respired carbon, which would have lowered atmospheric carbon dioxide (CO2) by sequestering CO2 away from the atmosphere and by increasing ocean alkalinity through a transient dissolution event in the deep sea. The magnitude of change in preformed nutrients suggested by the North Pacific data would have accounted for a majority of the observed decrease in glacial atmospheric pCO2.

Geochemistry of Lesser Antilles forearc sediments

Oceanic sediments contain the products of erosion of continental crust, biologic activity and chemical precipitation. These processes create a large diversity of their chemical and isotopic compositions. Here we focus on the influence of the distance from a continental platform on the trace element and isotopic compositions of sediments deposited on the ocean floor and highlight the role of zircons in decoupling high-field strength elements and Hf isotopic compositions from other trace elements and Nd isotopic compositions. We report major and trace element concentrations as well as Sr and Hf isotopic data for 80 sediments from the Lesser Antilles forearc region. The trace-element characteristics and the Sr and Hf isotopic compositions are generally dominated by detrital material from the continental crust but are also variably influenced by chemical or biogenic carbonate and pure biogenic silica. Next to the South American continent, at DSDP Site 144 and on Barbados Island, sediments, coarse quartz arenites, exhibit marked Zr and Hf excesses that we attribute to the presence of zircon. In contrast, the sediments from DSDP Site 543, which were deposited farther away from the continental platform, consist of fine clay and they show strong deficiencies in Zr and Hf. The enrichment or depletion of Zr-Hf is coupled to large changes in Hf isotopic compositions (-30 < epsilon-Hf < +4) that vary independently from the Nd isotopes. We interpret this feature as a clear expression of the "zircon effect" suggested by Patchett and coauthors in 1984. Zircon-rich sediments deposited next to the South American continent have very low epsilon-Hf values inherited from old zircons. In contrast, in detrital clay-rich sediments deposited a few hundred kilometers farther north, the mineral fraction is devoid of zircon and they have drastically higher epsilon-Hf values inherited from finer, clay-rich continental material. In the two DSDP sites, average Hf isotopes are very unradiogenic relative to other oceanic sediments worldwide (epsilon-Hf = -14.4 and -7.4) and they define the low Hf end member of the sedimentary field in Hf-Nd space. Their compositions correspond to end members that, when mixed with mantle, are able to reproduce the pattern of volcanic rocks from the Lesser Antilles. More generally, we find a relationship between Nb/Zr ratios and the vertical deviation of Hf isotope ratios from the Nd-Hf terrestrial array and we suggest that this relationship can be used as a tool to distinguish sediment input from fractionation during melting during the formation of arc lavas.

Chemical composition of bottom sediments from the Baltic Sea

According to geochemical analyses carbonaceous sediments from deep basins of the Baltic Sea containing 3-5% of organic carbon are enriched in some metals such as Cu, Mo, Ni, Pb, Zn, V, and U relative to shallow-water facies of the Bay of Finland. These metals also enrich (relative to background values in clayey rocks) ancient carbonaceous shales, where the average Cu and V contents are slightly higher and that of Mo, Pb, and Zn lower than in deep-sea carbonaceous sediments of the Baltic Sea. In addition, the deep-sea carbonaceous sediments of the Baltic Sea are enriched (but less notably than ancient shales) in Ag, As, Bi, and Cd. These data confirm previous assumptions that carbonaceous sediments accumulating now in seas and oceans can be considered as recent analogs of ancient metalliferous shales.