Chemical element concentrations in sediments from DSDP Holes 60-458 and 60-459

The development of laser ablation-inductively coupled plasma-mass spectrometry has revolutionized the analysis of tephras by providing (1) an efficient and precise method for determining abundances of a wide variety of trace elements at low concentrations in individual glass shards and (2) assessment of geochemical heterogeneities within individual ash horizons. This development is important for petrogenetic studies of intraoceanic arc systems, where tephras provide the most complete temporal record of magmatism. Results from the Izu-Bonin and Mariana arc systems indicate that despite close geographical proximity and similar tectonic evolution, they contrast strongly in terms of geochemical evolution since 35 Ma. Whereas the Mariana tephras have exceptional compositional diversity, ranging from low-K (Oligocene), to high-K (Miocene), and subsequently medium-K compositions (Pliocene-Quaternary), the Izu-Bonin arc has been dominated by low-K compositions throughout. The Mariana increases in K are paralleled by increases in abundances of incompatible trace elements and by increased values of diagnostic ratios (e.g., Nb/yb and Th/yb) regarded as monitors of potential mantle-source fertility. The relative uniformity of Nb/yb and Nb/Zr ratios in Izu-Bonin tephras indicates that cyclic processes of backarc basin development and mantle depletion do not necessarily induce large-scale temporal geochemical variations in the associated arc. Temporal variability within the Mariana arc, and its divergence from the Izu-Bonin arc ca. 13 Ma, can be traced to a major injection of subducted sediment in the Mariana system at this time.

Composition of Fe-Mn minerals from island arcs of the West Pacific

This paper presents materials on the chemical and mineralogical composition of Fe-Mn mineralization in island arcs (Kuril, Nampo, Mariana, New Britain, New Hebrides, and Kermadec) in the western part of the Pacific Ocean. The mineralization was proved to be of hydrothermal and/or hydrogenic genesis. The former is produced by hydrothermal Fe and Mn oxi-hydroxides that cement volcanic-terrigenous material in sediments. Some Fe oxyhydroxides can be derived via the halmyrolysis of volcaniclastic material. Crusts of this stage are characterized by fairly low concentrations of trace and rare elements, and their REE composition is inherited from the volcanic-terrigenous material. The minerals of the Mn oxyhydroxides are todorokite and "Ca-birnessite". The Mn/Fe ratio increases away from the discharge sites of the hydrothermal solutions. The hydrogenic Fe-Mn crusts are characterized by high concentrations of trace and minor elements of both the Mn group (Co, Ni, Tl, and Mo) and the Fe group (REE, Y, and Th). The hydrogenic crusts consist of Fe-vernadite and Mn-feroxyhyte. Some of the hydrothermal crusts originally had a hydrothermal genesis. The first data were obtained on crust B30-72-10 from the Macauley Seamount in the Kermadec island arc, which contained anomalously high concentrations of Co (2587 ppm) and other Mn-related trace elements in the absence of hydrogeneous Fe oxyhydroxides.

Geochemistry of ODP Leg 127 igneous rocks

Legs 127 and 128 of the Ocean Drilling Program cored basement samples from two sites in the Yamato Basin (Sites 794 and 797) and one site in the Japan Basin (Site 795) of the Japan Sea. These samples represent sills and lava flows erupted or shallowly intruded in a marine environment during backarc extension and spreading in the middle Miocene. In this paper, we describe the geochemical characteristics of these igneous units using 52 new instrumental neutron activation analyses (INAA), 8 new X-ray fluorescence (XRF) analyses, and previous shipboard XRF analyses. The sills intruded into soft sediment at Sites 794 and 797 were subject to extensive hydrothermal activity, estimated at <230° C under subgreenschist facies conditions, which heavily to totally altered the fine-grained unit margins and moderately to heavily altered the coarse-grained unit interiors. Diagenesis further altered the composition of these igneous bodies and lava flows at Sites 794, 795, and 797, most intensely at unit margins. Our study of two well-sampled units shows that Mg, Ca, Sr, and the large-ion lithophile elements (LILE) mobilized during alteration, and that the concentrations of Y, Yb, and Lu decreased and Ce increased in the most severely altered samples. Nevertheless, our study shows that the rare-earth elements (REE) were relatively immobile in the majority of the samples, even where secondary mixed-layer clays comprised the great majority of the rock. Fresher Yamato Basin samples are compositionally heterogenous tholeiitic basalts and dolerites. At Site 794 in the north-central portion of the basin, Units 1 to 5 (upper basement) comprise mildly light rare-earth element (LREE) enriched basalts and dolerites (chondrite-normalized La/Sm of 1.4-1.8), while the stratigraphically lower Units 6 to 9 are less enriched dolerites with (La/Sm)N of 0.7-1.3. All Site 794 samples lack Nb and Ta depletions and LILE enrichments, lacking a strong subduction-related incompatible element geochemical signature. At Site 797 in the western margin of the basin, two stratigraphically-definable unit groups also occur. The upper nine units are incompatible-element depleted tholeiitic sills and flows with strong depletions of Nb and Ta relative to normal mid-ocean ridge basalt (N-MORB). The lower twelve sills represent LREE-enriched tholeiites (normalized La/Sm ranges from 1.1 to 1.8), with distinctly higher LILE and high field-strength element (HFSE) contents. At Site 795 at the northern margin of the Japan Sea, three eruptive units consist of basaltic andesite to calc-alkaline basalt (normalized La/Sm of 1.1 to 1.5) containing moderate depletions of the HFSE relative to N-MORB. The LILE-depleted nature of these samples precludes their origin in a continental arc, indicating that they more likely erupted within a rifting oceanic arc system. The heterogenous nature of the Japan Sea rocks indicate that they were derived at each site from multiple parental magmas generated from a compositionally heterogenous mantle source. Their chemistry is intermediate in character between arc basalts, MORB, and intraplate basalts, and implies little involvement of continental crust at any point in their genesis. Their flat chondrite-normalized, medium-to-heavy rare earth patterns indicate that the primary magmas which produced them last equilibrated with and segregated from spinel lherzolite at shallow depths (<30 kbar). In strong contrast to their isotopic compositional arrays, subduction-related geochemical signatures are usually poorly defined. No basin-wide temporal or geographic systematics of rock chemistry may be confidently detailed; instead, the data show both intimate (site-specific) and widespread backarc mantle heterogeneity over a narrow (2 Ma or so) range in time, with mantle heterogeneity most closely resembling a "plum-pudding" model.

Geochemistry on manganese nodules from Timor

Fossil Mn nodules of Cretaceous age from western Timor exhibit chemical, structural and radioisotope compositions consistent with their being of deep-sea origin. These nodules show characteristics similar to nodules now found at depths of 3,500-5,000 m in the Pacific and Indian Oceans. Slight differences in the fine structure and chemistry of these nodules and modern deep-sea nodules are attributed to diagenetic alteration after uplift of enclosing sediments.

Isotopic and chemical compositions of DSDP site 18-174 sediments

The Astoria submarine fan, located off the coast of Washington and Oregon, has grown throughout the Pleistocene from continental input delivered by the Columbia River drainage system. Enormous floods from the sudden release of glacial lake water occurred periodically during the Pleistocene, carrying vast amounts of sediment to the Pacific Ocean. DSDP site 174, located on the southern distal edge of the Astoria Fan, is composed of 879 m of terrigenous sediments. The section is divided into two major units separated by a distinct seismic discontinuity: an upper, turbidite fan unit (Unit I), and an underlying finer-grained unit (Unit II). Both units have overlapping ranges of Nd and Hf isotope compositions, with the majority of samples having e-Nd values of -7.1 to -15.2 and eHf values -6.2 to -20.0; the most notable exception is the uppermost sample in the section, which is identical to modern Columbia River sediment. Nd depleted mantle model ages for the site range from 2.0 to 1.2 Ga and are consistent with derivation from cratonic Proterozoic source regions, rather than Cenozoic and Mesozoic terranes proximal to the Washington-Oregon coast. The Astoria Fan sediments have significantly less radiogenic Nd (and Hf) isotopic compositions than present day Columbia River sediment (e-Nd=-3 to -4; [Goldstein, S.J., Jacobsen, S.B., 1987. Nd and Sr isotopic systematics of river water suspended material: implications for crustal evolution. Earth. Planet. Sci. Lett. 87, 249-265; doi:10.1016/0012-821X(88)90013-1]), and suggest that outburst flooding, tapping Proterozoic source regions, was the dominant sediment transport mechanism in the genesis and construction of the Astoria Fan. Pb isotopes form a highly linear 207Pb/204Pb - 206Pb/204Pb array, and indicate the sediments are a binary mixture of two disparate sources with isotopic compositions similar to Proterozoic Belt Supergroup metasediments and Columbia River Basalts. The combined major, trace and isotopic data argue that outburst flooding was responsible for depositing the majority (top 630 m) of the sediment in the Astoria Fan.

Geochemistry at DSDP Leg 59

Deep Sea Drilling Project Legs 59 and 60 drilled 15 sites along an east-west transect at 18°N from the West Philippine Basin to the Mariana Trench (Fig. 1) in order to study the nature and genesis of the back-arc, marginal basins and the remnant and active arcs of the region. Leg 59 drilled at five sites at the western end of the traverse: Site 447 in the West Philippine Basin; Site 448 on the Palau-Kyushu Ridge; Sites 449 and 450 in the Parece Vela Basin; and Site 451 on the West Mariana Ridge. Penetration into basaltic basement of these sites was 183.5 meters at 447 (8 basalt flows); 623 meters at 448 (46 basalt flows, sills, and dikes and volcaniclastic units); 40.5 meters at 449 (2 basalt flows); 7 meters at 450 (1 basalt intrusion); and 4 meters of basalt breccia at 451 overlain by 861 meters of volcaniclastic sedimentary rocks.

Rare earth and other element contents in surface layer bottom sediments and ferromanganese nodules along the Transatlantic profile

Behavior of rare earth elements (REE) and Th is studied along the Transatlantic transect at 22°N. It is shown that both REE and Th contents relative to Al (the most lithogenic element) increase toward the pelagic region. The increasing trend becomes more complicated due to variations in content of biogenic calcium carbonate that acts as a diluting component in sediments. REE composition varies symmetrically relative to the Mid-Atlantic Ridge (MAR) emphasizing weak hydrothermal influence on sediments of the ridge axis, although the well-known criteria for hydrothermal contribution, such as Al/(Al+Mn+Fe) and (Fe+Mn)/Ti, do not reach critical values. Variations in REE content and composition allowed to distinguish the following five sediment zones in the transect: (I) terrigenous sediments of the Nares abyssal plain; (II) pelagic sediments of the North American Basin; (III) carbonate ooze of the MAR axis; (IV) pelagic sediments of the Canary Basin; and (V) terrigenous clay and calcareous mud of the African continental slope and slope base. Ferromanganese nodules of the hydrogenous type with extremely high Ce (up to 1801 ppm) and Th (up to 138 ppm) contents occur in pelagic sediments. It is ascertained that P, REE, and Th contents depend on Fe content in Atlantic sediments. Therefore, one can suggest that only minor amount of phosphorus is bound with bone debris. Low concentration of bone debris phosphorus is a result of relatively high sedimentation rates in the Atlantic Ocean, as compared with those in pelagic regions of the Pacific Ocean.

Calcite accumulation in the eastern equatorial Pacific

The eastern equatorial Pacific (EEP) is an important center of biological productivity, generating significant organic carbon and calcite fluxes to the deep ocean. We reconstructed paleocalcite flux for the past 30,000 years in four cores collected beneath the equatorial upwelling and the South Equatorial Current (SEC) by measuring ex230Th-normalized calcite accumulation rates corrected for dissolution with a newly developed proxy for "fraction of calcite preserved". This method produced very similar results at the four sites and revealed that the export flux of calcite was 30-50% lower during the LGM compared to the Holocene. The internal consistency of these results supports our interpretation, which is also in agreement with emerging data indicating lower glacial productivity in the EEP, possibly as a result of lower nutrient supply from the southern ocean via the Equatorial Undercurrent. However, these findings contradict previous interpretations based on mass accumulation rates (MAR) of biogenic material in the sediment of the EEP, which have been taken as reflecting higher glacial productivity due to stronger wind-driven upwelling.

Chemical composition of ferromanganese nodules from the Black Sea

Ferruginate shells and tubular worm burrows from the oxygenated zone of the Black Sea (Kalamit Bay and Danube River mouth) are studied by transmission and scanning electron microscopy combined with analyses of elemental composition. Iron and manganese oxyhydroxide nodules considered here are enriched in phosphorus. They contain variable amounts of terrigenous and biogenic material derived from host sediments. Oxyhydroxides are mainly characterized by colloform structure, whereas globular and crystalline structures are less common. The dominating iron phase is represented by ferroxyhite and protoferroxyhite, whereas the manganese phase is composed of Fe-free vernadite. Concentrations of Mn, As, and Mo are 12-18 times higher relative to sediments, while concentrations of Fe, P, Ni, and Co increase 5-7 times during nodule formation.

Petrology and geochemistry of basalt at DSDP Hole 66-487

Major oxide and trace element determinations of the composition basalts from the bottom of Hole 487, together with microprobe analyses of their minerals (olivine, magnesiochromite, salite, and plagioclase), prove that they are depleted oceanic tholeiites.

Radioisotopes and He accumulation in deep sea sediments of the Ontong Java Plateau

The accumulation of extraterrestrial 3He, a tracer for interplanetary dust particles (IDPs), in sediments from the Ontong Java Plateau (OJP; western equatorial Pacific Ocean) has been shown previously to exhibit a regular cyclicity during the late Pleistocene, with a period of ~100 ka. Those results have been interpreted to reflect periodic variability in the global accretion of IDPs that, in turn, has been linked to changes in the inclination of Earth's orbit with respect to the invariable plane of the solar system. Here we show that the accumulation in OJP sediments of authigenic 230Th, produced by radioactive decay of 234U in seawater, exhibits a 100-ka cyclicity similar in phase and amplitude to that evident in the 3He record. We interpret the similar patterns of 230Th and 3He accumulation to reflect a common origin within the ocean-climate system. Comparing spatial and temporal patterns of sediment accumulation against regional patterns of biological productivity and against the well-established pattern of CaCO3 dissolution in the deep Pacific Ocean leads to the further conclusion that a common 100-ka cycle in accumulation of biogenic, authigenic and extraterrestrial constituents in OJP sediments reflects the influence of climate-related changes in sediment focusing, rather than changes in the rate of production or supply of sedimentary constituents.

Composition of dikes and lavas from the Pito Deep Rift

The northwest trending walls of the Pito Deep Rift (PDR), a tectonic window in the southeast Pacific, expose in situ oceanic crust generated ?3 Ma at the superfast spreading southern East Pacific Rise (SEPR). Whole rock analyses were performed on over 200 samples of dikes and lavas recovered from two ~8 km**2 study areas. Most of the PDR samples are incompatible-element-depleted normal mid-ocean ridge basalts (NMORB; (La/Sm)N < 1.0) that show typical tholeiitic fractionation trends. Correlated variations in Pb isotope ratios, rare earth element patterns, and ratios of incompatible elements (e.g., (Ce/Yb)N) are best explained by mixing curves between two enriched and one depleted mantle sources. Pb isotope compositions of most PDR NMORB are offset from SEPR data toward higher values of 207Pb/204Pb, suggesting that an enriched component of the mantle was present in this region in the past ?3 Ma but is not evident today. Overall, the PDR crust is highly variable in composition over long and short spatial scales, demonstrating that chemically distinct lavas and dikes can be emplaced within the same segment over short timescales. However, the limited spatial distribution of high 206Pb/204Pb samples and the occurrence of relatively homogeneous MgO compositions (ranging <2.5 wt %) within a few of the individual dive transects (over distances of ~1 km) suggests that the mantle source composition evolved and magmatic temperatures persisted over timescales of tens of thousands of years. The high degree of chemical variability between pairs of adjacent dikes is interpreted as evidence for along-axis transport of magma from chemically distinct portions of the melt lens. Our findings suggest that lateral dike propagation occurs to a significant degree at superfast spreading centers.

(Table 2) Chemical composition of phosphates from the Namibian and Chilean shelves

This study on phosphorites of different compositions and ages from shelf sediments and seamounts of the Pacific Ocean by means of analytical electron microscopy showed that these phosphorites contain ultra-microscopic inclusions of authigenic minerals and, more rarely, of rare earth element (REE) minerals. In some of phosphorite samples of Pleistocene-Pliocene age from the Namibian shelf both kinds of minerals were found. Uranium minerals were represented by uraninite, coffinite, and ningioite; those of REE - by monazite, xenotime, and bastnesite, which points to their potential accumulation not only as isomorphous admixtures in calcium phosphate but also as independent mineral phases. Coexistence of the minerals noted in shelf phosphorites is caused by repeated changes in redox conditions during formation and then redeposition of phosphate concretions. Presence of uranium minerals in phosphorites from seamounts shows that during an initial step of formation of these phosphorites environment was rather suboxic or reductive than oxic.