Chemistry of volcanic ash from Celebes and Sulu Sea Basins

During Leg 124, off the Philippines, volcanic material was recovered in deep-sea sediments dating from the late Oligocene in the Celebes Sea Basin, and from the early Miocene in the Sulu Sea Basin. Chemical and petrological studies of fallout ash deposits are used to characterize volcanic pulses and to determine their possible origin. All of the glass and mineral compositions belong to medium-K and high-K calc-alkaline arc-related magmatic suites including high-Al basalts, pyroxene-hornblende andesites, dacites, and rhyolites. Late Oligocene and early Miocene products may have originated from the Sunda arc or from the Sabah-Zamboanga old Sulu arc. Late early Miocene Sulu Sea tuffs originated from the Cagayan arc, whereas early late Miocene fallout ashes are attributed to the Sulu arc. A complex magmatic production is distinguished in the Plio-Quaternary with three sequences of basic to acidic lava suites. Early Pliocene strata registered an important activity in both Celebes Sea and Sulu Sea areas, from the newly born Sangihe arc (low-alumina andesite series) and from the Sulu, Zamboanga, and Negros arcs (high-alumina basalt series and high-K andesite series). In the late Pliocene and the early Pleistocene, renewal of activity affects the Sangihe-Cotobato arc as well as the Sulu and Negros arcs (same magmatic distinctions). The last volcanic pulse took place in the late Pleistocene with revival of all the present arc systems.

Mg/Ca ratios of Cenozoic benthic foraminifera from the Indian and South Atlantic Ocean

We investigate the evolution of Cenozoic climate and ice volume as evidenced by the oxygen isotopic composition of seawater (delta18Osw) derived from benthic foraminiferal Mg/Ca ratios to constrain the temperature effect contained in foraminiferal delta18O values. We have constructed two benthic foraminiferal Mg/Ca records from intermediate water depth sites (Ocean Drilling Program sites 757 and 689 from the subtropical Indian Ocean and the Weddell Sea, respectively). Together with the previously published composite record of Lear et al. (2002, doi:10.1126/science.287.5451.269) and the Neogene record from the Southern Ocean of Billups and Schrag (2002, doi:10.1029/2000PA000567), we obtain three, almost complete representations of the delta18Osw for the past 52 Myr. We discuss the sensitivity of early Cenozoic Mg/Ca-derived paleotemperatures (and hence the delta18Osw) to assumptions about seawater Mg/Ca ratios. We find that during the middle Eocene (~ 49-40 Ma), modern seawater ratios yield Mg/Ca-derived temperatures that are in good agreement with the oxygen isotope paleothermometer assuming ice-free conditions. Intermediate waters cooled during the middle Eocene reaching minimum temperatures by 40 Ma. The corresponding delta18Osw reconstructions support ice growth on Antarctica beginning by at least 40 Ma. At the Eocene/Oligocene boundary, Mg/Ca ratios (and hence temperatures) from Weddell Sea site 689 display a well-defined maximum. We caution against a paleoclimatic significance of this result and put forth that the partitioning coefficient of Mg in benthic foraminifera may be sensitive to factors other than temperature. Throughout the remainder of the Cenozoic, the temporal variability among delta18Osw records is similar and similar to longer-term trends in the benthic foraminiferal delta18O record. An exception occurs during the Pliocene when delta18Osw minima in two of the three records suggest reductions in global ice volume that are not apparent in foraminiferal delta18O records, which provides a new perspective to the ongoing debate about the stability of the Antarctic ice sheet. Maximum delta18Osw values recorded during the Pleistocene at Southern Ocean site 747 agree well with values derived from the geochemistry of pore waters (Schrag et al., 1996, doi:10.1126/science.272.5270.1930) further highlighting the value of the new Mg/Ca calibrations of Martin et al. (2002, doi:10.1016/S0012-821X(02)00472-7) and Lear et al. (2002, doi:10.1016/S0016-7037(02)00941-9) applied in this study. We conclude that the application of foraminiferal Mg/Ca ratios allows a refined view of Cenozoic ice volume history despite uncertainties related to the geochemical cycling of Mg and Ca on long time scales.

Element and Sr isotope composition of interstitial waters in sediments of ODP Leg 129

Interstitial water samples from Leg 129, Sites 800, 801, and 802 in the Pigafetta and Mariana basins (central western Pacific), have been analyzed for major elements, B, Li, Mn, Sr, and 87Sr/86Sr. At all sites waters show enrichment in Ca and Sr and are depleted in Mg, K, Na, SO4, B, alkalinity, and 87Sr compared to seawater. These changes are related to alteration of basaltic material into secondary smectite and zeolite and recrystallization of biogenic carbonate. Water concentration depth profiles are characterized by breaks due to the presence of barriers to diffusion such as chert layers at Sites 800 and 801 and highly cemented volcanic ash at Site 802. In Site 800, below a chert layer, concentration depth profiles are vertical and reflect slight alteration of volcanic matter, either in situ or in the upper basaltic crust. Release of interlayer water from clay minerals is likely to induce observed Cl depletions. At Site 801, two units act as diffusion barrier and isolate the volcaniclastic sediments from ocean and basement. Diagenetic alteration of volcanic matter generates a chemical signature similar to that at Site 800. Just above the basaltic crust, interstitial waters are less evolved and reflect low alteration of the crust, probably because of the presence in the sediments of layers with low diffusivities. At Site 802, in Miocene tuffs, the chemical evolution generated by diagenetic alteration is extreme (Ca = 130 mmol, 87Sr/86Sr = 0.7042 at 83 meters below seafloor) and is accompanied by an increase of the Cl content (630 mmol) due to water uptake in secondary hydrous phases. Factors that enhance this evolution are a high sediment accumulation rate, high cementation preventing diffusive exchange and the reactive composition of the sediment (basaltic glass). The chemical variation is estimated to result in the alteration of more than 20% of the volcanic matter in a nearly closed system.

Geochemistry and age determination of zircons in Cretaceous to Quaternary sediments

In central Antarctica, drainage today and earlier back to the Paleozoic radiates from the Gamburtsev Subglacial Mountains (GSM). Proximal to the GSM past the Permian-Triassic fluvial sandstones in the Prince Charles Mountains (PCM) are Cretaceous, Eocene, and Pleistocene sediment in Prydz Bay (ODP741, 1166, and 1167) and pre-Holocene sediment in AM04 beneath the Amery Ice Shelf. We analysed detrital zircons for U-Pb ages, Hf-isotope compositions, and trace elements to determine the age, rock type, source of the host magma, and "crustal" model age (T(C)DM). These samples, together with others downslope from the GSM and the Vostok Subglacial Highlands (VSH), define major clusters of detrital zircons interpreted as coming from (1) 700 to 460 Ma mafic granitoids and alkaline rock, epsilon-Hf 9 to -28, signifying derivation 2.5 to 1.3 Ga from fertile and recycled crust, and (2) 1200-900 Ma mafic granitoids and alkaline rock, epsilon-Hf 11 to -28, signifying derivation 1.8 to 1.3 Ga from fertile and recycled crust. Minor clusters extend to 3350 Ma. Similar detrital zircons in Permian-Triassic, Ordovician, Cambrian, and Neoproterozoic sandstones located along the PaleoPacific margin of East Antarctica and southeast Australia further downslope from central Antarctica reflect the upslope GSM-VSH nucleus of the central Antarctic provenance as a complex of 1200-900 Ma (Grenville) mafic granitoids and alkaline rocks and older rocks embedded in 700-460 Ma (Pan-Gondwanaland) fold belts. The wider central Antarctic provenance (CAP) is tentatively divided into a central sector with negative ?Hf in its 1200-900 Ma rocks bounded on either side by positive epsilon-Hf. The high ground of the GSM-VSH in the Permian and later to the present day is attributed to crustal shortening by far-field stress during the 320 Ma mid-Carboniferous collision of Gondwanaland and Laurussia. Earlier uplifts in the ~500 Ma Cambrian possibly followed the 700-500 Ma assembly of Gondwanaland, and in the Neoproterozoic the 1000-900 Ma collisional events in the Eastern Ghats-Rayner Province at the end of the 1300-1000 Ma assembly of Rodinia.

Composition of Fe-Mn micronodules, nodules and host bottom sediments from the Northeast Pacific Basin

Authigenic ferromanganese manifestations in bottom sediments from two horizons (0-10 and 240-250 cm) located in the low/high bioproductive transitional zone of the Pacific Ocean were studied. In addition two compositionally different types of micronodules, crusts and ferromanganese nodules were detected in the surface horizon (0-1 cm). Three size fractions (50-100, 100-250, and 250-500 µm) of manganese micronodules were investigated. In terms of surface morphology, color, and shape, the micronodules are divided into dull round (MN1) and angular lustrous (MN2) varieties with different mineral and chemical compositions. MN1 are enriched in Mn and depleted in Fe as compared with MN2. Mn/Fe ratio in MN1 varies from 13 to 14. Asbolane-buserite and birnessite are the major manganese minerals in them. MN2 is mainly composed of vernadite with Mn/Fe ratio from 4.3 to 4.8. Relative to MN1, fraction 50-100 µm of MN2 is enriched in Fe (2.6 times), W (1.8), Mo (3.2), Th (2.3), Ce (5.8), and REE (from 1.2 to 1.8). Relative to counterparts from MN1, separate fractions of MN2 are characterized by greater compositional difference. For example, increase in size of micronodules leads to decrease in contents of Fe (by 10 rel. %), Ce (2 times), W (2.1 times), Mo (2.2 times), and Co (1.5 times). At the same time one can see increase in contents of other elements: Th and Cu (2.1 times), Ni (1.9 times), and REE (from 1.2 to 1.6 times). Differences in chemical and mineral compositions of MN1 and MN2 fractions can be related to alternation of oxidative and suboxidative conditions in the sediments owing to input of labile organic matter, which acts as the major reducer, and allochthonous genesis of MN2.

Rocks of the Western Kamchatka-Koryak continental margin volcanogenic belt: age, chemical and mineral compositions

An isotope-geochemical study of Eocene-Oligocene magmatic rocks from the Western Kamchatka-Koryak volcanogenic belt revealed lateral heterogeneity of mantle magma sources in its segments: Western Kamchatka, Central Koryak, and Northern Koryak ones. In the Western Kamchatka segment magmatic melts were generated from isotopically heterogeneous (depleted and/or insignificantly enriched) mantle sources significantly contaminated by quartz-feldspathic sialic sediments; higher 87Sr/86Sr (0.70429-0.70564) and lower 143Nd/144Nd [eNd(T) = 0.06-2.9] ratios in volcanic rocks from the Central Koryak segment presumably reflect contribution of an enriched mantle source; high positive eNd(T) and low 87Sr/86Sr ratios in magmatic rocks from the Northern Koryak segment area indicate their derivation from an isotopically depleted mantle source without significant contamination by sialic or mantle material enriched in radiogenic Sr and Nd. Significantly different contamination histories of Eocene-Oligocene mantle magmas in Kamchatka and Koryakia are related to their different thermal regimes: higher heat flow beneath Kamchatka led to crustal melting and contamination of mantle suprasubduction magmas by crustal melts. Cessation of suprasubduction volcanism in the Western Kamchatka segment of the continental margin belt was possibly related to accretion of the Achaivayam-Valagin terrane 40 Ma ago, whereas suprasubduction activity in the Koryak segment stopped due to closure of the Ukelayat basin in Oligocene.

Re-OS and Pb isotope ratios of sediments from Saanich Inlet, Western Canada

Re-Os and Pb-Pb isotopic analysis of reduced varved sediments cored in the deeper basin of Saanich Inlet (B.C.) are presented. From core top to 61 cm down-core, spanning approximately the last 100 yrs of sedimentation, 187Os/188Os ratio and Os concentration respectively increase from ~0.8 to ~0.9 and from 55 to 60 ppt, whereas Re concentration decreases from 3600 to 2600 ppt. Re correlates with Corg (R2=0.6) throughout the entire section, whereas Os follows Re and Corg trends deeper down-core, suggesting a decoupling of a Re- and Os-geochemistry during burial and/or very early diagenesis. No systematic compositional differences are observed between seasonal laminae. 204Pb-normalized lead isotope ratios increase from sediment surface down to 7 cm down-core, then decrease steadily to pre-industrial levels at ~50 cm down-core. This pattern illustrates the contamination from leaded gasoline until the recent past. The measured Pb isotopic ratios point primarily toward gasoline related atmospheric lead from the USA. The osmium isotopic values measured are significantly lower than those of modern seawater-Os. In comparison with other anoxic environments, the osmium content of Saanich Inlet sediments is low, and its Os isotopic composition suggests significant inputs from unradiogenic sources (detrital and/or dissolved). Ultramafic lithologies in the watershed of the Fraser River are suspected to contribute to sedimentary inputs as well as to the input of dissolved unradiogenic osmium in the water of Saanich Inlet. The presence of some unradiogenic Os from anthropogenic contamination cannot be discounted near the core top, but since deeper, pre-anthropogenic levels also yielded unradiogenic Os results, one is led to conclude that the overall low 187Os/188Os ratios result from natural geochemical processes. Thus, the bulk sediment of Saanich Inlet does not appear to record 187Os/188Os composition of the marine end-member of the only slightly below normal salinity, fjord water. The low seawater-derived Os content of the sediment, coupled with unradiogenic Os inputs from local sources, explains the overall low isotopic values observed. As a consequence, such near-shore anoxic sediments are unlikely to record changes in the past ocean Os isotopic composition.

Geochemistry of North Atlantic Igneous Province basalts

New Sr-Nd-Pb-Hf data require the existence of at least four mantle components in the genesis of basalts from the the North Atlantic Igneous Province (NAIP): (1) one (or more likely a small range of) enriched component(s) within the Iceland plume, (2) a depleted component within the Iceland plume (distinct from the shallow N-MORB source), (3) a depleted sheath surrounding the plume and (4) shallow N-MORB source mantle. These components have been available since the major phase of igneous activity associated with plume head impact during Paleogene times. In Hf-Nd isotope space, samples from Iceland, DSDP Leg 49 (Sites 407, 408 and 409), ODP Legs 152 and 163 (southeast Greenland margin), the Reykjanes Ridge, Kolbeinsey Ridge and DSDP Leg 38 (Site 348) define fields that are oblique to the main ocean island basalt array and extend toward a component with higher 176Hf/177Hf than the N-MORB source available prior to arrival of the plume, as indicated by the compositions of Cretaceous basalts from Goban Spur (~95 Ma). Aside from Goban Spur, only basalts from Hatton Bank on the oceanward side of the Rockall Plateau (DSDP Leg 81) lie consistently within the field of N-MORB, which indicates that the compositional influence of the plume did not reach this far south and east ~55 Ma ago. Thus, Hf-Nd isotope systematics are consistent with previous studies which indicate that shallow MORB-source mantle does not represent the depleted component within the Iceland plume (Thirlwall, J. Geol. Soc. London 152 (1995) 991-996; Hards et al., J. Geol. Soc. London 152 (1995) 1003-1009; Fitton et al., 1997 doi:10.1016/S0012-821X(97)00170-2). They also indicate that the depleted component is a long-lived and intrinsic feature of the Iceland plume, generated during an ancient melting event in which a mineral (such as garnet) with a high Lu/Hf was a residual phase. Collectively, these data suggest a model for the Iceland plume in which a heterogeneous core, derived from the lower mantle, consists of 'enriched' streaks or blobs dispersed in a more depleted matrix. A distinguishing feature of both the enriched and depleted components is high Nb/Y for a given Zr/Y (i.e. positive DeltaNb), but the enriched component has higher Sr and Pb isotope ratios, combined with lower epsilon-Nd and epsilon-Hf. This heterogeneous core is surrounded by a sheath of depleted material, similar to the depleted component of the Iceland plume in its epsilon-Nd and epsilon-Hf, but with lower 87Sr/86Sr, 208Pb/204Pb and negative DeltaNb; this material was probably entrained from near the 670 km discontinuity when the plume stalled at the boundary between the upper and lower mantle. The plume sheath displaced more normal MORB asthenosphere (distinguished by its lower epsilon-Hf for a given epsilon-Nd or Zr/Nb ratio), which existed in the North Atlantic prior to plume impact. Preliminary data on MORBs from near the Azores plume suggest that much of the North Atlantic may be 'polluted' not only by enriched plume material but also by depleted material similar to the Iceland plume sheath. If this hypothesis is correct, it may provide a general explanation for some of the compositional diversity and variations in inferred depth of melting (Klein and Langmuir, 1987 doi:10.1029/JB092iB08p08089) along the MAR in the North Atlantic.