Geochemistry of ODP Sites 128-798 and 128-799 sediments

Nineteen trace elements, including seven rare earth elements (REE's), and 10 major and minor elements in 76 sediment samples from Sites 798 (Oki Ridge) and 799 (Yamato Trough) were determined by means of instrumental neutron activation analysis and X-ray fluorescence spectrometry. Most REE patterns (chondrite-normalized) of the sediments from both sites were nearly identical to the patterns of terrigenous materials. The cerium anomaly (slightly positive) frequently appeared in REE patterns of the sediments (200-750 mbsf) from Site 799. Cerium may be selectively incorporated into the sediments with hydrogenous manganese precipitation. However, the degree of the anomaly was not well correlated with manganese content, suggesting that cerium may behave as a trivalent REE (like the other REE's) during diagenesis while manganese is transported in the sediment column accompanied by reduction to a lower oxidation state. The Th/Sc ratio of the sediments from Sites 798 and 799 tended to decrease with penetration depth. Such a depth profile may indicate a decrease in basic volcanism activities from the Pliocene (Site 798) and Miocene (Site 799). The La/Yb ratio and degree of europium anomaly also varied with depth, which may imply that two or more components with different REE patterns were supplied throughout sedimentation at sites in the Japan Sea.

Composition of surface layer bottom sediments from the Kem' River estuary, White Sea

Based on grain-size, mineralogical and chemical analyses of samples collected in cruises of R/V Ekolog (Institute of Northern Water Problems, Karelian Research Centre of RAS, Petrozavodsk) in 2001 and 2003 regularities of chemical element distribution in surface layer bottom sediments of the Kem' River Estuary in the White Sea were studied. For some toxic elements labile and refractory forms were determined. Correlation analysis was carried out and ratios Me/Al were calculated as proxies of terrigenous contribution. Distribution of such elements as Fe, Mn, Zn, Cr, Ti was revealed to be influenced by natural factors, mainly by grain size composition of bottom sediments. These metals have a tendency for accumulation in fine-grained sediments with elevated organic carbon contents. Distribution of Ni is different from one of Fe, Mn, Zn, Cr, Ti. An assumption was made that these distinctions were caused by anthropogenic influence.

Trace-element geochemistry of tholeiitic basalts from DSDP Hole 55-433C

Hole 433C, a multiple re-entry hole drilled in 1862 meters of water on Suiko Seamount in the central Emperor Seamounts, penetrated 387.5 meters of lava flows overlain by 163.0 meters of sediments. The recovered volcanic rocks consist of three flow units (1-3) of alkalic basalt underlain by more than 105 flows or flow lobes (Flow Units 4-67) of tholeiitic basalt. This study reports trace-element, including rare-earth element (REE), data for 25 samples from 24 of the least altered tholeiitic flows. These data are used to evaluate the origin and evolution of tholeiitic basalts from Suiko Seamount and to evaluate changes in the mantle source between the time when Suiko Seamount formed, 64.7 ± 1.1 m.y. ago (see Dalrymple et al., 1980), and the present day. Stearns (1946), Macdonald and Katsura (1964) and Macdonald (1968) have established that chemically distinct lavas erupt during four eruptive stages of development of a Hawaiian volcano. These stages, from initial to final, are shield-building, caldera-filling, post-caldera, and post-erosional. The lavas of the shield-building stage are tholeiitic basalts, which erupt rapidly and in great volume. The shield-building stage is quickly followed by caldera collapse and by the caldera-filling stage, during which the caldera is filled by tholeiitic and alkalic lavas. During the post-caldera stage, a relatively thin veneer of alkalic basalts and associated differentiated lavas are erupted, sometimes accompanied by minor eruptions of tholeiitic lava. After a period of volcanic quiescence and erosion, lavas of the nephelinitic suite, which include both alkalic basalts and strongly SiO2-undersaturated nephelinitic basalts, may erupt from satellite vents during the post-erosional stage. Many Hawaiian volcanoes develop through all four stages; but individual volcanoes have become extinct before the cycle is complete. We interpret the tholeiitic lavas drilled on Suiko Seamount to have erupted during either the shield-building or the caldera-filling stage, and the overlying alkalic flows to have erupted during either the caldera-filling or the post-caldera stage (see Kirkpatrick et al., 1980).

Chemical and isotopic compositions of lavas from the Broken Ridge and Southern Kerguelen Plateau

Lavas from several major bathymetric highs in the eastern Indian Ocean that are likely to have formed as Early to Middle Cretaceous manifestations of the Kerguelen hotspot are predominantly tholeiitic; so too are glass shards from Eocene to Paleocene volcanic ash layers on Broken Ridge, which are believed to have come from eruptions on the Ninetyeast Ridge. The early dominance of tholeiitic compositions contrasts with the more recent intraplate, alkalic volcanism of the Kerguelen Archipelago. Isotopic and incompatible-element ratios of the plateau lavas are distinct from those of Indian mid-ocean ridge basalts; their Nd, Sr, 207Pb/204Pb and 2078b/204Pb isotopic ratios overlap with but cover a much wider range than measured for more recent oceanic products of the Kerguelen hotspot (including the Ninetyeast Ridge) or, indeed, oceanic lavas from any other hotspot in the world. Samples from the Naturaliste Plateau and ODP Site 738 on the southern tip of the Kerguelen Plateau are particularly noteworthy, with e-Nd(T) = -13 to -7, (87Sr/86Sr)T=0.7090 to 0.7130 and high 207Pb/204Pb relative to 206Pb/204Pb. In addition, the low-e-Nd(T) Naturaliste Plateau samples are elevated in SiO2 (>54 wt%). In contrast to "DUPAL" oceanic islands such as the Kerguelen Archipelago, Pitcairn and Tristan da Cunha, the plateau lavas with extreme isotopic characteristics also have relative depletions in Nb and Ta (e.g., Th/Ta, La Nb > primitive mantle values); the lowest e-Nd(T) and highest Th/Ta and La Nb values occur at sites located closest to rifted continental margins. Accepting a Kerguelen plume origin for the plateau lavas, these characteristics probably reflect the shallow-level incorporation of continental lithosphere in either the head of the early Kerguelen plume or in plume-derived magmas, and suggest that the influence of such material diminished after the period of plateau construction. Contamination of asthenosphere with the type of material affecting Naturaliste Plateau and Site 738 magmatism appears unlikely to be the cause of low-206Pb/204Pb Indian mid-ocean ridge basalts. Finally, because isotopic data for the plateaus do not cluster or form converging arrays in isotope-ratio plots, they provide no evidence for either a quickly evolving, positive ?Nd, relatively high-206Pb/204Pb plume composition, or a plume source dominated by mantle with e-Nd of -3 to ~0.

Iridium and other element concentrations and magnetostratigraphy across the Cretaceous/Tertiarty boundary in ODP Hole 122-761C

Samples from Ocean Drilling Program Hole 761C, collected on both sides of the Cretaceous/Tertiary boundary have been analyzed for their chemical and mineralogical content. The sediment consists of nannofossil ooze with variable amounts of clay. The boundary is marked by a color change associated with a nearly step-like decrease of the carbonate fraction. Paleomagnetic data and the drop of the carbonate content indicate that a strong reduction of the sedimentation rate occurred at the boundary and persisted for million of years. An iridium anomaly of 80 ng/cm**2, together with overabundances of Cr and Fe, are found in close coincidence with the planktonic crisis. These enrichments can be explained by the infall of =0.16 g/cm2 of Cl-like chondritic material. Co and Ni enrichments and a great quantity of Ni-rich magnetites are also observed in the basal Danian. These elements and minerals excepted, the composition of the insoluble fraction appears to be nearly unchanged across the boundary. Chemical and mineralogical observations support a cosmic origin for the Cretaceous/Tertiary event but do not reveal the presence of any significant impact ejecta.

(Table 1) Geochemistry of ODP Hole 130-807C carbonates across the K/T boundary

Paleontological, stable isotopic, trace elemental abundance, and magnetostratigraphic studies have been performed on limestones spanning the Cretaceous/Tertiary boundary transition at Ocean Drilling Program (ODP) Hole 807C. Paleontological evidence exists for considerable resedimentation, which we attribute to the fact that Hole 807C is located in a basement graben. Age estimates based on planktonic foraminiferal biostratigraphy, as well as magnetostratigraphy, indicate that sedimentation rates could have been on the order of 12-14 m/m.y. This is significantly higher than those documented in other important Deep Sea Drilling Project (DSDP) and ODP Cretaceous/Tertiary boundary sections using the same age control points (e.g., DSDP Hole 577 and ODP Hole 690B), although not as high as those documented from DSDP Hole 524. The expanded nature of this succession has resulted in the Cretaceous/Tertiary boundary d13C decrease occurring over approximately a 9-m interval. Ir analysis of these sediments do not show a single large anomaly, as has been found in other Cretaceous/Tertiary boundary sections, but trivial background levels instead. Ce data support the hypothesis that this section has been expanded by secondary sedimentological processes.

(Table 3) Lanthanum and scandium contents in phosphorites from seamounts and submarine rises

Scandium and lanthanum were analyzed using neutron activation and ICP-MS methods in 60 samples of oceanic phosphorites of various composition and age recovered from continental margins and seamounts in the Atlantic and Pacific Oceans. In the samples studied scandium content ranges from 0.1 to 60 ppm, lanthanum content ranges from 0.4 to 513 ppm, and La/Sc ratio varies from 1.1 to 114. The lowest scandium content occurs in recent phosphorite nodules, intermediate - in Pleistocene phosphatic sand, and the highest - in ancient seamount phosphorites. Process of scandium accumulation in the phosphorites is mainly controlled by their specific surface area and duration of their contact with ocean water. Lanthanum concentrates in the phosphorites much more intensely than scandium. Correlation between scandium and lanthanum distribution is weak, and it appears only when average concentrations of these elements in various groups of samples are compared.

(Table 1) Platinoids in Fe-Mn crusts and nodules from the Pacific Ocean

Platinoid element contents were determined in 16 samples of Fe-Mn crusts and nodules collected during dredging deep-sea mound slopes of the Pacific Ocean from the equator to 27°N. The method of neutron activation analysis with pre-concentration of the platinoids was used for these determinations. There is no relationship between platinoid contents in deep-sea (>3000 m) Fe-Mn nodules with depth of sampling, as well as with age of nodule layers. It is concludet that ultramafic rocks are the primary source of platinoids in Fe-Mn nodules.

Rare earth elements in bottom sediments from the deeps of the Red Sea rift zone

Analysis of rare earth element (REE) distribution and behavior in ore-bearing hydrothermal-sedimentary deposits from the Red Sea is carried out. Geochemical patterns and mechanisms of REE accumulation in metalliferous sediments of the open ocean and in deposits adjoined to areas of hydrothermal discharge are shown. Main factors, which determine composition of REE and the level of their accumulation in hydrothermal occurrences of the Red Sea, are considered.

Sediment geochemical evidence for an early-middle Gilbert (early Pliocene) productivity peak in the North Pacific Red Clay Province

Current attempts to understand climatic variability during the early to middle Pliocene require paleoceanographic information from the Pacific and Indian Oceans that may serve to test and/or constrain future circulation models. Ocean Drilling Program (ODP) Sites 885/886 are located in the central subarctic North Pacific at water depths exceeding 5700 m. Recent studies of rock magnetic properties suggest that the fine-grained Fe oxide component in sediment at Sites 885/886 experienced reductive dissolution during the early-middle Gilbert. Because such an interval in the North Pacific Red Clay Province suggests a maximum in the sedimentary flux of organic carbon and/or a minimum in bottom water dissolved O2 concentrations (and hence, a peak change in North Pacific oceanographic conditions), a geochemical investigation was conducted to test the hypothesis. Quaternary sediment at Hole 886B was subjected to an oxyhydroxide removal procedure, and chemical analyses indicate that bulk sediment concentrations of Fe and the Fe/Sc ratio decrease significantly upon reductive dissolution. Downcore chemical analyses of untreated sediment at Hole 886B demonstrate that similar depletions also occur across the proposed interval of reduced sediment. Downcore chemical analyses also indicate that a pronounced increase in the Ba/Sc ratio occurs across the interval. These results are consistent with an interpretation that abyssal sediment of the North Pacific experienced a decrease in redox conditions during the early-middle Gilbert, and that this change in oxidation state was related to a peak in paleoproductivity. If the zenith of late Miocene to middle Pliocene enhanced productivity observed at other Indo-Pacific divergence regions similarly can be constrained to the early-middle Gilbert, there exists an oceanographic boundary condition in which to test future models concerning Pliocene warmth.

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.