(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.

Contents and accumulation rates of the rare earth and some other elements in metalliferous sediments from DSDP Hole 92-598

The sediments recovered during DSDP Leg 92 (Site 598) include a complete 16 m.y. record of hydrothermal sedimentation along the western flank of the East Pacific Rise at 19°S. Fifty samples from this sediment column were analyzed to test the hypothesis that the REE composition of the hydrothermal component is primarily acquired via scavenging from seawater. Site 598 provides an ideal sample suite for this purpose: the sediments are lithologically "simple," primarily consisting of a mixture of hydrothermal materials and biogenous carbonates; the composition of the hydrothermal component is essentially constant through space and time; and the sediments have undergone minimal diagenetic alteration. The following observations suggest the above-stated hypothesis is true. The Ce anomaly as well as key indices of light and heavy REE behavior all show that the REE pattern of hydrothermal sediments approaches that of seawater with increasing paleodistance from the rise crest. Moreover, shale-normalized REE patterns are similar to that of seawater, varying only in absolute REE content: the REE content increases with distance from the paleo-rise crest and exhibits a pronounced increase in sediments deposited below the paleolysocline. Based on significant correlative relationships between paleodistance from the rise crest and both the concentration and mass accumulation rates (MARs) of REEs and Fe, we conclude the REEs in the hydrothermal component are derived from the interaction of seawater and Fe in the hydrothermal plume.

Geochemistry and mineralogy of ODP Leg 107 basalts

During ODP Leg 107, the basement of the Tyrrhenian Sea was drilled at Site 650, located in the Marsili basin, and at Sites 651 and 655, both located in the Vavilov basin. In addition, a lava flow was drilled at Site 654 on the Sardinia rifted margin. Mineral and whole rock major and trace element chemistry, including rare earth element (REE) and Sr and Nd isotopic ratios, were determined in samples of these rocks. Site 654 lava was sampled within uppermost Pliocene postrift sediments. This lava is a basaltic andesite of intraplate affinity, and is analogous to some Plio-Pleistocene tholeiitic lavas from Sardinia. Site 650 basalts, drilled beneath 1.7-1.9-Ma-old basal sediment, are strongly altered and vesicular suggesting a rapid subsidence of the Marsili basin. Based on incompatible trace elements, these basalts show calc-alkaline affinity like some products of the Marsili Seamount and the Eolian arc. The basement of the two sites drilled within Vavilov basin shows contrasting petrologies. Site 655, located along the Gortani ridge in the western part of the basin, drilled a 116-m-thick sequence of basalt flows beneath 3.4-3.6-Ma-old basal sediments. These basalts are chemically relatively homogeneous and show affinity to transitional MORB. Four units consisting of slightly differentiated basaltic lavas, have been identified. Site 655 basalts are geochemically similar to the high Ti lavas from DSDP Leg 42, Site 373 (Vavilov Basin). The basement at Site 651, overlain by 40 m of metalliferous dolostone covered by fossiliferous sediments with an age of 2 Ma, consists of two basalt units separated by a dolerite-albitite intrusive body; serpentinized harzburgites were drilled for 30 m at the base of the hole. The two basalt units of Site 651 are distinct petrochemically, though both show incompatible elements affinity with high-K calc-alkaline/calc-alkaline magmas from Eolian arc. The cpx chemistry and high K/Na ratio of the lower unit lavas suggest a weak alkaline tendency of potassic lineage. Leg 107 basement rock data, together with data from DSDP Site 373 and from dredged samples, indicate that the deepest basins of the central Tyrrhenian Sea are underlain by a complex back-arc basin crust produced by magmas with incompatible element affinities to transitional MORB (Site 655 and DSDP Site 373), and to calc-alkaline and high-K calc-alkaline converging plate margin basalts (Sites 650 and 651). This petrogenetic complexity is in accordance with the back-arc setting of the Vavilov and Marsili basins. Other back-arc basin basalts, particularly those from ensialic basins such as the Bransfield Strait (Antarctica), show a comparable petrogenetic complexity (cf., Sounders and Tarney, 1984).

Composition of particulate matter in the neutrally buoyant plumes of the TAG and Broken Spur Hydrothermal Fields

This publication considers data on aquatic anomalies (hydrothermal plumes) in the areas of 26° and 29°N of the Mid-Atlantic Ridge (MAR). Mass of hydrothermal iron supply and intensity of iron sedimentation onto the bottom were estimated by means of sediment traps. It was found that the plume of the TAG hydrothermal vent 6 km**3 in volume contained about 67 tons of particulate Fe; the plume of the Broken Spur field (up to 8.24 km**3 in volume) contained 23.5 tons of particulate Fe or less because of its lower concentration. Data on sediment matter fluxes showed that 0.3-0.5% of hydrothermal iron was precipitated immediately from the neutrally buoyant plume onto the bottom; the bulk of iron was dissipated into environment. From dimensions of the plumes, flow dynamics, iron concentrations in the plumes, and amounts of iron supplied by hydrothermal vents, it was found that resident time of the plumes considered was from 5 to 10 days.

Geochemistry of ODP Leg 135 basalts

Cr-spinels in cores drilled during Ocean Drilling Program Leg 135 exhibit wide variations in composition and morphology that reflect complex petrogenetic histories. These Cr-spinels are found within basaltic lava flows that erupted in north-trending sub-basins within the Lau Basin backarc. Cr-spinels from Sites 834 and 836 occur as euhedral groundmass grains and inclusions in plagioclase, and range up to 300 ?m in size. These Cr-spinels are similar in composition, morphology, and mode of occurrence to Cr-spinels found within depleted, N-type mid-ocean-ridge basalts (N-MORB), reflecting similar crystallization conditions and host lava composition to N-MORB. Their compositional range is relatively narrow, with Cr/(Cr + Al + Fe3+) (Cr#) and Mg/(Mg + Fe2+) (Mg#) varying from 0.38 to 0.48 and 0.56 to 0.72, respectively; like Cr-spinels from N-MORB, they contain low amounts of TiO2 (0.37%-1.05%) and Fe3+/(Cr + Al + Fe3+) (Fe3+#; <0.11). In contrast, Cr-spinels from Site 839 have much higher Cr# at a given Mg#, with Cr# varying from 0.52 to 0.76 and Mg# varying from 0.27 to 0.75. These Cr-spinels are similar in composition to those from primitive, boninitic or low-Al2O3 arc basalts, sharing their low TiO2 and Fe3+# (typically below 0.35% and 0.1, respectively for spinel grain interiors). Site 839 Cr-spinels occur as small (to 50 µm) euhedra within strongly zoned olivine or as unusually large (to 3 mm), euhedral to subhedral megacrysts. These megacrysts are strongly zoned in Mg#, but they display little zoning in Cr#, providing evidence of strong compositional disequilibria with the host melt. The magnesian cores of the megacrysts crystallized from primitive, near-primary melts derived from harzburgitic or highly depleted lherzolitic sources, and they provide evidence that the Site 839 spinel-bearing lavas were derived by the mixing of melt with a Mg# of 0.75-0.80 and evolved, Cr-spinel barren melt with a Mg# < 0.6 shortly before eruption.

Geochemistry of DSDP Leg 65 basalts

Leg 65 of the Deep Sea Drilling Project successfully recovered basalts from four sites in the mouth of the Gulf of California, thus completing a transect begun during Leg 64 from the continental margin of Baja California to the east side of the East Pacific Rise (EPR). Sixty-three whole-rock samples from Sites 482, 483, and 485 have been analyzed by X-ray fluorescence techniques, and a further eleven samples by instrumental neutron-activation techniques, in order to assess magma variability within and between sites. Although the major element compositions and absolute hygromagmatophile (HYG) element abundances are quite variable, all of the basalts are subalkaline tholeiites exhibiting strong more-HYG element (e.g., Rb, La, Nb, Ta) depletion (LaN/YbN ~ 0.4; Nb/Zr ~ 0.02; Ba/Zr ~ 0.23; Th/Hf ~ 0.05). These ratios, together with La/Ta ratios of 20 and Th/Ta ratios of 1.25, demonstrate that the Leg 65 basalts resemble the depleted "N-type" ocean ridge basalts recovered from the Mid-Atlantic Ridge (MAR) at 22 °N and other sections of the EPR. Zr/Ti, Zr/Y, and La/Yb ratios increase with increasing fractionation. It is clear that the basalts recovered from Sites 482, 483, and 485 were all derived from a compositionally similar source and that the compositional differences observed between lithological units can be explained by varying degrees of open system fractional crystallization (magma mixing) in subridge magma chambers. The basaltic rocks recovered from Site 474 near the margin of Baja California, and Sites 477, 478, and 481 in the Guaymas Basin, all drilled during Leg 64, have consistently higher Th/Hf, La/Sm, Zr/Ti, and Zr/Y ratios and higher absolute Sr contents than the Leg 65 basalts. While some of these variations may be explained by different conditions of partial melting, it is considered more likely that the mantle source underlying the Guaymas Basin is chemically distinct from that feeding the EPR at the mouth of the Gulf. These source variations probably reflect the complex tectonic setting of the Gulf of California, the magmas formed at the inception of spreading and in the central part of the Gulf containing a minor but significant component of sub-continental (calc-alkaline) material.

Precious metals and volatiles in rocks of the Mid-Atlantic Ridge near 15°20'N

Distribution patterns of gold, platinum group metals (PGE), and volatile components are studied in the main rock types of the Mid-Atlantic Ridge lithosphere (ultrabasites, gabbro, and basalts) from the transform fracture zone at 15°20'N. It is ascertained that PGE content depends on the reduction degree of fluids, on rock types, and on their formation conditions. It is noted that concentrations of refractory elements (Os, Ir, Rh) decrease, while those of fusible elements (Pt, Pd, Au) increase with depth. The chondrite type of distribution is only noted in the ultrabasite rocks. Increase in water and CO2 contents and in oxidation degree of fluids occurs with transition from basalts to ultrabasites, as well as from normal magmatic systems to fluid-enriched anomalous systems.

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.

Elemental and stable isotopic composition of some metalliferous and pelagic sediments at DSDP Leg 70 Holes

Nontronite, the main metalliferous phase of the Galapagos mounds, occurs at subsurface depths of about 2 to 20 meters; Mn-oxide material is limited to the upper 2 meters of the mounds. The nontronite forms intervals of up to a few meters' thickness, consisting essentially of 100% nontronite granules, which alternate with intervals of normal pelagic sediment. Electron microprobe analyses of nontronite granules from different core samples indicate that: (1) there is little difference in major element composition between nontronites from varying locations within the mounds, with adjacent granules from a given sample having very similar compositions; (2) individual granules show little internal variation in composition. This indicates that the granules are composed of a single mineral of essentially constant composition, consistent with relatively uniform conditions of Eh and composition during nontronite formation. Mn-oxide crusts have very low Fe contents, a feature characteristic of rapidly deposited Mn-oxide crusts formed under hydrothermal influences. The rare-earth element (REE) abundances of the nontronites are generally extremely low, totalling less than several ppm. Two samples have the negatively Ce anomaly typical of authigenic precipitates formed relatively rapidly from seawater. A Mn-oxide crust sample has low REE contents, typical of Mn-oxide crusts formed under hydrothermal influences, but no negative Ce anomaly. A sample of unusual Mn-Fe-oxide mud has relatively high REE concentrations and a seawater-type pattern; both of these features are also found for metalliferous sediments from the East Pacific Rise. The oxygen and hydrogen isotopic composition of the nontronites define a restricted field within a d18O-dD plot. In manganiferous sediments, d18O and dD appear to decrease with increase in the Mn-oxide content of the sediment. From the d18O values of the nontronites, formation temperatures in the range of about 20-30°C have been estimated. By comparison, temperatures of up to 11.5 °C at a 9-meter depth have been directly measured within the mounds (Corliss et al., 1979), and heat-flow data suggest present basement/sediment interface temperatures of 15-25°C. In a plot of Fe + Mn vs. d18O, the Mn-oxide crust and Mn-Fe-ooze plot near the tie-lines for authigenic Mn nodules and silicate phases, implying that they have formed in isotopic equilibrium with seawater at or close to bottom-water temperatures.