(Table 1) Rare earth element contents in basalts and glasses of DSDP Legs 45 and 51

Rare-earth element (REE) distributions in altered basalts and glasses collected during some Legs of the Deep Sea Drilling Project show that a fractionation of these elements occurs during submarine weathering. When the alteration is well-marked, the REE distribution in altered glasses shows an enrichment in light rare-earths relative to the fresh glass. In particular, Ce is selectively enriched in palagonitized glasses that comprise, besides polymetallic nodules, another phase liable to explain the Ce depletion in seawater. Taking in account these processes of submarine weathering of the oceanic crust, a geochemical balance of Ce between authigenic phases of the marine environment is attempted.

Annotated record and chemical composition of manganese nodules from station VITYAZ 4575, Indian Ocean

Analyses are given for the core and outer colliform shell of a manganese nodule collected at a depth of 5000 m in the Indian Ocean, and for the red clay that encloses the nodules. Trace elements determined include rare earths, Nb, Ta, Th, and V. The cores of the nodules were once composed of basaltic rock, but now are phillipsite and nontronite. The outer shell is composed of manganite, with admixed quartz, phillipsite, and some geothite. The correlations established between the redox potentials and the concentration coefficients for 12 elements indicate that Eh plays a greater role in the formation of the manganiferous shells than coprecipitation properties.

Geochemistry of Fe-Mn crusts in sediments of the Central Indian Ridge

Layered Fe-Mn crusts from the off-axis region of the first segment of the Central Indian Ridge north of the Rodrigues Triple Junction were studied geochemically and mineralogically. Vernadite (delta-MnO2) is the main mineral oxide phase. 230Thxs and Co concentrations suggest high growth rates of up to 29 mm/Myr and a maximum age of the basal crust layer of 1 Ma. Whereas most of the major and minor elements show concentrations which are typical of hydrogenetic formation, Co, Pb, Ni and Ti concentrations are strikingly lower. Concentrations and distribution of the strictly trivalent rare-earths and yttrium (REY) are typical of hydrogenetic ferromanganese oxide precipitates, but in marked contrast, the crusts are characterized by negative CeSN (shale normalized) anomalies and (Ce/Pr)SN ratios less than unity. Profiles through the crusts reveal only minor variations of the REY distribution and (Ce/Pr)SN ratios range from 0.45 to 0.68 (compared to ratios of up to 2 for typical hydrogenetic crusts from the Central Indian Basin). The apparent bulk partition coefficients between the crusts and seawater suggest that for the strictly trivalent REY the adsorption-desorption equilibrium has been reached. Positive Ce anomalies in the partition coefficient patterns reveal preferential uptake of Ce, but to a lesser extent than in normal hydrogenetic crusts. A new parameter (excess Ce, Cexs) to quantify the degree of decoupling of Ce from REY(III) is established on the basis of partition coefficients. Cexs/Cebulk ratios suggest that the CIR crusts formed by precipitation of Fe-Mn oxides from a hydrothermal plume and that in hydrothermal plumes and normal seawater the enrichment of Ce results from the same oxidative sorption process. The growth rates, calculated with 230Thxs data as well as with the Co formula, are inversely related to Cexs.

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.

Geochemistry of fallout tephra from ODP Hole 125-782A

Very rare, halogen-rich andesite melt inclusions (HRA) in bytownitic plagioclase phenocrysts (An89-90) from tephra fallout of the Izu arc volcanic front (Izu VF) provide new insights into the processes of fluid release from slab trenchward to the volcanic front in a cool subduction zone. These HRA are markedly enriched in Cl, F and Li - by factors of up to 8 (Cl, F) and 1.5 (Li) - but indistinguishable with respect to the fluid-mobile large-ion lithophile elements (LILE; K, Sr, Rb, Cs, Ba, Pb, U), rare earths (REE) or high field strength elements (HFSE) from the low-K tholeiitic magmas of the Izu VF. We suggest that the chemical signature of the HRA reflects the presence of a fluid in the mantle source that originated from the serpentinized mantle peridotite above the metacrust. This "wedge serpentinite" presumably formed by fluid infiltration beneath the forearc and was subsequently down-dragged with the slab to arc front depths. The combined evidence from the Izu VF (?110 km above slab) and the outer forearc serpentinite seamounts (~25 to 30 km above slab) suggests that the slab flux of B and Cl is highest beneath the forearc, and decreases with increasing slab depths. In contrast, the slab flux of Li is minor beneath the forearc, but increases with depth. Fluorine may behave similarly to Li, whereas the fluid-mobile LILE appear to be largely retained in the slab trenchward from the Izu VF. Consequently, the chemical signatures of both Izu trench sediments and basaltic rocks appear preserved until arc front depths.

Geochemistry and provenance of basaltic clasts within volcaniclastic debris flows at DSDP Site 89-585

Pebble-sized basaltic and glassy clasts were extracted from seamount-derived volcaniclastic debris flows and analyzed for various trace elements, including the rare earths, to determine their genetic relationships and provenance. All the clasts were originally derived from relatively shallow submarine lava flows prior to sedimentary reworking, and have undergone minor low-grade alteration. They are classified into three petrographic groups (A, B, and C) characterized by different phenocryst assemblages and variable abundances and ratios of incompatible elements. Group A (clast from Hole 585) is a hyaloclastite fragment which is olivine-normative and distinct from the other clasts, with incompatibleelement ratios characteristic of transitional or alkali basalts. Groups B and C (clasts from Hole 585A) are quartz-normative, variably plagioclase-clinopyroxene-olivine phyric tholeiites, all with essentially similar ratios of highly incompatible elements and patterns of enrichment in light rare earth elements (chrondrite-normalized). Variation within Groups B and C was governed by low-pressure fractionation of the observed phenocryst phases, whereas the most primitive compositions of each group may be related by variable partial melting of a common source. The clasts have intraplate chemical characteristics, although relative to oceanic hot-spot-related volcanics (e.g., Hawaiian tholeiites) they are marginally depleted in most incompatible elements. The source region was enriched in all incompatible elements, compared with a depleted mid-ocean-ridge basalt source.

Geochemistry of basalts at DSDP Hole 83-504B

The major element geochemistry of basalts recovered from Leg 83, Hole 504B, shows the typical features of midocean ridge basalts (MORB). The range of variation in their composition, together with the behavior of compatible trace elements (Co, Ni, Cr), indicate the well-known relative abundance of minerals that crystallize from these basaltic liquids: plagioclase, olivine, pyroxene, and spinel in decreasing abundance. The hygromagmaphile (or LILE or incompatible) elements are extremely depleted in light rare earths. Nevertheless, some units show flat and enriched REE patterns. These patterns, together with the values of the La/Ta ratio, are interpreted in terms of local mantle heterogeneity.

(Table 1) Major and trace elements analyses from FAMOUS-Project and DSDP Site 54-424

Hydrothermal deposits "sensu stricto" have been recovered during the FAMOUS cruise and Leg 54 of the Deep Sea Drilling Project near the Galapagos Spreading Centre. The studied sediments, mainly composed of clay material, have very poor REE concentrations, below about ten ppm. The shale-normalized patterns are characterized by a significant enrichment in heavy rare earths and show a negative Ce anomaly. The magnitude of this anomaly fluctuates but is generally lower than the seawater Ce anomaly. The geochemical characteristics of these hydrothermal deposits are in contrast with those of metalliferous sediments which are more enriched in trace elements, especially in REE.

Annotated record of the detailed examination of ferromanganese concretions from the Gulf of Bothnia in the Baltic Sea

Ferromanganese concretions cover large areas of the Gulf of Bothnia. They are flat to well-rounded, the rounded ones being richer in oxyhydroxides of iron and manganese. Rounded and ellipsoidal nodules, particularly those in the northern Gulf of Bothnia, are richest in Mn, Ni, Ba and Cu, which probably coexist in a Mn oxyhydroxide phase. Flat nodules are enriched in Fe, P, rare earths and As, probably associated with an Fe oxy-hydroxide component. Aluminum, V, Cr and Ti occur in still another phase. The sediments of the gulf generally consist of a 10-50 mm-thick layer of oxidized surface sediment, enriched in Mn, Ba, P and Ni lying on top of reduced sediments which are diagenetically depleted in these elements. The remobilized elements have redeposited in the nodules, but this process cannot explain the origin of all the nodular material. Some released Mn, Ba and Ni furthermore enter into suspended phases, which eventually leave the Baltic Sea. The economic value of the nodules in the Gulf of Bothnia is probably limited at present.