Major and trace element composition of sepentine muds and metabasic rocks of ODP Leg 195 and Leg 125 sites

New geochemical data on serpentinite muds and metamorphic clasts recovered during Ocean Drilling Program Legs 195 (Holes 1200A-1200E) and 125 (Holes 778A and 779A) provide insights into the proportions of rock types of various sources that compose the serpentinite mudflows and the fluid-rock interactions that predominate in these muds. We interpret the metamorphic rock fragments as derivatives of mostly metamorphosed mafic rocks from the descending Pacific oceanic crust. Based on their mid-ocean-ridge basalt (MORB)-like Al2O3, TiO2, CaO, Si/Mg, and rare earth element (REE) systematics, these metamorphic rocks are classified as metabasalts/metagabbros and, therefore, ~30-km depths represent an active subduction zone setting. The serpentinite muds from Holes 1200A and 1200E have slightly lower REE when compared to Hole 1200D, but overall the REE abundance levels range between 0.1-1 x chondrite (CI) levels. The chondrite-normalized patterns have [La/Sm]N ~ 2.3 and [Sm/Yb]N ~ 2. With the exception of one sample, the analyzed metamorphic clasts show flat to slightly depleted light REE patterns with 1.0-15 x CI levels, resembling MORBs. Visually, ~6 vol% of the serpentinized muds are composed of 'exotic' materials (metamorphic clasts [schists]). Our mixing calculations confirm this result and show that the serpentinite muds are produced by additions of ~5% metamafic materials (with flat and up to 10 x CI REE levels) to serpentinized peridotite clast material (with very low REE abundances and U-shaped chondrite-normalized patterns). The preferential incorporation of B, Cs, Rb, Li, As, Sb, and Ba into the structure of H2O-bearing sheet silicates (different than serpentine) in the Leg 125 and Leg 195 metamorphic clasts (chlorite, amphibole, and micas) have little effect on the overall fluid-mobile element (FME) enrichments in the serpentinite muds (average B = ~13 ppm; average Cs = ~0.05 ppm; average As = ~1.25 ppm). The extent of FME enrichment in the serpentinized muds is similar to that described for the serpentinized peridotites, both recording interaction with fluids very rich in B, Cs, and As originating from the subducting Pacific slab.

Composition and origin of sediments at DSDP Site 54-424

The sediments recovered on Deep Sea Drilling Project Leg 54 appear to be mixtures of the normal pelagic sediments of the area and hydrothermally produced manganese and iron phases. The latter are mineralogically and chemically very similar to phases recovered from surficial sampling of the mounds. The hydrothermal nontronite which is approximately 15 meters thick in the three holes is essentially free of carbonate or detrital contaminants. The basal sediments are similar to the carbonate oozes presently being deposited in the region, but are enriched in Mn and Fe. This enrichment appears to be the result of hydrothermal deposition that took place at or near the spreading center and may not be associated with the mounds formation. Three different hypotheses for the formation of the nontronite layer and the mounds deposits are considered. An initial deposition of a widespread nontronite layer and subsequent diapiric-like movement of the layer into carbonates could account for the observed stratigraphy; however, if this be correct, analogous deposits should be present in other DSDP sites. The second hypothesis - replacement of the normal sediments by nontronite - may be feasible, but the high purity of the nontronite requires dissolution and removal of refractory elements. The third hypothesis, metal deposition in an advancing oxidation gradient, is compatible with submersible observations of the mounds; however, it can account only for the high purity of the nontronite by very rapid deposition of the hydrothermal phases.

Chemical composition of ferromanganese manifestations from the Sea of Okhotsk

New data on microstructures and mineral and chemical compositions of ferromanganese crusts sampled from the western slope of the Kuril Island Arc in the Sea of Okhotsk during cruises of R/V Vulkanolog are discussed. The study of the crusts using analytical electron microscopy methods revealed that their manganese phase is represented by vernadite, Fe-vernadite, todorokite, asbolane, and asbolane-buserite, while iron phase consists of hematite, hydrohematite, ferroxyhite, and magnetite. Lithic mineral assemblage includes apatite, quartz, epidote, and montmorillonite. According to chemical analysis most of the crusts contain significant part of volcanogenic and hydrothermal material. It is evident from elevated values of Mn/Fe and (Mn+Fe)/Ti ratios, low concentrations of some trace elements, and positive Eu anomaly.

Geochemistry and isotopic ratios of basalts obtained during R/V Akademik Nikolaj Strakhov cruise ANS25

Based on the investigation of samples recovered during Cruise 25 of the R/V ''Akademik Nikolai Strakhov'', the character of magmatism was determined in the flank parts of the rift zone at the 74°05'N and 73°50'N region, where the direction of the rift valley changes from the north-northwest in the Knipovich Ridge to the northeast-trending structures of the Mohns Ridge. It was shown that the tholeiitic magmas of this region shows all the geochemical characteristics of TOR-2, which is typical of the Mohns Ridge and most oceanic rift zones worldwide, and differ from the basalts of the Knipovich Ridge, which are assigned to a shallower type of tholeiitic magmatism (Na-TOR). The persistent depletion of the magmas in terms of lithophile element contents and radiogenic isotope ratios of Sr, Nd, and Pb reflects the conditions of their formation during the ascent of the depleted oceanic mantle, which has occurred without significant complications since the early stages of the formation of the Mohns Ridge.

Chemical composition of Ninetyeast Ridge basalts

On Leg 121 of the Ocean Drilling Program, we recovered basaltic rocks from a total of three basement sites in the southern, central, and northern regions of Ninetyeast Ridge. These new sites complement the previous four basement holes drilled during Legs 22 and 26 of the Deep Sea Drilling Project, and confirm the predominantly tholeiitic, light rare earth element-enriched character of the basalts that cap the ridge. The basalts show marked iron enrichment; ferrobasalts occur at Sites 214 and 216 and oceanic andesites at Site 253. All of the basalts recovered during Leg 121 are altered, and range from aphyric olivine tholeiites (Site 756), to strongly plagioclase-phyric basalts (Site 757). Basalts from Site 758, which were clearly erupted in a submarine environment (pillow basalts are present in the section), are sparsely to strongly plagioclase-phyric. The basalts recovered at any one hole are isotopically homogeneous (except for the basalts from Site 758, which show a range of Pb isotopes), and it is possible to relate the magmas at any one site by high-level fractionation processes. However, there are significant variations in isotope ratios and highly incompatible element ratios between sites, which suggest that the mantle source for the ridge basalts was compositionally variable. Such variation, in view of the large volume of magmatic products that form the ridge system, is not surprising. There is not, however, a systematic variation in basalt composition along the ridge. We agree with previous models that relate Ninetyeast Ridge to a mantle plume in the southern Indian Ocean. The tholeiitic, iron-enriched, and voluminous character of the ridge basalts is typical of oceanic islands associated with plumes on or near a mid-ocean ridge (e.g., Iceland, Galapagos Islands, and St. Paul/Amsterdam islands). The absence of recovered alkalic suites is inconsistent with an intraplate setting, such as the Hawaiian Islands or Kerguelen Island. Thus, the major element data, like the gravity data, strongly suggest that the ridge was erupted on or very close to an active spreading center. Isotopically, the most likely plume that created the excess magmatism on the Ridge is the Kerguelen-Heard plume system, but the Ninetyeast Ridge basalts do not represent a simple mixing of the Kerguelen plume and mid-ocean Ninetyeast Ridge basalt mantle.

Geochemistry and mineralogy of interstitial waters and clays in sediments of ODP Leg 180 sites

Oxygen and strontium isotopes and Rb and Ba were determined in interstitial water (IW) collected from Sites 1109, 1115, and 1118 drilled on the Woodlark Rise during Ocean Drilling Program Leg 180. The trace element and mineralogical composition of the clay fraction of sediments isolated from the squeeze cakes corresponding to IW samples from Site 1109 was also determined.

Chemical and isotopic composition of rocks and minerals at ODP Site 209-1275

This paper reports results of an investigation of a representative collection of samples recovered by deep-sea drilling from the oceanic basement 10 miles west of the rift valley axis in the crest zone of the Mid- Atlantic Ridge at 15°44'N (Sites 1275B and 1275D). Drilling operations were carried out during Leg 209 of the Drilling Vessel JOIDES Resolution within the framework of the Ocean Drilling Program (ODP). The oceanic crust was penetrated to depth of 108.7 m at Site 1275B and 209 m at Site 1275D. We reconstructed the following sequence of magmatic and metamorphic events resulting in the formation of a typical oceanic core complex of slow-spreading ridges: (1) formation of strongly fractionated (enriched in iron and titanium) tholeiitic magmatic melt parental to gabbroids under investigation in a large magma chamber located in a shallow mantle and operating for a long time under steady-state conditions; (2) transfer of the parental magmatic melt of the gabbroids to the base of the oceanic crust, its interaction with host mantle peridotites, and formation of troctolites and plagioclase peridotites; (3) intrusion of enriched trondhjemite melts as veins and dikes in the early formed plutonic complex, contact recrystallization of the gabbro, and development in the peridotite-gabbro complex of enriched geochemical signatures owing to influence of trondhjemite injections; (4) emplacement of dolerite dikes (transformed to diabases); (5) metamorphism of upper epidoteamphibolite facies with participation of marine fluids; and (6) rapid exhumation of the plutonic complex to the seafloor accompanied by greenschist-facies metamorphism. Distribution patterns of Sr and Nd isotopes and strongly incompatible elements in the rocks suggest contributions from two melt sources to the magmatic evolution of the MAR crest at 15°44'N: a depleted reservoir responsible for formation of the gabbros and diabases and an enriched reservoir, from which trondhjemites (granophyres) were derived.

Measurements of trace metal abundances and isotopes in carbonate sediments, Exuma, Bahamas

In order to validate the use of 238U/235U as a paleoredox proxy in carbonates, we examined the incorporation and early diagenetic evolution of U isotopes in shallow Bahamian carbonate sediments. Our sample set consists of a variety of primary precipitates that represent a range of carbonate producing organisms and components that were important in the past (scleractinian corals, calcareous green and red algae, ooids, and mollusks). In addition, four short push cores were taken in different depositional environments to assess the impact of early diagenesis and pore water chemistry on the U isotopic composition of bulk carbonates. We find that U concentrations are much higher in bulk carbonate sediments (avg. 4.1 ppm) than in primary precipitates (avg. 1.5 ppm). In almost all cases, the lowest bulk sediment U concentrations were as high as or higher than the highest concentrations found in primary precipitates. This is consistent with authigenic accumulation of reduced U(IV) during early diagenesis. The extent of this process appears sensitive to pore water H2S, and thus indirectly to organic matter content. d238/235U values were very close to seawater values in all of the primary precipitates, suggesting that these carbonate components could be used to reconstruct changes in seawater U geochemistry. However, d238/235U of bulk sediments from the push cores was 0.2-0.4 per mil heavier than seawater (and primary precipitates). These results indicate that authigenic accumulation of U under open-system sulfidic pore water conditions commonly found in carbonate sediments strongly affects the bulk U concentrations and 238U/235U ratios. We also report the occurrence of dolomite in a tidal pond core which contains low 234U/238U and 238U/235U ratios and discuss the possibility that the dolomitization process may result in sediments depleted in 238U. From this initial exploration, it is clear that 238U/235U variations in ancient carbonate sediments could be driven by changes in global average seawater, by spatial and temporal variations in the local deposition environment, or subsequent diagenesis. To cope with such effects, proxies for syndepositional pore water redox conditions (e.g., organic matter content, iron speciation, and trace metal distributions) and careful consideration of possible post-deposition alteration will be required to avoid spurious interpretation of 238U/235U data from ancient carbonate sediments.

Geochemistry of ODP Site 125-786 volcanic rocks

Eocene-Oligocene volcanic rocks drilled at Site 786 in the Izu-Bonin forearc cover a wide range of compositions from primitive boninites to highly evolved rhyolites. K-Ar dating reveals at least two distinct episodes of magmatism; one at 41 Ma and a later one at 35 Ma. The early episode produced low-Ca boninites and bronzite andesites that form an oceanic basement of pillow lavas and composite intrusive sheets, overlain by flows and intrusive sheets of intermediate-Ca boninites and bronzite-andesites and a fractionated series of andesites, dacites, and rhyolites. The later episode produced high-Ca boninites and intermediate-Ca boninites, exclusively as intrusive sheets.