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.

Mineralogy and geochemistry at DSDP Hole 62-465A

Core recovered from Hess Rise contains concentrations of pyrite, marcasite, and barite in the lowermost meter of limestone (Unit II) and in the brecciated upper part of the underlying volcanic basement (Unit HI). Petrographic and chemical data indicate that the sulfide-barite assemblage in the limestone is mainly a product of low-temperature diagenetic processes. The iron-sulfide phases are biogenic and their concentrations mark the diffusion of sea water sulfate through sedimentary horizons containing abundant organic matter and mafic, glassy volcanogenic detritus. There is some evidence, however, that elevated temperatures augmented or intensified the synsedimentary diagenetic process.

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.

Geochemistry of volcanivlastic sediments of ODP Sites 134-832 and 134-833

Volcaniclastic sediments of North Aoba Basin (Vanuatu) recovered during Ocean Drilling Program (ODP) Leg 134 show a mineralogical and chemical overprint of low grade hydrothermal alteration superimposed on the primary magmatic source compositions. The purpose of this study was to identify authigenic mineral phases incorporated in the volcaniclastic sediments, to distinguish authigenic chemical and mineralogical signals from the original volcaniclastic mineralogical and chemical compositions, and to determine the mechanism of authigenic minerals formation. Mineralogical, micro-chemical and bulk chemical analyses were utilized to identify and characterize authigenic phases and determine the original unaltered ash compositions. 117 volcaniclastic sediment samples from North Aoba Basin Sites 832 and 833 were analyzed. Primary volcaniclastic materials accumulated in North Aoba Basin can be divided into three types. The older basin-filling sequences show three different magmatic trends: high K, calc-alkaline, and low K series. The most recent accumulations are rhyodacitic composition and can be attributed to Santa Maria or Aoba volcanic emissions. Original depositional porosity of volcaniclastic sediments is an important factor in influencing distribution of authigenic phases. Finer-grained units are less altered and retain a bulk mineralogical and chemical composition close to the original pyroclastic rock composition. Coarser grained units (microbreccia and sandstones) are the major hosts of authigenic minerals. At both sites, authigenic minerals (including zeolites, clay minerals, Mg-carbonates, and quartz) exhibit complex zonation with depth that crosses original ash depositional boundaries and stratigraphic limits. The zeolite minerals phillipsite and analcime are ubiquitous throughout the altered intervals. At Site 832, the first zeolite minerals (phillipsite) occur in Pleistocene deposits as shallow as 146 meters below seafloor (mbsf). At Site 833 the first zeolite minerals (analcime) occur in Pleistocene deposits as shallow as 224 mbsf. The assemblage phillipsite + analcime + chabazite appears at 635 mbsf (Site 832) and at 376 mbsf (Site 833). Phillipsite + analcime + chabazite + thomsonite + heulandite are observed between 443 and 732 mbsf at Site 833. Thomsonite is no longer observed below 732 mbsf at Site 833. Heulandite is present to the base of the sections cored. The zeolite assemblages are associated with authigenic clay minerals (nontronite and saponite), calcite, and quartz. Chlorite is noticeable at Site 832 as deep as 851 mbsf. Zeolite zones are present but are less well defined at Site 832. Dolomite and rare magnesite are present below 940 m at Site 832. The coarse-grained authigenic mineral host intervals exhibit geochemical signatures that can be attributed to low grade hydrothermal alteration. The altered intervals show evidence of K2O, CaO, and rare earth elements mobilization. When compared to fine-grained, unaltered units, and to Santa Maria Island volcanics rocks, the altered zones are relatively depleted in rare earth elements, with light rare earth elements-heavy rare earth elements fractionation. Drilling at Site 833 penetrated a sill complex below 840 m. No sill was encountered at Site 832. Complex zonation of zeolite facies, authigenic smectites, carbonates and quartz, and associated geochemical signatures are present at both sites. The mineralogical and chemical alteration overprint is most pronounced in the deeper sections at Site 832. Based on mineralogical and chemical evidence at two locations less than 50 km apart, there is vertical and lateral variation in alteration of the volcaniclastic sediments of North Aoba Basin. The alteration observed may be activated by sill intrusion and associated expulsion of heated fluids into intervals of greater porosity. Such spatial variation in alteration could be attributed to the evolution of the basin axis associated with subduction processes along the New Hebrides Trench.

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.

Mineralogical and isotopic compositions of ODP Hole 107-650A

Red-brown dolomitic claystones overlay the Marsili Basin basaltic basement at ODP Site 650. Sequential leaching experiments reveal that most of the elements considered to have a hydrothermal or hydrogenous origin in a marine environment, such as Fe, Cu, Zn, Pb, Co, Ni, are present mainly in the aluminosilicate fraction of the dolomitic claystones. Their vertical distribution, content and partitioning chemistry of trace elements, and REE patterns suggest enhanced terrigenous input during dolomite formation, but no significant hydrothermal influence from the underlying basaltic basement. Positive correlations in the C and O isotopes in the dolomites reflect complex conditions during the dolomitization. The stable isotopes can be controlled in part by temperature variations during the dolomitization. Majority of the samples, however, form a trend that is steeper than expected for only temperature control on the C and O isotopes. The latter indicates possible isotopic heterogeneity in the proto-carbonate that can be related to arid climatic conditions during the formation of the basal dolomitic claystones. In addition, the dolostones stable isotopic characteristics can be influenced by diagenetic release of heavier delta18O from clay dehydration and/or alteration of siliciclastic material. Strontium and Pb isotopic data reveal that the non-carbonate fraction, the "dye" of the dolomitic claystones, is controlled by Saharan dust (75%-80%) and by material with isotopic characteristics similar to the Aeolian Arc volcanoes (20%-25%). The non-carbonate fraction of the calcareous ooze overlying the dolomitic claystones has a Sr and Pb isotopic composition identical to that of the dolomitic claystones, indicating that no change in the input sources to the sedimentary basin occurred during and after the dolomitization event. Combination of climato-tectonic factors most probably resulted in suitable conditions for dolomitization in the Marsili and the nearby Vavilov Basins. The basal dolomitic claystone sequence was formed at the initiation of the opening of the Marsili Basin (~2 Ma), which coincided with the consecutive glacial stage. The glaciation caused arid climate and enhanced evaporation that possibly contributed to the stable isotope variations in the proto-carbonate. The conductive cooling of the young lithosphere produced high heat flow in the region, causing low-temperature passive convection of pore waters in the basal calcareous sediment. We suggest that this pumping process was the major dolomitization mechanism since it is capable of driving large volumes of seawater (the source of Mg2+) through the sediment. The red-brown hue of the dolomitic claystones is terrigenous contribution of the glacially induced high eolian influx and was not hydrothermally derived from the underlying basaltic basement. The detailed geochemical investigation of the basal dolomitic sequence indicates that the dolomitization was most probably related to complex tectono-climatic conditions set by the initial opening stages of the Marsili Basin and glaciation.

Major element oxides, trace element content and isotopic ratios of dolerites from the Schirmacher Oasis

New results on the petrochemistry and geochemistry of dolerites from the Schirmacher Oasis shed light on the development of the Karoo-Maud plume in Antarctica. The basalts and dolerites are petrologically identical to the rocks of western Dronning Maud Land (DML), which were previously studied and interpreted as a manifestation of the Karoo-Maud plume in Antarctica. The spatial distribution of the dikes suggests eastward spreading of the plume material, up to the Schirmacher Oasis for at least 10 Ma. The geochemical characteristics of magmas from the Schirmacher Oasis reflect the influence of crustal contamination, which accompanied both the ascent and spreading of the plume. The magmas of the initial stage of plume activity (western DML) appeared to be the most contaminated in crustal components. It was found that the geochemical characteristics of Mesozoic magmas from the Schirmacher Oasis are identical to those of enriched tholeiites from the Afanasy Nikitin Rise and the central Kerguelen Plateau (Hole 749), which indicates that their enrichment was related to the ancient material of the Gondwana continent. This was caused by the opening of the Indian Ocean under the influence of the Karoo-Maud plume. This process was peculiar in that it occurred in the presence of nonspreading blocks of varying thickness, for instance, Elan Bank in the central Kerguelen Plateau, and was accompanied by the formation of intraplate volcanic rises, which are documented in the seafloor relief of basins around Antarctica. The geochemical characteristics of igneous rocks from the resulting rises (Afanasy Nikitin, Kerguelen, Naturaliste, and Ninetyeast Ridge) indicate the influence of processes related to crustal assimilation. The magmatism that occurred 40 Ma after the main phase of the Karoo-Maud volcanism at the margins of the adjacent continents of Australia (Bunbury basalts) and India (Rajmahal trapps) could be generated by the Karoo-Maud plume flowing along the developing spreading zone. The plume moved subsequently and was localized at the Kerguelen Plateau, where it occurs at present as an active hotspot.

Geochemistry, trace elements and minerals at DSDP Holes 80-550B and 80-551

The Leg 80 basalts drilled on the Porcupine Abyssal Plain 10 km southwest of Goban Spur (Hole 550B) and on the western edge of Goban Spur (Hole 551), respectively, are typical light-rare-earth-element- (LREE-) depleted oceanic tholeiites. The basalts from the two holes are almost identical; most of their primary geochemical and mineralogical characteristics have been preserved, but they have undergone some low-temperature alteration by seawater, such as enrichment in K, Rb, and Cs and development of secondary potassic minerals of the "brownstone facies." K/Ar dating fail to give realistic emplacement ages; the apparent ages obtained become younger with alteration (causing an increase in K2O). Hole 551 basalts are clearly different from the continental tholeiites emplaced on the margins of oceanizing domains during the prerift and synrift stages.

Geochemical composition of sediment samples from Krasnov field in the Mid Atlantic Ridge

This paper is dedicated to the geochemical studies of two bottom sediment cores that were taken during cruise 28 of the R/V Professor Logachev in the Mid-Atlantic Ridge (MAR) 16°38'N area in 2006. The chemical compositions of background metalliferous and ore (ore-bearing) carbonate sediments are presented and inter-element correlations are examined. Individual episodes are distinguished in the accumulation history of the ore-bearing and metalliferous sediments on the basis of element factor analysis.

Dissolved chemical elements in river waters of the Wrangel Island

Pioneer information about chemical composition of river waters in the Wrangel Island has been obtained. It is shown that water composition reflects the lithogeochemical specifics of primary rocks and ore mineralization. In contrast to many areas of the Russian Far North river waters of the island are characterized by elevated background value of total mineralization (i.e., total dissolved solids, TDS) (0.3-2 g/l) and specific chemical type (SO4-Ca-Mg). This is related to abundance of Late Carboniferous gypsiferous and dolomitic sequences in the mountainous area of the island. It has also been established that salt composition of some streams is appreciably governed by supergene alterations of sulfide mineralization associated with quartz-carbonate vein systems. They make up natural centers of surface water contamination. Waters in such streams are characterized by low pH values (2.4-5.5), high TDS (up to 6-23 g/l) and SO4-Mg composition. These waters are also marked by anomalously high concentrations of heavy and non-ferrous metals, as well as REE, U, and Th.

Chemical composition of phillipsites from Core AKO26-35

Behavior of rare earth elements (REE) was examined in oceanic phillipsites collected from four horizons of eupelagic clay in the Southwest Basin of the Pacific Ocean. REE concentrations were determined in >50 ?m size fraction phillipsite samples by the ICP-MS method. Composition of separate phillipsite aggregates was studied by electron microprobe and secondary ion mass-spectrometry. Rare earth elements in phillipsite samples are related to admixture of ferrocalcium hydroxophosphates. Analysis of separate phillipsite aggregates reveals low (<0.1-18.1 ppm) REE(III) concentrations. Ce concentration varies between 2.7 and 140 ppm. The correlation analysis shows that REE(III) present in admixture of iron oxyhydroxides in separate phillipsite aggregates. Based on the REE(III) concentration in iron oxyhydroxides we can identify two generations of phillipsite aggregates. Massive rounded aggregates (phillipsite I) are depleted in REE, while pseudorhombic (phillipsite II) aggregates are enriched in REE and marked by a positive Ce anomaly. Oceanic phillipsites do not accumulate REE or inherit the REE signature of volcaniclastic material and oceanic deep water. Hence, REE distribution in phillipsites does not depend on sedimentation rate and composition of host sediments.