Petrographic description and geochemistry of basalts and altered volcanic rocks from ODP Leg 183 sites

The basalts recovered during Legs 183 and 120 from the southern, central, and northernmost parts of the Kerguelen Plateau (Holes 1136A, 1138A, 1140A, and 747C, respectively), as well as those recovered from the eastern part of the crest of Elan Bank (Hole 1137A), represent derivates from tholeiitic melts. In the northern part of the Kerguelen Plateau (Hole 1140A), basalts may have formed from two sources located at different depths. This is reflected in the presence of both low- and high-titanium basalts. The basalts are variably altered by low-temperature hydrothermal processes (at temperatures up to 120°C), and some are affected by subaerial weathering. The hydrothermal alteration led mainly to the formation of smectites, chlorite minerals, mixed-layer hydromica-smectite and smectite-chlorite minerals, hydromica, serpentine(?), clinoptilolite, heulandite, stilbite, analcime, mordenite, thomsonite, natrolite(?), calcite, quartz, and dickite(?). Alteration of extrusive basalts is mainly related to horizontal fluid flow within permeable contact zones between lava flows. Under a nonoxidizing environment of alteration, the tendency to lose most of elements, including rare earth elements, from basalts dominates. Under on oxidizing environment, basalts accumulate many elements.

Igneous geochemistry of OP Leg 126 samples

Major element, trace element, and radiogenic isotope compositions of samples collected from Ocean Drilling Program Leg 126 in the Izu-Bonin forearc basin are presented. Lavas from the center of the basin (Site 793) are high-MgO, low-Ti, two-pyroxene basaltic andesites, and represent the products of synrift volcanism in the forearc region. These synrift lavas share many of the geochemical and petrographic characteristics of boninites. In terms of their element abundances, ratios, and isotope systematics they are intermediate between low-Ti arc tholeiites from the active arc and boninites of the outer-arc high. These features suggest a systematic geochemical gradation between volcanics related to trench distance and a variably depleted source. A basement high drilled on the western flank of the basin (Site 792) comprises a series of plagioclase-rich two-pyroxene andesites with calc-alkaline affinities. These lavas are similar to calc-alkaline volcanics from Japan, but have lower contents of Ti, Zr, and low-field-strength elements (LFSE). Lavas from Site 793 show inter-element variations between Zr, Ti, Sr, Ni, and Cr that are consistent with those predicted during crystallization and melting processes. In comparison, concentrations of P, Y, LFSE, and the rare-earth elements (REE) are anomalous. These elements have been redistributed within the lava pile, concentrating particularly in sections of massive and pillowed flows. Relative movement of these two-element groupings can be related to the alteration of interstitial basaltic andesite glass to a clay mineral assemblage by a post-eruptive process. Fluid-rock interaction has produced similar effects in the basement lavas of Site 792. In this sequence, andesites and dacites have undergone a volume change related to silica mobility. As a result of this process, some lithologies have the major element characteristics of basaltic andesite and rhyolite, but can be related to andesitic or dacitic precursors by silica removal or addition.

Major, trace and rare earth elements and minerals at DSDP Legs 69-70 Holes

We obtained major and trace element data on 113 samples from basalts drilled during DSDP Legs 69 and 70 in the Costa Rica Rift area. The majority have major and trace element characteristics typical of ocean-ridge tholeiities. Most of the basalts are relatively MgO rich (MgO > 8 wt.%) and have Mg values (MgO/MgO + 0.85FeO x 100) of about 53, characteristics that clearly indicate that the various magmas underwent only a small amount of crystal fractionation before being erupted onto the seafloor. According to their normative mineralogies, the rocks are olivine tholeiites. A few samples plot close to the diopside-hypersthene join of the projected basalt tetrahedron. Except for basalts from two thin intervals in Hole 504B, which differ significantly from all the other basalts of the hole, practically no chemical downhole variation could be established. In the two exceptional intervals, both TiO2 and P2O5 contents are markedly enriched among the major oxides. The trace elements in these intervals are distinguished by relatively high contents of magmatophile elements and have flat to enriched chondrite-normalized distribution patterns of light rare earth elements (LREE). Most of the rocks outside these intervals are strongly depleted in large-ionlithophile (LIL) elements and LREE. We offer no satisfactory hypothesis for the origin of these basalts at this time. They might have originated within pockets of mantle materials that were more primitive than the LIL-element-depleted magmas that were the source of the other basalts. A significant change with depth in the type of alteration occurs in the 561 meters of basalt cored in Hole 504B. According to the behavior of such alteration-sensitive species as K2O, H2O-, CO2, S, Tl, and the iron oxidation ratio, the alteration is oxidative in the upper part and nonoxidative or even reducing in the lower part. The oxidative alteration may have resulted from low temperature basalt/seawater interaction, whereas hydrothermal solutions may be responsible for the nonoxidative alteration.

Radiocarbon ages, carbon and oxygen isotopes and Mg/Ca and Sr/Ca ratios of Globigerinoides in sediment core MD99-2203, Cape Hatteras

This study presents high-resolution foraminiferal-based sea surface temperature, sea surface salinity and upper water column stratification reconstructions off Cape Hatteras, a region sensitive to atmospheric and thermohaline circulation changes associated with the Gulf Stream. We focus on the last 10,000 years (10 ka) to study the surface hydrology changes under our current climate conditions and discuss the centennial to millennial time scale variability. We observed opposite evolutions between the conditions off Cape Hatteras and those south of Iceland, known today for the North Atlantic Oscillation pattern. We interpret the temperature and salinity changes in both regions as co-variation of activities of the subtropical and subpolar gyres. Around 8.3 ka and 5.2-3.5 ka, positive salinity anomalies are reconstructed off Cape Hatteras. We demonstrate, for the 5.2-3.5 ka period, that the salinity increase was caused by the cessation of the low salinity surface flow coming from the north. A northward displacement of the Gulf Stream, blocking the southbound low-salinity flow, concomitant to a reduced Meridional Overturning Circulation is the most likely scenario. Finally, wavelet transform analysis revealed a 1000-year period pacing the d18O signal over the early Holocene. This 1000-year frequency band is significantly coherent with the 1000-year frequency band of Total Solar Irradiance (TSI) between 9.5 ka and 7 ka and both signals are in phase over the rest of the studied period.

Geochemistry of low-temperatuer altered basalts of ODP Hole 136-843B

The mineralogy and chemistry of altered basalts and the stable isotopic compositions of secondary vein carbonates were studied in cores from Ocean Drilling Program Hole 843B, located in 95-Ma crust of the Hawaiian Arch. Millimeter- to centimeter-sized dark alteration halos around veins are 5%-15% altered to celadonite and Fe-oxyhydroxides, plus minor saponite and calcite. Adjacent gray host rocks are about 15% altered to saponite and calcite. The dark halos are enriched in H2O+, CO2, FeT, K2O, MnO, and Fe3+/FeT and depleted in SiO2, Al2O3, MgO, and TiO2 relative to gray host rocks. Brown alteration halos occur around veins where veins are more abundant, and are similar to dark halos, but contain more Fe-oxyhydroxides and exhibit greater Fe2O3T contents and higher Fe3+/FeT. Stable isotopic compositions of vein carbonates are consistent with their precipitation from seawater at temperatures of 5°-40°C. Crosscutting relationships of veins and zoned vein and vesicle fillings reveal a sequence of secondary mineral formation and alteration conditions. Celadonite and Fe-oxyhydroxides formed and dark alteration halos developed relatively early, under oxidizing conditions at low temperatures (<50°C). Saponite formed later at lower seawater/rock ratios and under more reducing conditions. Calcite and pyrite formed last in veins and vesicles from more evolved, seawaterderived fluids at temperatures of 5°-40°C. A second stage of celadonite, with compositions distinct from the early celadonite, also occurred relatively late (within the "calcite stage"), and may be related to refracturing of the crust and introduction of less-evolved seawater solutions into the rocks. Trends to higher K2O contents are attributed to alteration, but high K/Ti, Ba, and Zr contents indicate the presence of enriched or transitional MORB. CO2 contents of Pacific ODP cores exhibit a general increase with age suggesting progressive fixation of CO2 as calcite in the crust, but this could be complicated by local heterogeneities in fracturing and calcite formation in the crust.

Geochemistry of the volcanic basement of ODP Hole 134-831B

The basement of Bougainville Guyot drilled at Site 831 consists of andesitic hyalobreccias derived from a submarine arc volcano. The volcanic sequence has been dated by K/Ar at approximately 37 Ma. The 121 m of andesitic hyalobreccias drilled in Hole 831B have been divided into five subunits of two types: one appears to be primary, and the other contains evidence of reworking and a subaerial clastic input. Variations are attributed to fluctuations in water depth. The distinctive hyalobreccias consist of andesitic blebs with chilled margins and peripheral fractures set in a chaotic greenish matrix that is mainly altered glass, with crystals similar to those in the blebs or clasts. Their formation is attributed to violent reaction of andesitic magma discharged into seawater, in perhaps the submarine equivalent of fire-fountaining. There was limited reworking by currents and debris flows on the flanks of the submarine volcano. The andesite shows no significant compositional variation in phenocryst phases throughout the drilled sequence and contains phenocrysts of plagioclase (An88-43), clinopyroxene (Ca44Mg46Fe10-Ca41Mg40Fe19), orthopyroxene (Ca4Mg79Fe17-Ca3Mg58Fe39), and titanomagnetite. There is a systematic change in volcanic composition with height in the section, from more mafic andesites at the base, to overlying more acid andesites, and strong evidence exists that magma mixing may have played a significant role in the genesis of these lavas. The andesites have affinities with the low-K arc tholeiite series. Trace element and isotopic systematics for these rocks indicate very minor involvement of a LILE- and 87Sr-enriched slab-derived fluid in their petrogenesis. This accords with the previous suggestion that Bougainville Guyot forms part of an Eocene proto-island arc developed along the southern side of the d'Entrecasteaux Zone, above a southward-dipping subduction zone.

Mineralogy and diagenesis of slope sediments at DSDP Leg 84 holes

The distribution and composition of minerals in the silt and clay fraction of the fine-grained slope sediments were examined. Special interest was focused on diagenesis. The results are listed as follows. (1) Smectite, andesitic Plagioclase, quartz, and low-Mg calcite are the main mineral components of the sediment. Authigenic dolomite was observed in the weathering zones of serpentinites, together with aragonite, as well as in clayey silt. (2) The mineralogy and geochemistry of the sediments is analogous to that of the andesitic rocks of Costa Rica and Guatemala. (3) Unstable components like volcanic glass, amphiboles, and pyroxenes show increasing etching with depth. (4) The diagenetic alteration of opal-A skeletons from etching pits and replacement by opal-CT to replacement by chalcedony as a final stage corresponds to the typical opal diagenesis. (5) Clinoptilolite is the stable zeolite mineral according to mineral stability fields; its neoformation is well documented. (6) The early diagenesis of smectites is shown by an increase of crystallinity with depth. Only the smectites in the oldest sediments (Oligocene and early Eocene) contain nonexpanding illite layers.

Major oxides, trace elements and rare earth elements of selected basalt samples at DSDP Hole 83-504B

DSDP Hole 504B is the deepest section drilled into oceanic basement, penetrating through a 571.5-m lava pile and a 209-m transition zone of lavas and dikes into 295 m of a sheeted dike complex. To define the basement composition 194 samples of least altered basalts, representing all lithologic units, were analyzed for their major and 26 trace elements. As is evident from the alteration-sensitive indicators H2O+, CO2, S, K, Mn, Zn, Cu, and the iron oxidation ratio, all rocks recovered are chemically altered to some extent. Downhole variation in these parameters enables us to distinguish five depth-related alteration zones that closely correlate with changes in alteration mineralogy. Alteration in the uppermost basement portion is characterized by pronounced K-uptake, sulfur loss, and iron oxidation and clearly demonstrates low-temperature seawater interaction. A very spectacular type of alteration is confined to the depth range from 910 to 1059 m below seafloor (BSF). Rocks from this basement portion exhibit the lowest iron oxidation, the highest H2O+ contents, and a considerable enrichment in Mn, S, Zn, and Cu. At the top of this zone a stockwork-like sulfide mineralization occurs. The chemical data suggest that this basement portion was at one time within a hydrothermal upflow zone. The steep gradient in alteration chemistry above this zone and the ore precipitation are interpreted as the result of mixing of the upflowing hydrothermal fluids with lower-temperature solutions circulating in the lava pile. Despite the chemical alteration the primary composition and variation of the rocks can be reliably established. All data demonstrate that the pillow lavas and the dikes are remarkably uniform and display almost the same range of variation. A general characteristic of the rocks that classify as olivine tholeiites is their high MgO contents (up to 10.5 wt.%) and their low K abundances (-200 ppm). According to their mg-values, which range from 0.60 to 0.74, most basalts appear to have undergone some high-level crystal fractionation. Despite the overall similarity in composition, there are two major basalt groups that have significantly different abundances and ratios of incompatible elements at similar mg-values. The majority of the basalts from the pillow lava and dike sections are chemically closely related, and most probably represent differentiation products of a common parental magma. They are low in Na2O, TiO2, and P2O5, and very low in the more hygromagmaphile elements. Interdigitated with this basalt group is a very rarely occurring basalt that is higher in Na2O, TiO2, P2O5, much less depleted in hygromagmaphile elements, and similar to normal mid-ocean ridge basalt (MORB). The latter is restricted to Lithologic Units 5 and 36 of the pillow lava section and Lithologic Unit 83 of the dike section. The two basalt groups cannot be related by differentiation processes but have to be regarded as products of two different parental magmas. The compositional uniformity of the majority of the basalts suggests that the magma chamber beneath the Costa Rica Rift reached nearly steady-state conditions. However, the presence of lavas and dikes that crystallized from a different parental magma requires the existence of a separate conduit-magma chamber system for these melts. Occasionally mixing between the two magma types appears to have occurred. The chemical characteristics of the two magma types imply some heterogeneity in the mantle source underlying the Costa Rica Rift. The predominant magma type represents an extremely depleted source, whereas the rare magma type presumably originated from regions of less depleted mantle material (relict or affected by metasomatism).

Zooplankton and seston in the White Sea and its chemical composition

A technique of zooplankton net sampling at night in the Kandalaksha and Dvinskii Bays and during the full tide in the Onezhskii Bay of the White Sea allowed us to obtain "clean" samples without considerable admixtures of terrigenous particulates. Absence of elements-indicators of the terrigenous particulates (Al, Ti, and Zr) in the EDX spectra allows to conclude that ash composition of tested samples is defined by constitutional elements comprising organic matter and integument (chitin, shells) of plankton organisms. A quantitative assessment of accumulation of ca. 40 chemical elements by zooplankton based on a complex of modern physical methods of analysis is presented. Values of the coefficient of the biological accumulation of the elements (Kb) calculated for organic matter and the enrichment factors (EF) relative to Clarke concentrations in shale are in general determined by mobility of the chemical elements in aqueous solution, which is confirmed by calculated chemical speciation of the elements in the inorganic subsystem of surface waters of Onezhskii Bay.

Trace metals in sediments of the Var Canyon turbidite system at the DYFAMED station in the Ligurian Sea

The magnitude and the chronology of anthropogenic impregnation by Hg and other trace metals of environmental concern (V, Cr, Ni, Cu, Zn, Ag, Cd and Pb, including its stable isotopes) in the sediments are determined at the DYFAMED station, a site in the Ligurian Sea (Northwestern Mediterranean) chosen for its supposed open-sea characteristics. The DYFAMED site (VD) is located on the right levee of the Var Canyon turbidite system, at the end of the Middle Valley. In order to trace the influence of the gravity current coming from the canyon on trace metal distribution in the sediment, we studied an additional sediment core (VA) from a terrace of the Var Canyon, and material collected in sediment traps at the both sites at 20 m above sea bottom. The patterns of Hg and other trace element distribution profiles are interpreted using stable Pb isotope ratios as proxies for its sources, taking into account the sedimentary context (turbidites, redox conditions, and sedimentation rates). Major element distributions, coupled with the stratigraphic examination of the sediment cores point out the high heterogeneity of the deposits at VA, and major turbiditic events at both sites. At the DYFAMED site, we observed direct anthropogenic influence in the upper sediment layer (<2 cm), while on the Var Canyon site (VA), the anthropization concerns the whole sedimentary column sampled (19 cm). Turbiditic events superimpose their specific signature on trace metal distributions. According to the 210Pbxs-derived sedimentation rate at the DYFAMED site (0.4 mm yr-1), the Hg-enriched layer of the top core corresponds to the sediment accumulation of the last 50 years, which is the period of the highest increase in Hg deposition on a global scale. With the hypothesis of the absence of significant post-depositional redistribution of Hg, the Hg/C-org ratio changes between the surface and below are used to estimate the anthropogenic contribution to the Hg flux accumulated in the sediment. The Hg enrichment, from pre-industrial to the present time is calculated to be around 60%, consistent with estimations of global Hg models. However, based on the chemical composition of the trapped material collected in sediment traps, we calculated that epibenthic mobilization of Hg would reach 73%. Conversely, the Cd/C-org ratio decreases in the upper 5 cm, which may reflect the recent decrease of atmospheric Cd inputs or losses due to diagenetic processes.

Chemical composition and age of metamorphic rocks from the Khavyven Highland, Eastern Kamchatka

Metamorphic rocks of the Khavyven Highland in eastern Kamchatka were determined to comprise two complexes of metavolcanic rocks that have different ages and are associated with subordinate amounts of metasediments. The complex composing the lower part of the visible vertical section of the highland is dominated by leucocratic amphibole-mica (+/-garnet) and epidote-mica (+/-garnet) crystalline schists, whose protoliths were andesites and dacites and their high-K varieties of island-arc calc-alkaline series. The other complex composing the upper part of the vertical section consists of spilitized basaltoids transformed into epidote-amphibole and phengite-epidote-amphibole green schists, which form (together with quartzites, serpentinized peridotites, serpentinites, and gabbroids) a sea-margin ophiolitic association. High LILE concentrations, high K/La, Ba/Th, Th/Ta, and La/Nb ratios, deep Ta-Nb minima, and low (La/Yb)_N and high 87Sr/86Sr ratios of the crystalline schists of the lower unit are demonstrated to testify to their subduction nature and suggest that their protolithic volcanics were produced in the suprasubduction environment of the Ozernoi-Valaginskii (Achaivayam-Valaginskii) island volcanic arc of Campanian-Paleogene age. The green schists of the upper unit show features of depleted MOR tholeiitic melts and subduction melts, which cause the deep Ta-Nb minima, and low K/La and 87Sr/86Sr ratios suggesting that the green schists formed in a marginal basin in front of the Ozernoi-Valaginskaya island arc. Recently obtained K-Ar ages in the Khavyven Highland vary from 32.4 to 39.3 Ma and indicate that metamorphism of the protolithic rocks occurred in Eocene under effect of collision and accretion processes of the arc complexes of the Ozernoi-Valaginskii and Kronotskii island arcs with the Asian continent and the closure of forearc oceanic basins in front of them. The modern position of the collision suture that marks the fossil subduction zone of the Ozernoi-Valaginskii arc and is spatially restricted to the buried Khavyven uplift in the Central Kamchatka Depression characterized by well-pronounced linear gravity anomalies.

Composition of ocean suspended matter

Compositions of different types of ocean suspended matter are under consideration.

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.

Petrology and geochemistry of silicified upper Miocene chalk at DSDP Site 69-504

Chert, Porcellanite, and other silicified rocks formed in response to high heat flow in the lower 50 meters of 275 meters of sediments at Deep Sea Drilling Project Site 504, Costa Rica Rift. Chert and Porcellanite partly or completely replaced upper Miocene chalk and limestone. Silicified rock occurs as nodules, laminae, stringers, and casts of burrows, and consists of quartz and opal-CT in varying amounts, associated with secondary calcite. The secondary silica was derived from dissolution of opal-A (biogenic silica), mostly diatom frustules and radiolarian tests. Temperature data obtained at the site indicate that transformation of opal-A to opal-CT began at about 50°C, and transformation from opal-CT to quartz at about 55°C. Quartz is most abundant close to basement basalts. These silica transformations occurred over the past 1 m.y., and took place so rapidly that there was incomplete ordering of opal-CT before transformation to quartz; opal-CT formed initially with an uncommonly wide d spacing. Quartz shows poor crystallinity. Chemical data show that the extensively silicified rocks consist of over 96% SiO2; in these rocks, minor and trace elements decreased greatly, except for boron, which increased. Low Al2O3 and TiO2 contents in all studied rocks preclude the presence of significant volcanic or terrigenous detritus. Mn content increases with depth, perhaps reflecting contributions from basalts or hydrothermal solutions. Comparisons with cherts from oceanic plateaus in the central Pacific point to a more purely biogenic host sediment for the Costa Rica Rift cherts, more rapid precipitation of quartz, and formation nearer a spreading center. Despite being closer to continental sources of ash and terrigenous detritus, Costa Rica Rift cherts have lower Al2O3, Fe2O3, and Mn concentrations.