Geochemistry on water profiles from the Kara Sea

As a part of the Russian-German project "Siberian River-Runoff (SIRRO)" the major element composition of the dissolved load and the major and trace element composition of particulate load and bottom sediment of the Yenisei River and Estuary were analyzed and examined in context of the basin lithology and climate. In addition, the processes controlling the transformation of the river load in the estuarine mixing zone were investigated. The chemical composition of the dissolved and particulate load of the Yenisei fluvial endmember is generally comparable to that of other major world rivers. The dissolved load is chiefly controlled by carbonate weathering and the chemical composition of the river suspended particulate matter (SPM) is similar to that of the North American Shale Composite (NASC), which represents the weathering product of the upper continental crust. The Chemical Index of Alteration (CIA) of the Yenisei SPM amounts to 71, which indicates moderate chemical weathering. With regard to the SPM geochemistry, the Yenisei occupies an intermediate position between the adjacent rivers Khatanga and the Lena. Drastic changes in the composition of the river load are seen in the mixing zone between fresh and salt water. While dissolved Na, Ca, Mg, K, CI, S04, F, Br, Sr and HC03 behave conservatively, dissolved Fe is completely removed from solution at very low salinities. Particulate Mn exhibits a pronounced mid-salinity minimum concomitant with a maximum of dissolved Mn, which is probably related to suboxic conditions in the area of the so-called "marginal filter", where highest turbidities are found. The Mn-minimum in SPM is paralleled by depletions of the elements Ba, Zn, Cd, Ni, Cu and V, which can be associated with manganese particles. The estuarine bottom sediments are composed of mud and sand and the sedimentological parameters of the bottom sediments have to be considered for the interpretation of the bulk geochemical data. The chemical composition of the mud is comparable to the SPM, whereas the sand is relatively enriched in Si/Al, Ba/Al, Zr/Al and Sr/Al ratios and depleted in transition metals.

Neodymium isotope record of late Paleocene to eraly Eocene fish teeth

High-resolution, fish tooth Nd isotopic records for eight Deep Sea Drilling Project and Ocean Drilling Program sites were used to reconstruct the nature of late Paleocene-early Eocene deep-water circulation. The goal of this reconstruction was to test the hypothesis that a change in thermohaline circulation patterns caused the abrupt 4-5°C warming of deep and bottom waters at the Paleocene/Eocene boundary - the Paleocene-Eocene thermal maximum (PETM) event. The combined set of records indicates a deep-water mass common to the North and South Atlantic, Southern and Indian oceans characterized by mean epsilon-Nd values of ~-8.7, and different water masses found in the central Pacific Ocean (epsilon-Nd ~-4.3) and Caribbean Sea (epsilon-Nd ~1.2). The geographic pattern of Nd isotopic values before and during the PETM suggests a Southern Ocean deep-water formation site for deep and bottom waters in the Atlantic and Indian ocean basins. The Nd data do not contain evidence for a change in the composition of deep waters prior to the onset of the PETM. This finding is consistent with the pattern of warming established by recently published stable isotope records, suggesting that deep- and bottom-water warming during the PETM was gradual and the consequence of surface-water warming in regions of downwelling.

Geochemistry of Pleistocene volcanic rocks in the Mariana Forearc

Geophysical surveys of the Mariana forearc, in an area equidistant from the Mariana Trench and the active Mariana Island Arc, revealed a 40-m-deep graben about 13 km northwest of Conical Seamount, a serpentine mud volcano. The graben and its bounding horst blocks are part of a fault zone that strikes northwest-southeast beneath Conical Seamount. One horst block was drilled during Leg 125 of the Ocean Drilling Program (Site 781). Three lithologic units were recovered at Site 781: an upper sedimentary unit, a middle basalt unit, and a lower sedimentary unit. The upper unit, between 0 and 72 mbsf, consists of upper Pliocene to Holocene diatomaceous and radiolarian-bearing silty clay that grades down into vitric silty clay and vitric clayey silt. The middle unit is a Pleistocene vesicular, porphyritic basalt, the top of which corresponds to a high-amplitude reflection on the reflection profiles. The lower unit is a middle to upper (and possibly some lower) Pliocene vitric silty clay and vitric clayey silt similar to the lower part of the upper unit. The thickness of the basalt unit can only be estimated to be between 13 and 25 m because of poor core recovery (28% to 55%). The absence of internal flow structures and the presence of an upper glassy chilled zone and a lower, fine-grained margin suggest that the basalt unit is either a single lava flow or a near-surface sill. The basalt consists of plagioclase phenocrysts with subordinate augite and olivine phenocrysts and of plagioclase-augite-olivine glomerocrysts in a groundmass of plagioclase, augite, olivine, and glass. The basalt is an island arc tholeiite enriched in large-ion-lithophile elements relative to high-field-strength elements, similar to the submarine lavas of the southern arc seamounts. In contrast, volcanic rocks from the active volcanoes on Pagan and Agrigan islands, 100 km to the west of the drill site, are calc-alkaline. The basalt layer, the youngest in-situ igneous layer reported from the Izu-Bonin and Mariana forearcs, is enigmatic because of its location more than 100 km from the active volcanic arc. The sediment layers above and below the basalt unit are late Pliocene in age (about 2.5 Ma) and normally magnetized. The basalt has schlierenlike structures, reverse magnetization, and a K-Ar age of 1.68±0.37 Ma. Thus, the basalt layer is probably a sill fed by magma intruded along a fault zone bounding the horst and graben in the forearc. The geochemistry of the basalt is consistent with a magma source similar to that of the active island arc and from a mantle source above the subducting Pacific plate.

(Table 1) Estimated e-Nd(0) input calculated using the relative fraction of ODP Hole 105-647A amphibole grains originated from different provinces of the North America

Many marine radiogenic isotope records show both spatial and temporal variations, reflecting both the degree of mixing of distinct sources in the oceans and changes in the distribution of chemical weathering on the continents. However, changes in weathering and transport processes may themselves affect the composition of radiogenic isotopes released into seawater. The provenance of physically weathered material in the Labrador Sea, constrained through the use of Ar-Ar ages of individual detrital minerals, has been used to estimate the relative contributions of chemically weathered terranes releasing radiogenic isotopes into the Labrador Sea. A simple box-model approach for balancing observed Nd-isotope variations has been used to constrain the relative importance of localised input in the Labrador Sea, and the subsequent mixing of Labrador Sea Water into North Atlantic Deep-Water. The long-term pattern of erosion and deep-water formation around the North Atlantic seems to have been a relatively stable feature since 1.5 Ma, although there has been a dramatic shift in the nature of physical and chemical weathering affecting the release of Hf and Pb isotopes. The modelled Nd isotopes imply a relative decrease in water mass advection into the Labrador Sea between 2.4 and 1.5 Ma, accompanied by a decrease in the rate of overturning, possibly caused by an increased freshwater input into the Labrador Sea.

Geochemistry of basalts at DSDP Leg 73 Holes

During Deep Sea Drilling Project Leg 73 (South Atlantic), basaltic pillow lava, flows, and sills were encountered in Holes 519A, 520, 522B, and 524. Paleomagnetic data indicate that the basalts from Holes 519A (magnetic Anomaly 51) and 522B (Anomaly 16) have ages of about 12 m.y. and about 38 m.y., respectively. The major- and trace- (including rare-earth-) element characteristics of the Hole 519A basalts (a total of 27 m) demonstrate that these basalts are typical normal-type mid-ocean-ridge basalts (N-type MORB). In composition the basalts overlap olivine tholeiites from other normal Mid-Atlantic Ridge segments. Both the spectra of incompatible, or less-hygromagmatophile elements (such as Ti, V, Y, and Zr) and REE abundances indicate that these basalts are the result of a low-pressure fractionation of olivine, spinel, and Plagioclase prior to eruption. In Hole 520 only 1.7 m of basalt were recovered from a total drilling depth of 10.5 m. These pillow basalts crystallized from fairly evolved (N-type MORB) tholeiitic melts. In total, 19 m of basaltic pillow lavas and flows were penetrated in Hole 522B. Thirteen cooling units were distinguished on the basis of glassy margins and fine quench textures. In contrast to Holes 519A and 520, the basalts of the Hole 522B ridge section can be divided into two major groups of tholeiites: (1) Cooling Units 1 through 12 and (2) Cooling Unit 13. The basalts in this ridge section are also N-type MORBs but are generally more differentiated than those of Holes 519A and 520. The lowermost basalts (Cooling Unit 13) have the most primitive composition and make up a compositional group distinct from the more evolved basalts in the twelve units above it. Hole 524 was drilled on the south flank of the Walvis Ridge and thus provided samples from a more complex part of the South Atlantic seafloor. Three different basaltic rock suites, interlayered with volcanic detrital sediments, were encountered. The rock suites are, from top to bottom, an alkali basaltic pillow lava; a 16-m-thick alkaline diabase sill with an age of about 65 m.y. (according to K-Ar dating and planktonic foraminifers); and a second sill that is approximately 9 m thick, about 74 m.y. in age, and tholeiitic in composition, thus contrasting strongly with the overlying alkaline rocks. The alkali basalts of Hole 524 show chemical characteristics that are very similar to the basaltic lavas of the Tristan da Cunha group volcanoes, which are located approximately 400 km east of the Mid-Atlantic Ridge crest. Thus, the Walvis Ridge may plausibly be interpreted as a line of hot-spot alkaline volcanoes.

H, O, Sr, and Nd isotope ratios and water, Rb, Sr, Sm, and Nd content of ODP Hole 116-717C and 116-718C samples (Table 2)

Mineralogical and H, O, Sr, and Nd isotope compositions have been analyzed on a set of representative samples from the 17-m.y. section in ODP Leg 116 Holes 717C and 718C. Based on the mineralogical composition of the fraction <2 µm together with the lithogenic-biogenic composition of the fraction >63 µm, the whole section can be subdivided into three major periods of sedimentation. Between 17.1 and 6 m.y., and between 0.8 m.y. to present, the sediments are characterized by sandy and silty turbiditic inputs with a high proportion of minerals derived from a gneissic source without alteration. In the fraction <2 µm, illite and chlorite are dominant over smectite and kaolinite. The granulometric fraction >63 µm contains quartz, muscovite, biotite, chlorite, and feldspars. The 6-to 0.8-m.y. period is represented by an alternation of sandy/silty horizons, muds, and calcareous muds rich in smectite, and kaolinite (50% to 85% of the fraction <2 µm) and bioclastic material. The presence of smectite and kaolinite, as well as the 18O/16O and the 87Sr/86Sr ratios of the fraction <2 µm, imply an evolution in a soil environment and exchanges with meteoric ground water. The ranges of isotopic compositions are limited throughout the section: d18O quartz = 11.7 to 13.3 per mil, 87Sr/86Sr = 0.733 to 0.760 and epsilon-Nd (0) = -17.4 to -13.8. These values are within those of the High Himalaya Crystalline series, and they are considered to reflect this source region. The data imply that, since 17 Ma, this formation has supplied the major part of the eroded material.

Chemistry of altered basaltic glass shards and zeolites of volcaniclastic sediments from ODP Hole 157-953C

Trace element concentrations of altered basaltic glass shards (layer silicates) and zeolites in volcaniclastic sediments drilled in the volcanic apron northeast of Gran Canaria during Ocean Drilling Program (ODP) leg 157 document variable element mobilities during low-temperature alteration processes in a marine environment. Clay minerals (saponite, montmorillonite, smectite) replacing volcanic glass particles are enriched in transition metals and rare earth elements (REE). The degree of retention of REE within the alteration products of the basaltic glass is correlated with the field strength of the cations. The high field-strength elements are preferentially retained or enriched in the alteration products by sorption through clay minerals. Most trace elements are enriched in a boundary layer close to the interface mineral-altered glass. This boundary layer has a key function for the physico-chemical conditions of the subsequent alteration process by providing a large reactive surface and by lowering the fluid permeability. The release of most elements is buffered by incorporation into secondary precipitates (sodium-rich zeolites, phillipsite, Fe- and Mn-oxides) as shown by calculated distribution coefficients between altered glasses and authigenic minerals. Chemical fluxes change from an open to a closed system behavior during prograde low-temperature alteration of volcaniclastic sediments with no significant trace metal flux from the sediment to the water column.

Element analyses and isotope composition of basalts from the West Valley segment, Juan de Fuca Ridge, northeast Pacific

The 50 km-long West Valley segment of the northern Juan de Fuca Ridge is a young, extension-dominated spreading centre, with volcanic activity concentrated in its southern half. A suite of basalts dredged from the West Valley floor, the adjacent Heck Seamount chain, and a small near-axis cone here named Southwest Seamount, includes a spectrum of geochemical compositions ranging from highly depleted normal (N-) MORB to enriched (E-) MORB. Heck Seamount lavas have chondrite-normalized La/Sm en -0.3, 87Sr/86Sr = 0.70235 - 0.70242, and 206Pb/204Pb = 18.22 - 18.44, requiring a source which is highly depleted in trace elements both at the time of melt generation and over geologic time. The E-MORB from Southwest Seamount have La/Sm en -1.8, 87Sr/86Sr = 0.70245 - 0.70260, and 206Pb/204Pb = 18.73 - 19.15, indicating a more enriched source. Basalts from the West Valley floor have chemical compositions intermediate between these two end-members. As a group, West Valley basalts from a two-component mixing array in element-element and element-isotope plots which is best explained by magma mixing. Evidence for crustal-level magma mixing in some basalts includes mineral-melt chemical and isotopic disequilibrium, but mixing of melts at depth (within the mantle) may also occur. The mantle beneath the northern Juan de Fuca Ridge is modelled as a plum-pudding, with "plums" of enriched, amphibole-bearing peridotite floating in a depleted matrix (DM). Low degrees of melting preferentially melt the "plums", initially removing only the amphibole component and producing alkaline to transitional E-MORB. Higher degrees of melting tap both the "plums" and the depleted matrix to yield N-MORB. The subtly different isotopic compositions of the E-MORBs compared to the N-MORBs require that any enriched component in the upper mantle was derived from a depleted source. If the enriched component crystallized from fluids with a DM source, the "plums" could evolve to their more evolved isotopic composition after a period of 1.5-2.0 Ga. Alternatively, the enriched component could have formed recently from fluids with a lessdepleted source than DM, such as subducted oceanic crust. A third possibility is that enriched material might be dispersed as "plums" throughout the upper mantle, transported from depth by mantle plumes.

Neodymium isotope signature of Holocene corals

The neodymium isotopic composition of marine precipitates is increasingly recognized as a powerful tool for identifying changes in ocean circulation and mixing on million year to millennial timescales. Unlike nutrient proxies such as ?13C or Cd/Ca, Nd isotopes are not thought to be altered in any significant way by biological processes, and thus they can serve as a quasi-conservative water mass tracer. However, the application of Nd isotopes in understanding the role of thermohaline circulation in rapid climate change is currently hindered by the lack of direct constraints on the signature of the North Atlantic end-member through time. Here we present the first results of Nd isotopes measured in U-Th-dated deep-sea corals from the New England seamounts in the northwest Atlantic Ocean. Our data are consistent with the conclusion that the Nd isotopic composition of North Atlantic deep and intermediate water has remained nearly constant through the last glacial cycle. The results address long-standing concerns that there may have been significant changes in the Nd isotopic composition of the North Atlantic end-member during this interval and substantiate the applicability of this novel tracer on millennial timescales for paleoceanography research.

Geochemistry of ODP Leg 125 peridotites

Ocean Drilling Program Leg 125 recovered serpentined harzburgites and dunites from a total of jive sites on the crests and flanks of two serpen finite seamounts, Conical Seamount in the Mariana forearc and Torishima Forearc Seamount in the Izu-Bonin forearc. These are some of the first extant forearc peridotites reported in the literature and they provide a window into oceanic, supra-subduction zone (SSZ) mantle processes. Harzbutrgites from both seamounts are very refractory with low modal clinopyroxene (<4%), chrome-rich spinels (cx-number = 0.40-0.80), very low incompatible element contents, and (with the exception of amphibole-bearing samples) U-shaped rare earth element (REE) profiles with positive Eu anomalies. Both sets of peridotites have olivine-spinel equilibration temperatures that are low compared with abyssal peridotites, possibly because of water-assisted diffusional equilibration in the SSZ environment However, other features indicate that the harzburgites from the two seamounts have very different origins. Harzburgites from Conical Seamount are characterized by calculated oxygen fugacities between FMQ (fayalite- magnetite- quartz) - 1.1 (log units) and FMQ + 0.4 which overlap those of mid-ocean ridge basalt (MORB) peridotites. Dunites from Conical Seamotmt contain small amounts of clinopyroxene, orthopyroxene and amphibole and are light REE (LREE) enriched. Moreover; they are considerably more oxidized than the harzburgites to which they are spatially related, with calculated oxygen fugacities of FMQ -0.2 toFMQ + 1.2. Using textural and geochemical evidence, we interpret these harzburgites as residual MORB mantle (from 15 to 20 % fractional melting) which has subsequently been modified by interaction with boninitic melt ivithin the mantle wedge, and these dunites as zones of focusing of this melt in which pyroxene has preferentially been dissolved from the harzbutgite protolith. In contrast, harzburgites from Torishima Forearc Seamount give calculated oxygen fugacities between FMQ + 0.8 and FMQ + l.6, similar to those calculated for other subduction-zone related peridotites and similar to those calculated for the dunites (FMQ + 1.2 to FMQ + 1.8) from the same seamount. In this case, we interpret both the harzburgites and dunites as linked to mantle melting (20-25 % fractional melting) in a supra-subduction zone environment The results thus indicate that the forearc is underlain by at least two types of mantle lithosphere, one being trapped or accreted oceanic lithosphere, the other being lithosphere formed by subduction-related melting. They also demonstrate that both types of mantle lithosphere may have undergone extensive interaction with subduction-derived magmas.

Geochemistry of basaltic rocks from ODP Hole 183-1137A on the Kerguelen Plateau

Cretaceous basalts recovered during Ocean Drilling Program Leg 183 at Site 1137 on the Kerguelen Plateau show remarkable geochemical similarities to Cretaceous continental tholeiites located on the continental margins of eastern India (Rajmahal Traps) and southwestern Australia (Bunbury basalt). Major and trace element and Sr-Nd-Pb isotopic compositions of the Site 1137 basalts are consistent with assimilation of Gondwanan continental crust (from 5 to 7%) by Kerguelen plume-derived magmas. In light of the requirement for crustal contamination of the Kerguelen Plateau basalts, we re-examine the early tectonic environment of the initial Kerguelen plume head. Although a causal role of the Kerguelen plume in the breakup of Eastern Gondwana cannot be ascertained, we demonstrate the need for the presence of the Kerguelen plume early during continental rifting. Activity resulting from interactions by the newly formed Indian and Australian continental margins and the Kerguelen plume may have resulted in stranded fragments of continental crust, isolated at shallow levels in the Indian Ocean lithosphere.

Chemical and isotope compositions of rocks dredged from the Shatsky Rise

Magmatic rocks of the Shatsky Rise form two groups replacing one another in time. The earlier ferrotholeiites enriched in potassium compose large massifs. Trachybasalts form seamounts and neotectonic ridges. Composition of volcanites indicates that two sources of magmatism took part in their formation: a depleted source characteristic of basalts of mid-ocean ridges and a ''plume'' source participating in formation of oceanic plateaus.

Lead and strontium isotope composition, mass accumulation rates and rare earth elements of selected samples from DSDP Sites 92-597 to 92-601

Most of the Pb isotope data for the Leg 92 metalliferous sediments (carbonate-free fraction) form approximately linear arrays in the conventional isotopic plots, extending from the middle of the field for mid-ocean ridge basalts (MORB) toward the field for Mn nodules. These arrays are directed closely to the average values of Mn nodules, the composition of which reflects the Pb isotope composition of seawater (Reynolds and Dasch, 1971). Since the Leg 92 samples are almost devoid of continentally derived detritus, it can be inferred that the more radiogenic end-member is seawater. The less radiogenic end-member lies in the very middle of the MORB field, and hence can be considered to reflect the Pb isotope composition of typical ocean-ridge basalt. The array of data lying between these two end-members is most readily interpreted in terms of simple linear mixing of Pb from the two different end-member sources. According to this model, eight samples from Sites 599 to 601 contain 50 to 100% basaltic Pb. Five of these samples have compositions that are identical within the uncertainty of the analyses. We use the average of these five values to define our unradiogenic end-member in the linear mixing model. The ratios used for this average are 206Pb/204Pb = 18.425 ± 0.010; 207Pb/204Pb = 15.495 ± 0.018; 208Pb/204Pb = 37.879 ± 0.068. These values should approximate the average Pb isotope composition of discharging hydrothermal solutions, and therefore also that of the basaltic crust, over the period of time represented by these samples ( 4 m.y., from 4 to 8 Ma). Sr isotope ratios show a significant range of values, from 0.7082 to 0.7091. The lower ratios are well outside the value of 0.70910 ± 6 for modern-day seawater (Burke et al., 1982). However, most values correspond very closely to the curve of 87Sr/86Sr versus age for seawater, with older samples having progressively lower 87Sr/86Sr ratios. The simplest explanation for this progressive reduction is that recrystallization of the abundant biogenic carbonate in the sediments released older seawater Sr which was incorporated into ferromanganiferous phases during diagenesis. Leg 92 metalliferous sediments have total rare earth element (REE) contents that range on a carbonate-free basis from 131 to 301 ppm, with a clustering between 167 and 222 ppm. The patterns have strong negative Ce anomalies. Samples from Sites 599 to 601 display a slight but distinct enrichment in the heavy REE relative to the light REE, whereas those from Sites 597 to 598 show almost no heavy REE enrichment. The former patterns (those for Sites 599 to 601) are interpreted as indicating moderate diagenetic alteration of metalliferous sediments originating at the EPR axis; the latter reflect more complete diagenetic modification.