Chemical composition of clay minerals from ODP Leg 168 sites

The exchangeable cation compositions of organic-poor terrigenous sediments containing smectite as primary ion exchanger from a series of holes along ODP Leg 168 transect on the eastern flank of the Juan de Fuca Ridge have been examined as a function of distance from the ridge axis and burial depth. The total cation exchange capacity (CEC) values of the sediments ranged from 2 to 59 meq/100 g, increasing with increases in the wt.% smectite. At the seafloor, the exchangeable cation compositions involving Na, K, Mg, and Ca, expressed in terms of equivalent fraction, are nearly constant regardless of the different transect sites: XNa = 0.21 ± 0.04, XK = 0.08 ± 0.01, XMg = 0.33 ± 0.09, and XCa = 0.38 ± 0.09. The calculated selectivity coefficients of the corresponding quaternary exchange reactions, calculated using porewater data, are in log units -5.45 ± 0.39 for Na, 1.97 ± 0.49 for K, 0.42 ± 0.41 for Mg, and 3.06 ± 0.69 for Ca. The exchangeable cation compositions below the seafloor change systematically with distance from the ridge crest and burial depth, conforming to the trends of the same cations in the porewaters. The selectivities for Na and Mg are roughly constant at temperatures from 2 to 66°C, indicating that the equivalent fractions of these two cations are independent of sediment alteration taking place on the ridge flank. Unlike Na and Mg, the temperature influence is significant for K and Ca, with Ca-selectivity decreases being coupled with increases in K-selectivity. Although potentially related to diagenetic and/or hydrothermal mineral precipitation or recrystallization, no evidence of such alteration was detected by XRD and TEM. In sites where upwelling of hydrothermal fluids from basement is occurring, the K-selectivity of the sediment is appreciably higher than at the other sites and corresponds to the formation of (Fe, Mg) rich smectite and zeolites. Our study indicates that local increases in K-selectivity at hydrothermal sites are caused by the formation of these authigenic minerals.

Rocks and minerals from the Strakhov Fracture Zone, 4°N Mid-Atlantic Ridge

Geological-geophysical data obtained during Cruises 7, 11, and 12 of R/V Akademic Nikolay Strakhov (1989-1991) within the international project EQUARIDGE in the Strakhov Fracture Zone region (4°N) are presented. The trough of the fracture is interpreted as an open extension joint, a graben produced by stretching along the axis of the Mid-Atlantic Ridge. Bedrock studies showed that typical mid-ocean tholeiitic basalts occur within the narrow (60 nm wide) axial rift zone, whereas igneous rocks not typical for the ocean were found on the eastern and western flank plateaus. This allows to suppose that a reworked relict continental-type basement of pre-Upper Jurassic age possibly exists beneath the flank plateaus, within the segment under discussion. The above data correspond to the hypothesis of E. Bonatti about nonspreading nature of the basement of Mid-Atlantic Ridge within the equatorial segment and the Strakhov Fracture Zone.

Geochemistry of ODP Leg 125 peridotites

Trace element analyses (first-series transition elements, Ti, Rb, Sr, Zr, Y, Nb, and REE) were carried out on whole rocks and minerals from 10 peridotite samples from both Conical Seamount in the Mariana forearc and Torishima Forearc Seamount in the Izu-Bonin forearc using a combination of XRF, ID-MS, ICP-MS, and ion microprobe. The concentrations of incompatible trace elements are generally low, reflecting the highly residual nature of the peridotites and their low clinopyroxene content (<2%). Chondrite-normalized REE patterns show extreme U shapes with (La/Sm)n ratios in the range of 5.03-250.0 and (Sm/Yb)n ratios in the range of 0.05-0.25; several samples show possible small positive Eu anomalies. LREE enrichment is common to both seamounts, although the peridotites from Conical Seamount have higher (La/Ce)n ratios on extended chondrite-normalized plots, in which both REEs and other trace elements are organized according to their incompatibility with respect to a harzburgitic mantle. Comparison with abyssal peridotite patterns suggests that the LREEs, Rb, Nb, Sr, Sm, and Eu are all enriched in the Leg 125 peridotites, but Ti and the HREEs exhibit no obvious enrichment. The peridotites also give positive anomalies for Zr and Sr relative to their neighboring REEs. Covariation diagrams based on clinopyroxene data show that Ti and the HREEs plot on an extension of an abyssal peridotite trend to more residual compositions. However, the LREEs, Rb, Sr, Sm, and Eu are displaced off this trend toward higher values, suggesting that these elements were introduced during an enrichment event. The axis of dispersion on these plots further suggests that enrichment took place during or after melting and thus was not a characteristic of the lithosphere before subduction. Compared with boninites sampled from the Izu-Bonin-Mariana forearc, the peridotites are significantly more enriched in LREEs. Modeling of the melting process indicates that if they represent the most depleted residues of the melting events that generated forearc boninites they must have experienced subsolidus enrichment in these elements, as well as in Rb, Sr, Zr, Nb, Sm, and Eu. The lack of any correlation with the degree of serpentinization suggests that low-temperature fluids were not the prime cause of enrichment. The enrichment in the high-field-strength elements also suggests that at least some of this enrichment may have involved melts rather than aqueous fluids. Moreover, the presence of the hydrous minerals magnesio-hornblende and tremolite and the common resorption of orthopyroxene indicate that this high-temperature peridotite-fluid interaction may have taken place in a water-rich environment in the forearc following the melting event that produced the boninites. The peridotites from Leg 125 may therefore contain a record of an important flux of elements into the mantle wedge during the initial formation of forearc lithosphere. Ophiolitic peridotites with these characteristics have not yet been reported, perhaps because the precise equivalents to the serpentinite seamounts have not been analyzed.

Isotopic geochemistry of granitoids in the Jinshajiang suture zone, SW China

The Jinshajiang suture zone, located in the eastern part of the Tethyan tectonic domain, is noticeable for a large-scale distribution of Late Jurassic to Triassic granitoids. These granitoids were genetically related to the evolution of the Paleo-Tethys Ocean. The Beiwu, Linong and Lunong granitoids occur in the middle zone of the Jinshajiang Suture Zone, and possess similar geochemical features, indicating they share a common magma source. SIMS zircon U-Pb dating reveals the Beiwu, Linong and Lunong granitic intrusions were emplaced at 233.9±1.4 Ma (2 sigma), 233.1 ±1.4 Ma (2 sigma) and 231.0±1.6 Ma (2 sigma), respectively. All of these granitoids are enriched in abundances of Si (SiO2 =65.2-73.5 wt.%), and large-ion-lithophile-elements (LILEs), but depleted in high-field-strength-elements contents (HFSEs, e.g., Nb, Ta, Ti). In addition, they have low P2O5 contents (0.06-0.11 wt.%), A/CNK values ([molecular Al2O3/(CaO+Na2O+K2O)], mostly<1.1) and 10000Ga/Al ratios (1.7-2.2), consistent with the characteristics of I-type granites. In terms of isotopic compositions, these granitoids have high initial 87Sr/86Sr ratios (0.7078-0.7148), Pb isotopic compositions [(206Pb/204Pb)t=18.213-18.598, (207Pb/204Pb)t=15.637-15.730 and (208Pb/204Pb)t=38.323-38.791], zircon d18O values (7. per mil-9.3 per mil) and negative eNd(t) values (-5.1 to -6.7), suggesting they were predominantly derived from the continental crust. Their Nb/Ta ratios (average value=8.6) are consistent with those of the lower continental crust (LCC). However, variable ?Hf(t) values (-8.6 to +2.8) and the occurrences of mafic microgranular enclaves (MMEs) suggest that mantle-derived melts and lower crustal magmas were involved in the generation of these granitoids. Moreover, the high Pb isotopic ratios and elevated zircon d18O values of these rocks indicate a significant contribution of the upper crustal composition. We propose a model in which the Beiwu, Linong and Lunong granitoids were generated under a late collisional or post-collisional setting. It is possible that this collision was completed before Late Triassic. Decompression induced mantle-derived magmas underplated and provided the heat for the anatexis of the crust. Hybrid melts including mantle-derived and the lower crustal magmas were then generated. The hybrid melts thereafter ascended to a shallow depth and resulted in some degree of sedimentary rocks assimilation. Such three-component mixing magmas source and subsequent fractional crystallization could be responsible for the formation of the Beiwu, Linong and Lunong granitoids.

Geochemistry of the lower sheeted dike complex of ODP Holes 137-504B and 140-504B

Sixty-three samples representing 379 m of sheeted dikes from Deep Sea Drilling Project/Ocean Drilling Program Site 504B have been analyzed for major and selected trace elements by X-ray fluorescence. The samples range from microcrystalline aphyric basalts to moderately phyric (2%-10% phenocrysts) diabase that are typically multiply saturated with plagioclase, olivine, and clinopyroxene, in order of relative abundance. All analyzed samples are classified as Group D compositions with moderate to slightly elevated compatible elements (MgÆ-value = 0.65% ± 0.03%; Al2O3 = 15.5% ± 0.8%; CaO = 13.0% ± 0.3%; Ni = 114 ± 29 ppm), and unusually depleted levels of moderate to highly incompatible elements (Nb < 1 ppm; Zr = 44 ± 7 ppm; Rb < 0.5 ppm; Ba ~ 1 ppm; P2O5 = 0.07% ± 0.02%). These compositions are consistent with a multistage melting of a normal ocean ridge basaltic mantle source followed by extensive fractionation of olivine, plagioclase, and clinopyroxene. Leg 140 aphyric to sparsely phyric (0%-2% phenocrysts) basalts and diabases are compositionally indistinguishable from similarly phyric samples at higher levels in the hole. An examination of the entire crustal section, from the overlying volcanics through the sheeted dikes observed in Leg 140, reveals no significant trends indicating the enrichment or depletion of Costa Rica Rift Zone source magmas over time. Similarly, significant trends toward increased or decreased differentiation cannot be identified, although compositional patterns reflecting variable amounts of phenocryst addition are apparent at various depths. Below ? 1700 mbsf to the bottom of the Leg 140 section, there is a broadly systematic pattern of Zn depletion with depth, the result of high-temperature hydrothermal leaching. This zone of depletion is thought to be a significant source of Zn for the hydrothermal fluids depositing metal sulfides at ridge-crest hydrothermal vents and the sulfide-mineralization zone, located in the transition between pillow lavas and sheeted dikes. Localized zones of intense alteration (60%-95% recrystallization) are present on a centimeter to meter scale in many lithologic units. Within these zones, normally immobile elements Ti, Zr, Y, and rare-earth elements are strongly depleted compared with "fresher" samples centimeters away. The extent of compositional variability of these elements tends to obscure primary igneous trends if the highly altered samples are not identified or removed. At levels up to 40% (or possibly 60%) recrystallization, Ti, Zr, and Y retain their primary signatures. Although the mechanisms are unclear, it is possible that these intense alteration zones are a source of Y and rare-earth elements for the typically rare-earth-element-enriched hydrothermal vent fluids of mid-ocean ridges.

Radiocarbon dating of mollusk shells from southern Kara Sea sediments

Riverine water and sediment discharge to the Arctic Ocean is among the most important parameters influencing Arctic climate. It is clear that the evaluation of Arctic paleoclimate requires information on the paleodischarge of major rivers entering the sedimentation basin. Presently, the water discharge of the Ob River accounts for about 12% of the total input of river water into the Arctic Ocean. During the investigation of the Kara Sea in the framework of the Russian-German SIRRO Project, the history of Yenisei discharge received much attention in a number of publications. This paper presents the results of lithological and geochemical investigations with application to the Holocene discharge of the Ob River. Qualitative (SiO2, Al2O3, K2O, and some modules) and quantitative (sedimentation rates and absolute masses of sedimentary material) parameters were used to characterize the history of the Ob sediment discharge. It was shown that the investigated paleochannels of the Ob were initiated at the Pleistocene-Holocene boundary, and during the first half of the Holocene, the river discharge decreased irregularly with decreasing age of sediments. The observed maxima are in fairly good agreement with the data for the Yenisei. We proposed a hypothesis on the influence of glacioisostatic movements in the marginal region of the former Kara ice sheet of late Valdai age on the cessation of marine-fluvial glaciation in the paleochannels of Ob and Yenisei in the periphery of the Ob-Yenisei shoal.

Composition and fluxes of sinking particulate material and bottom sediments in the northeast Black Sea in 1998-1999

For the first time deep-sea mooring stations with sediment traps were deployed in the northeast Black Sea. One sediment trap for long-term studies was located at Station 1 (44°15'N, 37°43'E, deployment depth 1800 m, depth 1900 m). The trap collected sinking sedimentary material from January to May 1998. Material collectors were changed every 15 days. Other stations with sediment traps for short-term studies (September-October 1999) were located on the shelf: Station 2 (44°16'N, 38°37'E, deployment depth 45 m, depth 50 m) and on the bottom of the canyon: Station 3 (44°16'N, 38°22'E, deployment depth 1145 m, depth 1150 m), Station 4 (44°11'N, 38°21'E, deployment depths 200, 1550, 1650 m, depth 1670 m). Collected material indicates that vertical particle fluxes are controlled by seasonal changes of in situ production and by dynamics of terrigenous matter input. Higher vertical particle flux of carbonate and biogenic silica was in spring due to bloom of plankton organisms. Maximum of coccolith bloom is in April-May. Bloom of diatoms begins in March. In winter and autumn lithogenic material dominates in total flux. Its amount strongly depends on storms and river run-off. Suspended particle material differs from surface shelf sediments by finer particles (mainly clay fraction) and high content of clay minerals and biogenic silica. This material may form lateral fluxes with higher concentration of particles transported along the bottom of deep-sea canyons from the shelf to the deep basin within the nepheloid layer. In winter such transportation of sedimentary material is more intensive due to active vertical circulation of water masses.

Major-oxides and trace-elements at DSDP Hole 78-543A

Four chemically distinct basalts were cored in 44 m of basement penetration at Deep Sea Drilling Project Site 543, in Upper Cretaceous crust just seaward of the deformation front of the Barbados Ridge and north of the Tiburon Rise. All four types are moderately fractionated abyssal tholeiites. The four types have different magnetic inclinations, all of reversed polarity, suggesting eruption at different times which recorded secular variation of the earth's magnetic field. Extensive replacement of Plagioclase by K-feldspar has occurred at the top of the basalts, giving analyses with K2O contents up to 5 %. The earliest stages of alteration were dominantly oxidative, resulting in fractures lined with celadonite and dioctahedral smectite, and pervasive replacement of olivine and most intersertal glass with iron hydroxides and green clay minerals. Latef, non-oxidative alteration resulted in formation of olive-green clays and pyrite veins in a portion of the rocks. Basalts affected by this alteration actually lost K2O (to abundances lower than in adjacent fresh basalt glasses), and gained MgO (to abundances higher than in the glasses). Finally, fractures and interpillow voids were lined with calcite, sealing in much fresh glass. Oxygen-isotope measurements on the calcite indicate that this occurred at 12 to 25C. Either altering fluids were warm or the basalts had become buried with a considerable thickness of sediments, such that temperatures increased until a conductive thermal gradient was established, when the veining occurred.

Chemical and isotopic compositions of rocks and minerals from the Palenyi Island, Por'ya Guba (Bay), White Sea

Hypersthene-garnet-sillimanite-quartz enclaves were studied in orthopyroxene-plagioclase and orthopyroxene-clinopyroxene crystalline schists and gneisses from shear zones exposed in the Palenyi Island within the Early Proterozoic Belomorian Mobile Belt. Qualitative analysis of mineral assemblages indicates that these rocks were metamorphosed to the granulite facies (approximately 900°C and 10-11 kbar). Oxygen isotopic composition was determined in rock-forming minerals composing zones of the enclaves of various mineral and chemical composition. Closure temperatures of the isotopic systems obtained by methods of oxygen isotopic thermometry are close to values obtained with mineralogical geothermometers (garnet-orthopyroxene and garnet-biotite) and correspond to the high-temperature granulite facies (860-900°C). Identified systematic variations in d18O values were determined in the same minerals from zones of different mineral composition. Inasmuch as these zones are practically in contact with one another, these variations in d18O cannot be explained by primary isotopic heterogeneity of the protolith. Model calculations of the extent and trend of d18O variations in minerals suggest that fluid-rock interaction at various integral fluid/rock ratios in discrete zones was the only mechanism that could generate the zoning. This demonstrates that focused fluid flux could occur in lower crustal shear zones. Preservation of high-temperature isotopic equilibria of minerals testifies that the episode of fluid activity at the peak of metamorphism was very brief.

Petrology and geochemistry of the Izu-Bonin Forearc tephras

Numerous marine tephra layers cored at Sites 792 and 793 in the Izu-Bonin forearc region offer additional information about the timing and spatial characteristics of arc volcanism and the evolution of island arcs. Explosive volcanism along the Izu-Bonin Arc, with maxima just before rifting of the arc at ~40 and 5-0 Ma, produced black and white tephras of variable grain sizes and chemical compositions. Most of the tephras belong chemically to low-K and low-alkali tholeiitic rock series with a few tephra of the high-K and alkalic rock series. Most of the tephras (low-K series) were derived from the Izu-Bonin Arc, although a few were produced far to the west of the Izu-Bonin Arc (e.g., from the Ryukyu Arc). Black tephras may have come from nearby sources, such as Aogashima, Sumisu, and Torishima islands. The high-K series of tephras, within the sediments younger than 3 Ma, may reflect thickening of the island-arc crust.

Geochemistry of lavas from the Lau-Tonga arc and back-arc system

Detailed comparison of mineralogy, and major and trace geochemistry are presented for the modern Lau Basin spreading centers, the Sites 834-839 lavas, the modern Tonga-Kermadec arc volcanics, the northern Tongan boninites, and the Lau Ridge volcanics. The data clearly confirm the variations from near normal mid-ocean-ridge basalt (N-MORB) chemistries (e.g., Site 834, Central Lau Spreading Center) to strongly arc-like (e.g., Site 839, Valu Fa), the latter closely comparable to the modern arc volcanoes. Sites 835 and 836 and the East Lau Spreading Center represent transitional chemistries. Bulk compositions range from andesitic to basaltic, but lavas from Sites 834 and 836 and the Central Lau Spreading Center extend toward more silica-undersaturated compositions. The Valu Fa and modern Tonga-Kermadec arc lavas, in contrast, are dominated by basaltic andesites. The phenocryst and groundmass mineralogies show the strong arc-like affinities of the Site 839 lavas, which are also characterized by the existence of very magnesian olivines (up to Fo90-92) and Cr-rich spinels in Units 3 and 6, and highly anorthitic plagioclases in Units 2 and 9. The regional patterns of mineralogical and geochemical variations are interpreted in terms of two competing processes affecting the inferred magma sources: (1) mantle depletion processes, caused by previous melt extractions linked to backarc magmatism, and (2) enrichment in large-ion-lithophile elements, caused by a subduction contribution. A general trend of increasing depletion is inferred both eastward across the Lau Basin toward the modern arc, and northward along the Tongan (and Kermadec) Arc. Numerical modeling suggests that multistage magma extraction can explain the low abundances (relative to N-MORB) of elements such as Nb, Ta, and Ti, known to be characteristic of island arc magmas. It is further suggested that a subduction jump following prolonged slab rollback could account for the initiation of the Lau Basin opening, plausibly allowing a later influx of new mantle, as required by the recognition of a two-stage opening of the Lau Basin.

Geochemical composition and granulometry of ODP Hole 167-1017E sediments

Intensification of North Pacific Intermediate Water during the Younger Dryas and stadials of the last glacial episode has been advocated by Kennett and his colleagues based on studies of ventilation history in Santa Barbara Basin. Because Santa Barbara Basin is a semi-isolated marginal basin, this hypothesis requires testing in sequences on the upper continental margin facing the open-ocean of the Pacific. Ocean Drilling Program Site 1017 is located on the upper slope of southern California off Point Conception close to the entrance of Santa Barbara Basin, an ideal location to test the hypothesis of late Quaternary switching in intermediate waters. We examined chemical and mineral composition, sedimentary structures, and grain size of hemipelagic sediments representing the last 80 k.y. at this site to detect changes in behavior of intermediate waters. We describe distinct compositional and textual variations that appear to reflect changes in grain size in response to flow velocity fluctuations of bottom waters. Qualitative estimates of changes in degree of pyritization indicate better ventilation of bottom water during intervals of stronger bottom-water flow. Comparison between variations in the sediment parameters and the planktonic d18O record indicates intensified bottom-current activity during the Younger Dryas and stadials of marine isotope Stage 3. This result strongly supports the hypothesis of Kennett and his colleagues. Our investigation also suggests strong grain-size control on organic carbon content (and to less extent carbonate carbon content). This, in turn, suggests the possibility that organic carbon content of sediments, which is commonly used as an indicator of surface productivity, can be influenced by bottom currents.

Chemical composition of iron-manganese and phosphate rocks from aseismic ridges of the Indian Ocean and from the continental slope of the Southeast Africa

Study of chemical composition of 26 samples collected at depths from 400 to 1400 m on vertex surfaces of the Southeast Indian Ridge, Mascarene Ridge, Madagascar Ridge, and Mozambique Ridge, as well as on the upper part of the Southeast Africa continental slope showed that the samples represent three groups of rocks: 1) low phosphate or phosphate-free ferromanganese rocks, 2) phosphate ferromanganese rocks 3) phosphorites and phosphatized limestones.

Pebbles and carbonate nodules Legs 56-57 Holes

At all DSDP Leg 56 drilling sites, exotic pebbles occur commonly, throughout the cores. Chips of carbonate nodules occur only at Site 434 on the lower inner trench wall. Both exotic pebbles and carbonate nodule chips sometimes tend to be concentrated at particular levels of cores. Exotic pebbles are generally well rounded and consist of various rock types, such as dacite, andesite, basalt, tuff, gabbro, granodiorite, metaquartzite, biotite hornfels, lithic wacke, mudstone, etc., of which dacite occurs commonly at all the sites. Almost all pebbles at Site 436 and most at Sites 434 and 435 may have been rafted by ice. Some at the latter sites may have been derived by down-slope slumping. Carbonate nodules consist of microcrystalline dolomite, manganoan calcite, and siderite; CaCO3 content ranges from 22 to 65 per cent. They are also generally characterized by a high content of P2O5. The nodules are commonly rich in diatom remains, some of which indicate that the nodules are autochthonous. Some nodules contain abundant glass shards, with a modal refractive index of 1.499, almost identical to shards in the surrounding mud and ooze. These facts suggest that the carbonate nodules may have been formed diagenetically, in situ. This may throw light on problems of the formation of carbonate nodules in ancient "geosynclinal" sediments. It is also very important to point out that these carbonate nodules were formed within sediment deposited well below the CCD.

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.