Inorganic and organic geochemistry and sediment descriptions at DSDP Hole 93-603B

About one hundred samples of sediments and rocks recovered in Hole 603B were analyzed for type, abundance, and isotopic composition of organic matter, using a combination of Rock-Eval pyrolysis, C-H-N-S elemental analysis, and isotope-ratio mass spectrometry. Concentrations of major, minor, and trace inorganic elements were determined with a combination of X-ray fluorescence and induction-coupled plasma spectrometry. The oldest strata recovered in Hole 603B (lithologic Unit V) consist of interbedded light-colored limestones and marlstones, and black calcareous claystones of Neocomian age. The inorganic and organic geochemical results suggest a very terrigenous aspect to the black claystones. The organic geochemical results indicate that the limestones and marlstones contain a mixture of highly degraded marine and terrestrial organic matter. Comparison of the Neocomian carbonates at Site 603 with those on the other side of the North Atlantic, off Northwest Africa at Site 367, shows that the organic matter at Site 367 contains more marine organic matter, as indicated by higher pyrolysis hydrogen indices and lighter values of d13C. Comparison of inorganic geochemical results for the carbonate lithologies at Site 603 with those for carbonate lithologies at Site 367 suggests that the Site 603 carbonates may contain clastic material from both North American and African sources. The black claystones at Site 603, on the other hand, probably were derived almost entirely from North American clastic sources. Lithologic Unit IV overlying the Neocomian carbonates, consists of interbedded red, green, and black claystones. The black claystones at Site 603 contain more than ten times the organic carbon concentration of the interbedded green claystones. The average concentration of organic carbon in the black claystones (2.8%), however, is low relative to most mid-Cretaceous black claystones and shales in the Atlantic, particularly those found off Northwest Africa. The geochemical data all suggest that the organic matter in the black claystones is more abundant but generally more degraded than the organic matter in the green claystones, and that it was derived mainly from terrestrial sources and deposited in oxygenated bottom waters. The increased percentage of black claystone beds in the upper Cenomanian section, and the presence of more hydrogen-rich organic matter in this part of the section, probably resulted from the increased production and accumulation of marine organic matter that is represented worldwide near the Cenomanian/Turonian boundary in deep-sea and land sections. A few upper Cenomanian black claystone samples that have hydrogen indices > 150 also contain particularly high concentrations of V and Zn. Most samples of black claystone, however, are not particularly metal-rich compared with other black claystones and shales. Compared with red claystones from lithologic Unit IV, the green and black claystones are enriched in many trace transition elements, especially V, Zn, Cu, Co, and Pb. The main difference between the "carbonaceous" claystones of lithologic Unit IV and "variegated" or "multicolored" claystones of the overlying Upper Cretaceous to lower Tertiary Unit III is the absence of black claystone beds. As observed at several other sites (105 and 386), the multicolored claystones at Site 603 are somewhat enriched in several trace transition elements-especially Cu, Ni, and Cr-relative to most deep-sea clays. The multicolored claystones are not enriched in Fe and Mn, and therefore are not "metalliferous" sediments in the sense of those found at several locations in the eastern Pacific. The source of the slightly elevated concentrations of transition metals in the multicolored claystones probably is upward advection and diffusion of metals from the black claystones of the underlying Hatteras Formation. The red, orange, and green claystone beds of lithologic Unit II (Eocene), like those of Unit III, really represent a continuation of deposition of multicolored claystone that began after the deposition of the Neocomian carbonates. The color of the few black beds that occur within this unit results from high concentrations of manganese oxide rather than high concentrations of organic matter.

Geochemistry and fluxes at DSDP Hole 83-504B

This chapter documents the chemical changes produced by hydrothermal alteration of basalts drilled on Leg 83, in Hole 504B. It interprets these chemical changes in terms of mineralogical changes and alteration processes and discusses implications for geochemical cycling. Alteration of Leg 83 basalts is characterized by nonequilibrium and is heterogeneous on a scale of centimeters to tens or hundreds of meters. The basalts exhibit trends toward losses of SiO2, CaO, TiO2; decreases in density; gains of MnO, Na2O, CO2, H2O+ , S; slight gains of MgO; increased oxidation of Fe; and variable changes in A12O3. Some mobility of rare earth elements (REE) also occurred, especially the light REE and Eu. The basalts have lost Ca in excess of Mg + Na gains. Variations in chemical trends are due to differing water/rock ratios, substrate control of secondary mineralogy, and superimposition of greenschist and zeolite facies mineralogies. Zeolitization resulted in uptake of Ca and H2O and losses of Si, Al, and Na. These effects are different from the Na uptake observed in other altered basalts from the seafloor attributed to the zeolite facies and are probably due to higher temperatures of alteration of Leg 83 basalts. Basalts from the transition zone are enriched in Mn, S, and CO2 relative to the pillow and dike sections and contain a metal-sulfide-rich stockwork zone, suggesting that they once were located within or near a hydrothermal upflow zone. Samples from the bottom of the dike section are extensively fractured and recrystallized indicating that alteration was significantly affected by local variations in permeability.

Geochemistry and minerals of glass shards at DSDP Leg 66 Holes

Deep Sea Drilling Project Leg 66 drilled eight sites along a transect across the Middle America Trench off Mexico, including continental (Sites 493 and 489), oceanic (Site 487), and trench (Site 486) reference sites and four sites (490, 492, 491, 488) in the trench inner wall. Because of their location - close to volcanic sources and subject to prevailing winds and marine currents (N to S, NW to SE) - analysis of airborne ashes intercalated within the sediments at these sites provides a reliable record of explosive volcanism in the area. Intense onshore volcanic activity in Mexico during the Oligo-Miocene has been well documented by the andesites and ignimbrites of the Sierra Madre Occidental and Sierra Madre del Sur and in the Plio-Quaternary by the andesites and basalts from the Trans-Mexican Neovolcanic Belt and the eastern border of Baja California.

Geochemical and isotopic composition of basalts from the axial Mid-Atlantic Ridge, South Atlantic

One of the essential problems of oceanic tectonics is estimation of the influence of plumes of the deep hot mantle on processes in the axial spreading zone. Areas of two giant (St. Helena and Tristan da Cunha) plumes in the Mid-Atlantic Ridge (MAR) rift zone (South Atlantic) are characterized by the effusion of basalts that differ from typical depleted riftogenic tholeiites by anomalously high contents of lithophile components and specific isotopic compositions. Moreover, the rift valley floor with basalt effusion is significantly uplifted above the adjacent sectors of the rift. The formation of the St. Helena Seamount located 400 km east of the MAR axis is related to magmatism that is active to this day. St. Helena Island is a member of the structural ensemble of large volcanic seamounts (Bonaparte, Bagration, and Kutuzov). Like St. Helena Island, each seamount incorporates a series of smaller rises of different morphologies and dimensions. Thus, a system of subparallel series of NE-trending (~45°) rises extend from the seamount ensemble to the African continent. According to the plate tectonics concept, the seamount series represent hotspots related to a deep mantle plume that can be projected onto the present-day St. Helena Island area (St. Helena plume). At the same time, the inferred topographic map based on satellite altimetry data shows that the seamount series also extend along the opposite southwestern direction (~225°) toward the axial MAR and even intersect the latter structure. This fact cannot be explained by the hotspot hypothesis, which suggests stationary positions of plumes relative to the mobile oceanic plate. In the course of Cruise 10 of the R/V Akademik Ioffe (2002), detailed geological and geophysical investigations were carried out at the junction of one structural series with the MAR rift zone located near the Martin Vaz Fracture Zone (Martin Vaz test area, 19°-20° S). The present communication is devoted to the study of lithology, geochemistry, and isotopy of basalts dredged at the test area.

Composition of Holocene lithificates at the slopes of the Untersee Mountain Valley, East Antarctica

It was found out that the lower parts of slopes of the Untersee mountain valley (East Antarctica) were locally covered with lithificates (both carbonate-free and carbonate-poor). They occur in three modes: crusts, films, and impregnates. All of them cover Late Pleistocene moraine material and consist of mixture of lacustrine sedimentary material and filling material of moraines. A mechanism of their genesis is offered.

Chemistry of serpentinized peridotites from ODP Hole 109-670A

In this paper we describe textural relationships in hydrated upper mantle peridotites emplaced at a nonconstructive ridge segment. Development of serpentinites and partially serpentinized peridotites takes place in four main stages: (1) pervasive serpentinization forming mainly lizardite, (2) a tensional stage forming chrysotile + talc + chlorite, (3) a deformational stage forming antigorite + tremolite, and (4) a late local tensional stage forming another generation of chrysotile veinlets. Mineral chemistry of serpentine pseudomorphs reflects in part primary mineral compositions. Olivine pseudomorphs are typically nickeliferous and depleted in aluminum and chromium. Orthopyroxene pseudomorphs have lower nickel contents and relatively high iron, aluminum, and chromium contents. Clinopyroxene pseudomorphs have very low nickel contents and relatively high aluminum and chromium contents. These chemical patterns in the serpentinites can be used to help discriminate between harzburgitic and lherzolitic protoliths. Oxygen isotopes and mineral parageneses suggest serpentine is derived from circulation of hydrothermal (200?C) fluids through the peridotite body. Crystallization of tremolite, talc, and chlorite may have occurred at temperatures up to 525?C if C02/H20 ratios were less than 0.25. Open fissures developing in aging upper mantle provide paths for important seawater circulation through a thin basaltic carapace down to shallow mantle rocks.

Geochemistry of ODP Site 123-765 sediments

Drilling at Site 765 in the Argo Abyssal Plain sampled sediments and oceanic crust adjacent to the Australian margin. Some day, this site will be consumed in the Java Trench. An intensive analytical program was conducted to establish this site as a geochemical reference section forcrustal recycling calculations. About 150 sediment samples from Site 765 were analyzed for major and trace elements. Downhole trends in the sediment analyses agree well with trends in sediment mineralogy, as well as in Al and K logs. The primary signal in the geochemical variability is dilution of a detrital component by both biogenic silica and calcium carbonate. Although significant variations in the nonbiogenic component occur through time, its overall character is similar to nearby Canning Basin shales, which are typical of average post-Archean Australian shales (PAAS). The bulk composition of the hole is calculated using core descriptions to weight the analyses appropriately. However, a remarkably accurate estimate of the bulk composition of the hole can be made simply from PAAS and the average calcium carbonate and aluminum contents of the hole. Most elements can be estimated within 30% in this way. This means that estimating the bulk composition of other sections dominated by detrital and biogenic components may require little analytical effort: calcium carbonate contents, average Al contents, and average shale values can be taken from core descriptions, geochemical logs, and the literature, respectively. Some of the geochemical systematics developed at Site 765 can be extrapolated along the entire Sunda Trench. However, results are general, and Site 765 should serve as a useful reference for estimating the compositions of other continental margin sections approaching trenches around the world (e.g., outboard of the Lesser Antilles, Aegean, and Eolian arcs).

Inorganic major, minor, and trace element geochemistry and clay mineralogy of sediments from the Deep Sea Drilling Project Leg 96, Gulf of Mexico

Sediment samples collected at DSDP Leg 96 Mississippi Fan Sites 615, 616, 620, 621, and 623, Orca Basin Site 618, and Pigmy Basin Site 619 were analyzed for 22 major, minor, and trace elements. This study was undertaken to document the downhole variability in inorganic geochemistry between sites. The mineralogy of the clays, including those from Sites 614, 617, and 622 on the fan, was determined by X-ray diffraction to define the principal clay minerals present at the sites, examine any downhole trends in clay mineralogy, and aid in the interpretation of the geochemical signature of the sediments. Clay mineral composition at all the sites is smectite:illite:chlorite:kaolinite in the approximate percentage ratio 50:20:20:10. Geochemical results indicate only slight variation between and within the sites, with the exception of a discrete unit of carbonates that occurs near the bottom of Site 615. Variation in the major, minor, and trace element composition can be explained by a change in the relative abundance of quartz, clay minerals, and carbonates.

Geochemical compositions of minerals from chilled dike margins of ODP Hole 140-504B

Mineral and whole-rock geochemical data are presented for chilled dike margins from the lower sheeted dike complex of Deep Sea Drilling Project/Ocean Drilling Program (DSDP/ODP) Hole 504B. Compositions of phenocrystic plagioclase (An80-89); olivine (Fo82-86); clinopyroxene (Wo52En40Fs8, with Cr2O3 up to 1.2%); and rare chromian spinel (Cr# 43) are consistent with those from the lavas and the upper dike complex recovered previously (DSDP Legs 69, 70, 83, and ODP Leg 111). Major and trace element compositions fall in group D of Autio and Rhodes (1983) and have high CaO/Na2O, and low TiO2, K2O, and (La/Sm)N values consistent with previous analyses from this site.

Chemical composition of sediments from DSDP Legs 45 and 71

Results of mineralogical and geochemical investigations of post-Middle Jurassic deposits of the Atlantic Ocean are based on materials of the Deep Sea Drilling Project. Comparative characteristics of primary matter for ''black shales'' are given. Exhalative origin of heavy metal accumulation in near-axial sedimentary deeps of the Mid-Atlantic Ridge (23°N) are shown. History of post-Middle Jurassic sedimentation is considered on the base of clay mineral-, clastic component-, trace and rare- chemical element studies.

Geochemistry data from the Toupugol volcanogenic complex

A large fragment of a paleovolcano of Silurian to Early Devonian age was discovered in the Voikar volcanic belt suggesting an ensimatic island are as its geodynamic environment. Formationally, the rocks under study are comparable to Pleistocene island arc volcanites and their paleo-analogues. The volcanites of the Toupugol complex underwent strong hydrothermal-metasomatic alteration: propylites, acid metasomatic rocks and quartz-carbonate veins, which must have resulted from hydrothermal-metasomatic alteration of andesitoids. Both volcanites and apovolcanic hydrothermal rocks in Toupugol were found to host noble metal mineralisation. It is found in close association with sulphides, particularly pyrite. Free gold was discovered in all investigated volcanites and hydrothermal rocks and is characterised by low mercury content and an unusual set of microimpurities (Pt, Pd, Cu, Fe, S) suggesting its links to the mantle substrate.

Mineralogy and textures of gabbros from ODP Hole 118-735B

Abundant iron-titanium (Fe-Ti) oxide gabbro, olivine gabbro, and troctolite were drilled at Hole 735B adjacent to the Atlantis II Fracture Zone of the Southwest Indian Ridge during Leg 118. The Fe-Ti oxide gabbro occurs as intrusive bodies into olivine gabbro with very sharp intrusive contacts. The size of the intrusive bodies varies from a millimeter to a few tens of meters. Mineralogical parameters, such as anorthite content of plagioclase and Mg/(Mg+Fe) ratios of mafic minerals exhibit bimodal distributions corresponding to olivine and Fe-Ti oxide gabbros, respectively. When the two major gabbro types are looked at separately, several downhole mineralogical cycles are recognized. The Fe-Ti oxide gabbros exhibit two such cycles with plagioclase becoming more sodic and mafic minerals becoming more iron-rich downward in the drill core. The olivine gabbros and troctolites, however, exhibit two cycles showing an upward increase in sodium in plagioclase and iron in mafic minerals. The mineralogical variations of these gabbros and the intrusive contact relationships probably resulted from downward intrusion of evolved magma into underlying solid or almost solidified olivine gabbros and troctolite. The dense evolved melt at the top of the cumulus pile probably formed from the crystallization of olivine gabbro cumulates followed by extreme fractional crystallization of residual melt in an isolated, ephemeral magma chamber. The interlayered occurrence of evolved and primitive gabbros from Hole 735B represents a typical section of lower ocean crust formed at a very slow spreading ridge.

Composition of standard reference samples of Fe-Mn nodules and bottom sediments

The first series of Soviet standard reference samples of composition of ore materials and ocean pelagic sediments has been created. It includes iron-manganese nodules (SDO-4, SDO-5 and SDO-6), ore crusts (SDO-7) diatomaceous ooze (SDO-8), and deep-sea red clays (SDO-9). The standards are intended to serve as a metrologic basis for physical, physicochemical and chemical analyses of iron-manganese minerals and ocean sediments. The standards are provided with certified analyses of rock-forming components and certain trace elements. Certified characteristics are based on statistical analysis of data obtained from an inter-laboratory experiment involving analysis of the standard reference samples by a variety of methods.

Geochemistry and oxidation state of Lau Basin basalts

The backarc glasses recovered during Ocean Drilling Program Leg 135 are unique among submarine tholeiitic glasses with respect to their oxygen fugacity and sulfur concentrations. Unlike mid-ocean-ridge basalt glasses, fO2 in these samples (inferred from ratios Fe3+/Fe2+) is high and variable, and S variations (90-1140 ppm) are not coupled with FeO concentration. Strong correlations occur between the alkali and alkaline-earth elements and both fO2 (positive correlations) and S concentrations (negative correlations). Correlations between fO2 and various trace elements are strongest for those elements with a known affinity for hydrous fluids (perhaps produced during slab dehydration), suggesting the presence of a hydrous fluid with high fO2 and high alkali and alkaline earth element concentrations in the Lau Basin mantle. Concentrations of S and fO2 are strongly correlated; high fO2 samples are characterized by low S in addition to high alkali and alkaline earth element concentrations. The negative correlations between S and these trace elements are not consistent with incompatible behavior of S during crystallization. Mass balance considerations indicate that the S concentrations cannot result simply from mixing between low-S and high-S sources. Furthermore, there is no relationship between S and other trace elements or isotope ratios that might indicate that the S variations reflect mixing processes. The S variations more likely reflect the fact that when silicate coexists with an S-rich vapor phase the solubility of S in the silicate melt is a function of fO2 and is at a minimum at the fO2 conditions recorded by these glasses. The absence of Fe-sulfides and the high and variable vesicle contents are consistent with the idea that S concentrations reflect silicate-vapor equilibria rather than silicate-sulfide equilibria (as in MORB). The low S contents of some samples, therefore, reflect the high fO2 of the supra-subduction zone environment rather than a low-S source component.

Geochemistry of basal dolomitic and Fe-Mn sediments from the Tyrrhenian Sea

In the Tyrrhenian Sea (Western Mediterranean), unusual reddish, soft to lithified, dolomitic sediments up to 45 m thick overlie igneous crust at the base of thick Pliocene-Quaternary deep-sea sediment successions in the Marsili (Site 650) and Vavilov (Site 651) basins. These sediments also overlie the Gortani Ridge, a basaltic Seamount near the base of the Sardinian continental margin (Site 655). At both basinal sites (650, 651), the lowest sediments are dolomitic, with manganese oxide (MnO) segregations. Whole-rock X-ray diffraction indicates abundant dolomite and quartz, with subordinate calcite, illite (authigenic), feldspar and minor kaolinite, chlorite, and anhydrite. Chemical analyses show strong enrichment in magnesium oxide (MgO) and MnO relative to shale or deep-sea clay. Mg and Mn correlate positively and exhibit decreasing concentrations up the succession in the Marsili Basin (Site 650). The following scenario is proposed: peridotites were exposed on the seafloor in the Vavilov Basin (Site 651) and then eroded, depositing talc in local fine-grained dolomitic sediments within the igneous basement. After local magmatism ended, the igneous basement at each site subsided rapidly (about 800 m/m.y.) and was blanketed with calcareous and clay-rich oozes. During early diagenesis (from isotopic evidence; McKenzie et al., this volume) tepid fluids, of modified seawater composition, reacted with and dolomitized the overlying deep-sea sediments. At Site 651 additional Mg may have been extracted from asthenosphere peridotite cored at shallow depths (about 100 m). One can hypothesize that fluids rich in Mg and Mn were flushed from the igneous basement, triggered by extensional faulting and local tilting during subsidence of the basement, and that these fluids then dolomitized the base of the overlying sediment succession. Late tectonic movements in the Vavilov Basin (Site 651) fractured already lithified dolomitic sediments and more reducing (? hydrothermal) fluids locally remobilized Fe and Mn and corroded dolomite crystals.