Geochemistry of Neogene-Quaternary sediments in ODP Site 105-645

Subcontinuously cored early(?)-middle Miocene to recently deposited sediments from ODP Site 645 were studied texturally, mineralogically, and geochemically. The entire sequence contains minerals and associated chemical elements that are chiefly of detrital origin. In particular, the clay minerals, which include smectite, kaolinite, chlorite, and illite, are detrital. No obvious evidence of diagenesis with depth, of burial, of volcanism, or of hydrothermal alteration was observed. The sedimentary textures, clay mineralogy, and <2-µm fraction geochemistry of the early middle Miocene sediments (630 to 1147 mbsf) suggest the pronounced but variable influence of a southward bottom current. Two clay facies are defined. The lower one, Cj (780 to 1147 mbsf), is characterized by the great abundance of discrete smectite (with less than 15% illite interlayers), probably detrital in origin, and reworked older, discrete, smectite-rich sediments. The upper clay facies, C2 (630 to 780 mbsf), shows a net decrease of the fully expandable clay abundances, with a great abundance of mixed-layer, illite-smectite clays (60 to 80% of illite interlayers). Such clay assemblages can be inherited from paleosoils or older sedimentary rocks. An important change occurs at 630 mbsf (clay fraction) or 600 mbsf (sedimentary texture), which may be explained by the beginning of continental glaciation (630 mbsf, ~9 Ma) and the onset of ice rafting in Baffin Bay (600 mbsf, ~8 Ma). Above this level, the characteristics and modifications of the clay assemblages are controlled climatically and can be explained by the fluctuations of (1) ice-rafting, (2) speed of weak bottom currents, and (3) some supply by mud turbiditic currents. Three clay facies (C3, C4, and C5) can be defined by the abrupt increases of the inherited chlorite and illite clays.

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.

Mineralogy of ODP Site 105-645

Cores from the upper 70 meters below seafloor (mbsf) (upper Pleistocene) at Ocean Drilling Program (ODP) Site 645 in Baffin Bay show dramatic meter-scale changes in color and mineralogy. Below this interval, mineralogical changes are more gradual to the top of the Miocene at about 550 mbsf. The Pliocene-Pleistocene section can be divided into five facies: Facies 1 - massive, poorly sorted, gravel-bearing muds; Facies 2 - gray silty clays and silty muds; Facies 3 - laminated detricarbonate silty muds; Facies 4 - silty sand and sandy silt; and Facies 5 - poorly sorted muddy sands and silty muds. Facies 4 and 5 are restricted to the Pliocene section below depths of about 275 mbsf. The mineralogical/color cycles in the upper 70 mbsf are the result of alternations between Facies 2 and three lithotypes of Facies 1: lithotype A - tan-colored, carbonate-rich, gravel-bearing mud; lithotype B - weak, red-colored, gravel-bearing mud rich in sedimentary rock fragments; and lithotype C - gray, gravel-bearing mud. A fourth lithotype, D, is restricted to depths of 168-275 mbsf and is dark gray, carbonate-poor, gravel-bearing mud. We believe that all lithotypes of Facies 1 and the sand and gravel fractions of Facies 2 and 3 were deposited by ice rafting. Depositional processes for Facies 4 and 5 probably include ice rafting and bottom- and turbidity-current transport. Data from petrographic analyses of light and heavy sand-sized grains and X-ray analyses of silt- and clay-size fractions suggest that tan-colored sediments (lithotype A of Facies 1; Facies 3) were derived mainly from Paleozoic carbonates of Ellesmere, Devon, and northern Baffin islands. Weak red sediments (lithotype B) contain significant red sedimentary clasts, reworked quartzarenite grains and clasts, and rounded colorless garnets, all derived from Proterozoic sequences of the Borden and Thule basins, and from minor Mesozoic red beds. Other sediments in the upper 335 mbsf at Site 645 contain detritus from a heterogeneous mixture of sources, including Precambrian shield terranes around Baffin Bay. Sediments from 335 to 550 mbsf (Facies 5) are rich in friable sedimentary clasts and detrital micas and contain glauconite and, in a few samples, reworked diatoms. These components suggest derivation from poorly consolidated Mesozoic-Tertiary sediments in coastal outcrops and beneath the modern shelves of northeastern Baffin Island and western Greenland. For the upper Pleistocene section (about 0-100 mbsf), marked mineralogical cyclicity is attributed to fluctuating glacial margins, calving rates, and iceberg melting rates, particularly around the northern end of Baffin Bay. Tan-colored, carbonate-rich units were derived at times of maximum advance of glaciers on Ellesmere and Devon islands, during relatively warm intervals induced by incursion of warm Atlantic surface water into the bay. At the beginning of these warmer episodes, most icebergs were contributed by glaciers near sea level around the Arctic channels, which resulted in deposition of weak red, ice-rafted units rich in Proterozoic sedimentary clasts.

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.

Concentrations of As and other chemical elements in bottom sediments of the Baltic Sea

As is less toxic than Hg, Cd, Pb, Se, Zn, and Cu. The As clarke for clays and shales is 10 ppm. Our samples of bottom sediments from Kurshskii Bay were determined to contain from 15 to 26 ppm As and up to 34 ppm As in the vicinity of the Neman River mouth. Elevated As concentrations (50-114 ppm) were detected in four columns of subsurface bottom sediments (at depths of 10-65 cm) from the Vistula Lagoon. Elevated As concentrations (50-180 ppm) were also found in a few surface samples of sand from the Gdansk Deep near oil platform D-6. These sediments are either partly contaminated with anthropogenic As or contain Fe sulfides and glauconite, which can concentrate As and contain its elevated concentrations. The As concentration in columns of bottom sediments from the Gulf of Finland were at the natural background level (throughout the columns) typical of the area (9-34 ppm). We repeatedly detected very high As concentrations (up to 227 ppm As) in politic ooze from Bornholm Deep, in the vicinity of the sunken vessel with chemical weapons. The sources of elevated As concentrations in the Baltic Sea are the following: (1) chemical weapon (CW) material buried in the floor of the Baltic Sea; (2) As-bearing pesticides, agricultural mineral fertilizers, and burned coal and other fuels; (3) kerogen-bearing Ordovician rocks exposed on the bottom; and (4) As-rich Fe sulfides brought to the area together with construction sand and gravel. This mixture was used in paper production and for the construction of hydraulic engineering facilities in the Vistula Lagoon in the early 20th century and later caused the so-called lagoon disease.

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.

Concentrations and accumulation rates of platinum-group elements and rhenium in Pacific and Atlantic sediments, DSDP and ODP data

The nature of Re-platinum-group element (PGE; Pt, Pd, Ir, Os, Ru) transport in the marine environment was investigated by means of marine sediments at and across the Cretaceous-Tertiary boundary (KTB) at two hemipelagic sites in Europe and two pelagic sites in the North and South Pacific. A traverse across the KTB in the South Pacific pelagic clay core found elevated levels of Re, Pt, Ir, Os, and Ru, each of which is approximately symmetrically distributed over a distance of ~1.8 m across the KTB. The Re-PGE abundance patterns are fractionated from chondritic relative abundances: Ru, Pt, Pd, and Re contents are slightly subchondritic relative to Ir, and Os is depleted by ~95% relative to chondritic Ir proportions. A similar depletion in Os (~90%) was found in a sample of the pelagic KTB in the North Pacific, but it is enriched in Ru, Pt, Pd, and Re relative to Ir. The two hemipelagic KTB clays have near-chondritic abundance patterns. The ~1.8-m-wide Re-PGE peak in the pelagic South Pacific section cannot be reconciled with the fallout of a single impactor, indicating that postdepositional redistribution has occurred. The elemental profiles appear to fit diffusion profiles, although bioturbation could have also played a role. If diffusion had occurred over ~65 Ma, the effective diffusivities are ~10**?13 cm**2/s, much smaller than that of soluble cations in pore waters (~10**?6 cm**2/s). The coupling of Re and the PGEs during redistribution indicates that postdepositional processes did not significantly fractionate their relative abundances. If redistribution was caused by diffusion, then the effective diffusivities are the same. Fractionation of Os from Ir during the KTB interval must therefore have occurred during aqueous transport in the marine environment. Distinctly subchondritic Os/Ir ratios throughout the Cenozoic in the South Pacific core further suggest that fractionation of Os from Ir in the marine environment is a general process throughout geologic time because most of the inputs of Os and Ir into the ocean have Os/Ir ratios >/=1. Mass balance calculations show that Os and Re burial fluxes in pelagic sediments account for only a small fraction of the riverine Os (<10%) and Re (<0.1%) inputs into the oceans. In contrast, burial of Ir in pelagic sediments is similar to the riverine Ir input, indicating that pelagic sediments are a much larger repository for Ir than for Os and Re. If all of the missing Os and Re is assumed to reside in anoxic sediments in oceanic margins, the calculated burial fluxes in anoxic sediments are similar to observed burial fluxes. However, putting all of the missing Os and Re into estuarine sediments would require high concentrations to balance the riverine input and would also fail to explain the depletion of Os at pelagic KTB sites, where at most ~25% of the K-T impactor's Os could have passed through estuaries. If Os is preferentially sequestered in anoxic marine environments, it follows that the Os/Ir ratio of pelagic sediments should be sensitive to changes in the rates of anoxic sediment deposition. There is thus a clear fractionation of Os and Re from Ir in precipitation out of sea water in pelagic sections. Accordingly, it is inferred here that Re and Os are removed from sea water in anoxic marine depositional regimes.

Chemical composition of sediments from DSDP Hole 149

The diagenesis and geochemical evolution of deep-sea sediments are controlled by the interaction between sediments and their associated pore waters. With increasing depth, the pore water of Hole 149 (DSDP) exhibits a strong depletion in Mg and a corresponding enrichment in Ca, while the alkalinity remains relatively constant. Dissolved SiO2 is nearly constant in the upper 100 m of sediment, but is highly enriched in the deepest pore waters. The pore waters exhibit a depletion in K with increasing depth, and O18/O16 pore water ratios also decrease. The sediment section has three zones of sedimentary regimes with increasing depth in the drill hole: an upper 100 m section of detrital clays, a middle section enriched in calc-akalic volcanics which have undergone submarine weathering to a smectite phase, and a lower section of siliceous ooze which still has a diagenetic smectite phase. The quartz-feldspar ratios and O18/O16 composition of the silicate phases are in agreement with these interpretations. The submarine weathering of volcanics to a smectite can account for the observed pore water gradients. Volcanics release Ca and Mg to the pore waters causing the alkalinity values to increase. Smectite is formed, depletes the pore waters in Mg and O18 and causes the alkalinity to decrease. The net reaction allows for the observed relationship between pore water Ca and Mg gradients with little net change in alkalinity. Given the abundance of volcanics in many deep-sea sediments, especially in lower sections which often form near ridge crests, the submarine formation of smectite may be an additional oceanic Mg sink which has not yet been fully considered.

Geochemistry at DSDP Leg 73 Holes

In the South Atlantic, at Sites 519 to 523, the dissolution of calcareous oozes ended in the formation of red clays rich in iron and manganese. The early authigenesis of manganese oxides and clays is described in Miocene marly calcareous oozes. The mineralogical and geochemical influences of basaltic basement weathering are shown by the occurrence of palagonite, authigenic clays, and oxides in the basal sediments. The development of red clay facies can be inhibited by local topographic and paleoceanographic changes, as at Site 520.

Radiolarians of the Celebes Sea

Two sites were drilled in the Celebes Sea as part of Ocean Drilling Program Leg 124; Site 767 and Site 770. Radiolarians are preserved in Paleogene pelagic claystones with minor occurrences in certain Neogene successions. The brown clays that immediately overlie basalt at both sites contain radiolarians of the late middle Eocene Podocyrtis chalara Zone. Late Eocene radiolarians are not found, due to dissolution and probable hiatus. The Oligocene is represented by the Theocyrtis tuberosa and Dorcadospyris ateuchus Zones. Oligocene sediments are strongly dominated by abundant and diverse radiolarians of the TristylospyrislDorcadospyris lineage. Preservation of Paleogene radiolarian assemblages ranges from good to very poor. Late Miocene radiolarians of the Didymocyrtis antepenultima Zone are found only in Site 770. Other Neogene sediments are barren of radiolarian remains, with the exception of latest Pleistocene and Holocene sediments.

Chemical and mineral compositions of Northwest Pacific bottom sediments and their grain size fractions

A detailed study of chemical composition of bottom sediments along a profile through the Northwest Pacific Basin has allowed to identify and describe four lithofacies types of bottom sediments. Distinguished types of sediments form a genetic series reflecting changing conditions of sedimentation from near-shore to central regions of the ocean. Along the strike of pelagic clays a gradual transition from ash containing clays to zeolite containing clays is established. Ash particles and zeolites have similar forms of occurrence. Together with other data it suggests that zeolites have been formed by diagenetic transformation of rhyolitic glass. Regular changes of CaCO3, amorphous SiO2, Fe and Mn contents in bottom sediments from the coast to the pelagic zone are shown.

Geochemistry and stable isotope record of carbonate oozes and chalks of ODP Hole 130-807B

Light greenish gray and pale purple color bands are common in the ooze and chalk of the Ontong Java Plateau. Analyses of Pleistocene and Pliocene ooze samples that contain abundant bands indicate that the purple bands are colored by finely disseminated iron sulfide, whereas the green bands are colored by finely disseminated Fe- and Al-bearing silicates (probably clays). No local contrasts in the total organic carbon contents, carbon and oxygen isotopic compositions, and grain sizes were found. Band abundances, counted from core photographs of all Leg 130 holes, can be correlated from hole to hole on the basis of age rather than depth. The temporal distribution of these color bands is also comparable with that of the green bands described from the Lord Howe Rise, which were previously interpreted as products of altered volcanic glass. This may indicate that the green and purple bands on the Ontong Java Plateau originate from the early alteration of volcanic ash. The crosscutting relationships between the green and purple bands and original structures in the host sediment indicate that the bands have been locally altered by redox conditions in the sediments after the bands were formed.

Phosphorus in bottom sediments and micronodules from Core VITYAZ7414, Central Indian Ocean

Study of phosphorus distribution in grain size fractions of eupelagic clays showed high (up to 3%) content of P in Fe-Mn micronodules that can contain up to 20-30% of total P. Mineral P associated with Fe in ocean sediments is an analog of manganese in ocean sedimentogenesis. Sharp decrease of P contents in ocean Fe-Mn nodules compared to ones from seas results from decrease of Fe contents and partial neutralization of Fe activity by Mn.