Geochemical and mineralogical analyses of clay-rich intervals in ODP Sites 166-1006 and 166-1007

The western flank of the Great Bahama Bank, drilled during ODP Leg 166 at seven sites, represents a prograding carbonate sequence from late Oligocene to Holocene [Eberli et al., Proc. ODP Init. Reports 166 (1997)]. The signatures of the detrital input and of diagenetic alteration are evident in clay enriched intervals from the most distal Sites 1006 and 1007 in the Straits of Florida. Mineralogical and chemical investigations (XRD, TEM, SEM, ICP-MS) run on bulk rocks and on the clay fractions enable the origin and evolution of silicate parageneses to be characterized. Plio-Pleistocene silt and clay interbeds contain detrital clay assemblages comprising chlorite, illite, interstratified illite smectite, smectite, kaolinite and palygorskite. The greater smectite input within late Pliocene units than in Pleistocene oozes may relate either varying source areas or change in paleoclimatic conditions and weathering intensity. The clay intervals from Miocene-upper Oligocene wackestone sections are fairly different, with prevalent smectite in the fine fraction, whose high crystallinity and Mg contents that point towards an authigenic origin. The lower Miocene section, below 1104 mbsf, at depths where compaction features are well developed, is particularly characterized by abundant authigenic Na-K-clinoptilolite filling foraminifer tests. The authigenic smectite and clinoptilolite paragenesis is recorded by the chemical trends, both of the sediment and the interstitial fluid. This diagenetic evolution implies Si- and Mg rich fluids circulating in deeper and older sequences. For lack of any local volcaniclastic input, the genesis of zeolite and the terms of water rock interaction are discussed. The location of the diagenetic front correlates with that of the seismic sequence boundary P2 dated as 23.2 Ma. This correspondence may allow the chronostratigraphic significance of some specific seismic reflections to be reassessed.

Spherules and basement analyses from DSDP Hole 5-32

Lower Miocene basaltic glass spherules from DSDP Site 32 pelagic sediments in the eastern Pacific are compositionally diverse, and new analyses and interpretations have been added to those of earlier workers. The spherules are of titanian ferrobasalt which is compositionally similar to highly evolved abyssal basalts and to some oceanic island eruptives, and they were most likely shaped during intense lava fountaining during a number of separate eruptions. These eruptions tapped distinct but related magma batches in terms, for example, of distinctively high TiO2 and FeO* contents. Their age overlaps that of some of the eruptions of the Columbia River Plateau Basalts, but they are compositionally distinct from most of the latter basalts. Although about 15 m.y. old, they show little alteration. The low chlorine and sulfur contents compared to those of abyssal ferrobasalts are consistent with degassing prior to quenching during subaerial eruptions, and rule out production of the spherules by submarine fountaining. Lava fountaining alone is insufficient to account for the distance of about 100 km from even the closest possible seamount source. Instead, large phreatomagmatic eruption columns reaching at least 15 km and including lava fountaining immediately after the initial explosion are required. Alternatively, and deemed less likely, is their deposition by turbidites derived from Pioneer Seamount.

Mineralogy micromorphology, and geochemistry at DSDP Site 89-585

At Site 585 of Deep Sea Drilling Project Leg 89 more than 500 m of volcaniclastic to argillaceous middle-Late Cretaceous sediments were recovered. Analyses by X-ray diffraction (bulk sediment and clay fraction), transmission electron microscopy, molecular and atomic absorption, and electron microprobe were done on Site 585 samples. We identify four successive stages and interpret them as the expression of environments evolving under successive influences: Stage 1, late Aptian to early Albian - subaerial and proximal volcanism, chiefly expressed by the presence of augite, analcite, olivine, celadonite, small and well-shaped transparent trioctahedral saponite, Al hydroxides, Na, Fe, Mg, and various trace elements (Mn, Ni, Cr, Co, Pb, V, Zn, Ti). Stage 2, early to middle Albian - submarine and less proximal volcanic influence, characterized by dioctahedral and hairy Mg-beidellites, a paucity of analcite and pyroxenes, the presence of Mg and K, and local alteration of Mg-smectites to Mg-chlorites. Stage 3, middle Albian to middle Campanian - early marine diagenesis, marked by the development of recrystallization from fleecy smectites to lathed ones (all of alkaline Si-rich Fe-beidellite types), by the development of opal CT and clinoptilolite, and by proximal to distal volcanic influences (Na parallel to Ti, K). Local events consist of the supply of reworked palygorskite during the Albian-Cenomanian, and the recurrence of proximal volcanic activity during the early Campanian. Stage 4, late Campanian to Maestrichtian - development of terrigenous supply resulting from the submersion of topographic barriers; this terrigenous supply is associated with minor diagenetic effects and is marked by a clay diversification (beidellite, illite, kaolinite, palygorskite), the rareness of clay recrystallizations, and the disappearance of volcanic markers.

Elemental analyses (XRF), total organic carbon (TOC), grain size analyses, lamination index of sediment core SO130-289KL

The Dansgaard-Oeschger oscillations and Heinrich events described in North Atlantic sediments and Greenland ice are expressed in the climate of the tropics, for example, as documented in Arabian Sea sediments. Given the strength of this teleconnection, we seek to reconstruct its range of environmental impacts. We present geochemical and sedimentological data from core SO130-289KL from the Indus submarine slope spanning the last ~ 80 kyr. Elemental and grain size analyses consistently indicate that interstadials are characterized by an increased contribution of fluvial suspension from the Indus River. In contrast, stadials are characterized by an increased contribution of aeolian dust from the Arabian Peninsula. Decadal-scale shifts at climate transitions, such as onsets of interstadials, were coeval with changes in productivity-related proxies. Heinrich events stand out as especially dry and dusty events, indicating a dramatically weakened Indian summer monsoon, potentially increased winter monsoon circulation, and increased aridity on the Arabian Peninsula. This finding is consistent with other paleoclimate evidence for continental aridity in the northern tropics during these events. Our results strengthen the evidence that circum-North Atlantic temperature variations translate to hydrological shifts in the tropics, with major impacts on regional environmental conditions such as rainfall, river discharge, aeolian dust transport, and ocean margin anoxia.

Geochemical and Nd isotopic investigations of sediments from the South China Sea

Secular variations in geochemistry and Nd isotopic data have been documented in sediment samples at ODP Site 1148 in the South China Sea. Major and trace elements show significant changes at ca. 29.5 Ma and 26-23 Ma, whereas epsilon-Nd values show a single change at ca. 26-23 Ma. Increases in Al/Ti, Al/K, Rb/Sr, and La/Lu ratios and a decrease in the Th/La ratio of the sediments beginning at 29.5 Ma are consistent with more intense chemical weathering in the source region. The abrupt change in Nd isotopes and geochemistry at ca. 26-23 Ma coincides with a major discontinuity in the sedimentology and physical properties of the sediments, implying a drastic change in sedimentary provenance and environment at the drill site. Comparison of the Nd isotopes of sediments from major rivers flowing into the South China Sea suggests that pre-27 Ma sediments were dominantly derived from a southwestern provenance (Indochina-Sunda Shelf and possibly northwestern Borneo), whereas post-23 Ma sediments were derived from a northern provenance (South China). This change in provenance from southwest to north was largely caused by ridge jumping during seafloor spreading of the South China Sea, associated with a southwestward expansion of the ocean basin crust and a global rise in sea level. Thus, the geochemical and Nd isotopic changes in the sediments at ODP Site 1148 are interpreted as a response to a major plate reorganization in SE Asia at ca. 25 Ma.

Geochemistry of ODP Site 162-907, North Atlantic

A geochemical analysis is conducted on hemipelagic sediments at ODP Leg 162, Site 907, North Atlantic. On the basis of major and minor element concentrations, the sequence is divided into five units. Geochemical data reveal that the sediments originated from two specific source areas, i.e., continental icerafted debris (IRD) and Icelandic basalt. In the upper part (lithological units I and II, 0 to 63.1 meters below sea floor (mbsf)), sediments were derived from continental IRD, whereas in the lower part, sediments (lithological units III, IV, and V, below 63.1 mbsf) comprise mixture of continental IRD and minor supply from the Icelandic basalt. The ratio of TiO2/Al2O3 to SiO2 content and the Th to Ti/Al molar ratio clearly provide a key to discriminate provenances. The change in source area is most likely related to the oceanographic and climatic evolution in the North Atlantic since the middle Miocene. Biogenic fossil-barren intervals (Units II and V) are considered as a consequence of dissolution caused by oceanic circulation. The timing of IRD initiation confers with that of geochemical analysis. Total organic carbon to total nitrogen (C/N) ratio shows a striking variation in the entire core. The C/N ratios exceed 10 below approximately 196 mbsf (lithological unit V) with a gradual downward increase. This suggests that terrigenous organic matters have been supplied from the neighboring continents. The total organic carbon to total sulfur (C/S) ratio also shows such possibility as well as diagenetic changes in Units IV and V. The carbonate-barren intervals presented in Units II and V, and intermittently in Units III and IV are interpreted as a consequence of dissolution effect related with climatic variation and deep-water circulation. Additional low surface productivity was considerable.

Rare earth element contents in deposits and minerals of the ocean floor

Current understanding of rare earth element (REE) geochemistry in the ocean is given in the book. Chemical properties determining REE migration ability in natural processes, sources of REE in the ocean, behavior of REE in river-sea mixing zones, fractionation of dissolved and particulate REE in ocean waters under aerobic and anaerobic conditions, distribution of REE in terrigenous, authigenic, hydrothermal and biogenic sediment components (clay, bone detritus, barite, phillipsite, Fe- and Mn-oxyhydroxides, Fe-Ca hydroxophosphate, diatoms and foraminiferas) are under consideration.

Tephrostratigraphy and radiometric dating of authigenic carbonates

At convergent margins, fluids rise through the forearc in response to consolidation of the upper plate and dewatering of the subducting plate, and produce various cold-seep-related features on the seafloor (mud diapirs, mud mounds). At the Central American forearc, authigenic carbonates precipitated from rising fluids within such structures during active venting while typical mixed-mud sediments were ejected onto the surrounding seafloor where they became intercalated with normal pelagic background sediments, indicating that mud mounds evolved unsteadily through alternating active and inactive phases. Intercalated regional ash layers from Plinian eruptions at the Central American volcanic arc provide time marks that constrain the ages of mud ejection activity. U/Th dating of drill core samples of authigenic carbonate caps of mud mounds yields ages agreeing well with those constrained by ash layers and showing that carbonate caps grow inward rather than outward during active venting. Both dating approaches show that offshore Nicaragua and Costa Rica (1) active and inactive phases can occur simultaneously at neighboring mounds, (2) mounds along the forearc have individual histories of activity, but there are distinct time intervals when nearly all mounds have been active or inactive, (3) lifetimes of mounds reach several hundred thousand years, and (4) highly active periods last 10-50 k.y. with intervening periods of >10 k.y. of relative quiescence.

Sedimentary facies, clay mineralogy and geochemistry of the Paleogene sediments of ODP Site 105-647

Claystones immediately overlying the early Eocene age ocean-floor basalt, cored at Ocean Drilling Program (ODP) Site 647, underwent hydrothermal and thermal alterations originating from the basalt, which resulted in changes in both the mineralogical and chemical composition of the sediments. Chlorites and higher magnesium and iron concentrations were found in the lowermost sediment sequence. Upcore, changes in the bulk chemical composition of the sediments become smaller, when compensated for variations in the carbonate content originating from biogenic and authigenic components. Chlorite disappears upcore, but still only part of the swelling clay minerals have survived the thermal influence. Thirty meters above the basalt, the clay mineralogy and chemical composition become uniform throughout the Paleogene section. Iron-rich smectites (i.e., nontronitic types), totally dominate the clay mineral assemblage. Biogenic components, responsible for the dominant part of the calcite and cristobalite contents, vary in amount in the upper part, and so do the authigenic carbonate and sulfide contents. Detrital components, such as kaolinite, illite, quartz, and feldspars, make up a very small proportion of the sediment record. The nontronitic smectites are believed to be authigenic, formed by a supply of iron from the continuous formation of ocean-floor basalt in the ridge area that reacted with the detrital and biogenic silicates and alumina silicates.

Chemical composition of Black Sea bottom sediments

Concentrations of major-, trace- and rare earth elements in recent and Old Black Sea bottom sediments are reported in the paper. Data presented suggest that accumulation of black shale deposits was not constrained to a certain time span but proceeds in certain modern basins and generates sediments with metal contents close to those in their ancients analogues in hydrogen sulfide contaminated environments. If REE are involved in the process, their composition can vary depending on such factors as variations in redox conditions and occurrence of phosphate and barite nodules, which can induce development of either positive or negative Eu anomalies.

Tie points and goechemical analysis from different Holes of ODP Site 165-1002

The fine-grained sediments of the Cariaco Basin, Venezuela, of the last 130 ky, whose deposition history is well characterized, were analyzed geochemically in order to test the validity of sediment bulk geochemistry as an indicator of detrital provenance. Several binary and ternary diagrams as well as the chemical index of alteration (CIA) were tested for their capacity to discriminate the poorly contrasted detrital sources to the Cariaco Basin, and to describe the temporal evolution of the contributions of these different sources. Most of the diagrams tested did not allow a good discrimination of sources or, when sources were well discriminated, did not allow an interpretation of the temporal variations consistent with the known history. A relatively good discrimination of sources and a consistent interpretation of temporal variations were however obtained using Hf vs. Th and La/Yb vs. Gd/Yb binary diagrams, as well as Ti-Zr-Th, Ti-Zr-La, and Lu-Hf-Th ternary diagrams. Compared to the previous studies of the detrital content of the Cariaco Basin sediments, the geochemical approach permitted the recognition of a sediment contribution eroded from the Unare platform and Gulf of Cariaco during rapid sea level oscillations, and the contribution of Saharan eolian particles during the Younger Dryas-Preboreal and MIS6-5 transition. The choice of plotted elements was determined after considering carrier minerals, so that different elements may be informative in different sedimentary contexts. Overall, mineral sorting during transport appears as a major limit to quantitative estimation of the different contributions. In particular mineral sorting leads to the selective enrichment of elements associated with clays (Al, Rb, Th and LREE) in sediments deposited in the basin. Unless the geochemical effect of mineral sorting can be measured, it appears that quantitative provenance analysis should be performed on fractions of similar grain size instead of bulk sediment.

Chemical profiles in sediment and basalt at DSDP Hole 74-525A

Forty sediment and four basement basalt samples from DSDP Hole 525A, Leg 74, as well as nine basalt samples from southern and offshore Brazil, were subjected to instrumental neutron activation analysis. Thirty-two major, minor, and trace elements were determined. The downcore element concentration profiles and regression analyses show that the rare earth elements (REE) are present in significant amounts in both the carbonate and noncarbonate phases in sediments; Sr is concentrated in the carbonate phase, and most of the other elements determined exist mainly in the noncarbonate phase. The calculated partition coefficients of the REE between the carbonate phase and the free ion concentrations in seawater are high and increase with decreasing REE ionic radii from 3.9 x 10**6 for La to 15 x 10**6 for Lu. Calculations show that the lanthanide concentrations in South Atlantic seawater have not been changed significantly over the past 70 Ma. The Ce anomaly observed in the carbonate phase is a redox indicator of ancient seawater. Study of the Ce anomaly reveals that seawater was anoxic over the Walvis Ridge during the late Campanian. As the gap between South America and West Africa widened and the Walvis Ridge subsided from late Campanian to late Paleocene times, the water circulation of the South Atlantic improved and achieved oxidation conditions about 54 Ma that are similar to present seawater redox conditions in the world oceans. The chemical compositions of the basement rocks correspond to alkalic basalts, not mid-ocean ridge basalts (MORBs). The results add more evidence to support the hypothesis that the Walvis Ridge was formed by a series of volcanos moving over a "hot spot" near the Mid-Atlantic Ridge. From the chemical composition and REE pattern, one 112 Ma old basalt on the Brazilian continental shelf has been identified as an early stage MORB. To date, this is the oldest oceanic tholeiite recovered from the South Atlantic. This direct evidence indicates that the continental split between South America and Africa commenced > 112 Ma.

Composition of fossil manganese nodules from Costa Rica

Horizons of several types of Upper Jurassic to Lower Cretaceous manganese nodules occur locally in sequences of radiolarian cherts within the Nicoya Ophiolite Complex (NW Costa Rica). Field studies, X-ray diffraction analysis, petrographic, chemical and experimental studies give evidence of a sedimentary, early diagenetic origin of the nodules, in contrast to earlier suggestions. Smooth, discoidal, compact and very dense nodules with diameters of some mm to 9 cm dominate. They are characterized by braunite, hollandite, pyrolusite and quartz as well as 39-61% Mn, 0.9-1.6% Fe, 5-26% SiO2, 1.3-1.9% Al2O3, 1.5-3.0% Ba, 460-5400 ppm Cu, 85-340 ppm Ni and 40-130 ppm Co, among others. It is suggested that the original mineralogy (todorokite?) was altered during thermometamorphic (braunite) and hydrothermal (hollandite. pyrolusite) events. Petrographic similarities between the fossil nodules and modern deep-sea nodules are striking. Using standard hydrothermal techniques in an experimental study it is shown that under special conditions, braunite can be produced from modern nodule material.

Geochemistry of tephra layers in ODP Site 121-758

A tephrochronology of the past 5 Ma is constructed with ash layers recovered from Neogene sediments during drilling at ODP Leg 121 Site 758 on northern Ninetyeast Ridge. The several hundred tephra layers observed in the first 80 m of cores range in thickness from a few millimeters to 34 cm. Seventeen tephra layers, at least 1 cm thick, were sampled and analyzed for major elements. Relative ages for the ash layers are estimated from the paleomagnetic and d18O chronostratigraphy. The ash layers comprise about 1.7% by volume of the sediments recovered in the first 72 m. The median grain size of the ashes is about 75 ?m, with a maximum of 150 ?m. The ash consists of rhyolitic bubble junction and pumice glass shards. Blocky and platy shards are in even proportion (10%-30%) and are dominated by bubble wall shards (70%-90%). The crystal content of the layers is always less than 2%, with Plagioclase and alkali feldspar present in nearly every layer. Biotite was observed only in the thickest layers. The major element compositions of glass and feldspar reflect fractionation trends. Three groupings of ash layers suggest different provenances with distinct magmatic systems. Dating by d18O and paleomagnetic reversals suggests major marine ash-layer-producing eruptions (marine tephra layers > 1 cm in thickness) occur roughly every approximately 414,000 yr. This value correlates well with landbased studies and dates of Pleistocene Sumatran tuffs (average 375,000-yr eruptive interval). Residence times of the magmatic systems defined by geochemical trends are 1.583, 2.524, and 1.399 Ma. The longest time interval starts with the least differentiated magma. The Sunda Arc, specifically Sumatra, is inferred to be the source region for the ashes. Four of the youngest five ash layers recovered correlate in time and in major element chemistry to ashes observed on land at the Toba caldera.

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.