Geochemistry of middle Eocene-lower Oligocene pelagic sediments of ODP Hole 105-647A

Geochemical analyses of the middle Eocene through lower Oligocene lithologic Unit IIIC (260-518 meters below seafloor [mbsf]) indicate a relatively constant geochemical composition of the detrital fraction throughout this depositional interval at Ocean Drilling Program (ODP) Site 647 in the southern Labrador Sea. The main variability occurs in redox-sensitive elements (e.g., iron, manganese, and phosphorus), which may be related to early diagenetic mobility in anaerobic pore waters during bacterial decomposition of organic matter. Initial preservation of organic matter was mediated by high sedimentation rates (36 m/m.y.). High iron (Fe) and manganese (Mn) contents are associated with carbonate concretions of siderite, manganosiderite, and rhodochrosite. These concretions probably formed in response to elevated pore-water alkalinity and total dissolved carbon dioxide (CO2) concentrations resulting from bacterial sulfate reduction, as indicated by nodule stable-isotope compositions and pore-water geochemistry. These nodules differ from those found in upper Cenozoic hemipelagic sequences in that they are not associated with methanogenesis. Phosphate minerals (carbonate-fluorapatite) precipitated in some intervals, probably as the result of desorption of phosphorus from iron and manganese during reduction. The bulk chemical composition of the sediments differs little from that of North Atlantic Quaternary abyssal red clays, but may contain a minor hydrothermal component. The silicon/ aluminum (Si/Al) ratio, however, is high and variable and probably reflects original variations in biogenic opal, much of which is now altered to smectite and/or opal CT. An increase in the sodium/potassium (Na/K) ratio in the upper Eocene corresponds to the beginning of coarsergrained feldspar flux to the site, possibly marking the onset of more vigorous deep currents. Although the Site 647 cores provide a nearly complete high-resolution, high-latitude Eocene-Oligocene record, the high sedimentation rate and somewhat unusual diagenetic conditions have led to variable alteration of benthic foraminifers and fine-fraction carbonate and have overprinted the original stable-isotope records. Planktonic foraminifers are less altered, but on the whole, there is little chance of sorting out the nature and timing of environmental change on the basis of our stable-isotope analyses.

Chemistry and mineralogy of ODP Leg 124 sediment samples

From X-ray mineralogical studies and chemical analyses of the whole rocks and the fine fractions (<2 µm) of ten to fifteen samples at each site of ODP Leg 124, two major sources were identified in the sedimentary components of the Celebes and Sulu basins: (1) a terrestrial and continental contribution; (2) a volcanic influx that gives way to well-defined volcanic units or to a dilute contamination, consisting of coarse-grained minerals (Plagioclase, pyroxene, olivine, spinel) or a smectitic-rich fraction produced by the alteration of volcanic glasses and ashes. The continental signature increases the amount of quartz in the rocks and the phyllitic association is complex: micas, kaolinite, disordered interstratified clay-minerals. The chemical compositions of the bulk rocks and the fractions <2 µm are more potassic and aluminum-rich. The volcanic imprint depends on the grain-size and chemical properties of the components. Ca/Na contents highly variable compared to the K content of the bulk composition are due to the presence of coarse-grained volcanic Plagioclase. The fractions <2 µm are more magnesian than in the continental regime. The diagenesis is revealed by the crystallization of zeolites, the fixation of magnesium into the smectites that depletes the pore fluids in this element. Smectitization of the disordered interstratified clay minerals enriches the alkalinity of the pore fluids. Some deep formations of the Sulu Basin are affected by a thermal event, but no thermal event was recognized in the Celebes Basin.

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).

Sedimentology and geochemistry of ODP Leg 129 siliceous deposits

Siliceous deposits drilled on Ocean Drilling Program Leg 129 accumulated within a few degrees of the equator during the Jurassic through early Tertiary, as constrained by paleomagnetic data. During the Jurassic and Early Cretaceous, radiolarian ooze, mixed with a minor amount of pelagic clay, was deposited near the equator, and overall accumulation rates were moderate to low. At a smaller scale, in more detail, periods of relatively higher accumulation rates alternated with periods of very low accumulation rates. Higher rates are represented by radiolarite and limestone; lower rates are represented by radiolarian claystone. Our limited data from Leg 129 suggests that accumulation of biogenic deposits was not symmetrical about the equator or consistent over time. In the Jurassic, sedimentation was siliceous; in the Cretaceous there was significant calcareous deposition; in the Tertiary claystone indicates significantly lower accumulation rates at least the northern part of the equatorial zone. Accumulation rates for Leg 129 deposits in the Cretaceous were higher in the southern part of the equatorial zone than in the northern part, and the southern side of this high productivity zone extended to approximately 15°S, while the northern side extended only to about 5°N. Accumulation rates are influenced by relative contributions from various sediment sources. Several elements and element ratios are useful for discriminating sedimentary sources for the equatorial depositional environments. Silica partitioning calculations indicate that silica is dominantly of biogenic origin, with a detrital component in the volcaniclastic turbidite units, and a small hydrothermal component in the basal sediments on spreading ridge basement of Jurassic age at Site 801. Iron in Leg 129 sediments is dominantly of detrital origin, highest in the volcaniclastic units, with a minor hydrothermal component in the basal sediments at Site 801. Manganese concentrations are highest in the units with the lowest accumulation rates. Fe/Mn ratios are >3 in all units, indicating negligible hydrothermal influence. Magnesium and aluminum concentrations are highest in the volcaniclastic units and in the basal sediments at Site 801. Phosphorous is very low in abundance and may be detrital, derived from fish parts. Boron is virtually absent, as is typical of deep-water deposits. Rare earth element concentrations are slightly higher in the volcaniclastic deposits, suggesting a detrital source, and lower in the rest of the lithologic units. Rare earth element abundances are also low relative to "average shale." Rare earth element patterns indicate all samples are light rare earth element enriched. Siliceous deposits in the volcaniclastic units have patterns which lack a cerium anomaly, suggesting some input of rare earth elements from a detrital source; most other units have a distinct negative Ce anomaly similar to seawater, suggesting a seawater source, through adsorption either onto biogenic tests or incorporation into authigenic minerals for Ce in these units. The Al/(Al + Fe + Mn) ratio indicates that there is some detrital component in all the units sampled. This ratio plotted against Fe/Ti shows that all samples plot near the detrital and basalt end-members, except for the basal samples from Site 801, which show a clear trend toward the hydrothermal end-member. The results of these plots and the association of high Fe with high Mg and Al indicate the detrital component is dominantly volcaniclastic, but the presence of potassium in some samples suggests some terrigenous material may also be present, most likely in the form of eolian clay. On Al-Fe-Mn ternary plots, samples from all three sites show a trend from biogenic ooze at the top of the section downhole to oceanic basalt. On Si-Fe-Mn ternary plots, the samples from all three sites fall on a trend between equatorial mid-ocean spreading ridges and north Pacific red clay. Copper-barium ratios show units that have low accumulation rates plot in the authigenic field, and radiolarite and limestone samples that have high accumulation rates fall in the biogenic field.

Chemical, isotopic and mineral compositions of basal metalliferous sediments from DSDP Legs 5 and 7

Sediments from near the basement of a number of Deep Sea Drilling Project (DSDP) sites, from the Bauer Deep, and from the East Pacific Rise have unusually high transition metal-to-aluminum ratios. Similarities in the chemical, isotopic, and mineralogical compositions of these deposits point to a common origin. All the sediments studied have rare-earth-element (REE) patterns strongly resembling the pattern of sea water, implying either that the REE's were coprecipitated with ferromanganese hydroxyoxides (hydroxyoxides denote a mixture of unspecified hydrated oxides and hydroxides), or that they are incorporated in small concentrations of phosphatic fish debris found in all samples. Oxygen isotopic data indicate that the metalliferous sediments are in isotopic equilibrium with sea water and are composed of varying mixtures of two end-member phases with different oxygen isotopic compositions: an iron-manganese hydroxyoxide and an iron-rich montmorillonite. A low-temperature origin for the sediments is supported by mineralogical analyses by x-ray diffraction which show that goethite, iron-rich montmorillonite, and various manganese hydroxyoxides are the dominant phases present. Sr87/Sr86 ratios for the DSDP sediments are indistinguishable from the Sr87/Sr86 ratio in modern sea water. Since these sediments were formed 30 to 90 m.y. ago, when sea water had a lower Sr87/Sr86 value, the strontium in the poorly crystalline hydroxyoxides must be exchanging with interstitial water in open contact with sea water. In contrast, uranium isotopic data indicate that the metalliferous sediments have formed a closed system for this element. The sulfur isotopic compositions suggest that sea-water sulfur dominates these sediments with little or no contribution of magmatic or bacteriologically reduced sulfur. In contrast, ratios of lead isotopes in the metalliferous deposits resemble values for oceanic tholeiite basalt, but are quite different from ratios found in authigenic marine manganese nodules. Thus, lead in the metalliferous sediments appears to be of magmatic origin. The combined mineralogical, isotopic, and chemical data for these sediments suggest that they formed from hydrothermal solutions generated by the interaction of sea water with newly formed basalt crust at mid-ocean ridges. The crystallization of solid phases took place at low temperatures and was strongly influenced by sea water, which was the source for some of the elements found in the sediments.

Geochemistry of ODP Hole 108-658C sediments

During the African Humid Period (AHP), much of the modern hyperarid Saharan desert was vegetated and covered with numerous lakes. In marine sediments off northwestern Africa, the AHP is represented by markedly reduced siliciclastic sediment flux between ~ 12.3 and 5.5 ka. Changes in the origin of this terrigenous sediment fraction can be constrained by sediment chemistry and radiogenic isotope tracers. At Ocean Drilling Program (ODP) Site 658, Hole C (20°44.95'N, 18°34.85'W, 2263 mbsl), the neodymium (Nd) isotope composition of terrigenous detritus shows little variability throughout the last 25 kyr, indicating that the contributing geological terranes have not changed appreciably since the last glacial period. In contrast, there were large and abrupt changes in strontium (Sr) isotope ratios and chemical compositions associated with the AHP, during which 87Sr/86Sr ratios were markedly less radiogenic, and sediments show higher chemical indices of alteration. We show that sediment geochemical changes during the AHP cannot be attributed to changes in the source terranes, physical sorting, or intensity of chemical weathering. The low 87Sr/86Sr and high Sr concentrations of AHP-age samples also conflict with the interpretation of increased fine-grained, fluvially derived sediments. We propose that the most significant compositional changes at ODP 658C are due to the addition of an aluminosilicate component that has a highly altered major element signature but is enriched in soluble elements like Sr and magnesium (Mg) compared to aluminum (Al) and has low 87Sr/86Sr relative to local terrigenous source areas. We interpret these characteristics to reflect authigenic sediment supply from extensive North African paleolake basins that were prevalent during the AHP.