Geochemistry at DSDP Hole 69-504B

Cores from Deep Sea Drilling Project Holes 501, 504B and 505B have an unusual near-vein zonation in basalts. Megascopically, zonation occurs as differently colored strips and zones whose typical thickness does not exceed 6 to 7 cm. Microscopically, the color of zones depends on variably colored clay minerals which are the products of low-temperature hydrothermal alteration in basalt. These differently colored zones form the so called "oxidative" type of alteration of basalts. Another "background," or, less precisely termed, "non-oxidative," type of alteration in basalts is characterized by large-scale, homogeneous replacement of olivine, and filling of vesicles and cracks by an olive-brown or olive-green clay mineral. The compositions of clay minerals of the "background" type of alteration, as well as the composition of co-existing titanomagnetites, were determined with an electron microprobe. There are sharp maxima in potassium and iron content, and minima in alumina, silica, and magnesia in clay minerals in the colored zones near veins. Coloring of clay and rock-forming minerals by iron hydroxides and a decrease of the amount of titanomagnetite, which apparently was the source of redeposited iron, occur frequently in colored zones. We assume that the large-scale "background" alteration in the basalts occurred under the effect of pore waters slowly penetrating through bottom sediments. Faulting can facilitate access of fresh sea water to basalts; thus above the general homogeneous background arise zones of "oxidative" alteration along fractures in basalts. The main factors controlling these processes are time (age of basalt), grain size, temperature, thickness of sedimentary cover, and heat flow.

Pb isotopes in Cenozoic sediments of ODP Site 177-1090

Nd and Pb isotopic compositions extracted from bulk deep sea sediments have been shown to be robust proxies for deep water circulation as well as weathering provenance and intensity over geologically young time scales. In this study we evaluated ten deep sea samples from Ocean Drilling Program (ODP) site 1090 ranging in age from mid Eocene to early-Miocene to test whether Pb isotopic compositions extracted from geologically older sediments record reliable seawater isotopic ratios and to evaluate the source of the extracted Pb. The sequential extraction protocol used in this study is similar to protocols reported for previous studies and produces acetic acid, hydroxylamine hydrochloride (HH) and residue fractions. Each extracted fraction was analyzed for Pb isotopes, rare earth elements (REEs), and a suite of major elements. Similar 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios are recorded from the acetic acid and HH fractions for ~70-80% of the samples, suggesting that either the acetic acid dissolves Fe-Mn oxides or multiple phases are recording the same seawater isotopic value. Several indirect tests, such as Al mass balance, comparison of Sr isotopes in HH extracts to contemporaneous seawater Sr isotopes, and comparison of Nd isotopic compositions in HH extracts to published fossil fish teeth values, provide evidence that Pb isotopic compositions measured in our bulk HH extracts record bottom water values. The relationship between Pb, Mn and Ca concentrations in HH fractions indicates that Fe-Mn oxides and a Mn-bearing carbonate are the dominant phases contributing seawater Pb. Comparison of REE patterns derived from the HH fraction and total digestions of Fe-Mn nodule standards reveals that the trivalent REEs exhibit patterns consistent with the parent archive, but Ce can be fractionated during extraction. Ratios of REEs also produce unique fields for each fraction and can be used to test the purity of the seawater signal of the extraction protocol. Finally, an initial evaluation of Pb isotopic compositions in fossil fish indicates that this archive is not suitable for bottom water Pb isotope studies.

Lithium and strontium isotopic compositions of sediments and pore waters at ODP Sites 152-918 and 152-919

The distribution of Li isotopes in pore waters to a depth of 1157 m below seafloor is presented for ODP Sites 918 and 919 in the Irminger Basin, offshore Greenland. Lithium isotope data are accompanied by strontium isotope ratios to decipher diagenetic reactions in the sediments which are characterized by the pervasive presence of volcanic material, as well as by very high accumulation rates in the upper section. The lowering of the 87Sr/86Sr ratio below contemporaneous seawater values indicates several zones of volcanic material alteration. The Li isotope profiles are complex suggesting a variety of exchange reactions with the solid phases. These include cation exchange with NH4+ and mobilization from sediments at depth, in addition to the alteration of volcanic matter. Lithium isotopes are, therefore, a sensitive indicator of sediment-water interaction. d6Li values of pore waters at these two sites vary between -42 and -25?. At shallow depths (<100 mbsf), rapid decreases in the Li concentration, accompanied by a shift to heavier isotopic compositions, indicate uptake of Li into alteration products. A positive anomaly of d6Li observed at both sites is coincident with the NH4+ maximum produced by organic matter decomposition and may be related to ion exchange of Li from the sediments by NH4+. In the lower sediment column at Site 918, dissolved Li increases with depth and is characterized by enrichment of 6Li. The Li isotopic compositions of both the waters and the solid phase suggest that the enrichment of Li in deep interstitial waters is a result of release from pelagic sediments. The significance of sediment diagenesis and adsorption as sinks of oceanic Li is evaluated. The maximum diffusive flux into the sediment due to volcanic matter alteration can be no more than 5% of the combined inputs from rivers and submarine hydrothermal solutions. Adsorption on to sediments can only account for 5-10% of the total inputs from rivers and submarine hot springs.

Stable isotope record of ODP Sites 108-658 and 108-659

Ocean Drilling Program Site 658, cored below a major upwelling cell offshore Cap Blanc, contains a largely undisturbed hemipelagic sediment section spanning the Brunhes Chron and the early Quaternary and late Pliocene. The companion Site 659 recovered a complete and undisturbed Neogene profile further offshore that serves as a nonupwelling pelagic reference section. Oxygen and carbon isotope ratios in benthic (C. wuellerstorfi and in part Uvigerina sp.) and planktonic foraminifers (G. inflata) provide a climatic record of high resolution for the Brunhes Chron. At Site 658 the record extends back to the early Pleistocene and late Pliocene. The standard oxygen isotope record of the last 730,000 yr is markedly refined by a well-documented high-frequency variation (e.g., by a new "aborted" ice age at stage 13.2 and by Younger-Dryas style climatic setbacks during most terminations). In the late Pliocene, the numerical oxygen isotope stage taxonomy was extended back to stage 137 about 3.3 Ma ago. In comparison with published records, stage 114 at 2.7 Ma represents the first major glaciation event, when 18O was short-term enriched up to a middle Pleistocene glacial d18O level. About 3.17 Ma ago (stage 133), the interglacial oxygen isotope values of C. wuellerstorfi started to increase by 0.5 per mil until 2.7 Ma and then remained largely constant until the Holocene. Based on the d13C difference between C. wuellerstorfi and G. inflata, the dissolved CO2 in the ambient bottom water of Site 658 was dominated by the flux of particulate carbon from the overlying upwelling cell during the last 630,000 yr. In contrast, the advection of (upper) North Atlantic Bottom Water dominated in the control of the local CO2 content during the early Pleistocene and late Pliocene.

Quaternary planktonic foraminifera of DSDP Hole 72-517

Quaternary sediments were recovered at all four Sites at Leg 72. Planktonic foraminifers were abundant and well preserved, especially in the holes shielded from Antarctic Bottom Water (AABW) influence. The fauna belonged to the subtropical province marked by Globigerinoides ruber and to a lesser extent by Globorotalia inflata. Thirty planktonic foraminiferal species were distinguished, and a detailed study of the Site 517 stratigraphy was made. The Quaternary sequence of the Rio Grande Rise was subdivided slightly differently from the Bolli and Premoli Silva (1973) pattern. Five subzones were identified but some difficulties arose when a precise correlation became necessary in the subzones of the tropical provinces. Correlations could nevertheless be made, particularly with respect to the earliest Quaternary. Quaternary faunal data have been dated by isotopic stratigraphy (Vergnaud Grazzini et al.,1983) and partially contradict results previously published for this part of the Atlantic (Williams and Ledbetter, 1979). By studying the occurrence of planktonic foraminifers, we obtained more information about hydrologic variations during the Quaternary sequence of Hole 517; two broad periods were recognized. Finally, we identified the interaction between the Brazil Current and the subtropical convergence

Deep drilling of glaciers: Russian projects in the Arctic (1975-1995)

The data collection "Deep Drilling of Glaciers: Soviet-Russian projects in Arctic, 1975-1995" was collected by the following basic considerations: - compilation of deep (>100 m) drilling projects on Arctic glaciers, using data of (a) publications; (b) archives of IGRAN; (c) personal communication of project participants; - documentation of parameters, references. Accuracy of data and techniques applied to determine different parameters are not evaluated. The accuracy of some geochemical parameters (up to 1984 and heavy metalls) is uncertain. Most reconstructions of ice core age and of annual layer thickness are discussed; - digitizing of published diagrams (in case, when original numerical data were lost) and subsequent data conversion to equal range series and adjustment to the common units. Therefore, the equal-range series were calculated from original data or converted from digitized chart values as indicated in the metadata. For the methodological purpose, the equal-range series obtained from original and reconstructed data were compared repeatedly; the systematic difference was less then 5-7%. Special attention should be given to the fact, that the data for individual ice core parameters varies, because some parameters were originally measured or registered. Parameters were converted in equal-range series using 2 m steps; - two or more parameter values were determined, then the mean-weighted (i.e. accounting the sample length) value is assigned to the entire interval; - one parameter value was determined, measured or registered independently from the parameter values in depth intervals which over- and underlie it, then the value is assigned to the entire interval; - one parameter value was determined, measured or registered for two adjoining depth intervals, then the specific value is assigned to the depth interval, which represents >75% of sample length ; if each of adjoining depth intervals represents <75% of sample length, then the correspondent parameter value is assigned to both intervals of depth. This collection of ice core data (version 2000) was made available through the EU funded QUEEN project by S.M. Arkhipov, Moscow.

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.

Eocene-Oligocene nannofossils from the Labrador Sea

During Ocean Drilling Program (ODP) Leg 105, a thick sequence of lower Eocene to lower Oligocene sediments was recovered from Hole 647A in the southern Labrador Sea. These sediments contain diverse, well-preserved, high-latitude calcareous nannofossil flora. The nannofossil biostratigraphy of the hole indicates the presence of a minor hiatus between Zones NP 16 and NP 17 in the upper middle Eocene and a barren interval separating Zones NP 13 and NP 15. Species abundance is highest within the lower to middle Eocene and starts to decline near the base of the upper Eocene. No major change in the nannoflora was observed across the Eocene/Oligocene boundary, although a slight decrease in species abundance was recorded. The Paleogene calcareous nannofossils of nearby DSDP Site 112 were reexamined and compared with those of Site 647. Several cores were reassigned to different nannofossil zones. The calcareous nannoflora are dominated by high-latitude indicative species and also exhibit a high diversity, which suggests the influence of more temperate water masses in this region during Eocene and Oligocene time. One new subspecies from the middle Eocene, Sphenolithus furcatolithoides labradorensis, is described.

Summary of physical properties on cores used for petrofabric analyses triaxial experiments at DSDP Leg 67 Holes

Deformation features within the cores are studied with a view towards elucidating the structure of the Middle America Trench along the transect drilled during Leg 67. Where possible, inferences are made as to the physical environment of deformation. Extensional tectonics prevails in the area of the seaward slope and trench. Fracturing and one well-preserved normal fault are found mostly within the lower Miocene chalks, at the base of the sedimentary section. These chalks have high porosities (40%-60%) and water content (30%-190%, based on % dry wt.). Experimental triaxial compression tests conducted on both dry and water-saturated samples of chalk from Holes 495 and 499B show that only in the saturated samples is more brittle behavior observed. Brittle failure of the chalks is greatly facilitated by pore fluid pressures that lead to low effective pressures. Additional embrittlement (weakening) can take place as a result of the imposed extensional stress resulting from bending of a subducting elastic oceanic plate. The chalks exhibit, in a landward direction, an increase in density and mechanical strength and a decrease in water content. These changes are attributed to mechanical compaction that may have resulted from tectonic horizontal compression. The structure of the landward slope is not well understood because the slope sites had to be abandoned due to the presence of gas hydrate. The relationship of the chaotic, brittle deformation (observed in the cores from Hole 494A) at the base of the landward slope to tectonic processes remains unclear. The deformation observed on the slope sites (Holes 496 and 497) is mostly fracturing and near-vertical sigmoidal veinlets. These are interpreted as being the result of gas/fluid overpressurization due to the decomposition of the gas hydrate, and not due to tectonic loading of accreted sediments. Aside from four small displacement (less than 1cm) reverse faults observed in the lower Miocene chalks (which may be the product of soft-sediment deformation), there is a noticeable absence of structures reflecting a dominance of horizontal (tectonic) compression along the transect drilled. The absence of such features, the lack of continuity of sediment types across the trench-landward slope, and the normal stratigraphic sequence in Hole 494A do not support any known accretionary model.

Assamblages and cluster analysis from DSDP Hole 22-214 of the eastern Indian Ocean

Multivariate analyses of latest Pliocene through Holocene benthic foraminifera from 61 samples from Deep-Sea Drilling Project (DSDP) Site 214, eastem Indian Ocean were carried out. The 46 highest ranked species were used in R-mode factor analysis which has enabled to the identification of three environmentally significant assemblages at Site 214. Assemblage 1 is characterized by Uvigerina hispido-costata, Osangularia culter , Gavelinopsis lobatulus, Cibicides wuellerstorfi and Karreriella baccata as principal species. This assemblage is inferred to reflect high-energy, well-oxygenated and probably low-organic carbon deep-sea environment at Site 214. Assemblage 2 is defined principally by Globocassidulina pacifica and U. proboscidea and is considered to indicate an organic carbon-rich environment which resulted from high surface productivity irrespective of dissolved oxygen content. Assemblage 3 is marked by Oridorsalis umbonatus, Textularia lythostrota, Hoeglundina elegans, Pyrgo murrhina, and Pullenia quinqueloba as principal species. This assemblage is inferred to indicate a low-organic carbon environment with high pore water oxygen concentration leading to better preservation of deep-sea sediments.

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.