Magnetic mineralogy and geochemistry of ODP Holes 137-504B and 140-504B samples

Leg 140 of the Ocean Drilling Program deepened Hole 504B to a total depth of 2000.4 m below seafloor (mbsf), making it the deepest hole drilled into ocean crust. Site 504, south of the Costa Rica Rift, is considered the most important in-situ reference section for the structure of shallow ocean crust. We present the results of studies of magnetic mineralogy and magnetic properties of Hole 504B upper crustal rocks recovered during Legs 137 and 140. Results from this sample set are consistent with those discussed in Pariso et al. (this volume) from Legs 111, 137, and 140. Coercivity (Hc) ranges from 5.3 to 27.7 mT (mean 12 mT), coercivity of remanence (HCR) ranges from 13.3 to 50.6 mT (mean 26 mT), and the ratio HCR/HC ranges from 1.6 to 3.19 (mean 2.13). Saturation magnetization (JS) ranges from 0.03 to 5.94 * 10**-6 Am**2, (mean 2.52 * 10**-6 Am**2), saturation remanence (JR) ranges from 0.01 to 0.58 * 10**-6 Am2 (mean 0.37 * 10**-6 Am**2), and the ratio JR/JS ranges from 0.08 to 0.29 (mean 0.16), consistent with pseudo-single-domain behavior. Natural remanent magnetization (NRM) intensity ranges from 0.029 to 7.18 A/m (mean 2.95 A/m), whereas RM10 intensity varies only from 0.006 to 4.8 A/m and has a mean of only 1.02 A/m. Anhysteretic remanent magnetization (ARM) intensity ranges from 0.04 to 6.0 A/m, with a mean of 2.46 A/m, and isothermal remanent magnetization (IRM) intensity ranges from 0.5 to 1683 A/m, with a mean of 430.7 A/m. Volume susceptibility ranges from 0.0003 to 0.043 SI (mean 0.011 SI). In all samples examined, high-temperature oxidation of primary titanomagnetite has produced lamellae or pods of magnetite and ilmenite. Hydrothermal alteration has further altered the minerals in some samples to a mixture of magnetite, ilmenite, titanite, and a high-titanium mineral (either rutile or anatase). Electron microprobe analyses show that magnetite lamellae are enriched in the trivalent oxides Cr2O3, Al2O3, and V2O5, whereas divalent oxides (MnO and MgO) are concentrated in ilmenite lamellae.

Fossil manganese deposits buried within DSDP/ODP cores, Legs 1-126

Probable in-situ manganese deposits larger than 1 cm in diameter buried in ODP/DSDP cores were selected for study after examining previous descriptions of the manganese deposits in site reports and the ODP data base. Most of the selected samples from 11 cores occur at or just above sedimentary hiatuses or in slowly deposited sediments and are overlain by rapidly deposited sediments of biogenic, terrigenous or volcanogenic origin. The changes in sedimentation recorded in the lithostratigraphic sections around these deposits are closely related to changes in tectonic evolution, deep water circulation or biological productivity at the sites. The similarity in composition and structure of the buried deposits to those of the modern manganese nodules and crusts with no evidence of post-depositional change suggest that buried manganese deposits may be used as indicators of past sedimentary conditions during which they formed. Their major components are hydrogenetic and earlydiagenetic manganese minerals as well as detrital minerals. The characteristics of these manganese deposits suggests that similar processes of deposition have taken place since the Paleogene or older.

Iron and manganese in bottom sediments and interstitial waters sampled in the White Sea on August 21-30, 2003

Iron and manganese in bottom sediments studied along the sublatitudinal transect from Kandalaksha to Arkhangelsk are characterized by various contents and speciations depending on sedimentation environment, grain size of sediments, and diagenetic processes. The latter include redistribution of reactive forms leading to enrichment in Fe and Mn of surface sediments, formation of films, incrustations, and ferromanganese nodules. Variations in total Fe content (2-8%) are accompanied by changes in concentration of its reactive forms (acid extraction) and concentration of dissolved Fe in interstitial waters (1-14 µM). Variations in Mn content in bottom sediments (0.03-3.7%) and interstitial waters (up to 500 µM) correspond to high diagenetic mobility of this element. Changes in oxidation degree of chemical elements result in redox stratification of sediment strata with maximum concentrations of Fe, Mn, and sulfides. Organic matter of bottom sediments with considerable terrestrial constituent is oxidized by bottom water oxygen mainly at the sediment surface or in anaerobic conditions within the sediment strata. The role of inorganic components in organic matter oxidation changes from surface layer bottom sediments (where manganese oxyhydroxide dominates among oxidants) to deeper layers (where sulfate of interstitial water serves as the main oxidant). Differences in river runoff and hydrodynamics are responsible for geochemical asymmetry of the transect. The deep Kandalaksha Bay serves as a sediment trap for manganese (Mn content in sediments varies within 0.5-0.7%), whereas the sedimentary environment in the Dvina Bay promotes its removal from bottom sediments (Mn 0.05%).

Geochemistry and mineralogy of Eocene-Oligocene sediments of IODP Hole 302-M0002A

In 2004, Integrated Ocean Drilling Program Expedition 302 (Arctic Coring Expedition, ACEX) to the Lomonosov Ridge drilled the first Central Arctic Ocean sediment record reaching the uppermost Cretaceous (~430 m composite depth). While the Neogene part of the record is characterized by grayish-yellowish siliciclastic material, the Paleogene part is dominated by biosiliceous black shale-type sediments. The lithological transition between Paleogene and Neogene deposits was initially interpreted as a single sedimentological unconformity (hiatus) of ~26 Ma duration, separating Eocene from Miocene strata. More recently, however, continuous sedimentation on Lomonosov Ridge throughout the Cenozoic was proclaimed, questioning the existence of a hiatus. In this context, we studied the elemental and mineralogical sediment composition around the Paleogene-Neogene transition at high resolution to reconstruct variations in the depositional regime (e.g. wave/current activity, detrital provenance, and bottom water redox conditions). Already below the hiatus, mineralogical and geochemical proxies imply drastic changes in sediment provenance and/or weathering intensity in the hinterland, and point to the existence of another, earlier gap in the sediment record. The sediments directly overlying the hiatus (the Zebra interval) are characterized by pronounced and abrupt compositional changes that suggest repeated erosion and re-deposition of material. Regarding redox conditions, euxinic bottom waters prevailed at the Eocene Lomonosov Ridge, and became even more severe directly before the hiatus. With detrital sedimentation rates decreasing, authigenic trace metals were highly enriched in the sediment. This continuous authigenic trace metal enrichment under persistent euxinia implies that the Arctic trace metal pool was renewed continuously by water mass exchange with the world ocean, so the Eocene Arctic Ocean was not fully restricted. Above the hiatus, extreme positive Ce anomalies are clear signs of a periodically well-oxygenated water column, but redox conditions were highly variable during deposition of the Zebra interval. Significant Mn enrichments only occur above the Zebra interval, documenting the Miocene establishment of stable oxic conditions in the Arctic Ocean. In summary, extreme and abrupt changes in geochemistry and mineralogy across the studied sediment section do not suggest continuous sedimentation at the Lomonosov Ridge around the Eocene-Miocene transition, but imply repeated periods of very low sedimentation rates and/or erosion.

Major, trace and rare earth elements and minerals at DSDP Legs 69-70 Holes

We obtained major and trace element data on 113 samples from basalts drilled during DSDP Legs 69 and 70 in the Costa Rica Rift area. The majority have major and trace element characteristics typical of ocean-ridge tholeiities. Most of the basalts are relatively MgO rich (MgO > 8 wt.%) and have Mg values (MgO/MgO + 0.85FeO x 100) of about 53, characteristics that clearly indicate that the various magmas underwent only a small amount of crystal fractionation before being erupted onto the seafloor. According to their normative mineralogies, the rocks are olivine tholeiites. A few samples plot close to the diopside-hypersthene join of the projected basalt tetrahedron. Except for basalts from two thin intervals in Hole 504B, which differ significantly from all the other basalts of the hole, practically no chemical downhole variation could be established. In the two exceptional intervals, both TiO2 and P2O5 contents are markedly enriched among the major oxides. The trace elements in these intervals are distinguished by relatively high contents of magmatophile elements and have flat to enriched chondrite-normalized distribution patterns of light rare earth elements (LREE). Most of the rocks outside these intervals are strongly depleted in large-ionlithophile (LIL) elements and LREE. We offer no satisfactory hypothesis for the origin of these basalts at this time. They might have originated within pockets of mantle materials that were more primitive than the LIL-element-depleted magmas that were the source of the other basalts. A significant change with depth in the type of alteration occurs in the 561 meters of basalt cored in Hole 504B. According to the behavior of such alteration-sensitive species as K2O, H2O-, CO2, S, Tl, and the iron oxidation ratio, the alteration is oxidative in the upper part and nonoxidative or even reducing in the lower part. The oxidative alteration may have resulted from low temperature basalt/seawater interaction, whereas hydrothermal solutions may be responsible for the nonoxidative alteration.

Nd and Mn concentration in planktonic foraminifera

Neodymium isotopes are becoming widely used as a palaeoceanographic tool for reconstructing the source and flow direction of water masses. A new method using planktonic foraminifera which have not been chemically cleaned has proven to be a promising means of avoiding contamination of the deep ocean palaeoceanographic signal by detrital material. However, the exact mechanism by which the Nd isotope signal from bottom waters becomes associated with planktonic foraminifera, the spatial distribution of rare earth element (REE) concentrations within the shell, and the possible mobility of REE ions during changing redox conditions, have not been fully investigated. Here we present REE concentration and Nd isotope data from mixed species of planktonic foraminifera taken from plankton tows, sediment traps and a sediment core from the NW Atlantic. We used multiple geochemical techniques to evaluate how, where and when REEs become associated with planktonic foraminifera as they settle through the water column, reside at the surface and are buried in the sediment. Analyses of foraminifera shells from plankton tows and sediment traps between 200 and 2938 m water depth indicate that only ~20% of their associated Nd is biogenically incorporated into the calcite structure. The remaining 80% is associated with authigenic metal oxides and organic matter, which form in the water column, and remain extraneous to the carbonate structure. Remineralisation of these organic and authigenic phases releases ions back into solution and creates new binding sites, allowing the Nd isotope ratio to undergo partial equilibration with the ambient seawater, as the foraminifera fall through the water column. Analyses of fossil foraminifera shells from sediment cores show that their REE concentrations increase by up to 10-fold at the sediment-water interface, and acquire an isotopic signature of bottom water. Adsorption and complexation of REE3+ ions between the inner layers of calcite contributes significantly to elevated REE concentrations in foraminifera. The most likely source of REE ions at this stage of enrichment is from bottom waters and from the remineralisation of oxide phases which are in chemical equilibrium with the bottom waters. As planktonic foraminifera are buried below the sediment-water interface redox-sensitive ion concentrations are adjusted within the shells depending on the pore-water oxygen concentration. The concentration of ions which are passively redox sensitive, such as REE3+ ions, is also controlled to some extent by this process. We infer that (a) the Nd isotope signature of bottom water is preserved in planktonic foraminifera and (b) that it relies on the limited mobility of particle reactive REE3+ ions, aided in some environments by micron-scale precipitation of MnCO3. This study indicates that there may be sedimentary environments under which the bottom water Nd isotope signature is not preserved by planktonic foraminifera. Tests to validate other core sites must be carried out before downcore records can be used to interpret palaeoceanographic changes.

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.

Primary mineralogy of ODP Leg 115 basalts

Basement rocks were recovered at four sites on Leg 115 along the Reunion hotspot track in the western Indian Ocean. Plate tectonic reconstructions indicate that the drilled structures formed in three different volcanic environments. Sites 706 and 713 from the eastern side of the Saya de Malha Bank and the northern end of the Chagos Bank, respectively, are on a large volcanic platform analogous to Iceland on the Mid-Atlantic Ridge. Lavas at Site 707 on the northwestern side of the Saya de Malha Bank erupted during the early stages of rifting of the Seychelles from India. Basalts from Site 715 were erupted onto an isolated oceanic island that was distant from ocean ridges and continents much as Reunion Island is today. Many of the rocks were examined in thin section and found to be primarily augite-plagioclase basalts with minor olivine and rare opaque oxides. Site 715 is unusual in that it contains a variety of basalts including olivine-rich and aphyric Fe-Ti basalts. At each of the four sites the rocks were grouped into chemical types (units) on the basis of ship- board bulk-rock analyses and at least one thin section from each chemical unit was analyzed by electron microprobe. The plagioclase and augite chemistry reflects the bulk-rock chemistry and, in general, these minerals were in equilibrium with their host magmas at the time the basalts were quenched. Olivine was rarely preserved, but where it is still present it also appears to have crystallized in equilibrium with the host magma. At three of the drill sites plagioclase phenocrysts or megacrysts that crystallized from a primitive magma are also present. The one site (715) that does not contain these primitive plagioclase phenocrysts is also the site that appears to have been influenced the least by ocean- ridge or Deccan-type magmas. Site 715, furthermore, has a mineralogy that is dominated by olivine as compared with the plagioclase-rich lavas of the other sites.

Investigation of Manganese nodules in the southern Baltic Sea

Die Genese von Mangan-Eisen-Akkumulaten der Kieler Bucht wurde durch In-situ-Experimente vor allem in Tauchgängen unter Berücksichtigung der hydrographischen und sedimentologischen Gegebenheiten sowie natürlicher Akkumulatvorkommen und Krusten auf künstlichen Substraten untersucht. An den diagenetisch gebildeten Akkumulaten wurden chemische Zusammensetzung, Mineralogie, physikalische Parameter, Morphologie und Internstrukturen untersucht. Wichtige Faktoren für die Entstehung der Mangan-Eisen-Akkumulate sind geringe Sedimentationsraten am Entstehungsort, das Vorhandensein geeigneter Anlagerungskerne sowie ausreichende Zufuhr von gelöstem Mangan und anderen Metallen durch Diffusion aus dem Sediment und durch lateralen Transport im freien Wasser vor allem im Sommer und Frühherbst infolge absinkender Sauerstoffgehalte im Bodenwasser der Rinnen. Die Experimente ergaben eine saisonale Abscheidungscharakteristik der Mangan-Eisen-Oxide in Abhängigkeit von der hydrographischen Jahresentwicklung mit niedrigen Zuwachsraten im Winter und Frühjahr und hohen Werten im Sommer und Herbst. Die 1981 experimentell ermittelte Wachstumsrate liegt im Bereich der südlichen Kieler Bucht (Boknis Eck) bei ca. 20 mm/1000 a. Für das Vorkommen vor Schleimünde wurden in Anlehnung an SUESS & DJAFARI (1977) 30-50 mm/1000 a berechnet. Unter reduzierenden Bedingungen infolge Sedimentüberdeckung können Mangan-Eisen-Akkumulate partiell oder vollständig wieder aufgelöst werden. Für den Verbleib der Akkumulate an der Sedimentoberfläche wird die Bedeutung der Seenelke Metridium senile nachgewiesen.

Chemical composition of iron-manganese and phosphate rocks from aseismic ridges of the Indian Ocean and from the continental slope of the Southeast Africa

Study of chemical composition of 26 samples collected at depths from 400 to 1400 m on vertex surfaces of the Southeast Indian Ridge, Mascarene Ridge, Madagascar Ridge, and Mozambique Ridge, as well as on the upper part of the Southeast Africa continental slope showed that the samples represent three groups of rocks: 1) low phosphate or phosphate-free ferromanganese rocks, 2) phosphate ferromanganese rocks 3) phosphorites and phosphatized limestones.

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.

Geochemistry, isotopic ratios and mineral composition of samples from ODP Leg 163 sites

Thirty-five samples from the drill core of the three Leg 163 sites (Sites 988, 989, and 990) off the southeast coast of Greenland were analyzed for 27 major, minor, and trace elements by X-ray fluorescence (XRF) and for 25 trace elements, including 14 rare-earth elements (REEs), by an inductively coupled plasma source mass spectrometer (ICP/MS). Sr- and Nd-isotope data are reported for seven samples and oxygen-isotope data are reported for 19 plagioclase separates. In addition, a reconnaissance survey of the composition of the main mineral phases, plagioclase, pyroxene, and oxides was determined on an electron microprobe to provide the basic information required for petrogenetic modeling. Olivine pseudomorphs are present in many of the samples, but in no case was an olivine grain found that was fresh enough to give a reliable analysis. The chemical and isotopic data recorded here were determined to provide a comparison with the larger data sets acquired by the Edinburgh, Copenhagen, and Leicester laboratories from both Legs 152 and 163 drill cores. This will permit a detailed comparison of the North Atlantic flood basalt province as a whole with the better known Columbia River, Deccan, and Karoo continental flood basalt provinces, for which substantial chemical data sets are already available at Washington State University.

Geochemistry of ODP Leg 129 igneous rocks

This report presents all the available major and trace elemental analyses and Sr, Nd, and Pb isotopic compositions of basaltic rocks recovered from Ocean Drilling Program Sites 800, 801, and 802 during Leg 129 (Table 1). Its main purpose is to provide other investigators a complete summary of geochemical data for Leg 129 basement basalts that they can use for later work. Detailed discussions of the data are presented elsewhere in the volume by Floyd and Castillo (Site 801 geochemistry and petrogenesis, dataset: doi:10.1594/PANGAEA.779154) Floyd et al. (Sites 800 and 802 geochemistry and petrography, dataset: doi:10.1594/PANGAEA.779129), Alt et al. (Site 801 alteration, dataset: doi:10.1594/PANGAEA.779207), and Castillo et al. (Sr, Nd, and Pb isotope geochemistry of Leg 129 basalts, dataset: doi:10.1594/PANGAEA.779191).