(Table 1) Estimated e-Nd(0) input calculated using the relative fraction of ODP Hole 105-647A amphibole grains originated from different provinces of the North America

Many marine radiogenic isotope records show both spatial and temporal variations, reflecting both the degree of mixing of distinct sources in the oceans and changes in the distribution of chemical weathering on the continents. However, changes in weathering and transport processes may themselves affect the composition of radiogenic isotopes released into seawater. The provenance of physically weathered material in the Labrador Sea, constrained through the use of Ar-Ar ages of individual detrital minerals, has been used to estimate the relative contributions of chemically weathered terranes releasing radiogenic isotopes into the Labrador Sea. A simple box-model approach for balancing observed Nd-isotope variations has been used to constrain the relative importance of localised input in the Labrador Sea, and the subsequent mixing of Labrador Sea Water into North Atlantic Deep-Water. The long-term pattern of erosion and deep-water formation around the North Atlantic seems to have been a relatively stable feature since 1.5 Ma, although there has been a dramatic shift in the nature of physical and chemical weathering affecting the release of Hf and Pb isotopes. The modelled Nd isotopes imply a relative decrease in water mass advection into the Labrador Sea between 2.4 and 1.5 Ma, accompanied by a decrease in the rate of overturning, possibly caused by an increased freshwater input into the Labrador Sea.

Geochemistry of basalts at DSDP Leg 73 Holes

During Deep Sea Drilling Project Leg 73 (South Atlantic), basaltic pillow lava, flows, and sills were encountered in Holes 519A, 520, 522B, and 524. Paleomagnetic data indicate that the basalts from Holes 519A (magnetic Anomaly 51) and 522B (Anomaly 16) have ages of about 12 m.y. and about 38 m.y., respectively. The major- and trace- (including rare-earth-) element characteristics of the Hole 519A basalts (a total of 27 m) demonstrate that these basalts are typical normal-type mid-ocean-ridge basalts (N-type MORB). In composition the basalts overlap olivine tholeiites from other normal Mid-Atlantic Ridge segments. Both the spectra of incompatible, or less-hygromagmatophile elements (such as Ti, V, Y, and Zr) and REE abundances indicate that these basalts are the result of a low-pressure fractionation of olivine, spinel, and Plagioclase prior to eruption. In Hole 520 only 1.7 m of basalt were recovered from a total drilling depth of 10.5 m. These pillow basalts crystallized from fairly evolved (N-type MORB) tholeiitic melts. In total, 19 m of basaltic pillow lavas and flows were penetrated in Hole 522B. Thirteen cooling units were distinguished on the basis of glassy margins and fine quench textures. In contrast to Holes 519A and 520, the basalts of the Hole 522B ridge section can be divided into two major groups of tholeiites: (1) Cooling Units 1 through 12 and (2) Cooling Unit 13. The basalts in this ridge section are also N-type MORBs but are generally more differentiated than those of Holes 519A and 520. The lowermost basalts (Cooling Unit 13) have the most primitive composition and make up a compositional group distinct from the more evolved basalts in the twelve units above it. Hole 524 was drilled on the south flank of the Walvis Ridge and thus provided samples from a more complex part of the South Atlantic seafloor. Three different basaltic rock suites, interlayered with volcanic detrital sediments, were encountered. The rock suites are, from top to bottom, an alkali basaltic pillow lava; a 16-m-thick alkaline diabase sill with an age of about 65 m.y. (according to K-Ar dating and planktonic foraminifers); and a second sill that is approximately 9 m thick, about 74 m.y. in age, and tholeiitic in composition, thus contrasting strongly with the overlying alkaline rocks. The alkali basalts of Hole 524 show chemical characteristics that are very similar to the basaltic lavas of the Tristan da Cunha group volcanoes, which are located approximately 400 km east of the Mid-Atlantic Ridge crest. Thus, the Walvis Ridge may plausibly be interpreted as a line of hot-spot alkaline volcanoes.

Iron isotope and trace metal record of Cenomanian-Turonian sediments

he global carbon cycle during the mid-Cretaceous (~125-88 million years ago, Ma) experienced numerous major perturbations linked to increased organic carbon burial under widespread, possibly basin-scale oxygen deficiency and episodes of euxinia (anoxic and H2S-containing). The largest of these episodes, the Cenomanian-Turonian boundary event (ca. 93.5 Ma), or oceanic anoxic event (OAE) 2, was marked by pervasive deposition of organic-rich, laminated black shales in deep waters and in some cases across continental shelves. This deposition is recorded in a pronounced positive carbon isotope excursion seen ubiquitously in carbonates and organic matter. Enrichments of redox-sensitive, often bioessential trace metals, including Fe and Mo, indicate major shifts in their biogeochemical cycles under reducing conditions that may be linked to changes in primary production. Iron enrichments and bulk Fe isotope compositions track the sources and sinks of Fe in the proto-North Atlantic at seven localities marked by diverse depositional conditions. Included are an ancestral mid-ocean ridge and euxinic, intermittently euxinic, and oxic settings across varying paleodepths throughout the basin. These data yield evidence for a reactive Fe shuttle that likely delivered Fe from the shallow shelf to the deep ocean basin, as well as (1) hydrothermal sources enhanced by accelerated seafloor spreading or emplacement of large igneous province(s) and (2) local-scale Fe remobilization within the sediment column. This study, the first to explore Fe cycling and enrichment patterns on an ocean scale using iron isotope data, demonstrates the complex processes operating on this scale that can mask simple source-sink relationships. The data imply that the proto-North Atlantic received elevated Fe inputs from several sources (e.g., hydrothermal, shuttle and detrital inputs) and that the redox state of the basin was not exclusively euxinic, suggesting previously unknown heterogeneity in depositional conditions and biogeochemical cycling within those settings during OAE-2.

(Table 1) Percentage of non-opaque heavy minerals, heavy residue, magnetite, and opaque heavy minerals, DSDP Sites 58-445 and 58-446

Heavy-mineral analyses were made for 39 samples, 27 from DSDP Site 445 and 12 from Site 446. About one-fourth of the samples were so loose that they were easily disaggregated in water. The amount of heavy residue and the magnetite content of the heavy fraction were very high, 0.2 to 44 per cent and (on the average) more than 20 per cent, respectively. Among the non-opaque heavy minerals, common hornblende (0 to 80%) and augite (0 to 98%) are most abundant. Pale-green and bluish-green amphiboles (around 10%) and the epidote group (a few to 48%) are next in abundance. Euhedral apatite and biotite and irregularly shaped chromite are not abundant, but are present throughout the sequence. Hacksaw structure is developed in pale-green amphibole and augite. At Site 445, a fair amount of chlorite and a few glauconite(?) grains are present from Core 445-81 downward. The content of common hornblende and opaque minerals also changes from Core 445-81 downward. A geological boundary may exist between Cores 445-77 and 445-81. Source rocks of the sediments at both sites were basaltic volcanic rocks (possibly alkali suite), schists, and ultramafic rocks. The degree of lithification and amount of heavy residue, and the content of magnetite, non-opaque heavy minerals (excluding mafic minerals), and mafic minerals in the cores were compared with Eocene, Oligocene, and Miocene sandstones of southwest Japan. In many respects, the sediments at Sites 445 and 446 are quite different from those of southwest Japan. From the early Eocene to the early Miocene, the area of these sites belonged to a different geologic province than southwest Japan.

Mineralogy and geochemistry of Mg-phyllosilicates from Middle Valley, northern Juan de Fuca Ridge

We present results of a detailed mineralogical and geochemical study of the progressive hydrothermal alteration of clastic sediments recovered at ODP Site 858 in an area of active hydrothermal venting at the sedimented, axial rift valley of Middle Valley (northern Juan de Fuca Ridge). These results allow a characterization of newly formed phyllosilicates and provide constraints on the mechanisms of clay formation and controls of mineral reactions on the chemical and isotopic composition of hydrothermal fluids. Hydrothermal alteration at Site 858 is characterized by a progressive change in phyllosilicate assemblages with depth. In the immediate vent area, at Hole 858B, detrital layers are intercalated with pure hydrothermal precipitates at the top of the section, with a predominance of hydrothermal phases at depth. Sequentially downhole in Hole 858B, the clay fraction of the pure hydrothermal layers changes from smectite to corrensite to swelling chlorite and finally to chlorite. In three pure hydrothermal layers in the deepest part of Hole 858B, the clay minerals coexist with neoformed quartz. Neoformed and detrital components are clearly distinguished on the basis of morphology, as seen by SEM and TEM, and by their chemical and stable isotope compositions. Corrensite is characterized by a 24 Å stacking sequence and high Si- and Mg-contents, with Fe/(Fe+Mg) ratio of = 0.08. We propose that corrensite is a unique, possibly metastable, mineralogical phase and was precipitated directly from seawater-dominated hydrothermal fluids. Hydrothermal chlorite in Hole 858B has a stacking sequence of 14 Å with Fe/(Fe+Mg) ratios of ? 0.35. The chemistry and structure of swelling chlorite suggest that it is a corrensiteychlorite mixed-layer phase. The mineralogical zonation in Hole 858B is accompanied by a systematic decrease in d18O, reflecting both the high thermal gradients that prevail at Site 858 and extensive sediment-fluid interaction. Precipitation of the Mg-phyllosilicates in the vent region directly controls the chemical and isotopic compositions of the pore fluids. This is particularly evident by decreases in Mg and enrichments in deuterium and salinity in the pore fluids at depths at which corrensite and chlorite are formed. Structural formulae calculated from TEM-EDX analyses were used to construct clay-H2O oxygen isotope fractionation curves based on oxygen bond models. Our results suggest isotopic disequilibrium conditions for corrensite-quartz and swelling chlorite-quartz precipitation, but yield an equilibrium temperature of 300° C ± 30° for chlorite-quartz at 32 m below the surface. This estimate is consistent with independent estimates and indicates steep thermal gradients of 10-11°/m in the vent region.

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.

Heavy and light minerals at DSDP Leg 67 Holes

Heavy and light minerals were examined in 29 samples from Sites 494, 498, 499, 500, and 495 on the Deep Sea Drilling Project Leg 67 Middle America Trench transect; these sites represent lower slope, trench, and oceanic crust environments off Guatemala. All samples are Quaternary except those from Hole 494A (Pliocene) and Hole 498A (Miocene). Heavy-mineral assemblages of the Quaternary sediments are characterized by an immature pyroxene-amphibole suite with small quantities of olivine and epidote. The Miocene sediments yielded an assemblage dominated by epidote and pyroxene but lacking olivine; the absence of olivine is attributed to selective removal of the most unstable components by intrastratal solution. Light-mineral assemblages of all samples are predominantly characterized by volcanic glass and plagioclase feldspar. The feldspar compositions are compatible with andesitic source rocks and frequently exhibit oscillatory zoning. The heavy- and light-mineral associations of these sediments suggest a proximal volcanic source, most probably the Neogene highland volcanic province of Guatemala. Sand-sized components from Site 495 are mainly biogenic skeletons and volcanic glass and, in one instance (Section 495-5-3), euhedral crystals of gypsum.

Pb isotope and geochemical record of Arctic sediments

Elemental and Pb isotope measurements were performed on leachates and residues from surface sediments and two <50 cm cores (MC04 and MC16) collected along a NE-SW transect through Fram Strait. Geochemical and isotopic properties of residues from surface sediments define three distinct spatial domains within the Strait: 1) the easternmost edge of the Strait; 2) the eastern part of the Strait off the Svalbard margins; and 3) the western part of the Strait, influenced by supplies from Svalbard, the Nordic seas with possible contributions from northwestern Siberian margins, and sea ice and water outflow from the Arctic, respectively. Core MC16, in the third domain beneath the outflowing Arctic waters, spans the Last Glacial Maximum present interval. Sediments from this core were leached to obtain detrital (residues) and exchangeable (leachates) fractions. Detrital supplies to core MC16 are believed to originate mainly from melting of the overlying sea ice and thus can be used to document changes in Arctic sedimentary sources. Detrital 206Pb/204Pb and 208Pb/206Pb ratios illustrate two mixing trends, Trends A and B, corresponding to the pre- and post-Younger Dryas (YD) intervals, respectively. These trends represent binary mixtures with a common end-member (Canadian margins) and either a Siberian (Trend A) or Greenland (Trend B) margin end-member. The YD is marked by an isotopic excursion toward the Canadian end-member, suggesting a very active Beaufort Gyre possibly triggered by massive drainage of the Laurentide ice sheet. Pb isotope compositions of leachates, thought to represent the signature of the overlying water masses, define a unique linear trend coincident with Trend A. This suggests that water masses acquired their signature through exchange with particulate fluxes along the Canadian and Siberian continental margins.

Mineral composition and experimental results from XRD analyses of sediments from ODP Leg 190 sites

X-ray diffraction analyses of the clay-sized fraction of sediments from the Nankai Trough and Shikoku Basin (Sites 1173, 1174, and 1177 of the Ocean Drilling Program) reveal spatial and temporal trends in clay minerals and diagenesis. More detrital smectite was transported into the Shikoku Basin during the early-middle Miocene than what we observe today, and smectite input decreased progressively through the late Miocene and Pliocene. Volcanic ash has been altered to dioctahedral smectite in the upper Shikoku Basin facies at Site 1173; the ash alteration front shifts upsection to the outer trench-wedge facies at Site 1174. At greater depths (lower Shikoku Basin facies), smectite alters to illite/smectite mixed-layer clay, but reaction progress is incomplete. Using ambient geothermal conditions, a kinetic model overpredicts the amount of illite in illite/smectite clays by 15%-20% at Site 1174. Numerical simulations come closer to observations if the concentration of potassium in pore water is reduced or the time of burial is shortened. Model results match X-ray diffraction results fairly well at Site 1173. The geothermal gradient at Site 1177 is substantially lower than at Sites 1173 and 1174; consequently, volcanic ash alters to smectite in lower Shikoku Basin deposits but smectite-illite diagenesis has not started. The absolute abundance of smectite in mudstones from Site 1177 is sufficient (30-60 wt%) to influence the strata's shear strength and hydrogeology as they subduct along the Ashizuri Transect.

Geochemistry of Mid-Atlantic Ridge sediments

Geochemical compositions and Sr and Nd isotopes were measured in two cores collected ~2 and 5 km from the Rainbow hydrothermal vent site on the Mid-Atlantic Ridge. Overall, the cores record enrichments in Fe and other metals from hydrothermal fallout, but sequential dissolution of the sediments allows discrimination between a leach phase (easily leachable) and a residue phase (refractory). The oxy-anion and transition metal distribution combined with rare earth element (REE) patterns suggest that (1) the leach fraction is a mixture of biogenic carbonate and hydrothermal Fe-Mn oxy-hydroxide with no significant contribution from detrital material and (2) >99.5% of the REE content of the leach fraction is of seawater origin. In addition, the leach fraction has an average 87Sr/86Sr ratio indistinguishable from modern seawater at 0.70916. Although we lack the epsilon-Nd value of present-day deep water at the Rainbow vent site, we believe that the REE budget of the leach fraction is predominantly of seawater origin. We suggest therefore that the leach fraction provides a record of local seawater epsilon-Nd values. Nd isotope data from these cores span the period of 4-14 ka (14C ages) and yield epsilon-Nd values for North East Atlantic Deep Water (NEADW) that are higher (-9.3 to -11.1) than those observed in the nearby Madeira Abyssal Plain from the same depth (-12.4 ± 0.9). This observation suggests that either the Iceland-Scotland Overflow Water (ISOW) and Lower Deep Water contributions to the formation of NEADW are higher along the Mid-Atlantic Ridge than in the surrounding basins or that the relative proportion of ISOW was higher during this period than is observed today. This study indicates that hydrothermal sediments have the potential to provide a higher-resolution record of deep water epsilon-Nd values, and hence deepwater circulation patterns in the oceans, than is possible from other types of sediments.

Sedimentology and Th, Pa, U, and N isotopic composition of core MD84-527

High-resolution records of opal, carbonate, and terrigenous fluxes have been obtained from a high-sedimentation rate core (MD84-527: 43°50'S; 51°19'E; 3269 m) by normalization to 230Th. This method estimates paleofluxes to the seafloor on a point-by-point basis and distinguishes changes in sediment accumulation due to variations in vertical rain rates from those due to changes in syndepositional sediment redistribution by bottom currents. We also measured sediment delta15N to evaluate the changes in nitrate utilization in the overlying surface waters associated with paleoflux variations. Our results show that opal accumulation rates on the seafloor during the Holocene and stage 3, based on 14C dating, were respectively tenfold and fivefold higher than the vertical rain rates, At this particular location, changes in opal accumulation on the seafloor appear to be mainly controlled by sediment redistribution by bottom currents rather than variations in opal fluxes from the overlying water column. Correction for syndepositional sediment redistribution and the improved time resolution that can be achieved by normalization to 230Th disclose important variations in opal rain rates. We found relatively high but variable opal paleoflux during stage 3, with two maxima centered at 36 and 30 kyr B.P., low opal paleoflux during stage 2 and deglaciation and a pronounced maximum during the early Holocene, We interpret this record as reflecting variations in opal production rates associated with climate-induced latitudinal migration of the southern ocean frontal system. Sediments deposited during periods of high opal paleoflux also have high authigenic U concentrations, suggesting more reducing conditions in the sediment, and high Pa-231/Th-230 ratios, suggesting increased scavenging from the water column. Sediment delta15N is circa 1.5 per mil higher during isotopic stage 2 and deglaciation. The low opal rain rates recorded during that period appear to have been associated with increased nitrate depletion. This suggests that opal paleofluxes do not simply reflect latitudinal migration of the frontal system but also changes in the structure of the upper water column. Increased stratification during isotopic stage 2 and deglaciation could have been produced by a meltwater lid, leading to lower nitrate supply rates to surface waters.

Chemical and mineral compositions of bottom sediments and ferromanganese crusts and nodules near Iceland

Results of study of bottom sediments near Iceland and on the Jan Mayen Island are reported. It was found that in recent sediments chemical elements are mainly associated with pyro- and volcanoclastics. In some areas adjusted to deep-seated faults ancient iron-manganese crusts and sediments occur. They are rich in Ni, Co, V, Cu, Mo, Cd and other elements associated with endogenic matter.

Composition of bottom sediments from the Guinea Basin

Geomorphology of the Guinea Basin is described along with sediments from cores collected on the abyssal plain, within the abyssal hill zone, and in the eastern part of the Chain Fracture Zone. Stratigraphic differentiation of deep-sea sediments was based on diatom analysis, geochemical and lithological data. Holocene and Pleistocene were identified by these criteria. The lower boundary of Holocene is was found from a marked decrease in CaCO3 concentration and total diatom count. Mineral and chemical compositions are given for coarse silt fraction of various Late Pleistocene sediments. It is shown that this facial complex is determined by tectonic position of the Guinea Basin.