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.

Geochemistry of Eocene sediments from ODP Site 171-1052 on the Black Nose, Atlantic Ocean

We use an X-ray fluorescence (XRF) Core Scanner to obtain records of elemental concentrations in sediment cores from Ocean Drilling Program (ODP) Leg 171B, Site 1052 (Blake Nose, Atlantic margin of northern Florida).This record spans the Middle to Late Eocene, as indicated by bio- and magnetostratigraphy, and displays cyclicity that can be attributed to the orbital forcing of a combination of climate, ocean circulation, or productivity. We use the XRF counts of iron and calcium as a proxy of the relative contribution from calcium carbonate and terrestrial material to construct a new composite depth record. This new composite depth record provides the basis to extend the astronomically calibrated geological time scale into the Middle Eocene and results in revised estimates for the age and duration of magnetochrons C16 through C18. In addition, we find an apparent change in the dominance of orbitally driven changes in obliquity and climatic precession at around 36.7 Ma on our new time scale. Long term amplitude modulation patterns of eccentricity and obliquity in the data do not seem to match the current astronomical model any more, suggesting the possibility of new constraints on astronomical calculations.

Chemistry of smectite and volcanic glass of ODP Site 159-959

The Ocean Drilling Program (ODP) Site 959 was drilled in the northern border of the Côte d'Ivoire-Ghana Ridge at a water depth of 2100 m. Pleistocene total thickness does not exceed 20 m. Winnowing processes resulted in a low accumulation rate and notable stratigraphic hiatuses. During the Late Pleistocene, bottom circulation was very active and controlled laminae deposition (contourites) which increased the concentration of glauconitic infillings of foraminifera, and of volcanic glass and blue-green grains more rarely, with one or several subordinate ferromagnesian silicates. Volcanic glass generally was X-ray amorphous and schematically classified as basic to intermediate (44-60% SiO2). Opal-A or opal-CT suggested the beginning of the palagonitisation process, and previous smectitic deposits may have been eroded mechanically. The blue-green grains presented two main types of mineralogic composition: (1) neoformed K, Fe-smectite associated with zeolite (like phillipsite) and unequal amounts of quartz and anorthite; (2) feldspathic grains dominated by albite but including quartz, volcanic glass and smectites as accessory components. They were more or less associated with the volcanic glass. On the basis of their chemical composition, the genetic relationship between the blue-green grains and the volcanic glass seemed to be obvious although some heterogeneous grains seemed to be primary ignimbrite and not the result of glass weathering. The most reasonable origin of these pyroclastic ejecta would be explosive events from the Cameroon Volcanic Ridge, especially from the Sao Thome and Principe Islands and Mount Cameroon area. This is supported both by grain geochemistry and the time of volcanic activity, i.e. Pleistocene. After westward wind transport (some 1200 km) and ash fall-out, the subsequent winnowing by bottom currents controlled the concentration of the volcanic grains previously disseminated inside the hemipelagic sediment. Palagonitisation, and especially phillipsite formation, may result from a relatively rapid reaction during burial diagenesis (<1 m.y.), in deep-sea deposits at relatively low sedimentation rate. However, it cannot be excluded that the weathering had begun widely on the Cameroon Ridge before the explosive event.

Chemical and Sr isotopic compositions of 3 step leachates and residues of bulk samples, zeolites, and smectites from Lower Miocene sediments at ODP Site 166-1007

Massive clinoptilolite authigenesis was observed at about 1105 meters below sea floor (mbsf) in lower Miocene wellcompacted carbonate periplatform sediments from the Great Bahama Bank [Ocean Drilling Program, ODP Leg 166, Site 1007]. The diagenetic assemblage comprises abundant zeolite crystallized within foraminifer tests and sedimentary matrix, as well as Mg smectites. In carbonate-rich deposits, the formation of the zeolite requires a supply of silica. Thus, the objective of the study is to determine the origin of the silica supply, its diagenetic evolution, and consequently the related implications on interpretation of the sedimentary record, in terms of local or global paleoceanographic change. For lack of evidence for any volcaniclastic input or traces of Si-enriched deep fluids circulation, an in situ biogenic source of silica is validated by isotopic data and chemical modeling for the formation of such secondary minerals in shallow-water carbonate sequences. Geochemical and strontium isotopic data clearly establish the marine signature of the diagenetic zeolite, as well as its contemporaneous formation with the carbonate deposition (Sr model ages of 19.6-23.2 Ma). The test of saturation for the pore fluids specifies the equilibrium state of the present mineralogical assemblage. Seawater-rock modeling specifies that clinoptilolite precipitates from the dissolution of biogenic silica, which reacts with clay minerals. The amount of silica (opal-A) involved in the reaction has to be significant enough, at least 10 wt.%, to account for the observed content of clinoptilolite occurring at the most zeolite-rich level. Modeling also shows that the observed amount of clinoptilolite (~19%) reflects an in situ and short-term reaction due to the high reactivity of primary biogenic silica (opal-A) until its complete depletion. The episodic occurrence of these well-lithified zeolite-rich levels is consistent with the occurrence of seismic reflectors, particularly the P2 seismic sequence boundary located at 1115 mbsf depth and dated as 23.2 Ma. The age range of most zeolitic sedimentary levels (biostratigraphic ages of 21.5-22 Ma) correlates well with that of the early Miocene glaciation Mi-1 and Mi-1a global events. Thus, the clinoptilolite occurrence in the shallow carbonate platform environment far from volcanogenic supply, or in other sensitive marine areas, is potentially a significant new proxy for paleoproductivity and oceanic global events, such as the Miocene events, which are usually recognized in deep-sea pelagic sediments and high latitude deposits.

Sedimentation at Manop Site H in the eastern equatorial Pacific

Gravity cores recovered from Manganese Nodule Project site H (6°33'N, 92°49'W) show marked downcore variations in the abundance of calcium carbonate, organic carbon, opal, manganese, and other components deposited over the past 400,000 years. Variations in the downcore abundance of organic carbon, which ranges from 0.2 to 1.0%, can be used to hindcast redox conditions in the surface sediments over this time. The results indicate that the depth to the manganese redox boundary varied from about 5 to 25 cm below the seafloor during four major cycles. Downcore variations in solid phase Mn, Ni, and Cu can be produced by such changes in redox conditions. A model which predicts that solid phase Mn can be trapped and buried when the Mn redox boundary migrates rapidly upward is consistent with the observed organic carbon and Mn records and supports the reconstructed redox variations. The history of redox variations at site H can be explained by changes with time in surface water productivity. Major productivity variations at the site occur over 100-kyr cycles, with relatively higher productivity occurring during glacial stages. Thus Quaternary climate changes influence surface water productivity, redox conditions in sediments, and the cycling of transition metals.

Texture, geochemistry, isotope composition, petrography and epoch at DSDP Site 93-603

Abundant Fe-Mn carbonate concretions (mainly siderite, manganosiderite, and rhodochrosite) were found in the hemipelagic claystones of Site 603 on the eastern North American continental rise. They occur as nodules, micronodules, or carbonate-replaced burrow fills and layers at a subbottom depth of between ~ 120 (Pliocene) and 1160 m (Albian-Cenomanian). In general, the Fe-Mn carbonate concretions form from CO3- produced by the microbiological degradation of organic matter in the presence of abundant Fe + or Mn + and very low S- concentrations. However, there is also some evidence for diagenetic replacement of preexisting calcite by siderite. The carbon isotope composition of diagenetic Fe-Mn carbonate nodules is determined by CO2 reduction during methanogenesis. Carbonate nodules in Cretaceous sediments at sub-bottom depths of 1085 and 1160 m have distinctly lower d13C values (- 12.2 and - 12.9 per mil) than Neogene siderites, associated with abundant biogenic methane in the pore space (-8.9 to 1.7 per mil between 330 and 780 m depth). Since no isotopic zonation could be detected within individual nodules, we assume that the isotopic composition reflects more or less geochemical conditions at the present burial depth of the carbonate nodules. Carbonates did not precipitate within the zone of sulfate reduction (approximately 0.01 to 10 m), where all of the pyrite was formed. The oxygen isotope composition indicates precipitation from seawater-derived interstitial waters. The d18O values decrease with increasing burial depth from + 5.1 to - 1.2 per mil, suggesting successively higher temperatures during carbonate formation.

Major and rare earth element composition of ODP Site 191-1179 sediments, northwest Pacific

Depth profiles of major element and rare earth element (REE) abundances in sediment samples (mainly siliceous ooze and clay) recovered from Holes 1179B and 1179C at Site 1179, Ocean Drilling Program Leg 191 (41.4°N, 159.6°E) were determined. The oxidation states of Mn and Ce were determined by X-ray absorption near-edge structure. Some geochemical indicators were tested, including the MnO/TiO2 ratios, a bivariate diagram of La/Ce vs. Al2O3/(Al2O3+Fe2O3), and other discrimination diagrams. The oxidation state of Mn is reduced Mn(II) in the depth profile below 0.60 meters below seafloor (mbsf), which is consistent with relatively low and high abundances of Mn in the sediments and pore waters, respectively. It is possible that the diagenetic effect on the oxidation state and abundance of Mn makes it difficult for the MnO/TiO2 ratio to reflect the depositional environment. The normalized ratio of La and Ce does not change very much with depth, suggesting that the diagenetic effect does not affect the REE signature in the sediments. On the diagram of La/Ce vs. Al2O3/(Al2O3+Fe2O3), the sediments studied here plot at the boundary of the pelagic and continental margin fields. This suggests that continental material has contributed to the sediment to some degree, even though Site 1179 is in a pelagic region of the northwestern Pacific Ocean, >1600 km from Japan.

Magnetic properties of ODP Site 175-1075

We present sediment magnetic and chemical analysis of cyclic ocean sediments of the upwelling region of the Lower Congo Basin (equatorial Atlantic). We investigated two >100-k.y. intervals from Ocean Drilling Program Site 1075 to analyze the hysteresis properties, sources of magnetic susceptibility, anhysteretic remanent magnetizations, thermomagnetic behavior, and element concentrations of Fe, Ca, Ti, Mn, and K using an X-ray fluorescence (XRF) core scanner. The upper interval was sampled between 14 and 32 meters composite depth (mcd; 0.09-0.21 Ma) and the lower between 141 and 163 mcd (1.31-1.54 Ma) at a resolution of 20 cm, which represents a temporal resolution of 2.0 and 1.3 k.y., respectively. XRF core-scanner data were acquired at 5-cm intervals. The measurements show that ferri(o)magnetic minerals have no significant influence on the cyclicity of the magnetic susceptibility, which is dominated by paramagnetic and diamagnetic minerals and reflects changes of sediment input from the Congo River. The Fe, Ti, K, and Mn concentrations covary with the magnetic susceptibility where high concentrations of these elements correlate with intervals of high susceptibility and low concentrations with intervals of low susceptibility. The Ca counts correlate well with the calcium carbonate concentration but do not show the same cyclicity as the other elements or the susceptibility. With the exception of the Ca concentration, which is significantly higher in the upper interval, and the magnetic grain size, which indicates that less fine grained magnetite is present in the lower interval, no significant differences in the properties of the upper and the lower intervals were detected.

XRF scanning, pollen and spores of ODP Site 108-659

Pliocene vegetation dynamics and climate variability in West Africa have been investigated through pollen and XRF-scanning records obtained from sediment cores of ODP Site 659 (18°N, 21°W). The comparison between total pollen accumulation rates and Ti/Ca ratios, which is strongly correlated with the dust input at the site, showed elevated aeolian transport of pollen during dusty periods. Comparison of the pollen records of ODP Site 659 and the nearby Site 658 resulted in a robust reconstruction of West African vegetation change since the Late Pliocene. Between 3.6 and 3.0 Ma the savannah in West Africa differed in composition from its modern counterpart and was richer in Asteraceae, in particular of the Tribus Cichorieae. Between 3.24 and 3.20 Ma a stable wet period is inferred from the Fe/K ratios, which could stand for a narrower and better specified mid-Pliocene (mid-Piacenzian) warm time slice. The northward extension of woodland and savannah, albeit fluctuating, was generally greater in the Pliocene. NE trade wind vigour increased intermittently around 2.7 and 2.6 Ma, and more or less permanently since 2.5 Ma, as inferred from increased pollen concentrations of trade wind indicators (Ephedra, Artemisia, Pinus). Our findings link the NE trade wind development with the intensification of the Northern Hemisphere glaciations (iNHG). Prior to the iNHG, little or no systematic relation could be found between sea surface temperatures of the North Atlantic with aridity and dust in West Africa.

Composition and origin of sediments at DSDP Site 54-424

The sediments recovered on Deep Sea Drilling Project Leg 54 appear to be mixtures of the normal pelagic sediments of the area and hydrothermally produced manganese and iron phases. The latter are mineralogically and chemically very similar to phases recovered from surficial sampling of the mounds. The hydrothermal nontronite which is approximately 15 meters thick in the three holes is essentially free of carbonate or detrital contaminants. The basal sediments are similar to the carbonate oozes presently being deposited in the region, but are enriched in Mn and Fe. This enrichment appears to be the result of hydrothermal deposition that took place at or near the spreading center and may not be associated with the mounds formation. Three different hypotheses for the formation of the nontronite layer and the mounds deposits are considered. An initial deposition of a widespread nontronite layer and subsequent diapiric-like movement of the layer into carbonates could account for the observed stratigraphy; however, if this be correct, analogous deposits should be present in other DSDP sites. The second hypothesis - replacement of the normal sediments by nontronite - may be feasible, but the high purity of the nontronite requires dissolution and removal of refractory elements. The third hypothesis, metal deposition in an advancing oxidation gradient, is compatible with submersible observations of the mounds; however, it can account only for the high purity of the nontronite by very rapid deposition of the hydrothermal phases.

Chemistry of Globigerinoides ruber shells from ODP Site 160-963

Here we present a high-resolution faunal, floral and geochemical (stable isotopes and trace elements) record from the sediments of Ocean Drilling Program Site 963 (central Mediterranean basin), which shows centennial/millennial-scale resemblance to the high-northern latitude rapid temperature fluctuations documented in the Greenland ice cores between 20 and 70 kyr BP. Oxygen and carbon isotopes, planktic foraminifera and calcareous nannofossil distributions suggest that Dansgaard-Oeschger (D/O) and Heinrich events (HE) are distinctly expressed in the Mediterranean climate record. Moreover, recurrent though subdued oscillations not previously identified in the Lateglacial Mediterranean sediments document a significant centennial-scale climate variability in the basin that is greater than previously thought. Alternations between climate regimes dominated by polar outbreaks during D/O stadials and warm D/O interstadials, with associated intensification of continental runoff, are well expressed in the ODP Site 963. These place the Mediterranean basin as an often overlooked recorder of the interplay between large- and regional- scale climate controls at intermediate latitudes, and of the possible interactions between different components of the climate system. Significant changes in Ba/Ca values measured in Globigerinoides ruber shells from a number of D/O stadials and interstadials suggest enhanced freshwater input from the north-eastern Mediterranean borderland during the D/O interstadials. However, the short duration of 3D stratification events never led to complete oxygen consumption along the water column, but clear effects of sluggish 3D circulation in the basin are testified to by negative excursions in d13C measured in selected species of planktic and benthic foraminifera. HEs are constantly associated with lightening in the d18O record of planktic foraminifera, possibly because of the impact of iceberg melting in the Iberian Margin on Mediterranean thermohaline circulation. Interestingly, in two cases in particular, HE2 and HE5, fresher water inputs also affected deeper horizons of intermediate waters, suggesting a basin-wide impact.

Geochemistry of FeMn oxyhydroxides of IODP Site 303-U1302 and 303-1303

Regional weathering intensity must have changed dramatically at high latitudes during the Quaternary as a consequence of repeated continental glaciation. Investigation of these glacial/interglacial changes at high temporal resolution is possible with the recent development of Pb isotopes in FeMn oxyhydroxide phases as a proxy for region-specific weathering intensity, where increases in the radiogenic component are thought to correspond to increased continental weathering fluxes. Here we present a Pb isotope record sourced from the FeMn oxyhydroxide fraction in marine sediments from IODP Sites U1302/3 on Orphan Knoll (~3500 mbsl, NW Atlantic), spanning the last 37 ka. Located at the eastern edge of the Laurentide Ice Sheet (LIS), Site U1302/3 is well-placed to monitor changes in weathering intensity associated with LIS glacial history. Overall, the data show a close correspondence to local surface water d18O, with least radiogenic values during times of heavy d18O (glacial maximum) and most radiogenic values during times of light d18O (Holocene). This supports the prediction that weathering intensity in glaciated regions of the North Atlantic correlates with the exposure age of glacial debris. Superimposed on these background trends are extreme radiogenic excursions (e.g. variation in 206Pb/204Pb from ~19.2-21.0) contemporaneous with Heinrich events and the Younger Dryas. These data are substantially more radiogenic than existing records from the NW Atlantic, and most likely represent episodes of exceptionally high inputs of pre-formed FeMn oxyhydroxides during drainage of the LIS. Due to its extreme isotope composition, at least in the NW Atlantic region, Pb would appear to be a good proxy for the fluxes of weathered continental material and perhaps, by inference, nutrients to the surface ocean

Isotope ratios, trace elements and ultrastructure results of Mytilus galloprovincialis shells and experimental site data off Ischia (Italy)

Bivalve shells can provide excellent archives of past environmental change but have not been used to interpret ocean acidification events. We investigated carbon, oxygen and trace element records from different shell layers in the mussels Mytilus galloprovincialis combined with detailed investigations of the shell ultrastructure. Mussels from the harbour of Ischia (Mediterranean, Italy) were transplanted and grown in water with mean pHT 7.3 and mean pHT 8.1 near CO2 vents on the east coast of the island. Most prominently, the shells recorded the shock of transplantation, both in their shell ultrastructure, textural and geochemical record. Shell calcite, precipitated subsequently under acidified seawater responded to the pH gradient by an in part disturbed ultrastructure. Geochemical data from all test sites show a strong metabolic effect that exceeds the influence of the low-pH environment. These field experiments showed that care is needed when interpreting potential ocean acidification signals because various parameters affect shell chemistry and ultrastructure. Besides metabolic processes, seawater pH, factors such as salinity, water temperature, food availability and population density all affect the biogenic carbonate shell archive.

Geochemistry at DSDP Site 76-533

Bulk X-ray mineralogy of 47 hemipelagic mud and clay samples from the Blake Outer Ridge has revealed that the sediments contain low magnesian calcite, calcian dolomite, ferroan dolomite, and magnesian siderite. Dolomite and siderite are authigenic and occur as rhombohedrons scattered through the sediments, whereas calcite is mostly biogenic. Pliocene dolomitic lenses are made up of interlocking polyhedral grains of ferroan dolomite. The contents of authigenic dolomite and siderite are 3 to 8% in carbonate sediments and 70 to 89% in dolomitic lenses. Dolomite occurs largely in the cores above 192 m sub-bottom depth, whereas siderite occurs in the cores below 87 m. The distribution and occurrence of dolomite and siderite have determined the diagenetic zonation of carbonates as Zone I (dolomitic zone, top-90 m), Zone II (transition zone, 90-180 m), and Zone III (sideritic zone, 180 m-bottom). Measurements of major and minor elements in the untreated total sediment samples and the insoluble residues after digestion in acid-reducing solution have revealed that the soluble fraction concentrates carbonates and ferromanganese associations (Ca, Mg, Sr, Fe, and Mn). Typical "hydrogenous elements" (Co, Cu, Ni, and V) are more concentrated in the insoluble residues rather than in the soluble fraction; the concentrations of these four elements are low and comparable to modern offshore mud, probably because the Site 533 sediments were deposited at a high rate of sedimentation. The contents of Fe2O3 and MnO are somewhat high for rapidly accumulated mud, particularly in the Pliocene sediments (8.09 and 0.26%, respectively, on a Carbonate-free basis). The high Fe and Mn contents are mainly due to the high contribution of the leacheable nonlithogenous fraction; leacheable Fe and Mn originate in the ferromanganese oxide accumulated on the seafloor. Only a small amount of ferric oxide was converted to iron sulfide in the surficial part of Zone I. Most ferromanganese oxide was reduced and precipitated as ferroan dolomite and magnesian siderite in Zones II and III under high alkalinity and high pH conditions in the organic-matter-rich sediments. Fe2+ and Mn2+ in the deeper sediments beneath Zone III possibly migrated upward and concentrated as siderite in Zone III, hence resulting in high contents of Fe and Mn in the Pliocene sediments. Analysis of carbonate zonation on the Blake Outer Ridge has revealed that the zonation is subparallel to the bedding plane rather than to the present seafloor. The sediments at Site 103 on the flank region of the Ridge are lacking Zone I and most of Zone II, probably the result of erosion of the most of the Pleistocene and Pliocene sediments by the enhanced bottom currents during the Pleistocene.

Geochemistry and isotopes at DSDP Site 68-503

Nodules occur in the siliceous calcareous ooze and siliceous marl at Site 503 in the eastern equatorial Pacific. They are present below a depth of about 11 meters throughout the green-colored reduced part of the section down to 228 meters, although they are most abundant between 30 and 85 meters. They are cylindrical or barrel-shaped, up to 70 mm long, and usually have an axial channel through them or are hollow. They appear to have formed around and/or within burrows. XRD studies and microprobe analyses show that they are homogeneous and consist of calcian rhododrosite and minor calcite; Mn is present to the extent of about 30%. Isotopic analyses of the carbonate give carbon values which range from -1.2 per mil to -3.8 per mil, and oxygen isotope compositions vary from +4.0 per mil to +6.0 per mil. These values are different from those for marine-derived carbonates as exemplified by the soft sediment filling of a burrow: d13C, -0.26 per mil; d18O, +1.05 per mil. The carbon isotope data indicate that carbonate derived (possibly indirectly) from seawater was mixed with some produced by organic diagenesis to form the nodules. The d18O values suggest that although they formed near the sediment surface, some modification or the introduction of additional diagenetic carbonate occurred during burial.