Petrographic description and geochemistry of basalts and altered volcanic rocks from ODP Leg 183 sites

The basalts recovered during Legs 183 and 120 from the southern, central, and northernmost parts of the Kerguelen Plateau (Holes 1136A, 1138A, 1140A, and 747C, respectively), as well as those recovered from the eastern part of the crest of Elan Bank (Hole 1137A), represent derivates from tholeiitic melts. In the northern part of the Kerguelen Plateau (Hole 1140A), basalts may have formed from two sources located at different depths. This is reflected in the presence of both low- and high-titanium basalts. The basalts are variably altered by low-temperature hydrothermal processes (at temperatures up to 120°C), and some are affected by subaerial weathering. The hydrothermal alteration led mainly to the formation of smectites, chlorite minerals, mixed-layer hydromica-smectite and smectite-chlorite minerals, hydromica, serpentine(?), clinoptilolite, heulandite, stilbite, analcime, mordenite, thomsonite, natrolite(?), calcite, quartz, and dickite(?). Alteration of extrusive basalts is mainly related to horizontal fluid flow within permeable contact zones between lava flows. Under a nonoxidizing environment of alteration, the tendency to lose most of elements, including rare earth elements, from basalts dominates. Under on oxidizing environment, basalts accumulate many elements.

Strontium isotopic data for calcareous ooze, chalk, and pore waters from DSDP Hole 590B

A detailed study of strontium isotope variations in Neogene marine carbonate sediments from Deep Sea Drilling Project Site 590B, using techniques that allow the 87Sr/86Sr ratio to be determined to better than +/-0.00001, gives a high-resolution record of the Sr isotopic evolution of seawater. The data show that the rate of change of the marine 87Sr/86Sr ratio has varied significantly even on time scales as short as 1 m.y. Periods of particularly rapid growth appear to follow major marine regressions and probably reflect an increase in the delivery of radiogenic Sr from the continents coupled with a decreased submarine carbonate dissolution rate (greater carbonate compensation depth). Periods of relatively slowly changing 87Sr/86Sr follow major marine transgressions. On the basis of correlations with the marine oxygen isotope record and the times of major continental glacier growth, it is inferred that the effects of sea-level variations are modified by climatic factors that affect the intensity of continental weathering and runoff. The effects of sea-floor generation rate variations are not discernible for the Neogene. The maximum attainable stratigraphic resolution using Sr isotopes is between 0.1 and 2 m.y. for this time period.

Isotope ratios of osmiun, carbon and oxygen of Miocene sediments and benthic foraminifera

Seawater 187Os/188Os ratios for the Middle Miocene were reconstructed by measuring the 187Os/188Os ratios of metalliferous carbonates from the Pacific (DSDP 598) and Atlantic (DSDP 521) oceans. Atlantic and Pacific 187Os/188Os measurements are nearly indistinguishable and are consistent with previously published Os isotope records from Pacific cores. The Atlantic data reported here provide the first direct evidence that the long-term sedimentary 187Os/188Os record reflects whole-ocean changes in the Os isotopic composition of seawater. The Pacific and the Atlantic Os measurements confirm a long-term 0.01/Myr increase in marine 187Os/188Os ratios that began no later than 16 Ma. The beginning of the Os isotopic increase coincided with a decrease in the rate of increase of marine 87Sr/86Sr ratios at 16 Ma. A large increase of 1? in benthic foraminiferal delta18O values, interpreted to reflect global cooling and ice sheet growth, began approximately 1 million years later at 14.8 Ma, and the long-term shift toward lower bulk carbonate delta13C values began more than 2 Myr later around 13.6 Ma. The post-16 Ma increase in marine 187Os/188Os ratios was most likely forced by weathering of radiogenic materials, either old sediments or sialic crust with a sedimentary protolith. We consider two possible Miocene-specific geologic events that can account for both this increase in marine 187Os/188Os ratios and also nearly constant 87Sr/86Sr ratios: (1) the first glacial erosion of sediment-covered cratons in the Northern Hemisphere; (2) the exhumation of the Australian passive margin-New Guinea arc system. The latter event offers a mechanism, via enhanced availability of soluble Ca and Mg silicates in the arc terrane, for the maintenance of assumed low CO2 levels after 15 Ma. The temporal resolution (three samples/Myr) of the 187Os/188Os record from Site 598, for which a stable isotope stratigraphy was also constructed, is significantly higher than that of previously published records. These high resolution data suggest oscillations with amplitudes of 0.01 to 0.02 and periods of around 1 Myr. Although variations in the 187Os/188Os record of this magnitude can be easily resolved analytically, this higher frequency signal must be verified at other sites before it can be safely interpreted as global in extent. However, the short-term 187Os/188Os variations may correlate inversely with short-term benthic foraminiferal delta18O and bulk carbonate delta13C variations that reflect glacioeustatic events.

Climatic impact on Al, K, Sc and Ti in marine sediments: Evidence from ODP Site 1144, South China Sea

Al, K, Sc and Ti concentrations of the terrestrial material-dominant sediments from ODP site 1144 were reported. Comparison between the bulk and the acid-leached sediments indicates that about 20~30% of the Al, K and Sc in the bulk sediments are not hosted in terrestrial detritus, rather they are of authigenic origin. However, authigenic Ti is negligible. The results indicate that Ti rather than Al is the best proxy for terrestrial materials. Significant climate controls are displayed in the Al/Ti, K/Ti and Sc/Ti variation patterns both for the bulk and the acid leached sediments. Such variation patterns can be mainly accounted for in terms of climate change in their provenance areas in South China. Elevated Al/Ti, K/Ti and Sc/Ti ratios during interglacial periods indicate that chemical weathering then was stronger than during glacial periods, which might be related to a more humid climate in interglacial periods.

(Appendix 1) Age, Ge/Si ratio, aluminium and opal contents in ODP Sites 175-1081 and 175-1084

As a result of both culture and sediment core studies, the ratio of germanium (Ge) to silicon (Si) in diatom shells has been proposed as a proxy for monitoring whole-ocean changes in seawater Ge/Si, a ratio affected by changes in continental weathering. However, because of the difficulties of extracting and cleaning diatom frustules from deep-sea sediments, only samples from highly pure diatom oozes in the Antarctic region have been previously analyzed. Here we present data on diatom Ge/Si ratios, (Ge/Si)opal, for the time interval between 3.1 and 1.9 Ma from a mid-latitude, coastal upwelling area where significant terrigenous sediment input complicated the sample processing and analyses. In general, our (Ge/Si)opal values show the same decreasing trend after 2.6 Ma than previously measured in Antarctic sediments (Shemesh et al., 1989. Paleoceanography 4, 221-231), but with a noisier background that may reflect the local imprint of proximal continental input superimposed upon global changes in the ocean reservoir. The time of initiation of large-scale North Hemisphere glaciation at ~2.6 Ma is characterized by a declining pattern of diatom Ge/Si ratios, which could have resulted from a global increase in the input of riverine Si due to enhanced silica weathering and/or equatorward (northward) intrusions of subantarctic waters enriched in silica. High (Ge/Si)opal ratios are associated with high opal contents from the same sediment samples and with warm climate as indicated by depleted benthic foraminiferal d18O values from the North and Equatorial Atlantic. Cold periods signified by enriched benthic d18O values, on the contrary, are associated with lower (Ge/Si)opal ratios. We interpret diatom Ge/Si values to reflect the prevailing weathering state on the continents, with greater chemical weathering during warm and wet periods of the Pliocene and less during cooler and drier intervals.

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.

A time-slice study in Heinrich Stadial 1 and Mid Holocene sediment cores off northern Senegal

Sediment dynamics in limnic, fluvial and marine environments can be assessed by granulometric and rock-magnetic methodologies. While classical grain-size analysis by sieving or settling mainly bears information on composition and transport, the magnetic mineral assemblages reflect to a larger extent the petrology and weathering conditions in the sediment source areas. Here, we combine both methods to investigate Late Quaternary marine sediments from five cores along a transect across the continental slope off Senegal. This region near the modern summer Intertropical Convergence Zone is particularly sensitive to climate change and receives sediments from several aeolian, fluvial and marine sources. From each of the investigated five GeoB sediment cores (494-2956 m water depth) two time slices were processed which represent contrasting climatic conditions: the arid Heinrich Stadial 1 (~ 15 kyr BP) and the humid Mid Holocene (~ 6 kyr BP). Each sediment sample was split into 16 grain-size fractions ranging from 1.6 to 500 µm. Concentration and grain-size indicative magnetic parameters (susceptibility, SIRM, HIRM, ARM and ARM/IRM) were determined at room temperature for each of these fractions. The joint consideration of whole sediment and magnetic mineral grain-size distributions allows to address several important issues: (i) distinction of two aeolian sediment fractions, one carried by the north-easterly trade winds (40-63 µm) and the other by the overlying easterly Harmattan wind (10-20 µm) as well as a fluvial fraction assigned to the Senegal River (< 10 µm); (ii) identification of three terrigenous sediment source areas: southern Sahara and Sahel dust (low fine-grained magnetite amounts and a comparatively high haematite content), dust from Senegalese coastal dunes (intermediate fine-grained magnetite and haematite contents) and soils from the upper reaches of the Senegal River (high fine-grained magnetite content); (iii) detection of partial diagenetic dissolution of fine magnetite particles as a function of organic input and shore distance; (iv) analysis of magnetic properties of marine carbonates dominating the grain-size fractions 63-500 µm.

Chert intervals in DSDP and ODP sites (Table 1)

Radiolarian cherts in the Tethyan realm of Jurassic age were recently interpreted as resulting from high biosiliceous productivity along upwelling zones in subequatorial paleolatitudes the locations of which were confirmed by revised paleomagnetic estimates. However, the widespread occurrence of cherts in the Eocene suggests that cherts may not always be reliable proxies of latitude and upwelling zones. In a new survey of the global spatio-temporal distribution of Cenozoic cherts in Deep Sea Drilling Project (DSDP) and Ocean Drilling Program (ODP) sediment cores, we found that cherts occur most frequently in the Paleocene and early Eocene, with a peak in occurrences at ~50 Ma that is coincident with the time of highest bottom water temperatures of the early Eocene climatic optimum (EECO) when the global ocean was presumably characterized by reduced upwelling efficiency and biosiliceous productivity. Cherts occur less commonly during the subsequent Eocene global cooling trend. Primary paleoclimatic factors rather than secondary diagenetic processes seem therefore to control chert formation. This timing of peak Eocene chert occurrence, which is supported by detailed stratigraphic correlations, contradicts currently accepted models that involve an initial loading of large amounts of dissolved silica from enhanced weathering and/or volcanism in a supposedly sluggish ocean of the EECO, followed during the subsequent middle Eocene global cooling by more vigorous oceanic circulation and consequent upwelling that made this silica reservoir available for enhanced biosilicification, with the formation of chert as a result of biosilica transformation during diagenesis. Instead, we suggest that basin-basin fractionation by deep-sea circulation could have raised the concentration of EECO dissolved silica especially in the North Atlantic, where an alternative mode of silica burial involving widespread direct precipitation and/or absorption of silica by clay minerals could have been operative in order to maintain balance between silica input and output during the upwelling-deficient conditions of the EECO. Cherts may therefore not always be proxies of biosiliceous productivity associated with latitudinally focused upwelling zones.

Geochemistry at DSDP Leg 75 Holes

Samples of sediments and rocks collected at DSDP Sites 530 and 532 were analyzed for 44 major, minor, and trace elements for the following purposes: (1) to document the downhole variability in geochemistry within and between lithologic units; (2) to document trace-element enrichment, if any, in Cretaceous organic-carbon-rich black shales at Site 530; (3) to document trace-element enrichment, if any, in Neogene organic-carbon-rich sediments at Site 532; (4) to document trace-element enrichment, if any, in red claystone above basalt basement at Site 530 that might be attributed to hydrothermal activity or weathering of basalt. Results of the geochemical analyses showed that there are no significant enrichments of elements in the organic-carbon-rich sediments at Site 532, but a number of elements, notably Cd, Co, Cr, Cu, Mo, Ni, Pb, V, and Zn, are enriched in the Cretaceous black shales. These elements have different concentration gradients within the black-shale section, however, which suggests that there was differential mobility of trace elements during diagenesis of interbedded more-oxidized and less-oxidized sediments. There is little or no enrichment of elements from hydrothermal activity in the red claystone immediately overlying basalt basement at Site 530, but slight enrichments of several elements in the lowest meter of sediment may be related to subsea weathering of basalt