Chert petrology and geochemistry at DSDP Leg 62 Holes

Sixty-five chert, porcellanite, and siliceous-chalk samples from Deep Sea Drilling Project Leg 62 were analyzed by petrography, scanning electron microscopy, analysis by energy-dispersive X-rays, X-ray diffraction, X-ray spectroscopy, and semiquantitative emission spectroscopy. Siliceous rocks occur mainly in chalks, but also in pelagic clay and marlstone at Site 464. Overall, chert probably constitutes less than 5% of the sections and occurs in deposits of Eocene to Barremian ages at sub-bottom depths of 10 to 820 meters. Chert nodules and beds are commonly rimmed by quartz porcellanite; opal-CT-rich rocks are minor in Leg 62 sediments 65 to 108 m.y. old and at sub-bottom depths of 65 to 520 meters. Chert ranges from white to black, shades of gray and brown being most common; yellow-brown and red-brown jaspers occur at Site 464. Seventy-eight percent of the studied cherts contain easily recognizable burrow structures. The youngest chert at Site 463 is a quartz cast of a burrow. Burrow silica maturation is always one step ahead of host-rock silicification. Burrows are commonly loci for initial silicification of the host carbonate. Silicification takes place by volume-f or-volume replacement of carbonate sediment, and more-clay-rich sediment at Site 464. Nannofossils are commonly pseudomorphically replaced by quartz near the edges of chert beds and nodules. Other microfossils, mostly radiolarians and foraminifers, whether in chalk or chert, can be either filled with or replaced by calcite, opal-CT, and (or) quartz. Chemical micro-environments ultimately control the removal, transport, and precipitation of calcite and silica. Two cherts from Site 465 contain sulfate minerals replaced by quartz. Site 465 was never subaerially exposed after sedimentation began, and the formation of the sulfate minerals and their subsequent replacement probably occurred in the marine environment. Several other cherts with odd textures are described in this paper, including (1) a chert breccia cemented by colloform opal-CT and chalcedony, (2) a transition zone between white porcellanite containing opal-CT and quartz and a burrowed brown chert, consisting of radial aggregates of opal-CT with hollow centers, and (3) a chert that consists of silica-replaced calcite pseudospherules interspersed with streaks and circular masses of dense quartz. X-ray-diffraction analyses show that when data from all sites are considered there are poorly defined trends indicating that older cherts have better quartz crystallinity than younger ones, and that opal-CT crystallite size increases and opal-CT cf-spacings decrease with depth of occurrence in the sections. In a general way, depth of burial and the presence of calcite promote the ordering in the opal-CT crystal structure which allows its eventual conversion to quartz. Opal-CT in porcellanites converts to quartz after reaching a minimum d-spacing of 4.07 Å. Quartz/opal-CT ratios and quartz crystallinity vary randomly on a fine scale across four chert beds, but quartz crystallinity increases from the edge to the center of a fifth chert bed; this may indicate maturation of the silica. Twenty-four rocks were analyzed for their major- and minor-element compositions. Many elements in cherts are closely related to major mineral components. The carbonate component is distinguished by high values of CaO, MgO, Mn, Ba, Sr, and (for unknown reasons) Zr. Tuffaceous cherts have high values of K and Al, and commonly Zn, Mo, and Cr. Pure cherts are characterized by high SiO2 and B. High B may be a good indicator of formation of chert in an open marine environment, isolated from volcanic and terrigenous materials.

Stable isotope record of planktonic foraminifera from the Sulu Sea

A high-resolution, accelerator mass spectroscopy 14C dated sediment record from the Sulu Sea clearly indicates that the Younger Dryas event affected the western equatorial Pacific. Planktonic foraminiferal delta18O and abundance data both record significant changes during Younger Dryas time. In particular, a 0.4 per mil increase in the delta18O value of Globigerinoides ruber and the reappearance of the cool water planktonic foraminifera, Neogloboquadrina pachyderma, occur during the Younger Dryas at this location. These isotopic and faunal changes are a response to either surface water temperature or salinity changes, or some combination of the two. Changes in surface salinities could have been accomplished through either local or global processes. Intensification of the monsoon climate system and increased precipitation at approximately 11 ka is one mechanism that may have resulted in local changes in salinity. A meltwater pulse derived from the Tibetan Plateau is another mechanism which may have caused local changes in salinity. The presence of the Younger Dryas in the tropical western Pacific clearly indicates that this climatic event is not restricted to the North Atlantic or high latitudes, but rather is global in extent.

Mg/Ca and stable oxygen measurement of the past 27 Ma of ODP Hole 120-747A

We explore the applicability of paired Mg/Ca and 18O/16O measurements on benthic foraminifera from Southern Ocean site 747 to paleoceanographic reconstructions on pre-Pleistocene timescales. We focus on the late Oligocene through Pleistocene (27-0 Ma) history of paleotemperatures and the evolution of the d18O values of seawater (d18Osw) at a temporal resolution of ~100-200 kyr. Absolute paleotemperature estimates depend on assumptions of how Mg/Ca ratios of seawater have changed over the past 27 Myr, but relative changes that occur on geologically brief timescales are robust. Results indicate that at the Oligocene to Miocene boundary (23.8 Ma), temperatures lag the increase in global ice-volume deduced from benthic foraminiferal d18O values, but the smaller-scale Miocene glaciations are accompanied by ocean cooling of -1°C. During the mid-Miocene phase of Antarctic ice sheet growth (~15-13 Ma), water temperatures cool by ~3°C. Unlike the benthic foraminiferal d18O values, which remain relatively constant thereafter, temperatures vary (by 3°C) and reach maxima at ~12 and ~8.5 Ma. The onset of significant Northern Hemisphere glaciation during the late Pliocene is synchronous with an ~4°C cooling at site 747. A comparison of our d18Osw curve to the Haq et al. (1987, doi:10.1126/science.235.4793.1156 ) sea level curve yields excellent agreement between sequence boundaries and times of increasing seawater 18O/16O ratios. At ~12-11 Ma in particular, when benthic foraminiferal d18O values do not support a further increase in ice volume, the d18Osw curve comes to a maximum that corresponds to a major mid-Miocene sea level regression. The agreement between the character of our Mg/Ca-based d18Osw curve and sequence stratigraphy demonstrates that benthic foramaniferal Mg/Ca ratios can be used to trace the d18Osw on pre-Pleistocene timescales despite a number of uncertainties related to poorly constrained temperature calibrations and paleoseawater Mg/Ca ratios. The Mg/Ca record also highlights that deep ocean temperatures can vary independently and unexpectedly from ice volume changes, which can lead to misinterpretations of the d18O record.

Lead isotopic ratios of Barremian-Aptian marine sediments

We present initial isotopic ratios of lead for Early Cretaceous (Barremian-Aptian) sections from Shatsky Rise (Pacific) and Gorgo a Cerbara (Italy). Our Pb isotopic data track an interval representing Oceanic Anoxic Event (OAE)-1a, which is characterized by quasi-global deposition of organic carbon-rich black shale. Pb isotopic compositions of sediments from Shatsky Rise decrease at the end of Barremian time, from radiogenic continental values to unradiogenic values, and subsequently remained less radiogenic until the end of early Aptian time. We explain the isotopic shift by a significant increase in supply rate of unradiogenic Pb, most likely due to massive volcanism. In contrast, the Pb isotopic compositions from the Italian section, which was situated at the western end of Tethys, are mostly identical to those of upper continental crust, showing no significant change in supply rate of unradiogenic Pb. The discrepancy between two sites is attributed to quiescent deep-submarine eruptions of Pacific large igneous provinces (LIPs) such as the Ontong Java Plateau (OJP), which severely limited dispersion of Pb-carrying particles out of the Pacific Ocean. Published Os isotopic data from the Italian section indicate two episodes of massive eruptions of OJP or contemporaneous Manihiki and Hikurangi plateaus starting from earliest Aptian time, slightly later than that indicated by the sedimentary Pb isotopic record from Shatsky Rise. Differences in isotopic variations between Pb and Os likely reflect differences in their chemical behaviors in the oceans, i.e., Pb isotopic compositions would have varied in response to local or regional changes in sediment provenances, whereas large-scale changes in Os inputs are required to explain variations in seawater Os isotopic compositions. Our Pb isotopic data, together with the published Os isotopic record, provide new evidence for the eruptive history of OJP together with contemporaneous Pacific plateaus and its environmental consequences, starting from end-Barremian time and extending through early Aptian time.

Calcium isotope composition of Oceanic Anoxic Events 1a and 2 sediments

Calcium-isotope ratios (d44/42Ca) were measured in carbonate-rich sedimentary sections deposited during Oceanic Anoxic Events 1a (Early Aptian) and 2 (Cenomanian-Turonian). In sections from Resolution Guyot, Mid-Pacific Mountains; Coppitella, Italy; and the English Chalk at Eastbourne and South Ferriby, UK, a negative excursion in d44/42Ca of ~0.20 per mil and ~0.10 per mil is observed for the two events. These d44/42Ca excursions occur at the same stratigraphic level as the carbon-isotope excursions that define the events, but do not correlate with evidence for carbonate dissolution or lithological changes. Diagenetic and temperature effects on the calcium-isotope ratios can be discounted, leaving changes in global seawater composition as the most probable explanation for d44/42Ca changes in four different carbonate sections. An oceanic box model with coupled strontium- and calcium-isotope systems indicates that a global weathering increase is likely to be the dominant driver of transient excursions in calcium-isotope ratios. The model suggests that contributions from hydrothermal activity and carbonate dissolution are too small and short-lived to affect the oceanic calcium reservoir measurably. A modelled increase in weathering flux, on the order of three times the modern flux, combined with increased hydrothermal activity due to formation of the Ontong-Java Plateau (OAE1a) and Caribbean Plateau (OAE2), can produce trends in both calcium and strontium isotopes that match the signals recorded in the carbonate sections. This study presents the first major-element record of a weathering response to Oceanic Anoxic Events.

(Figure 2) Proxy records of sediment core GeoB6007-2

Central waters of the North Atlantic are fundamental for ventilation of the upper ocean and are also linked to the strength of the Atlantic Meridional Overturning Circulation (AMOC). Here, we show based on benthic foraminiferal Mg/Ca ratios, that during times of enhanced melting from the Laurentide Ice Sheet (LIS) between 9.0-8.5 thousand years before present (ka) the production of central waters weakened the upper AMOC resulting in a cooling over the Northern Hemisphere. Centered at 8.54 ± 0.2 ka and 8.24 ± 0.1 ka our dataset records two ~150-year cooling events in response to the drainage of Lake Agassiz/Ojibway, indicating early slow-down of the upper AMOC in response to the initial freshwater flux into the subpolar gyre (SPG) followed by a more severe weakening of both the upper and lower branches of the AMOC at 8.2 ka. These results highlight the sensitivity of regional North Atlantic climate change to the strength of central-water overturning and exemplify the impact of both gradual and abrupt freshwater fluxes on eastern SPG surface water convection. In light of the possible future increase in Greenland Ice Sheet melting due to global warming these findings may help us to better constrain and possibly predict future North Atlantic climate change.

Age model, raw data and interpolated raw data from proxy records of sediment cores GeoB6007-1 and GeoB6007-2

Here we present a 1200 yr long benthic foraminiferal Mg/Ca based temperature and oxygen isotope record from a ~900 m deep sediment core off northwest Africa to show that atmosphere-ocean interactions in the eastern subpolar gyre are transferred at central water depth into the eastern boundary of the subtropical gyre. Further we link the variability of the NAO (over the past 165 yrs) and solar irradiance (Late Holocene) and their control on subpolar mode water formation to the multidecadal variability observed at mid-depth in the eastern subtropical gyre. Our results show that eastern North Atlantic central waters cooled by up to ~0.8± 0.7 °C and densities decreased by Sigma theta=0.3±0.2 during positive NAO years and during minima in solar irradiance during the Late Holocene. The presented records demonstrate the sensitivity of central water formation to enhanced atmospheric forcing and ice/freshwater fluxes into the eastern subpolar gyre and the importance of central water circulation for cross-gyre climate signal propagation during the Late Holocene.

Geochemistry of rare earth elements in basalts from Walvis Ridge

Selected basalts from a suite of dredged and drilled samples (IPOD sites 525, 527, 528 and 530) from the Walvis Ridge have been analysed to determine their rare earth element (REE) contents in order to investigate the origin and evolution of this major structural feature in the South Atlantic Ocean. All of the samples show a high degree of light rare earth element (LREE) enrichment, quite unlike the flat or depleted patterns normally observed for normal mid-ocean ridge basalts (MORBs). Basalts from Sites 527, 528 and 530 show REE patterns characterised by an arcuate shape and relatively low (Ce/Yb)N ratios (1.46-5.22), and the ratios show a positive linear relationship to Nb content. A different trend is exhibited by the dredged basalts and the basalts from Site 525, and their REE patterns have a fairly constant slope, and higher (Ce/Yb)N ratios (4.31-8.50). These differences are further reflected in the ratios of incompatible trace elements, which also indicate considerable variations within the groups. Mixing hyperbolae for these ratios suggest that simple magma mixing between a 'hot spot' type of magma, similar to present-day volcanics of Tristan da Cunha, and a depleted source, possibly similar to that for magmas being erupted at the Mid-Atlantic Ridge, was an important process in the origin of parts of the Walvis Ridge, as exemplified by Sites 527, 528 and 530. Site 525 and dredged basalts cannot be explained by this mixing process, and their incompatible element ratios suggest either a mantle source of a different composition or some complexity to the mixing process. In addition, the occurrence of different types of basalt at the same location suggests there is vertical zonation within the volcanic pile, with the later erupted basalts becoming more alkaline arid more enriched in incompatible elements. The model proposed for the origin and evolution of the Walvis Ridge involves an initial stage of eruption in which the magma was essentially a mixture of enriched and depleted end-member sources, with the N-MORB component being small. The dredged basalts and Site 525, which represent either later-stage eruptives or those close to the hot spot plume, probably result from mixing of the enriched mantle source with variable amounts and variable low degrees of partial melting of the depleted mantle source. As the volcano leaves the hot spot, these late-stage eruptives continue for some time. The change from tholeiitic to alkalic volcanism is probably related either to evolution in the plumbing system and magma chamber of the individual volcano, or to changes in the depth of origin of the enriched mantle source melt, similar to processes in Hawaiian volcanoes.

Strontium isotope dating of ODP Leg 133 sediments

The strontium-isotope dating method, based on the strontium-isotope seawater curve, was used to date stratigraphic events recognized in carbonate sediments drilled during Leg 133 on the Queensland and Marion plateaus. The strontium isotope ages of these events are used to correlate paleoceanographic changes, delineated from oxygen isotope signals, and paleoenvironmental or facies changes recorded in the lithostratigraphy. Results indicate that a strong connection exists between prevailing paleoenvironmental conditions and the developmental style of a carbonate platform. Also, the strontium-isotope ages of discrete dolomite intervals within the sequences were determined, indicating that multiple dolomitization events took place and that a hydrodynamically driven process may be currently active within the modern carbonate platform.

Stable isotope record of benthic foraminifera from the Gulf of California

A high-resolution, accelerator radiocarbon dated climate record of the interval 8,000-18,000 years B.P. from Deep Sea Drilling Project site 480 (Guaymas Basin, Gulf of California) shows geochemical and lithological oscillations of oceanographic and climatic significance during deglaciation. Nonlaminated sediments are associated with cooler climatic conditions during the late glacial (up to 13,000 years B.P.), and from 10,300 to 10,800 years B.P., equivalent to the Younger Dryas event of the North Atlantic region. We propose that the changes from laminated (varved) to nonlaminated sediments resulted from increased oxygen content in Pacific intermediate waters during the glacial and the Younger Dryas episodes, and that the forcing for the latter event was global in scope. Prominent events of low delta18O are recorded in benthic foraminifera from 8,000 to 10,000 and at 12,000 years B.P.; evidence for an earlier event between 13,500 and 15,000 years B.P. is weaker. Maximum delta18O is found to have occurred 10,500, 13,500, and 15,000 years ago (and beyond). Oxygen isotopic variability most likely reflects changing temperature and salinity characteristics of Pacific waters of intermediate depth during deglaciation or environmental changes within the Gulf of California region. Several lines of evidence suggest that during deglaciation the climate of the American southwest was marked by increased precipitation that could have lowered salinity in the Gulf of California. Recent modelling studies show that cooling of the Gulf of Mexico due to glacial meltwater injection, which is believed to have occurred at least twice during deglaciation, would have resulted in increased precipitation with respect to evaporation in the American southwest during summertime. The timing of deglacial events in the Gulf of Mexico and the Gulf of California supports such an atmospheric teleconnection.

AMS 14C and 230Th/U dates determined on 24 coral species from the Gulf of Cádiz

This paper presents the first compilation of information on the spatial distribution of scleractinian cold-water corals in the Gulf of Cádiz based on literature research and own observations (video footage, sediment samples). Scleractinian cold-water corals are widely distributed along the Spanish and Moroccan margins in the Gulf of Cádiz, where they are mainly associated with mud volcanoes, diapiric ridges, steep fault escarpments, and coral mounds. Dendrophyllia cornigera, Dendrophyllia alternata, Eguchipsammia cornucopia, Madrepora oculata and Lophelia pertusa are the most abundant reef-forming species. Today, they are almost solely present as isolated patches of fossil coral and coral rubble. The absence of living scleractinian corals is likely related to a reduced food supply caused by low productivity and diminished tidal effects. In contrast, during the past 48 kyr scleractinian corals were abundant in the Gulf of Cádiz, although their occurrence demonstrates no relationship with main climatic or oceanographic changes. Nevertheless, there exists a conspicuous relationship when the main species are considered separately. Dendrophylliids are associated with periods of relatively stable and warm conditions. The occurrence of L. pertusa mainly clusters within the last glacial when bottom current strength in the Gulf of Cádiz was enhanced and long-term stable conditions existed in terms of temperature. Madrepora oculata shows a higher tolerance to abrupt environmental changes.