Strontium-isotope stratigraphy and oxygen- and carbon-isotope record of Middle Jurassic to Early Cretaceous belemnites in the South Atlantic

87Sr/86Sr data of belemnites are presented from a Middle Jurassic-Early Cretaceous succession from the Falkland Plateau (Deep Sea Drilling Project Sites 511 and 330) that was deposited in a periodically anoxic, semi-enclosed shallow water basin. Diagenetically screened strontium-isotope values of 0.706789 rise to 0.707044 before increasing sharply to 0.707428 in the uppermost part of the sampled succession. Comparison with published strontium calibration curves suggests that the oldest samples were Callovian to Oxfordian in age, whilst the remainder of the Jurassic part of the succession consisted of Kimmeridgian and Early Tithonian age sediments. The nannofossil, dinoflagellate and molluscan assemblages provide comparable age determinations. The strontium-isotope analysis of the youngest belemnites points to a Hauterivian-Barremian age, whilst age interpretations based upon the fauna provide a wide age range from the Barremian to early Albian. Strontium-isotope stratigraphy of this succession hence offers increased age resolution providing data regarding the timing of episodes of bottom water anoxia which have been recorded throughout the South Atlantic Basin. Well-preserved belemnite specimens display an oxygen-isotope range between +0.08 and -2.22? (PDB, Peedee belemnite international standard) and a carbon-isotope range from +2.35 to -1.33? (PDB). Delta13C values become increasingly negative through the Late Jurassic-Early Cretaceous and in concert with the 87Sr/86Sr data reveal a trend that could be accounted for by increasing levels of weathering and erosion. The oxygen-isotope data if interpreted in terms of palaeotemperature are consistent with warm palaeotemperatures in the Kimmeridgian and slightly cooler temperatures for the Tithonian and Early Cretaceous parts of the succession. The proposed relative Kimmeridgian warmth (based upon strontium-isotope age assignments) is thus in good agreement with other published palaeotemperature records.

Holocene Labrador Sea planktonic foraminiferal oxygen isotopes and trace element data, and ice rafted debris percentage

Formation of Labrador Sea Water proper commenced about 7000 years ago during the Holocene interglacial. To test whether fresher surface water conditions may have inhibited Labrador Sea Water convection during the early Holocene we measured planktonic foraminiferal (Globigerina bulloides) oxygen isotopes (d18O) and Mg/Ca ratios at Orphan Knoll (cores HU91-045-093 and MD95-2024, 3488 m) in the Labrador Sea to reconstruct shallow subsurface summer conditions (temperature and seawater d18O). Lighter foraminiferal d18O values are recorded during the early Holocene between 11000 and 7000 years ago. Part of these lighter foraminiferal d18O values can be explained by increased calcification temperatures. Reconstructed seawater d18O values were, however, still on average 0.5 per mil lighter compared with those of recent times, confirming that fresher surface waters in the Labrador Sea were probably a limiting factor in Labrador Sea Water formation during the early Holocene.

Strontium isotope ratios of fish teeth from ODP sites in the central North Pacific

Strontium isotopic compositions of ichthyoliths (microscopic fish remains) in deep-sea clays recovered from the North Pacific Ocean (ODP holes 885A, 886B, and 886C) are used to provide stratigraphic age control within these otherwise undatable sediments. Age control within the deep-sea clays is crucial for determining changes in sedimentation rates, and for calculating fluxes of chemical and mineral components to the sediments. The Sr isotopic ages are in excellent agreement with independent age datums from above (diatom ooze), below (basalt basement) and within (Cretaceous-Tertiary boundary) the clay deposit. The 87Sr/86Sr ratios of fish teeth from the top of the pelagic clay unit (0.7089891), indicate an Late Miocene age (5.8 Ma), as do radiolarian and diatom biostratigraphic ages in the overlying diatom ooze. The 87Sr/86Sr ratio (0.707887) is consistent with a Cretaceous-Tertiary boundary age, as identified by anomalously high iridium, shocked quartz, and sperules in Hole 886C. The 87Sr/86Sr ratios of pretreated fish teeth from the base of the clay unit are similar to Late Cretaceous seawater (0.707779-0.7075191), consistent with radiometric ages from the underlying basalt of 81 Ma. Calculation of sedimentation rates based on Sr isotopic ages from Hole 886C indicate an average sedimentation rate of 17.7 m/Myr in Unit II (diatom ooze), 0.55 m/Myr in Unit IIIa (pelagic clay), and 0.68 m/Myr in Unit IIIb (distal hydrothermal precipitates). The Sr isotopic ages indicate a period of greatly reduced sedimentation (or possible hiatus) between about 35 and 65 Ma (Eocene-Paleocene), with a linear sedimentation rate of only 0.04 m/Myr The calculated sedimentation rates are generally inversely proportional to cobalt accumulation rates and ichthyolith abundances. However, discrepancies between Sr isotope ages and cobalt accumulation ages of l0-15 Myr are evident, particularly in the middle of the clay unit IIIa (Oligocene-Paleocene).

Strontium isotope ratios and concentrations in fossil fish teeth

We analyzed 87Sr/86Sr ratios in foraminifera, pore fluids, and fish teeth for samples ranging in age from Eocene to Pleistocene from four Ocean Drilling Program sites distributed around the globe: Site 1090 in the Cape Basin of the Southern Ocean, Site 757 on the Ninetyeast Ridge in the Indian Ocean, Site 807 on the Ontong-Java Plateau in the western equatorial Pacific, and Site 689 on the Maud Rise in the Southern Ocean. Sr isotopic ratios for dated foraminifera consistently plot on the global seawater Sr isotope curve. For Sites 1090, 757, and 807 Sr isotopic values of the pore fluids are generally less radiogenic than contemporaneous seawater values, as are values for fossil fish teeth. In contrast, pore fluid 87Sr/86Sr values at Site 689 are more radiogenic than contemporaneous seawater, and the corresponding fish teeth also record more radiogenic values. Thus, Sr isotopic values preserved in fossil fish teeth are consistently altered in the direction of the pore fluid values; furthermore, there is a correlation between the magnitude of the offset between the pore fluids and the seawater curve, and the associated offset between the fish teeth and the seawater curve. These data suggest that the hydroxyfluorapatite of the fossil fish teeth continues to recrystallize and exchange Sr with its surroundings during burial and diagenesis. Therefore, Sr chemostratigraphy can be used to determine rough ages for fossil fish teeth in these cores, but cannot be used to fine-tune age models. In contrast to the Sr isotopic system, our Nd concentration data, combined with published isotopic and rare earth element data, suggest that fish teeth acquire Nd during early diagenesis while they are still in direct contact with seawater. The concentrations of Nd acquired at this stage are extremely high relative to the concentrations in surrounding pore fluids. As a result, Nd isotopes are not altered during burial and later diagenesis. Therefore, fossil fish teeth from a variety of marine environments preserve a reliable and robust record of deep seawater Nd isotopic compositions from the time of deposition.

Age and strontium isotope composition for Cretaceous in DSDP Hole 74-525

Firm stratigraphic correlations are needed to evaluate the global significance of unconformity bounded units (sequences). We correlate the well-developed uppermost Campanian and Maestrichtian sequences of the New Jersey Coastal Plain to the geomagnetic polarity time scale (GPTS) by integrating Sr-isotopic stratigraphy and biostratigraphy. To do this, we developed a Maestrichtian (ca. 73-65 Ma) Sr-isotopic reference section at Deep Sea Drilling Project Hole 525A in the southeastern Atlantic Ocean. Maestrichtian strata can then be dated by measuring their 87Sr/86Sr composition, calibrating to the GPTS of S. C. Cande and D. V. Kent (1993, personal commun.), and using the equation Age (Ma) = 37326.894-52639.89 (87Sr/86Sr). Sr-stratigraphic resolution for the Maestrichtian is estimated as +-1.2 to +-2 m.y. At least two unconformity-bounded units comprise the uppermost Campanian to Maestrichtian strata in New Jersey. The lower one, the Marshalltown sequence, is assigned to calcareous nannofossil Zones CC20/21 (~NC19) and CC22b (~NC20). It ranges in age from ~74.1 to 69.9 Ma based on Sr-isotope age estimates. The overlying Navesink sequence is assigned to calcareous nannoplankton Zones CC25-26 (~NC21-23); it ranges in age from 69.3 to 65 Ma based on Sr-isotope age estimates. The upper part of this sequence, the Tinton Formation, has no calcareous planktonic control; Sr-isotopes provide an age estimate of 66 +- 1.2 Ma (latest Maestrichtian). Sequence boundaries at the base and the top of the Marshalltown sequence match boundaries elsewhere in the Atlantic Coastal Plain (Owens and Gohn, 1985) and the inferred global sea-level record of Haq et al. (1987); they support eustatic changes as the mechanism controlling depositional history of this sequence. However, the latest Maestrichtian record in New Jersey does not agree with Haq et al. (1987); we attribute this to correlation and time-scale differences near the Cretaceous/Paleogene boundary. High sedimentation rates in the latest Maestrichtian of New Jersey (Shrewsbury Member of the Red Bank Formation and the Tinton Formation) suggest tectonic uplift and/or rapid progradation during deposition of the highstand systems tract.

Geochemistry and radiogenic isotopes of ODP Hole 157-953C lavas

The Canary Island primitive basaltic magmas are thought to be derived from an HIMU-type upwelling mantle containing isotopically depleted (NMORB)-type component having interacted with an enriched (EM)-type component, the origin of which is still a subject of debate. We studied the relationships between Ni, Mn and Ca concentrations in olivine phenocrysts (85.6-90.0 mol.% Fo, 1,722-3,915 ppm Ni, 1,085-1,552 ppm Mn, 1,222-3,002 ppm Ca) from the most primitive subaerial and ODP Leg 157 high-silica (picritic to olivine basaltic) lavas with their bulk rock Sr-Nd-Pb isotope compositions (87Sr/86Sr = 0.70315-0.70331, 143Nd/144Nd = 0.51288-0.51292, 206Pb/204Pb = 19.55-19.93, 207Pb/204Pb = 15.60-15.63, 208Pb/204Pb = 39.31-39.69). Our data point toward the presence of both a peridotitic and a pyroxenitic component in the magma source. Using the model (Sobolev et al., 2007, Science Vol 316) in which the reaction of Si-rich melts originated during partial melting of eclogite (a high pressure product of subducted oceanic crust) with ambient peridotitic mantle forms olivine-free reaction pyroxenite, we obtain an end member composition for peridotite with 87Sr/86Sr = 0.70337, 143Nd/144Nd = 0.51291, 206Pb/204Pb = 19.36, 207Pb/204Pb = 15.61 and 208Pb/204Pb = 39.07 (EM-type end member), and pyroxenite with 87Sr/86Sr = 0.70309, 143Nd/144Nd = 0.51289, 206Pb/204Pb = 20.03, 207Pb/204Pb = 15.62 and 208Pb/204Pb = 39.84 (HIMU-type end member). Mixing of melts from these end members in proportions ranging from 70% peridotite and 30% pyroxenite to 28% peridotite and 72% pyroxenite derived melt fractions can generate the compositions of the most primitive Gran Canaria shield stage lavas. Combining our results with those from the low-silica rocks from the western Canary Islands (Gurenko et al., 2009, doi:10.1016/j.epsl.2008.11.013), at least four distinct components are required. We propose that they are (1) HIMU-type pyroxenitic component (representing recycled ocean crust of intermediate age) from the plume center, (2) HIMU-type peridotitic component (ancient recycled ocean crust stirred into the ambient mantle) from the plume margin, (3) depleted, MORB-type pyroxenitic component (young recycled oceanic crust) in the upper mantle entrained by the plume, and (4) EM-type peridotitic component from the asthenosphere or lithosphere above the plume center.

Organic carbon content, stable isotopes and planktonic foraminifera in sediments of tghe norther Arabian Sea oxygen minimum zone

The northern Arabian Sea is one of the few regions in the open ocean where thermocline water is severely depleted in oxygen. The intensity of this oxygen minimum zone (OMZ) has been reconstructed over the past 225,000 years using proxies for surface water productivity, water column denitrification, winter mixing, and the aragonite compensation depth (ACD). Changes in OMZ intensity occurred on orbital and suborbital timescales. Lowest O2 levels correlate with productivity maxima and shallow winter mixing. Precession-related productivity maxima lag early summer insolation maxima by ~6 kyr, which we attribute to a prolonged summer monsoon season related to higher insolation at the end of the summer. Periods with a weakened or even non-existent OMZ are characterized by low productivity conditions and deep winter mixing attributed to strong and cold winter monsoonal winds. The timing of deep winter mixing events corresponds with that of periods of climatic cooling in the North Atlantic region.

Biomarker and radiogenic isotopes from sediment core POS362-2_33

The termination of the African Humid Period in northeastern Africa during the early Holocene was marked by the southward migration of the rain belt and the disappearance of the Green Sahara. This interval of drastic environmental changes was also marked by the initiation of food production by North African huntergatherer populations and thus provides critical information on human-environment relationships. However, existing records of regional climatic and environmental changes exhibit large differences in timing and modes of the wet/dry transition at the end of the African Humid Period. Here we present independent records of changes in river runoff, vegetation and erosion in the Nile River watershed during the Holocene obtained from a unique sedimentary sequence on the Nile River fan using organic and inorganic proxy data. This high-resolution reconstruction allows to examine the phase relationship between the changes of these three parameters and provides a detailed picture of the environmental conditions during the Paleolithic/Neolithic transition. The data show that river runoff decreased gradually during the wet/arid transition at the end of the AHP whereas rapid shifts of vegetation and erosion occurred earlier between 8.7 and about 6 ka BP. These asynchronous changes are compared to other regional records and provide new insights into the threshold responses of the environment to climatic changes. Our record demonstrates that the degradation of the environment in northeastern Africa was more abrupt and occurred earlier than previously thought and may have accelerated the process of domestication in order to secure sustainable food resources for the Neolithic African populations.

Stable isotopes and element concentrations of samples from the Wadi Bih, United Arab Emirates

Ocean acidification triggered by Siberian Trap volcanism was a possible kill mechanism for the Permo-Triassic Boundary mass extinction, but direct evidence for an acidification event is lacking. We present a high-resolution seawater pH record across this interval, using boron isotope data combined with a quantitative modeling approach. In the latest Permian, increased ocean alkalinity primed the Earth system with a low level of atmospheric CO2 and a high ocean buffering capacity. The first phase of extinction was coincident with a slow injection of carbon into the atmosphere, and ocean pH remained stable. During the second extinction pulse, however, a rapid and large injection of carbon caused an abrupt acidification event that drove the preferential loss of heavily calcified marine biota.

Element ratios and stable isotopes of foraminifers from ODP Site 202-1237

Downcore records of magnesium/calcium, strontium/calcium, manganese/calcium, and oxygen and carbon isotopes of planktonic and benthic foraminifers from Ocean Drilling Program (ODP) Site 1237 on the Peru-Chile margin provide critical information regarding the history of climate in the region over the past 6 m.y. Specifically, these records can be used to infer the sea-surface temperature (SST) and sea-surface salinity (SSS) history of a region that today is associated with substantial wind stress curl-driven upwelling (Shipboard Scientific Party, 2003, doi:10.2973/odp.proc.ir.202.108.2003). This report provides data tables and other supporting information for measurements made on planktonic and benthic foraminifers from Site 1237. Items included in this report are (1) oxygen and carbon isotopic measurements of planktonic and benthic foraminifers and (2) Mg/Ca, Sr/Ca, and Mn/Ca ratio measurements of planktonic foraminifers from Holes 1237B, 1237C, and 1237D.

Neodymium isotopes in benthic foraminifera from the South Atlantic

Records of the past neodymium (Nd) isotope composition of the deep ocean can resolve ambiguities in the interpretation of other tracers. We present the first Nd isotope data for sedimentary benthic foraminifera. Comparison of the epsilon-Nd of core-top foraminifera from a depth transect on the Cape Basin side of the Walvis Ridge to published seawater data, and to the modern dissolved SiO2- epsilon-Nd trend of the deep Atlantic, suggests that benthic foraminifera represent a reliable archive of the deep water Nd isotope composition. Neodymium isotope values of benthic foraminifera from ODP Site 1264A (Angola Basin side of the Walvis Ridge) from the last 8 Ma agree with Fe-Mn oxide coatings from the same samples and are also broadly consistent with existing fish teeth data for the deep South Atlantic, yielding confidence in the preservation of the marine Nd isotope signal in all these archives. The marine origin of the Nd in the coatings is confirmed by their marine Sr isotope values. These important results allow application of the technique to down-core samples. The new epsilon-Nd datasets, along with ancillary Cd/Ca and Nd/Ca ratios from the same foraminiferal samples, are interpreted in the context of debates on the Neogene history of North Atlantic Deep Water (NADW) export to the South Atlantic. In general, the epsilon-Nd and delta13C records are closely correlated over the past 4.5 Ma. The Nd isotope data suggest strong NADW export from 8 to 5 Ma, consistent with one interpretation of published delta13C gradients. Where the epsilon-Nd record differs from the nutrient-based records, changes in the pre-formed delta13C or Cd/Ca of southern-derived deep water might account for the difference. Maximum NADW-export for the entire record is suggested by all proxies at 3.5-4 Ma. Chemical conditions from 3 to 1 Ma are totally different, showing, on average, the lowest NADW export of the record. Modern-day values again imply NADW export that is about as strong as at any stage over the past 8 Ma.

Geochemistry, mineralogy and isotopes at DSDP Hole 62-464

The relationships between mineralogical and geochemical data on the three successive sedimentary facies at Deep Sea Drilling Project Site 464 are studied. The evolution of siliceous biogenic sediments is derived from the analyses of one Fe-Ti smectite concretion, and of siliceous aggregates occurring in the pelagic "brown clays." Along the sedimentary section, the trace elements enriching the authigenic silicates and the Fe-Mn oxyhydroxides vary, depending on the marine environment. The proportion of clays and carbonates into the siliceous deposits controls the diagenetic evolution of silica making up the quartz aggregates from the "brown clay" or the cristobalite cherts.