Strontium isotopes in pore waters of east equatorial Pacific sediments

Pore-water samples from the equatorial sedimentary bulge area show reversals in depth profiles of 87Sr/86Sr ratios at the sediment/basement interface. Results of this work support inferences made from previous pore-water data (from DSDP drilling in the area) that large-scale horizontal advection of seawater has occurred through the basement underlying the thick sedimentary sequence in this region. The area of apparent advection includes the eastern part of the equatorial high-productivity zone and part of the Guatemala Basin. We attempted to find links between the observed near-basement reversals in pore-water chemistry and sedimentary thickness, age, and topography of the area. Most of the sites that show horizontal advection have disturbed basement topography or outcrops within 10 to 20 km, suggesting that the cooling effects of outcrops may extend for at least 20 km horizontally. Heat-flow data from the area were compared to determine whether sites showing near-bottom chemistry reversals were consistent with areas of low conductive heat flow. This was generally true for the area of the sedimentary bulge and Guatemala Basin. Not enough pore-water data from the Nazca Plate were available to establish any reliable systematics. Because the high-productivity area is well-sealed from hydrothermal circulation, the missing heat must be lost by horizontal advective heat transport. From profiles of strontium isotopes and other elements that show departure from seawater values with increasing depth in the sediments, but return to seawater values near the basement, it appears that water flows relatively freely through much of the oceanic crust, even when sealed by considerable sedimentary cover.

Nd isotopes of ODP Sites 146-893 and 167-1017 samples

Changes in the source of intermediate waters to the southern California margin may have caused variations in seafloor oxygen levels on stadial-interstadial time scales. We test this hypothesis using the Nd isotopic composition of benthic foraminifera and fossil fish debris from ODP Sites 893 and 1017 to track the composition of intermediate waters across interstadials 8-14 (~37-52 ka) during Marine Isotope Stage 3. The epsilon-Nd values of waters bathing the seafloor at Site 893 were typically ~-9 and those bathing Site 1017 were ~-7, both of which are significantly less radiogenic than waters that had originated in either the North Pacific or Southern Ocean (by the time such waters reached the southern California margin). Detrital silicate epsilon-Nd values of nearly -12 suggest that this offset toward lower epsilon-Nd values was likely caused by boundary scavenging that partially overprinted the water mass composition with local/regional fluvial Nd inputs. In spite of the evidence for boundary scavenging, the lack of systematic seawater Nd isotope changes on a stadial-interstadial basis suggests that the provenance of the intermediate waters did not change, and that the waters were derived from the Southern Ocean. Instead, changes in local/regional sea surface productivity may have caused the recorded changes in seafloor oxygenation.

Geochemistry, SiO2 minerals and isotopes at DSDP Hole 72-516F

Cherts recovered during DSDP Leg 72 from Rio Grande Rise sediments (Site 516) consist of both cristobalite and quartz, and contain ghosts of foraminifers and (more rare) radiolarians. Porcelanite made of disordered cristobalite is found in most old enclosing sediments. Local dissolution of siliceous microfossils during diagenesis is the most likely source of the silica required for the chert formation. As sediment age increases, the proportion of biogenic silica decreases and authigenic silica increases.

Major nannofossils, carbon and oxygen isotopes and carbon composition of ODP leg 194 site survey gravity cores

Biostratigraphic, sedimentologic, and geochemical analyses of hemipelagic periplatform sediments from shallow gravity cores taken during the Ocean Drilling Program Leg 194 site survey reveal that, despite the strong currents and almost infilled intraplatform bathymetric depressions, recent sedimentation at the location of the Leg 194 drill sites recorded glacial-interglacial cycles. Sediment analyses included determination of sediment type, carbonate content, bulk stable oxygen isotope composition, and calcareous nannofossil zones. Glacial periods, identified by elevated bulk d18O, are characterized by darker sediment color, coarser grain size, and lower carbonate content, whereas interglacial periods yield lighter-colored, finer, and carbonate-rich sediments. These data from the shallowmost few meters of Marion Plateau sediments complement the subsurface information of Leg 194 holes, in which the top few meters have not been analyzed in such a high-resolution fashion. In addition, these gravity cores are more likely to have recovered the sediments closest to the sediment/water interface as compared to the hydraulic piston cores collected during Leg 194.

Stable carbon and oxygen isotopes of foraminifera fand carbon content of ODP Leg 107 holes

High-resolution bio- and chemostratigraphy of an earliest Pliocene section from ODP Site 652 indicates that postflood paleoceanographic conditions in the Tyrrhenian Sea can be sub-divided into two discrete intervals. The first is manifested by an acme of Sphaeroidinellopsis spp., increasing carbonate contents, and a progressive decrease upsection in both the d13C and dl8O values of the planktonic foraminifera. The lower part of the acme interval contains unusual surface-to-bottom water isotope gradients suggesting a stratification of two water masses. Normal gradients in the upper part of the acme interval suggest a well-mixed water body. Between the end of the acme interval and the MP11/MP12 boundary, denoted by the first occurrence (F.O.) of Globorotalia margaritae, a migrational first appearance, there was a catastrophic collapse of the gradient marking an onset of the second post-flood interval. The disintegration of habitable conditions is suggested by a sharp decrease in carbonate content and the disappearance of the benthonic assemblage, which is subsequently replaced predominantly by Uvigerinapygmea, indicative of cold, low-oxygenated bottom waters. The introduction of benthonic species denoting well-oxygenated bottom conditions occurs within the lower MP12 zone. Superimposed on these overall trends are shorter term, warm-cold cycles, which are interpreted as orbitally induced, climatic fluctuations. Correlative studies of the less complete earliest Pliocene sections from ODP Holes 653B and 654A confirm these interpretations. A scenario derived from an integration of all the stratigraphic data indicates that normal paleoceanographic conditions were operating in the Tyrrhenian Sea only approximately 250,000 yr after the cessation of Messinian evaporative conditions at the Miocene/Pliocene boundary. The post-flood interval is marked by an initial period of gradual infilling, the Sphaeroidinellopsis spp. acme interval, followed by a disintegration of oceanographic conditions and a second recovery period. A sudden influx of cold, deep Atlantic waters into the Tyrrhenian Sea, resulting from a major tectonic break in the Gibraltar sill, may have caused this catastrophic reversal in the orderly recovery of normal paleoceanographic conditions in the post-flood period.

Oligocene-Miocene strontium isotopes of ODP Hole 120-747A

This study tests and improves on previously published early and middle Miocene 87Sr/86Sr marine correlations, presents Sr isotopic age correlations for this interval using the new timescale of Cande and Kent [1992 doi:10.1029/92JB01202], and evaluates Sr isotopic changes against an inferred glacioeustatic proxy. We generated a latest Oligocene to early late Miocene 87Sr/86Sr isotope record from Ocean Drilling Program (ODP) Hole 747A; this site provides an excellent magnetostratigraphic record during most of this interval for independent age estimates, very good foraminiferal preservation, and excellent core recovery. Comparisons of new 87Sr/86Sr data from Hole 747A with previously published data from Deep Sea Drilling Project (DSDP) Sites 608 [Miller et al., 1991 doi:10.1029/90PA01941] and 588 [Hodell et al., 1991 doi:10.1130/0091-7613(1991)019<0024:VITSIC>2.3.CO;2] yield the following results: (1) confirmation and refinement of the early Miocene Sr isotope changes, (2) improved definition of the timing of the changes in slope of 87Sr/86Sr near 15.4 Ma and 22.8 Ma, (3) improved Sr isotopic age resolution for the middle Miocene with resolution as good as +/- 0.7 m.y., and (4) identification of an inflection in the Sr isotope record at 28.0 Ma based on the combined records from DSDP Site 522 [Miller et al., 1988 doi:10.1029/PA003i002p00223] and ODP Hole 747A. We have been unable to determine the cause of middle Miocene offset between Site 588 and Hole 747A data, although we believe it may be attributed to problems in the age assignments for Hole 588A for the interval ~14-11 Ma and Site 747 for the interval 11-8 Ma. Because Hole 747A results provide a better chronology than Site 588 for most of the Miocene and a better middle Miocene Sr isotope record than Site 608, we propose that Hole 747A serves as the best reference section for Miocene 87Sr/86Sr variations from ca. 23 to 11 Ma. Using 87Sr/86Sr data from Sites 522, 608, and 747A, we relate late Eocene to early Miocene inflections in the 87Sr/86Sr isotope record to oxygen isotope increases and decreases inferred to represent glacioeustatic events. The decreases (deglaciations) observed in the ?18O record apparently lead the 87Sr/86Sr inflections by 1 to 1.5 m.y.

Calcium carbonate, isotopes and Rock-Eval pyrolysis at DSDP Holes 77-535 and 77-540

At DSDP Sites 534 (Central Atlantic) and 535 and 540 (Gulf of Mexico), and in the Vocontian Basin (France), Lower Cretaceous deposits show a very pronounced alternation of limestone and marl. This rhythm characterizes the pelagic background sedimentation and is independent of detritic intercalations related to contour and turbidity currents. Bed-scale cycles, estimated to be 6000-26,000 yr. long, comprise major and minor units. Their biological and mineralogic components, burrowing, heavy isotopes C and O, and some geochemical indicators, vary in close correlation with CaCO3 content. Vertical changes of frequency and asymmetry of the cycles are connected with fluctuations of the sedimentation rate. Plots of cycle thickness ("cyclograms") permit detailed correlations of the three areas and improve the stratigraphic subdivision of Neocomian deposits at the DSDP sites. Small-scale alternations, only observed in DSDP cores, comprise centimetric to millimetric banding and millimetric to micrometric lamination, here interpreted as varvelike alternations between laminae that are rich in calcareous plankton and others rich in clay. The laminations are estimated to correspond to cycles approximately 1,3, and 13 yr. in duration. The cyclic patterns appear to be governed by an interplay of continental and oceanic processes. Oceanic controls express themselves in variations of the biogenic carbonate flux, which depends on variations of such elements as temperature, oxygenation, salinity, and nutrient content. Continental controls modulate the influxes of terrigenous material, organic matter, and nutrients derived from cyclic erosion on land. Among the possible causes of cyclic sedimentation, episodic carbonate dissolution has been ruled out in favor of climatic fluctuations with a large range of periods. Such fluctuations are consistent with the great geographic extension shown by alternation controls and with the continuous spectrum of scales that characterizes limestone-marl cycles. The climatic variations induced by the Earth's orbital parameters (Milankovitch cycles) could be connected to bed-interbed alternations.

Oxygen and carbon isotopes of planktic foraminifera and ageprofile datum description at DSDP Hole 69-504

A detailed oxygen isotope record (resolution: about 2500 years) has been obtained for the Pleistocene sediments at Hole 504. Preliminary measurements made deeper in the section suggest that at least the upper Pliocene section is also amenable to detailed stable isotope work. The record for the middle Pleistocene resembles that obtained previously from piston cores in the western equatorial Pacific, although the superior resolution of this high-accumulation-rate site reveals a greater amplitude of isotope variation than previously observed. The record for the lower Pleistocene reveals variation that is both greater in amplitude and higher in frequency than apparent from previously analyzed piston cores. The site provides the best material recovered to date for the study of the evolution of climatic variability during the past few million years.

Geochemistry and isotopes at DSDP Leg 80 Holes

Thirty-eight samples from DSDP Sites 549 to 551 were analyzed for major and minor components and trace element abundances. Multivariate statistical analysis of geochemical data groups the samples into two major classes: an organic-carbon- rich group (> 1% TOC) containing high levels of marine organic matter and certain trace elements (Cu, Zn, V, Ni, Co, Ba, and Cr) and an organic-carbon-lean group depleted in these components. The greatest organic and trace metal enrichments occur in the uppermost Albian to Turanian sections of Sites 549 to 551. Carbon-isotopic values of bulk carbonate for the middle Cenomanian section of Site 550 (2.35 to 2.70 per mil) and the upper Cenomanian-Turonian sections of Sites 549 (3.35 to 4.47 per mil) and 551 (3.13 to 3.72 per mil) are similar to coeval values reported elsewhere in the region. The relatively heavy d13C values from Sites 549 and 551 indicate that this interval was deposited during the global "oceanic anoxic event" that occurred at the Cenomanian/Turonian boundary. Variation in the d18O of bulk carbonate for Section 550B-18-1 of middle Cenomanian age suggests that paleosalinity and/or paleotemperature variations may have occurred concurrently with periodic anoxia at this site. Climatically controlled increases in surface-water runoff may have caused surface waters to periodically freshen, resulting in stable salinity stratification

Stable isotopes and calcium carbonate at DSDP Holes 85-574 and 85-574A

Detailed stable isotopic and calcium carbonate records (with a sampling resolution of 3000 yr.) from the middle Miocene section of hydraulic piston corer (HPC) Hole 574A provide a sequence that records the major shift in the oxygen isotopic composition of the world's oceans that occurred at about 14 Ma. The data suggest that this transition was rapid and spans about 30,000 yr. of sediment deposition. In intervals before and after the shift, the mean d18O values are characterized by a constant mean with a high degree of variability. The degree of variability in both the d18O and d13C records is comparable to that observed for the Pliocene and earliest Pleistocene and does not show a significant change before or after the major shift in the d18O record. Whereas the oxygen isotopic record is characterized by relatively stable mean values before and after the middle Miocene event, the d13C record shows a number of significant offsets in the mean value separated by intervals of high-frequency variations. Time and frequency domain analysis of all records from Hole 574A indicate that the frequency components shown to be related to orbital changes in the Pleistocene record are also present in the middle Miocene. The high variability observed in the Site 574 isotopic records places important constraints on models describing the role of formation of the Antarctic ice sheet during the middle Miocene climatic transitions. Thus, HPC Hole 574A provides a valuable sequence for detailed study of climatic variability during an important time in the Earth's history, although we cannot provide a definitive explanation of the major oxygen isotopic event of the middle Miocene.

Geochemistry and Mg-isotopes of carbonate sediments and porefluids of ODP Site 130-807

Deep-sea pore fluids are potential archives of ancient seawater chemistry. However, the primary signal recorded in pore fluids is often overprinted by diagenetic processes. Recent studies have suggested that depth profiles of Mg concentration in deep-sea carbonate pore fluids are best explained by a rapid rise in seawater Mg over the last 10-20 Myr. To explore this possibility we measured the Mg isotopic composition of pore fluids and carbonate sediments from Ocean Drilling Program (ODP) site 807. Whereas the concentration of Mg in the pore fluid declines with depth, the isotopic composition of Mg in the pore fluid increases from -0.78 per mil near the sediment-water interface to -0.15 per mil at 778 mbsf. The Mg isotopic composition of the sediment, with few important exceptions, does not change with depth and has an average d26Mg value of -4.72 per mil. We reproduce the observed changes in sediment and pore-fluid Mg isotope values using a numerical model that incorporates Mg, Ca and Sr cycling and satisfies existing pore-fluid Ca isotope and Sr data. Our model shows that the observed trends in magnesium concentrations and isotopes are best explained as a combination of two processes: a secular rise in the seawater Mg over the Neogene and the recrystallization of low-Mg biogenic carbonate to a higher-Mg diagenetic calcite. These results indicate that burial recrystallization will add Mg to pelagic carbonate sediments, leading to an overestimation of paleo-temperatures from measured Mg/Ca ratios. The Mg isotopic composition of foraminiferal calcite appears to be only slightly altered by recrystallization making it possible to reconstruct the Mg isotopic composition of seawater through time.

Oxygen- and carbon-isotopes of Globigerina bulloides and Neogloboquadrina pachyderma at DSDP Holes 80-548 and 80-549A

Oxygen- and carbon-isotope analyses have been performed on the Quaternary planktonic foraminifers of Sites 548 and 549 (DSDP Leg 80) to investigate major water mass changes that occurred in the northeastern Atlantic at different glacial-interglacial cycles and to compare them with the well-defined picture of 18,000 yr. ago. Oxygen-isotope stratigraphy also provides a chronological framework for the more important data on the fauna and flora. Although bioturbation and sedimentary gaps obliterate the climatic and stratigraphic record, general trends in the oceanographic history can be deduced from the isotopic data. Isotopic stratigraphy has tentatively been delineated down to isotopic Stage 16 at Site 548 and in Hole 549A. This stratigraphy fits well with that deduced from benthic foraminiferal d18O changes and with bioclimatic zonations based on foraminiferal associations at Site 549. Variations in the geographic extension and in the flux of the Gulf Stream subtropical waters are inferred from both d18O and d13C changes. Maximal fluxes occurred during the late Pliocene. Northward extension of subtropical waters increased through the various interglacial phases of the early Pleistocene and decreased through the late Pleistocene interglacial phases. Conversely, glacial maxima were more intense after Stage 16. Isotopic Stages 12 and 16 mark times of important change in water mass circulation. Oxygen- and carbon-isotope analyses have been performed on the Quaternary planktonic foraminifers of Sites 548 and 549 (DSDP Leg 80) to investigate major water mass changes that occurred in the northeastern Atlantic at different glacial-interglacial cycles and to compare them with the well-defined picture of 18,000 yr. ago. Oxygen-isotope stratigraphy also provides a chronological framework for the more important data on the fauna and flora. Although bioturbation and sedimentary gaps obliterate the climatic and stratigraphic record, general trends in the oceanographic history can be deduced from the isotopic data. Isotopic stratigraphy has tentatively been delineated down to isotopic Stage 16 at Site 548 and in Hole 549A. This stratigraphy fits well with that deduced from benthic foraminiferal d18O changes and with bioclimatic zonations based on foraminiferal associations at Site 549. Variations in the geographic extension and in the flux of the Gulf Stream subtropical waters are inferred from both d18O and d13C changes. Maximal fluxes occurred during the late Pliocene. Northward extension of subtropical waters increased through the various interglacial phases of the early Pleistocene and decreased through the late Pleistocene interglacial phases. Conversely, glacial maxima were more intense after Stage 16. Isotopic Stages 12 and 16 mark times of important change in water mass circulation.

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.