Strontium isotope ratios of planktonic foraminifera from sediment samples acroos the K/T boundary

Seawater 87Sr/86Sr values increase abruptly by 28 * 10**-6 across the Cretaceous/Tertiary boundary (KTB). This small, but rapid shift is superimposed on the larger scale structure of the seawater Sr isotope curve. The time scale of radiogenic Sr addition appears to be too rapid to reconcile with sources associated with volcanism, and we show that the amount of Sr required to produce even this small increase is too large to be derived from: (1) a KT bolide of the size constrained by the Ir anomaly, (2) continental crust ejecta from the impact of such a bolide, (3) soot from global wildfires initiated by an impact, or (4) any combination of these sources. The probable source of the radiogenic Sr is enhanced continental weathering, but the high rate of increase appears to rule out processes such as sea level regression, glaciation or tectonism. A plausible mechanism for rapid addition of radiogenic Sr to the oceans is enhanced weathering associated with globally distributed acid rain (pH c. 1) which is a proposed by-product of a bolide impact (Prinn and Fegley, 1987, doi:10.1016/0012-821X(87)90046-X).

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.

Sr stratigraphy and biostratigraphy for samples from DSDP Hole 32-305 and ODP Hole 123-766A

The strontium isotope ratios (87Sr/86Sr) of marine barite microcrystals separated from Cretaceous sedimentary deposits from Ocean Drilling Program and Deep Sea Drilling Project sites from the Pacific and Indian Oceans have been compared to the composite Sr isotope curve of McArthur et al. The barite in these cores accurately recorded the seawater 87Sr/86Sr ratio, thereby reaffirming the composite Cretaceous strontium curve. Moreover, marine barite is a more reliable recorder of 87Sr/86Sr than is carbonate in sedimentary deposits with high clay content, thereby providing an opportunity for Sr isotope stratigraphy and dating in carbonate-poor or diagenetically altered sections. We have used the barite-derived Sr isotope record to refine the biostratigraphic age models of the sites investigated.

Stable and strontium isotope ratios and age determination of ODP Site 130-803

Stratigraphic information from strontium, oxygen, and carbon isotopic ratios has been integrated with diatom and planktonic foraminifer datums to refine the Oligocene to early Miocene chemostratigraphy of Site 803. The Sr isotope results are based on analyses of mixed species of planktonic foraminifer and bulk carbonate samples. 87Sr/86Sr ratios of bulk carbonate samples are, in most cases, less radiogenic than contemporaneous seawater. Estimated sediment ages based on planktonic foraminifer 87Sr/86Sr ratios, using the Sr-isotope-age relation determined by Hess and others in 1989, are in moderately good agreement with the biostratigraphic ages. Chronological resolution is significantly enhanced with the correlation of oxygen and carbon isotope records to those of the standard Oligocene section tied to the Geomagnetic Polarity Time Scale at Site 522. Ages revised by this method and other published ages of planktonic foraminifer datums are used to revise the Oligocene stratigraphy of Site 77 to correlate the stable isotope records of Sites 77 and 803. Comparison of the Cibicidoides stable isotope records of Sites 77 and 574 with paleodepths below 2500 m in the central equatorial Pacific, and Site 803 at about 2000-m paleodepth in the Ontong Java Plateau reveals inversions in the vertical d18O gradient at several times during the Oligocene and in the early Miocene. The shallower water site had significantly-higher d18O values than the deeper water sites after the earliest Oligocene 18O enrichment and before 34.5 Ma, in the late Oligocene from 27.5 to at least 25 Ma, and in the early Miocene from 22.5 to 20.5 Ma. It is not possible to ascertain if the d18O inversion persisted during the Oligocene/Miocene transition because the deeper sites have hiatuses spanning this interval. We interpret this pattern to reflect that waters at about 2000 m depth were cold and may have formed from mixing with colder waters originating in northern or southern high-latitude regions. The deeper water appear to have been warmer and may have been a mixture with warm saline waters from mid- or low-latitude regions. No apparent vertical d13C gradient is present during the Oligocene, suggesting that the age difference of these water masses was small.

(Table A1) Isotopic ratios of Sr, Nd, and Pb for sediments in ODP Leg 138 sites

The provenance of eolian dust supplied to deep-sea sediments has the potential to offer insights into changes in past atmospheric circulation. Specifically, measuring temporal changes in dust provenance can shed light on changes in the mean position of the Intertropical Convergence Zone (ITCZ), a region acting as a barrier separating wind-blown material derived from northern versus southern hemisphere sources. Here we have analyzed Nd, Sr, and Pb isotope ratios in the operationally-defined detrital component extracted from deep-sea sediments in the eastern equatorial Pacific (EEP) along a meridional transect at 110°W from 3°S to 7°N (ODP Leg 138, sites 848-853). Sr isotope results show that barite Sr has a significant influence on 87Sr/86Sr isotope ratios of samples in the upwelling zone of the EEP. However, sites located >3° or more away from the equator (sites 852 and 853) are believed to not be affected by barite Sr and provide useful detrital Sr signals. 208Pb/206Pb and 207Pb/206Pb ratios in all cores fall into the Pb-isotope space of five potential dust sources (Asia, North and Central/South America, Sahara, and Australia), with no distinct isotopic fingerprinting of the dominant source(s). epsilon-Nd values were most valuable for discerning detrital source provenance, and their values at all sites, ranging from ~5.46 to ~3.25, were more unradiogenic for sediments deposited during the last glacial than for those deposited during the Holocene. There are distinct latitudinal trends in the epsilon-Nd values, with more radiogenic values further south and less radiogenic values further north, excluding site 848. This distinction holds true for both Holocene and last glacial periods. For the most southerly site, 848, we invoke, for the first time, a distinct southern hemisphere Australian source as being responsible for the unradiogenic Nd isotope ratios. Both average last glacial and Holocene epsilon-Nd values show similar sharp gradients along the transect between 5.29°N and 2.77°N, suggesting little movement of the glacial ITCZ in the EEP. However, during the deglacial, this gradient is stronger and shifted further north between 5.29°N and 7.21°N, suggesting a more northerly, possibly stronger, deglacial ITCZ.

Lead and strontium isotope composition, mass accumulation rates and rare earth elements of selected samples from DSDP Sites 92-597 to 92-601

Most of the Pb isotope data for the Leg 92 metalliferous sediments (carbonate-free fraction) form approximately linear arrays in the conventional isotopic plots, extending from the middle of the field for mid-ocean ridge basalts (MORB) toward the field for Mn nodules. These arrays are directed closely to the average values of Mn nodules, the composition of which reflects the Pb isotope composition of seawater (Reynolds and Dasch, 1971). Since the Leg 92 samples are almost devoid of continentally derived detritus, it can be inferred that the more radiogenic end-member is seawater. The less radiogenic end-member lies in the very middle of the MORB field, and hence can be considered to reflect the Pb isotope composition of typical ocean-ridge basalt. The array of data lying between these two end-members is most readily interpreted in terms of simple linear mixing of Pb from the two different end-member sources. According to this model, eight samples from Sites 599 to 601 contain 50 to 100% basaltic Pb. Five of these samples have compositions that are identical within the uncertainty of the analyses. We use the average of these five values to define our unradiogenic end-member in the linear mixing model. The ratios used for this average are 206Pb/204Pb = 18.425 ± 0.010; 207Pb/204Pb = 15.495 ± 0.018; 208Pb/204Pb = 37.879 ± 0.068. These values should approximate the average Pb isotope composition of discharging hydrothermal solutions, and therefore also that of the basaltic crust, over the period of time represented by these samples ( 4 m.y., from 4 to 8 Ma). Sr isotope ratios show a significant range of values, from 0.7082 to 0.7091. The lower ratios are well outside the value of 0.70910 ± 6 for modern-day seawater (Burke et al., 1982). However, most values correspond very closely to the curve of 87Sr/86Sr versus age for seawater, with older samples having progressively lower 87Sr/86Sr ratios. The simplest explanation for this progressive reduction is that recrystallization of the abundant biogenic carbonate in the sediments released older seawater Sr which was incorporated into ferromanganiferous phases during diagenesis. Leg 92 metalliferous sediments have total rare earth element (REE) contents that range on a carbonate-free basis from 131 to 301 ppm, with a clustering between 167 and 222 ppm. The patterns have strong negative Ce anomalies. Samples from Sites 599 to 601 display a slight but distinct enrichment in the heavy REE relative to the light REE, whereas those from Sites 597 to 598 show almost no heavy REE enrichment. The former patterns (those for Sites 599 to 601) are interpreted as indicating moderate diagenetic alteration of metalliferous sediments originating at the EPR axis; the latter reflect more complete diagenetic modification.

Chemical and isotope compositions of sediments from DSDP Hole 86-576A and Core LL44-GPC-3

A record of changes in Pb and Sr isotopic composition of two cores (DSDP 86-576A and LL44- GPC-3) from the red clay region of the central North Pacific has been determined for the past 60-65 million years. The isotope records of the eolian silicate fraction of the red clays reflect the change in source area as the core sites migrated under different wind systems. The Sr isotope compositions of eolian silicate material are consistent with Asian loess and North American arc volcanism that has been recognized from mineralogical studies. The silicate-bound eolian Pb isotopic compositions similarly reflect Asian loess and arc volcanism. The isotope records of three ferromanganese crusts from similar locations in the central Pacific are similar to the eolian component of red clays, but offset to less radiogenic values. This may be due to two mechanisms: (1) Pb that can be removed from eolian material by seawater is much less radiogenic, or less likely (2) hydrothermal Pb can be transported further away from venting sites through particle exchange with seawater, despite hydrothermal venting acting as a net sink of oceanic Pb. The temporal changes in Pb isotopes in the ferromanganese crusts, bulk red clays and eolian silicates are similar although offset from each other suggesting that eolian deposition is an important source of Pb to seawater and to ferromanganese crusts. This contrasts with the Atlantic and Southern Ocean where more intense deep water flow leads to isotopic gradients in FeMn crusts that do not reflect surface water conditions immediately above the crust. A mechanism is proposed which accounts for Pacific deepwater Pb being isotopically influenced by eolian deposition.