Chemical and Sr isotopic compositions and timing of carbonate mineral precipitation, ODP Leg 115

The strontium isotope ratios of authigenic carbonates from Indian Ocean sea-floor basalts have been used to determine the timing of carbonate mineral precipitation and fluid flow. The samples include calcites from 57.2 Ma crust from Ocean Drilling Project (ODP) Site 715, and calcites, aragonites, and siderites from 63.7 Ma crust from ODP Site 707. At Site 715, calcite precipitation may have begun at any time after the basalts cooled, and it continued until approximately 31 Ma, or 26 m.y. after basalt eruption. At Site 707, aragonite and siderite did not begin to precipitate until about 36 Ma, almost 30 m.y. after basalt eruption, and continued to precipitate until at least 30 and 28 Ma, respectively. Calcite precipitation began at approximately 32 Ma and continued until 22 Ma. These ages suggest that vein mineral deposition and low-temperature fluid circulation in the ocean crust may continue for much longer periods of time than previously observed.

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.

Chemical and isotopic compositions of deep-sea carbonate sediments and interstitial waters from DSDP Sites 30-288 and 30-289

Interstitial waters and sediments from DSDP sites 288 and 289 contain information on the chemistry and diagenesis of carbonate in deep-sea sediments and on the role of volcanic matter alteration processes. Sr/Ca ratios are species dependent in unaltered foraminifera from site 289 and atom ratios (0.0012-0.0016) exceed those predicted by distribution coefficent data (~0.0004). During diagenesis Sr/Ca ratios of carbonates decrease and reach the theoretical distribution at a depth which is identical to the depth of Sr isotopic equilibration, where 87Sr/86Sr ratios of interstitial waters and carbonates converge. Mg/Ca ratios in the carbonates do not increase with depth as found in some other DSDP sites, possibly because of diagenetic re-equilibration with interstitial waters showing decreasing Mg(2+)/Ca(2+) ratios with depth due to Ca input and Mg removal by alteration of volcanic matter. Interstitial 18O/16O ratios increase with depth at site 289 to d18O = 0.67? (SMOW), reflecting carbonate recrystallization at elevated temperatures (>/= 20°C), the first recorded evidence of this effect in interstitial waters. Interstitial Sr2+ concentrations reach high levels, up to 1 mM, chiefly because of carbonate recrystallization. However, 87Sr/86Sr ratios decrease from 0.7092 to less than 0.7078, lower than for contemporaneous sea water, showing that there is a volcanic input of strontium at depth. This volcanic component is recorded in the Sr isotopic composition of recrystallized calcites. Isotopic compositions of the unrecrystallized calcites suggests that the rate of increase of the 87Sr/86Sr ratio of sea water with time has been faster since 3 my ago than in the preceding 13 my.

Strontium isotope geochemistry of ODP Leg 113 sites

The concentration of dissolved Sr and the distribution of 87Sr/86Sr isotope ratios in Leg 113 interstitial waters may be interpreted in terms of mixing of Sr from four different reservoirs: indigenous seawater, marine carbonate minerals, and basaltic and siliceous detrital material. The input to the pore water from these reservoirs is determined by the reactivity of the reservoir rather than its size. The presence of strontium derived from siliceous detrital material is unequivocally demonstrated in the pore waters of the hemipelagic deposits, and is also significant in the calcareous Maud Rise sediments due to the unusually low degree of carbonate recrystallization. Also, alteration of basic volcanic material is important at several sites.

(Table 1) Strontium isotope data for marine carbonates of sediment core CRP-3

Strontium isotope stratigraphy was used to date 5 discrete horizons within the CRP-3 drillhole. A single in situ modiolid bivalve fragment at 10.88 mbsf gives an age of 30.9 (±0.8) Ma for the associated sediment. The four remaining well preserved fragments recovered from 29.94-190.31 mbsf are within error of this age, indicating a high sedimentation rate and suggesting little time is missing in disconformities. The diagenetic alteration of carbonate macrofossils by continental fluids (and possibly seawater) is a common feature to 320 mbsf.

Calcium carbonate and trace element composition of ODP Leg 182 sites

An intensive geochemical investigation was conducted on carbonate sediments recovered during Ocean Drilling Program Leg 182. Four trace elements in 635 sediment samples from Sites 1126-1132 on the Great Australian Bight were examined by atomic absorption spectrometry on the acid-soluble fraction. Downhole profiles of these elements exhibit complicated fluctuations throughout the late Eocene to Pleistocene, principally because of the variations in the acid-soluble fraction. The purpose of this study is to present initial results on the geochemical composition of Cenozoic cool-water carbonates as a basis for a future detailed investigation to determine the paleoenvironment of a carbonate-dominated continental margin during the evolution of the Southern Ocean.

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.

Strontium and oxygen isotope data for DSDP Hole 44-390A and ODP Leg 171 holes

Differences in regional responses to climate fluctuations are well documented on short time scales (e.g., El Niño-Southern Oscillation), but with the exception of latitudinal temperature gradients, regional patterns are seldom considered in discussions of ancient greenhouse climates. Contrary to the expectation of global warming or global cooling implicit in most treatments of climate evolution over millions of years, this paper shows that the North Atlantic warmed by as much as 6°C (1.5% decrease in d18O values of planktic foraminifera) during the Maastrichtian global cooling interval. We suggest that warming was the result of the importation of heat from the South Atlantic. Decreasing North Atlantic d18O values are also associated with increasing gradients in planktic d13C values, suggesting increasing surface-water stratification and a correlated strengthening of the North Atlantic Polar Front. If correct, this conclusion predicts arctic cooling during the late Maastrichtian. Beyond implications for the Maastrichtian, these data demonstrate that climate does not behave as if there is a simple global thermostat, even on geologic time scales.

Strontium and neodymium isotope data for barite separates and pore waters, and isotope and concentration data for foraminifera and fish teeth from DSDP Leg 85 sediments

Strontium and neodymium isotopic data are reported for barite samples chemically separated from Late Miocene to Pliocene sediments from the eastern equatorial Pacific. At a site within a region of very high productivity close to the equator, 87Sr/86Sr ratios in the barite separates are indistinguishable from those of foraminifera and fish teeth from the same samples. However, at two sites north of the productivity maximum barite separates have slightly, but consistently lower (averaging 0.000062) ratios than the coexisting phases, although values still fall within the total range of published values for the contemporaneous seawater strontium isotope curve. We examine possible causes for this offset including recrystallization of the foraminifera, fish teeth or barite, the presence of non-barite contaminants, or incorporation of older, reworked deep-sea barite; the inclusion of a small amount of hydrothermal barite in the sediments seems most consistent with our data, although there are difficulties associated with adequate production and transportation of this phase. Barite is unlikely to replace calcite as a preferred tracer of seawater strontium isotopes in carbonate-rich sediments, but may prove a useful substitute in cases where calcite is rare or strongly affected by diagenesis. In contrast to the case for strontium, neodymium isotopic ratios in the barite separates are far from expected values for contemporary seawater, and appear to be dominated by an (unobserved) eolian component with high neodymium concentration and low 143Nd/144Nd. These results suggest that the true potential of barite as an indicator of paleocean neodymium isotopic ratios and REE patterns will be realized only when a more selective separation procedure is developed.

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.

Strontium isotope ratios of planktonic foraminifera from late Neogene sediment samples

A curve describing the variation of the strontium isotopic composition of seawater for the late Neogene (9 to 2 Ma) was constructed from 87Sr/86Sr analyses of marine carbonate in five Deep Sea Drilling Project (DSDP) sites: 502, 519, 588, 590, and 593. The strontium isotopic composition of the oceans increased between 9 and 2 Ma with several changes in slope. From 9 to 5.5 Ma, 87Sr/86Sr values were nearly constant at ~0.708925. Between 5.5 and 4.5 Ma, 87Sr/86Sr ratios increased monotonically at a rate of not, vert, similar 1 * 10**-4 per million years. The steep slope during this interval provides the potential for high resolution strontium isotope stratigraphy across the Miocene/Pliocene boundary. The rate of change of 87Sr/86Sr decreases to near zero again during the interval 4.5-2.5 Ma, and ratios average 0.709025. The relatively rapid increase of 87Sr/86Sr between 5.5 and 4.5 Ma must be related to changes in the flux or average 87Sr/86Sr ratios of the major inputs of Sr to the oceans. Quantitative modelling of these inputs suggests that the increase was most probably caused by an increase in the dissolved riverine flux of strontium to the oceans, an increase in the average 87Sr/86Sr composition of river water, or some combination of these parameters. Modelling of this period as a transient-state requires a pulse-like increase in the input of 87Sr to the oceans between 5.5 and 4.5 Ma. Alternatively, the 5.5-4.5 Ma period can be modelled as a simple transition from one steady-state to another if the oceanic residence time of strontium was eight times less than the currently accepted value of 4 Ma. During the time interval of steep 87Sr/86Sr increase, other geochemical and sedimentologic changes also occur including an increase in sediment accumulation rates, a drop in the calcite compensation depth (CCD), and a decrease in the delta13C of dissolved bicarbonate (i.e., "carbon shift"). The simplest mechanism to explain 87Sr/86Sr variation and these related geochemical changes is to invoke an increase in the dissolved chemical fluxes carried by rivers to the oceans. This, in turn, implies increased chemical denudation rates of the continents and shelves during the late Neogene. The increase in chemical weathering rates is attributed to increased exposure of the continents by eustatic regression, intensified glacial/interglacial cycles, and accelerated rates of global tectonism beginning at 5.5 Ma during the latest Miocene.

Carbonate sedimentology of the Propeller Mound, Northeast Atlantic

High resolution studies from the Propeller Mound, a cold-water coral carbonate mound in the NE Atlantic, show that this mound consists of >50% carbonate justifying the name "carbonate mound". Through the last ~300,000 years approximately one third of the carbonate has been contributed by cold-water corals, namely Lophelia pertusa and Madrepora oculata. This coral bound contribution to the carbonate budget of Propeller Mound is probably accompanied by an unknown portion of sediments buffered from suspension by the corals. However, extended hiatuses in Propeller Mound sequences only allow the calculation of a net carbonate accumulation. Thus, net carbonate accumulation for the last 175 kyr accounts for only <0.3 g/cm2/kyr, which is even less than for the off-mound sediments. These data imply that Propeller Mound faces burial by hemipelagic sediments as has happened to numerous buried carbonate mounds found slightly to the north of the investigated area.