Stable oxygen isotope ratios in zircons from oceanic crust

Lower ocean crust is primarily gabbroic, although 1-2% felsic igneous rocks that are referred to collectively as plagiogranites occur locally. Recent experimental evidence suggests that plagiogranite magmas can form by hydrous partial melting of gabbro triggered by seawater-derived fluids, and thus they may indicate early, high-temperature hydrothermal fluid circulation. To explore seawater-rock interaction prior to and during the genesis of plagiogranite and other late-stage magmas, oxygen-isotope ratios preserved in igneous zircon have been measured by ion microprobe. A total of 197 zircons from 43 plagiogranite, evolved gabbro, and hydrothermally altered fault rock samples have been analyzed. Samples originate primarily from drill core acquired during Ocean Drilling Program and Integrated Ocean Drilling Program operations near the Mid-Atlantic and Southwest Indian Ridges. With the exception of rare, distinctively luminescent rims, all zircons from ocean crust record remarkably uniform d18O with an average value of 5.2 ± 0.5 per mil (2SD). The average d18O(Zrc) would be in magmatic equilibrium with unaltered MORB [d18O(WR) ~5.6-5.7 per mil], and is consistent with the previously determined value for equilibrium with the mantle. The narrow range of measured d18O values is predicted for zircon crystallization from variable parent melt compositions and temperatures in a closed system, and provides no indication of any interactions between altered rocks or seawater and the evolved parent melts. If plagiogranite forms by hydrous partial melting, the uniform mantle-like d18O(Zrc) requires melting and zircon crystallization prior to significant amounts of water-rock interactions that alter the protolith d18O. Zircons from ocean crust have been proposed as a tectonic analog for >3.9 Ga detrital zircons from the earliest (Hadean) Earth by multiple workers. However, zircons from ocean crust are readily distinguished geochemically from zircons formed in continental crustal environments. Many of the >3.9 Ga zircons have mildly elevated d18O (6.0-7.5 per mil), but such values have not been identified in any zircons from the large sample suite examined here. The difference in d18O, in combination with newly acquired lithium concentrations and published trace element data, clearly shows that the >3.9 Ga detrital zircons did not originate by processes analogous to those in modern mid-ocean ridge settings.

Stable carbon and oxygen isotope ratios across the Cretaceous/Tertiary boundray on the Walvish Ridge

The isotopic composition and diversity of nannofossils were studied in cores from the Deep Sea Drilling Project (DSDP) Sites 525A, 527, 528, and 529 from the Walvis Ridge, South Atlantic to better understand the changes which occurred across the Cretaceous/Tertiary boundary (K/T boundary). The stratigraphic range of the samples is from the Arkhangelskiella cymbiformis Zone in the Maastrichtian to the Heliolithus kleinpelli Zone in the Danian. Nannofossil diversity was high (Shannon-Weaver diversity index, 'H= 2.5-3) in the late Cretaceous, but decreased sharply (H c. 1 ) across the K/T boundary. The delta13C values also decrease across the K/T boundary at the four sites, suggesting a reduction in surface productivity in the South Atlantic concomitant with the reduction in diversity. During the Danian, nannofossil diversity and delta13C show some recovery approximately 500-700 k.y. after the boundary event. However, not until 2.5 Ma after the boundary event did diversity become constant. Diversity values similar to those for the late Cretaceous were not attained again in the early Paleocene interval studied. Carbon isotopic compositions similar to those from the Cretaceous were not attained until 4.5 Ma after the K/T event.

Stable carbon and oxygen isotope ratios of benthic foraminifera from Paleocene to Oligocene sediments

Benthic oxygen and carbon isotopic results from a depth transect on Maud Rise, Antarctica, provide the first evidence for Warm Saline Deep Water (WSDW) in the Paleogene oceans. Distinct reversals occur in the oxygen isotopic gradient between the shallower Hole 689B (Eocene depth ~1400 m; present-day depth 2080 m) and the deeper Hole 690B (Eocene depth ~2250 m; present-day depth 2914 m). The isotopic reversals, well developed by at least 46 Ma (middle middle Eocene), existed for much of the remaining Paleogene. We do not consider these reversals to be artifacts of differential diagenesis between the two sites or to have resulted from other potentially complicating factors. This being so, the results show that deep waters at Hole 690B were significantly warmer than deep waters at the shallower Hole 689B. A progressive decrease and eventual reversal in benthic to planktonic delta18O gradients in Hole 690B, demonstrate that the deeper waters became warmer relative to Antarctic surface waters during the Eocene. The warmer deep waters of the Paleogene are inferred to have been produced at middle to low latitudes, probably in the Tethyan region which contained extensive shallow-water platforms, ideal sites for the formation of high salinity water through evaporative processes. The ocean during the Eocene, and perhaps the Paleocene, is inferred to have been two-layered, consisting of warm, saline deep waters formed at low latitudes and overlain by cooler waters formed at high latitudes. This thermospheric ocean, dominated by halothermal circulation we name Proteus. The Neogene and modern psychrospheric ocean Oceanus is dominated by thermohaline circulation of deep waters largely formed at high latitudes. An intermediate condition existed during the Oligocene, with a three-layered ocean that consisted of cold, dense deep waters formed in the Antarctic (Proto-AABW), overlain by warm, saline deep waters from low latitudes, and in turn overlain by cool waters formed in the polar regions. This we name Proto-oceanus which combined both halothermal and thermohaline processes. The sequence of high latitude, major, climatic change inferred from the oxygen isotopic records is as follows: generally cooler earlier Paleocene; warming during the late Paleocene; climax of Cenozoic warmth during the early Eocene and continuing into the early middle Eocene; cooling mainly in a series of steps during the remainder of the Paleogene. Superimposed upon this Paleogene pattern, the Paleocene/Eocene boundary is marked by a brief but distinct warming that involved deep to surface waters and a reduction in surface to deep carbon and oxygen isotopic gradients. This event coincided with major extinctions among the deep-sea benthic foraminifers as shown by Thomas (1990 doi:10.2973/odp.proc.sr.113.123.1990). Salinity has played a major role in deep ocean circulation, and thus paleotemperatures cannot be inferred directly from the oxygen isotopic composition of Paleogene benthic foraminifers without first accounting for the salinity effect.

Measurements of stable carbon isotope ratios of CO2 over the last 24000 years and CO2 concentration measurements on Antarctic ice cores using three different methods

The stable carbon isotope ratio of atmospheric CO2 (d13Catm) is a key parameter in deciphering past carbon cycle changes. Here we present d13Catm data for the past 24,000 years derived from three independent records from two Antarctic ice cores. We conclude that a pronounced 0.3 per mil decrease in d13Catm during the early deglaciation can be best explained by upwelling of old, carbon-enriched waters in the Southern Ocean. Later in the deglaciation, regrowth of the terrestrial biosphere, changes in sea surface temperature, and ocean circulation governed the d13Catm evolution. During the Last Glacial Maximum, d13Catm and atmospheric CO2 concentration were essentially constant, which suggests that the carbon cycle was in dynamic equilibrium and that the net transfer of carbon to the deep ocean had occurred before then.

Stable and radiogenic isotope ratios in pore waters from ODP Leg 127 sites

Interstitial waters from four sites of the Japan Sea (794 to 797) have been analyzed for stable isotopes (delta D, delta11B, delta18O, and delta34S) and 87Sr/86Sr, besides major and minor ions. The isotopic composition is dominated by organic matter degradation, alteration of ash layers and volcaniclastic sands, silica transformation (opal A/CT), and basement alteration. Organic matter degradation and corresponding sulfate reduction leads to 32S depletion and is dependent upon sedimentation rate. The remaining sulfate reservoir is characterized by very "heavy" delta34S ratios, up to +93 ? (rel. CDT = Canyon Diabolo Troilite). "Barite fronts," which may develop in such sediments, should also be characterized by very "heavy" sulfur isotopes. The alteration of volcaniclastic material in the Quaternary sections influences the delta18O (-1.5 ? shift) and delta11B (desorption and later adsorption of "labile"11B). A pronounced positive delta11B anomaly at Site 795 represents the depth range of preferential 10B uptake by alteration products of the ash layers. At Site 796 delta D, delta11B, and 87Sr/86Sr are severely affected by alteration processes of volcaniclastic sands. The opal A/CT transformation may influence the oxygen isotopes and serves as a potential source for B, which is liberated at this interval at Site 795. This positive B anomaly is not reflected in the delta11B profile. Basement alteration processes dominate the sedimentary sequence below the opal A/CT transition, which serves as a chemical and physical boundary. The decreases in delta D and delta18O are probably related to a "paleo ocean water reservoir" situated in the permeable Layer II of the oceanic crust, as is indicated by the positive correlation between these two parameters. Besides Mg, alkalies and delta18O basement rocks also serve as a sink for 11 B (Site 795) and are the source for the Ca and Sr increases, as is documented by the less radiogenic 87Sr/86Sr ratio. 87Sr/86Sr ratios for the lowermost pore waters from Site 795 (0.70529) are comparable to those from volcaniclastic rocks from the "Green Tuff' region (0.704 to 0.706) and oil field brines from the Niigata Oil Field.

Stable oxygen and carbon isotope ratios of foraminifera from Oligocene to Miocene sediments of DSDP Hole 39-354 from Ceara Rise, West Altlantic (Table 1)

The oxygen- and carbon-isotope compositions of planktic and benthic foraminifera and calcareous nannofossils from Middle Oligocene-Early Miocene Equatorial Atlantic sediments (DSDP Site 354) indicate two important paleoceanographic changes, in the Late Oligocene (foraminiferal Zone P.21) and in the Early Miocene (foraminiferal Zone N.5). The first change, reflected by a delta18O increase of 1.45? in Globigerina venezuelana, affected only intermediate pelagic and not surface, deep or bottom waters. The second change affected surface and intermediate waters, whereas deep and bottom waters showed only minor fluctuations. In the case of the former the isotope effect of the moderate ice accumulation on the Antarctic continent is amplified in the Equatorial Atlantic by changes in the circulation pattern. The latter paleoceanographic change, reflected by a significant increase in 18O in both planktic and benthic forms (about 1.0? and 0.5?, respectively), may have been caused by ice volume increase and temperature decrease. Both oxygen- and carbon-isotope compositions indicate a marked depth-habitat stratification for planktic foraminifera and calcareous nannofossils. Three different dwelling groups are recognized: shallow Globigerinoides, Globoquadrina dehiscens, Globorotalia mayeri and nannofossils; intermediate Globigerina venezuelana; and deep Catapsydrax dissimilis. The comparison of foraminifera and calcareous nannofossils suggests that the isotopic compositions of nannofossils are generally controlled by the same parameters which control the isotopic composition of shallow-dwelling foraminifera, but the former are more enriched in 18O.

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.

Stable isotope and Mg/Ca ratios of Paleogene benthic foraminifera in the western North Atlantic

Global cooling and the development of continental-scale Antarctic glaciation occurred in the late middle Eocene to early Oligocene (~38 to 28 million years ago), accompanied by deep-ocean reorganization attributed to gradual Antarctic Circumpolar Current (ACC) development. Our benthic foraminiferal stable isotope comparisons show that a large d13C offset developed between mid-depth (~600 meters) and deep (>1000 meters) western North Atlantic waters in the early Oligocene, indicating the development of intermediate-depth d13C and O2 minima closely linked in the modern ocean to northward incursion of Antarctic Intermediate Water. At the same time, the ocean's coldest waters became restricted to south of the ACC, probably forming a bottom-ocean layer, as in the modern ocean. We show that the modern four-layer ocean structure (surface, intermediate, deep, and bottom waters) developed during the early Oligocene as a consequence of the ACC.

Stable carbon isotope ratios of Cibicidoides wuellerstorfi of MIS 2 time slices

The interval of time represented by marine isotope stages 11 and 12 (~360-470 ka) contains what may be the most extreme glacial and interglacial climate conditions of the Late Pleistocene. It has been suggested that sea level rose by ~160 m at the termination of glacial stage 12. This is 30% greater than the sea level rise that followed the most recent glacial maximum. There have been few detailed studies of the unique conditions that existed during the stage 11-12 time period because of the lack of high-quality core material. This problem has been addressed by the collection of high deposition rate cores from sediment drifts in the western North Atlantic during Ocean Drilling Project Leg 172. Benthic foraminiferal d13C data from cores collected between ~4600 and 1800 m were used to reconstruct bathymetric gradients in deep and intermediate water properties for selected time slices during this glacial-interglacial cycle. During glacial stage 12, the deep western North Atlantic was filled by a water mass that was more nutrient-enriched than modern Antarctic Bottom Water. Above 2000 m, a more nutrient-depleted water mass existed during this glacial stage. Such an intermediate water mass has been described for more recent glacial periods and presumably forms in a more proximate region of the North Atlantic. Interglacial stage 11 water mass properties closely resemble those of the present-day western North Atlantic. A nutrient-depleted water mass (d13C of 0.75-1.0 per mil), similar to modern North Atlantic Deep Water existed between 3500 and 2000 m. This was underlain by a water mass with lower d13C values (<0.75 per mil) that probably was derived from a southern source. Using Leg 172 data, along with previously published results from the Atlantic and Pacific oceans, we estimate a mean global d13C change of 0.95 per mil from stage 12 to stage 11. This is twice the whole ocean ?13C change reported for the transition from the last glacial maximum to the Holocene.

Age determination and stable carbon isotope ratios of Cassidulina laevigata of sediment core Svanic90_9004

A well-dated high-resolution d13C record of the last 2400 a, based on the benthic foraminifera Cassidulina laevigata, is presented for Gullmar Fjord, Sweden. The time interval covers die Roman Warm Period (RWP), the Viking Age/Medieval Warm Period (VA/MWP), the little Ice Age (LIA) and the most recent warming. There is little variation in the d13C record until the early Viking Age (AD 800), when the d13C signal becomes significantly more negative and continues to decrease throughout the VA/MWP, The d13C signal increases both at the beginning and at the end of the LIA but is marked by more negative values during the larger part of the period. Since about 1970, the d13C values are more negative than the long-term average. This general negativity of the record may result from a higher flux of organic matter, possibly of terrestrial origin due to land-use changes together with moderate changes in stagnation periods since the VA/MWP. In most recent times, the oceanic Suess effect together with increased number of extended stagnation periods are probably the main causes of the shift towards more negative d13C values.

Stable carbon and oxygen isotope ratios of Miocene to Recent foraminifera from the Rio Grande Rise, South Atlantic

Miocene to Recent species of planktic foraminifera in the Globorotalia (Globoconella) lineage evolved entirely within the thermocline. All species are most abundant within subtropical-temperate watermasses throughout their history. The near stasis in distribution within the thermocline and the subtropical convergence suggests the major morphological changes in Globorotalia (Globoconella) may have occurred through habitat subdivision rather than by vicariant shifts into new watermasses. At the Rio Grande Rise, in the South Atlantic, modern G. inflata is 0.66-0.84? more positive for delta18O than the most enriched coexisting Globigerinoides sacculifer and probably grows in the mid thermocline deeper than 325 m. All extinct globoconellid species have mean delta18O ratios 0.5-0.8? more positive than Globigerinoides trilobus and G. sacculifer and probably lived within the thermocline as well. Major events in skeletal evolution are poorly correlated with changes in delta18O in this group. These include evolutionary transitions to compressed, smooth-walled tests and acquisition of keels. In addition, morphological reversals from the umbilically-inflated G. conomiozea to biconvex G. pliozea and to unkeeled G. puncticulata occur in the absence of changes in delta18O signature. Instead, the ranges of delta18O between different species almost completely overlap once corrected for temporal changes in delta18O of sea water. Foraminifera morphologies have been widely considered to evolve in response to changes in watermasses or depth habitats. However, the variety of skeletal shapes in the globoconellid lineage apparently are not adaptations to a progressive radiation from the surface mixed layer into deeper waters.