(Table 1) Oxygen and carbon isotope compositions of altered carbonates from DSDP Hole 6-53 from the western Pacific Ocean

In the lower part of DSDP core 53.0, partly recrystallized carbonate sediments and well recrystallized limestone breccias of Oligo-Miocene age are associated with altered volcanic flows, lithified tuffs, and tuff breccias, suggesting that carbonate alteration was the result of thermal metamorphism. However, the oxygen isotope compositions of these carbonates (-3.4 to +0.6 per mil rel. PDB) are not compatible with recrystallization and isotope exchange with sea water at high temperatures. Evaluating the effects of the composition of the water which exchanged with the carbonates and of carbonate-water isotope exchange in closed systems yields the following approximate maximum temperature of recrystallization: limestone breccias, 100°C; calcite veins rimming breccia clasts, 30°C; and unconsolidated sediments overlying the breccias, 20°C. Therefore, the volcanics at site 53.0 must have been emplaced into the primary carbonate sediments at relatively low temperatures. Subsequent carbonate alteration was probably a consequence of chemical changes in ambient pore waters resulting from the submarine weathering of volcanic material.

Pore water chemistry of ODP Sites 201-1225, 201-1226 and 201-1231

High-resolution analyses of the oxygen isotope ratio (18O/16O) of dissolved sulfate in pore waters have been made to depths of >400 meters below seafloor (mbsf) at open-ocean and upwelling sites in the eastern equatorial Pacific Ocean. d18O values of dissolved sulfate (d18O-SO4) at the organic-poor open-ocean Site 1231 gave compositions close to modern seawater (+9.5 per mil vs. Vienna-standard mean ocean water, providing no chemical or isotopic evidence for microbial sulfate reduction (MSR). In contrast, the maximum d18O values at Sites 1225 and 1226, which contain higher organic matter contents, are +20 per mil and +28 per mil, respectively. Depth-correlative trends of increasing d18O-SO4, alkalinity, and ammonium and the presence of sulfide indicate significant oxidation of sedimentary organic matter by sulfate-reducing microbial populations at these sites. Although sulfate concentration profiles at Sites 1225 and 1231 both show similarly flat trends without significant net MSR, d18O-SO4 values at Site 1225 reveal the presence of significant microbial sulfur-cycling activity, which contrasts to Site 1231. This activity may include contributions from several processes, including enzyme-catalyzed equilibration between oxygen in sulfate and water superimposed upon bacterial sulfate reduction, which would tend to shift d18O-SO4 toward higher values than MSR alone, and sulfide oxidation, possibly coupled to reduction of Fe and Mn oxides and/or bacterial disproportionation of sulfur intermediates. Large isotope enrichment factors observed at Sites 1225 and 1226 (epsilon values between 42 per mil and 79 per mil) likely reflect concurrent processes of kinetic isotope fractionation, equilibrium fractionation between sulfate and water, and sulfide oxidation at low rates of sulfate reduction. The oxygen isotope ratio of dissolved pore water sulfate is a powerful tool for tracing microbial activity and sulfur cycling by the deep biosphere of deep-sea sediments.

Stable isotope record and sediment composition of the subantarctic Pacific

Benthic foraminiferal stable carbon isotope records from the South Atlantic show significant declines toward more "Pacific-like" values at ~7 and ~2.7 Ma, and it has been posited that these shifts may mark steps toward increased CO2 sequestration in the deep Southern Ocean as climate cooled over the late Neogene. We generated new stable isotope records from abyssal subantarctic Pacific cores MV0502-4JC and ELT 25-11. The record from MV0502-4JC suggests that the Southern Ocean remained well mixed and free of vertical or interbasinal d13C gradients following the late Miocene carbon shift (LMCS). According to the records from MV0502-4JC and ELT 25-11, however, cold, low d13C bottom waters developed in the Southern Ocean in the late Pliocene and persisted until ~1.7 Ma. These new data suggest that while conditions in the abyssal Southern Ocean following the LMCS were comparable to the present day, sequestration of respired CO2 may have increased in the deepest parts of the Southern Ocean during the late Pliocene, a critical period for the growth and establishment of the Northern Hemisphere ice sheets.

1.2 Ma stacked benthic foraminiferal carbon isotope record

Pleistocene stable carbon isotope (d13C) records from surface and deep dwelling foraminifera in all major ocean basins show two distinct long-term carbon isotope fluctuations since 1.00 Ma. The first started around 1.00 Ma and was characterised by a 0.35 per mil decrease in d13C values until 0.90 Ma, followed by an increase of 0.60 per mil lasting until 0.50 Ma. The subsequent fluctuation started with a 0.40 per mil decrease between 0.50 and 0.25 Ma, followed by an increase of 0.30 per mil between 0.25 and 0.10 Ma. Here, we evaluate existing evidence and various hypotheses for these global Pleistocene d13C fluctuations and present an interpretation, where the fluctuations most likely resulted from concomitant changes in the burial fluxes of organic and inorganic carbon due to ventilation changes and/or changes in the production and export ratio. Our model indicates that to satisfy the long-term 'stability' of the Pleistocene lysocline, the ratio between the amounts of change in the organic and inorganic carbon burial fluxes would have to be close to a 1:1 ratio, as deviations from this ratio would lead to sizable variations in the depth of the lysocline. It is then apparent that the mid-Pleistocene climate transition, which, apart from the glacial cycles, represents the most fundamental change in the Pleistocene climate, was likely not associated with a fundamental change in atmospheric pCO2. While recognising that high frequency glacial/interglacial cycles are associated with relatively large (100 ppmv) changes in pCO2, our model scenario (with burial changes close to a 1:1 ratio) produces a maximum long-term variability of only 20 ppmv over the fluctuation between 1.00 and 0.50 Ma.

Chemistry of siliciclastic and volcanoclastic sediments of DSDP Site 47-397

The Lower Cretaceous and Miocene sequences of the NW African passive continental margin consist of siliciclastic, volcaniclastic and hybrid sediments. These sediments contain a variety of diagenetic carbonates associated with zeolites, smectite clays and pyrite, reflecting the detrital mineralogical composition and conditions which prevailed during opening of the North Atlantic. In the Lower Cretaceous siliciclastic sediments, siderite (-6 per mil to +0.7per mil d18O PDB, -19.6 per mil to +0.6 per mil d13C PDB) was precipitated as thin layers and nodules from modified marine porewaters with input of dissolved carbon from the alteration of organic matter. Microcrystalline dolomite layers, lenses, nodules and disseminated crystals (-3.0 per mil to +2.5 per mil d18O PDB, -7.2 per mil to +4.9 per mil d13C PDB) predominate in slump and debris-flow deposits within the Lower Miocene sequence. During the opening of the Atlantic, volcanic activity in the Canary Islands area resulted in input of volcaniclastic sediments to the Middle and Upper Miocene sequences. Calcite is the dominant diagenetic carbonate in the siliciclastic-bioclastic-volcaniclastic hybrid and in the volcaniclastic sediments, which commonly contain pore-rimming smectite. Diagenetic calcite (-22 per mil to +1.6 per mil d18O PDB, -35.7 per mil to +0.8 per mil d13C PDB) was precipitated due to the interaction of volcaniclastic and bioclastic grains with marine porewaters. Phillipsite is confined to the alteration of volcaniclastic sediments, whereas clinoptilolite is widely disseminated, occurring essentially within foraminiferal chambers, and formed due to the dissolution of biogenic silica.

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 isotope stratigraphy of ODP Site 167-1014

Late Quaternary oxygen (d18O) and carbon (d13C) isotopic records for the benthic foraminifer Uvigerina and the planktonic foraminifer Globigerina bulloides are presented for the upper 20 meters composite depth sediment sequence of Ocean Drilling Program Site 1014, Tanner Basin, in the outer California Borderland province. The benthic oxygen isotopic record documents a continuous >160-k.y. sequence from marine isotope Stage (MIS) 6 to the present day. The record closely resembles other late Quaternary North Pacific benthic isotope records, as well as the well-dated deep-sea sequence (SPECMAP), and thus provides a detailed chronologic framework. Site 1014 provides a useful record of the California response to climate change as it enters the southern California Border-land. Sedimentation rates are relatively constant and high (~11.5 cm/k.y. ). The planktonic foraminiferal record is well pre-served except during marine isotope Substages 5b and 5d, when normally high G. bulloides abundance is strongly diminished as a result of dissolution. The planktonic oxygen isotopic shift of ~3 per mil between the last glacial maximum and the Holocene suggests a surface water temperature shift of <7°C, similar to estimates from Hole 893A (Leg 146) to the north. Unlike Santa Barbara Basin, G. bulloides d18O values during the last interglacial (MIS 5) at Site 1014 were significantly higher than during the Holocene. In particular, marine isotope Substage 5e (Eemian) was ~0.8 per mil higher. This is unlikely to reflect a cooler Eemian but is instead the result of preferential dissolution of thin-shelled (low d18O) specimens during this interval. In this mid-depth basin, a large benthic d18O shift during Termination I suggests dramatic temperature and salinity changes in response to switches in the source of North Pacific Intermediate Water. Although d13C values of the planktonic foraminifer G. bulloides are in disequilibria with seawater and hence interpretations are limited, the G. bulloides record exhibits several negative d13C excursions found at other sites in the region (Sites 1017 and 893). This indicates a response of G. bulloides d13C to regional surface water processes along the southern California margin. A general increase in benthic carbon isotopic values (-1.75 per mil to -0.75 per mil) in Tanner Basin during the last 200 k.y. is overprinted with smaller fluctuations correlated with climate change. The coolest intervals during the last glacial maximum (MISs 2 and 4) exhibit lower benthic d13C values, which correlate with global 13C shifts. The opposite relationship is exhibited during the last interglacial before 85 ka, when lower benthic d13C values are associated with warmer intervals (marine isotope Substages 5c and 5e) of the last interglacial. These time intervals were also marked by decreased intermediate water ventilation. Increased dissolution and organic accumulation during Substages 5b and 5d are anticorrelated with the benthic d13C record. These results suggest that a delicate balance in intermediate water d13C has existed between the relative influences of global 13C and regional ventilation changes at the 1165-m water depth of Site 1014.

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.

Stable isotope ratios of planktonic foraminifera from the West Equatorial Pacific

Differential dissolution affects the isotopic composition of different species of planktonic foraminifera in different ways. In the two species studied here in cores from Ontong Java Plateau, the less resistant species, Globigerinoides sacculifer, is more readily affected at a shallower depth than the more resistant species, Pulleniatina obliquiloculata (2.9 versus 3.4 km), but shows a smaller and less predictable response to partial dissolution (0.2 to 0.3 per mil versus 0.6 to 0.7 per mil). Comparison of isotopic values from the last glacial period with those from the late Holocene indicates that the apparent dissolution effect is considerably reduced during the last glacial, presumably due to reduced dissolution intensity during glacial time. A change in the level of the lysocline of about 400 m is suggested. In the published isotope records from Pacific cores V28-238 and V28-239, the dissolution-generated difference in delta18O (noted previously by Shackleton and Opdyke [1976]) is seen to describe a mid-Brunhes dissolution maximum, between 300 and 500 thousand years ago. This mid-Brunhes dissolution excursion is well known from the Pacific and the Indian Ocean.

Calcium isotope composition of Oceanic Anoxic Events 1a and 2 sediments

Calcium-isotope ratios (d44/42Ca) were measured in carbonate-rich sedimentary sections deposited during Oceanic Anoxic Events 1a (Early Aptian) and 2 (Cenomanian-Turonian). In sections from Resolution Guyot, Mid-Pacific Mountains; Coppitella, Italy; and the English Chalk at Eastbourne and South Ferriby, UK, a negative excursion in d44/42Ca of ~0.20 per mil and ~0.10 per mil is observed for the two events. These d44/42Ca excursions occur at the same stratigraphic level as the carbon-isotope excursions that define the events, but do not correlate with evidence for carbonate dissolution or lithological changes. Diagenetic and temperature effects on the calcium-isotope ratios can be discounted, leaving changes in global seawater composition as the most probable explanation for d44/42Ca changes in four different carbonate sections. An oceanic box model with coupled strontium- and calcium-isotope systems indicates that a global weathering increase is likely to be the dominant driver of transient excursions in calcium-isotope ratios. The model suggests that contributions from hydrothermal activity and carbonate dissolution are too small and short-lived to affect the oceanic calcium reservoir measurably. A modelled increase in weathering flux, on the order of three times the modern flux, combined with increased hydrothermal activity due to formation of the Ontong-Java Plateau (OAE1a) and Caribbean Plateau (OAE2), can produce trends in both calcium and strontium isotopes that match the signals recorded in the carbonate sections. This study presents the first major-element record of a weathering response to Oceanic Anoxic Events.

Stable isotope ratios and geochemical composition of authigenic carbonates from ODP Sites 186-1150 and 186-1151

Several carbonaceous layers or fragments were recovered from sediments of Sites 1150 and 1151 on the deep-sea terrace of the Japan Trench during Leg 186. The X-ray diffraction analysis (XRD) data indicate that these are predominantly dolomitic. In this study, carbon and oxygen isotopes of these carbonates recovered at Sites 1150 and 1151 are presented. The oxygen isotope ratios of the dolomites analyzed range from +0.4 per mil to +4.1 per mil vs. Peedee formation belemnite (PDB) and those of calcites from +0.6 per mil to +2.8 per mil PDB. The isotopic composition of carbon varies from -7.0 per mil to +12.3 per mil PDB in dolomite and from -13.4 per mil to -24.1 per mil PDB in calcite. The wide range of carbon isotopic compositions indicates that the carbonate samples were formed by the decomposition of organic matter through reactions such as oxidation, sulfate reduction, and methane formation during diagenesis.

Stable isotope and geochemical record of ODP Hole 124-769A

Deep marine late Pleistocene sediments from Ocean Drilling Program Sulu Sea Site 769 contain a high-resolution record of paleoceanographic change in this strongly monsoonal climatic setting in the tropical western Pacific. Detailed time series of planktonic foraminifer (G.ruber; white variety) d18O, d13C, and bulk CaCO3 mass accumulation rate (MAR) were generated, spanning the last 750 k.y. Sedimentation rates in this portion of the record average 8.5 cm/k.y., and vary from 4 to 16 cm/k.y. Cross spectral analysis of the d18O and d13C time-series demonstrate that each contains increased variance at the primary orbital periodicities. The d18O record shows strong variability in the precessional-band and closely correlates with the SPECMAP d18O record and other high-resolution records. The dominance of a 23-k.y cycle in the d18O record agrees with other studies of the monsoon system in the Indian Ocean that have documented the importance of precessional insolation as a monsoon-forcing mechanism. In addition, d13C is strongly coherent, with d18O at a period of 41 k.y (obliquity), suggesting a connection between surface water CO2 chemistry in the Sulu Sea and high- latitude climatic change. The d18O and d13C time-series both contain increased spectral variance at a period of 30 k.y. Although the source of 30-k.y. variability is unknown, other studies have documented late Pleistocene Pacific Oceanographic variability with a period of 30 k.y. Major- and trace-metal analyses were performed on a second, less-detailed sample series to independently assess paleoproductivity changes and bottom-water conditions through time. Glacial periods are generally times of increased calcium carbonate and copper accumulation. The positive association between these independent indicators of paleoproductivity suggests an increase in productivity in the basin during most glacial episodes. Changing bottom-water redox conditions were also assessed using the geochemical data. Low concentrations of molybdenum throughout the record demonstrate that bottom waters at this site were never anoxic during the last 750 k.y. The bioturbated character of the sediments agrees with this interpretation.

Stable isotope record of foraminifera from sediment core EW9209-1JPC

Stable isotopic measurements of G. sacculifer and C. wuellerstorfi in a core from the western equatorial Atlantic imply that there are parallel, suborbital oscillations in surface water hydrography and deep water circulation occurring during oxygen isotope stages 2 and 3. Low values of G. sacculifer delta18O accompany high values of C. wuellerstorfi delta13C, linking warmer sea surface temperatures (SSTs) in the tropics with increased production of lower North Atlantic Deep Water (NADW). The amplitude of the delta18O oscillations is 0.6 per mil (or 2°-3°C), which is superimposed on a glacial/interglacial amplitude of about 2.1per mil. Using the G. sacculifer delta18O data, we calculate that surface waters were colder during stage 2 than calculated by CLIMAP [1976, 1981]. The longer-period (>2 kyr) oscillations in air temperature recorded in the Greenland and Antarctic ice cores appear to correlate with oscillations in sea surface temperature in the equatorial Atlantic. The magnitude of these oscillations in tropical SST is too large to have resulted from changes in meridional heat transport caused by the global conveyor alone. The apparent synchroneity of equatorial SST and polar air temperature changes, as well as the amplitude of the SST changes at the equator, are consistent with the climate effects expected from changes in the atmosphere's greenhouse gas content (H2Ovapor, CO2, and CH4).

Age model and stable isotope record of DSDP holes 48-401 and 86-577

Early Paleogene warm climates may have been linked to different modes and sources of deepwater formation. Warm polar temperatures of the Paleocene and Eocene may have resulted from either increased atmospheric trace gases or increased heat transport through deep and intermediate waters. The possibility of increasing ocean heat transport through the production of warm saline deep waters (WSDW) in the Tethyan region has generated considerable interest. In addition, General Circulation Model results indicate that deepwater source regions may be highly sensitive to changing basin configurations. To decipher deepwater changes, we examined detailed benthic foraminiferal faunal and isotopic records of the late Paleocene through the early Eocene (~60 to 50 Ma) from two critical regions: the North Atlantic (Bay of Biscay Site 401) and the Pacific (Shatsky Rise Site 577). These records are compared with published data from the Southern Ocean (Maud Rise Site 690, Islas Orcadas Rise Site 702). During the late Paleocene, similar benthic foraminiferal delta18O values were recorded at all four sites. This indicates uniform deepwater temperatures, consistent with a single source of deep water. The highest delta13C values were recorded in the Southern Ocean and were 0.5 per mil more positive than those of the Pacific. We infer that the Southern Ocean was proximal to a source of nutrient-depleted deep water during the late Paleocene. Upper Paleocene Reflector Ab was cut on the western Bermuda Rise by cyclonically circulating bottom water, also suggesting a vigorous source of bottom water in the Southern Ocean. A dramatic negative excursion in both carbon and oxygen isotopes occurred in the latest Paleocene in the Southern Ocean. This is a short-term (<100 kyr), globally synchronous event which also is apparent in both the Atlantic and Pacific records as a carbon isotopic excursion of approximately 1 per mil. Faunal analyses from the North Atlantic and Pacific sites indicate that the largest benthic foraminiferal faunal turnover of the Cenozoic was synchronous with the isotopic excursion, lending support to the hypothesis that the extinctions were caused by a change in deepwater circulation. We speculate that the Southern Ocean deepwater source was reduced or eliminated at the time of the excursion. During the early Eocene, Southern Ocean delta13C values remained enriched relative to the North Atlantic and Pacific. However, the Southern Ocean was also enriched in delta18O relative to these basins. We interpret that these patterns indicate that although the Southern Ocean was proximal to a source of cool, nutrient-depleted water, the intermediate to upper deep water sites of the North Atlantic and Pacific were ventilated by a different source that probably originated in low latitudes, i.e., WSDW.

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.