Stable carbon and oxygen isotope compositions of benthic foraminifera N. truempyi samples and coarse fraction analyses from ODP Site 198-1209

We have compiled the first stratigraphically continuous high-resolution benthic foraminiferal stable isotope record for the Paleocene from a single site utilizing cores recovered at Pacific ODP Site 1209. The long-term trend in the benthic isotope record suggests a close coupling of volcanic CO2 input and deep sea warming. Over the short-term the record is characterized by slow excursions with a pronounced periodic beat related to the short (100-kyr) and long (405-kyr) eccentricity cycle. The phase relationship between the benthic isotope record and eccentricity is similar to patterns documented for the Oligocene and Miocene confirming the role of orbital forcing as the pace maker for paleoclimatic variability on Milankovitch time scales. In addition, the record documents an unusual transient warming of 2°C coeval with a 0.6 per mil carbon isotope excursion and a decrease in carbonate content at 61.75 Ma. This event, which bears some resemblance to Eocene hyperthermals, marks the onset of a long-term decline in d13C. The timing indicates it might be related to the initiation of volcanism along Greenland margin.

Stable isotope record of ODP Sites 108-658 and 108-659

Ocean Drilling Program Site 658, cored below a major upwelling cell offshore Cap Blanc, contains a largely undisturbed hemipelagic sediment section spanning the Brunhes Chron and the early Quaternary and late Pliocene. The companion Site 659 recovered a complete and undisturbed Neogene profile further offshore that serves as a nonupwelling pelagic reference section. Oxygen and carbon isotope ratios in benthic (C. wuellerstorfi and in part Uvigerina sp.) and planktonic foraminifers (G. inflata) provide a climatic record of high resolution for the Brunhes Chron. At Site 658 the record extends back to the early Pleistocene and late Pliocene. The standard oxygen isotope record of the last 730,000 yr is markedly refined by a well-documented high-frequency variation (e.g., by a new "aborted" ice age at stage 13.2 and by Younger-Dryas style climatic setbacks during most terminations). In the late Pliocene, the numerical oxygen isotope stage taxonomy was extended back to stage 137 about 3.3 Ma ago. In comparison with published records, stage 114 at 2.7 Ma represents the first major glaciation event, when 18O was short-term enriched up to a middle Pleistocene glacial d18O level. About 3.17 Ma ago (stage 133), the interglacial oxygen isotope values of C. wuellerstorfi started to increase by 0.5 per mil until 2.7 Ma and then remained largely constant until the Holocene. Based on the d13C difference between C. wuellerstorfi and G. inflata, the dissolved CO2 in the ambient bottom water of Site 658 was dominated by the flux of particulate carbon from the overlying upwelling cell during the last 630,000 yr. In contrast, the advection of (upper) North Atlantic Bottom Water dominated in the control of the local CO2 content during the early Pleistocene and late Pliocene.

Simulated change in atmospheric CO2 and D14C around 14.6 kyr BP, at the onset of the northern hemispheric warming into the Bølling/Allerød

One of the most abrupt and yet unexplained past rises in atmospheric CO2 (10 p.p.m.v. in two centuries) occurred in quasi-synchrony with abrupt northern hemispheric warming into the Bølling/Allerød, 14,600 years ago. Here we use a U/Th-dated record of atmospheric D14C from Tahiti corals to provide an independent and precise age control for this CO2 rise. We also use model simulations to show that the release of old (nearly 14C-free) carbon can explain these changes in CO2 and D14C. The D14C record provides an independent constraint on the amount of carbon released (125 Pg C). We suggest, in line with observations of atmospheric CH4 and terrigenous biomarkers, that thawing permafrost in high northern latitudes could have been the source of carbon, possibly with contribution from flooding of the Siberian continental shelf during meltwater pulse 1A. Our findings highlight the potential of the permafrost carbon reservoir to modulate abrupt climate changes via greenhouse-gas feedbacks.

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 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.

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.

(Table S3) Benthic foraminiferal Mg/Ca, Li/Ca and stable isotope ratios of ODP Site 122-761

The sensitivities of benthic foraminiferal Mg/Ca and Li/Ca to bottom water temperature and carbonate saturation state have recently been assessed. Here we present a new approach that uses paired Mg/Ca and Li/Ca records to calculate simultaneous changes in temperature and saturation state. Using previously published records, we first use this approach to document a cooling of deep ocean waters associated with the establishment of the Antarctic ice sheet at the Eocene-Oligocene climate transition. We then apply this approach to new records of the Middle Miocene Climate Transition from ODP Site 761 to estimate variations in bottom water temperature and the oxygen isotopic composition of seawater. We estimate that the oxygen isotopic composition of seawater varied by ~1 per mil between the deglacial extreme of the Miocene Climatic Optimum and the glacial maximum following the Middle Miocene Climate Transition, indicating large amplitude variations in ice volume. However, the longer-term change between 15.3 and 12.5 Ma is marked by a ~1°C cooling of deep waters, and an increase in the oxygen isotopic composition of seawater of ~0.6 per mil. We find that bottom water saturation state increased in the lead up to the Middle Miocene Climate Transition and decreased shortly after. This supports decreasing pCO2 as a driver for global cooling and ice sheet expansion, in agreement with existing boron isotope and leaf stomatal index CO2 records but in contrast to the published alkenone CO2 records.

Sediment and pore water N and d15N concentrations of ODP Holes 202-1234A and 202-1235A

The isotopic composition of nitrogen in pore water ammonium and in sedimentary organic matter (Norg) was measured at Sites 1234 and 1235 in order to evaluate the impact of long-term (>100 k.y.) diagenesis on d15N of preserved organic matter. At both sites, the average d15N of pore water ammonium and Norg are within 0.2 per mil to 0.4 per mil. The small difference is less than the analytical uncertainty, indicating that no significant isotopic fractionation is associated with decomposition of organic matter in these sediments. A mass balance for nitrogen was also computed, indicating that ~20% of the organic matter flux buried below 1.45 meters composite depth (mcd) is degraded between this depth and 40 mcd (Site 1235) to 60 mcd (Site 1234) depth. Two factors determine the absence of isotopic fractionation in these sediments: 1. A high degree of organic matter preservation due to rapid sediment accumulation rates at both sites. 2. The dominance of a marine component in the sedimentary organic matter (with only a small fraction contributed by a terrestrial component).

Stable isotopes and ages from sediment core FR01/97-12, Tasman Sea

Deep-sea sediment core FR1/97 GC-12 is located 990 mbsl in the northern Tasman Sea, southwest Pacific, where Antarctic Intermediate Water (AAIW) presently impinges the continental slope of the southern Great Barrier Reef. Analysis of carbon (d13C) and oxygen (d18O) isotope ratios on a suite of planktonic and benthic foraminifera reveals rapid changes in surface and intermediate water circulation over the last 30 kyr. During the Last Glacial Maximum, there was a large d13C offset (1.1 per mil) between the surface-dwelling planktonic foraminifera and benthic species living within the AAIW. In contrast, during the last deglaciation (Termination 1), the d13C(planktonic-benthic) offset reduced to 0.4 per mil prior to an intermediate offset (0.7 per mil) during the Holocene. We suggest that variations in the dominance and direction of AAIW circulation in the Tasman Sea, and increased oceanic ventilation, can account for the rapid change in the water column d13C(planktonic-benthic) offset during the glacial-interglacial transition. Our results support the hypothesis that intermediate water plays an important role in propagating climatic changes from the polar regions to the tropics. In this case, climatic variations in the Southern Hemisphere may have led to the rapid ventilation of deep water and AAIW during Termination 1, which contributed to the postglacial rise in atmospheric CO2.

Stable isotope record of planktonic foraminifera from the Sulu Sea

A high-resolution, accelerator mass spectroscopy 14C dated sediment record from the Sulu Sea clearly indicates that the Younger Dryas event affected the western equatorial Pacific. Planktonic foraminiferal delta18O and abundance data both record significant changes during Younger Dryas time. In particular, a 0.4 per mil increase in the delta18O value of Globigerinoides ruber and the reappearance of the cool water planktonic foraminifera, Neogloboquadrina pachyderma, occur during the Younger Dryas at this location. These isotopic and faunal changes are a response to either surface water temperature or salinity changes, or some combination of the two. Changes in surface salinities could have been accomplished through either local or global processes. Intensification of the monsoon climate system and increased precipitation at approximately 11 ka is one mechanism that may have resulted in local changes in salinity. A meltwater pulse derived from the Tibetan Plateau is another mechanism which may have caused local changes in salinity. The presence of the Younger Dryas in the tropical western Pacific clearly indicates that this climatic event is not restricted to the North Atlantic or high latitudes, but rather is global in extent.

(Table 1) Oxygen and carbon isotopes and calcium carbonte of bulk carbonate at DSDP Hole 72-516F

A detailed oxygen and carbon isotope study of the upper Maestrichtian-lower Paleocene section of Hole 516F from the Rio Grande Rise reveals that large isotopic anomalies are clearly associated with the Cretaceous/Tertiary boundary. Across the Cretaceous/Tertiary boundary, the total carbonate content reaches a maximum exceeding 80% before rapidly decreasing in covariance with the carbon isotope record. This strong covariance between d13C and percent CaCO3 suggests either a significant reduction in primary productivity or a rapid shoaling of the calcium carbonate compensation depth. Importantly, the d13C record 2 Ma after the Cretaceous/Tertiary boundary remained depleted in 13C by at least 0.5 per mil compared to the late Maestrichtian.

Early Eocene benthic foraminifera of DSDP Hole 48-401

Within the last decade, several early Eocene hyperthermals have been detected globally. These transient warming events have mainly been characterized geochemically - using stable isotopes, carbonate content measurements or XRF core scanning - yet detailed micropaleontological records are sparse, limiting our understanding of the driving forces behind hyperthermals and of the contemporaneous paleoceanography. Here, detailed geochemical and quantitative benthic foraminiferal records are presented from lower Eocene pelagic sediments of Deep Sea Drilling Project Site 401 (Bay of Biscay, northeast Atlantic). In calcareous nannofossil zone NP11, several clay-enriched levels correspond to negative d13C and d18O bulk-rock excursions with amplitudes of up to ~0.75 per mil, suggesting that significant injections of 12C-enriched greenhouse gasses and small temperature rises took place. Coeval with several of these hyperthermal events, the benthic foraminiferal record reveals increased relative abundances of oligotrophic taxa (e.g. Nuttallides umbonifera) and a reduction in the abundance of buliminid species followed by an increase of opportunistic taxa (e.g. Globocassidulina subglobosa and Gyroidinoides spp.). These short-lived faunal perturbations are thought to be caused by reduced seasonality of productivity resulting in a decreased Corg flux to the seafloor. Moreover, the sedimentological record suggests that an enhanced influx of terrigenous material occurred during these events. Additionally, the most intense d13C decline (here called level d) gives rise to a small, yet pronounced long-term shift in the benthic foraminiferal composition at this site, possibly due to the reappraisal of upwelling and the intensification of bottom water currents. These observations imply that environmental changes during (smaller) hyperthermal events are also reflected in the composition of deep-sea benthic communities on both short (<100 kyr) and longer time scales. We conclude that the faunal patterns of the hyperthermals observed at Site 401 strongly resemble those observed in other deep-sea early Paleogene hyperthermal deposits, suggesting that similar processes have driven them.

Mg/Ca, Sr/Ca and Ca isotope ratios in benthonic foraminifers of surface sediment samples

We analysed Mg/Ca, Sr/Ca and Ca isotope ratios of benthonic foraminifers from sediment core tops retrieved during several research cruises in the Atlantic Ocean, in order to improve the understanding of isotope fractionation and element partitioning resulting from biomineralisation processes and changes in ambient conditions. Species include foraminifers secreting tests composed of hyaline low magnesium calcite, porcelaneous high magnesium calcite as well as aragonite. Our results demonstrate systematic isotope fractionation and element partitioning patterns specific for these foraminiferal groups. Calcium isotope fractionation is similar in porcelaneous and hyaline calcite tests and both groups demonstrate the previously described anomaly with enrichment of heavy isotopes around 3 - 4 °C (Gussone and Filipsson, 2010). Calcium isotope ratios of the aragonitic species Hoeglundina elegans, on the other hand, are about 0.4 per mil lighter compared to the calcitic species, which is in general agreement with stronger fractionation in inorganic aragonite compared to calcite. However, the low and strongly variable Sr content suggests additional processes during test formation, and we propose that transmembrane ion transport or a precursor phase to aragonite may be involved. Porcelaneous tests, composed of high Mg calcite, incorporate higher amounts of Sr compared to hyaline low Mg calcite, in agreement with inorganic calcite systematics, but also porcelaneous tests with reduced Mg/Ca show high Sr/Ca. While calcium isotopes, Sr/Ca and Mg/Ca in benthonic foraminifers primarily appear to fractionate and partition with a dominant inorganic control, d44/40Ca temperature and growth rate dependencies of benthonic foraminifer tests favour a dominant contribution of light Ca by transmembrane transport relative to unfractionated seawater Ca to the calcifying fluid, thus controlling the formation of foraminiferal d44/40Ca and Sr/Ca proxy signals.

Calcium isotopes of planktonic foraminifera

Measurements of the calcium isotopic composition (d44/40Ca) of planktonic foraminifera from the western equatorial Pacific and the Indian sector of the Southern Ocean show variations of about 0.6 per mil over the past 24 Myr. The stacked d44/40Ca record of Globigerinoides trilobus and Globigerina bulloides indicates a minimum in d44/40Casw (seawater calcium) at 15 to 16 Ma and a subsequent general increase toward the present, interrupted by a second minimum at 3 to 5 Ma. Applying a coupled calcium/carbon cycle model, we find two scenarios that can explain a large portion of the observed d44/40Casw variations. In both cases, variations in the Ca input flux to the ocean without proportional changes in the carbonate flux are invoked. The first scenario increases the riverine calcium input to the ocean without a proportional increase of the carbonate flux. The second scenario generates an additional calcium flux from the exchange of Ca by Mg during dolomitization. In both cases the calcium flux variations lead to drastic changes in the seawater Ca concentrations on million year timescales. Our d44/40Casw record therefore indicates that the global calcium cycle may be much more dynamic than previously assumed.