(Table 2) Stable isotope analysis of Nuttallides truempyi and Rugoglobigerina rugosa from DSDP Site 62-463

Strong climatic and temperature fluctuations mark the Late Campanian and Maastrichtian as indicated by stable isotope records from the equatorial Pacific (Site 463) and middle and high latitude South Atlantic (Sites 525, 689 and 690). The first major global cooling decreased intermediate water temperatures (IWT) by 5-6°C between 73-70 Ma. At the same time, sea surface temperature (SST) decreased by 4-5°C in middle and high latitudes. Intermediate waters (IW) temporarily warmed by 2°C in low and middle latitudes between 70-68.5 Ma. Global cooling resumed between 68.5-65.5 Ma when IWT decreased by 3-4°C and SST by 5°C in middle latitudes. About 450 ka before the Cretaceous-Tertiary boundary rapid global warming increased IWT and SST by 3-4°C, though SST in the tropics changed little. During the last 200 ka of the Maastrichtian, climate cooled rapidly with IWT and SST decreasing by 2-3°C. During the global cooling at 71-70 Ma and possibly at 67-65.5 Ma, the sources of cold intermediate waters in the equatorial Pacific, Indo-Pacific and South Atlantic were derived from the high latitude North Pacific. In contrast, during the global climate warming between 65.2-65.4 Ma, the middle latitude South Atlantic was closest to the source of IW production and implies that the low latitude Tethys played a major role in global climate change. Climate changes, sea-level fluctuations and associated restricted seaways appear to be the most likely mechanisms for the alternating sources of IW production.

Large carbon isotope fractionation associated with oxidation of methyl halides by methylotrophic bacteria

The largest biological fractionations of stable carbon isotopes observed in nature occur during production of methane by methanogenic archaea. These fractionations result in substantial (as much as ≈70‰) shifts in δ13C relative to the initial substrate. We now report that a stable carbon isotopic fractionation of comparable magnitude (up to 70‰) occurs during oxidation of methyl halides by methylotrophic bacteria. We have demonstrated biological fractionation with whole cells of three methylotrophs (strain IMB-1, strain CC495, and strain MB2) and, to a lesser extent, with the purified cobalamin-dependent methyltransferase enzyme obtained from strain CC495. Thus, the genetic similarities recently reported between methylotrophs, and methanogens with respect to their pathways for C1-unit metabolism are also reflected in the carbon isotopic fractionations achieved by these organisms. We found that only part of the observed fractionation of carbon isotopes could be accounted for by the activity of the corrinoid methyltransferase enzyme, suggesting fractionation by enzymes further along the degradation pathway. These observations are of potential biogeochemical significance in the application of stable carbon isotope ratios to constrain the tropospheric budgets for the ozone-depleting halocarbons, methyl bromide and methyl chloride.

Sulfur isotope rations in oceanic basement samples

Low temperature alteration of oceanic basement rocks is characterized by net gain of sulfur, which commonly yields low d34S values, suggesting involvement of microbial sulfate reduction. In order to test whether secondary sulfide minerals are consistent with a biogenic source, we apply high precision multiple sulfur isotope analysis to bulk rock sulfide and pyrite isolates from two contrasting types of altered oceanic basement rocks, namely serpentinized peridotites and altered basalts. Samples from two peridotite sites (Iberian Margin and Hess Deep) and from a basalt site on the eastern flank of the Juan de Fuca Ridge yield overlapping d34S values ranging from 0 per mil to -44 per mil. In contrast, sulfides in the basalt site are characterized by relatively low D33S values ranging from -0.06 per mil to 0.04 per mil, compared to those from peridotite sites (0.00 per mil to 0.16 per mil). The observed D33S signal is significant considering the analytical precision of 0.014 per mil (2 sigma). We present a batch reaction model that uses observed d34S and D33S relationships to quantify the effect of closed system processes and constrain the isotope enrichment factor intrinsic to sulfate reduction. The estimated enrichment factors as large as 61 per mil and 53 per mil, for peridotite and basalt sites respectively, suggest the involvement of microbial sulfate reduction. The relatively high D33S values in the peridotite sites are due to sulfate reduction in a closed system environment, whereas negative D33S values in the basalt site reflect open system sulfate reduction. A larger extent of sulfate reduction during alteration of peridotite to serpentinite is consistent with its higher H2 production capacity compared to basalt alteration, and further supports in-situ microbial sulfate reduction coupled with H2 production during serpentinization reactions.

Paleomagnetic and stable isotope measurements and distribution of benthic foraminifera in sediment core PS1388-3 from the Antarctic continental margin in the eastern Weddell Sea

A stable isotope record from the eastern Weddell Sea from 69°S is presented. For the first time, a 250,000-yr record from the Southern Ocean can be correlated in detail to the global isotope stratigraphy. Together with magnetostratigraphic, sedimentological and micropalaeontological data, the stratigraphic control of this record can be extended back to 910,000 yrs B.P. A time scale is constructed by linear interpolation between confirmed stratigraphic data points. The benthic d18O record (Epistominella exigua) reflects global continental ice volume changes during the Brunhes and late Matuyama chrons, whereas the planktonic isotopic record (Neogloboquadrina pachyderma) may be influenced by a meltwater lid caused by the nearby Antarctic ice shelf and icebergs. The worldwide climatic improvement during deglaciations is documented in the eastern Weddell Sea by an increase in production of siliceous plankton followed, with a time lag of approximately 10,000 yrs, by planktonic foraminifera production. Peak values in the difference between planktonic and benthic d13C records, which are 0.5 per mil higher during warm climatic periods than during times with expanded continental ice sheets, also suggest increased surface productivity during interglacials in the Southern Ocean.

Age determination and stable isotope record of sediment core MR06-04_PC23A

Millennial-scale variability in the behavior of North Pacific Intermediate Water during the last glacial and deglacial period, and its association with Dansgaard-Oeschger (D-O) cycles and Heinrich events, are examined based on benthic foraminiferal oxygen and carbon isotopes (d18Obf and d13Cbf) and %CaCO3 using a sediment core recovered from the northeastern slope of the Bering Sea. A suite of positive d18Obf excursions at intermediate depths of the Bering Sea, which seem at least in part associated with increases in the d18Obf gradients between the Bering and Okhotsk Seas, suggest the Bering Sea as a proximate source of intermediate water during several severe stadial episodes in the last glacial and deglacial period. Absence of such d18Obf gradients during periods of high surface productivity in the Bering and Okhotsk Seas, which we correlate to D-O interstadials, suggests a reduction in intermediate water production in the Bering Sea and subsequent introduction of nutrient-rich deep waters from the North Pacific into intermediate depths of the Bering Sea. We argue that a reorganization of atmospheric circulation in the high-latitude North Pacific during severe cold episodes in the last glacial and deglacial period created favorable conditions for brine rejection in the northeastern Bering Sea. The resulting salinity increase in the cold surface waters could have initiated intermediate (and deep) water formation that spread out to the North Pacific.

Pliocene-Pleistocene stack of globally distributed benthic stable oxygen isotope records

We present a 5.3-Myr stack (the ''LR04'' stack) of benthic d18O records from 57 globally distributed sites aligned by an automated graphic correlation algorithm. This is the first benthic delta18O stack composed of more than three records to extend beyond 850 ka, and we use its improved signal quality to identify 24 new marine isotope stages in the early Pliocene. We also present a new LR04 age model for the Pliocene-Pleistocene derived from tuning the delta18O stack to a simple ice model based on 21 June insolation at 65 N. Stacked sedimentation rates provide additional age model constraints to prevent overtuning. Despite a conservative tuning strategy, the LR04 benthic stack exhibits significant coherency with insolation in the obliquity band throughout the entire 5.3 Myr and in the precession band for more than half of the record. The LR04 stack contains significantly more variance in benthic delta18O than previously published stacks of the late Pleistocene as the result of higher resolution records, a better alignment technique, and a greater percentage of records from the Atlantic. Finally, the relative phases of the stack's 41- and 23-kyr components suggest that the precession component of delta18O from 2.7-1.6 Ma is primarily a deep-water temperature signal and that the phase of d18O precession response changed suddenly at 1.6 Ma.

Stable carbon and oxygen isotope composition of benthic foraminifera

Seventeen surface sediment samples from the North Atlantic Ocean off NE-Greenland between 76° and 81°N, and nine samples from the South Atlantic Ocean close to Bouvet Island between 48° and 55°S were taken with the aid of a Multiple Corer and investigated for their live (Rose Bengal stained) benthic foraminiferal content within the upper 15 cm of sediment. Preferentially endobenthic Melonis barleeanum, Melonis zaandami, and Bulimina aculeata as well as preferentially epibenthic Lobatula lobatula were counted from 1-cm-thick sediment slices each and analyzed for stable carbon and oxygen isotopic compositions of their calcareous tests. Live and dead specimens were counted and measured separately. The carbon isotopic composition of the foraminifera was compared to that of the dissolved inorganic carbon (DIC) of simultaneously sampled bottom water. During a period of one month, one station off NE-Greenland was replicately sampled once every week and samples were processed as above. Live specimens of Lobatula lobatula are confined to the uppermost two centimeters of sediment. Live specimens of Melonis spp. are found down to 8 cm within the sediment but with a distinct sub-surface maximum between 2 and 5 cm. The down-core distribution of live Bulimina aculeata shows a distinct surface maximum in the top centimeter and constant but low numbers down to 11-cm subbottom depth. The average stable carbon isotopic composition (d13C versus per mil PDB) of live Lobatula lobatula off NE-Greenland is by 0.4±0.1 per mil higher than the d13CDIC of the ambient bottom water at the time of sampling. There is evidence that this species calcify before the ice-free season, when bottom water d13CDIC is supposed to be higher. This would reconfirm the one-to-one relationship between d13C of ambient water DIC and cibicids, widely used by paleoceanographers. Live Melonis barleeanum show a negative offset from bottom water DIC of -1.7±0.6 per mil in the uppermost sediment and of -2.2±0.5 per mil in 3-4-cm subbottom depth. All d13C values of live Melonis spp. decrease within the upper four centimeters, regardless of the time of sampling and site investigated. The offset of live Bulimina aculeata from bottom water d13CDIC values of 8 stations rather constantly amounts to -0.6±0.1 per mil, no matter what subbottom depth the specimens are from. At one station however, where is strong indication of elevated organic carbon flux, the negative offset averaged over all sub-bottom depths increases to -1.5±0.2 per mil. Buliminids actively move within the sediment and by this either record an average isotope signal of the pore water or the signal of one specific calcification depth. The recorded signal, however, depends on the organic carbon flux and reflects general but site-specific pore water d13CDIC values. If compared with epibenthic d13C values from the same site, not influenced by pore water and related phytodetritus layer effects, Buliminad13C values bear some potential as a paleoproductivity proxy. Specimens of Melonis spp. seem to prefer a more static way of life and calcify at different but individually fix depths within the sediment. Although live specimens thus record a stratified pore water d13C signal, there is no means yet to correct for bioturbational and early diagenetic effects in fossil faunas.

Stable carbon and oxygen isotope ratios of planktonic and benthic foraminifera from ODP Site 162-982 in the North Atlantic

Changes in the intermediate water structure of the North Atlantic were reconstructed using benthic foraminiferal delta13C at Ocean Drilling Program (ODP) site 982 for the past 1.0 Myr. During most terminations of the late Pleistocene, melting of icebergs and low-salinity surface waters caused production of Glacial North Atlantic Intermediate Water to cease, resulting in decreased ventilation of the middepth North Atlantic. Poor ventilation of intermediate water masses lasted well into some interglacial stages until upper North Atlantic Deep Water (NADW) production resumed under full interglacial conditions. The magnitude of benthic delta13C minima and ice-rafted debris maxima at terminations at site 982 generally match the degree of glacial suppression of NADW inferred from site 607. These processes may be related and controlled by the spatial and seasonal extent of sea ice cover during glaciations in the Nordic Seas.

Stable isotope records and biogenic barium fluxes of sediment core SO202-07-06

Reduced nitrate supply to the subarctic North Pacific (SNP) surface during the last ice age has been inferred from coupled changes in diatom-bound d15N (DB-d15N), bulk sedimentary d15N, and biogenic fluxes. However, the reliability of bulk sedimentary and DB-d15N has been questioned, and a previously reported d15N minimum during Heinrich Stadial 1 (HS1) has proven difficult to explain. In a core from the western SNP, we report the foraminifera-bound d15N (FB-d15N) in Neogloboquadrina pachyderma and Globigerina bulloides, comparing them with DB-d15N in the same core over the past 25 kyr. The d15N of all recorders is higher during the Last Glacial Maximum (LGM) than in the Holocene, indicating more complete nitrate consumption. N. pachyderma FB-d15N is similar to DB-d15N in the Holocene but 2.2 per mil higher during the LGM. This difference suggests a greater sensitivity of FB-d15N to changes in summertime nitrate drawdown and d15N rise, consistent with a lag of the foraminifera relative to diatoms in reaching their summertime production peak in this highly seasonal environment. Unlike DB-d15N, FB-d15N does not decrease from the LGM into HS1, which supports a previous suggestion that the HS1 DB-d15N minimum is due to contamination by sponge spicules. FB-d15N drops in the latter half of the Bølling/Allerød warm period and rises briefly in the Younger Dryas cold period, followed by a decline into the mid-Holocene. The FB-d15N records suggest that the coupling among cold climate, reduced nitrate supply, and more complete nitrate consumption that characterized the LGM also applied to the deglacial cold events.

Stable carbon and oxygen isotope ratios of late Eocene and Oligocene foraminifera from the Atlantic Ocean

Oxygen isotope analyses of late Eocene and Oligocene planktonic foraminifers from low and middle latitude sites in the Atlantic Basin show that different species from the same samples can yield significantly different isotopic values. The range of isotopic values observed between species is greatest at low-latitudes and declines poleward. Many planktonic foraminifers exhibit a systematic isotopic ranking with respect to each other and can therefore be grouped on the basis of their isotopic ranking. The isotopic ranking of some taxa, however, appears to vary geographically and/or through time. Isotopic and paleontologic data from DSDP Site 522 indicate that commonly used isotopic temperature scales underestimate Oligocene sea surface temperatures. We suggest these temperature scales require revision to reflect the presence of Oligocene glaciation. Comparison of isotopic and paleontologic data from Sites 522, 511 and 277 suggests cold, low-salinity surface waters were present in high southern latitudes during the early Oligocene. Lowsalinity, high latitude surface waters could be caused by Eocene/Oligocene paleogeography or by the production of warm saline bottom water.

Osmium-isotope geochemistry of ODP Site 159-959

Analyses of Re, Os, and Ir concentrations, as well as Os-isotopic compositions, are reported for a suite of sediments from Ocean Drilling Program Site 959. These samples vary in age from late Neogene to Late Cretaceous, and represent a range in depositional oxidation-reduction conditions from suboxic in the Neogene to anoxic in the Late Cretaceous. Age assignments based on shipboard biostratigraphic data are used to calculate initial 187Os/186Os ratios of Neogene nannofossil/foraminifer oozes and Eocene to upper Oligocene laminated diatomites. These calculated initial ratios are in general agreement with published data constraining the Os-isotopic evolution of seawater through time, indicating that the Os-isotopic composition of these sediments is controlled largely by the Os isotopic composition of contemporaneous seawater. Results from analyses of Upper Cretaceous to lower Paleocene claystones do not exhibit elevated Ir concentrations and exhibit Re-Os systematics that are highly consistent with closed-system production of 187Os by in situ 187Re decay. Scatter in both the Cretaceous and Cenozoic data sets is likely the result of the influence of nonhydrogenous Os, carried by clastics, on the bulk sediment Os-isotopic composition, or post-depositional mobility of Re and/or Os.