Oxygen and Carbon stable isotope ratios for Site U1334

The Oligocene-Miocene transition (OMT) (~23 Ma) is interpreted as a transient global cooling event, associated with a large-scale Antarctic ice sheet expansion. Here we present a 2.23 Myr long high-resolution (~3 kyr) benthic foraminiferal oxygen and carbon isotope (d18O and d13C) record from Integrated Ocean Drilling Program Site U1334 (eastern equatorial Pacific Ocean), covering the interval from 21.91 to 24.14 Ma. To date, five other high-resolution benthic foraminiferal stable isotope stratigraphies across this time interval have been published, showing a ~1 per mil increase in benthic foraminiferal d18O across the OMT. However, these records are still few and spatially limited and no clear understanding exists of the global versus local imprints. We show that trends and the amplitudes of change are similar at Site U1334 as in other high-resolution stable isotope records, suggesting that these represent global deep water signals. We create a benthic foraminiferal stable isotope stack across the OMT by combining Site U1334 with records from ODP Sites 926, 929, 1090, 1264, and 1218 to best approximate the global signal. We find that isotopic gradients between sites indicate interbasinal and intrabasinal variabilities in deep water masses and, in particular, note an offset between the equatorial Atlantic and the equatorial Pacific, suggesting that a distinct temperature gradient was present during the OMT between these deep water masses at low latitudes. A convergence in the d18O values between infaunal and epifaunal species occurs between 22.8 and 23.2 Ma, associated with the maximum d18O excursion at the OMT, suggesting climatic changes associated with the OMT had an effect on interspecies offsets of benthic foraminifera. Our data indicate a maximum glacioeustatic sea level change of ~50 m across the OMT.

Benthic foraminifera stable isotope data from the South Pacific sediment cores PS75/059-2 and PS75/056-1

Investigating the inter-basin deep water exchange between the Pacific and Atlantic Oceans over glacial-interglacial climate cycles is important for understanding circum-Antarctic Southern Ocean circulation changes and their impact on the global Meridional Overturning Circulation. We use benthic foraminiferal d13C records from the southern East Pacific Rise to characterize the d13C composition of Circumpolar Deep Water in the South Pacific, prior to its transit through the Drake Passage into the South Atlantic. A comparison with published South Atlantic deep water records from the northern Cape Basin suggests a continuous water mass exchange throughout the past 500 ka. Almost identical glacial-interglacial d13C variations imply a common deep water evolution in both basins suggesting persistent Circumpolar Deep Water exchange and homogenization. By contrast, deeper abyssal waters occupying the more southern Cape Basin and the southernmost South Atlantic have lower d13C values during most, but not all, stadial periods. We conclude that these values represent the influence of a more southern water mass, perhaps AABW. During many interglacials and some glacial periods, the gradient between Circumpolar Deep Water and the deeper southern Cape Basin bottom water disappears suggesting either no presence of AABW or indistinguishable d13C values of both water masses.

Methane measurements during POLARSTERN cruise ARK-XXII/2

A methane surplus relative to the atmospheric equilibrium is a frequently observed feature of ocean surface water. Despite the common fact that biological processes are responsible for its origin, the formation of methane in aerobic surface water is still poorly understood. We report on methane production in the central Arctic Ocean, which was exclusively detected in Pacific derived water but not nearby in Atlantic derived water. The two water masses are distinguished by their different nitrate to phosphate ratios. We show that methane production occurs if nitrate is depleted but phosphate is available as a P source. Apparently the low N:P ratio enhances the ability of bacteria to compete for phosphate while the phytoplankton metabolite dimethylsulfoniopropionate (DMSP) is utilized as a C source. This was verified by experimentally induced methane production in DMSP spiked Arctic sea water. Accordingly we propose that methylated compounds may serve as precursors for methane and thermodynamic calculations show that methylotrophic methanogenesis can provide energy in aerobic environments.

Benthic foraminifers in Mesozoic and Cenozoic sediments of the southwestern Atlantic

Benthic foraminiferal assemblages in Mesozoic and Cenozoic sediments were studied at Sites 511, 512, 513, and 514 drilled during Leg 71 in the southwestern Atlantic on the Maurice Ewing Bank and in the Argentine Basin. Benthic foraminifers in almost all stratigraphic subdivisions of Sites 511 and 512 reflect the gradual subsidence of the Falkland Plateau from shelf depths in the Barremian-Albian, when a semiclosed basin with restricted circulation of water masses and anaerobic conditions existed, to lower bathyal depths in the Late Cretaceous and Cenozoic, with an abrupt acceleration at the boundary of Lower and Upper Cretaceous. The composition, distribution, and preservation of Late Cretaceous assemblages of benthic foraminifers suggest considerable fluctuations of the foraminiferal lysocline and the CCD. This is evidenced by dissolution facies and foraminiferal assemblages in which agglutinated and resistant calcareous forms predominated during high stands of the CCD and by calcareous facies in which rich assemblages of calcareous species predominated during low stands. The highest position of the CCD on the Plateau (less than 1500-2000 m) was in the late Cenomanian, Turonian, and Coniacian. In the Santonian and Campanian the CCD was at depths below 1500-2000 meters. At the end of the Campanian the CCD shifted again to depths comparable with those of Cenomanian and Turonian time. In the latest Campanian and the Maestrichtian the CCD was low and nanno-foraminiferal oozes with a rich assemblage of benthic foraminifers accumulated. Foraminiferal assemblages at Sites 513 and 514 in the Argentine Basin also testify to oceanic subsidence from lower bathyal depths in the Oligocene to abyssal ones at present. This process was complicated by the influence of geographical migrations of the Polar Front caused by extensions of the ice sheet in the Antarctic after the opening of the Drake Passage during the Oligocene. In Mesozoic and Cenozoic deposits of the Falkland Plateau and the Argentine Basin seven assemblages of benthic foraminifers were distinguished by age: early-middle Albian, middle-late Albian, Late Cretaceous (including four groups), middle Eocene, late Eocene-early Miocene, middle-late Miocene, and Pliocene-Quaternary. The Albian assemblages contain many species common to the foraminiferal fauna of the Austral Biogeographical Province. The Late Cretaceous assemblage contains, along with Austral species, species common to foraminifers of North America, Western Europe, the Russian platform, and the south of the U.S.S.R. Deep-sea cosmopolitan species prevail in Cenozoic assemblages.

(Appendix A) Abundance of selected coccolithophores in sediment core DS97-2P, North Atlantic

The calcareous nannofossil assemblages from sediment core DS97-2P from the Reykjanes Ridge have been investigated to document oceanographic changes in surface water during the Holocene. The recorded variations in coccolithophore species assemblages and accumulation rates indicate that the region was subjected to rapid changes of surface water masses throughout the entire Holocene. Coccolithophore assemblages generally are of low species diversity and consist mainly of Emiliania huxleyi and Coccolithus pelagicus ssp. pelagicus. Two major events occurred at 8.5-7 ka and at 4.5-3.5 ka, showing higher coccolith accumulation rates, suggesting that the influence of relatively warm Atlantic waters via the Irminger Current was strong in the investigated area. The coccolithophore assemblages have been compared with diatom, foraminifer and sedimentological records within the same core. These data, supported by a comparison with previously published proxy records, add credit to the hypothesis that Holocene changes did not occur uniformly across the North Atlantic. The results have highlighted the Holocene pattern in the North Atlantic, as a period influenced by strong regionalism with discrepancies in the hydrographical trends and in the distribution of the planktonic proxies.

(Appendix A) Relative abundance of Emiliania huxleyi in sediment cores of the North Atlantic

The coccolithophore species Emiliania huxleyi is characterized by a wide range of sizes, which can be easily distinguished in the light microscope. In this study we have quantified the abundance of large (coccoliths > 4 µm in maximum length) E. huxleyi specimens during the last 25 kyr in sedimentary records from eleven cores and drill sites in the NE Atlantic and W Mediterranean Sea, to prove its usefulness in the reconstruction of water mass dynamics and biostratigraphic potential. During the Last Glacial Maximum this large form, a cold-water indicator, was common in the NE Atlantic and Mediterranean, and its regional variation in abundance indicates a displacement of the climatic zones southwards in agreement with the development of ice sheets and sea ice in the Northern Hemisphere during this period. On the other hand, the gradient between northern and southern surface water masses in the Subtropical Gyre appears to have been more pronounced than at present, while the Portugal and Canary Currents were more intense. In the western Mediterranean basin temperatures were cooler than in the adjacent Atlantic, provoking a quasi-endemism of these specimens until the end of Heinrich Event 1. This may have been due to a restriction in the communication between the Atlantic and Mediterranean through the Strait of Gibraltar, the arrival of cold surface water and the amplification of cooling after the development of ice sheets in the Northern Hemisphere. During the deglaciation, large E. huxleyi specimens decreased in abundance at medium and low latitudes, but were still numerous close to the Subarctic region during the Holocene. In transitional waters this decrease to present day abundances occurred after Termination Ib. The abrupt change in abundance of this large E. huxleyi form is proposed as a new biostratigraphic event to characterize the Holocene in mid- to low-latitude water masses in the North Atlantic, although this horizon seems to be diachronous by 5 kyr from tropical to subarctic regions, in agreement with the gradual onset of warm conditions.

Benthic foraminiferal response to the emergence of the Isthmus of Panama and coincident paleoceanographic changes

Late Cenozoic benthic foraminiferal faunas from the Caribbean Deep Sea Drilling Project (DSDP) Site 502 (3052 m) and East Pacific DSDP Site 503 (3572 m) were analyzed to interpret bottom-water masses and paleoceanographic changes occurring as the Isthmus of Panama emerged. Major changes during the past 7 Myr occur at 6.7-6.2, 3.4, 2.0, and 1.1 Ma in the Caribbean and 6.7-6.4, 4.0-3.2, 2.1, 1.4, and 0.7 Ma in the Pacific. Prior to 6.7 Ma, benthic foraminiferal faunas at both sites indicate the presence of Antarctic Bottom Water (AABW). After 6.7 Ma benthic foraminiferal faunas indicate a shift to warmer water masses: North Atlantic Deep Water (NADW) in the Caribbean and Pacific Deep Water (PDW) in the Pacific. Flow of NADW may have continued across the rising sill between the Caribbean and Pacific until 5.6 Ma when the Pacific benthic foraminiferal faunas suggest a decrease in bottom-water temperatures. After 5.6 Ma deep-water to intermediate-water flow across the sill appears to have stopped as the bottom-water masses on either side of the sill diverge. The second change recorded by benthic foraminiferal faunas occurs at 3.4 Ma in the Caribbean and 4.0-3.2 Ma in the Pacific. At this time the Caribbean is flooded with cold AABW, which is either gradually warmed or is replaced by Glacial Bottom Water (GBW) at 2.0 Ma and by NADW at 1.1 Ma. These changes are related to global climatic events and to the depth of the sill between the Caribbean and Atlantic rather than the rising Isthmus of Panama. Benthic foraminiferal faunas at East Pacific Site 503 indicate a gradual change from cold PDW to warmer PDW between 4.0 and 3.2 Ma. The PDW is replaced by the warmer, poorly oxygenated PIW at 2.1 Ma. Although the PDW affects the faunas during colder intervals between 1.4 and 0.7 Ma, the PIW remains the principal bottom-water mass in the Guatemala Basin of the East Pacific.

Planktic foraminiferal abundance and faunal-derived sea surface temperature of eastern equatorial Pacific ODP Site 202-1240

Glacial cooling (~1-5°C) in the eastern equatorial Pacific (EEP) cold tongue is often attributed to increased equatorial upwelling, stronger advection from the Peru-Chile Current (PCC), and to the more remote subpolar southeastern Pacific water mass. However, evidence is scarce for identifying unambiguously which process plays a more important role in driving the large glacial cooling in the EEP. To address this question, here we adopt a faunal calibration approach using planktic foraminifers with a new compilation of coretop data from the eastern Pacific, and present new downcore variation data of fauna assemblage and estimated sea surface temperatures (SSTs) for the past 160 ka (Marine Isotope Stage (MIS) 6) from ODP Site 1240 in the EEP. With significant improvement achieved by adding more coretop data from the eastern boundary current, our downcore calibration results indicate that most of the glacial cooling episodes over the past 160 ka in the EEP are attributable to increased influence from the subpolar water mass from high latitudes of the southern Pacific. By applying this new calibration of the fauna SST transfer function to a latitudinal transect of eastern Pacific (EP) cores, we find that the subpolar water mass has been a major dynamic contributor to EEP cold tongue cooling since MIS 6.

Discrete carbonate chemistry measured during the M87/1 cruise in April 2012

The track of the cruise, and the location of the different stations cover a large range of water masses, many of which take part in the exchange across the Greenland-Scotland Ridge, and of importance for the biogeochemical fluxes in the region. These water masses are of very different origins, which can be observed in the concentration of the different biogeochemical parameters. The concentrations are a result of the combination of the physical and biogeochemical environment in each formation region, and the processes acting on the water masses as they are transported away from the formation areas. The aim of the biogeochemistry measurements was to achieve a better understanding of the strength and variability of the biological carbon pump in the North Atlantic and Nordic Seas.

Nutrient concentrations along a North-South transect in the North Atlantic measured during Maria S. Merain cruise MSM03/1 (VISION) cruise

Samples were taken along a transect in the North Atlantic Ocean from 66°139.27'N; 29°136.65'W to 34°124.87'N; 28°128.90'W during the VISION cruise (diVersIty, Structure and functION) MSM03/01 on board the research vessel Maria S. Merian from September 21 to September 30, 2006. Along this transect, each station was sampled at 12 depths, from 10m down to 250m or 500m. Samples were collected with a rosette of 20-l Niskin bottles mounted on a conductivity-temperature-density profiler. Water samples for nutrients analysis were filtered directly after sampling through 0.45-µm in-line filters attached to a 60-ml pre-cleaned syringe into two 12-ml polystyrole tubes. Samples were stored at 4°C (dissolved silicate) or 80°C (ammonium, phosphate, nitrate and nitrite) The samples were spectrophotometrically measured with a continuous-flow analyzer using standard AA3 methods (Seal Analytical, Norderstedt, Germany) using a variant of the method of Grasshoff et al. (1983).

Oxygen and hydrogen isotopes measured in the Northeast Atlantic

Only a few studies have examined the variation of oxygen and hydrogen isotopes of seawater in NE Atlantic water masses, and data are especially sparse for intermediate and deep-water masses. The current study greatly expands this record with 527 d18O values from 47 stations located throughout the mid- to low-latitude NE Atlantic. In addition, dD was analyzed in the 192 samples collected along the GEOTRACES North Atlantic Transect GA03 (GA03_e=KN199-4) and the 115 Iberia-Forams cruise samples from the western and southern Iberian margin. An intercomparison study between the two stable isotope measurement techniques (cavity ring-down laser spectroscopy and magnetic-sector isotope ratio mass spectrometry) used to analyze GA03_e samples reveals relatively good agreement for both hydrogen and oxygen isotope ratios. The surface (0-100 m) and central (100-500 m) water isotope data show the typical, evaporation related trend of increasing values equatorward with the exception for the zonal transect off Cape Blanc, NW Africa. Off Cape Blanc, surface water isotope signatures are modified by the upwelling of fresher Antarctic Intermediate Water (AAIW) that generally has isotopic values of 0.0 to 0.5 per mil for d18O and 0 to 2 per mil for dD. Along the Iberian margin the Mediterranean Outflow Water (MOW) is clearly distinguished by its high d18O (0.5-1.1 per mil) and dD (3-6 per mil) values that can be traced into the open Atlantic. Isotopic values in the NE Atlantic Deep Water (NEADW) are relatively low (d18O: -0.1 to 0.5 per mil; dD: -1 to 4 per mil) and show a broader range than observed previously in the northern and southern convection areas. The NEADW is best observed at GA03_e Stations 5 and 7 in the central NE Atlantic basin. Antarctic Bottom Water isotope values are relatively high indicating modification of the original Antarctic source water along the flow path. The reconstructed d18O-salinity relationship for the complete data set has a slope of 0.51, i.e., slightly steeper than the 0.46 described previously by Pierre et al. (1994, J. Mar. Syst. 5 (2), 159-170.) for the tropical to subtropical Northeast Atlantic. This slope decreases to 0.46 for the subtropical North Atlantic Central Water (NACW) and the MOW and to 0.32 for the surface waters of the upper 50 m. The dD-salinity mixing lines have estimated slopes of 3.01 for the complete data, 1.26 for the MOW, 3.47 for the NACW, and 2.63 for the surface waters. The slopes of the d18O-dD relationship are significantly lower than the one for the Global Meteoric Water Line with 5.6 for the complete data set, 2.30 for the MOW, 4.79 for the NACW, and 3.99 for the surface waters. The lower slopes in all the relationships clearly reflect the impact of the evaporation surplus in the subtropics.

Age determination and foraminiferal faunas in sediment core MD99-2275

A high-resolution study of palaeoceanographic changes off North Iceland during the time period 8600-5200 cal year BP is based on benthic and planktonic foraminiferal assemblages. The core material (MD99-2275) was obtained from about 440 m water depth on the eastern part of the North Icelandic shelf. Changes in the faunal composition are interpreted to be mainly caused by variations in the strength of the relatively warm, high-salinity Irminger Current and the cold East Icelandic Current, which have been shown to be linked to the climatic changes in the North Atlantic region. Environmental proxies at that site are particularly sensitive to palaeoceanographic changes due to its position close to the marine Polar Front. Benthic assemblages show that relatively cold conditions prevailed at the base of the record. An increase in the influence of Atlantic water masses at the sea floor is seen at around 8400 cal year BP, whereas the surface waters were relatively warm already at 8600 cal year BP. The warming was interrupted by a cold event at around 8100-8000 cal year BP, registered both in the bottom and surface waters and correlated with the so-called 8.2 kyr cooling event. Both the benthic and the planktonic faunal compositions indicate that the Irminger Current had maximum influence in the area between 8000 and about 7300 cal year BP, followed by a gradually decreasing influence through the remaining part of the studied time interval. It is suggested that the contribution of Atlantic water masses from the east and north-east to the Arctic Surface waters off North Iceland increased after around 7000 cal year BP, and that this was further intensified after 6200 cal year BP. At present, the Arctic Surface Water north of Iceland consists of Polar waters, intermittently with direct influence from the East Greenland Current, mixed with Atlantic waters derived from the eastern part of the Nordic Seas. A comparison of the mean values of selected environmental proxies in the interval 8600-5200 cal year BP with the upper part of the same core shows that the water masses north of Iceland were considerably warmer during the Holocene thermal maximum than during the last 2000 cal year. In general, results from core MD99-2275 are in accordance with other marine records from the North Icelandic shelf and the northern North Atlantic region, although a detailed comparison on a centennial time scale is hampered by problems with spatial as well as temporal changes in the marine reservoir ages in the region.

Compilation of sedimentation rates and smear slide analysis of DSDP sites

A history of Mesozoie and Cenozoic palaeoenvironments of the North Atlantie Oeean has been developed based on a detailed analysis of the temporal and spatial distribution of major pelagie sediment facies, of hiatuses. of bulk sediment accumulation rates, and of concentrations and fluxes of the main deep-sea sediment components. The depositional history of the North Atlantic can be subdivided into three major phase: (a) Late Jurassie and Early Cretaceous phase: clastic terrigenous and biogenic pelagic sediment components accumulated rapidly under highly productive surface water masses over the entire occan basin; (b) Late Cretaceous to Early Miocene phase: relatively little terrigenous and pelagic biogenic sediment reached the North Atlantic Ocean floor, intensive hiatus formation occurred at variable rates, and wide stretches of the deep-ocean floor were covered by slowly accumulating terrigenous muds: (c) Middle Miocene to Recent phase: accumulation rates of biogenic and terrigenous deep-sea sediment components increased dramatically up to Quaternary times, rates of hiatus formation and the intensity of deep-water circulation inferred from them seem to have decreased. However, accumulation rate patterns of calcareous pelagic sediment components suggest that large scale reworking and di splacement of deep-sea sediments occurred at a variable rate over wide areas of the North Atlantic during this period.

Nd isotope data for ODP Leg 208 holes

The flow of deep-water masses is a key component of heat transport in the modern climate system, yet the role of deep-ocean heat transport during periods of extreme warmth is poorly understood. The present mode of meridional overturning circulation is characterized by deep-water formation in both the North Atlantic and the Southern Ocean. However, a different mode of meridional overturning circulation operated during the extreme greenhouse warmth of the early Cenozoic, during which time the Southern Ocean was the dominant region of deep-water formation. The combination of general global cooling and tectonic evolution of the Atlantic basins over the past ~55 m.y. ultimately led to the development of a mode of overturning circulation characterized by both Southern Ocean and North Atlantic deep-water sources. The change in deep-water circulation mode may, in turn, have affected global climate; however, unraveling the causes and consequences of this transition requires a better understanding of the timing of the transition. New Nd isotope data from the southeastern Atlantic Ocean indicate that the initial transition to a bipolar mode of deep-water circulation occurred in the early Oligocene, ca. 33 Ma. The likely cause of significant deep-water production in the North Atlantic was tectonic deepening of the sill separating the Greenland-Norwegian Sea from the North Atlantic.

Paleogene and early Neogene stable isotope record of foraminifera from ODP Leg 119 samples

Oxygen and carbon isotopic records of monogeneric and monospecific benthic and planktonic foraminifer samples from Sites 744 and 738 drilled on the southern end of the Kerguelen Plateau during ODP Leg 119 reveal the evolution of polar Indian Ocean water masses from the early Paleocene to the middle Miocene. Results from Site 738 are from sediments of early Paleocene to late Eocene age and those from Site 744 are late Eocene to middle Miocene. They suggest that intermediate waters at this location did not originate in the high latitudes during the early Eocene. Surface and near-surface waters cooled gradually after the maximum warming at 56 Ma, when surface waters were about 18°C. Intermediate waters cooled after 52 Ma. The highest temperatures (lowest d18O values) of the Cenozoic occurred from 56 to 52 Ma. The records of equatorial Pacific Site 577 and Weddell Sea Site 690 resemble that of the polar Indian Ocean in this interval. The well-documented d13C excursions toward positive values in the late Paleocene and negative values in the early Eocene are represented by foraminifers increases of 1.5 per mil and following decreases of about 3 per mil. Most of the cooling in the Paleogene occurred in the middle and late Eocene. A 2°C decrease of surface water at about 38.4 Ma heralded the beginning of extensive glacial conditions in Antarctica in the early Oligocene. At Site 744, the global d18O shift just above the Eocene/Oligocene boundary is 1.15 per mil, and occurred gradually in sediments dated at 36.5-35.9 Ma. Ice-rafted debris was deposited beginning at 36.1 Ma for about the next 2 m.y. This simultaneous occurrence of the global d18O shift with ice-rafted debris is evidence for early Oligocene glaciation in East Antarctica. Moreover, early and late Oligocene Cibicidoides d18O values between 2 and 2.2 per mil indicate intermediate water cooling and a small ice-volume effect. Production of cold dense bottom water in Antarctica was intensified with continental cooling and glaciation in the early Oligocene. Comparison of Oligocene and early Miocene isotopic data from high-latitude and low-latitude deepsea sites indicates that there were probably at least two sources of bottom waters at this time.