A refined Pliocene to early Pleistocene chronostratigraphic frame at ODP Hole 653A (West Mediterranean)

Two planktonic foraminiferal oxygen isotope records of ODP Hole 653A (Tyrrhenian Sea) are presented for the time period extending from approximately 0.8 to 3.0 Ma. Six, generally accepted, synchronous bioevents were used to precise the oxygen isotope chronology and to identify the oxygen isotope stages 22 down to 114. Subsequently, this oxygen isotope chronology was used to determine the synchronism or diachronism of various other biostratigraphic events with those recorded in the Singa and Ficarazzi land sections (Italy) and those in other DSDP/ODP sites. New results concern the diachronity of the FOD of the planktonic foraminiferal species N. atlantica, G.truncatulinoides truncatulinoides and G. inflata between ODP Hole 653A and the Italian landsections. Because many species entered the Mediterranean in short term fluxes, strongly related to the southward migration of cool North Atlantic surface waters, their time distribution through the Pliocene-Pleistocene generally corresponds to alternated intervals of presence and absence. This should explain most of the apparently diachronous appearances and disappearances. Alternating presence-absence patterns are of less importance for the various nannofossil events. The LOD of D. surculus occurs during the transition of stage 100 to 101 in both ODP Hole 653A and the Singa section, which is in perfect agreement with the disappearance of this species from the open ocean. The LOD of D. pentaradiatus in the Mediterranean occurs in stages 100-99, which seems to be consistent with the extinction of this species in the southern Hemisphere. G. oceanica, which corresponds to the 4 µm < Gephyrocapsa spp <5.5 µm is recorded in stages 65 to 64 at ODP Hole 653A. The Gephyrocapsa spp. >5.5 µm first occurred in stage 51 at Hole 653A, which fits within the uncertainty interval for this event stretching from stage 51 to 47 in the open ocean and seems therefore a useful tool for conventional biostratigraphy in the Mediterranean.

Water chemistry, and biological traits and mercury content of Salvelinus alpinus and S. namaycush in Laflamme and Pingualuit lake

Pingualuk Lake fills a deep crater in the Parc National des Pingualuit on the Ungava Peninsula (Nunavik, Canada) and is isolated from nearby surface waters. The main objectives of this study were to determine and compare the concentrations of two atmospherically derived contaminants, mercury and perfluorinated chemicals (PFCs), in the lake water column and fish of Pingualuk Lake and to assess the physical and biological factors influencing contaminant concentrations. Mercury concentrations in arctic char muscle tissue were comparable to those of char in other Arctic lakes, while the total amount of PFCs was below reported levels for remote lakes in the Arctic and elsewhere. Stable isotope and stomach content analyses were made to investigate the feeding ecology of the Pingualuk Lake arctic char population and indicated the possibility of multiple feeding groups. Genetics characteristics (MH and mtDNA) of fish from Pingualuk Lake revealed that this population is likely distinct from that of nearby Laflamme Lake. However, both arctic char populations exhibit differential variation of their allele families. Physical characteristics determined for Lake Pingualuk revealed that the water column was inversely stratified beneath the ice and extremely transparent to visible and ultraviolet radiation. The highest mercury concentrations (3- 6 pg/mL THg) occurred just beneath the ice surface in each lake. Pingualuk Lake, given its near pristine state and exceptional limnological features, may serve as a most valuable reference ecosystem for monitoring environmental stressors, such as contaminants, in the Arctic.

Dissolved organic matter in the Lena River Delta Region, Siberia, Russia

Connectivity between the terrestrial and marine environment in the Artic is changing as a result of climate change, influencing both freshwater budgets and the supply of carbon to the sea. This study characterizes the optical properties of dissolved organic matter (DOM) within the Lena Delta region and evaluates the behavior of DOM across the fresh water-marine gradient. Six fluorescent components (four humic-like; one marine humic-like; one protein-like) were identified by Parallel Factor Analysis (PARAFAC) with a clear dominance of allochthonous humic-like signals. Colored DOM (CDOM) and dissolved organic carbon (DOC) were highly correlated and had their distribution coupled with hydrographical conditions. Higher DOM concentration and degree of humification were associated with the low salinity waters of the Lena River. Values decreased towards the higher salinity Laptev Sea shelf waters. Results demonstrate different responses of DOM mixing in relation to the vertical structure of the water column, as reflecting the hydrographical dynamics in the region. Two mixing curves for DOM were apparent. In surface waters above the pycnocline there was a sharper decrease in DOM concentration in relation to salinity indicating removal. In the bottom water layer the DOM decrease within salinity was less. We propose there is a removal of DOM occurring primarily at the surface layer, which is likely driven by photodegradation and flocculation.

Stable isotope ratios and chemistry on corals from the Caribbean Sea

Instrumental climate data are limited in length and only available with low spatial coverage before the middle of the 20th century. This is too short to reliably determine and interpret decadal and longer scale climate variability and to understand the underlying mechanisms with sufficient accuracy. A proper knowledge of past variability of the climate system is needed to assess the anthropogenic impact on climate and ecosystems, and also important with regard to long-range climate forecasting. Highly-resolved records of past climate variations that extend beyond pre-industrial times can significantly help to understand long-term climate changes and trends. Indirect information on past environmental and climatic conditions can be deduced from climate-sensitive proxies. Large colonies of massive growing tropical reef corals have been proven to sensitively monitor changes in ambient seawater. Rapid skeletal growth, typically ranging between several millimeters to centimeters per year, allows the development of proxy records at sub-seasonal resolution. Stable oxygen isotopic composition and trace elemental ratios incorporated in the aragonitic coral skeleton can reveal a detailed history of past environmental conditions, e.g., sea surface temperature (SST). In general, coral-based reconstructions from the tropical Atlantic region have lagged behind the extensive work published using coral records from the Indian and Pacific Oceans. Difficulties in the analysis of previously utilized coral archives from the Atlantic, typically corals of the genera Montastrea and Siderastrea, have so far exacerbated the production of long-term high-resolution proxy records. The objective of this study is the evaluation of massive fast-growing corals of the species Diploria strigosa as a new marine archive for climate reconstructions from the tropical Atlantic region. For this purpose, coral records from two study sites in the eastern Caribbean Sea (Guadeloupe, Lesser Antilles; and Archipelago Los Roques, Venezuela) were examined. At Guadeloupe, a century-long monthly resolved multi-proxy coral record was generated. Results present the first d18O (Sr/Ca)-SST calibration equations for the Atlantic braincoral Diploria strigosa, that are robust and consistent with previously published values using other coral species from different regions. Both proxies reflect local variability of SST on a sub-seasonal scale, which is a precondition for studying seasonally phase-locked climate variations, as well as track variability on a larger spatial scale (i.e., in the Caribbean and tropical North Atlantic). Coral Sr/Ca reliably records local annual to interannual temperature variations and is higher correlated to in-situ air temperature than to grid-SST. The warming calculated from coral Sr/Ca is concurrent with the strong surface temperature increase at the study site during the past decades. Proxy data show a close relationship to major climate signals from the tropical Pacific and North Atlantic (the El Niño Southern Oscillation (ENSO) and the North Atlantic Oscillation (NAO)) affecting the seasonal cycle of SST in the North Tropical Atlantic (NTA). Coral oxygen isotopes are also influenced by seawater d18O (d18Osw) which is linked to the hydrological cycle, and capture large-scale climate variability in the NTA region better than Sr/Ca. Results from a quantitative comparison between extreme events in the two most prominent modes of external forcing, namely the ENSO and NAO, and respective events recorded in seasonal coral d18O imply that SST variability at the study site is highly linked to Pacific and North Atlantic variability, by this means supporting the assumptions of observational- and model-based studies which suggest a strong impact of ENSO and NAO forcings onto the NTA region through a modulation of trade wind strength in winter. Results from different spectral analysis tools suggest that interannual climate variability recorded by the coral proxies is II largely dictated by Pacific ENSO forcing, whereas at decadal and longer timescales the influence of the NAO is dominan. tThe Archipelago Los Roques is situated in the southeastern Caribbean Sea, north of the Venezuelan coast. Year-to-year variations in monthly resolved coral d18O of a nearcentury- long Diploria strigosa record are significantly correlated with SST and show pronounced multidecadal variations. About half of the variance in coral d18O can be explained by variations in seawater d18O, which can be estimated by calculating the d18Oresidual via subtracting the SST component from measured coral d18O. The d18Oresidual and a regional precipitation index are highly correlated at low frequencies, suggesting that d18Osw variations are primarily atmospheric-driven. Warmer SSTs at Los Roques broadly coincide with higher precipitation in the southeastern Caribbean at multidecadal time scales, effectively strengthening the climate signal in the coral d18O record. The Los Roques coral d18O record displays a strong and statistically significant relationship to different indices of hurricane activity during the peak of the Atlantic hurricane season in boreal summer and is a particularly good indicator of decadal-multidecadal swings in the latter indices. In general, the detection of long-term changes and trends in Atlantic hurricane activity is hampered due to the limited length of the reliable instrumental record and the known inhomogeneity in the observational databases which result from changes in observing practice and technology over the years. The results suggest that coral-derived proxy data from Los Roques can be used to infer changes in past hurricane activity on timescales that extend well beyond the reliable record. In addition, the coral record exhibits a clear negative trend superimposed on the decadal to multidecadal cycles, indicating a significant warming and freshening of surface waters in the genesis region of tropical cyclones during the past decades. The presented coral d18O time series provides the first and, so far, longest continuous coral-based record of hurricane activity. It appears that the combination of both signals (SST and d18Osw) in coral d18O leads to an amplification of large-scale climate signals in the record, and makes coral d18O even a better proxy for hurricane activity than SST alone. Atlantic hurricane activity naturally exhibits strong multidecadal variations that are associated with the Atlantic Multidecadal Oscillation (AMO), the major mode of lowfrequency variability in the North Atlantic Ocean. However, the mechanisms underlying this multidecadal variability remain controversial, primarily because of the limited instrumental record. The Los Roques coral d18O displays strong multidecadal variability with a period of approximately 60 years that is closely related to the AMO, making the Archipelago Los Roques a very sensitive location for studying low-frequency climate variability in the Atlantic Ocean. In summary, the coral records presented in this thesis capture different key climate variables in the north tropical Atlantic region very well, indicating that fast-growing Diploria strigosa corals represent a promising marine archive for further proxy-based reconstructions of past climate variability on a range of time scales.

(Table 1) Water column biogenic silica concentrations and Si isotopic composition during Marion Dufresne cruise MD166 off South Africa

Southern Ocean biogeochemical processes have an impact on global marine primary production and global elemental cycling, e.g. by likely controlling glacial-interglacial pCO2 variation. In this context, the natural silicon isotopic composition (d30Si) of sedimentary biogenic silica has been used to reconstruct past Si-consumption:supply ratios in the surface waters. We present a new dataset in the Southern Ocean from a IPY-GEOTRACES transect (Bonus-GoodHope) which includes for the first time summer d30Si signatures of suspended biogenic silica (i) for the whole water column at three stations and (ii) in the mixed layer at seven stations from the subtropical zone up to the Weddell Gyre. In general, the isotopic composition of biogenic opal exported to depth was comparable to the opal leaving the mixed layer and did not seem to be affected by any diagenetic processes during settling, even if an effect of biogenic silica dissolution cannot be ruled out in the northern part of the Weddell Gyre. We develop a mechanistic understanding of the processes involved in the modern Si-isotopic balance, by implementing a mixed layer model. We observe that the accumulated biogenic silica (sensu Rayleigh distillation) should satisfactorily describe the d30Si composition of biogenic silica exported out of the mixed layer, within the limit of the current analytical precision on the d30Si. The failures of previous models (Rayleigh and steady state) become apparent especially at the end of the productive period in the mixed layer, when biogenic silica production and export are low. This results from (1) a higher biogenic silica dissolution:production ratio imposing a lower net fractionation factor and (2) a higher Si-supply:Si-uptake ratio supplying light Si-isotopes into the mixed layer. The latter effect is especially expressed when the summer mixed layer becomes strongly Si-depleted, together with a large vertical silicic acid gradient, e.g. in the Polar Front Zone and at the Polar Front.

Quantitative coccolithophore analyses in sediment core MD01-2446

Quantitative coccolithophore analyses were performed in core MD01-2446, located in the mid-latitude North Atlantic, to reconstruct climatically induced sea-surface water conditions throughout Marine Isotope Stages (MIS) 14-9. The data are compared to new and available paleoenvironmental proxies from the same site as well as other nearby North Atlantic records that support the coccolithophore signature at glacial-interglacial to millennial climate scale. Total coccolithophore absolute abundance increases during interglacials but abruptly drops during the colder glacial phases and deglaciations. Coccolithophore warm-water taxa (wwt) indicate that MIS11c and MIS9e experienced warmer and more stable conditions throughout the whole photic zone compared to MIS13. MIS11 was a long-lasting warmer and stable interglacial characterized by a climate optimum during MIS11c when a more prominent influence of the subtropical front at the site is inferred. The wwt pattern also suggests distinct interstadial and stadial events lasting about 4-10 kyr. The glacial increases of Gephyrocapsa margereli-G. muellerae 3-4 µm along with higher values of Corg, additionally supported by the total alkenone abundance at Site U1313, indicate more productive surface waters, likely reflecting the migration of the polar front into the mid-latitude North Atlantic. Distinctive peaks of G. margereli-muellerae (> 4 µm), C. pelagicus pelagicus, Neogloboquadrina pachyderma left coiling, and reworked nannofossils, combined with minima in total nannofossil accumulation rate, are tracers of Heinrich-type events during MIS12 and MIS10. Additional Heinrich-type events are suggested during MIS12 and MIS14 based on biotic proxies, and we discuss possible iceberg sources at these times. Our results improve the understanding of mid-Brunhes paleoclimate and the impact on phytoplankton diversity in the mid-latitude North Atlantic region.

Siliceous microfossils in middle Eocene sediments of ODP Holes 120-748B and 120-749B

The Middle Eocene Climatic Optimum (MECO) is a major transient warming event that occurred at ~ 40 Ma and reversed a long-term cooling trend through the early and middle Eocene. We report the results of a high-resolution, quantitative study of siliceous microfossils at Ocean Drilling Program Sites 748 and 749 (Southern Kerguelen Plateau, Southern Ocean, ~ 58°S) across a ~ 1.4 myr interval spanning the MECO event. At both sites, a significant increase in biosiliceous sedimentation is associated with the MECO event. Rich siliceous planktonic microfossil assemblages in this interval are unusual in that they are dominated by ebridians, with radiolarians as a secondary major component. Silicoflagellates and diatoms comprise only a minor fraction of the assemblage, in contrast to siliceous microfossil assemblages that characterize modern Southern Ocean sediments. Based on our new siliceous microfossil records, we interpret two ~ 300 kyr periods of elevated nutrient availability in Southern Ocean surface waters which span the peak warming interval of the MECO and the post-MECO cooling interval. A diverse assemblage of large silicoflagellates belonging to the Dictyocha grandis plexus is linked to the rapid rise in sea-surface temperatures immediately prior to peak warmth, and a pronounced turnover is observed in both ebridian and silicoflagellate assemblages at the onset of peak warming. The interval of peak warmth is also characterized by high abundance of cosmopolitan ebridians (e.g., Ammodochium spp.) and silicoflagellates (e.g., Naviculopsis spp.), and increased abundance of tropical and subtropical diatom genera (e.g., Asterolampra and Azpeitia). These observations confirm the relative pattern of temperature change interpreted from geochemical proxy data at multiple Southern Ocean sites. Furthermore, rapid assemblage changes in both autotrophic and heterotrophic siliceous microfossil groups indicate a reorganization of Southern Ocean plankton communities in response to greenhouse warming during the MECO event.

Organic nitrogen and organic phosphorus concentrations bays of the White Sea

Concentrations of organic and mineral nitrogen and phosphorus in waters from different types of bays were determined during summer of 1987. Content of organic nitrogen in surface waters reached 80-97% of total; content of mineral phosphorus was 60-100%. Concentrations of N_org and P_org in deep waters decreased to 70 and 40%, respectively. Distribution of organic matter in the bays was controlled by river run-off.

Calcareous nannofossils in sediments of the Japan Sea

Preliminary results of the biostratigraphic analysis of calcareous nannofossils recovered from Ocean Drilling Program Leg 128, Sites 798 and 799, provide clues to the Quaternary oceanography of the Japan Sea. The distribution of calcareous nannofossils from the Quaternary sediments at Site 798 (903 m water depth) may record the position of an Oceanographic frontal boundary between warm water derived from a branch of the Kuroshio Current as it entered the Japan Sea through the Tsushima Straits to the south, and colder water introduced into the western portion of the Japan Sea derived from the winter chilling of northern Japan Sea surface waters. This Oceanographic front probably oscillated north-south over Site 798 in response to glacial/interglacial cycles, or perhaps to some other climatic event or combination of events unique to the Japan Sea. During the last 1.5 m.y., six major intervals are recognized when the Oceanographic front may have been north of Site 798 separated by five major intervals when the frontal boundary may have been south of the site. These migrations were centered around approximately 0.125, 0.29, 0.56, 0.62, 0.85, 0.91, 0.98, 1.0, 1.11, and 1.5 Ma, which correspond to the boundaries separating nannofossil-rich sediments from barren or nearly barren, low-carbonate intervals. Nannofossil-rich intervals may represent times when the frontal boundary was north of Site 798, and the site was above the CCD. Barren or nearly barren intervals represent times when the frontal boundary may have been south of Site 798 and the CCD was probably higher. The distribution of calcareous nannofossils at Site 799 (2073 m water depth) appears to be controlled more by the depth of the CCD than by any climatic effects. The FOD (first occurrence datum) of Emiliania huxleyi, the LOD (last occurrence datum) of Psuedoemiliania lacunosa, Helicosphaera sellii, Calcidiscus macintyrei (10 ?m), and the FOD and LOD of Reticulofenestra asanoi are recognized from Site 798 cores. The LOD of P. lacunosa is observed in sediments from Site 799. Only in the sediments younger than 1.5 Ma are the nannofossils from Sites 798 and 799 preserved well enough and sufficiently numerous for age dating and paleoceanographic conjecture. In-situ dissolution in older sediments at both sites precludes any dating or paleoenvironmental interpretations.

Composition and stable isotope record of bulk sediment and belemnite rostra from ODP Hole 122-761C

A sedimentary sequence documenting the early history of the proto-Indian Ocean was drilled at Site 761 on the Wombat Plateau, northwest Australia. Directly above the post-rift unconformity, two lithologic units were recovered which reflect deposition in incipient oceanic environments. The lower unit, composed of sandstone, contains abundant belemnites and a few lenses composed of low-diversity coccolith assemblages. The second unit, composed of chalk, contains abundant calcispheres, thoracospheres, low-diversity coccolith assemblages, and a few radiolarians. Belemnites and organisms that produced calcispheres and thoracospheres are thought to be opportunistic. Their abundance, and the absence of a normal marine fauna and flora, reflects an unstable early ocean environment. Stable oxygen and carbon isotopic data for the two units fall into almost separate fields. Heavy delta18O values for the belemnites indicate that they have not been affected by recrystallization. Instead, these isotopic values are thought to indicate either the deep, cool habitat of the belemnites or strong vital effects. A bulk chalk delta18O value from the belemnite sand is 3 to 4 parts per mil lighter than the belemnite delta18O values, possibly because it is largely composed of coccoliths which inhabited warmer surface waters. Light delta13C values for bulk calcisphere-bearing nannofossil chalk samples are thought to be a direct result of upwelling or of vital effects. Heavy delta18O values for the chalk unit are interpreted as resulting from upwelling of cool waters. Assemblage and isotopic data are consistent with this incipient ocean basin being highly productive, either as a result of upwelling or runoff of nutrient-rich waters from nearby land areas. However, it is not possible to rule out the control of vital effects on the isotopic signature of any of the fossil groups.

Cadmium/Calcium and stable isotope ratios of benthic foraminifera from the northeast Atlantic Ocean

The delta13C and Cd measurements from benthic foraminifera from Biogeochemical Ocean Flux Study (BOFS) northeast Atlantic Ocean sediment cores are presented. The delta13C values in glacial foraminifera are consistent with those from elsewhere in the North Atlantic Ocean. For intermediate water (1000 - 2000 m water depth), delta13C values were higher at the last glacial maximum than in present North Atlantic Deep Water (NADW), whereas for deep water (>2000 m) they were lower during the glacial maximum. The Cd concentrations of glacial northeast Atlantic intermediate water were lower than those of present NADW. However, deepwater Cd concentrations increased to values between NADW and present Pacific Deep Water (PDW). The delta13C and Cd data are consistent and show that the northeast Atlantic Ocean was strongly stratified with 13C enriched, low Cd intermediate water overlying 13C depleted, high Cd deep water. The glacial water column comprised two different water masses: deep water, similar in character to present Antarctic Bottom Water (AABW), and intermediate water, different in character from both AABW and NADW, and any present intermediate-depth North Atlantic water. The characteristics of glacial intermediate water were, however, similar to present near-surface waters in the North Atlantic, which suggests rapid ventilation of the glacial ocean to depths of up to 2000 m by cold, nutrient-depleted young surface waters.

Geochemistry of Late Paleocene thermal maximum sediments

The late Paleocene thermal maximum (LPTM) was a dramatic, short-term global warming event that occurred ~55 Ma. Warming of high-latitude surface waters and global deep waters during the LPTM has been well documented; however, current data suggest that subtropical and tropical sea surface temperatures (SSTs) did not change during the event. Conventional paradigms of global climate change, such as CO2-induced greenhouse warming, predict greater warming in the high latitudes than in the tropics or subtropics but, nonetheless, cannot account for the stable tropical/subtropical SSTs. We measured the stable isotope values of well-preserved late Paleocene to early Eocene planktonic foraminifera from South Atlantic Deep Sea Drilling Project (DSDP) Site 527 to evaluate the subtropical response to the climatic and environmental changes of the LPTM. Planktonic foraminiferal d18O values at Site 527 decrease by ~0.94 per mil from pre-LPTM to excursion values, providing the first evidence for subtropical warming during the LPTM. We estimate that subtropical South Atlantic SSTs warmed by at least ~1°-4°C, on the basis of possible changes in evaporation and precipitation. The new evidence for subtropical SST warming supports a greenhouse mechanism for global warming involving elevated atmospheric CO2 levels.

Oxygen isotope record of Globorotalia tumida and Globigerinoides sacculifer in sediments at ODP Site 130-806

Planktonic foraminiferal oxygen isotope records from the western and eastern tropical Pacific and Atlantic Oceans suggest a southward shift in the Intertropical Convergence Zone toward its modern location between 4.4 and 4.3 Ma. A concomitant shift in the carbon isotope compositions of Atlantic benthic foraminifera provides strong evidence for an increased thermohaline overturn at this time. We suggest that the southward shift of the Intertropical Convergence Zone and associated change in trade-wind circulation altered equatorial surface hydrography, increased the advection of warmer and more saline surface waters into the subtropical and North Atlantic, and contributed to thermohaline overturn.