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

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

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

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

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

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

Mid-Pleistocene (800-400 ka) records of benthic and planktic foraminfer d18O and d13C, planktic foraminifer based SST, and IRD of IODP Site 306-U1314

Stable carbon and oxygen isotopes from benthic and planktic foraminifers, planktic foraminifer assemblages and ice rafted debris from the North Atlantic Site U1314 (Integrated Ocean Drilling Program Expedition 306) were examined to investigate orbital and millennial-scale climate variability in the North Atlantic and its impact on global circulation focusing on the development of glacial periods during the mid-Pleistocene (ca 800-400 ka). Glacial initiations were characterized by a rapid cooling (6-10 °C in less than 7 kyr) in the mean annual sea surface temperature (SST), increasing benthic d18O values and high benthic d13C values. The continuous increase in benthic d18O suggests a continuous ice sheet growth whereas the positive benthic d13C values indicate that the flow of the Iceland Scotland Overflow water (ISOW) was vigorous. Strong deep water formation in the Norwegian Greenland Sea promoted a high transfer of freshwater from the ocean to the continents. However, low SSTs at Site U1314 suggest a subpolar gyre cooling and freshening that may have reduced deep water formation in the Labrador Sea during glacial initiations. Once the 3.5 per mil threshold in the benthic d18O record was exceeded, ice rafting started and ice sheet growth was punctuated by millennial-scale waning events which returned to the ocean part of the freshwater accumulated on the continents. Ice-rafting events were associated with a rapid reduction in the ISOW (benthic d13C values dropped 0.5-1 per mil) and followed by millennial-scale warmings. The first two millennial-scale warm intervals of each glacial period reached interglacial temperatures and were particularly abrupt (6-10 °C in ~3 kyr). Subsequent millennial-scale warm events were cooler probably because the AMOC was rather reduced as suggested by the low benthic d13C values. These two abrupt warming events that occurred at early glacial periods were also observed in the Antarctic temperature and CO2 records, suggesting a close correlation between both Hemispheres. The comparison of the sea surface proxies with the benthic d18O record (as the Southern sign) indicates the presence of a millennial-scale seesaw pattern similar to that seen during the Last Glacial period.

Nd isotope composition of fossil fish teeth of ODP Hole 119-738B

We report an optimized method for extracting neodymium (Nd) from fossil fish teeth with a single-stage column (125 µl stem volume; LN Resin, Eichrom Industries, Darien Illinois) for isotopic analysis by multi-collector inductively coupled mass spectrometry (MC-ICMPS). Three reference materials (basalt: BCR-2, BHVO-2; phosphate: fossil bone composite) and splits of fossil fish teeth samples previously processed with existing two-stage column methods were processed using the single-stage column method. 143Nd/144Nd values of reference materials agree within error with published values, and the values for fish teeth correspond with sample splits processed with two-stage columns. Precision to ± ~0.23 epsilon-Nd was achieved for 30 ng Nd samples of reference materials, and Nd isotope measurements of fossil fish tooth sample replicates as small as 7 ng Nd were reproducible within long term instrumental uncertainty. We demonstrate the utility of the new method with the first high resolution Nd isotope record spanning the ~40.0 Ma middle Eocene Climatic Optimum, which shows an excursion of 0.65 epsilon-Nd during the peak warming at the study site (Ocean Drilling Program Leg 119, Site 738; 30 kyr sample spacing from 40.3 to 39.6 Ma). LN Resin is already used in standard methods for separating Nd, and Nd isotopes are routinely measured by MC-ICPMS with high efficiency inlet systems. Our innovation is a single, small volume LN Resin column for Nd separation. The streamlined approach results in a 10X increase in sample throughput.

(Table 1) Mercury concentrations and carbon and nitrogen isotopic ratios in 14 marine species from West Greenland sampled between 2003-2004

Total mercury (THg), methylmercury (MeHg) and stable isotopes of nitrogen (d15N) and carbon (d13C) were measured in three invertebrate, five fish, three seabird and three marine mammal species of central West Greenland to investigate trophic transfer of mercury in this Arctic marine food web. The food web magnification factor (FWMF) estimated as the slope of the regression between the natural logarithm of THg or MeHg concentrations (mg/kg dw) and tissue d15N (per mil) was estimated to 0.183 (SE = 0.052) for THg and 0.339 (SE = 0.075) for MeHg. The FWMFs were not only comparable with those reported for other Arctic marine food webs but also with quite different food webs such as freshwater lakes in the sub-Arctic, East Africa and Papua New Guinea. This suggests similar mechanisms of mercury assimilation and isotopic (d15N) discrimination among a broad range of aquatic taxa and underlines the possibility of broad ecosystem comparisons using the combined contaminant and stable isotope approach.

Stomach content and parasite characteristics of M. scorpius from Frobisher Bay, Baffin Island

Shorthorn sculpin (Myoxocephalus scorpius) from Frobisher Bay, Baffin Island, is a slow growing long-lived species. A wide range of diet items were present in the stomachs of the shorthorn sculpins sampled but 2-3 diet items (amphipod species) comprised 99.5 % of total food consumed. These amphipods were present in the stomachs in similar proportions among all age classes of shorthorn sculpin. Several new host records for parasites were reported and mean numbers of parasite species increased with shorthorn sculpin age. The increased diversity of parasite species and higher d15N values in older/larger individuals suggest that their diets were more diverse and the prey items consumed had higher d15N values. By contrast, the value of d13C in dominant diet items masked the d13C values of minor diet items. We conclude that parasites and stable isotope values provide complementary data on feeding patterns of the shorthorn sculpin. The ubiquitous marine acanthocephalan, Echinorhynchus gadi, was found at high prevalences (87-100 %) and mean intensities (28-35), and were localized in the midgut. In contrast to other studies on acanthocephalans, E. gadi did not influence fish condition as measured by condition factor, liver somatic and gonado-somatic indices.

(Table 1) Estimated e-Nd(0) input calculated using the relative fraction of ODP Hole 105-647A amphibole grains originated from different provinces of the North America

Many marine radiogenic isotope records show both spatial and temporal variations, reflecting both the degree of mixing of distinct sources in the oceans and changes in the distribution of chemical weathering on the continents. However, changes in weathering and transport processes may themselves affect the composition of radiogenic isotopes released into seawater. The provenance of physically weathered material in the Labrador Sea, constrained through the use of Ar-Ar ages of individual detrital minerals, has been used to estimate the relative contributions of chemically weathered terranes releasing radiogenic isotopes into the Labrador Sea. A simple box-model approach for balancing observed Nd-isotope variations has been used to constrain the relative importance of localised input in the Labrador Sea, and the subsequent mixing of Labrador Sea Water into North Atlantic Deep-Water. The long-term pattern of erosion and deep-water formation around the North Atlantic seems to have been a relatively stable feature since 1.5 Ma, although there has been a dramatic shift in the nature of physical and chemical weathering affecting the release of Hf and Pb isotopes. The modelled Nd isotopes imply a relative decrease in water mass advection into the Labrador Sea between 2.4 and 1.5 Ma, accompanied by a decrease in the rate of overturning, possibly caused by an increased freshwater input into the Labrador Sea.

Pollen records and lithology of profiles from Lobsigensee, Switzerland

Lobsigensee is a small kettle hole lake 15 km north-west of Bern on the Swiss Plateau, at an altitude of 514 m asl. Its surface is 2ha today, its maximum depth 2.7 m; it has no inlet and the overflow functions mainly during snow melting. The area was covered by Rhone ice during the Last Glaciation (map in Fig.2). Local geology, climate and vegetation are summarized in Figure 3A-C, the history of settlement in Figures 5-7. In order to reconstruct the vegetational and environmental history of the lake and its surroundings pollen analysis and other bio- and isotope stratigraphies were applied to twelve profiles cored across the basin with modified Livingstone corers (Fig.3 D). (1) The standard diagram: The central core LQ-90 is described as the standard pollen diagram (Chapter 3) with 10 local pollen assemblage zones of the Late-Glacial (local PAZ Ll to Ll0, from about 16'000(7) to 10'000 years BP) and 20 PAZ of the Holocene (local PAZ L11 to L30), see Figs. 8-10 and 20-24. Local PAZ L 1 to L3 are in the Late-Glacial clay and record the vegetational development after the ice retreat: L1 shows very low pollen concentration and high Pinus percentages due to long-distance transport and reworking; the latter mechanism is corroborated by the findings of thermophilous and pre-Quaternary taxa. Local PAZ L2 has a high di versi ty of non-arboreal pollen (NAP) and reflects the Late-Glacial steppe rich in heliophilous species. Local PAZ L3 is similar but additionally rich in Betula nana and Sal1x, thus reflecting a "shrub tundra". The PAZ L1 to L3 belong to the Oldest Dryas biozone. Local PAZ L4 to L 10 are found in the gyttja of the profundal or in the lake marl of the littoral and record the Late-Glacial forests. L4 is the shrub phase of reforestation with very high Junlperus and rapidly increasing Betula percentages. L5 is the PAZ with a first, L7 with a second dominance of tree-birches, separated by L6 showing a depression in the Betula curve. L4 to L7 can be assigned to the Balling biozone. Possible correlation of the Betula depression to the Older Dryas biozone is discussed. In local PAZ L8 Plnus immigrates and expands. L9 shows a facies difference in that Plnus dominates over Betula in littoral but not in profundal spectra. L8 and L9 belong to the Allerod biozone. In its youngest part the volcanic ash from Laach/Eifel is regularly found (11,000 BP). The local PAZ Ll0 corresponds to the Younger Dryas blozone. The merely slight increase of the NAP indicates that the pine forests of the lowland were not strongly affected by a cooler climate. In order to evaluate the significance of the littoral accumulation of coniferous pollen the littoral profile LQ-150 is compared to the profundal. Radiocarbon stratigraphies derived from different materials are presented in Figures 13 and 14 and in Tables 2 and 3. The hard-water errors in the gyttja samples and the carbonate samples are similar. The samples of terrestrial plant macrofossils are not affected by hard-water errors. Two plateaux of constant age appear in the age-depth relationship; their consequence for biostratigraphy as well as pollen concentration and influx diagrams are discussed. Radiocarbon ages of the Late-Glacial pollen zones are shown in Table 10. The Holocene vegetational history is recorded in the local PAZ L 11 to L30. After a Preboreal (PAZ L11) dominated by pine and birch the expansions of Corylus, Ulmus and Quercus are very rapid. Among these taxa Corylus dominates dur ing the Boreal (PAZ L 12 and L 1 3), whereas the components of the mixed oak forest dominate in the Older Atlantic (PAZ L14 to L16). In the Younger Atlantic (PAZ L 17 to L 19) Fagus and Alnus play an increasing, the mixed oak forest a decreasing role. During the period of local PAZ L19 Neolithic settlers lived on the shore of Lobsigensee. During the Subboreal (PAZ L20 and L21) and the Older Subatlantic (L22 to L25) strong fluctuations of Fagus and often antagonistic peaks of NAP, Alnus, Betula and Corylus can be interpreted as signs of human impact on vegetation. L23 is characterized not only by high values of NAP (especially apophytes and anthropochorous species) but also by the appearance of Juglans, Castanea and Secale which point to the Roman colonization of the area. For a certain period during the Younger Subatlantic (PAZ L26 to L30) the lake was used for retting hemp (Cannabis). Later the dominance of Quercus pollen indicates the importance of wood pastures. The youngest sediments reflect the wide-spread agricultural grass lands and the plantation of Pinus and Picea. Radiocarbon dates for the Holocene are given in Figure 23 and Table 4, the extrapolated ages of the Holocene pollen zones in Table 15. (2) The cross sections: Figures 25 and 26 give a summary of the litho- and palynostratigraphy of the two cross sections. Based on 11 Late-Glacial and 9 Holocene pollen diagrams (in addition to the standard ones), the consistency of the criteria for the definition of the pollen zones is examined in Tables 7 and 8 for the Late-Glacial and in Tables 11 to 14 for the Holocene. Sediment thicknesses across the basin for each pollen zone are presented in these tables as well as in Figures 43 to 45 for the Late-Glacial and in Figures 59 to 65 for the Holocene. Sediment focusing can explain differences between the gyttja cores of the profundal. Focusing is more than compensated for through "stretching" by carbonate precipitation on the littoral terrace. Pollen influx to the cross section are discussed (Chapters 4.1.5. and 4.2.3.). (3) The regional pollen zones: Based on some selected sites between Lake Geneva and Lake Constance regional pollen zones are proposed (Table 16, 17 and 19). (4) Paleoecology: Climatic change in the Late-Glacial can be inferred from Coleoptera, Trichoptera, Chironomidae and d18O of carbonates: a distinct warming is recorded around 12' 600 BP and around 10' 000 BP. The Younger Dryas biozone (10'700-10'000 BP) was the only cooling found in the Late-Glacial. The Betula depression often correlated wi th the Older Dryas biozone was possibl not colder but dryer than the previous period. During the Holocene the lowland site is not very sensitive to the minor climatic changes. Table 22 summarizes climatic and trophic changes before 8'000 BP as deduced from various biostratigraphies studied by a number of authors. Ostracods, Chironomids and fossil pigments indicate that anoxic conditions prevailed during the BoIling (possibly meromixis). Changes in the lake level are illustrated in Figure 74. A first lake-level lowering occurred in the early Holocene (10'000 to 9'000 BP), a second during the Atlantic (about 6'800 to 5'200 BP). The first "shrinking" of the lake volume resulted in a eutrophication recorded by laminations in the profundal and by pigments of Cyanophyceae. The second fall in water level corresponds to an increase of Nymphaeaceae. Human impact can be inferred in three ways: eutrophication of the lake (since the Neolithic), changes of terrestrial vegetation by deforestations (cyclicity of Fagus, see Figures 78 to 80), and enhanced erosion (increasing sedimentation rates by inwashed clay, particularly since the Roman Colonization, see Figures 49 and 81). Summary: This paper was planned as the final report on Lobsigensee. However, a number of issues are not answered but can only be asked more precisely, for example: (1) For the two periods with the highest rates of change, Le. the Bolling and the Preboreal biozones, pollen influx may reflect vegetation dynamics. Detailed investigations of these periods in annually laminated sediments are planned. (2) Biostratigraphies other than palynostratigraphy are needed to estimate the degree of linkage or independence in the development of terrestrial and lacustrine ecosystems. Often our sampling intervals were not identical, thus influencing our temporal resolution. (3) 6180- and 14C-stratigraPhies with high resolution will elucidate the leads and lags of these dynamic periods. Plateaux of constant age in the age-depth relationship have a strong bearing on both biological and geophysical understanding of Late-Glacial and early Holocene developments. (4) Numerical methods applied to the pollen diagrams of the cross section will help to quantify the significance of similari ties and dissimilarities across a single basin (with Prof. Birks). (5) Numerical methods applied to different sites on the Swiss Plateau and on the transect across the Alps will be helpful in evaluating the influence of different environmental factors (with Prof. Birks). (6) A new map 1: 1000 with 50cm-contour lines prov ided by Prof. Zurbuchen will be combined with a grid of cores sampling the transition from lake marl to peat enabling us to calculate paleo-volumes of the lake. This is interesting for the two "shrinking periods" (in Fig. 74A numbers 2-6 and 7-10), both accompanied by eutrophication. The pal eo-volume during the Neoli thic set tlement of the Cortaillod culture linked wi th an est l.mate of trophic change derived from diatoms (Prof. Smol in prep.) could possibly give an indication of the size of the human population of this period. (7) For the period with the antagonism between Fagus peaks and ABC-peaks close collaboration between palynologists, geochemists and archeologists should enable us to determine the influence of prehistoric and historic people on vegetation (collaboration with Prof. Stockli and Prof. Herzig). (8) The core LL-75 taken with a "cold letter box" will be analysed for major and trace elements by Dr. Sturm for 210pb and 137Cs by Prof.von Gunten and for pollen. We will see if our local PAZ L30 really corresponds to the surface sediment and if the small seepage lake reflects modern pollution.

Geochemistry of Mid-Atlantic Ridge sediments

Geochemical compositions and Sr and Nd isotopes were measured in two cores collected ~2 and 5 km from the Rainbow hydrothermal vent site on the Mid-Atlantic Ridge. Overall, the cores record enrichments in Fe and other metals from hydrothermal fallout, but sequential dissolution of the sediments allows discrimination between a leach phase (easily leachable) and a residue phase (refractory). The oxy-anion and transition metal distribution combined with rare earth element (REE) patterns suggest that (1) the leach fraction is a mixture of biogenic carbonate and hydrothermal Fe-Mn oxy-hydroxide with no significant contribution from detrital material and (2) >99.5% of the REE content of the leach fraction is of seawater origin. In addition, the leach fraction has an average 87Sr/86Sr ratio indistinguishable from modern seawater at 0.70916. Although we lack the epsilon-Nd value of present-day deep water at the Rainbow vent site, we believe that the REE budget of the leach fraction is predominantly of seawater origin. We suggest therefore that the leach fraction provides a record of local seawater epsilon-Nd values. Nd isotope data from these cores span the period of 4-14 ka (14C ages) and yield epsilon-Nd values for North East Atlantic Deep Water (NEADW) that are higher (-9.3 to -11.1) than those observed in the nearby Madeira Abyssal Plain from the same depth (-12.4 ± 0.9). This observation suggests that either the Iceland-Scotland Overflow Water (ISOW) and Lower Deep Water contributions to the formation of NEADW are higher along the Mid-Atlantic Ridge than in the surrounding basins or that the relative proportion of ISOW was higher during this period than is observed today. This study indicates that hydrothermal sediments have the potential to provide a higher-resolution record of deep water epsilon-Nd values, and hence deepwater circulation patterns in the oceans, than is possible from other types of sediments.