Nd, Pb and Sr isotopes in sediment cores from the Gulf of Cadiz and the Portuguese margin

Mediterranean Outflow Water (MOW) is characterised by higher temperatures and salinities than other ambient water masses. MOW spreads at water depths between 500 and 1500 m in the eastern North Atlantic and has been a source of salinity for the Atlantic Meridional Overturning Circulation in the North Atlantic. We used high-resolution Nd and Pb isotope records of past ambient seawater obtained from authigenic ferromanganese coatings of sediments in three gravity cores at 577, 1745 and 1974 m water depth in the Gulf of Cadiz and along the Portuguese margin complemented by a selection of surface sediments to reconstruct the extent and pathways of MOWover the past 23 000 years. The surface and downcore Nd isotope data from all water depths exhibit only a very small variability close to the present day composition of MOW but do not reflect the present day Nd isotopic stratification of the water column as determined from a nearby open ocean hydrographic station. In contrast, the Pb isotope records show significant and systematic variations, which provide evidence for a significantly different pattern of the MOW pathways between 20 000 and 12 000 years ago compared with the subsequent period of time.

(Supplement) Concentration in palynomorphs per gram of dry sediment in ANDRILL core AND-2A

An exceptional triple palynological signal (unusually high abundance of marine, freshwater, and terrestrial palynomorphs) recovered from a core collected during the 2007 ANDRILL (Antarctic geologic drilling program) campaign in the Ross Sea, Antarctica, provides constraints for the Middle Miocene Climatic Optimum. Compared to elsewhere in the core, this signal comprises a 2000-fold increase in two species of dinoflagellate cysts, a synchronous five-fold increase in freshwater algae, and up to an 80-fold increase in terrestrial pollen, including a proliferation of woody plants. Together, these shifts in the palynological assemblages ca. 15.7 Ma ago represent a relatively short period of time during which Antarctica became abruptly much warmer. Land temperatures reached 10 °C (January mean), estimated annual sea-surface temperatures ranged from 0 to 11.5 °C, and increased freshwater input lowered the salinity during a short period of sea-ice reduction.

Temperature variabilty in the southeastern Black-Sea during 64-20ka BP

The Eurasian inland propagation of temperature anomalies during glacial millennial-scale climate variability is poorly understood but this knowledge is crucial to understanding hemisphere-wide atmospheric teleconnection patterns and climate mechanisms. Based on biomarkers and geochemical paleothermometers, a pronounced continental temperature variability between 64,000 and 20,000 years ago, coinciding with the Greenland Dansgaard-Oeschger cycles, was determined in a well-dated sediment record from the formerly enclosed Black Sea. Cooling during Heinrich events was not stronger than during other stadials in the Black Sea. This is corroborated by modeling results showing that regular Dansgaard-Oeschger cycles penetrated deeper into the Eurasian continent than Heinrich events. The pattern of coastal ice-rafted detritus suggests a strong dependence on the climate background state, with significantly milder winters during periods of reduced Eurasian ice sheets and an intensified meridional atmospheric circulation.

(Table 2) Relative abundance of planktonic foraminifera species in Pliocene - Early Quaternary sediments from ODP Hole 111-677A

Planktonic foraminifera from Pliocene - Early Quaternary sediments of ODP Hole 111-677A were studied in detail. It was shown that the majority of detected zonal taxa are reliable biostratigraphic reference points. Between 30 and 210 m in the core zones of planktonic foraminifera from PL1b to Pt1 (according to the W.A. Berggren scale) were distinguished. Changes of planktonic foraminifera complexes from sediments of Hole 111-677A are closely associated with climate-controlled development of surface water masses of the Eastern Equatorial Pacific during 4.6-0.65 million years ago. Sharp decrease in equatorial-tropical species about 3.4 million years ago correlated with cessation of surface water exchange between tropical regions of the Pacific and Atlantic oceans due to formation of the Central American isthmus. The paleotemperature method of M.S Barash was used for reconstructing surface temperatures. Maximum temperatures were reconstructed in late Early Pliocene (26.4°C) and in Late Pliocene (26.6°C) and minimum ones - in the beginning of Early Pliocene (18.4°C), in the middle of Late Pliocene (19.6°C). Cold events occurred: 4.6-4.3, 2.8-2.5, and 1.7-1.2 million years ago, and warm: 4.3, 4.18-3.4, 2.5-2.3, and 1 million years ago. In general, the middle of Early Pliocene, the middle of late Pliocene and early Pleistocene are characterized by cold-water conditions, and the end of Early and the end of Late Pliocene - by warm-water conditions.

Planktic foraminifers, oxygen- and carbon isotopic compositions, and radiocarbon age in bottom sediments from Core AMK4-316GC

In a sediment core AMK4-316 (460 cm long) on the basis of radiocarbon, oxygen isotope, and lithological data climatostratigraphy is established for time interval about 145 ka. The method of factor analysis and spline interpolation applied to data on distribution of planktic foraminifera species has allowed to reconstruct average annual and seasonal temperatures and salinity at the surface and at depth 100 m. The optimum of the Last Interglaciation (5e) is characterized by maximal temperatures, low amplitudes of seasonal fluctuations, and by increased thickness of the upper homogeneous layer. The glacial hydrological mode has arisen here 115 ka ago. Coolings outstripped appropriate events of the global continental glaciation. Minimal average annual temperatures (4-4.5°C) are reconstructed for 47-45, 42, 36, 29-30, and 10 ka. For 50-30 ka interval numerous strong temperature fluctuations that reflect migrations of the polar front are established. Maximal differences of salinity at the surface and depth 100 m showing influence of melting waters were in the beginning of deglaciations (135 and 20 ka) and repeatedly arose in 50-30 ka interval. The Last Glacial Maximum (18 ka) is characterized by the lowest salinity but not by a peak of low temperatures at the surface. Surface temperature was lowered up to 10 ka. Average annual surface temperature of the Holocene optimum was 2°C above the modern one and 2°C below temperature in the Interglaciation optimum (5e), thickness of the upper homogeneous layer exceeded 100 m.

Geochemistry and P and Fe fractionation in anoxic sediments

We investigated the phosphorus (P) and iron (Fe) fractionation in four cores with anoxic sediments, deposited during the mid-Cretaceous oceanic anoxic event 2 (~94 Ma) and the Paleocene-Eocene thermal maximum (?55 Ma), that were exposed to oxygen after core recovery. Surprisingly, P associated with iron oxyhydroxides (Fe-bound P) was a major P phase in these laminated sediments deposited under euxinic conditions. A significant fraction of total Fe was present as (poorly) crystalline ferric Fe. This fraction increased with increasing storage time of the investigated cores. In carbonate-poor samples, Fe-bound P accounted for up to 99% of total P and its abundance correlated with pyrite contents. In samples with higher CaCO3 contents (>5 wt% in the investigated samples), P was mostly present in authigenic Ca-P minerals, irrespective of pyrite contents. We conclude that the P fractionation in anoxic, carbonate-poor, sediments is strongly affected by pyrite oxidation that occurs when these sediments are exposed to oxygen. Pyrite oxidation produces sulfuric acid and iron oxyhydroxides. The abundance of poorly crystalline Fe oxyhydroxides provides further evidence that these were indeed formed through recent (post-recovery) oxidation rather than in situ tens of millions of years ago. The acid dissolves apatite and the released phosphate is subsequently bound in the freshly formed iron oxyhydroxides. Pyrite oxidation thus leads to a conversion of authigenic Ca-P to Fe-bound P. In more calcareous samples, CaCO3 can act as an effective buffer against acidic dissolution of Ca-P minerals. The results indicate that shielding of sediments from atmospheric oxygen is vital to preserve the in situ P fractionation and to enable a valid reconstruction of marine phosphorus cycling based on sediment records.

Barite accumulation rates throughout Pliocene-Pleistocene in Eastern Equatorial Pacific at ODP Site 138-849

Export production is an important component of the carbon cycle, modulating the climate system by transferring CO2 from the atmosphere to the deep ocean via the biological pump. Here we use barite accumulation rates to reconstruct export production in the eastern equatorial Pacific over the past 4.3 Ma. We find that export production fluctuated considerably on multiple time scales. Export production was on average higher (51 g C/m**2/yr) during the Pliocene than the Pleistocene (40 g C/m**2/yr), decreasing between 3 and 1 Ma (from more than 60 to 20 g C/m**2/yr) followed by an increase over the last million years. These trends likely reflect basin-scale changes in nutrient inventory and ocean circulation. Our record reveals decoupling between export production and temperatures on these long (million years) time scale. On orbital time scales, export production was generally higher during cold periods (glacial maxima) between 4.3 and 1.1 Ma. This could be due to stronger wind stress and higher upwelling rates during glacial periods. A shift in the timing of maximum export production to deglaciations is seen in the last ~1.1 million years. Results from this study suggest that, in the eastern equatorial Pacific, mechanisms that affect nutrient supply and/or ecosystem structure and in turn carbon export on orbital time scales differ from those operating on longer time scales and that processes linking export production and climate-modulated oceanic conditions changed about 1.1 million years ago. These observations should be accounted for in climate models to ensure better predictions of future climate change.

Alkenone unsaturation index and alkenones in ODP Hole 161-977A

A number of essential elements closely related to each other are involved in the Earth's climatic system. The temporal and spatial distribution of insolation determines wind patterns and the ocean's thermohaline pump. In turn, these last two are directly linked to the extension and retreat of marine and continental ice and to the chemistry of the atmosphere and the ocean. The variability of these elements may trigger, amplify, sustain or globalize rapid climatic changes. Paleoclimatic oscillations have been identified in this thesis by using fossil organic compounds synthesized by marine and terrestrial flora. High sedimentation rate deposits at the Barents and the Iberian peninsula continental margins were chosen in order to estimate the climatic changes on centennial time resolution. At the Barents margin, the sediment recovered was up to 15,000 years old (unit ''a'', from latin ''annos'') (M23258; west of the Bjørnøya island). At the Iberian margin, the sediment cores studied covered a wide range of time spans: up to 115,000 a (MD99-2343; north of the Minorca island), up to 250,000 a (ODP-977A; Alboran basin) and up to 420,000 a (MD01-2442, MD01-2443, MD01-2444, MD01-2445; close to the Tagus abyssal plain). At the northern site, inputs containing marine, continental and ancient reworked organic matter provided a detailed reconstruction of climate history at the time of the final retreat of the Barents ice sheet. At the western Barents continental slope, warm climatic conditions were observed during the early Holocene (~from 8,650 a to 5,240 a ago); in contrast, an apparent long-term cooling trend occurred in the late Holocene (~from 5,240 a to 760 a ago), in consistence with other paleoarchives from northern and southern European latitudes. The Iberian margin sites, which were never covered with large ice sheets, preserved exceptionally complete sequences of rapid events during ice ages hitherto not studied in such great detail: during the last glacial (~from 70,900 a to 11,800 a ago), the second glacial (~from 189,300 a to 127,500 a ago), the third ice age (~from 278,600 a to 244,800 a ago) and the fourth (~from 376,300 a to 337,500 a ago). In this thesis, crucial research questions were brought up concerning the severity of different glacial periods, the intensity and rates of the recorded oscillations and the long distance connections related to rapid climate change. The data obtained provide a sound basis to further research on the mechanisms involved in this rapid climate variability. An essential point of the research was the evidence that, over the past 420,000 a, at the whole Iberian margin, warm and stable long periods similar to the Holocene always ended abruptly in few centuries after a gradual deterioration of climate conditions. The detailed estimate of past climate variability provides clues to the natural end of the present warm period. Returning to an ice age in European lands would be exacerbated by a number of factors: a lack of differential solar heating between northern and southern north Atlantic latitudes, enhanced evaporation at low latitudes, and an increase in snowfall or iceberg discharges at northern regions. It must be emphasized that all climatic oscillations observed in this thesis were caused by forces of nature, i.e. the last two centuries were not taken into consideration.

A 3.6 Ma sedimentological, geochemical and palynological record of sediment core ICDP5011-1 in Lake Elgygytgyn, NE Russia

Understanding the evolution of Arctic polar climate from the protracted warmth of the middle Pliocene into the earliest glacial cycles in the Northern Hemisphere has been hindered by the lack of continuous, highly resolved Arctic time series. Evidence from Lake El'gygytgyn, NE Arctic Russia, shows that 3.6-3.4 million years ago, summer temperatures were ~8°C warmer than today when pCO2 was ~400 ppm. Multiproxy evidence suggests extreme warmth and polar amplification during the middle Pliocene, sudden stepped cooling events during the Pliocene-Pleistocene transition, and warmer than present Arctic summers until ~2.2 Ma, after the onset of Northern Hemispheric glaciation. Our data are consistent with sea-level records and other proxies indicating that Arctic cooling was insufficient to support large-scale ice sheets until the early Pleistocene.

Table 3.5 Content and composition of air in fresh ice

Natural ice is formed by freezing of water or by sintering of dry or wet snow. Each of these processes causes atmospheric air to be enclosed in ice as bubbles. The air amount and composition as well as the bubble sizes and density depend not only on the kind of process but also on several environmental conditions. The ice in the deepest layers of the Greenland and thc Antarctic ice sheet was formed more than 100 000 years ago. In the bubbles of this ice, samples of atmospheric air from that time are preserved. The enclosure of air is discussed for each of the three processes. Of special interest are the parameters which control the amount and composition of the enclosed air. If the ice is formed by sintering of very cold dry snow, the air composition in the bubbles corresponds with good accuracy to the composition of atmospheric air.

(Table S1) Tie-points used in age model construction for ODP Leg 172 sites

ix Ocean Drilling Program (ODP) sites, in the Northwest Atlantic have been used to investigate kinematic and chemical changes in the "Western Boundary Undercurrent" (WBUC) during the development of full glacial conditions across the Marine Isotope Stage 5a/4 boundary (~70,000 years ago). Sortable silt mean grain size(sort s) measurements are employed to examine changes in near bottom flow speeds, together with carbon isotopes measured in benthic foraminifera and % planktic foraminiferal fragmentation as proxies for changes in water-mass chemistry. A depth transect of cores, spanning 1.8-4.6 km depth, allows changes in both the strength and depth of the WBUC to be constrained across millennial scale events. Sort s measurements reveal that the flow speed structure of the WBUC during warm intervals ("interstadials") was comparable to modern (Holocene) conditions. However, significant differences are observed during cold intervals, with higher relative flow speeds inferred for the shallow component of the WBUC (~2 km depth) during all cold "stadial" intervals (including Heinrich Stadial 6), and a substantial weakening of the deep component (~3-4 km) during full glacial conditions. Our results therefore reveal that the onset of full glacial conditions was associated with a regime shift to a shallower mode of circulation (involving Glacial North Atlantic Intermediate Water) that was quantitatively distinct from preceding cold stadial events. Furthermore, our chemical proxy data show that the physical response of the WBUC during the last glacial inception was probably coupled to basin-wide changes in the water-mass composition of the deep Northwest Atlantic.