Dissolved organic carbon concentrations, amino sugar concentrations and highly significantly correlating FT-ICR mass peak magnitudes obtained from solid phase extracted marine dissolved organic matter during POLARSTERN cruise ANT-XXV/1

Dissolved organic matter (DOM) was extracted with solid phase extraction (SPE) from 137 water samples from different climate zones and different depths along an Eastern Atlantic Ocean transect. The extracts were analyzed with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with electrospray ionization (ESI). D14C analyses were performed on subsamples of the SPE-DOM. In addition, the amount of dissolved organic carbon was determined for all water and SPE-DOM samples as well as the yield of amino sugars for selected samples. Linear correlations were observed between the magnitudes of 43% of the FT-ICR mass peaks and the extract D14C values. Decreasing SPE-DOM D14C values went along with a shift in the molecular composition to higher average masses (m/z) and lower hydrogen/carbon (H/C) ratios. The correlation was used to model the SPE-DOM D14C distribution for all 137 samples. Based on single mass peaks a degradation index was developed to compare the degradation state of marine SPE-DOM samples analyzed with FT-ICR MS. A correlation between D14C, degradation index, DOC values and amino sugar yield supports that SPE-DOM analyzed with FT-ICR MS reflects trends of bulk DOM. A relative mass peak magnitude ratio was used to compare aged SPE-DOM and fresh SPE-DOM regarding single mass peaks. The magnitude ratios show a continuum of different reactivities for the single compounds. Only few of the compounds present in the FT-ICR mass spectra are expected to be highly degraded in the oldest water masses of the Pacific Ocean. All other compounds should persist partly thermohaline circulation. Prokaryotic (bacterial) production, transformation and accumulation of this very stable DOM occurs probably primarily in the upper ocean. This DOM is an important contribution to very old DOM, showing that production and degradation are dynamic processes.

(Table 1) Age determination of surface sediment samples from the North Atlantic

Most seafloor sediments are dated with radiocarbon, and the sediment is assumed to be zero-age (modern) when the signal of atmospheric testing of nuclear weapons is present (Fraction modern (Fm) > 1). Using a simple mass balance, we show that even with Fm > 1, half of the planktonic foraminifera at the seafloor can be centuries old, because of bioturbation. This calculation, and data from four core sites in the western North Atlantic indicate that, first, during some part of the Little Ice Age (LIA) there may have been more Antarctic Bottom Water than today in the deep western North Atlantic. Alternatively, bioturbation may have introduced much older benthic foraminifera into surface sediments. Second, paleo-based warming of Sargasso Sea surface waters since the LIA must lag the actual warming because of bioturbation of older and colder foraminifera.

Age model and stable isotopes of sediment cores from north-central Chile and south-central Chile

Terrigenous sediment supply, marine transport, and depositional processes along tectonically active margins are key to decoding turbidite successions as potential archives of climatic and seismic forcings. Sequence stratigraphic models predict coarse-grained sediment delivery to deep-marine sites mainly during sea-level fall and lowstand. Marine siliciclastic deposition during transgressions and highstands has been attributed to sustained connectivity between terrigenous sources and marine sinks facilitated by narrow shelves. To decipher the controls on Holocene highstand turbidite deposition, we analyzed 12 sediment cores from spatially discrete, coeval turbidite systems along the Chile margin (29° - 40°S) with changing climatic and geomorphic characteristics but uniform changes in sea level. Sediment cores from intraslope basins in north-central Chile (29° - 33°S) offshore a narrow to absent shelf record a shut-off of turbidite deposition during the Holocene due to postglacial aridification. In contrast, core sites in south-central Chile (36° - 40°S) offshore a wide shelf record frequent turbidite deposition during highstand conditions. Two core sites are linked to the Biobío river-canyon system and receive sediment directly from the river mouth. However, intraslope basins are not connected via canyons to fluvial systems but yield even higher turbidite frequencies. High sediment supply combined with a wide shelf and an undercurrent moving sediment toward the shelf edge appear to control Holocene turbidite sedimentation and distribution. Shelf undercurrents may play an important role in lateral sediment transport and supply to the deep sea and need to be accounted for in sediment-mass balances.

Chemical composition of <0.001 mm grain size fractions of bottom sediments and cementing mass of basalt breccia from the North Atlantic

A comprehensive study of 102 samples of grain size fractions 0.010-0.005; 0.005-0.001, and <0.001 mm showns that clay mineral compositions from bottom sediments of the Faroe-Iceland Threshold and Faroe-Shetland Trench are different. In the first case it is essentially smectite-chlorite, in the second - mainly hydromicaceous. The difference in composition of clay minerals is due to influence of different source areas of terrigenous material.

(Appendix) Petrographic record from excavation profiles in Old-Luebeck (Liubice), north Germany

Die Frage einer Küstensenkung spielt seit Jahrzehnten bei der geologischen Erforschung des norddeutschen und niederländischen Flachlandes eine große Rolle. Der Schwerpunkt der bisherigen Arbeiten lag im südlichen Nordseeraum. Gerade dieses Gebiet bereitet aber wegen seines Aufbaues aus jungen, teilweise stark setzungsfähigen Gesteinen, des von Ort zu Ort und im Laufe der Zeit unterschiedlichen Einflusses der Gezeiten sowie wegen mancher anderer Bedingungen sehr große methodische Schwierigkeiten. Deshalb überrascht es nicht, daß die einzelnen Untersuchungen noch in den letzten beiden Jahrzehnten für die verschiedenen Abschnitte zu sehr abweichenden Folgerungen kamen, so daß die heute bekannten Einzeltatsachen nur ein recht widerspruchsvolles Gesamtbild ergeben. Da eine Klärung der Probleme durch eine Neubearbeitung an der Nordsee zunächst wenig erfolgversprechend erscheint, wird die Aufmerksamkeit unvermeidlich auf die Verhältnisse im südwestlichen Ostseeraum gelenkt. Hier bestehen in mancher Hinsicht einfachere Bedingungen, die eine derartige Untersuchung begünstigen. Vor allem die Nachbarschaft des skandinavischen Hebungsgebietes am gleichen Wasserbecken, die sehr geringen Gezeitenwirkungen und die hier weit verbreiteten Sandschüttungen bieten bessere Vergleichsmöglichkeiten und schalten viele Fehlerquellen aus. In der voliegenden Arbeit wurden die litorinazeitlichen und die nachlitorinazeitlichen Vertikalbewegungen des Landes und die eustatischen Schwankungen des Wasserstandes im südwestlichen Ostseeraum mit geologisch-morphologischen Methoden und durch die Auswertung von Lage und Verbreitung ur- und frühgeschichtlicher Funde sowie unter Auswertung von pollenanalytisch datierten Bohrprofilen und Pegelaufzeichnungen untersucht.

Stable isotope record, calcium carbonate conentrations, and sea surface temperture reconstructions of sediment cores from the North Atlantic

We analyze five high-resolution time series spanning the last 1.65 m.y.: benthic foraminiferal delta18O and delta13O, percent CaCO3, and estimated sea surface temperature (SST) at North Atlantic Deep Sea Drilling Project site 607 and percent CaCO3 at site 609. Each record is a multicore composite verified for continuity by splicing among multiple holes. These climatic indices portray changes in northern hemisphere ice sheet size and in North Atlantic surface and deep circulation. By tuning obliquity and precession components in the delta18O record to orbital variations, we have devised a time scale (TP607) for the entire Pleistocene that agrees in age with all K/Ar-dated magnetic reversals to within 1.5%. The Brunhes time scale is taken from Imbrie et al. [1984], except for differences near the stage 17/16 transition (0.70 to 0.64 Ma). All indicators show a similar evolution from the Matuyama to the Brunhes chrons: orbital eccentricity and precession responses increased in amplitude; those at orbital obliquity decreased. The change in dominance from obliquity to eccentricity occurred over several hundred thousand years, with fastest changes around 0.7 to 0.6 Ma. The coherent, in-phase responses of delta18O, delta13O, CaCO3 and SST at these rhythms indicate that northern hemisphere ice volume changes have controlled most of the North Atlantic surface-ocean and deep-ocean responses for the last 1.6 m.y. The delta13O, percent CaCO3, and SST records at site 607 also show prominent changes at low frequencies, including a prominent long-wavelength oscillation toward glacial conditions that is centered between 0.9 and 0.6 Ma. These changes appear to be associated neither with orbital forcing nor with changes in ice volume.

87Sr/86Sr ratios, Sr and Rb concentrations and stable oxygen isotope values for some basalts from ODP Hole 504B (Table 1)

Seventeen whole-rock samples, generally taken at 25-50 m intervals from 5 to 560 m sub-basement in Hole 504B, drilled in 6.2 m.y. old crust, were analysed for 87Sr/86Sr ratios, Sr and Rb concentrations, and 18O/16O ratios. Sr isotope ratios for 8 samples from the upper 260 m of the hole range from 0.70287 to 0.70377, with a mean of 0.70320. In the 330-560 m interval, 5 samples have a restricted range of 0.70255-0.70279, with a mean of 0.70266, the average value for fresh mid-ocean ridge basalts (MORB). In the 260-330 m interval, approximately intermediate Sr isotopic ratios are found. Delta18O values (?) range from 6.4 to 7.8 in the upper 260 m, 6.2-6.4 in the 270-320 m interval, and 5.8-6.2 in the 320-560 m interval. The values in the upper 260 m are typical for basalts which have undergone low-temperature seawater alteration, whereas the values for the 320-560 m interval correspond to MORB which have experienced essentially no oxygen isotopic alteration. The higher 87Sr/86Sr and 18O/16O ratios in the upper part of the hole can be interpreted as the result of a greater overall water/rock ratio in the upper part of the Hole 504B crust than in the lower part. Interaction of basalt with seawater (87Sr/86Sr = 0.7091) increased basalt 87Sr/86Sr ratios and produced smectitic alteration products which raised whole-rock delta18O values. Seawater circulation in the lower basalts may have been partly restricted by the greater number of relatively impermeable massive lava flows below about 230 m sub-basement. These flows may have helped to seal off lower basalts from through-flowing seawater.

Salinity of the Eocene Arctic Ocean from oxygen isotope analysis of fish bone carbonate

Stable isotope analysis was performed on the structural carbonate of fish bone apatite from early and early middle Eocene samples (~55 to ~45 Ma) recently recovered from the Lomonosov Ridge by Integrated Ocean Drilling Program Expedition 302 (the Arctic Coring Expedition). The d18O values of the Eocene samples ranged from -6.84 per mil to -2.96 per mil Vienna Peedee belemnite, with a mean value of -4.89 per mil, compared to 2.77 per mil for a Miocene sample in the overlying section. An average salinity of 21 to 25 per mil was calculated for the Eocene Arctic, compared to 35 per mil for the Miocene, with lower salinities during the Paleocene Eocene thermal maximum, the Azolla event at ~48.7 Ma, and a third previously unidentified event at ~47.6 Ma. At the Azolla event, where the organic carbon content of the sediment reaches a maximum, a positive d13C excursion was observed, indicating unusually high productivity in the surface waters.

Accumulation rates of volcanic glass and ice-rafted debris in sediments of the North Pacific Ocean

Mass accumulation rates (MAR) of different components of North Pacific deep-sea sediment provide detailed information about the timing of the onset of major Northern Hemisphere glaciation that occurred at 2.65 Ma. An increase in explosive volcanism in the Kamchatka-Kurile and Aleutian arcs occured at this same time, suggesting a link between volcanism and glaciation. Sediments recovered by piston-coring techniques during ODP Leg 145 provide a unique opportunity to undertake a detailed test of this possibility. Here we use volcanic glass as a proxy for explosive volcanism and ice-rafted debris (IRD) as a proxy for glaciation. The MAR of both glass and IRD increase markedly at 2.65 Ma. Further, the flux of the volcanic glass increased just prior the flix of ice-radted material, suggesting that the cooling resulting from explosive volcanic eruptions may have been the ultimate trigger for the mid-Pliocene glacial intensification.

Mid-Pliocene palynomorph record of the North Atlantic

The mid-Pliocene was an episode of prolonged global warmth and strong North Atlantic thermohaline circulation, interrupted briefly at circa 3.30 Ma by a global cooling event corresponding to marine isotope stage (MIS) M2. Paleoceanographic changes in the eastern North Atlantic have been reconstructed between circa 3.35 and 3.24 Ma at Deep Sea Drilling Project Site 610 and Integrated Ocean Drilling Program Site 1308. Mg/Ca ratios and d18O from Globigerina bulloides are used to reconstruct the temperature and relative salinity of surface waters, and dinoflagellate cyst assemblages are used to assess variability in the North Atlantic Current (NAC). Our sea surface temperature data indicate warm waters at both sites before and after MIS M2 but a cooling of ~2-3°C during MIS M2. A dinoflagellate cyst assemblage overturn marked by a decline in Operculodinium centrocarpum reflects a southward shift or slowdown of the NAC between circa 3.330 and 3.283 Ma, reducing northward heat transport 23-35 ka before the global ice volume maximum of MIS M2. This will have established conditions that ultimately allowed the Greenland ice sheet to expand, leading to the global cooling event at MIS M2. Comparison with an ice-rafted debris record excludes fresh water input via icebergs in the northeast Atlantic as a cause of NAC decline. The mechanism causing the temporary disruption of the NAC may be related to a brief reopening of the Panamanian Gateway at about this time.

Molar gas ratios and stable oxygen and nitrogen isotopes of air entrapped in ice, North America

The molar ratios of atmospheric gases change during dissolution in water due to differences in their relative solubilities. We exploited this characteristic to develop a tool to clarify the origin of ice formations in permafrost regions. Extracted from ice, molar gas ratios can distinguish buried glacier ice from intrasedimental ground ice formed by freezing groundwaters. An extraction line was built to isolate gases from ice by melting and trapping with liquid He, followed by analysis of N2, O2, Ar, 18O-O2 and 15N-N2, by continuous flow mass spectrometry. The method was tested using glacier ice, aufeis ice (river icing) and intrasedimental ground ice from sites in the Canadian Arctic. O2/Ar and N2/Ar ratios clearly distinguish between atmospheric gas in glacial ice and gases from intrasedimental ground ice, which are exsolved from freezing water. 615NN2 and 618OO2 in glacier ice, aufeis ice and intrasedimental ground ice do not show clear distinguishing trends as they are affected by various physical processes during formation such as gravitational settling, excess air addition, mixing with snow pack, and respiration.