High-resolution pore-water and solid-phase analyses of sediment cores GeoB6520-3 (Hydrate Hole) and GeoB6521-2 (Worm Hole) of the northern Congo Fan

The geochemical cycling of barium was investigated in sediments of pockmarks of the northern Congo Fan, characterized by surface and subsurface gas hydrates, chemosynthetic fauna, and authigenic carbonates. Two gravity cores retrieved from the so-called Hydrate Hole and Worm Hole pockmarks were examined using high-resolution pore-water and solid-phase analyses. The results indicate that, although gas hydrates in the study area are stable with respect to pressure and temperature, they are and have been subject to dissolution due to methane-undersaturated pore waters. The process significantly driving dissolution is the anaerobic oxidation of methane (AOM) above the shallowest hydrate-bearing sediment layer. It is suggested that episodic seep events temporarily increase the upward flux of methane, and induce hydrate formation close to the sediment surface. AOM establishes at a sediment depth where the upward flux of methane from the uppermost hydrate layer counterbalances the downward flux of seawater sulfate. After seepage ceases, AOM continues to consume methane at the sulfate/methane transition (SMT) above the hydrates, thereby driving the progressive dissolution of the hydrates "from above". As a result the SMT migrates downward, leaving behind enrichments of authigenic barite and carbonates that typically precipitate at this biogeochemical reaction front. Calculation of the time needed to produce the observed solid-phase barium enrichments above the present-day depths of the SMT served to track the net downward migration of the SMT and to estimate the total time of hydrate dissolution in the recovered sediments. Methane fluxes were higher, and the SMT was located closer to the sediment surface in the past at both sites. Active seepage and hydrate formation are inferred to have occurred only a few thousands of years ago at the Hydrate Hole site. By contrast, AOM-driven hydrate dissolution as a consequence of an overall net decrease in upward methane flux seems to have persisted for a considerably longer time at the Worm Hole site, amounting to a few tens of thousands of years.

Organic geochemistry of Upper Albian sediments from the Kirchrode I borehole

In the framework of a multidisciplinary research program, an organic geochemical study was carried out on a drill core which comprises a 245 m thick sequence of light-colored, Upper Albian marlstones that were deposited in the central part of the Lower Saxony basin (northern Germany). For part of the Upper Albian sequence, high-resolution measurements of carbonate contents reveal cycles which can be related to earth orbital forcing. Based on these data, sediment accumulation rates were calculated to be in the order of 15 g/m**2/yr. These high accumulation rates contrast with very low organic carbon contents and an extremely poor preservation of the autochthonous organic matter. Most of the sedimentary organic matter is of terrigenous origin and mainly derived from the erosion of older sedimentary rocks. Organic petrography reveals only a very small fraction of marine organic particles. Carbon/sulphur ratios, pristane/phytane ratios as well as the predominance of resedimented organic particles over autochthonous organic particles suggest that aerobic degradation processes rather than anaerobic processes (sulphate reduction) were responsible for the degradation of the organic matter. Furthermore, the scarcity of terrigenous organic particles (vitrinite) indicates that there was little vegetation on nearby land areas. To explain these analytical results, a depositional model was developed which could explain the scarcity of organic matter in the Upper Albian sediments. This model is based on downwelling of oxygen-rich, saline waters of Tethyan origin, which reduces the nutrient content of surface waters and thus primary bioproductivity while degradation of primary organic matter in the water column is enhanced at the same time. These conditions contrast to those which existed in Barremian and early Aptian times in this basin, when limited water exchange with adjacent oceans caused oxygen deficiency and the deposition of numerous organic carbon-rich black shales. The thick, organic matter-poor Upper Albian sequence of northern Germany also contrasts with comparatively thin, time-equivalent, deep-sea black shales from Italy. This discrepancy indicates that local and regional oceanographic factors (at least in this case) have a greater influence on organic matter deposition than global events.

Tie points and log-adjusted depth scales for ODP Leg 207 Sites

Multiple copies of Cretaceous black shales extending from the early Cenomanian to the end of the Santonian were recovered at five sites on Demerara Rise during Leg 207 of the Ocean Drilling Program. These sediments are primarily composed of laminated organic-rich claystones interbedded with coarser, lightly laminated foraminferal-bearing packstones and wackestones. The black shales represent the local expression of widespread organic-rich sedimentation in the Atlantic during the mid-Cretaceous. However, incomplete recovery prevented construction of continuous composite sections, resulting in uncertainties concerning the correct stratigraphic placement of individual cores. By combining high-resolution measurements of bulk density collected shipboard on the multisensor track with continuous downhole measurements of formation resistivity using the Formation MicroScanner, an equivalent logging depth scale was constructed for black shales recovered from Sites 1258, 1260, and 1261. The integrated depths approach centimeter-scale resolution and are supported by comparisons of coarser resolution natural gamma ray emissions collected on cores and through downhole logging operations. The new depths highlight the extent of both intra- and intercore gaps and provide an opportunity to further constrain temporal and spatial paleoceanographic changes captured in proxy records from these sediments.

Paleomagnetic and beryllium isotope record of West Equatorial Pacific sediments

The reliability of paleomagnetic records as proxies of the geomagnetic field intensity is still a matter of controversy since volcanic materials hardly provide continuous records, and marine sediments are suspected to carry a remanence biased by post-depositional realignments and/or by overprints. Such long standing debate emphasizes the need for the development of methods independent from paleomagnetism to decipher geomagnetic intensity variations. High resolution measurements of authigenic 10Be/9Be along with a detailed sedimentary record of directional and relative paleointensity variations evidence, over the 0.6-1.3 Ma time interval, frequent and recurrent excursions or short events in the late Matuyama and the early Brunhes epochs, among which two Brunhes-Matuyama reversal precursors and an intra-Jaramillo excursion. The results of this study confirm the idea of a highly unstable geomagnetic field as suggested by paleomagnetic evidences.

10Be and barium concentrations of sediment core GeoB1008-3

Particle reactive elements are scavenged to a higher degree at ocean margins than in the open ocean due to higher fluxes of biogenic and terrigenous particles. In order to determine the influence of these processes on the depositional fluxes of 10Be and barium we have performed high-resolution measurements on sediment core GeoB1008-3 from the Congo Fan. Because the core is dominated by terrigenous matter supplied by the Congo River, it has a high average mass accumulation rate of 6.5 cm/kyr. Biogenic 10Be and Ba concentrations were calculated from total concentrations by subtracting the terrigenous components of10Be and Ba, which are assumed to be proportional to the flux of Al2O3. The mean Ba/Al weight ratio of the terrigenous component was determined to be 0.0045. The unusualy high terrigenous 10Be concentrations of 9.1 * 10**9 atoms/g Al2O3 are either due to input of particles with high10Be content by the Congo River or due to scavenging of oceanic 10Be by riverine particles. The maxima of biogenic 10Be and Ba concentrations coincide with maxima of the paleoproductivity rates. Time series analysis of the 10Be and of Ba concentration profiles reveals a strong dominance of the precessional period of 24 kyr, which also controls the rates of paleoproductivity in this core. During the maxima of productivity the flux of biogenic Ba is enhanced to a larger extent than that of biogenic 10Be. Applying a model for coastal scavenging, we ascribe the observed higher sensitivity of Ba to biogenic particle fluxes to the fact that the ocean residence time of Ba is approximately 10 times longer than that of 10Be.

Stable oxygen and carbon isotope ratios of the planktonic foraminifera Pulleniatina obliquiloculata and the benthic foraminifera Uvigerina excellens of ODP Site 117-723 in the Arabian Sea (Table 1)

Site 723 is located in a water depth of 808 m at the center of the oxygen minimum zone and the middle part of the main thermocline on the Oman Margin. Oxygen isotope curves of planktonic delta18OP and benthic delta18OB can be traced back continuously to Stage 23 with high resolution measurements. A tentative correlation to Stage 53 has been tried using oxygen isotope stratigraphy. The amplitudes of the fluctuations of the benthic delta18OB curve are small, compared with the planktonic delta18OP curve. The delays of benthic oxygen isotopes delta18OB related to the planktonic delta18OP appear in the transgressive stages. Carbon isotopes of benthic delta13CB and planktonic delta13CP generally show an inverse correlation with oxygen isotope values delta18OB and delta18OB and delta18OP, however, the changes of delta13C are more gradual than those of delta18O during transgressive stages in spite of the synchronized changes of delta13C with those of delta18O during regressive stages. The difference of oxygen isotope between benthic and planktonic foraminifers represents the degree of pushing up the thermocline by upwelling, and the difference of carbon isotope represents the relative amount of upwelling Sigma[CO2] to the biological uptake in the surface water. These isotopic differences can be used as indicators of upwelling and show strong upwelling in the interglacial and weak upwelling in the glacial stages. The organic carbon content is correlated with the isotopic upwelling indicators, and higher content is correlated with the isotopic upwelling indicators and higher content appears in the interglacial stages. The calculated rate of sedimentation based on oxygen isotope stratigraphy in glacial stages is significantly high, two to four times that of interglacial stages, and the absolute flux of fluvial sediments with variability of lithofacies increased in the glacial stage. The present glacial-interglacial cycle with the fluctuation of upwelling relating to the southwest monsoon can be traced back to Stage 8, 250 ka. From Stage 8 to 12, 250-450 ka, the upwelling indicator of oxygen isotope difference did not show such distinct cyclicity. For Stages 12-15, 450-600 ka, the upwelling can be estimated as strong as in interglacial stage of the present cycles, with slightly weak upwelling in the glacial stage. This upwelling and climate can be traced back to the late Pliocene. The strongest upwelling can be estimated in the Pliocene-Pleistocene time by the isotopic indicators and the high organic carbon content.

Isotope measurements from late Paleocene - early Eocene of 5 cores from Atlantic and Pacific Ocean

High-resolution stable carbon isotope records for upper Paleocene - lower Eocene sections at Ocean Drilling Program Sites 1051 and 690 and Deep Sea Drilling Project Sites 550 and 577 show numerous rapid (40 - 60 kyr duration) negative excursions of up to 1 per mill. We demonstrate that these transient decreases are the expected result of nonlinear insolation forcing of the carbon cycle in the context of a long carbon residence time. The transients occur at maxima in Earth's orbital eccentricity, which result in high-amplitude variations in insolation due to forcing by climatic precession. The construction of accurate orbital chronologies for geologic sections older than ~ 35 Ma relies on identifying a high-fidelity recorder of variations in Earth's orbital eccentricity. We use the carbon isotope records as such a recorder, establishing a robust orbitally tuned chronology for latest Paleocene-earliest Eocene events. Moreover, the transient decreases provide a means of precise correlation among the four sites that is independent of magnetostratigraphic and biostratigraphic data at the <10^5-year scale. While the eccentricity-controlled transient decreases bear some resemblance to the much larger-amplitude carbon isotope excursion (CIE) that marks the Paleocene/Eocene boundary, the latter event is found to occur near a minimum in the ~400-kyr eccentricity cycle. Thus the CIE occurred during a time of minimal variability in insolation, the dominant mechanism for forcing climate change on 104-year scales. We argue that this is inconsistent with mechanisms that rely on a threshold climate event to trigger the Paleocene/Eocene thermal maximum since any threshold would more likely be crossed during a period of high-amplitude climate variations.

Sediment total reflectance measurements from the Cariaco Basin (MD03-2621) and northeastern Arabian Sea (SO130-289KL)

During the last glacial period, the North Atlantic region experienced pronounced, millennial-scale alternations between cold, stadial conditions and milder interstadial conditions-commonly referred to as Dansgaard-Oeschger oscillations-as well as periods of massive iceberg discharge known as Heinrich events. Changes in Northern Hemisphere temperature, as recorded in Greenland, are thought to have affected the location of the Atlantic intertropical convergence zone and the strength of the Indian summer monsoon. Here we use high-resolution records of sediment colour-a measure of terrigenous versus biogenic content-from the Cariaco Basin off the coast of Venezuela and the Arabian Sea to assess teleconnections with the North Atlantic climate system during the last glacial period. The Cariaco record indicates that the intertropical convergence zone migrated seasonally over the site during mild stadial conditions, but was permanently displaced south of the basin during peak stadials and Heinrich events. In the Arabian Sea, we find evidence of a weak Indian summer monsoon during the stadial events. The tropical records show a more variable response to North Atlantic cooling than the Greenland temperature records. We therefore suggest that Greenland climate is especially sensitive to variations in the North Atlantic system-in particular sea-ice extent-whereas the intertropical convergence zone and Indian monsoon system respond primarily to variations in mean Northern Hemisphere temperature.

Age model and color measurements of sediment cores from the eastern equatorial Pacific

High-resolution records of glacial-interglacial variations in biogenic carbonate, opal, and detritus (derived from non-destructive core log measurements of density, P-wave velocity and color; r >= 0.9) from 15 sediment sites in the eastern equatorial (sampling resolution is ~1 kyr) clear response to eccentricity and precession forcing. For the Peru Basin, we generate a high-resolution (21 kyr increment) orbitally-based chronology for the last 1.3 Ma. Spectral analysis indicates that the 100 kyr cycle became dominant at roughly 1.2 Ma, 200-300 kyr earlier than reported for other paleoclimatic records. The response to orbital forcing is weaker since the Mid-Brunhes Dissolution Event (at 400 ka). A west-east reconstruction of biogenic sedimentation in the Peru Basin (four cores; 91-85°W) distinguishes equatorial and coastal upwelling systems in the western and eastern sites, respectively. A north-south reconstruction perpendicular to the equatorial upwelling system (11 cores, 11°N-°3S) shows high carbonate contents (>= 50%) between 6°N and 4°S and highly variable opal contents between 2°N and 4°S. Carbonate cycles B-6, B-8, B-10, B-12, B-14, M-2, and M-6 are well developed with B-10 (430 ka) as the most prominent cycle. Carbonate highs during glacials and glacial-interglacial transitions extended up to 400 km north and south compared to interglacial or interglacial^glacial carbonate lows. Our reconstruction thus favors glacial-interglacial expansion and contraction of the equatorial upwelling system rather than shifting north or south. Elevated accumulation rates are documented near the equator from 6°N to 4°S and from 2°N to 4°S for carbonate and opal, respectively. Accumulation rates are higher during glacials and glacial-interglacial transitions in all cores, whereas increased dissolution is concentrated on Peru Basin sediments close to the carbonate compensation depth and occurred during interglacials or interglacial-glacial transitions.

Snow-pit measurements on Atka Bay landfast sea ice during ANT-Land 2012/2013 season

Up to now, snow cover on Antarctic sea ice and its impact on radar backscatter, particularly after the onset of freeze/thaw processes, are not well understood. Here we present a combined analysis of in situ observations of snow properties from the landfast sea ice in Atka Bay, Antarctica, and high-resolution TerraSAR-X backscatter data, for the transition from austral spring (November 2012) to summer (January 2013). The physical changes in the seasonal snow cover during that time are reflected in the evolution of TerraSAR-X backscatter. We are able to explain 76-93% of the spatio-temporal variability of the TerraSAR-X backscatter signal with up to four snowpack parameters with a root-mean-squared error of 0.87-1.62 dB, using a simple multiple linear model. Over the complete study, and especially after the onset of early-melt processes and freeze/thaw cycles, the majority of variability in the backscatter is influenced by changes in snow/ice interface temperature, snow depth and top-layer grain size. This suggests it may be possible to retrieve snow physical properties over Antarctic sea ice from X-band SAR backscatter.

Magnetic measurements of ODP Hole 178-1095B on the Pacific continental rise of the West Antarctic Peninsula

In this study we present a late Miocene - early Pliocene record of sixty-four zones with prominent losses in the magnetic susceptibility signal, taken on a sediment drift (ODP Site 1095) on the Pacific continental rise of the West Antarctic Peninsula. The zones are comparable in shape and magnitude and occur commonly at glacial-to-interglacial transitions. High resolution records of organic matter, magnetic susceptibility and clay mineral composition from early Pliocene intervals demonstrate that neither dilution effects nor provenance changes of the sediments have caused the magnetic susceptibility losses. Instead, reductive dissolution of magnetite under suboxic conditions seems to be the most likely explanation. We propose that during the deglaciation exceptionally high organic fluxes in combination with weak bottom water currents and prominent sediment draping diatom ooze layers produced temporary suboxic conditions in the uppermost sediments. It is remarkable that synsedimentary suboxic conditions can be observed in one of the best ventilated open ocean regions of the World.

Annual average Sr/Ca measurements from Porites lutea coral at Ha'afera Island, Tonga

In the South Pacific Convergence Zone (SPCZ), the variability in a sub-seasonally resolved microatoll Porites colony Sr/Ca record from Tonga and a previously published high-resolution record from Fiji are strongly influenced by sea surface temperature (SST) over the calibration period from 1981 to 2004 (R^2 = 0.67 - 0.68). However, the Sr/Ca-derived SST correlation to instrumental SST decreases back in time. The lower frequency secular trend (~1°C) and decadal-scale (~2 - 3°C) modes in Sr/Ca-derived SST are almost two times larger than that observed in instrumental SST. The coral Sr/Ca records suggest that local effects on SST generate larger amplitude variability than gridded SST products indicate. Reconstructed d18O of seawater (d18Osw) at these sites correlate with instrumental sea surface salinity (SSS; r = 0.64 - 0.67) but not local precipitation (r = -0.10 to - 0.22) demonstrating that the advection and mixing of different salinity water masses may be the predominant control on d18Osw in this region. The Sr/Ca records indicate SST warming over the last 100 years and appears to be related to the expansion of the western Pacific warm pool (WPWP) including an increasing rate of expansion in the last ~20 years. The reconstructed d18Osw over the last 100 years also shows surface water freshening across the SPCZ. The warming and freshening of the surface ocean in our study area suggests that the SPCZ has been shifting (expanding) southeast, possibly related to the southward shift and intensification of the South Pacific gyre over the last 50 years in response to strengthened westerly winds.