Biomarker and XRD results for the last 3.4 Ma from IODP Site 306-U1313

Various types of abrupt/millennial-scale climate variability such as Dansgaard/Oeschger and Heinrich Events characterized the last glacial period. Over the last decade, a number of studies demonstrated that such millennial-scale climate variability was not limited to the last glacial but inherent to Quaternary climate. Here we review the occurrence and origin of millennial ice-rafting events in the North Atlantic during the late Pliocene and Pleistocene (last 3.4 Ma) with a special focus on North Atlantic Hudson Strait (HS) Heinrich(-like) Events. Besides a clear biomarker signature, we show that Heinrich Layers 5, 4, 2, and 1 in marine sediment cores from across the North Atlantic all bear the organic geochemical fingerprint of the Hudson area. Using this framework and combining previously published results, detailed investigations into the organic and inorganic chemistry of ice-rafted debris (IRD) found across the North Atlantic demonstrate that prior to MIS 16 (~ 650 ka) IRD in the North Atlantic did not originate from the Hudson area of northern Canada. The signature of this early IRD is distinctly different compared to that of HS Heinrich Layers. Rather ice-rafting events during the late Pliocene and early Pleistocene predominantly emanated from the calving of the Greenland and Fennoscandian ice sheets and possibly minor contributions from local ice streams from the North American and British ice sheets. Compared to North Atlantic HS Heinrich Events, these early Pleistocene IRD-events had a limited impact on surface water characteristics in the North Atlantic. North Atlantic HS Heinrich(-like) Events first occurred during MIS 16. At the same time, the dominant frequency in silicate-rich IRD accumulation shifted from the obliquity (41-ka) to a 100-ka frequency across the North Atlantic. Iceberg survivability or a change in iceberg trajectory likely did not control this change in IRD-regime. These results lend further support for the existing hypothesis that an increase in size (thickness) of the Laurentide ice sheet controls the occurrence of North Atlantic HS Heinrich Events, favoring an internal dynamic mechanism for their occurrence.

(Table 4) Estimated surface water phosphate concentrations for the past 200 kyr at the location of sediment core GeoB1016-3

We compared ocean atlas values of surface water [PO4]3- and [CO2(aq)] against the carbon isotopic fractionation (ep) of alkenones obtained from surface sediments of the South Atlantic and the central Pacific (Pacific data are from Pagani et al. 2002, doi:10.1029/2002PA000756). We observed a positive correlation between ep and 1/[CO2(aq)], which is opposite of what would be expected if the concentration of CO2(aq) were the major factor controlling the carbon isotopic fractionation of C37:2 alkenones. Instead, we found inverse relationships between ep and [PO4]3- for the two ocean basins (for the Atlantic, ep = -4.6*[PO4]3- + 15.1, R = 0.76; for the Pacific, ep = -4.1*[PO4]3- + 13.7, R = 0.64), suggesting that ep is predominantly controlled by growth rate, which in turn is related to nutrient concentration. The similarity of the slopes implies that a general relationship between both parameters may exist. Using the relationship obtained from the South Atlantic, we estimated surface water nutrient concentrations for the past 200,000 years from a deep-sea sediment core recovered off Angola. Low ep values, indicating high nutrient concentrations, coincide with high contents of total organic carbon and C37 alkenones, low surface water temperatures, and decreased bulk d15N values, suggesting an increased upwelling of nutrient-rich cool subsurface waters as the main cause for the observed ep decrease.

Particle camera and settling chamber measurements at site PC (GeoB11834-3) and SC (GeoB12914-4) off Cape Blanc/Mauritania

Particles sinking out of the euphotic zone are important vehicles of carbon export from the surface ocean. Most of the particles produce heavier aggregates by coagulating with each other before they sink. We implemented an aggregation model into the biogeochemical model of Regional Oceanic Modelling System (ROMS) to simulate the distribution of particles in the water column and their downward transport in the Northwest African upwelling region. Accompanying settling chamber, sediment trap and particle camera measurements provide data for model validation. In situ aggregate settling velocities measured by the settling chamber were around 55 m d**-1. Aggregate sizes recorded by the particle camera hardly exceeded 1 mm. The model is based on a continuous size spectrum of aggregates, characterised by the prognostic aggregate mass and aggregate number concentration. Phytoplankton and detritus make up the aggregation pool, which has an averaged, prognostic and size dependent sinking. Model experiments were performed with dense and porous approximations of aggregates with varying maximum aggregate size and stickiness as well as with the inclusion of a disaggregation term. Similar surface productivity in all experiments has been generated in order to find the best combination of parameters that produce measured deep water fluxes. Although the experiments failed to represent surface particle number spectra, in the deep water some of them gave very similar slope and spectrum range as the particle camera observations. Particle fluxes at the mesotrophic sediment trap site off Cape Blanc (CB) have been successfully reproduced by the porous experiment with disaggregation term when particle remineralisation rate was 0.2 d**-1. The aggregation-disaggregation model improves the prediction capability of the original biogeochemical model significantly by giving much better estimates of fluxes for both upper and lower trap. The results also point to the need for more studies to enhance our knowledge on particle decay and its variation and to the role that stickiness play in the distribution of vertical fluxes.

Dissolved Si isotope composition measured in water samples during METEOR cruises M77/3 and M77/4

Silicon isotopes are a powerful tool to investigate the cycling of dissolved silicon (Si). In this study the distribution of the Si isotope composition of dissolved silicic acid (d30Si(OH)4) was analyzed in the water column of the Eastern Equatorial Pacific (EEP) where one of the globally largest Oxygen Minimum Zones (OMZs) is located. Samples were collected at 7 stations along two meridional transects from the equator to 14°S at 85°50'W and 82°00'W off the Ecuadorian and Peruvian coast. Surface waters show a large range in isotope compositions d30Si(OH)4 (+2.2 per mil to +4.4 per mil) with the highest values found at the southernmost station at 14°S. This station also revealed the most depleted silicic acid concentrations (0.2 µmol/kg), which is a function of the high degree of Si utilization by diatoms and admixture with waters from highly productive areas. Samples within the upper water column and the OMZ at oxygen concentrations below 10 µmol/kg are characterized by a large range in d30Si(OH)4, which mainly reflects advection and mixing of different water masses, even though the highly dynamic hydrographic system of the upwelling area off Peru does not allow the identification of clear Si isotope signals for distinct water masses. Therefore we cannot rule out that also dissolution processes have an influence on the d30Si(OH)4 signature in the subsurface water column. Deep water masses (>2000 m) in the study area show a mean d30Si(OH)4 of +1.2±0.2 per mil, which is in agreement with previous studies from the eastern and central Pacific. Comparison of the new deep water data of this study and previously published data from the central Pacific and Southern Ocean reveal substantially higher d30Si(OH)4 values than deep water signatures from the North Pacific. As there is no clear correlation between d30Si(OH)4 and silicic acid concentrations in the entire data set the distribution of d30Si(OH)4 signatures in deep waters of the Pacific is considered to be mainly a consequence of the mixing of several end member water masses with distinct Si isotope signatures including Lower Circumpolar Deep Water (LCDW) and North Pacific Deep Water (NPDW).