(Table 1) Age comparison between the GPTS and ODP Site 181-1123 age model for each chron base within the Middle Miocene section

Today the deep western boundary current (DWBC) east of New Zealand is the most important route for deep water entering the Pacific Ocean. Large-scale changes in deep water circulation patterns are thought to have been associated with the development of the East Antarctic Ice Sheet (EAIS) close to the main source of bottom water for the DWBC. Here we reconstruct the changing speed of the southwest Pacific DWBC during the middle Miocene from ~15.5-12.5 Ma, a period of significant global ice accumulation associated with EAIS growth. Sortable silt mean grain sizes from Ocean Drilling Program Site 1123 reveal variability in the speed of the Pacific inflow on the timescale of the 41 kyr orbital obliquity cycle. Similar orbital period flow changes have recently been demonstrated for the Pleistocene epoch. Collectively, these observations suggest that a strong coupling between changes in the speed of the deep Pacific inflow and high-latitude climate forcing may have been a persistent feature of the global thermohaline circulation system for at least the past 15 Myr. Furthermore, long-term changes in flow speed suggest an intensification of the DWBC under an inferred increase in Southern Component Water production. This occurred at the same time as decreasing Tethyan outflow and major EAIS growth between ~15.5 and 13.5 Ma. These results provide evidence that a major component of the deep thermohaline circulation was associated with the middle Miocene growth of the EAIS and support the view that this time interval represents an important step in the development of the Neogene icehouse climate.

Stable isotope record of Uvigerina peregrina from the Mediterranean Sea

Based on the glacial to postglacial delta13C differences between endobenthic Uvigerina peregrina species from the Alboran basin and from other mediterranean basins, changes in the fertility of the western part of this basin during the last deglaciation are reconstructed. As a result of particulate organic carbon (POC) rain from the highly productive upwelling cell along the northwestern margin of the Alboran basin, U. peregrina is presently depleted by about 1.6per mil with respect to the measured delta13C values of bottom water SumCO2 and by about 0.9per mil with respect to specimens from other areas of the western Mediterranean or from the Gulf of Cadiz within the Mediterranean Outflow Water. The Uvigerina delta13C difference between the Alboran Sea and the Gulf of Cadiz (Delta delta13C), was close to 0per mil at the beginning of the last deglaciation and during the late glacial time. This suggests that highly fertile systems set in the Alboran Sea near 16 kyr B.P. Two rapid increases in the Delta delta13C offset are recorded near 15 kyr and 11 kyr B.P. Fluctuations around 1.1 to 1.2per mil occurred during the early Holocene, and a maximum was reached near 9 kyr B.P. After 4 kyr the Delta delta13C offset decreased to its present-day average value of 0.9per mil. Changes in the intensity of surficial production cannot account for all the observed fluctuations, especially in the early Holocene time. A strong decrease in the intermediate and deep water ventilation of the Alboran basin may have occurred near 8-9 kyr, in phase with the last stagnant phase in the eastern Mediterranean and the deposition of Sapropel S1. As a result, the redistribution and remineralization at depth of the produced organic matter was incomplete. The POC rain reaching the sediment was locally intensified and caused the lowering of the delta13C values of endobenthic foraminifers such as U. peregrina. The benthic 13C signal suggests that the difference between the Alboran Sea and the Gulf of Cadiz was at its maximum. At the same time, an important modification in the water masses structure may have occurred near 9-8 kyr B.P. The deepening of the permanent pycnocline probably related to a thicker Atlantic jet at a stage of high sea level stand is recorded by the replacement of the right coiling N. pachyderma dominance (coincident with a shallow pycnocline) by the G. inflata dominance (coincident with a deep pycnocline). Diatom abundances were strongly reduced indicating an important modification of the productive system. The glacial-postglacial evolution of productivity within the Alboran basin was therefore more complex than in the adjacent Atlantic Ocean and opposite to the global one which displays a general increase in productivity during glacial time. Although it is the global budget of paleoproductivity that would drive the partitioning of carbon within the ocean, local or regional discrepancies with the global glacial-interglacial model must be addressed. Local winds and regional atmospheric pressure systems, which are the forcing factors for circulation and exchange with the Atlantic, control the fertile systems of the Alboran basin.

Long chain diols and diol indices of surface sediments of the Iberian Atlantic margin

Long chain diols are lipids that have gained interest over the last years due to their high potential to serve as biomarkers and diol indices have been proposed to reconstruct upwelling conditions and sea surface temperature (SST). However, little is known about the sources of the diols and the mechanisms impacting their distribution. Here we studied the factors controlling diol distributions in the Iberian Atlantic margin, which is characterized by a dynamic continental shelf under the influence of upwelling of nutrient-rich cold deep waters, and fluvial input. We analyzed suspended particulate matter (SPM) of the Tagus river, marine SPM and marine surface sediments along five transects off the Iberian margin, as well as riverbank sediments and soil from the catchment area of the Tagus river. Relatively high fractional abundances of the C32 1,15-diol (normalized with respect to the 1,13- and 1,15-diols) were observed in surface sediments in front of major river mouths and this abundance correlates strongly with the BIT index, a tracer for continental input of organic carbon. Together with an even higher fractional abundance of the C32 1,15-diol in the Tagus river SPM, and the absence of long chain diols in the watershed riverbank sediments and soils, we suggest that this long chain diol is produced in-situ in the river. Further support for this hypothesis comes from the small but distinct stable carbon isotopic difference of 1.3? with the marine C28 1,13-diol. The 1,14-diols are relatively abundant in surface sediments directly along the northern part of the coast, close to the upwelling zone, suggesting that Diol Indices based on 1,14-diols would work well as upwelling tracers in this region. Strikingly, we observed a significant difference in stable carbon isotopic composition between the monounsaturated C30:1 1,14- and the saturated C28 1,14-diol (3.8±0.7 per mil), suggesting different sources, in accordance with their different distributions. In addition, the Long chain Diol Index (LDI), a proxy for sea surface temperature, was applied for the surface sediments. The results correlate well with satellite SSTs offshore but reveal a significant discrepancy with satellite-derived SSTs in front of the Tagus and Sado rivers. This suggests that river outflow might compromise the applicability of this proxy.

(Table 2) Age determination of sediment cores from the Gulf of Cadiz

We present micropalaeontological and grain-size records for a set of sediment cores from the Gulf of Cadiz (southwest Spain) that reflect changes in the position and strength of the Mediterranean Outflow (MO) current. The cores sample a sediment drift (the Gil Eanes Drift) that is positioned lower on the slope in the Gulf of Cadiz than the position of the main current today. The data indicate that the drift is of glacial age and that the glacial MO current was positioned lower on the slope than today but also that it was active over a considerably reduced area of the slope. We argue that this observation is consistent with physical constraints on the Gibraltar Exchange and on the likely settling and spreading behavior of the MO plume along the Iberian Margin under glacial environmental and sea level conditions. The deeper settling of the MO is likely to have influenced the formation of glacial North Atlantic Intermediate Water and also may have exerted indirect influence on the formation of glacial North Atlantic Deep Water.

Stable isotope and Mg/Ca record of IODP Site 339-U1385

Although millennial-scale climate variability (<10 ka) has been well studied during the last glacial cycles, little is known about this important aspect of climate in the early Pleistocene, prior to the Middle Pleistocene Transition. Here we present an early Pleistocene climate record at centennial resolution for two representative glacials (marine isotope stages (MIS) 37-41 from approximately 1235 to 1320 ka) during the "41 ka world" at Integrated Ocean Drilling Program Site U1385 (the "Shackleton Site") on the southwest Iberian margin. Millennial-scale climate variability was suppressed during interglacial periods (MIS 37, MIS 39, and MIS 41) and activated during glacial inceptions when benthic d18O exceeded 3.2 per mil. Millennial variability during glacials MIS 38 and MIS 40 closely resembled Dansgaard-Oeschger events from the last glacial (MIS 3) in amplitude, shape, and pacing. The phasing of oxygen and carbon isotope variability is consistent with an active oceanic thermal bipolar see-saw between the Northern and Southern Hemispheres during most of the prominent stadials. Surface cooling was associated with systematic decreases in benthic carbon isotopes, indicating concomitant changes in the meridional overturning circulation. A comparison to other North Atlantic records of ice rafting during the early Pleistocene suggests that freshwater forcing, as proposed for the late Pleistocene, was involved in triggering or amplifying perturbations of the North Atlantic circulation that elicited a bipolar see-saw response. Our findings support similarities in the operation of the climate system occurring on millennial time scales before and after the Middle Pleistocene Transition despite the increases in global ice volume and duration of the glacial cycles.

Physical properties of sediment cores from the Iberian Continental Slope

Climatic changes cause alterations in circulation patterns of the world oceans. The highly saline Mediterranean Outflow Water (MOW), built within the Mediterranean Sea crosses the Strait of Gibraltar in westerly directions, turning north-westward to stick to the Iberian Slope within 600-1500m water depths. Circulation pattern and current speed of the MOW are strongly influenced by climatically induced variations and thus control sedimentation processes along the South- and West - Iberian Continental Slope. Sedimentation characteristics of the investigated area are therefore suitable to reconstruct temporal hydrodynamic changes of the MOW. Detailed investigations on the silt-sized grain distribution, physical properties and hydroacoustic data were performed to recalculate paleo-current-velocities and to understand the sedimentation history in the Golf of Cadiz and the Portuguese Continental Slope. A time model based on d18Odata and 14C-datings of planktic foraminifera allowed the stratigraphical classification of the core material and thus the dating of the current induced sediment layers showing the variations of paleo-current intensities. The evaluation and interpretation of the gathered data sets enabled us to reconstruct lateral and temporal sedimentation patterns of the MOW for the Holocene and the late Pleistocene, back to the Last Glacial Maximum (LGM).

(Table 2) Age determination of sediment cores from the Portuguese Margin

We demonstrate that changes in the behavior of the Mediterranean Outflow Water (MOW) prior to and through the last deglaciation played an important role in promoting Meridional Overturning Circulation (MOC). Estimation of past MOW salt and heat fluxes indicates that they gradually increased through the last deglaciation. Between 17.5 and 14.6 thousand years ago (ka B.P., where B.P. references year 1950), net evaporation from the Mediterranean exported sufficient fresh water from the North Atlantic catchment to cause an average salinity increase of 0.5 psu throughout the upper 2000 m of the entire North Atlantic to the north of 25°N. Combined with rapid intensification and shoaling of the MOW plume, which we identify around 15-14.5 ka B.P., this deglacial MOW-related salt accumulation preconditioned the North Atlantic for abrupt resumption of the MOC at 14.6 ka B.P.

ADCP current profiles and conductivity and temperature collected at two points of Camarinal Sill, Strait of Gibraltar

The present study addresses the hypothesis that the Western Alborán Gyre in the Alborán Sea (the westernmost Mediterranean basin adjacent to the Strait of Gibraltar) influences the composition of the outflow through the Strait of Gibraltar. The process invoked is that strong and well-developed gyres help to evacuate the Western Mediterranean Deep Water from the Alboran basin, thus increasing its presence in the outflow, whereas weak gyres facilitates the outflow of Levantine and other Intermediate waters. To this aim, in situ observations collected at Camarinal (the main) and Espartel (the westernmost) sills of the Strait have been analyzed along with altimetry data, which were employed to obtain a representative proxy of the strength of the gyre. An encouraging correlation of the expected sign was observed between the time series of potential temperature at Espartel sill, which is show to keep information on the outflow composition, and the proxy of the Western Alborán Gyre, which strongly suggests the correctness of the hypothesis, although the weakness of the involved signals does not allow for drawing definitive conclusions.

Results of Closed-Flow Column Experiments (zip-archive 2.3 MB)

The identification of transport parameters by inverse modeling often suffers from equifinality or parameter correlation when models are fitted to observations of the solute breakthrough in column outflow experiments. This parameters uncertainty can be approached by the application of multiple experimental designs such as column experiments in open-flow mode and the recently proposed closed-flow mode. Latter are characterized by the recirculation of the column effluent into the solution supply vessel that feeds the inflow. Depending on the experimental conditions, the solute concentration in the solution supply vessel and the effluent follows a damped sinusoidal oscillation. As a result, the closed-flow experiment provides additional observables in the breakthrough curve. The evaluation of these emergent features allows intrinsic control over boundary conditions and impacts the uncertainty of parameters in inverse modeling. We present a comprehensive sensitivity analysis to illustrate the potential application of closed-flow experiments. We show that the sensitivity with respect to the apparent dispersion can be controlled by the experimenter leading to a decrease in parameter uncertainty as compared to classical experiments by an order of magnitude for optimal settings. With these finding we are also able to reduce the equifinality found for situations, where rate-limited interactions impede a proper determination of the apparent dispersion and rate coefficients. Furthermore, we show the expected breakthrough curve for equilibrium and kinetic sorption, the latter showing strong similarities to the behavior found for completely mixed batch reactor experiments. This renders the closed-flow mode a useful complementary approach to classical column experiments.