(Table S1) Uranium and Thorium isotopes and U/Th ages of IODP Exp310 cores from offshore Tahiti

The timing of sea-level change provides important constraints on the mechanisms driving Earth's climate between glacial and interglacial states. Fossil corals constrain the timing of past sea level by their suitability for dating and their growth position close to sea level. The coral-derived age for the last deglaciation is consistent with climate change forced by Northern Hemisphere summer insolation (NHI), but the timing of the penultimate deglaciation is more controversial. We found, by means of uranium/thorium dating of fossil corals, that sea level during the penultimate deglaciation had risen to ~85 meters below the present sea level by 137,000 years ago, and that it fluctuated on a millennial time scale during deglaciation. This indicates that the penultimate deglaciation occurred earlier with respect to NHI than the last deglacial, beginning when NHI was at a minimum.

Radionuclides measured on 27 water bottle profiles during POLARSTERN cruise ANT-XXIV/3

As part of the GEOTRACES Polarstern expedition ANT XXIV/3 (ZERO and DRAKE) we have measured the vertical distribution of 234Th on sections through the Antarctic Circumpolar Current along the zero meridian and in Drake Passage and on an EW section through the Weddell Sea. Steady state export fluxes of 234Th from the upper 100m, derived from the depletion of 234Th with respect to its parent 238U, ranged from 621±105 dpm/m**2/d to 1773±90 dpm/m**2/d. This 234Th flux was converted into an export flux of organic carbon ranging from 3.1-13.2 mmolC/m**2/d (2.1-9.0 mmolC/m**2/d) using POC/234Th ratio of bulk (respectively >50 µm) suspended particles at the export depth (100 m). Non-steady state fluxes assuming zero flux under ice cover were up to 23% higher. In addition, particulate and dissolved 234Th were measured underway in high resolution in the surface water with a semi-automated procedure. Particulate 234Th in surface waters is inversely correlated with light transmission and pCO2 and positively with fluorescence and optical backscatter and is interpreted as a proxy for algal biomass. High resolution underway mapping of particulate and dissolved 234Th in surface water shows clearly where trace elements are absorbed by plankton and where they are exported to depth. Quantitative determination of the export flux requires the full 234Th profile since surface depletion and export flux become decoupled through changes in wind mixed layer depth and in contribution to export from subsurface layers. In a zone of very low algal abundance (54-58 °S at the zero meridian), confirmed by satellite Chl-a data, the lowest carbon export of the ACC was observed, allowing Fe and Mn to maintain their highest surface concentrations (Klunder et al., this issue, Middag et al., this issue). An ice-edge bloom that had developed in Dec/Jan in the zone 60-65 °S as studied during the previous leg (Strass et al., in prep) had caused a high export flux at 64.5 °S when we visited the area two months later (Feb/March). The ice-edge bloom had then shifted south to 65-69 °S evident from uptake of CO2 and dissolved Fe, Mn and 234Th, without causing export yet. In this way, the parallel analysis of 234Th can help to explain the scavenging behaviour of other trace elements.

Carbonate and Thorium concentrations of South Atlantic sediments

Rates of sedimentation of pelagic sediments in the South Atlantic have been determined using the ionium/thorium methodology. Values of the order of several millimeters per thousand years for sediments were found in the deposits in the valleys of the mid-Atlantic ridge. The equatorial deposits showed higher rates of accumulation than the corresponding deposits at higher latitudes, probably reflecting the added influx of materials to the sea floor from tropical rivers through the equatorial current systems. The deposits in the ridge valleys showed marked changes in sedimentation rates at about 115,000 years ago, at which time the present rates changed from higher to lower values. The ridge sediments were composed primarily of continentally derived materials, and there were no indications of solid phases being derived from the weathering of the ridge itself or from volcanic activity. The equatorial samples have mineral assemblages which are distinctly different from those in deposits at higher latitudes and which probably are indicative of contributions of materials from tropical weathering processes.

Polonium-210 and Lead-210 activities measured on 17 water bottle profiles and 50 surface water samples during POLARSTERN cruise ARK-XXII/2

Polonium-210 and Lead-210 have been measured in the water column and on suspended particulate matter during the POLARSTERN cruise ARK-XXII/2. The data have been submitted to Pangaea following a Polonium-Lead intercalibration exercise organized by GEOTRACES, where the AWI lab results range within the data standard deviation from 10 participating labs. Polonium-210 and Lead-210 in the ocean can be used to identify the sources and sinks of suspended matter. In seawater, Polonium-210 (210Po) and Lead-210 (210Pb) are produced by stepwise radioactive decay of Uranium-238. 210Po (138 days half life) and 210Pb (22.3 years half life) have high affinities for suspended particles. Those radionuclides are present in dissolved form and adsorbed onto particles. Following adsorption onto particle surfaces, 210Po especially is transported into the interior of cells where it bonds to proteins. In this way, 210Po also accumulates in the food chain. 210Po is therefore considered to be a good tracer for POC, and traces particle export over a timescale of month. 210Pb (22.3 years half life) adsorbs preferably onto structural components of cells, biogenic silica and lithogenic particles, and is therefore a better tracer more rapidly sinking matter. Our goal during ARK XXII/2 was to trace pathways of particulate and dissolved matter leaving the Siberian Shelf. The pathways of particulate and dissolved matter will be followed by the combined use of 210Po and 234Th as a tracer pair (and perhaps 210Pb) for particle flux (Cai, P.; Rutgers van der Loeff, MM (2008) doi:10.1594/PANGAEA.708354). This information gathered from the water column will be complemented with the results of the 210Po-210Pb study in sea ice (Camara-Mor, P, Instituto de Ciencias del Mar-SCIC, Barcelona, Spain) to provide a more thorough picture of particle transport from the shelf to the open sea and from surface to depth.

Th-234 and Po-210 as POC flux proxies during the ARK-XXVII/3 expedition (August-October 2012)

The Arctic sea-ice extent reached a record minimum in September 2012. Sea-ice decline increases the absorption of solar energy in the Arctic Ocean, affecting primary production and the plankton community. How this will modulate the sinking of particulate organic carbon (POC) from the ocean surface remains a key question. We use the 234Th/238U and 210Po/210Pb radionuclide pairs to estimate the magnitude of the POC export fluxes in the upper ocean of the central Arctic in summer 2012, covering time scales from weeks to months. The 234Th/238U proxy reveals that POC fluxes at the base of the euphotic zone were very low (2 ± 2 mmol C/m**2/d) in late summer. Relationships obtained between the 234Th export fluxes and the phytoplankton community suggest that prasinophytes contributed significantly to the downward fluxes, likely via incorporation into sea-ice algal aggregates and zooplankton-derived material. The magnitude of the depletion of 210Po in the upper water column over the entire study area indicates that particle export fluxes were higher before July/August than later in the season. 210Po fluxes and 210Po-derived POC fluxes correlated positively with sea-ice concentration, showing that particle sinking was greater under heavy sea-ice conditions than under partially ice-covered regions. Although the POC fluxes were low, a large fraction of primary production (>30%) was exported at the base of the euphotic zone in most of the study area during summer 2012, indicating a high export efficiency of the biological pump in the central Arctic. This article is protected by copyright. All rights reserved.

Radon 222 and Radium 226 measured on water bottle samples during POLARSTERN cruise ARK-XXVI/3 (TransArc)

Air-sea gas exchange plays a key role in the cycling of greenhouse and other biogeochemically important gases. Although air-sea gas transfer is expected to change as a consequence of the rapid decline in summer Arctic sea ice cover, little is known about the effect of sea ice cover on gas exchange fluxes, especially in the marginal ice zone. During the Polarstern expedition ARK-XXVI/3 (TransArc, August/September 2011) to the central Arctic Ocean, we compared 222Rn/226Ra ratios in the upper 50 m of 14 ice-covered and 4 ice-free stations. At three of the ice-free stations, we find 222Rn-based gas transfer coefficients in good agreement with expectation based on published relationships between gas transfer and wind speed over open water when accounting for wind history from wind reanalysis data. We hypothesize that the low gas transfer rate at the fourth station results from reduced fetch due to the proximity of the ice edge, or lateral exchange across the front at the ice edge by restratification. No significant radon deficit could be observed at the ice-covered stations. At these stations, the average gas transfer velocity was less than 0.1 m/d (97.5% confidence), compared to 0.5-2.2 m/d expected for open water. Our results show that air-sea gas exchange in an ice-covered ocean is reduced by at least an order of magnitude compared to open water. In contrast to previous studies, we show that in partially ice-covered regions, gas exchange is lower than expected based on a linear scaling to percent ice cover.

(Table 1) Uranium at DSDP Hole 69-504B pore water

Measurements of U concentration and 234U/238U ratio were made in five water samples from Deep Sea Drilling Project Hole 504B.The results indicate that a loss of U had occurred either during sampling or during the storage of the samples, probably as a result of adsorption by rust particles or by the walls of the sampling system. Within analytical uncertainty, the 234U/238U ratios in the samples were identical to those in unreacted seawater. Thus, it is not possible to detect any U exchange that may have occurred during the reaction of the solutions with the basement formation. Improvement in sampling technique is a necessity for future studies of uranium and probably other trace elements in drill hole water samples.

Grain size effects on excess Thorium-230 of sediment cores from the Southern Ocean and the South East Atlantic

Excess Thorium-230 (230Thxs) as a constant flux tracer is an essential tool for paleoceanographic studies, but its limitations for flux normalization are still a matter of debate. In regions of rapid sediment accumulation, it has been an open question if 230Thxs-normalized fluxes are biased by particle sorting effects during sediment redistribution. In order to study the sorting effect of sediment transport on 230Thxs, we analyzed the specific activity of 230Thxs in different particle size classes of carbonate-rich sediments from the South East Atlantic, and of opal-rich sediments from the Atlantic sector of the Southern Ocean. At both sites, we compare the 230Thxs distribution in neighboring high vs. low accumulation settings. Two grain-size fractionation methods are explored. We find that the 230Thxs distribution is strongly grain size dependent, and 50-90% of the total 230Thxs inventory is concentrated in fine material smaller than 10 µm, which is preferentially deposited at the high accumulation sites. This leads to an overestimation of the focusing factor Psi, and consequently to an underestimation of the vertical flux rate at such sites. The distribution of authigenic uranium indicates that fine organic-rich material has also been re-deposited from lateral sources. If the particle sorting effect is considered in the flux calculations, it reduces the estimated extent of sediment focusing. In order to assess the maximum effect of particle sorting on Psi, we present an extreme scenario, in which we assume a lateral sediment supply of only fine material (< 10 µm). In this case, the focusing factor of the opal-rich core would be reduced from Psi = 5.9 to Psi = 3.2. In a more likely scenario, allowing silt-sized material to be transported, Psi is reduced from 5.9 to 5.0 if particle sorting is taken into consideration. The bias introduced by particle sorting is most important for strongly focused sediments. Comparing 230Thxs-normalized mass fluxes biased by sorting effects with uncorrected mass fluxes, we suggest that 230Thxs-normalization is still a valid tool to correct for lateral sediment redistribution. However, differences in focusing factors between core locations have to be evaluated carefully, taking the grain size distributions into consideration.