Neodymium isotopic characterization of Ross Sea Bottom Water and its advection through the southern South Pacific, POLARSTERN cruise ANT-XXVI/2

Since the inception of the international GEOTRACES program, studies investigating the distribution of trace elements and their isotopes in the global ocean have significantly increased. In spite of this large-scale effort, the distribution of neodymium isotopes (143Nd/144Nd) and concentrations ([Nd]) in the high latitude south Pacific is still understudied. Here we report dissolved Nd isotopes and concentrations from 11 vertical water column profiles from the south Pacific between South America and New Zealand. Results suggest that Ross Sea Bottom Water (RSBW) is represented by an epsilon-Nd value of ~ -7, and is thus more radiogenic than Circumpolar Deep Water (epsilon-Nd ~ -8). RSBW and its characteristic epsilon-Nd signature can be traced far into the SE Pacific until progressive mixing with ambient Lower Circumpolar Deep water (LCDW) dilutes this signal north of the Antarctic Polar Front (APF). The SW-NE trending Pacific-Antarctic Ridge restricts the advection of RSBW into the SW Pacific, where bottom water density, salinity, and epsilon-Nd values of -9 indicate the presence of bottom waters of an origin different from the Ross Sea. Neodymium concentrations show low surface concentrations and a linear increase with depth north of the Polar Front. South of the APF, surface [Nd] is high and increases with depth but remains almost constant below ~1000 m. This vertical and spatial [Nd] pattern follows the southward shoaling density surfaces of the Southern Ocean frontal system and hence suggests supply of Nd to the upper ocean through upwelling of Nd-rich deep water. Low particle abundance dominated by reduced opal production and seasonal sea ice cover likely contributes to the maintenance of the high upper ocean [Nd] south of the APF. The reported data highlights the use of Nd isotopes as a water mass tracer in the Southern Ocean, with the potential for paleocenaographic reconstructions, and contributes to an improved understanding of Nd biogeochemistry.

(Table 2) Stable carbon and nitrogen isotope ratios and molar C/N ratio for euchaetid and aetideid copepods during POLARSTERN cruise ANT-XXIII/5

Stable isotope (SI) ratios of carbon (d13C) and nitrogen (d15N) were measured in omnivorous and carnivorous deep-sea copepods of the families Euchaetidae and Aetideidae across the Atlantic sector of the Southern Ocean to establish their trophic positions. Due to high and variable C/N ratios related to differences in lipid content, d13C was corrected using a lipid-normalisation model. d15N signals ranged from 3.0-6.9 per mil in mesopelagic species to 7.0-9.5 per mil in bathypelagic congeners. Among the carnivorous Paraeuchaeta species, the epi- to mesopelagic species Paraeuchaeta antarctica had lower d15N values than the mesopelagic P. rasa and bathypelagic P. barbata. The same trend was observed among omnivorous Aetideidae, but was not significant. In the most abundant species P. antarctica, individuals from the western Atlantic had higher d13C and d15N values than specimens at the eastern stations. These longitudinal changes in d13C and d15N values were attributed to regional differences in hydrography and sea surface temperature (SST), in particular related to a northward extension of the Antarctic Polar Front (APF) at the easternmost stations. The results indicate that even in a mesopelagic carnivorous species, the changes in surface stable isotope signatures are pronounced.

(Table 2) Zinc complexation data from POLARSTERN cruise ANT-XXIV/3

The speciation of dissolved zinc (Zn) was investigated by voltammetry in the Atlantic sector of the Southern Ocean along two transects across the major frontal systems: along the Zero Meridian and across the Drake Passage. In the Southern Ocean south of the APF we found detectable labile inorganic Zn throughout the surface waters in contrast to studies from lower latitudes. Using a combination of ASV titrations and pseudopolarography revealed the presence of significant concentration of electrochemically inert Zn ligands throughout the Southern Ocean. These ligands however were nearly always saturated due to the presence of excess concentrations of dissolved Zn that were associated with the high nutrient waters south of the Antarctic Polar Front (APF). Only in surface waters did the concentration of Zn complexing ligands exceed the dissolved Zn concentrations suggesting a biological source for these ligands. Our findings have clear implications for the biogeochemical cycling of Zn and for the interpretation of paleo records utilizing Zn in opal as a tracer of Zn speciation in the water column.

Physical oceanography and processed 2 minutes-averaged continuous VM-ADCP profiles during POLARSTERN cruise ANT-XXVIII/3

The physical and biological carbon pumps in the different hydrographic and biogeochemical regimes of the Atlantic Sector of the Southern Ocean are controlled by a series of coupled physical, chemical and biological processes and a project named Eddy-Pump was designed to study them. The Eddy Pump field campaign was carried out during RV Polarstern Cruise ANT-XXVIII/3 between January and March 2012. Particular emphasis was laid on the differences which occur along the axis of the Antarctic Circumpolar Current (ACC) with its associated mesoscale eddy field. The study sites were selected in order to represent (1) the central ACC with its regular separation in different frontal jets, investigated by a meridional transect along 10°E; (2) a large-scale bloom west of the Mid-Atlantic Ridge which lasted several months with conspicuous chlorophyll-poor waters to its immediate east studied by a three-dimensional mesoscale survey centred at 12°40'W; and (3) the Georgia Basin north of the island of South Georgia, which regularly features an extended and dense phytoplankton bloom, was investigated by a mesoscale survey centred at 38°12'W. While Eddy-Pump represents an interdisciplinary project by design, we here focus on describing the variable physical environment within which the different biogeochemical regimes developed. For describing the physical environment we use measurements of temperature, salinity and density, of mixed-layer turbulence parameters, of dynamic heights and horizontal current vectors, and of flow trajectories obtained from surface drifters and submerged floats. This serves as background information for the analyses of biological and chemical processes and of biogeochemical fluxes addressed by other papers in this issue. The section along 10°E between 44°S and 53°S showed a classical ACC structure with well-known hydrographic fronts, the Subantarctic Front (SAF) at 46.5°S, the Antarctic Polar Front (APF) split in two, at 49.25°S and 50.5°S, and the Southern Polar Front (SPF) at 52.5°S. Each front was associated with strong eastward flows. The West Mid-Atlantic Ridge Survey showed a weak and poorly resolved meander structure between the APF and the SPF. During the first eight days of the survey the oceanographic conditions at the Central Station at 12°40'W remained reasonably constant. However after that, conditions became more variable in the thermocline with conspicuous temperature inversions and interleavings and also a decrease in temperature in the surface layer. At the very end of the period of observation the conditions in the thermocline returned to being similar to those observed during the early part of the period with however the mixed layer temperature raised. The period of enhanced thermohaline variability was accompanied by increased currents. The Georgia Basin Survey showed a very strong zonal jet at its northern edge which connects to a large cyclonic meander that itself joins an anticyclonic eddy in the southeastern quadrant. The water mass contrasts in this survey were stronger than in the West Mid-Atlantic Ridge Survey, but similar to those met along 10°E with the exception that the warm and saline surface water typical of the northern side of the SAF was not covered by the Georgia Basin Survey. Mixed layers found during Eddy-Pump were typically deep, but varied between the three survey areas; the mean depths and standard variations of the mixed layer along the 10°E were 77.2±24.7 m, at the West Mid-Atlantic Ridge 66.7±17.7 m, and in the Georgia Basin 36.8±10.7 m.

Phytoplankton composition derived from CHEMTAX along 10°E during POLARSTERN cruise ANT-XXVIII/3, Jan-March 2012

Phytoplankton community structure and their physiological response in the vicinity of the Antarctic Polar Front (APF; 44°S to 53°S, centred at 10°E) were investigated as part of the ANT-XXVIII/3 Eddy-Pump cruise conducted in austral summer 2012. Our results show that under iron-limited (< 0.3 µmol/m**3) conditions, high total chlorophyll-a (TChl-a) concentrations (> 0.6 mg/m**3) can be observed at stations with deep mixed layer (> 60 m) across the APF. In contrast, light was excessive at stations with shallower mixed layer and phytoplankton were producing higher amounts of photoprotective pigments, diadinoxanthin (DD) and diatoxanthin (DT), at the expense of TChl-a, resulting in higher ratios of (DD+DT)/ TChl-a. North of the APF, significantly lower silicic acid (Si(OH)4) concentrations (< 2 mmol/m**3) lead to the domination of nanophytoplankton consisting mostly of haptophytes, which produced higher ratios of (DD+DT)/TChl-a under relatively low irradiance conditions. The Si(OH)4 replete (> 5 mmol/m**3) region south of the APF, on the contrary, was dominated by microphytoplankton (diatoms and dinoflagellates) with lower ratios of (DD+DT)/TChl-a, despite having been exposed to higher levels of irradiance. The significant correlation between nanophytoplankton and (DD+DT)/TChl-a indicates that differences in taxon-specific response to light are also influencing TChl-a concentration in the APF during summer. Our results reveal that provided mixing is deep and Si(OH)4 is replete, TChl-a concentrations higher than 0.6 mg/m**3 are achievable in the iron-limited APF waters during summer.

Occurrence of microtextures recorded from quartz sand grains of ODP Hole 178-1101A (Table 1)

Sediment drifts on the continental rise are located proximal to the western side of the Antarctic Peninsula and recorded changes in glacial volume and thermal regime over the last ca. 15 m.y. At Ocean Drilling Program (ODP) Site 1101 (Leg 178), which recovered sediments back to 3.1 Ma, glacial-interglacial cyclicity was identified based on the biogenic component and sedimentary structures observed in X-radiographs, magnetic susceptibility and lithofacies descriptions. Glacial intervals are dominated by fine-grained laminated mud and interglacial units consist of bioturbated muds enriched in biogenic components. From 2.2 to 0.76 Ma, planktonic foraminifera and calcareous nannofossils dominate in the interglacials suggesting a shift of the Antarctic Polar Front (APF) to the south near the drifts. Prior to 2.2 Ma, cyclicity cannot be identified and diatoms dominate the biogenic component and high percent opal suggests warmer conditions south of the APF and reduced sea ice over the drifts. Analyses of the coarse-grained terrigenous fraction (pebbles and coarse sand) from Sites 1096 and 1101 record glaciers at sea-level releasing iceberg-rafted debris (IRD) throughout the last 3.1 m.y. Analyses of quartz sand grains in IRD with the scanning electron microscope (SEM) show an abrupt change in the frequency of occurrence of microtextures at ~1.35 Ma. During the Late Pliocene to Early Pleistocene, the population of quartz grains included completely weathered grains and a low frequency of crushing and abrasion, suggesting that glaciers were small and did not inundate the topography. Debris shed from mountain peaks was transported supraglacially or englacially allowing weathered grains to pass through the glacier unmodified. During glacial periods from 1.35-0.76 Ma, glaciers expanded in size. The IRD flux was very high and dropstones have diverse lithologies. Conditions resembling those at the Last Glacial Maximum (LGM) have been episodically present on the Antarctic Peninsula since ~0.76 Ma. Quartz sand grains show high relief, fracture and abrasion common under thick ice and the IRD flux is low with a more restricted range of dropstone lithologies.

Abiotic characteristics and diatom abundance and biomass in different sectors of the Argentinien Shelf and antartic waters

A large spatial scale study of the diatom species inhabiting waters from the subantarctic (Argentine shelf) to antarctic was made for the first time in order to understand the relationships between these two regions with regard to the fluctuations in diatom abundances in relation with environmental features, their floristic associations and the effect of the Polar Front as a biogeographic barrier. Species-specific diatom abundance, nutrient and chlorophyll-a concentration were assessed from 64 subsurface oceanographic stations carried out during the austral summer 2002, a period characterized by an anomalous sea-ice coverage corresponding to a ''warm year". Significant relationships of both diatom density and biomass with chlorophyll-a (positive) and water temperature (negative) were found for the study area as a whole. Within the Subantarctic region, diatom density and biomass values were more uniform and significantly (in average: 35 and 11 times) lower than those of the Antarctic region, and did not correlate with chlorophyll-a. In antarctic waters, instead, biomass was directly related with chlorophyll-a, thus confirming the important contribution of diatoms to the Antarctic phytoplanktonic stock. A total of 167 taxa were recorded for the entire study area, with Chaetoceros and Thalassiosira being the best represented genera. Species richness was maximum in subantarctic waters (46; Argentine shelf) and minimum in the Antarctic region (21; Antarctic Peninsula), and showed a significant decrease with latitude. Floristic associations were examined both qualitatively (Jaccard Index) and quantitatively (correlation) by cluster analyses and results allowed differentiating a similar number of associations (12 vs. 13, respectively) and two main groups of stations. In the Drake Passage, the former revealed that the main floristic change was found at the Polar Front, while the latter reflected the Southern ACC Front as a main boundary, and yielded a higher number of isolated sites, most of them located next to different Antarctic islands. Such differences are attributed to the high relative density of Fragilariopsis kerguelensis in Argentine shelf and Drake Passage waters and of Porosira glacialis and species of Chaetoceros and Thalasiosira in the Weddell Sea and near the Antarctic Peninsula. From a total of 84 taxa recorded in antarctic waters, only 17 were found exclusively in this region, and the great majority (67) was also present in subantarctic waters but in extremely low (< 1 cell/l) concentrations, probably as a result of expatriation processes via the ACC-Malvinas Current system. The present results were compared with those of previous studies on the Antarctic region with respect to both diatom associations in regular vs. atypically warm years, and the distribution and abundance of some selected planktonic species reported for surface sediments.

Planktic foraminiferal and sea surface temperature record during the last 1 Myr across the Subtropical Front, Southwest Pacific

Planktic foraminiferal faunas and modern analogue technique estimates of sea surface temperature (SST) for the last 1 million years (Myr) are compared between core sites to the north (ODP 1125, 178 faunas) and south (DSDP 594, 374 faunas) of the present location of the Subtropical Front (STF), east of New Zealand. Faunas beneath cool subtropical water (STW) north of the STF are dominated by dextral Neogloboquadrina pachyderma, Globorotalia inflata, and Globigerina bulloides, whereas faunas to the south are strongly dominated by sinistral N. pachyderma (80-95% in glacials), with increased G. bulloides (20-50%) and dextral N. pachyderma (15-50%) in interglacials (beneath Subantarctic Water, or SAW). Canonical correspondence analysis indicates that at both sites, SST and related factors were the most important environmental influences on faunal composition. Greater climate-related faunal fluctuations occur in the south. Significant faunal changes occur through time at both sites, particularly towards the end of the mid-Pleistocene climate transition, MIS18-15 (e.g., decline of Globorotalia crassula in STW, disappearance of Globorotalia puncticulata in SAW), and during MIS8-5. Interglacial SST estimates in the north are similar to the present day throughout the last 1 Myr. To the south, interglacial SSTs are more variable with peaks 4-7 °C cooler than present through much of the early and middle Pleistocene, but in MIS11, MIS5.5, and early MIS1, peaks are estimated to have been 2-4 °C warmer than present. These high temperatures are attributed to southward spread of the STF across the submarine Chatham Rise, along which the STF appears to have been dynamically positioned throughout most of the last 1 Myr. For much of the last 1 Myr, glacial SST estimates in the north were only 1-2 °C cooler than the present interglacial, except in MIS16, MIS8, MIS6, and MIS4-2 when estimates are 4-7 °C cooler. These cooler temperatures are attributed to jetting of SAW through the Mernoo Saddle (across the Chatham Rise) and/or waning of the STW current. To the south, glacial SST estimates were consistently 10-11 °C cooler than present, similar to temperatures and faunas currently found in the vicinity of the Polar Front. One interpretation is that these cold temperatures reflect thermocline changes and increased Circumpolar Surface Water spinning off the Subantarctic Front as an enhanced Bounty Gyre along the south side of the Chatham Rise. For most of the last 1 Myr, the temperature gradient across the STF has been considerably greater than the present 4 °C. During glacial episodes, the STF in this region did not migrate northwards, but instead there was an intensification of the temperature gradient across it (interglacials 4-11 °C; glacials 8-14 °C).

(Table 1) Diatom mats from ODP Leg 177 Sites in the Southern Ocean, Atlantic Sector

The interaction between biogenic silica export and burial, paleoceanography, diatom species succession and mats formation was examined based on relative abundances data of Plio/Pleistocene diatoms from six cores recovered during ODP Leg 177 on a transect across the Antarctic Circumpolar Current (ACC) in the Atlantic sector of the Southern Ocean. Fragilariopsis kerguelensis, Actinocyclus ingens and species of the genus Thalassiothrix were the main contributors to the diatom assemblages. Three main steps marked the development of the silica system in the Southern Ocean: Step 1 (at ca. 2.77 Ma), establishment of increased biogenic silica burial in the Antarctic Circumpolar Current area, following the large-scale oceanic reorganization connected to the increased northern hemisphere glaciation; Step 2 (at ca. 1.93 Ma), the Antarctic Polar Front becomes the main biogenic silica sink, diatom mats are widespread, and are also found slightly to the north and south of the APF; Step 3 (at ca. 0.63 Ma), with the strong drop in abundance (and later extinction at 0.38 Ma) of A. ingens and the rise to dominance of F. kerguelensis, the system enters a glacial-interglacial mode, with diatom mats occurring during interglacials at the APF and in the Antarctic Zone, but disappearing north of it.

Relative abundance and ranges of selected diatoms from Pliocene-Pleistocene sections of ODP Leg 177, Atlantic sector of the Southern Ocean

During Ocean Drilling Program (ODP) Leg 177, seven sites were drilled aligned on a transect across the Antarctic Circumpolar Current in the Atlantic sector of the Southern Ocean. The primary scientific objective of Leg 177 was the study of the Cenozoic paleoceanographic and paleoclimatic history of the southern high latitudes and its relationship with the Antarctic cryosphere development. Of special emphasis was the recovery of Pliocene-Pleistocene sections, allowing paleoceanographic studies at millennial or higher time resolution, and the establishment of refined biostratigraphic zonations tied to the geomagnetic polarity record and stable isotope records. At most sites, multiple holes were drilled to ensure complete recovery of the section. A description of the recovered sections and the construction of a multihole splice for the establishment of a continuous composite is presented in the Leg 177 Initial Reports volume for each of the sites (Gersonde, Hodell, Blum, et al., 1999). Here we present the relative abundance pattern and the stratigraphic ranges of diatom taxa encountered from shore-based light microscope studies completed on the Pliocene-Pleistocene sequences from six of the drilled sites (Sites 1089-1094). No shore-based diatom studies have been conducted on the Pliocene-Pleistocene sediments obtained at Site 1088, located on the northern crest of the Agulhas Ridge, because of the scattered occurrence and poor preservation of diatoms in these sections (Shipboard Scientific Party, 1999b). The data included in our report present the baseline of a diatom biostratigraphic study of Zielinski and Gersonde (2002), which (1) includes a refinement of the southern high-latitude Pliocene-Pleistocene diatom zonation, in particular for the middle and late Pleistocene, and (2) presents a biostratigraphic framework for the establishment of age models of the recovered sediment sections. Zielinski and Gersonde (2002) correlated the diatom ranges with the geomagnetic polarity record established shipboard (Sites 1090 and 1092) (Shipboard Scientific Party, 1999c, 1999d) and on shore (Sites 1089, 1091, 1093, and 1094) by Channell and Stoner (2002). The Pliocene-Pleistocene diatom zonation proposed by Zielinski and Gersonde (2002) relies on a diatom zonation from Gersonde and Bárcena (1998) for the northern belt of the Southern Ocean. Because of latitudinal differentiation of sea-surface temperature, nutrients, and salinity between Antarctic and Subantarctic/subtropical water masses, the Pliocene-Pleistocene stratigraphic marker diatoms are not uniformly distributed in the Southern Ocean (Fenner, 1991; Gersonde and Bárcena, 1998). As a consequence, Zielinski and Gersonde (2002) propose two diatom zonations for application in the Antarctic Zone south of the Polar Front (Southern Zonation, Sites 1094 and 1093) and the area encompassing the Polar Front Zone (PFZ) and the Subantarctic Zone (Northern Zonation, Sites 1089-1092). This accounts especially for the Pleistocene zonation where Hemidiscus karstenii, whose first abundant occurrence datum and last occurrence datum defines the subzonation of the northern Thalassiosira lentiginosa Zone, occurs only sporadically in the cold-water realm south of the PFZ and thus is not applicable in sections from this area. However, newly established marker species assigned to the genus Rouxia (Rouxia leventerae and Rouxia constricta) are more related to cold-water environments and allow a refinement of the Pleistocene stratigraphic zonation for the southern cold areas. A study relying on quantitative counts of both Rouxia species confirms the utility of these stratigraphic markers for the identification of sequences attributed to marine isotope Stages 6 and 8 in the southern Southern Ocean (Zielinski et al., 2002).

Stable isotope record of planktonic foraminifera from sediment core MD96-2085

A high-resolution (~4-5cm/kyr) giant piston core record (MD962085) retrieved during an IMAGES II-NAUSICAA cruise from the continental slope of the southeast Atlantic Ocean reveals striking variations in planktonic foraminifer faunal abundances and sea-surface temperatures (SST) during the past 600 000 yr. The location and high-quality sedimentary record of the core provide a good opportunity to assess the variability of the Benguela Current system and associated important features of the ocean-climate system in the southeast Atlantic. The planktonic foraminifer faunal abundances of the core are dominated by three assemblages: (1) Neogloboquadrina pachyderma (right coiling) + Neogloboquadrina dutertrei, (2) Globigerina bulloides, and (3) Globorotalia inflata. The assemblage of N. pachyderma (right coiling) + N. dutertrei shows distinctive abundance changes which are nearly in-phase with glacial-interglacial variations. The high abundances of this assemblage are associated with major glacial conditions, possibly representing low SST/high nutrient level conditions in the southwestern Africa margin. In contrast, the G. bulloides and G. inflata assemblages show greater high-frequency abundance change patterns, which are not parallel to the glacial-interglacial changes. These patterns may indicate rapid oceanic frontal movements from the south, and a rapid change in the intensity of the Benguela upwelling system from the east. A single episode of maximum abundances of a polar water species N. pachyderma (left coiling) occurred in the beginning of stage 9 (~340-330 kyr). The event of the maximum occurrence of this species shown in this record may indicate instability in the Benguela coastal upwelling, or the Antarctic polar front zone position. A winter season SST estimate using transfer function techniques for this record shows primarily glacial-interglacial variations. The SST is maximal during the transitions from the major glacial to interglacial stages (Terminations I, II, IV, V), and is associated with the abundance maxima of a warm water species indicator Globigerinoides ruber. Cross-spectral analyses of the SST record and the SPECMAP stack reveal statistically significant concentrations of variance and coherencies in three major orbital frequency bands. The SST precedes changes in the global ice volume in all orbital frequency bands, indicating a dominant southern Hemispheric climate effect over the Benguela Current region in the southeast Atlantic.

Mineralogy and age determination of sediment core D11957P

The Tore Seamount is a circular, volcano-like feature 100 km in diameter with its summit at 2200 m water depth and a small, 5000 m deep basin in its interior. It is situated approximately 300 km west of Lisbon and is surrounded by deep abyssal plains. This site with a standard pelagic stratigraphy is the southernmost point where the so-called Heinrich events have so far been recorded. A succession of alternating interglacial/glacial periods reveals a stratigraphic record back to the beginning of isotopic stage 7 (225 kyr). Climatic changes are identifiable by coherent variations in colour, carbonate content and distribution of ice-rafted detritus in the carbonate-free fraction. Inputs of ice-rafted quartz are well defined. Characteristics in common with other sites showing Heinrich layers include a high terrigenous to biogenic ratio, a dramatic decrease in the accumulation rate of foraminifera shells, an increase in dolomite abundance and the occurrence of polar foraminiferal species indicating southwards penetration of cold waters which lead us to consider a wider southeastern extent of the North Atlantic ice-rafted detritus belt than hitherto. If the presently accepted position of the Polar Front is maintained, icebergs must have been swept southwards from the southern boundary of the pack ice in a current merging into the ancestral Canary Current, bringing ice-rafted material to the Tore Seamount. The coincidence of reddish-feldspar, probably derived from the northern Appalachian Triassic red facies, with the transparent quartz suggests at least a partial Labrador source for all the Heinrich layers here, including HL 3. In comparison to other sites in the entire North Atlantic, two exceptions stand out: the absence of HL 5 and the low detritus to biogenics ratio for HL 3. The simultaneous occurrence of these two types of ice-rafted minerals is a new piece in the puzzle of the origin of Heinrich layers.

Sedimentology of ODP Leg 119 samples

Cretaceous to Quaternary sediments recovered at Leg 119 Sites 738 and 744 on the southern tip of the Kerguelen Plateau were studied in order to determine the depositional environment and the paleoceanography of the southern Indian Ocean and especially the long-term glacial history of East Antarctica. Emphasis is given to bulk-sediment composition, grain-size data, and clay mineralogy. The sediment sequence at the two sites is generally of a highly pelagic character, with nannofossil oozes, chalks, and limestones dominant from the Turanian to upper Miocene and diatom oozes dominant within the uppermost Miocene to Holocene interval. The first indication of glaciation at sea level is the occurrence of isolated gravel and terrigenous sand grains, which indicate ice rafting in the middle Eocene interval of 45.0-42.3 Ma. A major intensification of glaciation, probably the onset of continental East Antarctic glaciation, is recorded in sediments of early Oligocene age (36.0 Ma). All major sediment parameters document this event. The clay mineralogy changes from smectite-dominated assemblages, typical of moderately warm and humid climatic conditions in which chemical weathering processes are prevalent, to illite- and chlorite-dominated assemblages, indicative of cooler climates and physical weathering. Ice-rafted debris of both gravel and sand size occurs in large quantities in that interval and coincides with a change in the mode of carbonate deposition. Carbonate contents are relatively high and uniform (90%-95%) in strata younger than early Oligocene; in Oligocene to upper Miocene strata they fluctuate between 65% and 95%. Oligocene and Neogene hiatuses reflect an intensification of oceanic circulation and the increased erosional force of Circumpolar Deep Water. The long-term Cenozoic cooling trend was interrupted by a phase of early Miocene warming indicated by maximum Neogene smectite concentrations. Although ice-rafted debris is present only in minor amounts and mainly in the silt fraction of early Oligocene to late Miocene age, it shows that glaciers advanced to the East Antarctic shoreline throughout that time. Ice-rafting activity drastically increased in latest Miocene time, when carbonate deposition decreased and diatom ooze sedimentation started. This suggests a pronounced intensification of Antarctic glaciation combined with a northward migration of the Polar Front.

(Table 1) Water column biogenic silica concentrations and Si isotopic composition during Marion Dufresne cruise MD166 off South Africa

Southern Ocean biogeochemical processes have an impact on global marine primary production and global elemental cycling, e.g. by likely controlling glacial-interglacial pCO2 variation. In this context, the natural silicon isotopic composition (d30Si) of sedimentary biogenic silica has been used to reconstruct past Si-consumption:supply ratios in the surface waters. We present a new dataset in the Southern Ocean from a IPY-GEOTRACES transect (Bonus-GoodHope) which includes for the first time summer d30Si signatures of suspended biogenic silica (i) for the whole water column at three stations and (ii) in the mixed layer at seven stations from the subtropical zone up to the Weddell Gyre. In general, the isotopic composition of biogenic opal exported to depth was comparable to the opal leaving the mixed layer and did not seem to be affected by any diagenetic processes during settling, even if an effect of biogenic silica dissolution cannot be ruled out in the northern part of the Weddell Gyre. We develop a mechanistic understanding of the processes involved in the modern Si-isotopic balance, by implementing a mixed layer model. We observe that the accumulated biogenic silica (sensu Rayleigh distillation) should satisfactorily describe the d30Si composition of biogenic silica exported out of the mixed layer, within the limit of the current analytical precision on the d30Si. The failures of previous models (Rayleigh and steady state) become apparent especially at the end of the productive period in the mixed layer, when biogenic silica production and export are low. This results from (1) a higher biogenic silica dissolution:production ratio imposing a lower net fractionation factor and (2) a higher Si-supply:Si-uptake ratio supplying light Si-isotopes into the mixed layer. The latter effect is especially expressed when the summer mixed layer becomes strongly Si-depleted, together with a large vertical silicic acid gradient, e.g. in the Polar Front Zone and at the Polar Front.