Opal chemistry of costal Antarctic sediments

During the last 50 years, the Antarctic Peninsula has experienced rapid warming with associated retreat of 87% of marine and tidewater glacier fronts. Accelerated glacial retreat and iceberg calving may have a significant impact on the freshwater and nutrient supply to the phytoplankton communities of the highly productive coastal regions. However, commonly used biogenic carbonate proxies for nutrient and salinity conditions are not preserved in sediments from coastal Antarctica. Here we describe a method for the measurement of zinc to silicon ratios in diatom opal, (Zn/Si)opal, which is a potential archive in Antarctic marine sediments. A core top calibration from the West Antarctic Peninsula shows (Zn/Si)opal is a proxy for mixed layer salinity. We present down-core (Zn/Si)opal paleosalinity records from two rapidly accumulating sites taken from nearshore environments off the West Antarctic Peninsula which show an increase in meltwater input in recent decades. Our records show that the recent melting in this region is unprecedented for over 120 years.

Profiles of iron concentration from GoFlow bottles during the CARUSO-EISENEX experiment

An in situ iron enrichment experiment was carried out in the Southern Ocean Polar Frontal Zone and fertilized a patch of water within an eddy of the Antarctic Circumpolar Current (EisenEx, Nov. 2000). During the experiment, a physical speciation technique was used for iron analysis in order to understand the changes in iron distribution and size-fractionations, including soluble Fe (<200 kDa), colloidal Fe (200 kDa-0.2 µm) and labile particle Fe (>0.2 µm), throughout the development of the phytoplankton bloom. Prior to the first infusion of iron, dissolved (<0.2 µm) iron concentrations in the ambient surface seawater were extremely low (0.06±0.015 nM) with colloidal iron being a minor fraction. For the iron addition, an acidified FeSO4 solution was released three times over a 23-day period to the eddy. High levels of dissolved iron concentrations (2.0±1.1 nM) were measured in the surface water until 4 days after the first iron infusion. After every iron infusion, when high iron concentrations were observed before storm events, there was a significant correlation between colloidal and dissolved iron concentrations ([Colloidal Fe]=0.7627[Dissolved Fe]+0.0519, R2=0.9346). These results indicate that a roughly constant proportion of colloidal vs. dissolved iron was observed after iron infusion (~76%). Storm events caused a significant decrease in iron concentrations (<0.61 nM in dissolved iron) and changed the proportions of the three iron size-fractions (soluble, colloidal and labile particle). The changes in each iron size-fraction indicate that colloidal iron was eliminated from surface mixed layer more easily than particulate and soluble fractions. Therefore, particle and soluble iron efficiently remain in the mixed layer, probably due to the presence of suspended particles and naturally dissolved organic ligands. Our data suggest that iron removal through colloidal aggregation during phytoplankton bloom should be considered in the oceanic iron cycle.

Chemical composition of samples from DSDP Holes 16-163 and 17-164

Considerable postsedimentational alteration of fine dispersed minerals in Cretaceous sedimentary sequences was found in three deep-sea drillholes (163, 164, 169). Original Fe-montmorillonites formed from basalts were converted during lithification to mixed-layer montmorillonite-hydromicas and then to pure hydromicas (celadonites). An assumption that the minerals were originally of authigenic-diagenetic composition is based on a broad spectrum of other diagenetic minerals present: silica group from opal A to opal CT and quartz, clinoptilolite and palygorskite. In addition, quartz-hydromica ratio is strikingly atypical of aeolian transport.

Underway measurements of dissolved gases along POLARSTERN cruise track ANT-XXVII/2

We present measurements of pCO2, O2 concentration, biological oxygen saturation (Delta O2/Ar) and N2 saturation (Delta N2) in Southern Ocean surface waters during austral summer, 2010-2011. Phytoplankton biomass varied strongly across distinct hydrographic zones, with high chlorophyll a (Chla) concentrations in regions of frontal mixing and sea-ice melt. pCO2 and Delta O2 /Ar exhibited large spatial gradients (range 90 to 450 µatm and -10 to 60%, respectively) and co-varied strongly with Chla. However, the ratio of biological O2 accumulation to dissolved inorganic carbon (DIC) drawdown was significantly lower than expected from photosynthetic stoichiometry, reflecting the differential time-scales of O2 and CO2 air-sea equilibration. We measured significant oceanic CO2 uptake, with a mean air-sea flux (~ -20 mmol m-2 d-1) that significantly exceeded regional climatological values. N2 was mostly supersaturated in surface waters (mean Delta N2 of +2.5 %), while physical processes resulted in both supersaturation and undersaturation of mixed layer O2 (mean Delta O2phys = 2.1 %). Box model calculations were able to reproduce much of the spatial variability of Delta N2 and Delta O2phys along the cruise track, demonstrating significant effects of air-sea exchange processes (e.g. atmospheric pressure changes and bubble injection) and mixed layer entrainment on surface gas disequilibria. Net community production (NCP) derived from entrainment-corrected surface Delta O2 /Ar data, ranged from ~ -40 to > 300 mmol O2 m-2 d-1 and showed good coherence with independent NCP estimates based on seasonal mixed layer DIC deficits. Elevated NCP was observed in hydrographic frontal zones and regions of sea-ice melt with shallow mixed layer depths, reflecting the importance of mixing in controlling surface water light and nutrient availability.

Oxygen Utilization and Downward Carbon Flux in an Oxygen-Depleted Eddy in the Eastern Tropical North Atlantic

The occurrence of mesoscale eddies that develop suboxic environments at shallow depth (about 40-100 m) has recently been reported for the eastern tropical North Atlantic (ETNA). Their hydrographic structure suggests that the water mass inside the eddy is well isolated from ambient waters supporting the development of severe near-surface oxygen deficits. So far, hydrographic and biogeochemical characterization of these eddies was limited to a few autonomous surveys, with the use of moorings, under water gliders and profiling floats. In this study we present results from the first dedicated biogeochemical survey of one of these eddies conducted in March 2014 near the Cape Verde Ocean Observatory (CVOO). During the survey the eddy core showed oxygen concentrations as low as 5 µmol kg-1 with a pH of around 7.6 at approximately 100 m depth. Correspondingly, the aragonite saturation level dropped to 1 at the same depth, thereby creating unfavorable conditions for calcifying organisms. To our knowledge, such enhanced acidity within near-surface waters has never been reported before for the open Atlantic Ocean. Vertical distributions of particulate organic matter and dissolved organic matter (POM and DOM), generally showed elevated concentrations in the surface mixed layer (0-70 m), with DOM also accumulating beneath the oxygen minimum. With the use of reference data from the upwelling region where these eddies are formed, the oxygen utilization rate was calculated by determining oxygen consumption through the remineralization of organic matter. Inside the core, we found these rates were almost 1 order of magnitude higher (apparent oxygen utilization rate (aOUR); 0.26 µmol kg-1 day-1) than typical values for the open North Atlantic. Computed downward fluxes for particulate organic carbon (POC), were around 0.19 to 0.23 g C m-2 day-1 at 100 m depth, clearly exceeding fluxes typical for an oligotrophic open-ocean setting. The observations support the view that the oxygen-depleted eddies can be viewed as isolated, westwards propagating upwelling systems of their own, thereby represent re-occurring alien biogeochemical environments in the ETNA.

Sea surface temperatures reconstructed from alkenones of surface sediment samples of the Argentine Basin at stations GeoB1501-1 to GeoB2830-1

We analysed the alkenone unsaturation ratio (UK'37) in 87 surface sediment samples from the western South Atlantic (5°N-50°S) in order to evaluate its applicability as a paleotemperature tool for this part of the ocean. The measured UK'37 ratios were converted into temperature using the global core-top calibration of Müller et al. (1998, doi:10.1016/S0016-7037(98)00097-0) and compared with annual mean atlas sea-surface temperatures (SSTs) of overlying surface waters. The results reveal a close correspondence (<1.5°C) between atlas and alkenone temperatures for the Western Tropical Atlantic and the Brazil Current region north of 32°S, but deviating low alkenone temperatures by -2° to -6°C are found in the regions of the Brazil-Malvinas Confluence (35-39°S) and the Malvinas Current (41-48°S). From the oceanographic evidence these low UK'37 values cannot be explained by preferential alkenone production below the mixed layer or during the cold season. Higher nutrient availability and algal growth rates are also unlikely causes. Instead, our results imply that lateral displacement of suspended particles and sediments, caused by strong surface and bottom currents, benthic storms, and downslope processes is responsible for the deviating UK'37 temperatures. In this way, particles and sediments carrying a cold water UK'37 signal of coastal or southern origin are transported northward and offshore into areas with warmer surface waters. In the northern Argentine Basin the depth between displaced and unaffected sediments appears to coincide with the boundary between the northward flowing Lower Circumpolar Deep Water (LCDW) and the southward flowing North Atlantic Deep Water (NADW) at about 4000 m.

Planktonic foraminiferal flux and shell geochemistry data in the sediment trap time series JAM 1-3 off south Java

Results from sediment trap experiments conducted in the seasonal upwelling area off south Java from November 2000 until July 2003 revealed significant monsoon-, El Niño-Southern Oscillation-, and Indian Ocean Dipole-induced seasonal and interannual variations in flux and shell geochemistry of planktonic foraminifera. Surface net primary production rates together with total and species-specific planktonic foraminiferal flux rates were highest during the SE monsoon-induced coastal upwelling period from July to October, with three species Globigerina bulloides, Neogloboquadrina pachyderma dex., and Globigerinita glutinata contributing to 40% of the total foraminiferal flux. Shell stable oxygen isotopes (d18O) and Mg/Ca data of Globigerinoides ruber sensu stricto (s.s.), G. ruber sensu lato (s.l.), Neogloboquadrina dutertrei, Pulleniatina obliquiloculata, and Globorotalia menardii in the sediment trap time series recorded surface and subsurface conditions. We infer habitats of 0-30 m for G. ruber at the mixed layer depth, 60-80 m (60-90 m) for P. obliquiloculata (N. dutertrei) at the upper thermocline depth, and 90-110 m (100-150 m) for G. menardii in the 355-500 mm (>500 µm) size fraction corresponding to the (lower) thermocline depth in the study area. Shell Mg/Ca ratio of G. ruber (s.l. and s.s.) reveals an exponential relationship with temperature that agrees with published relationships particularly with the Anand et al. (2003) equations. Flux-weighted foraminiferal data in sediment trap are consistent with average values in surface sediment samples off SW Indonesia. This consistency confirms the excellent potential of these proxies for reconstructing past environmental conditions in this part of the ocean realm.

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.

Middle Miocene evolution and stable isotope ratios of Globorotalia (Fohsella) in the western equatorial Pacific

Evolution of the planktic foraminiferal lineage Globorotalia (Fohsella) occurred during the Miocene between 23.7 and 11.8 Ma and forms the basis for stratigraphic subdivision of the early middle Miocene (Zones N 10 through N 12). Important morphologic changes within the G. (Fohsella) lineage included a marked increase in test size, a transition from a rounded to an acute periphery, and the development of a keel in later forms. We found that the most rapid changes in morphology of G. (Fohsella) occurred between 13 and 12.7 Ma and coincided with an abrupt increase in the delta18O ratios of shell calcite. Comparison of isotopic results of G. (Fohsella) with other planktic foraminifers indicate that delta18O values of the lineage diverge from surface-dwelling species and approach deep-dwelling species after 13.0 Ma, indicating a change in depth habitat from the surface mixed layer to intermediate depth near the thermocline. Isotopic and faunal evidence suggests that this change in depth stratification was associated with an expansion of the thermocline in the western equatorial Pacific. After adapting to a deeper water habitat at 13.0 Ma, the G. (Fohsella) lineage became extinct abruptly at 11.8 Ma during a period when isotopic and faunal evidence suggest a shoaling of the thermocline. Following the extinction of G. (Fohsella), the ecologic niche of the lineage was filled by the Globorotalia (Menardella) group, which began as a deep-water form and later evolved to an intermediate-water habitat. We suggest that the evolution of G. (Fohsella) and G. (Menardella) were tightly linked to changes in the structure of the thermocline in the western equatorial Pacific.

Upper-Pleistocene terrace deposits in Mediterranean climate: geomorphological and source-rock control on mineral and geochemical signatures (Betic Cordillera, SE Spain)

Mineral and chemical composition of alluvial Upper-Pleistocene deposits from the Alto Guadalquivir Basin (SE Spain) were studied as a tool to identify sedimentary and geomorphological processes controlling its formation. Sediments located upstream, in the north-eastern sector of the basin, are rich in dolomite, illite, MgO and KB2BO. Downstream, sediments at the sequence base are enriched in calcite, smectite and CaO, whereas the upper sediments have similar features to those from upstream. Elevated rare-earth elements (REE) values can be related to low carbonate content in the sediments and the increase of silicate material produced and concentrated during soil formation processes in the neighbouring source areas. Two mineralogical and geochemical signatures related to different sediment source areas were identified. Basal levels were deposited during a predominantly erosive initial stage, and are mainly composed of calcite and smectite materials enriched in REE coming from Neogene marls and limestones. Then the deposition of the upper levels of the alluvial sequences, made of dolomite and illitic materials depleted in REE coming from the surrounding Sierra de Cazorla area took place during a less erosive later stage of the fluvial system. Such modification was responsible of the change in the mineralogical and geochemical composition of the alluvial sediments.

The significance of nitrogen regeneration for new production within a filament of the Mauritanian upwelling system

The Lagrangian progression of a biological community was followed in a filament of the Mauritanian upwelling system, north-west Africa, during offshore advection. The inert dual tracers sulfur hexafluoride and helium-3 labelled a freshly upwelled patch of water that was mapped for 8 days. Changes in biological, physical, and chemical characteristics were measured, including phytoplankton productivity, nitrogen assimilation, and regeneration. Freshly upwelled water contained high nutrient concentrations but was depleted in N compared to Redfield stoichiometry. The highest rate of primary productivity was measured on the continental shelf, associated with high rates of nitrogen assimilation and a phytoplankton community dominated by diatoms and flagellates. Indicators of phytoplankton abundance and activity decreased as the labelled water mass transited the continental shelf slope into deeper water, possibly linked to the mixed layer depth exceeding the light penetration depth. By the end of the study, the primary productivity rate decreased and was associated with lower rates of nitrogen assimilation and lower nutrient concentrations. Nitrogen regeneration and assimilation took place simultaneously. Results highlighted the importance of regenerated NHC 4 in sustaining phytoplankton productivity and indicate that the upwelled NO3 pool contained an increasing fraction of regenerated NO3 as it advected offshore. By calculating this fraction and incorporating it into an f ratio formulation, we estimated that of the 12:38Tg C of annual regional production, 4:73Tg C was exportable.

The significance of nitrogen regeneration for new production within a filament of the Mauritanian upwelling system

The Lagrangian progression of a biological community was followed in a filament of the Mauritanian upwelling system, north-west Africa, during offshore advection. The inert dual tracers sulfur hexafluoride and helium-3 labelled a freshly upwelled patch of water that was mapped for 8 days. Changes in biological, physical, and chemical characteristics were measured, including phytoplankton productivity, nitrogen assimilation, and regeneration. Freshly upwelled water contained high nutrient concentrations but was depleted in N compared to Redfield stoichiometry. The highest rate of primary productivity was measured on the continental shelf, associated with high rates of nitrogen assimilation and a phytoplankton community dominated by diatoms and flagellates. Indicators of phytoplankton abundance and activity decreased as the labelled water mass transited the continental shelf slope into deeper water, possibly linked to the mixed layer depth exceeding the light penetration depth. By the end of the study, the primary productivity rate decreased and was associated with lower rates of nitrogen assimilation and lower nutrient concentrations. Nitrogen regeneration and assimilation took place simultaneously. Results highlighted the importance of regenerated NHC 4 in sustaining phytoplankton productivity and indicate that the upwelled NO3 pool contained an increasing fraction of regenerated NO3 as it advected offshore. By calculating this fraction and incorporating it into an f ratio formulation, we estimated that of the 12:38Tg C of annual regional production, 4:73Tg C was exportable.

Evidence for methane production by the marine algae Emiliania huxleyi

Methane (CH4), an important greenhouse gas that affects radiation balance and consequently the earth's climate, still has uncertainties in its sinks and sources. The world's oceans are considered to be a source of CH4 to the atmosphere, although the biogeochemical processes involved in its formation are not fully understood. Several recent studies provided strong evidence of CH4 production in oxic marine and freshwaters, but its source is still a topic of debate. Studies of CH4 dynamics in surface waters of oceans and large lakes have concluded that pelagic CH4 supersaturation cannot be sustained either by lateral inputs from littoral or benthic inputs alone. However, regional and temporal oversaturation of surface waters occurs frequently. This comprises the observation of a CH4 oversaturating state within the surface mixed layer, sometimes also termed the "oceanic methane paradox". In this study we considered marine algae as a possible direct source of CH4. Therefore, the coccolithophore Emiliania huxleyi was grown under controlled laboratory conditions and supplemented with two 13C-labeled carbon substrates, namely bicarbonate and a position-specific 13C-labeled methionine (R-S-13CH3). The CH4 production was 0.7 µg particular organic carbon (POC) g−1 d−1, or 30 ng g−1 POC h−1. After supplementation of the cultures with the 13C-labeled substrate, the isotope label was observed in headspace CH4. Moreover, the absence of methanogenic archaea within the algal culture and the oxic conditions during CH4 formation suggest that the widespread marine algae Emiliania huxleyi might contribute to the observed spatially and temporally restricted CH4 oversaturation in ocean surface waters.