Exploring the potential of clumped isotope thermometry on coccolith-rich sediments as a sea surface temperature proxy

Understanding past changes in sea surface temperatures (SSTs) is crucial; however, existing proxies for reconstructing past SSTs are hindered by unknown ancient seawater composition (foraminiferal Mg/Ca and d18O), or reflect subsurface temperatures (TEX86) or have a limited applicable temperature range (Uk'37). We examine clumped isotope (D47) thermometry to fossil coccolith-rich material as an SST proxy, as clumped isotopes are independent of original seawater composition and applicable to a wide temperature range and coccolithophores are widespread and dissolution resistant. The D47-derived temperatures from <63, <20, <10 and 2-5 µm size fractions of two equatorial Pacific late Miocene-early Pliocene sediment samples (c1; c2) range between ~18-29 {degree sign}C, with c1 temperatures consistently above c2. Removing the >63 µm fraction removes most non-mixed layer components; however, the D47-derived temperatures display an unexpected slight decreasing trend with decreasing size fraction. This unexpected trend could partly arise because larger coccoliths (5-12 µm) are removed during the size fraction separation process. The c1 and <63 µm c2 D47-derived temperatures are comparable to concurrent Uk'37 SSTs. The <20, <10 and 2-5 µm c2 D47-derived temperatures are consistently cooler than expected. The D47-Uk'37 temperature offset is probably caused by abiotic/diagenetic calcite present in the c2 2-5 µm fraction (~53% by area), which potentially precipitated at bottom water temperatures of ~6 {degree sign}C . Our results indicate that clumped isotopes on coccolith-rich sediment fractions have potential as an SST proxy, particularly in tropical regions, providing that careful investigation of the appropriate size fraction for the region and timescale is undertaken.

The seasonal sea-ice zone in the glacial Southern Ocean as a carbon sink, supplementary datasets

Reduced surface-deep ocean exchange and enhanced nutrient consumption by phytoplankton in the Southern Ocean have been linked to lower glacial atmospheric CO2. However, identification of the biological and physical conditions involved and the related processes remains incomplete. Here we specify Southern Ocean surface-subsurface contrasts using a new tool, the combined oxygen and silicon isotope measurement of diatom and radiolarian opal, in combination with numerical simulations. Our data do not indicate a permanent glacial halocline related to melt water from icebergs. Corroborated by numerical simulations, we find that glacial surface stratification was variable and linked to seasonal sea-ice changes. During glacial spring-summer, the mixed layer was relatively shallow, while deeper mixing occurred during fall-winter, allowing for surface-ocean refueling with nutrients from the deep reservoir, which was potentially richer in nutrients than today. This generated specific carbon and opal export regimes turning the glacial seasonal sea-ice zone into a carbon sink.

(Fig. 4) Multiproxy data set of box core MSM5/5-712-1

A multiproxy data set of an AMS radiocarbon dated 46 cm long sediment core from the continental margin off western Svalbard reveals multidecadal climatic variability during the past two millennia. Investigation of planktic and benthic stable isotopes, planktic foraminiferal fauna, and lithogenic parameters aims to unveil the Atlantic Water advection to the eastern Fram Strait by intensity, temperatures, and salinities. Atlantic Water has been continuously present at the site over the last 2,000 years. Superimposed on the increase in sea ice/icebergs, a strengthened intensity of Atlantic Water inflow and seasonal ice-free conditions were detected at ~ 1000 to 1200 AD, during the well-known Medieval Climate Anomaly (MCA). However, temperatures of the MCA never exceeded those of the 20th century. Since ~ 1400 AD significantly higher portions of ice rafted debris and high planktic foraminifer fluxes suggest that the site was located in the region of a seasonal highly fluctuating sea ice margin. A sharp reduction in planktic foraminifer fluxes around 800 AD and after 1730 AD indicates cool summer conditions with major influence of sea ice/icebergs. High amounts of the subpolar planktic foraminifer species Turborotalia quinqueloba in size fraction 150-250 µm indicate strengthened Atlantic Water inflow to the eastern Fram Strait already after ~ 1860 AD. Nevertheless surface conditions stayed cold well into the 20th century indicated by low planktic foraminiferal fluxes. Most likely at the beginning of the 20th century, cold conditions of the terminating Little Ice Age period persisted at the surface whereas warm and saline Atlantic Water already strengthened, hereby subsiding below the cold upper mixed layer. Surface sediments with high abundances of subpolar planktic foraminifers indicate a strong inflow of Atlantic Water providing seasonal ice-free conditions in the eastern Fram Strait during the last few decades.

Coccolithophores in surface sediments of the Arabian Sea (TAble 1)

One hundred surface sediment samples of the Arabian Sea (Indian Ocean) were investigated and relative abundances of coccoliths were compared to mean annual gradients of temperature, salinity, chlorophyll, PO4 and mixed layer depth. Total coccolith concentrations ranged from 42*10**6/g sediment in coastal areas to more than 19000*10**6/g sediment in oceanic regions. The general distribution does not seem to be dependent on coccolithophore productivity in surface waters alone, but also on the diluting input of terrigenous material. A total of 27 taxa were identified. The main species dominating the assemblages were Gephyrocapsa oceanica, Emiliania huxleyi and Florisphaera profunda with a combined average abundance of more than 70%. Several species and species groups reflect with their distribution the environmental parameters of the overlying water masses and may be successfully used to improve palaeoclimatic reconstructions, e.g. (a) F. profunda exhibits a high similarity or even positive correlation to the mean annual mixed layer depth, (b) calciosolenids can be described as coastal or shelf species. While temperature and salinity gradients do not seem to be crucial for coccolithophores in this region, the mean mixed layer depth as well as the PO4 concentration (representative for total nutrient availability) may control in part the coccolithophore assemblages. According to the results of a cluster analysis and the distribution pattern of all species, it was possible to differentiate three main coccolithophore assemblages. A G. oceanica dominated assemblage mainly occurs in the northern part of the study area and can be described as 'high nutrient assemblage'. The second assemblage, dominated by F. profunda, may be typical for oligotrophic and stable conditions in open ocean waters. A third assemblage, with high amounts of 'coastal species', characterises coastal conditions on the shelves.

(Table 1) AMS-14C ages determined in pairs of spreiten and directly adjacent host sediment of cores M39029-4 and M29039-8

he downward transport of surface sediment deep into the sediment column by the Zoophycos-producing animal leads not only to large age differences between the Zoophycos structure and surrounding host sediment but also to large differences in age between different foraminifer species found inside the trace fossil. In the late Quaternary material from the southwestern Portuguese continental slope examined in this study, age differences of up to 2590 years were observed between the planktic foraminifer species Globigerinoides ruber and Globigerina bulloides. These differences are caused by the mixing of surface and host material with different abundances of the two species. If there are differences in the abundance of the two species at the surface and/or in the host sediment, plenty of relatively young foraminifers may be mixed with few relatively old ones, or vice versa. The age differences between species caused by the combination of deep-reaching bioturbation by the Zoophycos producer and abundance variations may be considerably larger than the age differences caused by the homogenizing bioturbation in the mixed layer.

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.