Oxygen isotopic measurements from Holcene of sediment core MD02-2529, tropical pacific

Changes in El Niño-Southern Oscillation (ENSO) variability are difficult to extract from paleoceanographic reconstructions because they are superimposed on changes in seasonal variability that modulate the first-order climate signal. Here we address this problem by reconstructing thermocline structure from a marine sediment core retrieved from the eastern equatorial Pacific. At the core location, changes in hydrologic parameters within the thermocline are linked to ENSO activity, with a reduced influence of seasonal variability compared to surface waters. We performed repeated isotopic analyses (d18O) on single specimens of the thermocline-dwelling planktonic foraminifera Neogloboquadrina dutertrei at several targeted time periods over the last 50 ka to extract the total thermocline variance, a parameter supposed to reveal changes in ENSO. No fundamental changes in amplitude and frequency of the events were detected despite differences in climatic background. However, our data suggest that long-term variations in the thermocline variability occurred over the last 50 ka, with the highest and lowest ENSO activities occurring during the last glacial period and the Last Glacial Maximum, respectively.

Stable isotope data and calcification temperature from planktic foraminifera in sediment core BOFS31/1K

Determining the past record of temperature and salinity of ocean surface waters is essential for understanding past changes in climate, such as those which occur across glacial-interglacial transitions. As a useful proxy, the oxygen isotope composition (delta18O) of calcite from planktonic foraminifera has been shown to reflect both surface temperature and seawater delta18O, itself an indicator of global ice volume and salinity (Shackleton, 1974; Rostek et al., 1993, doi:10.1038/364319a0). In addition, magnesium/calcium (Mg/Ca) ratios in foraminiferal calcite show a temperature dependence (Nürnberg, 1995, doi:10.2113/gsjfr.25.4.350; Nürnberg et al., 1996, doi:10.1016/0016-7037(95)00446-7; Lea et al., 1999, doi:10.1016/S0016-7037(99)00197-0) due to the partitioning of Mg during calcification. Here we demonstrate, in a field-based calibration experiment, that the variation of Mg/Ca ratios with temperature is similar for eight species of planktonic foraminifera (when accounting for Mg dissolution effects). Using a multi-species record from the Last Glacial Maximum in the North Atlantic Ocean we found that past temperatures reconstructed from Mg/Ca ratios followed the two other palaeotemperature proxies: faunal abundance (CLIMAP, 1981; Mix et al., 1999, doi:10.1029/1999PA900012) and alkenone saturation (Müller et al., 1998, doi:10.1016/S0016-7037(98)00097-0 ). Moreover, combining Mg/Ca and delta18O data from the same faunal assemblage, we show that reconstructed surface water delta18O from all foraminiferal species record the same glacial-interglacial change-representing changing hydrography and global ice volume. This reinforces the potential of this combined technique in probing past ocean-climate interactions.

Phytoplanktonic microfossil groups of sediments from the South and Equatorial Atlantic

Individual planktonic microfossil species, or assemblage groups of different species, are often used to, qualitatively and/or quantitatively, reconstruct past (sub)surface-water conditions of the world's oceans and seas. Until now, little information has been available on the surface sediment distribution patterns and paleoenvironmental reconstruction potential of coccolith, calcareous dinoflagellate cyst and organic-walled dinoflagellate cyst assemblages of the South and equatorial Atlantic, especially at the species level. This paper (i) summarizes the distributions of these three phytoplanktonic microfossil groups in numerous Atlantic surface sediments from 20°N-50°S and 30°E-65°W and determines their relationship with the physicochemical and trophic conditions of the overlying (sub)surface-waters, and (ii) determines the synecology of the three phytoplankton groups by carrying out statistical analyses (i.e. detrended and canonical correspondence analyses) on all groups simultaneously. Ecological relationships are additionally strengthened by statistically comparing the distribution patterns of the phytoplankton groups with those of planktonic foraminifera (Pflaumann et al. 1996; Niebler et al. 1998), as the ecological preferences of the latter are much better known. Many of the analyzed phytoplanktonic microfossil species or groups of species in the surface sediments do show restricted distributions which primarily reflect the environmental conditions of the upper water masses above them (e.g. sea-surface temperature, productivity, stratification). The acquired 'reference' data sets are large and diverse enough to allow future development of transfer functions for the reconstruction of past surface-water conditions, and show that there is still an enormous paleoenvironmental reconstruction potential concealed in many fossil coccolith and dinoflagellate cyst assemblages.

Diatom-bound N isotope records over the last two glacial cycles in sediment core PS75/072-4

In a sediment core from the Pacific sector of the Antarctic Zone (AZ) of the Southern Ocean, we report diatom-bound N isotope (d15Ndb) records for total recoverable diatoms and two distinct diatom assemblages (pennate and centric rich). These data indicate tight coupling between the degree of nitrate consumption and Antarctic climate across the last two glacial cycles, with d15Ndb (and thus the degree of nitrate consumption) increasing at each major Antarctic cooling event. Coupled with evidence from opal- and barium-based proxies for reduced export production during ice ages, the d15Ndb increases point to ice age reductions in the supply of deep ocean-sourced nitrate to the AZ surface. The two diatom assemblages and species abundance data indicate that the d15Ndb changes are not the result of changing species composition. The pennate and centric assemblage d15Ndb records indicate similar changes but with a significant decline in their difference during peak ice ages. A tentative seasonality-based interpretation of the centric-to-pennate d15Ndb difference suggests that late summer surface waters became nitrate free during the peak glacials.

Seawater carbonate chemistry and processes during experiments with marine mussel, Mytilus galloprovincialis, 2005

In the context of future scenarios of progressive accumulation of anthropogenic CO2 in marine surface waters, the present study addresses the effects of long-term hypercapnia on a Mediterranean bivalve, Mytilus galloprovincialis. Sea-water pH was lowered to a value of 7.3 by equilibration with elevated CO2 levels. This is close to the maximum pH drop expected in marine surface waters during atmosextracellular pHric CO2 accumulation. Intra- and extracellular acid-base parameters as well as changes in metabolic rate and growth were studied under both normocapnia and hypercapnia. Long-term hypercapnia caused a permanent reduction in haemolymph pH. To limit the degree of acidosis, mussels increased haemolymph bicarbonate levels, which are derived mainly from the dissolution of shell CaCO3. Intracellular pH in various tissues was at least partly compensated; no deviation from control values occurred during long-term measurements in whole soft-body tissues. The rate of oxygen consumption fell significantly, indicating a lower metabolic rate. In line with previous reports, a close correlation became evident between the reduction in extracellular pH and the reduction in metabolic rate of mussels during hypercapnia. Analysis of frequency histograms of growth rate revealed that hypercapnia caused a slowing of growth, possibly related to the reduction in metabolic rate and the dissolution of shell CaCO3 as a result of extracellular acidosis. In addition, increased nitrogen excretion by hypercapnic mussels indicates the net degradation of protein, thereby contributing to growth reduction. The results obtained in the present study strongly indicate that a reduction in sea-water pH to 7.3 may be fatal for the mussels. They also confirm previous observations that a reduction in sea-water pH below 7.5 is harmful for shelled molluscs.

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.

(Appendix) Carbon and nitrogen isotope ratios of ODP Site 160-964

Nitrogen isotopes of chlorins, degradation products of chlorophyll, reflect the isotopic composition of nutrient N utilized by marine phytoplankton communities. Here we show that in sediments of the eastern Mediterranean Pleistocene and Holocene, values of d15N for chlorins and total nitrogen vary in concert, with a consistent offset of ~5 per mil reflecting the fractionation imparted during chlorophyll biosynthesis. Samples from the Integrated Ocean Drilling Program Sites 964 and 969 were analyzed at a sampling resolution of ~4-10 cm, clustered around sapropel events 2, 3, 4 and 5 (~100-170 ka). In low organic content sediments, chlorin values of ~0 per mil coincident with total nitrogen values of ~+ 5 per mil indicate that the latter reflects the original biomass and is not a consequence of diagenetic isotope enrichment. In sapropel horizons, the chlorin and total nitrogen values are 5 per mil more negative (~-5 per mil and ~ 0 per mil, respectively), resembling previously-reported, modern-day water-column particulates (~0 per mil). We suggest that nutrient conditions in the Eastern Mediterranean correspond to three scenarios and that the similarity between sapropel and modern-day bulk d15N is coincidental. Organic-poor marl sediments formed under oligotrophic conditions where surface productivity resulted from upwelling of Atlantic-sourced nitrate. Sapropels were characterized by enhanced diazotrophy that was likely fueled by increased riverine P fluxes to surface waters. Present-day conditions are dominated by anthropogenic N sources. These scenarios agree with a model of sapropel formation in which stratification caused by increased fresh-water inputs led to N fixation due to P:N nutrient imbalance. Enhanced production combined with stratification promoted and maintained anoxic deep waters, consequently increasing organic matter preservation. Such a model may be relevant to interpreting other episodes of intense organic matter deposition in past oceans.

Seawater carbonate chemistry and biological processes duirng experiments with bryozoan Myriapora truncata, 2010

There are serious concerns that ocean acidification will combine with the effects of global warming to cause major shifts in marine ecosystems, but there is a lack of field data on the combined ecological effects of these changes due to the difficulty of creating large-scale, long-term exposures to elevated CO2 and temperature. Here we report the first coastal transplant experiment designed to investigate the effects of naturally acidified seawater on the rates of net calcification and dissolution of the branched calcitic bryozoan Myriapora truncata (Pallas, 1766). Colonies were transplanted to normal (pH 8.1), high (mean pH 7.66, minimum value 7.33) and extremely high CO2 conditions (mean pH 7.43, minimum value 6.83) at gas vents off Ischia Island (Tyrrhenian Sea, Italy). The net calcification rates of live colonies and the dissolution rates of dead colonies were estimated by weighing after 45 days (May-June 2008) and after 128 days (July-October) to examine the hypothesis that high CO2 levels affect bryozoan growth and survival differently during moderate and warm water conditions. In the first observation period, seawater temperatures ranged from 19 to 24 °C; dead M. truncata colonies dissolved at high CO2 levels (pH 7.66), whereas live specimens maintained the same net calcification rate as those growing at normal pH. In extremely high CO2 conditions (mean pH 7.43), the live bryozoans calcified significantly less than those at normal pH. Therefore, established colonies of M. truncata seem well able to withstand the levels of ocean acidification predicted in the next 200 years, possibly because the soft tissues protect the skeleton from an external decrease in pH. However, during the second period of observation a prolonged period of high seawater temperatures (25-28 °C) halted calcification both in controls and at high CO2, and all transplants died when high temperatures were combined with extremely high CO2 levels. Clearly, attempts to predict the future response of organisms to ocean acidification need to consider the effects of concurrent changes such as the Mediterranean trend for increased summer temperatures in surface waters. Although M. truncata was resilient to short-term exposure to high levels of ocean acidification at normal temperatures, our field transplants showed that its ability to calcify at higher temperatures was compromised, adding it to the growing list of species now potentially threatened by global warming.

(Table S1) Age determination ofs ediment cores of the Azores Current System

In order to test the sensitivity of marine primary productivity in the midlatitude open ocean North Atlantic to changes in the Atlantic Meridional Overturning Circulation (AMOC), we investigated two spliced sediment cores from a site south of the Azores Islands at the northern rim of the North Atlantic subtropical gyre. For this purpose we analyzed coccolithophore assemblages, diatom abundances, alkenones and conducted X-ray fluorescence (XRF) core scanning. During times of reduced AMOC, especially during Heinrich event 1 (H1) and the Younger Dryas, we observe a strong increase in productivity as evidenced by high coccolith accumulation rates, high alkenone concentrations/accumulation rates, high Ba/Ti-ratios, high abundances of diatoms and low abundances ofF. profunda. The increased productivity is partly caused by a more southern position of the Azores Front (AzF), and hence by a less northward extension of the subtropical gyre, as deduced from high abundances of the temperate coccolithophore species G. muellerae and low abundances of subtropical species (Oolithotus spp., Umbellosphaera spp., Umbilicosphaeraspp.). However, to explain the full range of the observed productivity increase, other factors like increased westerly winds and advection of nutrient-rich surface waters have also to be considered. Because this pattern can also be observed in other sediment cores from the midlatitude North Atlantic, we propose that during times of reduced AMOC there has been a band of strongly increased productivity across the North Atlantic at the northern rim of the contracted subtropical gyre, which partly counteracts the decreased organic carbon pump in the high northern latitudes.

Seawater carbonate chemistry and biological processes of Sepia officinalis during experiments, 2010

Acidification of ocean surface waters by anthropogenic carbon dioxide (CO2) emissions is a currently developing scenario that warrants a broadening of research foci in the study of acid-base physiology. Recent studies working with environmentally relevant CO2 levels, indicate that some echinoderms and molluscs reduce metabolic rates, soft tissue growth and calcification during hypercapnic exposure. In contrast to all prior invertebrate species studied so far, growth trials with the cuttlefish Sepia officinalis found no indication of reduced growth or calcification performance during long-term exposure to 0.6 kPa CO2. It is hypothesized that the differing sensitivities to elevated seawater pCO2 could be explained by taxa specific differences in acid-base regulatory capacity. In this study, we examined the acid-base regulatory ability of S. officinalis in vivo, using a specially modified cannulation technique as well as 31P NMR spectroscopy. During acute exposure to 0.6 kPa CO2, S. officinalis rapidly increased its blood [HCO3] to 10.4 mM through active ion-transport processes, and partially compensated the hypercapnia induced respiratory acidosis. A minor decrease in intracellular pH (pHi) and stable intracellular phosphagen levels indicated efficient pHi regulation. We conclude that S. officinalis is not only an efficient acid-base regulator, but is also able to do so without disturbing metabolic equilibria in characteristic tissues or compromising aerobic capacities. The cuttlefish did not exhibit acute intolerance to hypercapnia that has been hypothesized for more active cephalopod species (squid). Even though blood pH (pHe) remained 0.18 pH units below control values, arterial O2 saturation was not compromised in S. officinalis because of the comparatively lower pH sensitivity of oxygen binding to its blood pigment. This raises questions concerning the potentially broad range of sensitivity to changes in acid-base status amongst invertebrates, as well as to the underlying mechanistic origins. Further studies are needed to better characterize the connection between acid-base status and animal fitness in various marine species.

Cape Lookout cold-water coral area, coral ages and environmental parameters for the last glacial cycle

Climatic and oceanographic changes, as occurring at a glacial-interglacial scale, may alter the environmental conditions needed for the development of prolific cold-water coral reefs and mounds. Studies constraining the temporal distribution of cold-water corals in the NE Atlantic suggested the cyclic changes of the Atlantic Meridional Overturning Circulation as the main driver for the development and dispersal of cold-water coral ecosystems. However, conclusions were hindered by lack of data from the NW Atlantic. Aiming to overcome this lack of data, the temporal occurrence of cold-water corals in the Cape Lookout area along the southeastern US margin was explored by U-series dating. Furthermore, the local influence of the regional water masses, namely the Gulf Stream, on cold-water coral proliferation and occurrence since the Last Glacial Maximum was examined. Results suggest that the occurrence of cold-water corals in the Cape Lookout area is restricted to interglacial periods, with corals being present during the last ~7 kyr and also during the Eemian (~125 ka). The reconstructed local environmental conditions suggest an offshore displacement of the Gulf Stream and increased influence from the Mid-Atlantic Bight shelf waters during the last glacial period. During the deglacial sea level rise, the Gulf Stream moved coastward providing present-day-like conditions to the surface waters. Nevertheless, present-day conditions at the ocean sea floor were not established before 7.5 cal ka BP once the ultimate demise of the Laurentide ice-sheet caused the final sea level rise and the displacement of the Gulf Stream to its present location. Occasional presence of the Gulf Stream over the site during the Mid- to Late Holocene coincides with enhanced bottom current strength and a slightly higher bottom water temperature, which are environmental conditions that are favorable for cold-water coral growth.

Under-ice export flux measurements by short-term drifting sediment traps at 27 stations in the Arctic Ocean during summer 1995, 1997, and 2012

A critical question regarding the organic carbon cycle in the Arctic Ocean is whether the decline in ice extent and thickness and the associated increase in solar irradiance in the upper ocean will result in increased primary production and particulate organic carbon (POC) export. To assess spatial and temporal variability in POC export, under-ice export fluxes were measured with short-term sediment traps in the northern Laptev Sea in July-August-September 1995, north of the Fram Strait in July 1997, and in the Central Arctic in August-September 2012. Sediment traps were deployed at 2-5 m and 20-25 m under ice for periods ranging from 8.5 to 71 h. In addition to POC fluxes, total particulate matter, chlorophyll a, biogenic particulate silica, phytoplankton, and zooplankton fecal pellet fluxes were measured to evaluate the amount and composition of the material exported in the upper Arctic Ocean. Whereas elevated export fluxes observed on and near the Laptev Sea shelf were likely the combined result of high primary production, resuspension, and release of particulate matter from melting ice, low export fluxes above the central basins despite increased light availability during the record minimum ice extent of 2012 suggest that POC export was limited by nutrient supply during summer. These results suggest that the ongoing decline in ice cover affects export fluxes differently on Arctic shelves and over the deep Arctic Ocean and that POC export is likely to remain low above the central basins unless additional nutrients are supplied to surface waters.

Dinoflagellate cycst in Neogene sediments of ODP Leg 178 holes

Protoperidiniacean dinoflagellate cysts were identified in 19 of 28 samples from two sites on the Antarctic Peninsula continental rise. Cysts are most common in the lower Pliocene and upper Miocene and include species of Brigantedinium, Lejeunecysta, and Selenopemphix. Autotrophic gonyaulacacean dinoflagellate cysts are very rare in the samples. The dominance of taxa derived from assumed heterotrophic dinoflagellate motile forms may indicate high nutrient content in the surface waters, which sustained a considerable diatom population.