Atmospheric and seawater carbon dioxide at time series station DYFAMED

A time series of fCO2, SST, and fluorescence data was collected between 1995 and 1997 by a CARIOCA buoy moored at the DyFAMed station (Dynamique des Flux Atmospheriques en Mediterranée) located in the northwestern Mediterranean Sea. On seasonal timescales, the spring phytoplankton bloom decreases the surface water fCO2 to approximately 290 µatm, followed by summer heating and a strong increase in fCO2 to a maximum of approximately 510 µatm. While the DELTA fCO2 shows strong variations on seasonal timescales, the annual average air-sea disequilibrium is only 2 µatm. Temperature-normalized fCO2 shows a continued decrease in dissolved CO2 throughout the summer and fall at a rate of approximately 0.6 µatm/d. The calculated annual air-sea CO2 transfer rate is -0.10 to -0.15 moles CO2 m-2 y-1, with these low values reflecting the relatively weak wind speed regime and small annual air-sea fCO2 disequilibrium. Extrapolating this rate over the whole Mediterranean Sea would lead to a flux of approximately -3 * 10**12 to -4.5 * 10**12 grams C/y, in good agreement with other estimates. An analysis of the effects of sampling frequency on annual air-sea CO2 flux estimates showed that monthly sampling is adequate to resolve the annual CO2 flux to within approximately ±10 - 18% at this site. Annual flux estimates made using temperature-derived fCO2 based on the measured fCO2-SST correlations are in agreement with measurement-based calculations to within ± 7-10% (depending on the gas transfer parameterization used), and suggest that annual CO2 flux estimates may be reasonably well predicted in this region from satellite or model-derived SST and wind speed information.

Auxiliary material and basic geochemical and benthic foraminiferal stable isotope data for the interval bracketing Eocene Thermal Maximum 2 (ETM2) at DSDP Sites 401 and 550 in the northeastern Atlantic Ocean

Ever since its discovery, Eocene Thermal Maximum 2 (ETM2; ~53.7 Ma) has been considered as one of the "little brothers" of the Paleocene-Eocene Thermal Maximum (PETM; ~56 Ma) as it displays similar characteristics including abrupt warming, ocean acidification, and biotic shifts. One of the remaining key questions is what effect these lesser climate perturbations had on ocean circulation and ventilation and, ultimately, biotic disruptions. Here we characterize ETM2 sections of the NE Atlantic (Deep Sea Drilling Project Sites 401 and 550) using multispecies benthic foraminiferal stable isotopes, grain size analysis, XRF core scanning, and carbonate content. The magnitude of the carbon isotope excursion (0.85-1.10 per mil) and bottom water warming (2-2.5°C) during ETM2 seems slightly smaller than in South Atlantic records. The comparison of the lateral d13C gradient between the North and South Atlantic reveals that a transient circulation switch took place during ETM2, a similar pattern as observed for the PETM. New grain size and published faunal data support this hypothesis by indicating a reduction in deepwater current velocity. Following ETM2, we record a distinct intensification of bottom water currents influencing Atlantic carbonate accumulation and biotic communities, while a dramatic and persistent clay reduction hints at a weakening of the regional hydrological cycle. Our findings highlight the similarities and differences between the PETM and ETM2. Moreover, the heterogeneity of hyperthermal expression emphasizes the need to specifically characterize each hyperthermal event and its background conditions to minimalize artifacts in global climate and carbonate burial models for the early Paleogene.

Haemolymph inorganic ion composition, physiology and behaviour dependent on temperature and magnesium in adult Paralomis granulosa (Decapoda, Anomura, Lithodidae)

A low capacity for regulation of extracellular Mg2+ has been proposed to exclude reptant marine decapod crustaceans from temperatures below 0°C and thus to exclude them from the high Antarctic. To test this hypothesis and to elaborate the underlying mechanisms in the most cold-tolerant reptant decapod family of the sub-Antarctic, the Lithodidae, thermal tolerance was determined in the crab Paralomis granulosa (Decapoda, Anomura, Lithodidae) using an acute stepwise temperature protocol (-1°, 1°, 4°, 7°, 10°, and 13°C). Arterial and venous oxygen partial pressures (Po2) in hemolymph, heartbeat and ventilation beat frequencies, and hemolymph cation composition were measured at rest and after a forced activity (righting) trial. Scopes for heartbeat and ventilation beat frequencies and intermittent heartbeat and scaphognathite beat rates at rest were evaluated. Hemolymph [Mg2+] was experimentally reduced from 30 mmol/L to a level naturally observed in Antarctic caridean shrimps (12 mmol/L) to investigate whether the animals remain more active and tolerant to cold (-1°, 1°, and 4°C). In natural seawater, righting speed was significantly slower at -1° and 13°C, compared with acclimation temperature (4°C). Arterial and venous hemolymph Po2 increased in response to cooling even though heartbeat and ventilation beat frequencies as well as scopes decreased. At rest, ionic composition of the hemolymph was not affected by temperature. Activity induced a significant increase in hemolymph [K+] at -1° and 1°C. Reduction of hemolymph [Mg2+] did not result in an increase in activity, an increase in heartbeat and ventilation beat frequencies, or a shift in thermal tolerance to lower temperatures. In conclusion, oxygen delivery in this cold-water crustacean was not acutely limiting cold tolerance, and animals may have been constrained more by their functional capacity and motility. In contrast to earlier findings in temperate and subpolar brachyuran crabs, these constraints remained insensitive to changing Mg2+ levels.

Mean sortable silt values from Holocene and glacial Scotia Sea sediments

The Antarctic Circumpolar Current is key to the mixing and ventilation of the world's oceans. This current flows from west to east between about 45° and 70° S connecting the Atlantic, Pacific and Indian oceans, and is driven by westerly winds and buoyancy forcing. High levels of productivity in the current regulate atmospheric CO2 concentrations. Reconstructions of the current during the last glacial period suggest that flow speeds were faster or similar to present, and it is uncertain whether the strength and position of the westerly winds changed. Here we reconstruct Antarctic Circumpolar Current bottom speeds through the constricting Drake Passage and Scotia Sea during the Last Glacial Maximum and Holocene based on the mean grain size of sortable silt from a suite of sediment cores. We find essentially no change in bottom flow speeds through the region, and, given that the momentum imparted by winds, and modulated by sea-ice cover, is balanced by the interaction of these flows with the seabed, this argues against substantial changes in wind stress. However, glacial flow speeds in the sea-ice zone south of 56° S were significantly slower than present, whereas flow in the north was faster, but not significantly so. We suggest that slower flow over the rough topography south of 56° S may have reduced diapycnal mixing in this region during the last glacial period, possibly reducing the diapycnal contribution to the Southern Ocean overturning circulation.

Radiocarbon ages and stable isotope measurements on sediment cores of the subarctic Pacific and its marginal seas

Under modern conditions only North Pacific Intermediate Water is formed in the northwest Pacific Ocean. This situation might have changed in the past. Recent studies with general circulation models indicate a switch to deep-water formation in the northwest Pacific during Heinrich Stadial 1 (17.5-15.0 ka) of the last glacial termination. Reconstructions of past ventilation changes based on paleoceanographic proxy records are still insufficient to test whether a deglacial mode of deep-water formation in the North Pacific Ocean existed. Here we present deglacial ventilation records based on radiocarbon-derived ventilation ages in combination with epibenthic stable carbon isotopes from the northwest Pacific including the Okhotsk Sea and Bering Sea, the two potential source regions for past North Pacific ventilation changes. Evidence for most rigorous ventilation of the intermediate-depth North Pacific occurred during Heinrich Stadial 1 and the Younger Dryas, simultaneous to significant reductions in Atlantic Meridional Overturning Circulation. Concurrent changes in d13C and ventilation ages point to the Okhotsk Sea as driver of millennial-scale changes in North Pacific Intermediate Water ventilation during the last deglaciation. Our records additionally indicate that changes in the d13C intermediate-water (700-1750 m water depth) signature and radiocarbon-derived ventilation ages are in antiphase to those of the deep North Pacific Ocean (>2100 m water depth) during the last glacial termination. Thus, intermediate- and deep-water masses of the northwest Pacific have a differing ventilation history during the last deglaciation.

Helium-3 in different carriers from pelagic clays of DSDP Hole 91-596B and Core LR-44-GPC-3

To better understand the composition, characteristics of helium diffusion, and size distribution of interplanetary dust particles (IDPs) responsible for the long-term retention of extraterrestrial 3He, we carried out leaching, stepped heating, and sieving experiments on pelagic clays that varied in age from 0.5 Ma to ~90 Myr. The leaching experiments suggest that the host phase(s) of 3He in geologically old sediments are neither organic matter nor refractory phases, such as diamond, graphite, Al2O3, and SiC, but are consistent with extraterrestrial silicates, Fe-Ni sulfides, and possibly magnetite. Stepped heating experiments demonstrate that the 3He release profiles from the magnetic and non-magnetic components of the pelagic clays are remarkably similar. Because helium diffusion is likely to be controlled by mineral chemistry and structure, the stepped heating results suggest a single carrier that may be magnetite, or more probably a phase associated with magnetite. Furthermore, the stepped outgassing experiments indicate that about 20% of the 3He will be lost through diffusion at seafloor temperatures after 50 Myrs, while sedimentary rocks exposed on the Earth's surface for the same amount of time would lose up to 60%. The absolute magnitude of the 3He loss is, however, likely to depend upon the 3He concentration profile within the IDPs, which is not well known. Contrary to previous suggestions that micrometeorites in the size range of 50-100 µm in diameter are responsible for the extraterrestrial 3He in geologically old sediments [Stuart, F.M., Harrop, P.J., Knott, S., Turner, G., 1999. Laser extraction of helium isotopes from Antarctic micrometeorites: source of He and implications for the flux of extraterrestrial 3He flux to earth. Geochimica et Cosmochimica Acta, 63, 2653-2665, doi:10.1016/S0016-7037(99)00161-1], our sieving experiment demonstrates that at most 20% of the 3He is carried by particles greater than 50 µm in diameter. The size-distribution of the 3He-bearing particles implies that extraterrestrial 3He in sediments record the IDP flux rather than the micrometeorite flux.

Benthic foraminifera accumulation rate and benthic foraminiferal productivity proxies at ODP Site 165-999 in the Caribbean (Appendix A)

This study tests the hypothesis that the late Miocene to early Pliocene constriction and closure of the Central American Seaway (CAS), connecting the tropical Atlantic and East quatorial Pacific (EEP), caused a decrease in productivity in the Caribbean, due to decreased coastal upwelling and an end to the connection with high-productivity tropical Pacific waters. The present study compared paleoceanographic proxies for the interval between 8.3 and 2.5 Ma in 47 samples from south Caribbean ODP Site 999 with published data on EEP DSDP Site 503. Proxies for Site 999 include the relative abundance of benthic foraminiferal species representing bottom current velocity and the flux of organic matter to the sea floor, the ratio of infaunal/epifaunal benthic foraminiferal species and benthic foraminifer accumulation rates (BFARs). In addition, we calculated % resistant planktic foraminifers species and used the previously published % sand fraction and benthic carbon isotope values from Site 999. During early shoaling of the Isthmus (8.3-7.9 Ma) the Caribbean was under mesotrophic conditions, with little ventilation of bottom waters and low current velocity. The pre-closure interval (7.6-4.2 Ma) saw enhanced seasonal input of phytodetritus with even more reduced ventilation, and enhanced dissolution between 6.8 and 4.8 Ma. During the post-closure interval (4.2-2.5 Ma) in the Caribbean, paleoproductivity decreased, current velocity was reduced, and ventilation improved, while the seasonality of phytodetrital input was reduced dramatically, coinciding with the establishment of the Atlantic-Pacific salinity contrast at 4.2 Ma. Our data support the hypothesis that late Miocene constriction of the CAS at 7.9 Ma and its closure at 4.2 Ma caused a gradual decrease in paleoproductivity in the Caribbean, consistent with decreased current velocity and seasonality of the phytodetrital input.

Ba, Mn, and Mg record derived from Hoeglundina elegans of sediment core SLA-9

The evolution of productivity, redox conditions, temperature, and ventilation during the deposition of an Aegean sapropel (S1) is independently constrained using bulk sediment composition and high-resolution single specimen benthic foraminiferal trace metal and stable isotope data. The occurrence of benthic foraminifer, Hoeglundina elegans (H. elegans), through a shallow water (260 m) sapropel, permits for the first time a comparison between dissolved and particulate concentrations of Ba and Mn and the construction of a Mg/Ca-based temperature record through sapropel S1. The simultaneous increase in sedimentary Ba and incorporated Ba in foraminiferal test carbonate, (Ba/Ca)H. elegans, points to a close coupling between Ba cycling and export productivity. During sapropel deposition, sedimentary Mn content ((Mn/Al)sed) is reduced, corresponding to enhanced Mn2+ mobilization from sedimentary Mn oxides under suboxic conditions. The consequently elevated dissolved Mn2+ concentrations are reflected in enhanced (Mn/Ca)H. elegans levels. The magnitude and duration of the sapropel interruption and other short-term cooling events are constrained using Mg/Ca thermometry. Based on integrating productivity and ventilation records with the temperature record, we propose a two-mode hysteresis model for sapropel formation.