Data and Code archive for the interpolation of surface ocean carbon dioxide

We have developed a statistical gap-filling method adapted to the specific coverage and properties of observed fugacity of surface ocean CO2 (fCO2). We have used this method to interpolate the Surface Ocean CO2 Atlas (SOCAT) v2 database on a 2.5°×2.5° global grid (south of 70°N) for 1985-2011 at monthly resolution. The method combines a spatial interpolation based on a 'radius of influence' to determine nearby similar fCO2 values with temporal harmonic and cubic spline curve-fitting, and also fits long term trends and seasonal cycles. Interannual variability is established using deviations of observations from the fitted trends and seasonal cycles. An uncertainty is computed for all interpolated values based on the spatial and temporal range of the interpolation. Tests of the method using model data show that it performs as well as or better than previous regional interpolation methods, but in addition it provides a near-global and interannual coverage.

Sedimentology and age on profile Lz1023

A 270 cm long sediment sequence was recovered with a piston corer from east lobe Bonney, Taylor Valley, Antarctica, and characterized according to its sedimentological, mineralogical, and geochemical properties. It is the first record of such length recovered from east lobe Bonney. The sediment core is mainly composed of halite crystals of different sizes, water, and a relatively low and stable proportion of clastic particles. Although the sediment surface was probably disturbed by the coring process and absence or low contents of organic material or carbonates hampers the establishment of a robust chronology by radiocarbon dating, the core probably contains at least several hundred years of information about the history of the lake and the Bonney basin. Variations in halite crystal sizes and amount as well as variations in the composition of clastic material can be related to past lake level changes and evaporation cycles.

Sedimentology and planktonic foraminiferal dissolution during the latest Cretaceous in the South Atlantic

A high-resolution (10-20 kyr) record of variations in CaCO3 content and dissolution was established for latest Cretaceous (last 0.7 Myr) deep-sea sediments from the South Atlantic Ocean (DSDP Site 516 from the Rio Grande Rise, and sites 525 and 527 from the Walvis Ridge). The degree of fragmentation of planktonic foraminifera (DFP) was used as a measure of calcite dissolution. High negative correlations between DFP and other independent measures of carbonate dissolution (percentage of sand fraction, absolute abundance of planktonic foraminifera, and planktonic/benthic foraminiferal ratio) validate its use as a sensitive index of calcite dissolution in upper Maastrichtian deep-sea sediments. Very high DFP and a significant negative correlation between DFP and CaCO 3 content suggest that Site 516 was located below the foraminiferal lysocline during the entire interval studied. Such a shallow position of the lysocline (paleodepth of Site 516 was 1.2 km) may be explained by "upwelling" of corrosive deep waters along the southern margin of the Rio Grande Rise. Sites 525 and 527 were located above the foraminiferal lysocline; however, three short periods of enhanced dissolution were recognised at Site 525 (paleodepth 1 km) and one interval of strong dissolution was identified at Site 527 (paleodepth 2.7 km). The lack of correspondence between the dissolution regimes at sites from the Walvis Ridge suggests limited deep-water communication across this physiographic barrier. Two of the dissolution maxima recognised at Site 525 correspond to carbonate maxima at Site 527. Variations in "upwelling" intensity along the Walvis Ridge, resulting in fluctuations in primary productivity in this area, may be the proximal cause of both carbonate cycles at Site 527 and dissolution cycles at Site 525. We suggest that development of the bottom Ekman layer between a hypothetical westward geostrophic current and the topographical height of the Rio Grande Rise-Walvis Ridge system may be a plausible hydrodynamical explanation for the proposed "'upwelling" along the southern margin of this topographical structure.

A high-resolution sedimentology and age determination of core PS2185 from the central Arctic Ocean

A high-resolution multiparameter stratigraphy allows the identification of late Quaternary glacial and interglacial cycles in a central Arctic Ocean sediment core. Distinct sandy layers in the upper part of the otherwise fine-grained sediment core from the Lomonosov Ridge (lat 87.5°N) correlate to four major glacials since ca. 0.7 Ma. The composition of these ice-rafted terrigenous sediments points to a glaciated northern Siberia as the main source. In contrast, lithic carbonates derived from North America are also present in older sediments and indicate a northern North American glaciation since at least 2.8 Ma. We conclude that large-scale northern Siberian glaciation began much later than other Northern Hemisphere ice sheets.

Seawater carbonate chemistry and growth rate of Emiliania huxleyi in lab experiment

Predicting the impacts of environmental change on marine organisms, food webs, and biogeochemical cycles presently relies almost exclusively on short-term physiological studies, while the possibility of adaptive evolution is often ignored. Here, we assess adaptive evolution in the coccolithophore Emiliania huxleyi, a well-established model species in biological oceanography, in response to ocean acidification. We previously demonstrated that this globally important marine phytoplankton species adapts within 500 generations to elevated CO2. After 750 and 1000 generations, no further fitness increase occurred, and we observed phenotypic convergence between replicate populations. We then exposed adapted populations to two novel environments to investigate whether or not the underlying basis for high CO2-adaptation involves functional genetic divergence, assuming that different novel mutations become apparent via divergent pleiotropic effects. The novel environment "high light" did not reveal such genetic divergence whereas growth in a low-salinity environment revealed strong pleiotropic effects in high CO2 adapted populations, indicating divergent genetic bases for adaptation to high CO2. This suggests that pleiotropy plays an important role in adaptation of natural E. huxleyi populations to ocean acidification. Our study highlights the potential mutual benefits for oceanography and evolutionary biology of using ecologically important marine phytoplankton for microbial evolution experiments.

Follow-up of the sponge and asteroid populations at the station Larsen A south (PS69/724-1 and PS77/253-1), Antarctic Peninsula, between 2007 and 2011

Over 30% of the Antarctic continental shelf is permanently covered by floating ice shelves, providing aphotic conditions for a depauperate fauna sustained by laterally advected food. In much of the remaining Antarctic shallows (<300 m depth), seasonal sea-ice melting allows a patchy primary production supporting rich megabenthic communities dominated by glass sponges (Porifera, Hexactinellida). The catastrophic collapse of ice shelves due to rapid regional warming along the Antarctic Peninsula in recent decades has exposed over 23,000 km**2 of seafloor to local primary production. The response of the benthos to this unprecedented flux of food is, however, still unknown. In 2007, 12 years after disintegration of the Larsen A ice shelf, a first biological survey interpreted the presence of hexactinellids as remnants of a former under-ice fauna with deep-sea characteristics. Four years later, we revisited the original transect, finding 2- and 3-fold increases in glass sponge biomass and abundance, respectively, after only two favorable growth periods. Our findings, along with other long-term studies, suggest that Antarctic hexactinellids, locked in arrested growth for decades, may undergo boom-and-bust cycles, allowing them to quickly colonize new habitats. The cues triggering growth and reproduction in Antarctic glass sponges remain enigmatic.

(Table 2) Major and trace elements in black smoker particulates

We present geochemical data of black smoker particulates filtered from hydrothermal fluids with seawater-dilutions ranging from 0-99%. Results indicate the dominance of sulphide minerals (Fe, Cu, and Zn sulphides) in all samples taken at different hydrothermal sites on the Mid-Atlantic Ridge. Pronounced differences in the geochemistry of the particles between Logatchev I and 5°S hydrothermal fields could be attributed to differences in fluid chemistry. Lower metal/sulphur ratios (Me/H2S < 1) compared to Logatchev I result in a larger amount of particles precipitated per liter fluid and the occurrence of elemental sulphur at 5°S, while at Logatchev I Fe oxides occur in larger amounts. Systematic trends with dilution degree of the fluid include the precipitation of large amounts of Cu sulphides at a low dilution and a pronounced drop with increasing dilution. Moreover, Fe (sulphides or oxides) precipitation increases with dilution of the vent fluid by seawater. Geochemical reaction path modeling of hydrothermal fluid-seawater mixing and conductive cooling indicates that Cu sulphide formation at Logatchev I and 5°S mainly occurs at high temperatures and low dilution of the hydrothermal fluid by seawater. Iron precipitation is enhanced at higher fluid dilution, and the different amounts of minerals forming at 5°S and Logatchev I are thermodynamically controlled. Larger total amounts of minerals and larger amounts of sulphide precipitate during the mixing path when compared to the cooling path. Differences between model and field observations do occur and are attributable to closed system modeling, to kinetic influences and possibly to organic constituents of the hydrothermal fluids not accounted for by the model.

Rare earth element concentrations and geochemistry of carbonate minerals from the Logatchev Hydrothermal Field and the Gakkel Ridge

The ultramafic-hosted Logatchev Hydrothermal Field (LHF) at 15°N on the Mid-Atlantic Ridge and the Arctic Gakkel Ridge (GR) feature carbonate precipitates (aragonite, calcite, and dolomite) in voids and fractures within different types of host rocks. We present chemical and Sr isotopic compositions of these different carbonates to examine the conditions that led to their formation. Our data reveal that different processes have led to the precipitation of carbonates in the various settings. Seawater-like 87Sr/86Sr ratios for aragonite in serpentinites (0.70909 to 0.70917) from the LHF are similar to those of aragonite from the GR (0.70912 to 0.70917) and indicate aragonite precipitation from seawater at ambient conditions at both sites. Aragonite veins in sulfide breccias from LHF also have seawater-like Sr isotope compositions (0.70909 to 0.70915), however, their rare earth element (REE) patterns show a clear positive europium (Eu) anomaly indicative of a small (< 1%) hydrothermal contribution. In contrast to aragonite, dolomite from the LHF has precipitated at much higher temperatures (~100 °C), and yet its 87Sr/86Sr ratios (0.70896 to 0.70907) are only slightly lower than those of aragonite. Even higher temperatures are calculated for the precipitation of deformed calcite veins in serpentine-talc fault schists form north of the LHF. These calcites show unradiogenic 87Sr/86Sr ratios (0.70460 to 0.70499) indicative of precipitation from evolved hydrothermal fluids. A simple mixing model based on Sr mass balance and enthalpy conservation indicates strongly variable conditions of fluid mixing and heat transfers involved in carbonate formation. Dolomite precipitated from a mixture of 97% seawater and 3% hydrothermal fluid that should have had a temperature of approximately 14 °C assuming that no heat was transferred. The much higher apparent precipitation temperatures based on oxygen isotopes (~ 100 °C) may be indicative of conductive heating, probably of seawater prior to mixing. The hydrothermal calcite in the fault schist has precipitated from a mixture of 67% hydrothermal fluid and 33% seawater, which should have had an isenthalpic mixing temperature of ~ 250 °C. The significantly lower temperatures calculated from oxygen isotopes are likely due to conductive cooling of hydrothermal fluid discharging along faults. Rare earth element patterns corroborate the results of the mixing model, since the hydrothermal calcite, which formed from waters with the greatest hydrothermal contribution, has REE patterns that closely resemble those of vent fluids from the LHF. Our results demonstrate, for the first time, that (1) precipitation from pure seawater, (2) conductive heating of seawater, and (3) conductive cooling of hydrothermal fluids in the sub-seafloor all can lead to carbonate precipitation within a single ultramafic-hosted hydrothermal system.

Seawater carbonate chemistry, physiology and skeletal mineralogy of coralline alga Corallina elongata in a laboratory experiment

Marine organisms inhabiting environments where pCO2/pH varies naturally are suggested to be relatively resilient to future ocean acidification. To test this hypothesis, the effect of elevated pCO2 was investigated in the articulated coralline red alga Corallina elongata from an intertidal rock pool on the north coast of Brittany (France), where pCO2 naturally varied daily between 70 and 1000 µatm. Metabolism was measured on algae in the laboratory after they had been grown for 3 weeks at pCO2 concentrations of 380, 550, 750 and 1000 µatm. Net and gross primary production, respiration and calcification rates were assessed by measurements of oxygen and total alkalinity fluxes using incubation chambers in the light and dark. Calcite mol % Mg/Ca (mMg/Ca) was analysed in the tips, branches and basal parts of the fronds, as well as in new skeletal structures produced by the algae in the different pCO2 treatments. Respiration, gross primary production and calcification in light and dark were not significantly affected by increased pCO2. Algae grown under elevated pCO2 (550, 750 and 1000 µatm) formed fewer new structures and produced calcite with a lower mMg/Ca ratio relative to those grown under 380 µatm. This study supports the assumption that C. elongata from a tidal pool, where pCO2 fluctuates over diel and seasonal cycles, is relatively robust to elevated pCO2 compared to other recently investigated coralline algae.

(Table 1) Chemical and isotopic composition of pore fluids in cores TGC-1 and TGC-6

The role of sediment diagenesis in the marine cycles of Li and B is poorly understood. Because Li and B are easily mobilized during burial and are consumed in authigenic clay mineral formation, their abundance in marine pore waters varies considerably. Exchange with the overlying ocean through diffusive fluxes should thus be common. Nevertheless, only a minor Li sink associated with the low-temperature alteration of volcanic ash has been observed. We describe a low-temperature diagenetic environment in the Black Sea dominated by the alteration of detrital plagioclase feldspars. Fluids expelled from the Odessa mud volcano in the Sorokin Trough originate from shallow (~100-400 m deep) sediments which are poor in volcanic materials but rich in anorthite. These fluids are depleted in Na+, K+, Li+, B, and 18O and enriched in Ca2+ and Sr2+, indicating that anorthite is dissolving and authigenic clays are forming. Using a simple chemical model, we calculate the pH and the partial pressure of CO2 (PCO2) in fluids associated with this alteration process. Our results show that the pH of these fluids is up to 1.5 pH units lower than in most deep marine sediments and that PCO2 levels are up to several hundred times higher than in the atmosphere. These conditions are similar to those which favor the weathering of silicate minerals in subaerial soil environments. We propose that in Black Sea sediments enhanced organic matter preservation favors CO2 production through methanogenesis and results in a low pore water pH, compared to most deep sea sediments. As a result, silicate mineral weathering, which is a sluggish process in most marine diagenetic environments, proceeds rapidly in Black Sea sediments. There is a potential for organic matter-rich continental shelf environments to host this type of diagenesis. Should such environments be widespread, this new Li and B sink could help balance the marine Li and Li isotope budgets but would imply an apparent imbalance in the B cycle.

Radionuclides of bulk and terrigenous surface sediments in the Southern Ocean

Sr and Nd isotopic compositions of Late Quaternary surface sediment and sediment cores from the south Atlantic and southeast Pacific sectors of the Southern Ocean are used to constrain the provenance and transport mechanisms of their terrigenous component. We report isotopic and mineralogical data for core samples from three localities, the Mid-Atlantic Ridge at 41°S and the northern and southern Scotia Sea. In addition, data for surface sediment samples from the south Atlantic and southeast Pacific sectors of the Southern Ocean are presented. The variations of Sr and Nd isotopic compositions of the bulk sediment samples in all cores were correlated with the magnetic susceptibility of the sediment and with the inferred glacial-interglacial stages. The isotopic data indicate that, during glacial periods, sediment was delivered from continental crust with a shorter residence time than that supplying material during interglacial periods. At the core site near the Mid-Atlantic Ridge, Nd isotopic, combined with mineralogical evidence indicates interglacial period deposition of a relatively high amount of kaolinite and silt with low epsilon-Nd values < -8. The material was probably supplied by North Atlantic Deep Water from low latitudes. For glacial periods, a high contribution of silt and clay with epsilon-Nd > -4.5, probably derived from southern South America, was indicated. The glacial-interglacial shift in sources may be due to either a decreasing influence of North Atlantic Deep Water during glacial times or by a larger contribution of glaciogenic detritus from southern South America. At the core site in the northern Scotia Sea, sediment of interglacial periods is dominated by smectite with epsilon-Nd < - 6 and silt with epsilon-Nd > -4. We suggest that smectite was derived from the Falkland shelf and silt was derived from the Argentinian shelf. During glacial periods, the Argentinian shelf was an important source for silt and chlorite with epsilon-Nd > -4. The contribution from the Falkland shelf seems to have remained similar during glacial and interglacial periods. Hydrographic transport by bottom currents and turbidites could account for the high glacial detrital flux. An evaluation of the significance of an aeolian contribution to deep sea sediment suggests that it plays only a minor role. In the southern Scotia Sea, the Antarctic Peninsula is considered an important source for young material with epsilon-Nd > -4, in particular during glacial periods. During interglacial periods, sediment supply from the Antarctic Peninsula was lower than during glacial times, resulting in a relatively high contribution of old material (epsilon-Nd < -8) from East Antarctica. Deep water currents and icebergs could account for the transport of the old component to the southern Scotia Sea. The accumulation rates of material from the various source regions for glacial times are in agreement with an increase in the strength of the Antarctic Circumpolar Current. The production rate and the circulation pattern of bottom water in the Weddell Sea appear to have remained similar over most of the last 150 kyr.