Strong shift from HCO3- to CO2 uptake in Emiliania huxleyi with acidification: new approach unravels acclimation versus short-term pH effects

Effects of ocean acidification on Emiliania huxleyi strain RCC 1216 (calcifying, diploid life-cycle stage) and RCC 1217 (non-calcifying, haploid life-cycle stage) were investigated by measuring growth, elemental composition, and production rates under different pCO2 levels (380 and 950 µatm). In these differently acclimated cells, the photosynthetic carbon source was assessed by a (14)C disequilibrium assay, conducted over a range of ecologically relevant pH values (7.9-8.7). In agreement with previous studies, we observed decreased calcification and stimulated biomass production in diploid cells under high pCO2, but no CO2-dependent changes in biomass production for haploid cells. In both life-cycle stages, the relative contributions of CO2 and HCO3 (-) uptake depended strongly on the assay pH. At pH values =< 8.1, cells preferentially used CO2 (>= 90 % CO2), whereas at pH values >= 8.3, cells progressively increased the fraction of HCO3 (-) uptake (~45 % CO2 at pH 8.7 in diploid cells; ~55 % CO2 at pH 8.5 in haploid cells). In contrast to the short-term effect of the assay pH, the pCO2 acclimation history had no significant effect on the carbon uptake behavior. A numerical sensitivity study confirmed that the pH-modification in the (14)C disequilibrium method yields reliable results, provided that model parameters (e.g., pH, temperature) are kept within typical measurement uncertainties. Our results demonstrate a high plasticity of E. huxleyi to rapidly adjust carbon acquisition to the external carbon supply and/or pH, and provide an explanation for the paradoxical observation of high CO2 sensitivity despite the apparently high HCO3 (-) usage seen in previous studies.

Dissolved aluminium measured on water bottle samples during POLARSTERN cruise ARK-XXII/2 (SPACE)

Concentrations of dissolved (0.2 µm filtered) aluminium (Al) have been determined for the first time in the Eurasian part of the Arctic Ocean over the entire water column during expedition ARK XXII/2 aboard R.V. Polarstern (2007). An unprecedented number of 666 samples was analysed for 44 stations along 5 ocean transects. Dissolved Al in surface layer water (SLW) was very low, close to 1 nM, with lowest SLW concentrations towards the Canadian part of the Arctic Ocean and higher values adjacent to and in the shelf seas. The low SLW concentrations indicate no or little influence from aeolian dust input. Dissolved Al showed a nutrient-type increase with depth up to 28 nM, but large differences existed between the different deep Arctic basins. The differences in concentrations of Al between water masses and basins could largely be related to the different origins of the water masses. In the SLW and intermediate water layers, Atlantic and Pacific inflows were of importance. Deep shelf convection appeared to influence the Al distribution in the deep Eurasian Basin. The Al distribution of the deep Makarov Basin provides evidence for Eurasian Basin water inflow into the deep Makarov Basin. A strong correlation between Al and Silicon (Si) was observed in all basins. This correlation and the nutrient-like profile indicate a strong biological influence on the cycling and distribution of Al. The biological influence can be direct by the incorporation of Al in biogenic silica, indirect by preferential scavenging of Al onto biogenic siliceous particles, or by a combination of both processes. From the slope of the overall Al-Si relationship in the intermediate water layer (AIDW; ~ 200-2000 m depth), an Al/Si ratio of 2.2 atoms Al per 1000 atoms Si was derived. This ratio is consistent with the range of previously reported Al/Si uptake ratio in biogenic opal frustules of diatoms. In the deepest waters (>2000 m depth) a steeper slope of the Al-Si relationship of 7.4 to 13 atoms Al per 1000 atoms Si likely results from entrainment of cold shelf water into the deep basins, carrying the signal of dissolution of terrigenous particles with a much higher Al:Si ratio of crustal abundance. Only a small enrichment with such crustal Al and Si component may readily account for the higher Al:Si slope in the deepest waters.

Barium measured on water bottle samples during POLARSTERN cruise ARK-XXII/2 (SPACE)

Dissolved barium has been shown to have the potential to distinguish Eurasian from North American (NA) river runoff. As part of the ARK-XXII/2 Polarstern expedition in summer 2007, Ba was analyzed in the Barents, Kara, Laptev seas, and the Eurasian Basins as well as the Makarov Basin up to the Alpha and Mendeleyev Ridges. By combining salinity, d18O and initial phosphate corrected for mineralization with oxygen (PO4*) or N/P ratios we identified the water mass fractions of meteoric water, sea ice meltwater, and marine waters of Atlantic as well as Pacific origin in the upper water column. In all basins inside the lower halocline layer and the Arctic intermediate waters we find Ba concentrations close to those of the Fram Strait branch of the lower halocline (41-45 nM), reflecting the composition of the incoming Atlantic water. A layer of upper halocline water (UHW) with higher Ba concentrations (45-55 nM) is identified in the Makarov Basin. Atop of the UHW, the Surface Mixed Layer (SML), including the summer and winter mixed layers, has high concentrations of Ba (58-67 nM). In the SML of the investigated area of the central Arctic the meteoric fraction can be identified by assuming a conservative behavior of Ba to be primarily of Eurasian river origin. However, in productive coastal regions biological removal compromises the use of Ba to distinguish between Eurasian and NA rivers. As a consequence, the NA river water fraction is underestimated in productive surface waters or waters that have passed a productive region, whereas this fraction is overestimated in subsurface waters containing remineralised Ba, particularly when these waters have passed productive shelf regions. Especially in the Laptev Sea and small regions in the Barents Sea, Ba concentrations are low in surface waters. In the Laptev Sea exceptionally high Ba concentrations in shelf bottom waters indicate that Ba is removed from surface waters to deep waters by biological activity enhanced by increasing ice-free conditions as well as by scavenging by organic matter of terrestrial origin. We interpret high Ba concentrations in the UHW of the Makarov Basin to result from enrichment by remineralisation in bottom waters on the shelf of the Chukchi Sea and therefore the calculated NA runoff is an artefact. We conclude that no NA runoff can be demonstrated unequivocally anywhere during our expedition with the set of tracers considered here. Small contributions of NA runoff may have been masked by Ba depletion and could only be resolved by supportive tracers on the uptake history. We thus suggest that Ba has to be used with care as it can put limits but not yield quantitative water mass distributions. Only if the extra Ba inputs exceed the cumulative biological uptake the signal can be unequivocally attributed to NA runoff.

Iron and aluminium and hydrogen peroxide measured on water bottle samples during Marion Dufresne cruise ANTARES-II

Total dissolvable iron (TDFe), particulate iron (PFe) and hydrogen peroxide (H2O2 measurements were performed along a N-S transect in the upper 250 m in the Southern Ocean (62°00E/66°42S - 49°00S, ANTARES II cruise, February 1994). TDFe was organically extracted (APDC/DDDC-chloroform) and analysed by Graphite Furnace Atomic Absorption Spectrometry (GFAAS), PFe was analysed by GFAAS following a strong mixed-acid leach, and H2O2 was analysed on board by fluorometry. The respective detection limits are equal to 0.13 nmol/kg, 0.02 nmol/kg, and 3.0 nmol/kg. TDFe concentrations vary from 0.4 to 6.2 nmol/kg and profiles are not completely depleted in the surface. PFe concentrations vary from 0.02 to 0.2 nmol/kg. Iron/carbon (Fe/C) uptake ratios for phytoplankton were calculated either from seawater or particle measurements. They are variable along the transect but are consistent when they could be compared. All the observed ratios are within the range of values proposed for the Fe/C uptake ratios by phytoplankton. Using our uptake ratio calculated in the Permanent Open Ocean Zone (4 x 10**?6 mol/mol), we estimate that the primary production which can be supported by the iron input flux into the surface waters is two times higher than the measured primary production in the same area. In the surface waters, H2O2 concentrations vary from 5.0 to 19.7 nmol/kg. Such low concentrations are due to strong vertical mixing, low dissolved organic matter concentrations and the latitude of the site.