Beschreibung: Carbon acquisition in relation to CO2 supply was investigated in three marine bloom-forming microalgae, the diatom Skeletonema costatum, the flagellate Phaeocystis globosa, and the coccolithophorid Emiliania huxleyi. In vivo activities of extracellular (eCA) and intracellular (iCA) carbonic anhydrase activity, photosynthetic O2 evolution, CO2 and HCO uptake rates were measured by membrane inlet mass spectrometry in cells acclimated to pCO2 levels of 36, 180, 360, and 1,800 ppmv. Large differences were obtained between species both with regard to the efficiency and regulation of carbon acquisition. While eCA activity increased with decreasing CO2 concentration in S. costatum and P. globosa, consistently low values were obtained for E. huxleyi. No clear trends with pCO2 were observed in iCA activity for any of the species tested. Half saturation concentrations (K1/2) for photosynthetic O2 evolution, which were highest for E. huxleyi and lowest for S. costatum, generally decreased with decreasing CO2 concentration. In contrast, K1/2 values for P. globosa remained unaffected by pCO2 of the incubation. CO2 and HCO3- were taken up simultaneously by all species. The relative contribution of HCO3- to total carbon uptake generally increased with decreasing CO2, yet strongly differed between species. Whereas K1/2 for CO2 and HCO3- uptake was lowest at the lowest pCO2 for S. costatum and E. huxleyi, it did not change as a function of pCO2 in P. globosa. The observed taxon-specific differences in CO2 sensitivity, if representative for the natural environment, suggest that changes in CO2 availability may influence phytoplankton species succession and distribution. By modifying the relative contribution of different functional groups, e.g., diatomaceous versus calcareous phytoplankton, to the overall primary production this could potentially affect marine biogeochemical cycling and air-sea gas exchange.

Beschreibung: The role of transparent exopolymer particles (TEP) and dissolved organic carbon (DOC) for organic carbon partitioning under different CO2 conditions was examined during a mesocosm experiment with the coccolithophorid Emiliania huxleyi. We designed 9 outdoor enclosures (similar to11 m(3)) to simulate CO2 concentrations of estimated 'Year 2100' (similar to710 ppm CO2), 'present' (similar to410 ppm CO2) and 'glacial' (similar to190 ppm CO2) environments, and fertilized these with nitrate and phosphate to favor bloom development. Our results showed fundamentally different TEP and DOC dynamics during the bloom. In all mesocosms, TEP concentration increased after nutrient exhaustion and accumulated steadily until the end of the study. TEP concentration was closely related to the abundance of E. huxleyi and accounted for an increase in POC concentration of 35 2 % after the onset of nutrient limitation. The production of TEP normalized to the cell Abundance of E. huxleyi was highest in the Year 2100 treatment. In contrast, DOC concentration exhibited considerable short-term fluctuations throughout the study. In all mesocosms, DOC was neither related to the abundance of E. huxleyi nor to TEP concentration. A statistically significant effect of the CO2 treatment on DOC concentration was not determined. However, during the course of the bloom, DOC concentration increased in 2 of the 3 Year 2100 mesocosms and in 1 of the present mesocosms, but in none of the glacial mesocosms. It is suggested that the observed differences between TEP and DOC were determined by their different bioavailability and that a rapid response of the microbial food web may have obscured CO2 effects on DOC production by autotrophic cells.

Beschreibung: In laboratory experiments with the coccolithophore species Emiliania huxleyi and Gephyrocapsa oceanica, the ratio of particulate inorganic carbon (PIC) to particulate organic carbon (POC) production decreased with increasing CO2 concentration ([CO2]). This was due to both reduced PIC and enhanced POC production at elevated [CO2]. Carbon dioxide concentrations covered a range from a preindustrial level to a value predicted for 2100 according to a “business as usual” anthropogenic CO2 emission scenario. The laboratory results were used to employ a model in which the immediate effect of a decrease in global marine calcification relative to POC production on the potential capacity for oceanic CO2 uptake was simulated. Assuming that overall marine biogenic calcification shows a similar response as obtained for E. huxleyi or G. oceanica in the present study, the model reveals a negative feedback on increasing atmospheric CO2 concentrations owing to a decrease in the PIC/POC ratio.

Beschreibung: The Redfield ratio [carbon:nitrogen:phosphorus (C:N:P)] of particle flux to the deep ocean is a key factor in marine biogeochemical cycling. Changes in oceanic carbon sequestration have been linked to variations in the Redfield ratio on geological time scales, but this ratio generally is assumed to be constant with time in the modern ocean. However, deep-water Redfield ratios in the northern hemisphere show evidence for temporal trends over the past five decades. The North Atlantic Ocean exhibits a rising N:P ratio, which may be related to increased deposition of atmospheric nitrous oxides from anthropogenic N emissions. In the North Pacific Ocean, increasing C:N and C:P ratios are accompanied by rising remineralization rates, which suggests intensified export production. Stronger export of carbon in this region may be due to enhanced bioavailability of aeolian iron. These findings imply that the biological part of the marine carbon cycle currently is not in steady state.

Beschreibung: Carbonic anhydrase (CA) is inactive unless associated with zinc, with possible substitution by cobalt. In this work, the complexation of zinc by CA was determined in sea-water using cathodic stripping voltammetry (CSV) with ligand competition. The zinc was found to be released from the CA over a period of 3 h when equilibrated with a competing complexing ligand and the complex was re-formed with the CA when zinc was added. A value of 8.90+/-0.27 was found for logK'ZnCA where K'ZnCA is the conditional stability constant for the complex of Zn2+ with CA in pH 8 sea-water. A value for the molecular weight of CA was calculated from its equivalent ligand concentration (in nM) obtained by titrations with zinc at various CA concentrations (1-4 mg l(-1)). The value found (34740 g mol(-1)) for the molecular weight is consistent with values found previously by other methods (29000-31000 g mol(-1)) confirming that the stoichiometry of the complex between zinc and CA is 1:1. This work confirms that the zinc-CA complex is reversible and that the interaction between zinc and CA can be determined using CSV with ligand competition.