Beschreibung: The Cretaceous ocean witnessed intervals of profound perturbations such as volcanic input of large amounts of CO2, anoxia, eutrophication and introduction of biologically relevant metals. Some of these extreme events were characterized by size reduction and/or morphological changes of a few calcareous nannofossil species. The correspondence between intervals of high trace metal concentrations and coccolith dwarfism suggests a negative effect of these elements on nannoplankton biocalcification processes in past oceans. In order to test this hypothesis, we explored the potential effect of a mixture of trace metals on growth and morphology of four living coccolithophore species, namely Emiliania huxleyi, Gephyrocapsa oceanica, Pleurochrysis carterae and Coccolithus pelagicus. The phylogenetic history of coccolithophores shows that the selected living species are linked to Mesozoic species showing dwarfism under excess metal concentrations. The trace metals tested were chosen to simulate the environmental stress identified in the geological record and upon known trace metal interactions with living coccolithophore algae. Our laboratory experiments demonstrated that elevated trace metal concentrations, similarly to the fossil record, affect coccolithophore algae size and/or weight. Smaller coccoliths were detected in E. huxleyi and C. pelagicus, while coccoliths of G. oceanica showed a decrease in size only at the highest trace metal concentrations. P. carterae coccolith size was unresponsive to changing trace metal concentrations. These differences among species allow discriminating the most- (P. carterae), intermediate- (E. huxleyi and G. oceanica) and least-tolerant (C. pelagicus) taxa. The fossil record and the experimental results converge on a selective response of coccolithophores to metal availability. These species-specific differences must be considered before morphological features of coccoliths are used to reconstruct paleo-chemical conditions.

Beschreibung: Iron chemistry measurements were conducted during summer 2007 at two distinct locations in the Baltic Sea (Gotland Deep and Landsort Deep) to evaluate the role of iron for cyanobacterial bloom development in these estuarine waters. Depth profiles of Fe(II) were measured by chemiluminescent flow injection analysis (CL-FIA). Up to 0.9 nmol Fe(II) L−1 were detected in light penetrated surface waters, which constitutes up to 20% to the dissolved Fe pool. This bioavailable iron source is a major contributor to the Fe requirements of Baltic Sea phytoplankton and apparently plays a major role for cyanobacterial bloom development during our study. Measured Fe(II) half life times in oxygenated water exceed predicted values and indicate organic Fe(II) complexation. Potential sources for Fe(II) ligands, including rainwater, are discussed. Fe(II) concentrations of up to 1.44 nmol L−1 were detected at water depths below the euphotic zone, but above the oxic anoxic interface. Mixed layer depths after strong wind events are not deep enough in summer time to penetrate the oxic-anoxic boundary layer. However, Fe(II) from anoxic bottom water may enter the sub-oxic zone via diapycnal mixing and diffusion.

Beschreibung: The speciation of dissolved iron (DFe) in the ocean is widely assumed to consist almost exclusively of Fe(III)-ligand complexes. Yet in most aqueous environments a poorly defined fraction of DFe also exists as Fe(II), the speciation of which is uncertain. Here we deploy flow injection analysis to measure in situ Fe(II) concentrations during a series of mesocosm/microcosm/multistressor experiments in coastal environments in addition to the decay rate of this Fe(II) when moved into the dark. During five mesocosm/microcosm/multistressor experiments in Svalbard and Patagonia, where dissolved (0.2 µm) Fe and Fe(II) were quantified simultaneously, Fe(II) constituted 24 %–65 % of DFe, suggesting that Fe(II) was a large fraction of the DFe pool. When this Fe(II) was allowed to decay in the dark, the vast majority of measured oxidation rate constants were less than calculated constants derived from ambient temperature, salinity, pH, and dissolved O2. The oxidation rates of Fe(II) spikes added to Atlantic seawater more closely matched calculated rate constants. The difference between observed and theoretical decay rates in Svalbard and Patagonia was most pronounced at Fe(II) concentrations 〈2 nM, suggesting that the effect may have arisen from organic Fe(II) ligands. This apparent enhancement of Fe(II) stability under post-bloom conditions and the existence of such a high fraction of DFe as Fe(II) challenge the assumption that DFe speciation in coastal seawater is dominated by ligand bound-Fe(III) species.

Beschreibung: Based on an international workshop (Gothenburg, 14–16 May 2008), this review article aims to combine interdisciplinary knowledge from coastal and open ocean research on iron biogeochemistry. The major scientific findings of the past decade are structured into sections on natural and artificial iron fertilization, iron inputs into coastal and estuarine systems, colloidal iron and organic matter, and biological processes. Potential effects of global climate change, particularly ocean acidification, on iron biogeochemistry are discussed. The findings are synthesized into recommendations for future research areas.

Beschreibung: The interaction between iron availability and the phytoplankton elemental composition was investigated during the in situ iron fertilization experiment EIFEX and in laboratory experiments with the Southern Ocean diatom species Fragilariopsis kerguelensis and Chaetoceros dichaeta. Contrary to other in situ iron fertilization experiments we observed an increase in the BSi:POC, BSi:PON, and BSi:POP ratios within the iron fertilized patch during EIFEX. This is possibly caused by a relatively stronger increase in diatom abundance compared to other phytoplankton groups and does not necessarily represent the amount of silicification of single diatom cells. In laboratory experiments with F. kerguelensis and C. dichaeta no changes in the POC:PON, PON:POP, and POC:POP ratios were found with changing iron availability in both species. BSi:POC, BSi:PON, and BSi:POP ratios were significantly lower in the high iron treatments compared to the controls. In F. kerguelensis this was caused by a decrease in cellular BSi concentrations and therefore possibly less silicification. In C. dichaeta no change in cellular BSi concentration was found. Here lower BSi:POC, BSi:PON, and BSi:POP ratios were caused by an increase in cellular C, N, and P under high iron conditions. These results indicate that iron limitation does not always increase silicification in diatoms and that changes in the BSi:POC, BSi:PON, and BSi:POP ratios under iron fertilization in the field are caused by a variety of different mechanisms. Our results therefore imply that simple cause-and-effect relationships are not always applicable for modeling of elemental ratios.

Beschreibung: Iron is a key micronutrient for phytoplankton growth in the surface ocean. Yet the significance of volcanism for the marine biogeochemical iron-cycle is poorly constrained. Recent studies, however, suggest that offshore deposition of airborne ash from volcanic eruptions is a way to inject significant amounts of bio-available iron into the surface ocean. Volcanic ash may be transported up to several tens of kilometers high into the atmosphere during large-scale eruptions and fine ash may stay aloft for days to weeks, thereby reaching even the remotest and most iron-starved oceanic regions. Scientific ocean drilling demonstrates that volcanic ash layers and dispersed ash particles are frequently found in marine sediments and that therefore volcanic ash deposition and iron-injection into the oceans took place throughout much of the Earth's history. Natural evidence and the data now available from geochemical and biological experiments and satellite techniques suggest that volcanic ash is a so far underestimated source for iron in the surface ocean, possibly of similar importance as aeolian dust. Here we summarise the development of and the knowledge in this fairly young research field. The paper covers a wide range of chemical and biological issues and we make recommendations for future directions in these areas. The review paper may thus be helpful to improve our understanding of the role of volcanic ash for the marine biogeochemical iron-cycle, marine primary productivity and the ocean-atmosphere exchange of CO2 and other gases relevant for climate in the Earth's history.