François M. M. Morel

Reduced calcification of marine plankton in response to increased atmospheric CO2.

The formation of calcareous skeletons by marine planktonic organisms and their subsequent sinking to depth generates a continuous rain of calcium carbonate to the deep ocean and underlying sediments. This is important in regulating marine carbon cycling and ocean–atmosphere CO2 exchange. The present rise in atmospheric CO2 levels causes significant changes in surface ocean pH and carbonate chemistry. Such changes have been shown to slow down calcification in corals and coralline macroalgae,, but the majority of marine calcification occurs in planktonic organisms. Here we report reduced calcite production at increased CO2 concentrations in monospecific cultures of two dominant marine calcifying phytoplankton species, the coccolithophorids Emiliania huxleyi and Gephyrocapsa oceanica . This was accompanied by an increased proportion of malformed coccoliths and incomplete coccospheres. Diminished calcification led to a reduction in the ratio of calcite precipitation to organic matter production. Similar results were obtained in incubations of natural plankton assemblages from the north Pacific ocean when exposed to experimentally elevated CO2 levels. We suggest that the progressive increase in atmospheric CO2 concentrations may therefore slow down the production of calcium carbonate in the surface ocean. As the process of calcification releases CO2 to the atmosphere, the response observed here could potentially act as a negative feedback on atmospheric CO2 levels.

The biogeochemical cycling of elemental mercury: Anthropogenic influences☆

Abstract A review of the available information on global Hg cycling shows that the atmosphere and surface ocean are in rapid equilibrium; the evasion of Hg0 from the oceans is balanced by the total oceanic deposition of Hg(II) from the atmosphere. The mechanisms whereby reactive Hg species are reduced to volatile Hg0 in the oceans are poorly known, but reduction appears to be chiefly biological. The rapid equilibrium of the surface oceans and the atmosphere, coupled with the small Hg sedimentation in the oceans makes deposition on land the dominant sink for atmospheric Hg. About half of the anthropogenic emissions appear to enter the global atmospheric cycle while the other half is deposited locally, presumably due to the presence of reactive Hg in flue gases. We estimate that over the last century anthropogenic emissions have tripled the concentrations of Hg in the atmosphere and in the surface ocean. Thus, two-thirds of the present Hg fluxes (such are deposition on land and on the ocean) are directly or indirectly of anthropogenic origin. Elimination of the anthropogenic load in the ocean and atmosphere would take fifteen to twenty years after termination of all anthropogenic emissions.

THE ELEMENTAL COMPOSITION OF SOME MARINE PHYTOPLANKTON1

We analyzed the cellular content of C, N, P, S, K, Mg, Ca, Sr, Fe, Mn, Zn, Cu, Co, Cd, and Mo in 15 marine eukaryotic phytoplankton species in culture representing the major marine phyla. All the organisms were grown under identical culture conditions, in a medium designed to allow rapid growth while minimizing precipitation of iron hydroxide. The cellular concentrations of all metals, phosphorus, and sulfur were determined by high‐resolution inductively coupled plasma mass spectrometry (HR‐ICPMS) and those of carbon and nitrogen by a carbon hydrogen nitrogen analyzer. Accuracy of the HR‐ICPMS method was validated by comparison with data obtained with 55Fe radioactive tracer and by a planktonic reference material. The cellular quotas (normalized to P) of trace metals and major cations in the biomass varied by a factor of about 20 among species (except for Cd, which varied over two orders of magnitude) compared with factors of 5 to 10 for major nutrients. Green algae had generally higher C, N, Fe, Zn, and Cu quotas and lower S, K, Ca, Sr, Mn, Co, and Cd quotas than coccolithophores and diatoms. Co and Cd quotas were also lower in diatoms than in coccolithophores. Although trace element quotas are influenced by a variety of growth conditions, a comparison of our results with published data suggests that the measured compositions reflect chiefly the intrinsic (i.e. genetically encoded) trace element physiology of the individual species. Published field data on the composition of the planktonic biomass fall within the range of laboratory values and are generally close to the approximate extended Redfield formula given by the average stoichiometry of our model species (excluding the hard parts): While clearly this elemental stoichiometry varies between species and, potentially, in response to changes in the chemistry of seawater, it provides a basis for examining how phytoplankton influence the relative distributions of the ensemble of major and trace elements in the ocean.

Preparation and Chemistry of the Artificial Algal Culture Medium Aquil

AbstractThe culture medium Aquil has been designed for studying trace metal physiology in algae. We describe recent modifications in the preparation of Aquil and discuss processes that affect its trace metals and their physiological effects. The major changes in Aquil preparation are purification of the Chelex column to avoid contamination by chelating agents, use of alternative sterilization procedures, and increases in the concentration of trace metal buffers. During growth, phytoplankton take up trace metals, thus continuously reducing their concentrations in the medium. Algae can also modify the redox state and degree of organic complexation of trace metals through the direct and indirect activity of cell surface enzymes and the release of metabolites. Illumination of the culture medium necessary to promote photosynthesis also promotes a variety of photochemical reactions that alter the chemistry of the medium and maintain it in a state of disequilibrium. In particular, light absorption by FeEDTA lead...

A Surface Precipitation Model for the Sorption of Cations on Metal Oxides

Abstract A new model for the sorption of cations on metal oxides is formulated which allows for a continuum between surface reactions and precipitation. The model extends the surface complexation approach by considering precipitation on the solid to be described by the formation of a solid solution whose composition varies continuously between that of the original solid and a pure precipitate of the sorbing cation. The ability of the surface precipitation model to describe the equilibrium sorption of metal cations on amorphous iron hydroxide is demonstrated. The model can also be extended to describe cation competition and anion sorption.

Structure and metal exchange in the cadmium carbonic anhydrase of marine diatoms.

Carbonic anhydrase, a zinc enzyme found in organisms from all kingdoms, catalyses the reversible hydration of carbon dioxide and is used for inorganic carbon acquisition by phytoplankton. In the oceans, where zinc is nearly depleted, diatoms use cadmium as a catalytic metal atom in cadmium carbonic anhydrase (CDCA). Here we report the crystal structures of CDCA in four distinct forms: cadmium-bound, zinc-bound, metal-free and acetate-bound. Despite lack of sequence homology, CDCA is a structural mimic of a functional β-carbonic anhydrase dimer, with striking similarity in the spatial organization of the active site residues. CDCA readily exchanges cadmium and zinc at its active site—an apparently unique adaptation to oceanic life that is explained by a stable opening of the metal coordinating site in the absence of metal. Given the central role of diatoms in exporting carbon to the deep sea, their use of cadmium in an enzyme critical for carbon acquisition establishes a remarkable link between the global cycles of cadmium and carbon.

The evolutionary inheritance of elemental stoichiometry in marine phytoplankton

Phytoplankton is a nineteenth century ecological construct for a biologically diverse group of pelagic photoautotrophs that share common metabolic functions but not evolutionary histories. In contrast to terrestrial plants, a major schism occurred in the evolution of the eukaryotic phytoplankton that gave rise to two major plastid superfamilies. The green superfamily appropriated chlorophyll b, whereas the red superfamily uses chlorophyll c as an accessory photosynthetic pigment. Fossil evidence suggests that the green superfamily dominated Palaeozoic oceans. However, after the end-Permian extinction, members of the red superfamily rose to ecological prominence. The processes responsible for this shift are obscure. Here we present an analysis of major nutrients and trace elements in 15 species of marine phytoplankton from the two superfamilies. Our results indicate that there are systematic phylogenetic differences in the two plastid types where macronutrient (carbon:nitrogen:phosphorus) stoichiometries primarily reflect ancestral pre-symbiotic host cell phenotypes, but trace element composition reflects differences in the acquired plastids. The compositional differences between the two plastid superfamilies suggest that changes in ocean redox state strongly influenced the evolution and selection of eukaryotic phytoplankton since the Proterozoic era.

Bioaccumulation of mercury and methylmercury

The factors controlling the accumulation of mercury in fish are poorly understood. The oil invoked lipid solubility of MMHg is an inadequate explanation because inorganic Hg complexes, which are not bioaccumulated, are as lipid soluble as their MMHg analogs and, unlike other hydrophobic compounds, MMHg in fish resides in protein rather than fat tissue. We show that passive uptake of the lipophilic complexes (primarily HgCl2 and CH3HgCl) results in high concentrations of both inorganic and MMHg in phytoplankton. However, differences in partitioning within phytoplankton cells between inorganic mercury — which is principally membrane bound — and MMHg — which accumulates in the cytoplasm — lead to a greater assimilation of MMHg during zooplankton grazing. Most of the discrimination between inorganic and MMHg thus occurs during trophic transfer while the major enrichment factor is between water and phytoplankton. As a result, MMHg concentrations in fish are ultimately determined by water chemistry which controls MMHg speciation and uptake at the base of the food chain.

Pitfalls of sequential extractions

Abstract An increasing number of researchers are using sequential extractions to determine the speciation of trace elements in sediments. Unfortunately, sequential extraction methods have not been successfully validated. The results are simply taken as providing “operational definitions” of the phases one is trying to measure. A more rigorous approach is required to gain insight into the geochemistry of trace elements or their bioavailability.

AQUIL: A CHEMICALLY DEFINED PHYTOPLANKTON CULTURE MEDIUM FOR TRACE METAL STUDIES12

The medium Aquil and its variations have been successfully used for trace metal studies of marine phytoplankton (diatoms and dinoflagellates) over the past three years. Here, the recipes, the methods of preparation and the chemical composition of Aquil are presented in detail. To permit complete definition of chemical speciation of the various components as calculated from thermodynamic equilibria, trace element contamination is controlled and the formation of precipitates and adsorbates is avoided. It is established that Aquil is suitable for physiological experiments with a variety of marine phytoplankters representing all major phyla. Modifications of the basic recipe and design of chemically defined media in general are discussed.