Overcoming adversity through diversity: aquatic carbon concentrating mechanisms.

Carbon concentrating mechanism (CCM) systems, asso- ciated with evolutionarily diverse aquatic photosynthetic organisms, make a major contribution to global net primary productivity and marine carbon sequestration. Here, an overview of these global contributions is pre- sented from their evolutionary origins, including a pos- sible trigger for their diversi cation when the aqueous O2/CO2 ratio rose above parity, and a re-de nition of the paradox of phytoplankton. The reviews and research in the special issue also include molecular physiology and ecology of CCMs, through to future potential applications for sustaining carbon sequestration and supporting ter- restrial crop productivity

Carbon isotope ratioss of coccolith-associated polysaccharides of Emiliania huxleyi as a function of growth rate and CO2 concentration

The calcite plates, or coccoliths, of haptophyte algae including Emiliania huxleyi are formed in intracellular vesicles in association with water–soluble acidic polysaccharides. These coccolith–associated polysaccharides (CAPs) are involved in regulating coccolith formation and have been recovered from sediment samples dating back to ∼180 Ma. Paired measurements of the carbon isotopic compositions of CAPs and coccolith calcite have been proposed as a novel paleo–pCO2 barometer, but additional proxy validation and development are still required. Here we present culture results quantifying carbon isotopic offsets between CAPs and other cellular components: bulk organic biomass, alkenones, and calcite. E. huxleyi was grown in nitrate–limited chemostat experiments at growth rates (µ) of 0.20–0.62/d and carbon dioxide concentrations of 10.7–17.6 µmol/kg. We find that CAPs are isotopically enriched by 4.5–10.1‰ relative to bulk organic carbon, exhibiting smaller isotopic offsets at faster growth rates and lower CO2 concentrations. This variability suggests that CAPs record a complementary signature of past growth conditions with different sensitivity than alkenones or coccolith calcite. By measuring the isotopic compositions of all three molecules and minerals of self-consistent origin, the ratio µ/[CO2(aq)] may be reconstructed with fewer assumptions than current approaches

Constraints on the vital effect in coccolithophore and dinoflagellate calcite by oxygen isotopic modification of seawater

Author Posting. © The Author(s), 2014. This is the author's version of the work. It is posted here by permission of Elsevier for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 141 (2014): 612-627, doi:10.1016/j.gca.2014.05.002.In this study, we show that there are independent controls of 18O/16O and 13C/12C fractionation in coccolithophore and dinoflagellate calcite due to the contrasting kinetics of each isotope system. We demonstrate that the direction and magnitude of the oxygen isotope fractionation with respect to equilibrium is related to the balance between calcification rate and the replenishment of the internal pool of dissolved inorganic carbon (DIC). As such, in fast growing cells, such as those of Emiliania huxleyi and Gephyrocapsa oceanica (forming the so-called “heavy group”), calcification of the internal carbon pool occurs faster than complete isotopic re-adjustment of the internal DIC pool with H2O molecules. Hence, coccoliths reflect the heavy oxygen isotope signature of the CO2 overprinting the whole DIC pool. Conversely, in large and slow growing cells, such as Coccolithus pelagicus ssp. braarudii, complete re-equilibration is achieved due to limited influx of CO2 leading to coccoliths that are precipitated in conditions close to isotopic equilibrium (“equilibrium group”). Species exhibiting the most negative oxygen isotope composition, such as Calcidiscus leptoporus (“light group”), precipitate coccolith under increased pH in the coccolith vesicle, as previously documented by the “carbonate ion effect”. We suggest that, for the carbon isotope system, any observed deviation from isotopic equilibrium is only “apparent”, as the carbon isotopic composition in coccolith calcite is controlled by a Rayleigh fractionation originating from preferential incorporation of 12C into organic matter. Therefore, species with low PIC/POC ratios as E. huxleyi and G. oceanica are shifted towards positive carbon isotope values as a result of predominant carbon fixation into the organic matter. By contrast, cells with higher PIC/POC as C. braarudii and C. leptoporus maintain, to some extent, the original negative isotopic composition of the CO2. The calcareous dinoflagellate Thoracosphaera heimii exhibits different behaviour for both isotopic systems, in particular with respect to its very negative carbon isotope composition, owing to coeval intra and extracellular biomineralisation in this group. In this study, we also investigate the sensitivity of 18O/16O fractionation to varying ambient oxygen isotope composition of the medium for inorganic, coccolithophore, and dinoflagellate calcite precipitated under controlled laboratory conditions. The varying responses of different taxa to increased oxygen isotope composition of the growth medium may point to a potential bias in sea surface temperature reconstructions that are based on the oxygen isotopic compositions of sedimentary calcite, especially during times of changing seawater oxygen isotopic composition. Overall, this study represent an important step towards establishing a mechanistic understanding of the “vital effect” in coccolith and dinoflagellate calcite, and provides valuable information for interpreting the geochemistry of the calcareous nannofossils in the sedimentary record, at both monospecific and interspecies levels.MH is grateful to the Natural Environment Research Council (NERC) for funding through Postdoctoral Fellowship (NE/H015523/1). TJH is supported by the Postdoctoral Scholar Program at the Woods Hole Oceanographic Institution, with funding provided by the Doherty Foundation. REMR was supported through European Research Council (ERC) grant SP2-GA-2008-200915

Reply to Morel : cadmium as a micronutrient and macrotoxin in the oceans

Author Posting. © The Author(s), 2013. This is the author's version of the work. It is posted here by permission of National Academy of Sciences for personal use, not for redistribution. The definitive version was published in Proceedings of the National Academy of Sciences of the United States of America 110 (2013): E1878, doi:10.1073/pnas.1305068110.We thank François Morel for his interest in our study. Morel states that our conclusions are based on the approximate match between the Cd-isotope composition of cultured bacteria and the fractionation of Cd isotopes seen in seawater (1). This match is only a minor component of our argument, and we welcome the opportunity to reiterate our case

Glacial-interglacial changes in bottom-water oxygen content on the Portuguese margin

During the last and penultimate glacial maxima, atmospheric CO2 concentrations were lower than present, possibly in part because of increased storage of respired carbon in the deep oceans. The amount of respired carbon present in a water mass can be calculated from its oxygen content through apparent oxygen utilization; the oxygen content can in turn be calculated from the carbon isotope gradient within the sediment column. Here we analyse the shells of benthic foraminifera occurring at the sediment surface and the oxic/anoxic interface on the Portuguese Margin to reconstruct the carbon isotope gradient and hence bottom-water oxygenation over the past 150,000 years. We find that bottom-water oxygen concentrations were 45 and 65 μmol kg−1 lower than present during the last and penultimate glacial maxima, respectively. We calculate that concentrations of remineralized organic carbon were at least twice as high as today during the glacial maxima. We attribute these changes to decreased ventilation linked to a reorganization of ocean circulation and a strengthened global biological pump. If the respired carbon pool was of a similar size throughout the entire glacial deep Atlantic basin, then this sink could account for 15 and 20 per cent of the glacial PCO2 drawdown during the last and penultimate glacial maxima

Declining metal availability in the Mesozoic seawater reflected in phytoplankton succession

Variable trace metal concentrations in the Precambrian ocean were closely linked to oxygen availability, although less is known about the drivers of seawater trace metal chemistry after the spread of complex life into the Phanerozoic eon. A major phytoplankton succession took place at the transition from the Palaeozoic to the Mesozoic era (~250 Myr ago), from an ocean dominated by the green Archaeplastida to secondary endosymbiotic algae with red-algal-derived plastids. Here, our comparative genomic analysis of 26 complete proteomes and metal domain analysis of additional 608 partially complete sequences of phytoplankton reveal that groups with different evolutionary history have distinct metal-binding proteins and contrasting metal acquisition strategies, adapted to differing availability of trace metals. The secondary-endosymbiont-bearing lineages are better adapted to well-oxygenated, nutrient-poor environments. This is supported by an enhanced thiol-based binding affinity of their transporters, coupled with minimized proteomic requirement for trace elements such as iron, copper and zinc at both protein and domain levels. Such different metal requirements across these lineages suggest a drastic decline in open-ocean trace metal concentrations at the inception of the Mesozoic, contributing to the shifts in phytoplankton communities that drove major changes in ocean chemical buffering.info:eu-repo/semantics/publishedVersio

The cadmium-phosphate relationship in brine: biological versus physical control over micronutrients in sea ice environments

Despite supporting productive ecosystems in the high latitudes, the relationship between macro- and micronutrients in sea ice environments and their impact on surface productivity is poorly documented. In seawater, the macronutrient phosphate and the micronutrient cadmium follow similar distributions, which are controlled by biological processes in surface waters. We investigated cadmium and phosphate in sea ice brine, and the biological and physical processes controlling their distribution. Cadmium concentrations in sea ice brine ranged from 0.092.4 nmol kg-1, and correlated well with salinity. Our results show that micronutrients in sea ice are most probably sourced from the seawater from which it froze rather than external sources such as atmospheric deposition. The weak correlation between sea ice cadmium and phosphate, and the positive relationship between cadmium and biomass, suggests against biological uptake being a principal control over micronutrient distribution even in a highly productive setting. Instead, brine expulsion and dilution play a dominant role in cadmium distribution in sea ice. Nutrient dilution within brine channels during melting, and contrasting sea ice and open water phytoplankton populations, suggests that late spring sea ice is not a significant source of nutrients or biomass to seawater. We suggest that future changes in sea ice seasonality may impact nutrient distribution and Antarctic marine ecosystems. © 2009 Antarctic Science Ltd

Pore fluid modeling approach to identify recent meltwater signals on the west Antarctic Peninsula

The sensitivity of sea level to melting from polar ice sheets and glaciers during recent natural and anthropogenic climate fluctuations is poorly constrained beyond the period of direct observation by satellite. We have investigated glacial meltwater events during the Anthropocene by adapting the pioneering approach of modeling trends in d18O in the pore waters of deep‐sea cores, previously used to constrain the size of ice sheets during the Last Glacial Maximum. We show that during recent warm periods, meltwater from glacier retreat drains into the coastal fjords, leaving a signature of depleted d18O values and low Cl concentrations in the pore water profiles of rapidly accumulating sediments. Here we model such pore water profiles in a piston core to constrain the timing and magnitude of an ice sheet retreat event at Caley Glacier on the west Antarctic Peninsula, and the result is compared with local ice front movement. This approach of pore water modeling was then applied in another kasten core and tested by a series of sensitivity analyses. The results suggest that our approach may be applied in fjords of different sedimentary settings to reconstruct the glacier history and allow insight into the sensitivity of polar glaciers to abrupt warming events