Claire P. Till

Structural Characterization of Natural Nickel and Copper Binding Ligands along the US GEOTRACES Eastern Pacific Zonal Transect

Organic ligands form strong complexes with many trace elements in seawater. Various metals can compete for the same ligand chelation sites, and the final speciation of bound metals is determined by relative binding affinities, concentrations of binding sites, uncomplexed metal concentrations, and association/dissociation kinetics. Different ligands have a wide range of metal affinities and specificities. However, the chemical composition of these ligands in the marine environment remains poorly constrained, which has hindered progress in modeling marine metal speciation. In this study, we detected and characterized natural ligands that bind copper (Cu) and nickel (Ni) in the eastern South Pacific Ocean with liquid chromatography tandem inductively coupled plasma mass spectrometry (LC-ICPMS), and high resolution electrospray ionization mass spectrometry (ESIMS). Dissolved Cu, Ni, and ligand concentrations were highest near the coast. Chromatographically unresolved polar compounds dominated ligands isolated near the coast by solid phase extraction. Offshore, metal and ligand concentrations decreased, but several new ligands appeared. One major ligand was detected that bound both Cu2+ and Ni2+. Based on accurate mass and fragmentation measurements, this compound has a molecular formula of [C20H21N4O8S2 + M]+ (M = metal isotope) and contains several azole-like metal binding groups. Additional lipophilic Ni complexes were also present only in oligotrophic waters, with masses of 649, 698, and 712 m/z (corresponding to the 58Ni metal complex). Molecular formulae of [C32H54N3O6S2Ni]+ and [C33H56N3O6S2Ni]+ were determined for two of these compounds. Addition of Cu and Ni to the samples also revealed the presence of additional compounds that can bind both Ni and Cu. Although these specific compounds represent a small fraction of the total dissolved Cu and Ni pool, they highlight the compositional diversity and spatial heterogeneity of marine Ni and Cu ligands, as well as variability in the extent to which different metals in the same environment compete for ligand binding.

Diatom Transcriptional and Physiological Responses to Changes in Iron Bioavailability across Ocean Provinces

Changes in iron (Fe) bioavailability influence diatom physiology and community composition, and thus have a profound impact on primary productivity and ecosystem dynamics. Iron limitation of diatom growth rates has been demonstrated in both oceanic and coastal waters of the Northeast Pacific Ocean and is predicted to become more pervasive in future oceans. However, it is unclear how the strategies utilized by phytoplankton to cope with low Fe bioavailability and resupply differ across these ocean provinces. We investigated the response of diatom communities to variable Fe conditions through incubation experiments performed in the Fe mosaic of the California Upwelling Zone and along a natural Fe gradient in the Northeast Pacific Ocean. Through coupling gene expression of two dominant diatom taxa (Pseudo-nitzschia and Thalassiosira) with biological rate process measurements, we provide an in-depth examination of the physiological and molecular responses associated with varying Fe status. Following Fe enrichment, oceanic diatoms showed distinct differential expression of gene products involved in nitrogen assimilation, photosynthetic carbon fixation and vitamin production compared to diatoms from low-Fe coastal sites, possibly driven by the chronic nature of Fe stress at the oceanic site. Genes of interest involved in Fe and N metabolism additionally exhibited divergent expression patterns between the two diatom taxa investigated, demonstrating that diverse diatoms may invoke alternative strategies when dealing with the identical changes in their environment. We report here several mechanisms used distinctly by coastal or oceanic diatom communities as well as numerous taxa-specific strategies for coping with Fe stress and rearranging nutrient metabolism following Fe enrichment.

Arctic deep-water ferromanganese-oxide deposits reflect the unique characteristics of the Arctic Ocean

Little is known about marine mineral deposits in the Arctic Ocean, an ocean dominated by continental shelf and basins semi-closed to deep-water circulation. Here, we present data for ferromanganese crusts and nodules collected from the Amerasia Arctic Ocean in 2008, 2009, and 2012 (HLY0805, HLY0905, HLY1202). We determined mineral and chemical compositions of the crusts and nodules and the onset of their formation. Water column samples from the GEOTRACES program were analyzed for dissolved and particulate scandium concentrations, an element uniquely enriched in these deposits. The Arctic crusts and nodules are characterized by unique mineral and chemical compositions with atypically high growth rates, detrital contents, Fe/Mn ratios, and low Si/Al ratios, compared to deposits found elsewhere. High detritus reflects erosion of submarine outcrops and North America and Siberia cratons, transport by rivers and glaciers to the sea, and distribution by sea ice, brines, and currents. Uniquely high Fe/Mn ratios are attributed to expansive continental shelves, where diagenetic cycling releases Fe to bottom waters, and density flows transport shelf bottom water to the open Arctic Ocean. Low Mn contents reflect the lack of a mid-water oxygen minimum zone that would act as a reservoir for dissolved Mn. The potential host phases and sources for elements with uniquely high contents are discussed with an emphasis on scandium. Scandium sorption onto Fe oxyhydroxides and Sc-rich detritus account for atypically high scandium contents. The opening of Fram Strait in the Miocene and ventilation of the deep basins initiated Fe-Mn crust growth ∼15 Myr ago.

Taxon‐specific contributions to silica production in natural diatom assemblages

The metabolic activity and growth of phytoplankton taxa drives their ecological function and contribution to biogeochemical processes. We present the first quantitative, taxon-resolved silica production rates, growth rates, and silica content estimates for co-occurring diatoms along two cross-shelf transects off the California coast using the fluorescent tracer PDMPO (2-(4-pyridyl)-5-((4-(2-dimethylaminoethylaminocarbamoyl)methoxy)phenyl)oxazole), and confocal microscopy. Taxon contribution to total diatom community silica production was predominantly a function of the surface area of new frustule that each taxon created as opposed to cell abundance or frustule thickness. The influential role of surface area made large diatoms disproportionately important to community silica production over short time scales (<1 d). In some cases, large taxa that comprised only ~15% of numerical cell abundance accounted for over 50% of total community silica production. Over longer time scales relevant to bloom dynamics, the importance of surface area declines and growth rate becomes the dominant influence on contribution to production. The relative importance of surface area and growth rate in relation to silica production was modeled as the time needed for a smaller, faster-growing taxon to create more surface area than a larger, slower-growing taxon. Differences in growth rate between the taxa effected the model outcome more than differences in surface area. Shifts in relative silica production among taxa are time restricted by finite resources that limit the duration of a bloom. These patterns offer clues as to how taxa respond to their environment and the consequences for both species succession and the potential diatom contribution to elemental cycling.

Divergent gene expression among phytoplankton taxa in response to upwelling

Frequent blooms of phytoplankton occur in coastal upwelling zones creating hotspots of biological productivity in the ocean. As cold, nutrient-rich water is brought up to sunlit layers from depth, phytoplankton are also transported upwards to seed surface blooms that are often dominated by diatoms. The physiological response of phytoplankton to this process, commonly referred to as shift-up, is characterized by rapid growth rates and increases in nitrate assimilation. To examine the molecular underpinnings behind this phenomenon, metatranscriptomics was applied to a simulated upwelling experiment using natural phytoplankton communities from the California Upwelling Zone. An increase in diatom growth following five days of incubation was attributed to the genera Chaetoceros and Pseudo-nitzschia. Here we show that certain bloom-forming diatoms exhibit a distinct transcriptional response that coordinates shift-up where diatoms exhibited the greatest transcriptional change following upwelling; however, comparison of coexpressed genes exposed overrepresentation of distinct sets within each of the dominant phytoplankton groups. The analysis revealed that diatoms frontload genes involved in nitrogen assimilation likely in order to outcompete other groups for available nitrogen during upwelling events. We speculate that the evolutionary success of diatoms may be due, in part, to this proactive response to frequently encountered changes in their environment.

Divergent gene expression among phytoplankton taxa in response to upwelling: Divergent phytoplankton responses to upwelling

Frequent blooms of phytoplankton occur in coastal upwelling zones creating hotspots of biological productivity in the ocean. As cold, nutrient-rich water is brought up to sunlit layers from depth, phytoplankton are also transported upwards to seed surface blooms that are often dominated by diatoms. The physiological response of phytoplankton to this process, commonly referred to as shift-up, is characterized by increases in nitrate assimilation and rapid growth rates. To examine the molecular underpinnings behind this phenomenon, metatranscriptomics was applied to a simulated upwelling experiment using natural phytoplankton communities from the California Upwelling Zone. An increase in diatom growth following 5 days of incubation was attributed to the genera Chaetoceros and Pseudo-nitzschia. Here, we show that certain bloom-forming diatoms exhibit a distinct transcriptional response that coordinates shift-up where diatoms exhibited the greatest transcriptional change following upwelling; however, comparison of co-expressed genes exposed overrepresentation of distinct sets within each of the dominant phytoplankton groups. The analysis revealed that diatoms frontload genes involved in nitrogen assimilation likely in order to outcompete other groups for available nitrogen during upwelling events. We speculate that the evolutionary success of diatoms may be due, in part, to this proactive response to frequently encountered changes in their environment.

Dissolved scandium, yttrium, and lanthanum in the surface waters of the North Atlantic: Potential use as an indicator of scavenging intensity

Recent work has begun to elucidate the biogeochemical cycling of scandium (Sc) in the open ocean, but so far no surface distribution data has been reported of dissolved Sc, and no basin-scale surface distributions have been reported of yttrium (Y) or lanthanum (La). This work presents basin-wide surface Sc, Y and La data in a section across the North Atlantic subtropical gyre (2011 GEOTRACES GA03) and investigates the potential utility of these distributions. This work uses dissolved and aerosol concentration data for La and Sc to estimate their surface ocean residence times in both the center of the oligotrophic gyre and near the African coastline. This work additionally shows that the surface distribution of Sc in the North Atlantic correlates with the shape of the gyre as inferred by isotherm depth, with lower Sc concentrations at the gyre boundaries. This pattern suggests that Sc could be drawn down by the elevated particle flux at the gyre boundaries. In this case, Sc removal could be used as an indicator of scavenging intensity. In order to account for variable input of Sc to the surface ocean, we propose normalizing the Sc distribution to that of Y or La, which are much less particle reactive and are input via dust to the surface North Atlantic in constant ratios with Sc. Such normalization improves the correlation with isotherm depth. We propose that the variations in dissolved Y/Sc and La/Sc ratios may be due to preferential Sc scavenging, and could therefore indicate scavenging intensity.