Structural characterization of natural nickel and copper binding ligands along the US GEOTRACES Eastern Pacific Zonal Transect

© The Author(s), 2016. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Frontiers in Marine Science 3 (2016): 243, doi:10.3389/fmars.2016.00243.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.Support was provided by the National Science Foundation (NSF) program in Chemical Oceanography (OCE-1356747, OCE-1233261, OCE-1233733, OCE-1233502, and OCE-1237034), the NSF Science and Technology Center for Microbial Oceanography Research and Education (C-MORE; DBI-0424599), the Gordon and Betty Moore Foundation (#3298 and 3934), and the Simons Foundation (#329108, DR)

Daily changes in phytoplankton lipidomes reveal mechanisms of energy storage in the open ocean

© The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Nature Communications 9 (2018): 5179, doi:10.1038/s41467-018-07346-z.Sunlight is the dominant control on phytoplankton biosynthetic activity, and darkness deprives them of their primary external energy source. Changes in the biochemical composition of phytoplankton communities over diel light cycles and attendant consequences for carbon and energy flux in environments remain poorly elucidated. Here we use lipidomic data from the North Pacific subtropical gyre to show that biosynthesis of energy-rich triacylglycerols (TAGs) by eukaryotic nanophytoplankton during the day and their subsequent consumption at night drives a large and previously uncharacterized daily carbon cycle. Diel oscillations in TAG concentration comprise 23 ± 11% of primary production by eukaryotic nanophytoplankton representing a global flux of about 2.4 Pg C yr−1. Metatranscriptomic analyses of genes required for TAG biosynthesis indicate that haptophytes and dinoflagellates are active members in TAG production. Estimates suggest that these organisms could contain as much as 40% more calories at sunset than at sunrise due to TAG production.This work was supported by a grant from the Simons Foundation, and is a contribution of the Simons Collaboration on Ocean Processes and Ecology (SCOPE award # 329108, B.A.S.V.M.). K.W.B. was further supported by the Postdoctoral Scholarship Program at Woods Hole Oceanographic Institution & U.S. Geological Survey

Seasonal and annual fluxes of nutrients and organic matter from large rivers to the Arctic Ocean and surrounding seas

Author Posting. © The Author(s), 2011. This is the author's version of the work. It is posted here by permission of Springer for personal use, not for redistribution. The definitive version was published in Estuaries and Coasts 35 (2012): 369-382, doi:10.1007/s12237-011-9386-6.River inputs of nutrients and organic matter impact the biogeochemistry of arctic estuaries and the Arctic Ocean as a whole, yet there is considerable uncertainty about the magnitude of fluvial fluxes at the pan-arctic scale. Samples from the six largest arctic rivers, with a combined watershed area of 11.3 x 106 km2, have revealed strong seasonal variations in constituent concentrations and fluxes within rivers as well as large differences among the rivers. Specifically, we investigate fluxes of dissolved organic carbon, dissolved organic nitrogen, total dissolved phosphorus, dissolved inorganic nitrogen, nitrate, and silica. This is the first time that seasonal and annual constituent fluxes have been determined using consistent sampling and analytical methods at the pan arctic scale, and consequently provide the best available estimates for constituent flux from land to the Arctic Ocean and surrounding seas. Given the large inputs of river water to the relatively small Arctic Ocean, and the dramatic impacts that climate change is having in the Arctic, it is particularly urgent that we establish the contemporary river fluxes so that we will be able to detect future changes and evaluate the impact of the changes on the biogeochemistry of the receiving coastal and ocean systems.This work was supported by the National Science Foundation through grants OPP-0229302, OPP-0519840, OPP-0732522, and OPP-0732944. Additional support was provided by the U. S. Geological Survey (Yukon River) and the Department of Indian and Northern Affairs (Mackenzie River)

Liquid chromatographic isolation of individual carbohydrates from environmental matrices for stable carbon analysis and radiocarbon dating

International audienceCarbohydrates are among the most abundant organic molecules in both aquatic and terrestrial ecosystems; however, very few studies have addressed their isotopic signature using compound-specific isotope analysis, which provides additional information on their origin (δ13C) and fate (Δ14C). In this study, semi-preparative liquid chromatography with refractive index detection (HPLC-RI) was employed to produce pure carbohydrate targets for subsequent offline δ13C and Δ14C isotopic analysis. δ13C analysis was performed by elemental analyzer-isotope ratio mass spectrometer (EA-IRMS) whereas Δ14C analysis was performed by an innovative measurement procedure based on the direct combustion of the isolated fractions using an elemental analyzer coupled to the gas source of a mini carbon dating system (AixMICADAS). In general, four successive purifications with Na+, Ca2+, Pb2+, and Ca2+ cation-exchange columns were sufficient to produce pure carbohydrates. These carbohydrates were subsequently identified using mass spectrometry by comparing their mass spectra with those of authentic standards.The applicability of the proposed method was tested on two different environmental samples comprising marine particulate organic matter (POM) and total suspended atmospheric particles (TSP). The obtained results revealed that for the marine POM sample, the δ13C values of the individual carbohydrates ranged from −18.5 to −16.8‰, except for levoglucosan and mannosan, which presented values of −27.2 and −26.2‰, respectively. For the TSP sample, the δ13C values ranged from −26.4 to −25.0‰. The galactose and glucose Δ14C values were 19 and 43‰, respectively, for the POM sample. On the other hand, the levoglucosan radiocarbon value was 33‰ for the TSP sample. These results suggest that these carbohydrates exhibit a modern age in both of these samples. Radiocarbon HPLC collection window blanks, measured after the addition of phthalic acid (14C free blank), ranged from −988 to −986‰ for the abovementioned compounds, indicating a very small background isotopic influence from the whole purification procedure. Overall, the proposed method does not require derivatization steps, produces extremely low blanks, and may be applied to different types of environmental samples

Siderophore-based microbial adaptations to iron scarcity across the eastern Pacific Ocean

Nearly all iron dissolved in the ocean is complexed by strong organic ligands of unknown composition. The effect of ligand composition on microbial iron acquisition is poorly understood, but amendment experiments using model ligands show they can facilitate or impede iron uptake depending on their identity. Here we show that siderophores, organic compounds synthesized by microbes to facilitate iron uptake, are a dynamic component of the marine ligand pool in the eastern tropical Pacific Ocean. Siderophore concentrations in iron-deficient waters averaged 9 pM, up to fivefold higher than in iron-rich coastal and nutrient-depleted oligotrophic waters, and were dominated by amphibactins, amphiphilic siderophores with cell membrane affinity. Phylogenetic analysis of amphibactin biosynthetic genes suggests that the ability to produce amphibactins has transferred horizontally across multiple Gammaproteobacteria, potentially driven by pressures to compete for iron. In coastal and oligotrophic regions of the eastern Pacific Ocean, amphibactins were replaced with lower concentrations (1–2 pM) of hydrophilic ferrioxamine siderophores. Our results suggest that organic ligand composition changes across the surface ocean in response to environmental pressures. Hydrophilic siderophores are predominantly found across regions of the ocean where iron is not expected to be the limiting nutrient for the microbial community at large. However, in regions with intense competition for iron, some microbes optimize iron acquisition by producing siderophores that minimize diffusive losses to the environment. These siderophores affect iron bioavailability and thus may be an important component of the marine iron cycle.National Science Foundation (U.S.) (OCE-1356747)National Science Foundation (U.S.) (OCE-1233261)National Science Foundation (U.S.) (OCE-1237034)National Science Foundation (U.S.) (DBI-0424599)Gordon and Betty Moore Foundation (Grant GBMF3298)Gordon and Betty Moore Foundation (Grant GBMF3934)Simons Foundation (329108

DOE Ocean Carbon Sequestration Research Workshop 2005 - May 26th thru 27th

The purpose of this workshop was to bring together the principal investigators of all the projects that were being funded under the DOE ocean carbon sequestration research program. The primary goal of the workshop was to interchange research results, to discuss ongoing research, and to identify future research priorities. In addition, we hoped to encourage the development of synergies and collaborations between the projects and to write an EOS article summarizing the results of the meeting. The primary outcome of the meeting was a decision to write two papers for the reviewed literature on carbon sequestration by iron fertilization, and on carbon sequestration by deep sea injection and to examine the possibility of an overview article in EOS on the topic of ocean carbon sequestration. There has been significant progress on several of these goals since the meeting: (1) Review of carbon sequestration by iron fertilization: One of the most interesting results of the meeting was a presentation by John Marshall of iron fertilization simulations carried out at MIT that suggested a much higher efficiency of CO2 uptake from the atmosphere with a newer generation model (since published by Dutkiewicz, et al., 2006]) than earlier studies had found with an older generation model (cf., Gnanadesikan, et al., 2003). The decision was made that this finding should be investigated with a new set of simulations using other newer generation models with realistic parameterization of biological processes. This research has progressed considerably, with the modeling groups of MIT, Princeton University, UCLA, Stanford University, and Los Alamos National Laboratory participating. A follow up meeting of the principal participants was held on September 11-15, 2006, using remaining funds from the original grant, and three manuscripts are now in an advanced state of preparation: Chavez, F., et al., in preparation. A review of iron fertilization Jin, X., N. Gruber, and H. Frenzel, in preparation. Factors impacting the atmospheric uptake efficiency of iron fertilization. Sarmiento, J. L., R. D. Slater, M. E. Maltrud, and J. Dunne, in preparation. Iron fertilization models revisited. The new iron fertilization simulation confirms some of the MIT results of higher efficiency, while also drawing attention to several additional processes not considered in previous studies such as the effect of eddies in an eddy resolving model (Jin et al., in preparation), and the effect of including a realistic atmospheric reservoir in the models as in Gnanadesikan, et al. [2003], which leads to a significant reduction in the overall efficiency (cf., Sarmiento et al., in preparation). (2) Review of carbon sequestration by deep sea injection: An outline of paper was completed by J. Barry, but this project has not progressed beyond this point. (3) Overview article for EOS on ocean carbon sequestration. This idea was put on hold until the issues raised by the MIT study of iron fertilization had been resolved. After the three papers on this topic are completed, we will decide if an overview article is still merited. References Dutkiewicz, S., et al. (2006), Controls on ocean productivity and air-sea carbon flux: An adjoint model sensitivity study, Geophysical Research Letters, 33, L02603, doi:10.1029/2005GL024987. Gnanadesikan, A., et al. (2003), Effects of patchy ocean fertilization on atmospheric carbon dioxide and biological production, Global Biogeochem. Cycles, 17, doi: 10.1029/2002GB001940