The role of polysaccharides and diatom exudates in the redox cycling of Fe and the photoproduction of hydrogen peroxide in coastal seawaters

Abstract. The effect of artificial acidic polysaccharides (PS) and exudates of Phaeodactylum tricornutum on the half-life of Fe(II) in seawater was investigated in laboratory experiments. Strong photochemical hydrogen peroxide (H2O2) production of 5.2 to 10.9 nM (mg C)−1 h−1 was found in the presence of PS and diatom exudates. Furthermore when illuminated with UV light the presence of algal exudates had a net stabilising effect on ferrous iron in seawater (initial value 100 nmol L−1) above that expected from oxidation kinetics. In the dark the PS gum xanthan showed no stabilising effect on Fe(II). The photochemical formation of superoxide (O2−) in the presence of diatom exudates and its reducing effect on Fe(III) appears to result in greater than expected concentrations of Fe(II). A model of the photochemical redox cycle of iron incorporating these processes supported the observed data well. Diatom exudates seem to have the potential to play an important role for the photochemistry of iron in coastal waters.

[1]  K. Timmermans,et al.  Enhancement of the reactive iron pool by marine diatoms , 2008 .

[2]  T. Waite,et al.  Superoxide-mediated reduction of organically complexed iron(III): Impact of pH and competing cations (Ca2+) , 2007 .

[3]  Andreas Oschlies,et al.  Iron profiles and speciation of the upper water column at the Bermuda Atlantic Time-series Study site: a model based sensitivity study , 2007 .

[4]  C. M. G. van den Berg,et al.  Wavelength dependence of the photochemical reduction of iron in arctic seawater. , 2007, Environmental science & technology.

[5]  T. Waite,et al.  Superoxide mediated reduction of organically complexed iron(III): comparison of non-dissociative and dissociative reduction pathways. , 2007, Environmental science & technology.

[6]  E. Boyle,et al.  Mesoscale Iron Enrichment Experiments 1993-2005: Synthesis and Future Directions , 2007, Science.

[7]  T. Waite,et al.  Superoxide-mediated reduction of ferric iron in natural aquatic systems , 2006 .

[8]  T. Waite,et al.  Role of superoxide in the photochemical reduction of iron in seawater , 2006 .

[9]  L. Balistrieri,et al.  Organic carbon to 234Th ratios of marine organic matter , 2006 .

[10]  L. Gerringa,et al.  Enhancement and inhibition of iron photoreduction by individual ligands in open ocean seawater , 2006 .

[11]  T. Waite,et al.  Superoxide-mediated dissolution of amorphous ferric oxyhydroxide in seawater. , 2006, Environmental science & technology.

[12]  F. Millero,et al.  Competition Between O2 and H2O2 in the Oxidation of Fe(II) in Natural Waters , 2006 .

[13]  B. Sulzberger,et al.  Effects of size and origin of natural dissolved organic matter compounds on the redox cycling of iron in sunlit surface waters , 2005, Aquatic Sciences.

[14]  A. Butler Marine Siderophores and Microbial Iron Mobilization , 2005, Biometals.

[15]  J. Nishioka,et al.  Spatial and temporal distribution of Fe(II) and H2O2 during EisenEx, an open ocean mescoscale iron enrichment , 2005 .

[16]  T. Waite,et al.  Reduction of organically complexed ferric iron by superoxide in a simulated natural water. , 2005, Environmental science & technology.

[17]  H. Wolterbeek,et al.  The influence of UV irradiation on the photoreduction of iron in the Southern Ocean , 2005 .

[18]  F. Millero,et al.  Oxidation of iron (II) nanomolar with H2O2 in seawater , 2005 .

[19]  S. Bertilsson,et al.  Iron enrichment and photoreduction of iron under UV and PAR in the presence of hydroxycarboxylic acid: implications for phytoplankton growth in the Southern Ocean , 2004 .

[20]  David L. Williams,et al.  Pharmacokinetics of fungal (1-3)-beta-D-glucans following intravenous administration in rats. , 2004, International immunopharmacology.

[21]  L. Gerringa,et al.  The influence of solar ultraviolet radiation on the photochemical production of H , 2004 .

[22]  F. Millero,et al.  The oxidation of Fe(II) in NaCl–HCO3− and seawater solutions in the presence of phthalate and salicylate ions: a kinetic model , 2004 .

[23]  R. Geider,et al.  The role of iron in phytoplankton photosynthesis, and the potential for iron-limitation of primary productivity in the sea , 1994, Photosynthesis Research.

[24]  T. Waite,et al.  Kinetics of iron complexation by dissolved natural organic matter in coastal waters , 2003 .

[25]  T. Waite,et al.  Predicting iron speciation in coastal waters from the kinetics of sunlight-mediated iron redox cycling , 2003, Aquatic Sciences.

[26]  W. Sunda,et al.  Effect of pH, light, and temperature on Fe–EDTA chelation and Fe hydrolysis in seawater , 2003 .

[27]  T. Waite,et al.  Effect of dissolved natural organic matter on the kinetics of ferrous iron oxygenation in seawater. , 2003, Environmental science & technology.

[28]  F. Morel,et al.  The Biogeochemical Cycles of Trace Metals in the Oceans , 2003, Science.

[29]  P. Croot,et al.  Continuous shipboard determination of Fe(II) in polar waters using flow injection analysis with chemiluminescence detection , 2002 .

[30]  T. Waite,et al.  Kinetic model for Fe(II) oxidation in seawater in the absence and presence of natural organic matter. , 2002, Environmental science & technology.

[31]  U. Passow Transparent exopolymer particles (TEP) in aquatic environments , 2002 .

[32]  K. Bruland,et al.  Collection and detection of natural iron-binding ligands from seawater , 2001 .

[33]  P. Croot,et al.  Organic complexation of iron in the Southern Ocean , 2001 .

[34]  A. Shiller,et al.  The distribution of hydrogen peroxide in the southern and central Atlantic ocean , 2001 .

[35]  A. Roychoudhury,et al.  The ferrozine method revisited: Fe(II)/Fe(III) determination in natural waters , 2000 .

[36]  K. Mopper,et al.  Photochemical production of hydrogen peroxide in Antarctic Waters , 2000 .

[37]  P. Croot,et al.  Determination of Iron Speciation by Cathodic Stripping Voltammetry in Seawater Using the Competing Ligand 2‐(2‐Thiazolylazo)‐p‐cresol (TAC) , 2000 .

[38]  F. Millero,et al.  The effect of organic compounds in the oxidation kinetics of Fe(II) , 2000 .

[39]  I. Obernosterer Photochemical transformations of dissolved organic matter and its subsequent utilization by marine bacterioplankton , 2000 .

[40]  A. Shiller,et al.  Determination of Subnanomolar Levels of Hydrogen Peroxide in Seawater by Reagent-Injection Chemiluminescence Detection , 1999 .

[41]  P. Worsfold,et al.  Shipboard determination of hydrogen peroxide in the western Mediterranean sea using flow injection with chemiluminescence detection , 1998 .

[42]  P. Falkowski,et al.  Biogeochemical Controls and Feedbacks on Ocean Primary Production , 1998, Science.

[43]  D. Hutchins,et al.  Iron-limited diatom growth and Si:N uptake ratios in a coastal upwelling regime , 1998, Nature.

[44]  Edward A. Boyle,et al.  What controls dissolved iron concentrations in the world ocean? — a comment , 1997 .

[45]  R. Zika,et al.  Hydrogen peroxide lifetimes in south Florida coastal and offshore waters , 1997 .

[46]  S. Myklestad,et al.  A sensitive and rapid method for analysis of dissolved mono- and polysaccharides in seawater , 1997 .

[47]  D. Lean,et al.  Hydrogen peroxide formation: The interaction of ultraviolet radiation and dissolved organic carbon in lake waters along a 43–75°N gradient , 1996 .

[48]  D. Sedlak,et al.  Iron reduction by photoproduced superoxide in seawater , 1995 .

[49]  D. King,et al.  Photochemical redox cycling of iron in coastal seawater , 1995 .

[50]  K. Bruland,et al.  Complexation of iron(III) by natural organic ligands in the Central North Pacific as determined by a new competitive ligand equilibration/adsorptive cathodic stripping voltammetric method , 1995 .

[51]  C. V. D. Berg Evidence for organic complexation of iron in seawater , 1995 .

[52]  K. Kuma,et al.  Photoreduction of Fe(III) by hydroxycarboxylic acids in seawater , 1995 .

[53]  S. Canonica,et al.  Determination of the Reaction Quantum Yield for the Photochemical Degradation of Fe(III)-EDTA: Implications for the Environmental Fate of EDTA in Surface Waters. , 1995, Environmental science & technology.

[54]  F. Millero,et al.  Rates and Mechanism of Fe(II) Oxidation at Nanomolar Total Iron Concentrations. , 1995, Environmental science & technology.

[55]  D. Sedlak,et al.  The role of copper and oxalate in the redox cycling of iron in atmospheric waters , 1993 .

[56]  F. Morel,et al.  Investigations of iron coordination and redox reactions in seawater using 59Fe radiometry and ion-pair solvent extraction of amphiphilic iron complexes , 1992 .

[57]  P. Hatcher,et al.  Bulk Chemical Characteristics of Dissolved Organic Matter in the Ocean , 1992, Science.

[58]  Yoshihiro Suzuki,et al.  Photo-reduction of Fe(III) by dissolved organic substances and existence of Fe(II) in seawater during spring blooms , 1992 .

[59]  O. Donard,et al.  The photolysis of colloidal iron in the oceans , 1991, Nature.

[60]  J. Moffett,et al.  An investigation ofhydrogen peroxide chemistry in surface waters of Vineyard Sound with H218O2 and 18O2 , 1990 .

[61]  O. Zafiriou Chemistry of superoxide ion-radical (O2−) in seawater. I. (HOO) and uncatalyzed dismutation kinetics studied by pulse radiolysis , 1990 .

[62]  F. Millero,et al.  The oxidation of Fe(II) with H2O2 in seawater , 1989 .

[63]  W. J. Cooper,et al.  Photochemical formation of hydrogen peroxide in natural waters exposed to sunlight. , 1988, Environmental science & technology.

[64]  D. Goodhead Spatial and temporal distribution of energy. , 1988, Health physics.

[65]  K. Bruland,et al.  Direct determination of dissolved cobalt and nickel in seawater by differential pulse cathodic stripping voltammetry preceded by adsorptive collection of cyclohexane-1,2-dione dioxime complexes , 1988 .

[66]  F. Millero,et al.  The oxidation kinetics of Fe(II) in seawater , 1987 .

[67]  W. Gehrmann Ultraviolet irradiances of various lamps used in animal husbandry , 1987 .

[68]  J. Rush,et al.  Pulse Radiolytic Studies of the Reactions of HO2/O2-with Fe(II)/Fe(III) Ions. , 1986 .

[69]  J. Rush,et al.  Pulse radiolytic studies of the reaction of perhydroxyl/superoxide O2- with iron(II)/iron(III) ions. The reactivity of HO2/O2- with ferric ions and its implication on the occurrence of the Haber-Weiss reaction , 1985 .

[70]  P. Brezonik,et al.  Oxygen consumption in humic-colored waters by a photochemical ferrous-ferric catalytic cycle. , 1981, Environmental science & technology.

[71]  R. Zepp,et al.  Rates of direct photolysis in aquatic environment , 1977 .

[72]  Thomas L. Theis,et al.  Complexation of iron(II) by organic matter and its effect on iron(II) oxygenation , 1974 .

[73]  Albert Gilbert Goursat,et al.  Oxidation of Iron , 1972 .

[74]  L. Stookey Ferrozine---a new spectrophotometric reagent for iron , 1970 .

[75]  J. A. Hellebust,et al.  EXCRETION OF SOME ORGANIC COMPOUNDS BY MARINE PHYTOPLANKTON1 , 1965 .

[76]  E. Percival,et al.  1298. The carbohydrates of phaeodactylum tricornutum. Part I. Preliminary examination of the organism, and characterisation of low molecular weight material and of a glucan , 1965 .

[77]  John A. Nelder,et al.  A Simplex Method for Function Minimization , 1965, Comput. J..