Dissolved iron (II) in the Baltic Sea surface water and implications for cyanobacterial bloom development

Abstract. Iron chemistry measurements were conducted during summer 2007 at two distinct locations in the Baltic Sea (Gotland Deep and Landsort Deep) to evaluate the role of iron for cyanobacterial bloom development in these estuarine waters. Depth profiles of Fe(II) were measured by chemiluminescent flow injection analysis (CL-FIA). Up to 0.9 nmol Fe(II) L−1 were detected in light penetrated surface waters, which constitutes up to 20% to the dissolved Fe pool. This bioavailable iron source is a major contributor to the Fe requirements of Baltic Sea phytoplankton and apparently plays a major role for cyanobacterial bloom development during our study. Measured Fe(II) half life times in oxygenated water exceed predicted values and indicate organic Fe(II) complexation. Potential sources for Fe(II) ligands, including rainwater, are discussed. Fe(II) concentrations of up to 1.44 nmol L−1 were detected at water depths below the euphotic zone, but above the oxic anoxic interface. Mixed layer depths after strong wind events are not deep enough in summer time to penetrate the oxic-anoxic boundary layer. However, Fe(II) from anoxic bottom water may enter the sub-oxic zone via diapycnal mixing and diffusion.

[1]  A. Kosakowska,et al.  Iron-dependent growth of and siderophore production by two heterotrophic bacteria isolated from brackish water of the southern Baltic Sea. , 2009, Microbiological research.

[2]  P. Statham,et al.  The role of polysaccharides and diatom exudates in the redox cycling of Fe and the photoproduction of hydrogen peroxide in coastal seawaters , 2009 .

[3]  M. Hassellöv,et al.  Fractionation of iron species and iron isotopes in the Baltic Sea euphotic zone , 2009 .

[4]  R. J. Kieber,et al.  Fe(II) in coastal rainwater: Changing stability and concentrations , 2009, Aquatic Sciences.

[5]  L. Yezek,et al.  Donnan effects in metal speciation analysis by DET/DGT. , 2008, Environmental science & technology.

[6]  S. Dahlke,et al.  Effects of short-term manipulations in iron nutrition of Nodularia spumigena from near-coast blooms (southern Baltic Sea) , 2008 .

[7]  P. Worsfold,et al.  Hydroxamate siderophores: occurrence and importance in the Atlantic Ocean. , 2008, Environmental science & technology.

[8]  R. J. Kieber,et al.  Rainwater as a source of Fe(II)‐stabilizing ligands to seawater , 2008 .

[9]  H. Ploug Cyanobacterial surface blooms formed by Aphanizomenon sp. and Nodularia spumigena in the Baltic Sea: Small‐scale fluxes, pH, and oxygen microenvironments , 2008 .

[10]  A. Omstedt,et al.  Distribution, long-term development and mass balance calculation of total alkalinity in the Baltic Sea , 2008 .

[11]  S. Fan Photochemical and biochemical controls on reactive oxygen and iron speciation in the pelagic surface ocean , 2008 .

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

[13]  D. King,et al.  Persistence of iron(II) in surface waters of the western subarctic Pacific , 2008 .

[14]  D. Dyrssen,et al.  Determination of hydrogen sulphide , 2007 .

[15]  C. Stedmon,et al.  Characteristics of dissolved organic matter in Baltic coastal sea ice: allochthonous or autochthonous origins? , 2007, Environmental science & technology.

[16]  U. Larsson,et al.  Blooms of Baltic Sea Aphanizomenon sp. (Cyanobacteria) collapse after internal phosphorus depletion , 2007 .

[17]  H. Meier Modeling the pathways and ages of inflowing salt- and freshwater in the Baltic Sea , 2007 .

[18]  Ragnar Elmgren,et al.  Satellite measurements of cyanobacterial bloom frequency in the Baltic Sea: interannual and spatial variability , 2007 .

[19]  T. Goepfert,et al.  Reduced iron associated with secondary nitrite maxima in the Arabian Sea , 2007 .

[20]  K. Barbeau,et al.  Organic and redox speciation of iron in the eastern tropical North Pacific suboxic zone , 2007 .

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

[22]  P. Croot,et al.  Surface active substances in the upper water column during a Southern Ocean Iron Fertilization Experiment (EIFEX) , 2007 .

[23]  T. Fukushima,et al.  Dissolved iron and its speciation in a shallow eutrophic lake and its inflowing rivers. , 2007, Water research.

[24]  H. Wolterbeek,et al.  Kinetic study reveals weak Fe-binding ligand, which affects the solubility of Fe in the Scheldt estuary , 2007 .

[25]  P. Boyd,et al.  Luminescent Whole-Cell Cyanobacterial Bioreporter for Measuring Fe Availability in Diverse Marine Environments , 2006, Applied and Environmental Microbiology.

[26]  P. Carlsson,et al.  Stimulation of nitrogen-fixing cyanobacteria in a Baltic Sea plankton community by land-derived organic matter or iron addition , 2006 .

[27]  K. Barbeau Photochemistry of Organic Iron(III) Complexing Ligands in Oceanic Systems , 2006, Photochemistry and photobiology.

[28]  T. Waite,et al.  The FeL model of iron acquisition: Nondissociative reduction of ferric complexes in the marine environment , 2006 .

[29]  K. Timmermans,et al.  Iron-binding ligands in Dutch estuaries are not affected by UV induced photochemical degradation , 2006 .

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

[31]  J. Ingri,et al.  Trace metal speciation in brackish water using diffusive gradients in thin films and ultrafiltration: comparison of techniques. , 2006, Environmental science & technology.

[32]  Martin A. Schmidt,et al.  A trace metal (Pb, Cd, Zn, Cu) balance for surface waters in the eastern Gotland Basin, Baltic Sea , 2006 .

[33]  F. Millero,et al.  The role of Fe(II) species on the oxidation of Fe(II) in natural waters in the presence of O2 and H2O2 , 2006 .

[34]  Hao Zhang,et al.  Diffusion coefficients of metals and metal complexes in hydrogels used in diffusive gradients in thin films. , 2006 .

[35]  S. Sander,et al.  Acquisition of iron bound to strong organic complexes, with different Fe binding groups and photochemical reactivities, by plankton communities in Fe‐limited subantarctic waters , 2005 .

[36]  J. Nishioka,et al.  Major deviations of iron complexation during 22 days of a mesoscale iron enrichment in the open Southern Ocean , 2005 .

[37]  Ulf Riebesell,et al.  Synthesis of iron fertilization experiments: From the iron age in the age of enlightenment , 2005 .

[38]  R. Zepp,et al.  Photochemical mineralization of dissolved organic nitrogen to ammonium in the Baltic sea. , 2005, Environmental science & technology.

[39]  F. Morel,et al.  Extracellular production of superoxide by marine diatoms: Contrasting effects on iron redox chemistry and bioavailability , 2005 .

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

[41]  F. Morel,et al.  A general kinetic model for iron acquisition by eukaryotic phytoplankton , 2005 .

[42]  C. Pohl,et al.  The coupling of long-term trace metal trends to internal trace metal fluxes at the oxic–anoxic interface in the Gotland Basin (57°19,20′N; 20°03,00′E) Baltic Sea , 2005 .

[43]  T. Waite,et al.  Use of superoxide as an electron shuttle for iron acquisition by the marine cyanobacterium Lyngbya majuscula. , 2005, Environmental science & technology.

[44]  M. Hassellöv Relative molar mass distributions of chromophoric colloidal organic matter in coastal seawater determined by Flow Field-Flow Fractionation with UV absorbance and fluorescence detection , 2005 .

[45]  B. J. Smith,et al.  Organic complexation of Fe(II) and its impact on the redox cycling of iron in rain. , 2005, Environmental science & technology.

[46]  A. Baker,et al.  Influence of the ITCZ on H2O2 in near surface waters in the equatorial Atlantic Ocean , 2004 .

[47]  I. Rodushkin,et al.  Size distribution of colloidal trace metals and organic carbon during a coastal bloom in the Baltic Sea , 2004 .

[48]  M. Öztürk,et al.  The distribution and speciation of iron along 6°E in the Southern Ocean , 2004 .

[49]  S. Bashir,et al.  Novel copper‐binding and nitrogen‐rich thiols produced and exuded by Emiliania huxleyi , 2004 .

[50]  S. Sander,et al.  Investigation of interparticle forces in natural waters: effects of adsorbed humic acids on iron oxide and alumina surface properties. , 2004, Environmental science & technology.

[51]  F. Morel,et al.  Simultaneous determination of iron reduction and uptake by phytoplankton , 2004 .

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

[53]  R. T. Powell,et al.  Photochemical degradation of organic iron complexing ligands in seawater , 2003, Aquatic Sciences.

[54]  K. Bruland,et al.  6.02 – Controls of Trace Metals in Seawater , 2003 .

[55]  Lucas J. Stal,et al.  BASIC: Baltic Sea cyanobacteria. An investigation of the structure and dynamics of water blooms of cyanobacteria in the Baltic Sea responses to a changing environment. , 2003 .

[56]  E. Carpenter,et al.  Iron requirements for dinitrogen‐ and ammonium‐supported growth in cultures of Trichodesmium (IMS 101): Comparison with nitrogen fixation rates and iron: carbon ratios of field populations , 2003 .

[57]  L. M. Laglera,et al.  Copper complexation by thiol compounds in estuarine waters , 2003 .

[58]  A. Butler,et al.  Photochemical reactivity of siderophores produced by marine heterotrophic bacteria and cyanobacteria based on characteristic Fe(III) binding groups , 2003 .

[59]  M. Brzezinski,et al.  Iron and zinc effects on silicic acid and nitrate uptake kinetics in three high-nutrient, low-chlorophyll (HNLC) regions , 2003 .

[60]  E. Carpenter,et al.  A REVISED ESTIMATE OF THE IRON USE EFFICIENCY OF NITROGEN FIXATION, WITH SPECIAL REFERENCE TO THE MARINE CYANOBACTERIUM TRICHODESMIUM SPP. (CYANOPHYTA) 1 , 2003 .

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

[62]  M. Öztürk,et al.  Iron Speciation in the Trondheim Fjord from the Perspective of Iron Limitation for Phytoplankton , 2002 .

[63]  Hao Zhang,et al.  Performance of the diffusive gradients in thin films technique for measuring Ca and Mg in freshwater , 2002 .

[64]  E. Carpenter,et al.  Iron and marine nitrogen fixation: progress and future directions. , 2002, Research in microbiology.

[65]  T. Waite,et al.  Chemiluminescence of luminol in the presence of iron(II) and oxygen: oxidation mechanism and implications for its analytical use. , 2001, Analytical chemistry.

[66]  Kenneth W. Bruland,et al.  Iron and macronutrients in California coastal upwelling regimes: Implications for diatom blooms , 2001 .

[67]  A. Butler,et al.  Photochemical cycling of iron in the surface ocean mediated by microbial iron(iii)-binding ligands , 2001, Nature.

[68]  P. Boyd,et al.  Retention of dissolved iron and Fe II in an iron induced Southern Ocean phytoplankton bloom , 2001 .

[69]  R Olsonen,et al.  The History of Cyanobacterial Blooms in the Baltic Sea , 2001, Ambio.

[70]  R. Elmgren,et al.  Baltic Sea nitrogen fixation estimated from the summer increase in upper mixed layer total nitrogen , 2001 .

[71]  C. Gobler,et al.  Phosphorus limitation of nitrogen fixation by Trichodesmium in the central Atlantic Ocean , 2001, Nature.

[72]  A. Vogler,et al.  Photoreduction of aqueous ferrioxamine B by oxalate induced by outer-sphere charge transfer excitation , 2001 .

[73]  N. M. Price,et al.  REDUCTION AND TRANSPORT OF ORGANICALLY BOUND IRON BY THALASSIOSIRA OCEANICA (BACILLARIOPHYCEAE) , 2001 .

[74]  B. Neilan,et al.  Ecological and molecular investigations of cyanotoxin production. , 2001, FEMS microbiology ecology.

[75]  G. B. Avery,et al.  Iron speciation in coastal rainwater: concentration and deposition to seawater , 2001 .

[76]  A. Ledin,et al.  Colloid dynamics and transport of major elements through a boreal river — brackish bay mixing zone , 2000 .

[77]  K. Bruland,et al.  The distribution of colloidal and particulate bioactive metals in Narragansett Bay, RI , 2000 .

[78]  N. M. Price,et al.  Nitrate regulation of Fe reduction and transport by Fe‐limited Thalassiosira oceanica , 2000 .

[79]  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 .

[80]  Susanne Menden-Deuer,et al.  Carbon to volume relationships for dinoflagellates, diatoms, and other protist plankton , 2000 .

[81]  A. Butler,et al.  Determination of conditional stability constants and kinetic constants for strong model Fe-binding ligands in seawater , 2000 .

[82]  N. M. Price,et al.  Utilization of iron bound to strong organic ligands by plankton communities in the subarctic Pacific Ocean , 1999 .

[83]  Hao Zhang,et al.  Diffusional characteristics of hydrogels used in DGT and DET techniques , 1999 .

[84]  L. Stal,et al.  NUTRIENT CONTROL OF CYANOBACTERIAL BLOOMS IN THE BALTIC SEA , 1999 .

[85]  C. Pohl,et al.  The effect of redox processes on the partitioning of Cd, Pb, Cu, and Mn between dissolved and particulate phases in the Baltic Sea , 1999 .

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

[87]  D. Hutchins,et al.  An iron limitation mosaic in the California upwelling regime , 1998 .

[88]  R. Hallberg,et al.  Trace metal speciation in sea and pore water of the Gotland Deep, Baltic Sea, 1994 , 1998 .

[89]  M. Wells Marine colloids: A neglected dimension , 1998, Nature.

[90]  M. Pamatmat Non-photosynthetic oxygen production and non-respiratory oxygen uptake in the dark: a theory of oxygen dynamics in plankton communities , 1997 .

[91]  R. Röttgers,et al.  Dynamics of UV‐driven hydrogen peroxide formation on an intertidal sandflat , 1997 .

[92]  G. Gadd,et al.  Binding of copper and zinc to three cyanobacterial microcystins quantified by differential pulse polarography , 1997 .

[93]  B. Allard,et al.  River Discharge of Humic Substances and Humic-bound Metals to the Gulf of Bothnia , 1997 .

[94]  M. Wedborg,et al.  Photobleaching of fluorescence and the organic carbon concentration in a coastal environment , 1996 .

[95]  D. Caron,et al.  Role of protozoan grazing in relieving iron limitation of phytoplankton , 1996, Nature.

[96]  Hao Zhang,et al.  Performance Characteristics of Diffusion Gradients in Thin Films for the in Situ Measurement of Trace Metals in Aqueous Solution , 1995 .

[97]  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 .

[98]  W. Sunda,et al.  Iron uptake and growth limitation in oceanic and coastal phytoplankton , 1995 .

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

[100]  H. Utkilen,et al.  Iron-stimulated toxin production in Microcystis aeruginosa , 1995, Applied and environmental microbiology.

[101]  K. Johnson,et al.  Iron photochemistry in seawater from the equatorial Pacific , 1994 .

[102]  W. Davison,et al.  In situspeciation measurements of trace components in natural waters using thin-film gels , 1994, Nature.

[103]  D. King,et al.  Photochemical redox cycling of iron in NaCl solutions , 1993 .

[104]  R. Grieken,et al.  Geochemistry of suspended matter from the Baltic Sea 2. Results of bulk trace metal analysis by AAS , 1992 .

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

[106]  D. O’Sullivan,et al.  Measurement of Fe(II) in surface water of the equatorial Pacific , 1991 .

[107]  L. Mayer,et al.  The phttoconversion of colloidal iron oxyhydroxides in seawater , 1991 .

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

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

[110]  J. Sanders-Loehr,et al.  Induction of siderophore activity in Anabaena spp. and its moderation of copper toxicity , 1987, Applied and environmental microbiology.

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

[112]  F. Morel,et al.  Photoreductive dissolution of colloidal iron oxides in natural waters. , 1984, Environmental science & technology.

[113]  J. Pempkowiak The origin of humic substances in the baltic sea evaluated on the basis of chemical properties , 1983 .

[114]  F. Morel,et al.  The influence of aqueous iron chemistry on the uptake of iron by the coastal diatom Thalassiosira weissflogii1 , 1982 .

[115]  E. Sholkovitz,et al.  The coagulation, solubility and adsorption properties of Fe, Mn, Cu, Ni, Cd, Co and humic acids in a river water , 1981 .

[116]  Siegfried Krüger,et al.  PUMP-CTD-System for trace metal sampling with a high vertical resolution. A test in the Gotland Basin, Baltic Sea. , 2008, Chemosphere.

[117]  A. Kustka,et al.  The role of unchelated Fe in the iron nutrition of phytoplankton , 2008 .

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

[119]  A. Kosakowska,et al.  The marine diatom cyclotella meneghiniana kűtzing as a producer of siderophore-like substances , 2005 .

[120]  C. Pohl,et al.  A sediment trap flux study for trace metals under seasonal aspects in the stratified Baltic Sea (Gotland Basin; 57°19.20′N; 20°03.00′E) , 2004 .

[121]  U. Larsson,et al.  Annual variability in ciliate community structure, potential prey and predators in the open northern Baltic Sea proper , 2004 .

[122]  F. Azam,et al.  Pelagic plankton growth and resource limitations in the Baltic Sea , 2001 .

[123]  P. Larsson,et al.  A Systems Analysis of the Baltic Sea , 2001, Ecological Studies.

[124]  S. Bergström,et al.  Climate and Hydrology of the Baltic Basin , 2001 .

[125]  I. Rodushkin,et al.  Determination of trace metals in estuarine and sea-water reference materials by high resolution inductively coupled plasma mass spectrometry , 1997 .

[126]  B. Allard,et al.  Photodegradation of aquatic humic substances : an important factor for the Baltic carbon cycle? , 1997 .

[127]  Jaan Laanemets,et al.  Initiation of cyanobacterial blooms in a frontal region at the entrance to the Gulf of Finland, Baltic Sea , 1996 .

[128]  S. Wilhelm,et al.  Growth, iron requirements, and siderophore production in iron‐limited Synechococcus PCC 72 , 1996 .

[129]  P. Herman,et al.  Comparison of the linear Van den Berg/Ružić transformation and a non-linear fit of the Langmuir isotherm applied to Cu speciation data in the estuarine environment , 1995 .

[130]  J. Pempkowiak Complexing properties of humic substances isolated from sea water; the contribution of these substances to complexing capacities of water from the Baltic Sea and geochemical implications of this phenomenon , 1991 .

[131]  D. Dyrssen,et al.  Increasing hydrogen sulfide concentration and trace metal behavior in the anoxic Baltic waters , 1990 .