Skip to main content
SpringerLink
Log in

Iron Speciation in Precipitation in the North-Eastern Mediterranean and Its Relationship with Sahara Dust

  • Published:
Journal of Atmospheric Chemistry Aims and scope Submit manuscript

Abstract

Precipitation samples collected at Erdemli, Turkey, during February 1996–June 1997 were analysed to determine iron content and speciation. The purpose of the measurements was to examine the atmospheric abundance of iron and to quantify its solubility in the region. Spectrophotometric analyses of Fe(II) and reducible Fe(III) in precipitation samples, along with measurements of pH, conductivity, filterable iron (Fefilt), particulate aluminium (Alpar) and particulateiron (Fepar) were performed to determine iron solubility, which principally affects its bioavailability. Backward trajectories corresponding to the sampling dates were analysed to determine the sources of atmospheric constituents arriving at the site. Among these, the mineral dust transported from the Great Sahara to the region is considered to be a rich source of iron. The concentration of Fe(II) varied from below detection limit (0.02 μM) up to 0.42 μM,while the maximum concentration of total reactive Fe (referred as Fe(II) + reducible Fe(III) = Fereac) was found to be 1.0 μM in precipitation. A strong correlation was found between particulate Fe and Al fractions, both of crustal origin. No correlation was observed between the soluble and insoluble fractions of iron. The soluble iron fraction, Fe(II) concentration varied independently from the concentrations of reducible Fe(III), Fefilt, Fepar, and from the pH of the precipitation. The Fefilt fraction (size < 0.45 μm), measuredby Atomic Absorption Spectrophotometer, and frequently interpreted to be the soluble iron fraction in the literature, was found to be significantly higher than the corresponding Fereac fraction inprecipitation samples, most likely due to the colloidal iron content of the Fefilt fraction passing through the 0.45 μm pore size filter. The volume weighted mean Fefilt concentration of the precipitation samples collected during the episodic `red rain' events was found to be relatively higher. The geometric mean ratios of soluble Fe(II) and of Fereac to Total Fe (Fefilt + Fepar), werefound to be 1.6% and 2.1%, respectively, while the mean ratioof Fefilt to Total Fe was 9.6%. The flux of bioavailable iron (Fereac)fraction in most atmospheric wet deposition events was found to be sufficient for supporting the maximum primary production rates that are typical for the Eastern Mediterranean Sea.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  • Anderson, M. A. and Morel, F. M. M., 1982: The influence of aqueous iron chemistry on the uptake of iron by coastal diatom Thalassiosira weissflogii, Limnol. Oceanogr. 27, 789–813.

    Google Scholar 

  • Baeyens, W., Dehairs, F., and Dedeurwaerder, H., 1990: Wet and dry deposition fluxes above the North Sea, Atmos. Environ. 24A (7), 1693–1703.

    Google Scholar 

  • Behra, P. and Sigg, L., 1990: Evidence for redox cycling of iron in atmospheric water droplets, Nature 344, 419–421.

    Google Scholar 

  • Benoit, G., Oktay-Marshall, S. D., Cantu, A., Hood, E. M., Coleman, C. H., Çorapçýo¢glu, M. O., and Santschi, P. H., 1994: Partitioning of Cu, Pb, Ag, Zn, Fe, Al and Mn between filter-retained particles, colloids and solution in six Texas estuaries, Mar. Chem. 45, 307–336.

    Google Scholar 

  • Bergametti, G., Remoudaki, E., Losno, R., Steiner, E., Chatenet, B., and Buat-Menard, P., 1992: Source, transport and deposition of atmospheric phosphorus over the northwestern Mediterranean, J. Atmos. Chem. 14, 501–513.

    Google Scholar 

  • Box, J. D., 1984: Observations on the use of iron(II) complexing agents to fractionate the total filterable iron in natural water samples, Water Res., 18 (4), 397–402.

    Google Scholar 

  • Boyd, P.W., Muggli, D. L., Varela, D. E., Goldblatt, R. H., Chretien, R., Orians, K. J., and Harrison, P. J., 1996: In vitro iron enrichment experiments in the NE subarctic Pacific, Marine Ecology Progress Series 136, 179–193.

    Google Scholar 

  • Brody, L. R. and Nestor, M. J. R., 1980: Handbook for Forecasters in the Mediterranean, Part 2. Regional forecasting aids for the Mediterranean Basin, Technical Report TR 80–10, pp. VII-1; VII-13, Naval Environmental Prediction Research Facility, Monterey, California.

  • Bruland, K. W., Donat, J. R., and Hutchins, D. A., 1991: Interactive influences of bioactive trace metals on biological production in oceanic waters, Limnol. Oceanogr. 36 (8), 1555–1577.

    Google Scholar 

  • Chester, R., Lin, F. J., and Murphy, K. J. T., 1989: A three stage sequential leaching scheme for the characterisation of the sources and environmental mobility of trace metals in the marine aerosol, Environ. Tech. Letts. 10, 887–900.

    Google Scholar 

  • Chester, R., Nimmo,M., Murphy, K. J. T., and Nicholas, E., 1990: Atmospheric trace metals transported to the Western Mediterranean: Data from a station on Cap Ferrat, EROS 2000 2nd workshop, Water Pollution Research Report 20, pp. 597–612, March 90, Blanes, Spain.

  • Chester, R., Murphy, K. J. T., Lin, F. J., Berry, A. S., Bradshaw, G. A., and Corcoran, P. A., 1993: Factors controlling the solubilities of trace metals from non-remote aerosols deposited to the sea surface by the ‘dry’ deposition mode, Mar. Chem. 42, 107–126.

    Google Scholar 

  • Chester, R., Nimmo, M., and Corcoran, P. A., 1997: Rain water-aerosol trace metal relationships at Cap Ferrat: A coastal site in the Western Mediterranean, Mar. Chem. 58, 293–312.

    Google Scholar 

  • Church, T. M., Arimoto, R., Barrie, L. A., Dehairs, F., Dulac, F., Jickells, T. D., Mart, L., Sturges, W. T., and Zoller, W. H., 1990: The long-range atmospheric transport of trace elements: A critical evaluation, in A. H. Knap (ed.), The Long-Range Atmospheric Transport of Natural and Contaminant Substances, Kluwer Academic Publishers, The Netherlands, pp. 37–58.

    Google Scholar 

  • Dedik, A. N., Hoffmann, P., and Ensling, J., 1992: Chemical characterization of iron in atmospheric aerosols, Atmos. Environ. 26, 2545–2548.

    Google Scholar 

  • De Haan, H., Veldhuis, M. J. W., and Moed, J. R., 1985: Availability of dissolved iron from Tjeukemeer, The Netherlands, for iron-limited growing Scenedesmus quadricauda, Water Res. 19, 235–239.

    Google Scholar 

  • De Haan, H. and De Boer, T., 1986: Geochemical aspects of aqueous iron, phosphorus and dissolved organic carbon in the humic Lake Tjeukemeer, The Netherlands, Freshwater Biology 16, 661–672.

    Google Scholar 

  • Donaghay, P. L., Liss, P. S., Duce, R. A., Kester, D. R., Hanson, A. K., Villareal, T., Tindale, N. W., and Gifford, D. J., 1991: The role of episodic atmospheric nutrient inputs in the chemical and biological dynamics of oceanic ecosystems, Oceanography 4 (2), 62–70.

    Google Scholar 

  • Duce, R. A. and Tindale, N. W., 1991: Atmospheric transport of iron and its deposition in the ocean, Limnol. Oceanogr. 36 (8), 1715–1726.

    Google Scholar 

  • Erel, Y., 1991: Transport of natural lead and cadmium in rivers: Global flux implications, PhD Thesis, California Inst. Technol.

  • Erel, Y., Pehkonen, S. O., and Hoffmann, M. R., 1993: Redox chemistry of iron in fog and stratus clouds, J. Geophys. Res. 98 (10), 18 423–18 434.

    Google Scholar 

  • Falconer, R. E. and Falconer, P. D., 1980: Determination of cloud water acidity at a mountain observatory in the Adirondack Mountains of New York State, J. Geophys. Res. 85, 7465–7470.

    Google Scholar 

  • Faust, B. C., 1994: Photochemistry of clouds, fogs and aerosols, Env. Sci. Tech. 28, 217–222.

    Google Scholar 

  • Finden, D. A. S., Tipping, E., Jaworski, G. H. M., and Reynolds, C. S., 1984: Light-induced reduction of natural iron (III) oxide and its relevance to phytoplankton, Nature 309, 783–784.

    Google Scholar 

  • Guieu, C., Martin, J.M., Thomas, A. J., and Poulichet, F. E., 1991: Atmospheric versus river inputs of metals to the Gulf of Lions. Total concentrations, partitioning and fluxes, Mar. Poll. Bull. 22 (4), 176–183.

    Google Scholar 

  • Guieu, C., Zhang, J., Thomas, A. J., Martin, J. M., and Brun-Cotton, J. C., 1993: Significance of the atmospheric fallout upon the upper layer water chemistry of the northwestern Mediterranean, J. Atmos. Chem. 17, 45–60.

    Google Scholar 

  • Guerzoni, S., Chester, R., Dulac, F., Herut, B., Loye-Pilot, M. D., Measures, C., Migon, C., Molinaroli, E., Moulin, C., Rossini, P., Saydam, C., Soudine, A., and Ziveri, P., 1999: The role of atmospheric deposition in the biogeochemistry of the Mediterranean Sea, Progress in Oceanography 44, 147–190.

    Google Scholar 

  • Heaney, S. I. and Davison, W., 1977: The determination of ferrous iron in natural waters with 2,2'-bipyridyl, Limnol. Oceanogr. 22, 753–760.

    Google Scholar 

  • Honeyman, B. D. and Santschi, P. H., 1988: Metals in aquatic systems, Environ. Sci. Technol. 22, 862–871.

    Google Scholar 

  • Johnson, K. S., Coale, K. H., Elrod, V. A., and Tindale, N.W., 1994: Iron photochemistry in seawater from the equatorial Pacific, Mar. Chem. 46, 319–334.

    Google Scholar 

  • Kester, D. R., 1994: Marine redox cycle of iron, in Iron Speciation and its Biological Availability in Seawater: AWorkshop, Bermuda Biological Station for Research, 1–5 May, 1994, Participant Abstracts, pp.45–46.

  • Kremling, K. and Streu, P., 1993: Saharan dust influenced trace element fluxes in deep north Atlantic subtropical waters, Deep-Sea Res. 40, 1155–1168.

    Google Scholar 

  • Kubilay, N., 1996: The Composition of atmospheric aerosol over the eastern Mediterranean: The coupling of geochemical and meteorological parameters, PhD Thesis, IMS-METU, Turkey, p. 214.

    Google Scholar 

  • Kubilay, N., Nickovic, S., Moulin, C., and Dulac, F., 2000: An illustration of the transport and deposition of mineral dust onto the eastern Mediterranean, Atmos. Environ. 34 (8), 1293–1303.

    Google Scholar 

  • Krom, M. D., Kress, N., and Brenner, S., 1991: Phosphorus limitation of primary productivity in the eastern Mediterranean, Limnol. Oceanogr. 36, 424–432.

    Google Scholar 

  • Lengweiler, H., Buser, W., and Feitknecht, W., 1961: Determination of the solubility of iron(III) hydroxide with iron-59. II. The state of very small amounts of iron(III) hydroxide in aqueous solution, Helv. Chim. Acta. 44, 805–811.

    Google Scholar 

  • Lim, B., Jickells, T. D., Colin, J. L., and Losno, R., 1994: Solubilities of Al, Pb, Cu and Zn in rain sampled in the marine environment over the North Atlantic Ocean and Mediterranean Sea, Global Biogeochemical Cycles 8, 349–362.

    Google Scholar 

  • Losno, R., Bergametti, G., Carlier, P., and Mouvier, G., 1991: Major ions in marine rainwater with attention to sources of alkaline and acidic species, Atmos. Environ. 25A, 763–770.

    Google Scholar 

  • Loye-Pilot, M. D., Martin, J. M., and Morelli, J., 1986: Influence of Saharan dust on the rain acidity and atmospheric input to the Mediterranean, Nature 321, 427–428.

    Google Scholar 

  • Mamane, Y., Dayan, U., and Miller, J. M., 1987: Contribution of alkaline and acidic sources to precipitation in Israel, Sci. Tot. Environ., 61, 15–22.

    Google Scholar 

  • Martin, D., Mithieux, C., and Strauss, B., 1987: On the use of the synoptic vertical wind component in a transport trajectory model, Atmos. Environ. 21, 45–52.

    Google Scholar 

  • Martin, D., Bergametti, G., and Strauss, B., 1990: On the use of the synoptic vertical velocity in trajectory model: validation by geochemical tracers, Atmos. Environ. 24A, 2059–2069.

    Google Scholar 

  • Martin, J. H. and Fitzwater, S. E., 1988: Iron deficiency limits phytoplankton growth in the northeast Pacific subarctic, Nature 331, 341–343.

    Google Scholar 

  • Martin, J. H., Fitzwater, S. E., Gordon, R. M., and Broenkow, W. W., 1989: VERTEX: phytoplankton/ iron studies in the Gulf of Alaska, Deep-Sea Res. 36, 649–680.

    Google Scholar 

  • Martin, J. H., Fitzwater, S. E., and Gordon, R. M., 1990: Iron deficiency limits phytoplankton growth in Antarctic waters. Global Biogeochemical Cycles 4, 5–12.

    Google Scholar 

  • Martin, J. H., Gordon, R. M., and Fitzwater, S. E., 1991: The case for iron, Limnol. Oceanogr. 36 (8), 1793–1803.

    Google Scholar 

  • Martin, J.M. and Whitfield, M., 1983: The significance of the river input of chemical elements to the ocean, in C. S. Wong, E. Boyle, K. W. Bruland, J. D. Burton, and E. D. Goldberg (eds), Trace Metals in Seawater, Plenum Publishing, New York. Corporation, pp. 265–296.

    Google Scholar 

  • Migon, C. and Sandroni, V., 1999: Phosphorus in rainwater: Partitioning inputs and impact on the surface coastal ocean, Limnol. Oceanogr. 44 (4), 1160–1165.

    Google Scholar 

  • Mill, A. J. B., 1980: Colloidal and macromolecular forms of iron in natural waters 1: A review, Env. Tech. Lett. 1, 97–108.

    Google Scholar 

  • Milliman, J. D., Jeftic, L., and Sestini, G., 1992: The Mediterranean Sea and climate change-An overview, in L. Jeftic, J. D. Milliman, and G. Sestini (eds), Climatic Change and Mediterranean, UNEP, pp. 1–14.

  • Morel, F. M. M. and Hudson, R. J. M., 1985: The geobiological cycle of trace elements in aquatic systems: Redfield revisited, in W. Stumm (ed.), Chemical Processes in Lakes, Wiley-Interscience, New York, pp. 251–281.

    Google Scholar 

  • Morel, F. M. M., Hudson, R. J. M., and Price, N. M., 1991: Limitation of productivity by trace metals in the sea, Limnol. Oceanogr. 36, 1742–1755.

    Google Scholar 

  • O'sullivan, D. W., Hanson, A. K., Miller, W. L., and Kester, D. R., 1991: Measurement of Fe(II) in surface water of the equatorial Pacific, Limnol. Oceanogr. 36, 1727–1741.

    Google Scholar 

  • Özsoy, E., 1981: On the Atmospheric Factors Affecting the Levantine Sea. European Centre for Medium Range Weather Forecasts, Technical Report No. 25, p. 29.

  • Özsoy, T., 1999: Kilikya Baseni kýyýsal sistemine ta¸sýnan atmosferik kirleticilerin kaynaklarýnýn belirlenmesi, Atmosferik girdilerin deniz ekosistemi üzerine olan etkileri, Doktora Tezi, Mersin Ñniversitesi, Fen Bilimleri Enstitüsü, Mersin, 209 sayfa.

    Google Scholar 

  • Özsoy, T. and Saydam, A. C., 2000: Acidic and alkaline precipitation in the Cilician Basin, northeastern Mediterranean Sea, Sci. Tot. Environ., 253 (1–3), 95–111.

    Google Scholar 

  • Powell, R. T. and Landing, W. M., 1994: Colloidal iron: Oceanic and estuarine size distributions and reactivity, in Iron Speciation and its Biological Availability in Seawater: A Workshop, Bermuda Biological Station for Research, 1–5 May, 1994, Participant Abstracts, pp. 67–68.

  • Prospero, J. M., 1981: Eolian transport to the world oceans, in C. Emiliani (ed.), The Sea 7, Wiley, New York, pp. 801–874.

    Google Scholar 

  • Prospero, J.M. and Nees, R. T., 1986: Deposition rate of particulate and dissolved Aluminum derived from Saharan dust in precipitation at Miami, Florida, J. Geophys. Res. 92, 14723–14731.

    Google Scholar 

  • Quetel, C. R., Remoudaki, E., Davies, J. E., Miquel, J. C., Fowler, S.W., Lambert, C. E., Bergametti, G., and Buat-Menard, P., 1993: Impact of atmospheric deposition on particulate iron flux and distribution in northwestern Mediterranean waters, Deep Sea Res. 40, 989–1002.

    Google Scholar 

  • Pandis, S. N. and Seinfeld, J. H., 1989: Mathematical modeling of acid deposition due to radiation fog, J. Geophys. Res. 94, 12 911–12 923.

    Google Scholar 

  • Reiff, J., Forbes, G. S., Spicksma, F. Th. M., and Reynders, J. J., 1986: African dust reaching northwestern Europe: A case study to verify trajectory calculations, Journal of Climate and Applied Meteorology 25, 1543–1567.

    Google Scholar 

  • Rich, H.W. and Morel F.M.M., 1990: Availability of well-defined iron colloids to the marine diatom Thalassiosiira weissflogii, Limnol. Oceanogr. 35, 652–662.

    Google Scholar 

  • Saydam, A. C., 1996: Can we predict harmful algae bloom, UNESCO/IOC Harmful Algae Newsletter 15, 5–9.

    Google Scholar 

  • Sheldon, R. W., 1972: Size separation of marine seston by membrane and glass-fibre filters, Limnol. Oceanogr. 17, 494–498.

    Google Scholar 

  • Sivan, O., Erel, Y., Mandler, D., and Nishri, A., 1998: The dynamic redox chemistry of iron in the epilimnion of lake Kinneret (Sea of Galilee), Geochim. Cosmochim. Acta 62, 565–576.

    Google Scholar 

  • Snell, F. D., Snell, C. T., and Snell, C. A., 1959: Colorimetric Methods of Analysis, Vol. IIA. Van Nostrand, Princetown.

    Google Scholar 

  • Spokes, L. J., Jickells, T. D., and Lim, B., 1994: Solubilisation of aerosol trace metals by cloud processing: A laboratory study, Geochim. Cosmochim. Acta 58 (15), 3281–3287.

    Google Scholar 

  • Spokes, L. J. and Jickells, T. D., 1996: Factors controlling the solubility of aerosol trace metals in the atmosphere and on mixing into seawater, Aquatic Geochemistry 1, 355–374.

    Google Scholar 

  • Stumm, W. and Lee, G. F., 1960: The chemistry of aqueous iron, Schweiz. Z. Hydrol. 22, 295–319.

    Google Scholar 

  • Sulzberger, B., 1992: The role of heterogeneous photochemical reactions for the formation of dissolved iron species in aquatic systems, in J. M. Martin and H. Barts (eds), Water Pollution Research Reports 13, EROS 2000, Fourth Workshop on the North-West Mediterranean Sea, Commission of the European Communities, Brussels, pp. 183–186.

    Google Scholar 

  • Sulzberger, B. and Laubscher, H., 1995: Reactivity of various types of iron(III) (hydr)oxides towards light-induced dissolution, Mar. Chem. 50, 103–115.

    Google Scholar 

  • Talbot, R. W., Harris, R. C., Brawl, E. V., Gregory, G. L., Debaucher, D. I., and Beck, S. M., 1986. Distribution and geochemistry of aerosols in the tropical North Atlantic troposphere: Relationship to Saharan dust, J. Geophys. Res. 91, 5173–5182.

    Google Scholar 

  • Taylor, S. R., 1964: Abundance of chemical elements in the continental crust: A new table, Geochim. Cosmochim. Acta 28, 1273–1285.

    Google Scholar 

  • Uematsu, M., 1987: Study of the continental material transported through the atmosphere to the ocean, Journal of Oceanographic Society, Japan 43, 395–401.

    Google Scholar 

  • UNEP (United Nations Environment Programme), 1995: Manual for the Geochemical Analyses of Marine Sediments and Suspended Particulate Matter. Reference Methods for Marine Pollution Studies. No.63.

  • Wachter, H., 1973: Meteorology, Forecasting the Weather, Collins Publisher, New York, p. 128.

    Google Scholar 

  • Wells, M. L. and Mayer, L. M., 1991: The photoconversion of colloidal iron oxyhydroxides in seawater, Deep-Sea Res. 38(11), 1379–1395.

    Google Scholar 

  • Wells, M. L., Mayer, L. M., and Guillard, R. R. L., 1991: Evaluation of iron as a triggering factor for red tide blooms, Marine Ecology Progress Series 69, 93–102.

    Google Scholar 

  • Wells, M. L., Price, N. M., and Bruland, K. W., 1995: Iron chemistry in seawater and its relationship to phytoplankton: A workshop report, Mar. Chem. 48, 157–182.

    Google Scholar 

  • Zhu, X. R., Prospero, J. M., Millero, F. J., Savoie, D. L., and Brass, G. W., 1992: The solubility of ferric ion in marine mineral aerosol solutions at ambient relative humidities, Mar. Chem. 38, 91–107.

    Google Scholar 

  • Zhu, X. R., Prospero, J. M., Savoie, D. L., Millero, F. J., Zika, R. G., and Saltzman, E. S., 1993: Photoreduction of iron(III) in marine mineral aerosol solutions, J. Geophys. Res. 98(D5), 9039–9046.

    Google Scholar 

  • Zhu, X. R., Prospero, J. M., and Millero, F. J., 1997: Diel variability of soluble Fe(II) and soluble total Fe in North African dust in the trade winds at Barbados, J. Geophys. Res. 102 (D17), 21 297–21 306.

    Google Scholar 

  • Zhuang, G., Duce, R. A., and Kester, D. R., 1990: The dissolution of atmospheric iron in surface seawater of the open ocean, J. Geophys. Res. 95, 16207–16216.

    Google Scholar 

  • Zhuang, G., Yi, Z., Duce, R. A., and Brown, P. R., 1992: Link between iron and sulphur cycles suggested by detection of Fe(II) in remote marine aerosols, Nature 355, 537–539.

    Google Scholar 

  • Zhuang, G., Yi, Z. and Wallace, G. T., 1995: Iron(II) in rainwater, snow and surface seawater from a coastal environment, Mar. Chem. 50, 41–50.

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Science and Literature Faculty, Department of Chemistry, Mersin University, 33342, Mersin, İçel, Turkey

    Türkan Özsoy

  2. Turkish Scientific and Technical Research Council (TÜBİTAK), Ankara, Turkey

    A. Cemal Saydam

Authors
  1. Türkan Özsoy
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. A. Cemal Saydam
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Özsoy, T., Saydam, A.C. Iron Speciation in Precipitation in the North-Eastern Mediterranean and Its Relationship with Sahara Dust. Journal of Atmospheric Chemistry 40, 41–76 (2001). https://doi.org/10.1023/A:1010602026579

Download citation

  • Issue Date:

  • DOI: https://doi.org/10.1023/A:1010602026579

Search

Navigation