Journal of Oceanography

, Volume 61, Issue 3, pp 561–568 | Cite as

Simultaneous Measurement of Hydrogen Peroxide and Fe Species (Fe(II) and Fe(tot)) in Okinawa Island Seawater: Impacts of Red Soil Pollution

  • Takemitsu ArakakiEmail author
  • Hiroyuki Fujimura
  • Asha Mansour Hamdun
  • Kouichirou Okada
  • Hiroaki Kondo
  • Tamotsu Oomori
  • Akira Tanahara
  • Hatsuo Taira


The northern part of Okinawa Island suffers from red soil pollution—runoff of red soil into coastal seawater—which damages coastal ecosystems and scenery. To elucidate the impacts of red soil pollution on the oxidizing power of seawater, hydrogen peroxide (HOOH) and iron species including Fe(II) and total iron (Fe(tot), defined as the sum of Fe(II) and Fe(III)) were measured simultaneously in seawater from Taira Bay (red-soil-polluted sea) and Sesoko Island (unpolluted sea), off the northern part of Okinawa Island, Japan. We performed simultaneous measurements of HOOH and Fe(II) because the reaction between HOOH and Fe(II) forms hydroxyl radical (•OH), the most potent environmental oxidant. Gas-phase HOOH concentrations were also measured to better understand the sources of HOOH in seawater. Both HOOH and Fe(II) in seawater showed a clear diurnal variation, i.e. higher in the daytime and lower at night, while Fe(tot) concentrations were relatively constant throughout the sampling period. Fe(II) and Fe(tot) concentrations were approximately 58% and 19% higher in red-soil-polluted seawater than in unpolluted seawater. Gas-phase HOOH and seawater HOOH concentrations were comparable at both sampling sites, ranging from 1.4 to 5.4 ppbv in air and 30 to 160 nM in seawater. Since Fe(II) concentrations were higher in red-soil-polluted seawater while concentrations of HOOH were similar, •OH would form faster in red-soil-polluted seawater than in unpolluted seawater. Since the major scavenger of •OH, Br, is expected to have similar concentrations at both sites, red-soil-polluted seawater is expected to have higher steady-state •OH concentrations.


Fe(II) hydrogen peroxide red soil pollution oxidizing power photochemistry hydroxyl radical Okinawa 


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  1. Anastasio, C., B. C. Faust and J. M. Allen (1994): Aqueous phase photochemical formation of hydrogen peroxide in authentic cloud waters. J. Geophys. Res., 99(D4), 8231–8248.CrossRefGoogle Scholar
  2. Arakaki, T. and B. C. Faust (1998): Sources, sinks, and mechanisms of hydroxyl radical (•OH) photoproduction and consumption in authentic acidic continental cloud waters from Whiteface Mountain, New York: the role of the Fe(r) (r = II, III) photochemical cycle. J. Geophys. Res., 103(D3), 3487–3504.CrossRefGoogle Scholar
  3. Buxton, G. V., C. L. Greenstock, W. P. Helman and A. B. Ross (1988): Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (•OH/•O) in aqueous solution. J. Phys. Chem. Ref. Data, 17, No.2, 513–599.CrossRefGoogle Scholar
  4. Cooper, W. J. and R. G. Zika (1983): Photochemical formation of hydrogen peroxide in surface and ground waters exposed to sunlight. Science, 220, 711–712.CrossRefGoogle Scholar
  5. Crossland, C. J. (1982): Dissolved nutrients in reef waters of Sesoko Island, Okinawa: a preliminary study. Galaxea, 1, 47–54.Google Scholar
  6. Faust, B. C. (1994): A review of the photochemical redox reactions of iron(III) species in atmospheric, oceanic, and surface waters: influences on geochemical cycles and oxidant formation. p. 3–37. In Aquatic and Surface Photochemistry, ed. by G. R. Helz, R. G. Zepp and D. G. Crosby, Lewis Publishers, Ann Arbor, Michigan.Google Scholar
  7. Faust, B. C. and J. Hoigne (1990): Photolysis of Fe(III)-hydroxy complexes as sources of OH radicals in clouds, fog and rain. Atmos. Environ., 24A, No.1, 79–89.CrossRefGoogle Scholar
  8. Faust, B. C., C. Anastasio, J. M. Allen and T. Arakaki (1993): Aqueous-phase photochemical formation of peroxides in authentic cloud and fog waters. Science, 260, 73–75.CrossRefGoogle Scholar
  9. Finlayson-Pitts, B. J. and J. N. Pitts (2000): Chemistry of the Upper and Lower Atmosphere. John Wiley & Sons, Inc., New York, 969 pp.Google Scholar
  10. Fujiwara, K., T. Ushiroda, K. Takeda, Y. Kumamoto and H. Tsubota (1993): Diurnal and seasonal distribution of hydrogen peroxide in seawater of the Seto Inland Sea. Geochem. J., 27, 103–115.CrossRefGoogle Scholar
  11. Hata, H., S. Kudo, H. Yamano, N. Kurano and H. Kayanne (2002): Organic carbon flux in Shiraho coral reef (Ishigaki island, Japan). Mar. Ecol. Prog. Ser., 232, 129–140.CrossRefGoogle Scholar
  12. Hirata, S., H. Yoshihara and M. Aihara (1999): Determination of iron(II) and total iron in environmental water samples by flow injection analysis with column preconcentration of chelating resin functionalized with N-hydroxyethylethylenediamine ligands and chemiluminescence detection. Talanta, 49, 1059–1067.CrossRefGoogle Scholar
  13. Johnson, K. S., S. W. Willason, D. A. Wiesenburg, S. E. Lohrenz and R. A. Arnone (1989): Hydrogen peroxide in the western Mediterranean sea: a tracer for vertical advection. Deep-Sea Res., 36, 241–254.CrossRefGoogle Scholar
  14. Kuma, K., S. Nakabayashi, Y. Suzuki, I. Kudo and K. Matsunaga (1992): Photo-reduction of Fe(III) by dissolved organic substances and existence of Fe(II) in seawater during spring blooms. Mar. Chem., 37, 1–27.CrossRefGoogle Scholar
  15. Martin, J. H. and S. E. Fitzwater (1988): Iron deficiency limits phytoplankton growth in the north-east Pacific subarctic. Nature, 331, 341–343.CrossRefGoogle Scholar
  16. Mopper, K. and X. Zhou (1990): Hydroxyl radical photoproduction in the sea and its potential impact on marine processes. Science, 250, 661–664.CrossRefGoogle Scholar
  17. Morgan, R. B. and A. V. Jackson (2002): Measurements of gasphase hydrogen peroxide and methyl hydroperoxide in the coastal environment during the PARFORCE project. J. Geophys. Res., 107(D19), 8109, doi: 10.1029/2000JD000257.CrossRefGoogle Scholar
  18. O’Sullivan, D. W., B. G. Heikes, M. Lee, W. Chang, G. L. Gregory, D. R. Blake and G. W. Sachse (1999): Distribution of hydrogen peroxide and methylhydroperoxide over the Pacific and South Atlantic Oceans. J. Geophys. Res., 104(D5), 5635–5646.CrossRefGoogle Scholar
  19. Rue, E. L. and K. W. Bruland (1995): Complexation of iron(III) by natural organic ligands in the central north Pacific as determined by a new competitive ligand equilibration/adsorption cathodic stripping voltametric method. Mar. Chem., 50, 117–138.CrossRefGoogle Scholar
  20. Sakugawa, H., I. R. Kaplan, W. Tsai and Y. Cohen (1990): Atmospheric hydrogen peroxide; does it share a role with ozone in degrading air quality? Environ. Sci. Technol., 24, 1452–1462.CrossRefGoogle Scholar
  21. Schwarzenbach, R. P., P. M. Gschwend and D. M. Imboden (1993): Environmental Organic Chemistry. John Wiley & Sons, Inc. New York, 681 pp.Google Scholar
  22. Stumm, W. and J. J. Morgan (1996): Aquatic Chemistry. John Wiley & Sons, Inc., New York, 1022 pp.Google Scholar
  23. Thompson, M. A. (1992): The oxidizing capacity of the earth’s atmosphere: probable past and future changes. Science, 256, 1157–1165.CrossRefGoogle Scholar
  24. Tokashiki, Y. (1993): Soil survey. (I) Jahgaru, Shimajiri Mahji, Feichisya, and Kunigami Mahji. p. 63–88. In Soil and Nature of Okinawa Island, ed. by R. Hirayama and I. Yamada, Japanese Society of Pedrology, Tsukuba (in Japanese).Google Scholar
  25. Tokashiki, Y. and T. Nakamura (1980): Studies of the Jahgaru soils and their parent materials VI. Physical and chemical properties and clay minerals of soil profiles at Gushikawa, Gushikawa-shi, Bimatabaru, Nago-shi, Okinawa Island. Bull. Coll. Agri. Univ. Ryukyus, 26, 27–41.Google Scholar
  26. van den Berg, C. M. G. (1995): Evidence for organic complexation of iron in seawater. Mar. Chem., 50, 139–157.CrossRefGoogle Scholar
  27. Vuai, S. A., M. Ishiki and A. Tokuyama (2003a): Acidification of freshwaters by red soil in a subtropical silicate rock area, Okinawa, Japan. Limnology, 4, 63–71.CrossRefGoogle Scholar
  28. Vuai, S. A., K. Nakamura and A. Tokuyama (2003b): Geochemical characteristics of runoff from acid sulfate soils in the northern area of Okinawa Island, Japan. Geochem. J., 37, 579–592.CrossRefGoogle Scholar
  29. Warneck, P. (1988): Chemistry of the Natural Atmosphere. Academic Press, Inc., San Diego, CA, 757 pp.Google Scholar
  30. Wood, E. D., F. A. J. Armstrong and P. A. Richards (1967): Determination of nitrate in seawater by cadmium-copper reduction to nitrite. J. Mar. Biol. Assoc., 47, 23–31.CrossRefGoogle Scholar
  31. Yamashita, T., H. Sakugawa and K. Fujiwara (1994): Measurements of hydrogen peroxide in the atmosphere and rainwater in Hiroshima and Higashi-Hiroshima, Japan. Nippon Kagaku Kaishi, 12, 1127–1133.CrossRefGoogle Scholar
  32. Yi, Z., G. Zhuang, R. P. Brown and A. R. Duce (1992): High-performance liquid chromatographic method for the determination of ultratrace amounts of iron(II) in aerosols, rain-water, and seawater. Anal. Chem., 64, 2826–2830.CrossRefGoogle Scholar
  33. Yocis, B. H., D. J. Kieber and K. Mopper (2000): Photochemical production of hydrogen peroxide in Antarctic waters. Deep-Sea Res. I, 47, 1077–1099.CrossRefGoogle Scholar
  34. Yuan, J. and A. M. Shiller (2001): The distribution of hydrogen peroxide in the southern and central Atlantic ocean. Deep-Sea Res. II, 48, 2947–2970.CrossRefGoogle Scholar
  35. Zepp, R. G., B. C. Faust and J. Hoigne (1992): Hydroxyl radical formation in aqueous reactions (pH 3–8) of iron(II) with hydrogen peroxide: the photo-Fenton reaction. Environ. Sci. Technol., 26, 313–319.CrossRefGoogle Scholar
  36. Zhuang, G., Z. Yi, R. A. Duce and P. R. Brown (1992): Link between iron and sulphur cycles suggested by detection of Fe(II) in remote marine aerosols. Nature, 355, 537–539.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, Inc. 2005

Authors and Affiliations

  • Takemitsu Arakaki
    • 1
    Email author
  • Hiroyuki Fujimura
    • 1
  • Asha Mansour Hamdun
    • 1
  • Kouichirou Okada
    • 1
  • Hiroaki Kondo
    • 1
  • Tamotsu Oomori
    • 1
  • Akira Tanahara
    • 2
  • Hatsuo Taira
    • 1
  1. 1.Department of Chemistry, Biology and Marine Science, Faculty of ScienceUniversity of the RyukyusSenbaru, Nishihara-cho, OkinawaJapan
  2. 2.Instrument Research CenterUniversity of the RyukyusSenbaru, Nishihara-cho, OkinawaJapan

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