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RESEARCH ARTICLE
Contents Vol 6(6)

Spatial and temporal variations and factors controlling the concentrations of hydrogen peroxide and organic peroxides in rivers

Khan M. G. Mostofa A B and Hiroshi Sakugawa B C
+ Author Affiliations
- Author Affiliations

A State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang, 550002, P. R. China.

B Graduate School of Biosphere Science, Department of Environmental Dynamics and Management, Hiroshima University, 1-7-1, Kagamiyama, Higashi-Hiroshima 739-8521, Japan.

C Corresponding author. Email: hsakuga@hiroshima-u.ac.jp

Environmental Chemistry 6(6) 524-534 https://doi.org/10.1071/EN09070
Submitted: 4 June 2009  Accepted: 28 October 2009   Published: 18 December 2009

Environmental context. Hydrogen peroxide (H2O2) and organic peroxides (ROOH) are ubiquitously present in natural waters and primarily essential for several redox reactions. This study examines the effects of various dissolved organic substances on the formation of H2O2 and ROOH and their relationship with different water quality parameters in two Japanese rivers. This study suggests that fulvic acid is primarily responsible for production of H2O2 and ROOH in river waters.

Abstract. Hydrogen peroxide (H2O2) and organic peroxides (ROOH) were examined in water samples collected from the upstream and downstream sites of two Japanese rivers (the Kurose and the Ohta). H2O2 concentrations during monthly measurements varied between 6 and 213 nM in the Kurose River and 33 and 188 nM in the Ohta River. ROOH varied between 0 and 73 nM in the Kurose River and 1 and 80 nM in the Ohta. Concentrations of peroxides were higher during the summer months than in winter. H2O2 concentrations correlated well with the measured content of dissolved organic carbon and/or the fluorescence intensity of the fluorescent dissolved organic matter (FDOM) in the water from these rivers, which suggested that the dissolved organic matter and FDOM are the major sources of H2O2. Further characterisation of FDOM components by excitation emission matrix spectroscopy and parallel factor (PARAFAC) analysis indicated that fulvic acid is a dominant source of H2O2 in river waters, which accounted for 23–70% of H2O2 production in the Ohta River, 25–61% in the upstream and 28–63% in the downstream waters of the Kurose River, respectively. A fluorescent whitening agent and its photoproduct (4-biphenyl carboxaldehyde) together contributed 3–7% of H2O2 production in the downstream waters of the Kurose River. Tryptophan-like substances were a minor source of H2O2 (<1%) in both rivers. An increase in the H2O2 concentration was observed in the diurnal samples collected at noon compared with the samples collected during the period before sunrise and after sunset, thus indicating that H2O2 was produced photochemically. This study demonstrates that H2O2 and ROOH are produced mainly from the photodegradation of FDOMs, such as fulvic acid.

Additional keywords: dissolved organic carbon, fluorescent dissolved organic matter, fulvic acid, tryptophan, upstream and downstream.


Acknowledgements

The authors are grateful to Ms Honda for her assistance during the sampling and experimental analysis. We thank Drs K. Takeda, N. Nakatani, S. Akane, T. Nehira, Ms K. Uobe, Mr T. Matsuda, K. Tanaka, H. Shindo, S. Makino, K. Tahara, H. Kondo, and J. Hata for their assistance during the sampling, experimental analysis and manuscript preparation. A part of this paper was presented on the 13th Annual V. M. Goldschmidt Conference, Kurashiki, Japan, 2003. We thank Cong-Qiang Liu, State Key Laboratory of Environmental Research, Institute of Geochemistry, Chinese Academy of Sciences, China for his assistance and inspiration during this research study and partly supported by Chinese Academy of Sciences, PR China. This study was also supported by the Grant-in-Aid for Scientific Research (B), MEXT (18310010).


References


[1]   L. E. Richard , B. M. Peake , S. A. Rusak , W. J. Cooper , D. J. Burritt , Production and decomposition dynamics of hydrogen peroxide in freshwater. Environ. Chem. 2007 , 4,  49.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[2]   L. J. A. Gerringa , M. J. A. Rjkenberg , K. R. Timmermans , A. G. J. Buma , The influence of solar ultraviolet radiation on the photochemical production of H2O2 in the equatorial Atlantic Ocean. J. Sea Res. 2004 , 51,  3.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[3]   Cooper W. J., Lean D. R. S., Hydrogen peroxide dynamics in marine and fresh water systems, in Encyclopedia of Earth System 1992, Vol. 2, pp. 527–535 (Academic Press Inc.: San Diego, CA).

[4]   R. G. Petasne , R. G. Zika , Hydrogen peroxide lifetimes in south Florida coastal and offshore waters. Mar. Chem. 1997 , 56,  215.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[5]   W. J. Cooper , R. G. Zika , Photochemical formation of hydrogen peroxide in surface and ground waters exposed to sunlight. Science 1983 , 220,  711.
        | Crossref | GoogleScholarGoogle Scholar | CAS | PubMed |  open url image1

[6]   Sakugawa H., Yamashita T., Kwai H., Masuda N., Hashimoto N., Makino S., Nakatani N., Takeda K., Measurements, and production and decomposition mechanisms of hydroperoxides in air, rain, dew, river and drinking waters, Hiroshima prefecture, Japan. Chikyukagaku (Geochemistry) 2006, 40, 47. [In Japanese with English abstract]

[7]   W. J. Cooper , D. R. S. Lean , Hydrogen peroxide concentration in a northern lake: photochemical formation and diel variability. Environ. Sci. Technol. 1989 , 23,  1425.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[8]   K. Fujiwara , T. Ushiroda , K. Takeda , Y. Kumamoto , H. Tsubota , Diurnal and seasonal distribution of hydrogen peroxide in seawater of Seto Inland Sea. Geochem. J. 1993 , 27,  103.
        |  CAS |  open url image1

[9]   Sakugawa H., Takami A., Kawai H., Takeda K., Fujiwara K., Hirata S., The occurrence of organic peroxide in seawater, in Dynamics and Characterization of Marine Organic Matter (Eds N. Handa, E. Tanoue, T. Hama) 2000, pp. 231–240 (TERRAPUB/Kluwer: Tokyo).

[10]   J. Yuan , A. M. Shiller , The distribution of hydrogen peroxide in the southern and central Atlantic ocean. Deep Sea Res. Part II Top. Stud. Oceanogr. 2001 , 48,  2947.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[11]   C. A. Moore , C. T. Farmer , R. G. Zika , Influence of the Orinoko River on hydrogen peroxide distribution and production in the Eastern Caribean. J. Geophys. Res. 1993 , 98,  2289.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[12]   D. W. O’Sullivan , P. J. Neale , R. B. Coffin , T. J. Boyd , C. L. Osburn , Photochemical production of hydrogen peroxide and methylhydroperoxide in coastal waters. Mar. Chem. 2005 , 97,  14.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[13]   R. G. Petasne , R. G. Zika , The fate of superoxide in coastal seawater. Nature 1987 , 325,  516.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[14]   H. Sakugawa , I. R. Kaplan , W. Tsai , Y. Cohen , Atmospheric hydrogen peroxide. Environ. Sci. Technol. 1990 , 24,  1452.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[15]   J. Perkowski , L. Kos , Treatment of textile dyeing wastewater by hydrogen peroxide and ferrous ions. Fibres Text. East. Eur. 2002 , 38,  78.
         open url image1

[16]   J. Perkowski , W. Jóźwiak , L. Kos , P. Stajszczyk , Applications of Fenton’s reagent in detergent separation in highly concentrated water solutions. Fibres Text. East. Eur. 2006 , 59,  114.
         open url image1

[17]   Sakugawa H., Yamashita T., Fujiwara K., Determination of hydrogen peroxide and organic peroxides in seawater, in Global Fluxes of Carbon and Its Related Substances in the Coastal Sea-Ocean-Atmosphere System (Eds S. Tsunogai, K. Iseki, I. Koike, T. Oba) 1995, pp. 452–457 (M & J International: Tokyo).

[18]   N. Senesi , Molecular and quantitative aspects of the chemistry of fulvic acid and its interactions with metal ions and organic chemicals. Part II. The fluorescence spectroscopy approach. Anal. Chim. Acta 1990 , 232,  77.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[19]   P. G. Coble , Marine optical biogeochemistry: The chemistry of ocean color. Chem. Rev. 2007 , 107,  402.
        | Crossref | GoogleScholarGoogle Scholar | CAS | PubMed |  open url image1

[20]   P. G. Coble , Characterization of marine and terrestrial DOM in sea water using excitation-emission matrix spectroscopy. Mar. Chem. 1996 , 51,  325.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[21]   K. M. G. Mostofa , T. Yoshioka , E. Konohira , E. Tanoue , Dynamics and characteristics of fluorescent dissolved organic matter in the groundwater, river and lake water. Water Air Soil Pollut. 2007 , 184,  157.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[22]   Mostofa K. M. G., Wu F. C., Yoshioka T., Sakugawa H., Tanoue E., Dissolved organic matter in the aquatic environment, in Natural Organic Matter and its Significance in the Environment (Eds F. C. Wu, B. Xing) 2009, pp. 3–66 (Science Press: Beijing).

[23]   A. V. Vähätalo , R. G. Wetzel , Photochemical and microbial decomposition of chromophoric dissolved organic matter during long (months-years) exposures. Mar. Chem. 2004 , 89,  313.
        | Crossref | GoogleScholarGoogle Scholar |  open url image1

[24]   K. M. G. Mostofa , Y. Honda , H. Sakugawa , Dynamics and optical nature of fluorescent dissolved organic matter in river waters in Hiroshima prefecture, Japan. Geochem. J. 2005 , 39,  257.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[25]   C. A. Stedmon , D. N. Thomas , M. Granskog , H. Kaartokallio , S. Papaditriou , H. Kuosa , Characteristics of dissolved organic matter in Baltic coastal sea ice: Allochthonous or autochthonous origins? Environ. Sci. Technol. 2007 , 41,  7273.
        | Crossref | GoogleScholarGoogle Scholar | CAS | PubMed |  open url image1

[26]   Malcolm R. L., Geochemistry of stream fulvic and humic substances, in Humic Substances in Soil, Sediment, and Water: Geochemistry, Isolation and Characterization (Eds G. R. Aiken, D. M. McKnight, R. L. Wershaw, P. MacCarthy) 1985, pp. 181–209 (Wiley: New York).

[27]   M. A. Moran , W. M. Jr Sheldon , R. G. Zepp , Carbon loss and optical property changes during long-term photochemical and biological degradation of estuarine dissolved organic matter. Limnol. Oceanogr. 2000 , 45,  1254.
        |  CAS |  open url image1

[28]   K. M. G. Mostofa , T. Yoshioka , E. Konohira , E. Tanoue , Photodegradation of fluorescent dissolved organic matter in river waters. Geochem. J. 2007 , 41,  323.
        |  CAS |  open url image1

[29]   J. W. Moffett , R. G. Zika , Reaction kinetics of hydrogen peroxide with copper and iron in seawater. Environ. Sci. Technol. 1987 , 21,  804.
        | Crossref | GoogleScholarGoogle Scholar | CAS | PubMed |  open url image1

[30]   J. Jeong , J. Yoon , pH effect on OH radical production in photo/ferrioxalate system. Water Res. 2005 , 39,  2893.
        | Crossref | GoogleScholarGoogle Scholar | CAS | PubMed |  open url image1

[31]   Moffett J. W., Zika R. G., Photochemistry of copper complexes in sea water, in Photochemistry of Environmental Aquatic Systems (Eds R. G. Zika, W. J. Cooper) 1987, pp. 116–130 (American Chemical Society: Washington, DC).

[32]   J. B. Kramer , S. Canonica , J. Hoigne , J. Kaschig , Degradation of fluorescent whitening agents in sunlit natural waters. Environ. Sci. Technol. 1996 , 30,  2227.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[33]   K. R. Millington , G. Maurdev , The generation of superoxide and hydrogen peroxide by exposure of fluorescent whitening agents to UVA radiation and its relevance to the rapid photoyellowing of whitened wool. J. Photochem. Photobiol. Chem. 2004 , 165,  177.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1

[34]   J. Mack , J. R. Bolton , Photochemistry of nitrite and nitrate in aqueous solution: a review. J. Photochem. Photobiol. Chem. 1999 , 128,  1.
        | Crossref | GoogleScholarGoogle Scholar | CAS |  open url image1