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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).


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