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Geochemical Journal
Geochemical Journal An open access journal for geochemistry
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Measurements, sources and sinks of photoformed reactive oxygen species in Japanese rivers

Taiwo Tolulope Ayeni, Waqar Azeem Jadoon, Adeniyi Olufemi Adesina, Michael Oluwatoyin Sunday, Adebanjo Jacob Anifowose, Kazuhiko Takeda, Hiroshi Sakugawa
Geochemical Journal, Vol. 55, No. 2, P. 89-102, 2021


Reactive oxygen species (ROS) are photochemically generated in sunlit natural water and are involved in degradation of organic matter, redox reactions, and biological processes. Hydroxyl radicals (·OH), nitric oxide radicals (NO·), and singlet oxygen (1O2) are some of the dominant ROS in natural water. In this study, these three ROS were measured in samples collected from nine rivers across 65 stations along the west to east axis of Japan. Quantification of ·OH, NO·, and 1O2 was performed by High-Performance Liquid Chromatography using benzene, 4, 5-diaminofluorescein-2, and furfuryl alcohol as chemical probes, respectively. The absorption coefficient at 300 nm (a300, m-1), which ranged from 2.44 to 36.2 m-1, was used to investigate the chromophoric dissolved organic matter (CDOM) properties of the rivers. The photoformation rate ranges were (13.9-944) × 10-12 M s-1 for ·OH, (2.76-2610) × 10-12 M s-1 for NO·, and (9.48-133) × 10-9 M s-1 for 1O2. The steady-state concentration ranges were (1.53-16) × 10-16 M for ·OH, (10.2-1520) × 10-12 M for NO·, and (3.79-53.4) × 10-14 M for 1O2. The results showed that nitrite was a major source for both ·OH and NO·, and CDOM was a major source for 1O2 across all the rivers. According to significant relationships with these sources, models were generated to predict the formation rates of the ROS (in M s-1) from known concentrations of source compounds using the equations R·OH (10-12) = 19.2 [NO2-1]-μM + 36.9, RNO· (10-12) = 41.4 [NO2-1]-μM + 44, and R1O2)(10-9) = 3.52 (a300)-m-1 + 1.61. Dissolved organic matter, escape to the atmosphere, and water molecules were the major sinks for river ·OH, NO·, and 1O2, respectively. A general scavenging rate constant of ·OH as a function of the dissolved organic carbon concentration was obtained [kC,OH = [(7.5 ± 6.8) × 108 L (mol C)-1 s-1]. These models will allow for easy prediction of ROS concentrations on a large-scale.


hydroxyl radical, nitric oxide radical, singlet oxygen, photochemistry, river water

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