Optical properties of dissolved organic matter in Japanese rivers and contributions to photoformation of reactive oxygen species.

The optical properties of dissolved organic matter (DOM) from five rivers (Kokubu, Kurose, Ohta, Yamato, and Yodo) in Japan were investigated and contributions of DOM to photoformation of three reactive oxygen species (ROS) (hydroxyl radicals (OH), nitric oxide radicals (NO), and singlet oxygen (1O2)) were assessed. The lowest and highest mean dissolved organic carbon concentrations were for the Ohta River (0.95 (mg C) L-1) and Yamato River (2.85 (mg C) L-1), respectively, and the concentrations correlated with some optical parameters. Absorption ratios (e.g., the E2:E3 and A280/A350 ratios) and the spectral slope S275-295 indicated that DOM from the Yodo and Kokubu rivers had the lowest and highest molecular weights, respectively. PARAFAC models and DOM excitation-emission matrices were used to assess the sources and fates of DOM in the rivers. The PARAFAC model indicated that the main types of fluorescent DOM in the rivers were terrestrial humic-like (TH-L) and tryptophan-like (TP-L) substances. The Kokubu River contained other compounds such as fluorescent whitening agents, autochthonous humic-like substances, and extracellular polymeric substances. Statistically significant relationships between the dissolved organic carbon and TH-L, TP-L, and extracellular polymeric substance concentrations suggested that TH-L, TP-L, and extracellular polymeric substances are important contributors to total DOM in the rivers. TH-L and TP-L substances strongly contribute to ROS photoformation, but TH-L substances play roles in both ROS generation and scavenging. Comprehensive models for estimating the photoformation rates of different ROS (in M s-1) were established by integrating the contributions of the relevant major and minor sources. Examples are ROH (10-12) = 21.0 [NO2-]_µM + 0.460 [TH-L]_QSU + 10.9, RNO (10-12) = 67.9 [NO2-]_µM + 35.2 [a300]_m-1 - 2.51 [TH-L]_QSU - 0.765 [TP-L]_QSU - 8.14, and R1O2 (10-9) = 3.81 [a300]_m-1 - 0.101 [TP-L]_QSU + 11.1.

Heterogeneity and potential aquatic toxicity of hydrogen peroxide concentrations in selected rivers across Japan.

Hydrogen peroxide (H2O2) is a reactive oxygen species formed in natural water. It is reportedly toxic to aquatic organisms with a predicted no-effect concentration (PNEC) of about 380 nM. In this study, a countrywide investigation of H2O2 concentrations in selected rivers across Japan was conducted to identify rivers that pose toxicity concerns. Twelve rivers with a total catchment area of 13,646 km2 were selected from different prefectures. Spatial and temporal variation studies showed that the H2O2 concentrations (avg. 320 nM, n = 111) varied by two orders of magnitude (range 21-2929 nM) across the rivers. The Yamato River in Osaka and Nara prefectures and the Kokubu River in Chiba Prefecture had the highest concentrations at 276-669 nM and 236-2929 nM, respectively. >75% of the data from the two rivers were either close to or exceeded the PNEC. Most of the results for the other rivers were less than the PNEC. There was a clear seasonal variation in the H2O2 concentrations, with the highest values obtained in summer because of high solar irradiation. The H2O2 concentration had the highest positive correlation (r = 0.61, p < 0.01, n = 111) with the product of dissolved organic carbon and solar radiation intensity, which suggests that these two factors in combination are important in determining the H2O2 concentrations in river water. It was also observed that bigger rivers had lower H2O2 concentration and vice-versa. This shows that the size of a river may influence its H2O2 concentration. This study is the first countrywide survey of H2O2 concentrations in different rivers and evaluation of their relationship with the PNEC. The data provide insight on the factors influencing the concentrations of H2O2 in river water.