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Characterizing the photochemical degradation of aquatic humic substances from a dystrophic lake using excitation-emission matrix fluorescence spectroscopy and parallel factor analysis

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Abstract

Three-dimensional excitation-emission matrix (EEM) fluorescence and parallel factor analysis (PARAFAC) were used to monitor composition and reactivity changes caused by the photochemical degradation of aquatic humic substances (AHS) from a dystrophic lake in Kushiro Wetland, Japan. AHS-rich lake water was exposed to three treatments in summer and winter 2014: radiation with the full solar wavelength range, radiation with the >320-nm solar wavelength range, and no solar radiation. Irradiation caused AHS-like peaks to shift to shorter wavelengths in the EEM contour plots, implying that AHS photodegradation caused the formation of lower-molecular-weight fractions or more simply structured components. Three components were identified from PARAFAC analyses: AHS-1 (excitation/emission wavelengths of maxima: <252 and 315 nm/426 nm), AHS-2 (360 and 261 nm/489 nm), and AHS-3 (276 nm/403 nm). These components had different photosensitivities. AHS-1 was most sensitive to full solar radiation, while AHS-2 was most sensitive to >320-nm radiation. More photodegradation of these components occurred in the summer than in the winter, indicating that photodegradation depended on light intensity. AHS-3 was photoresistant. The different characteristics of the components reflected the in situ dynamics of the components. The AHS-3 fluorescence intensity was positively correlated with the dissolved organic carbon concentration but the AHS-1 and AHS-2 fluorescence intensities were not. The EEM–PARAFAC method was found to be a good tool for tracing AHS-like materials in situ and in the laboratory.

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Acknowledgments

We thank Yasunori Watanabe and Seiichi Nohara for their helpful suggestions. This study was supported by a Grant-in-Aid for Exploratory Research (nos. 23710018 and 15K00525) from the Ministry of Education, Culture, Sports, Science and Technology of Japan.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Sciences, Toho University, 2-2-1 Miyama, Funabashi, Chiba, 274-8510, Japan

    Yukiko Senga, Satoshi Moriai, Chika Naruoka & Ryoma Nedachi

  2. Environment Grasp Promotion Network-PEG, Nonprofit Organization, 1-10 Kaizuka, Kushiro, Hokkaido, 085-0816, Japan

    Shigeharu Terui

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  1. Yukiko Senga
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  2. Satoshi Moriai
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  4. Ryoma Nedachi
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  5. Shigeharu Terui
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Correspondence to Yukiko Senga.

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Handling Editor: Youhei Yamashita.

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Senga, Y., Moriai, S., Naruoka, C. et al. Characterizing the photochemical degradation of aquatic humic substances from a dystrophic lake using excitation-emission matrix fluorescence spectroscopy and parallel factor analysis. Limnology 18, 97–110 (2017). https://doi.org/10.1007/s10201-016-0493-8

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