Water, Air, and Soil Pollution

, Volume 184, Issue 1–4, pp 157–176 | Cite as

Dynamics and Characteristics of Fluorescent Dissolved Organic Matter in the Groundwater, River and Lake Water

  • Khan M. G. MostofaEmail author
  • Takahito Yoshioka
  • Eiichi Konohira
  • Eiichiro Tanoue


Fluorescent dissolved organic matters (FDOM) in the groundwater-river-lake environments were investigated using three-dimensional excitation-emission matrix (EEM) and measuring the dissolved organic carbon (DOC), inorganic anions and electric conductivity (EC) in shallow groundwater, river and lake waters. DOC concentrations were high and largely varied in groundwater, 16–328 μM C (mean 109 ± 88 μM C), and in river waters, 43–271 μM C (mean 158 ± 62 μM C) and were very low in the lake Biwa waters, 89–97 μM C (mean 93 ± 2 μM C). The fluorescence properties of EEM showed that the fulvic-like components (peak C, peak A and peak M) were dominated in groundwater and river waters, but protein-like components (peak T) was in lake waters. The peak C was observed at \( {{\text{Ex}}} \mathord{\left/ {\vphantom {{{\text{Ex}}} {{\text{Em}}}}} \right. \kern-\nulldelimiterspace} {{\text{Em}}} = {320 \pm 9} \mathord{\left/ {\vphantom {{320 \pm 9} {424 \pm 5}}} \right. \kern-\nulldelimiterspace} {424 \pm 5}\;{\text{nm}} \) in groundwater, and 340 ± 5/432 ± 4 nm in river waters, but the lake waters detected the two peaks, 347 ± 7/441 ± 11 nm (peak C) as a minor peak and 304 ± 2/421 ± 8 nm (peak M) as a major peak. Emission wavelength of peak T was observed to shorten in wavelengths from groundwater to river and then lake waters. Peak T in lake waters showed at shorter in wavelengths (279 ± 2/338 ± 11 nm) at the middle point of Lake Biwa compared to those of lake shore site (283 ± 3/350 ± 7 nm). Photo-irradiation experiment on upstream waters suggested the changes in the fluorescence peaks of fulvic acid-like substances in lake waters, which might be caused by photo-degradation. DOC concentration was significantly correlated with inorganic anions and EC in river waters. However, such correlations were not observed in groundwater. Anion concentrations in lake waters were low with respect to DOC concentration. These results showed that the optical and chemical properties of FDOM are characteristically varied among groundwater, river and lake waters, indicating the impacts of environments to various FDOM at the same watershed level.


Dissolved organic carbon Fulvic acid-like substances Protein-like substances Excitation-emission matrix Fluorescence peak intensity Groundwater River water Lake water 



We wish to thank to Eitaro Wada of the Japan Agency for Marine-Earth Science and Technology and Feng Chang Wu of Chinese Academy of Sciences for their encouragement during this study and manuscript preparation. We are also grateful to Dr. Mikio Takahashi and Kazuhide Hayakawa of Lake Biwa Environmental Research Institute for their assistance for the collection of lake water samples. We thank and grateful to two anonymous reviewers for their thoughtful comments and editor for editorial assistance. We thank to Dr. X. D. Li for his assistance in statistical analysis of the Ex/Em wavelength shifts. This work was supported and financed by Grants-in-Aid for Scientific Research, for Scientific Research of Priority Area B and for the International Geosphere-Biosphere Programme (IGBP) at Nagoya University from the Ministry of Education, Culture, Sports, Science and Technology (MEXT) of Japan.


  1. Amador, J. A., Alexander, M., & Zika, R. G. (1989). Sequential photochemical and microbial degradation of organic molecules bound to humic acid. Applied and Environmental Microbiology, 55, 2843–2849.Google Scholar
  2. Amon, R. M. W., & Benner, R. (1994). Rapid cycling of high-molecular-weight dissolved organic matter in the ocean. Nature, 369, 549–552.CrossRefGoogle Scholar
  3. Arakaki, T., Miyake, T., Hirakawa, T., & Sakugawa, H. (1999). pH dependent photoformation of hydroxyl radical and absorbance of aqueous-phase N(III) (HNO2 and \( {\text{NO}}^{{\text{ - }}}_{{\text{2}}} \)). Environmental Science and Technology, 33, 2561–2565.CrossRefGoogle Scholar
  4. Artinger, R., Buckau, G., Geyer, S., Fritz, P., Wolf, M., & Kim, J. I. (2000). Characterization of groundwater humic substances: Influence of sedimentary organic carbon. Applied Geochemistry, 15, 97–116.CrossRefGoogle Scholar
  5. Azevedo, D. de A., Lacorte, S., Vinhas, T., Viana, P., & Barceló, D. (2000). Monitoring of priority pesticides and other organic pollutants in river water from Portugal by gas chromatography-mass spectrometry and liquid chromatography-atmospheric pressure chemical ionization mass spectrometry. Journal of Chromatography, 879, 13–26.CrossRefGoogle Scholar
  6. Back, W. (1992). Groundwater. Encyclopedia of Earth System Science, 2, 429–439.Google Scholar
  7. Baker, A. (2001). Fluorescence excitation-emission matrix characterization of some sewage impacted rivers. Environmental Science and Technology, 35, 948–953.CrossRefGoogle Scholar
  8. Baker, A., & Spencer, R. G. M. (2004). Characterization of dissolved organic matter from source to sea using fluorescence and absorbance spectroscopy. Science of the Total Environment, 333, 217–232.CrossRefGoogle Scholar
  9. Benner, R., & Kaiser, K. (2003). Abundance of amino sugars and peptidoglycan in marine particulate and dissolved organic matter. Limnology and Oceanography, 48, 118–128.CrossRefGoogle Scholar
  10. Boyd, T. J., & Osburn, C. L. (2004). Changes in CDOM fluorescence from allochthonous and autochthonous sources during tidal mixing and bacterial degradation in two coastal estuaries. Marine Chemistry, 89, 189–210.CrossRefGoogle Scholar
  11. Buckau, G., Antinger, R., Geyer, S., Wolf, M., Fritz, P., & Kim, J. I. (2000). Groundwater in-situ generation of aquatic humic and fulvic acid and the mineralization of sedimentary organic carbon. Applied Geochemistry, 15, 819–832.CrossRefGoogle Scholar
  12. Burdige, D. J., Kline, S. W., & Chen, W. (2004). Fluorescent dissolved organic matter in marine sediment pore waters. Marine Chemistry, 89, 289–311.CrossRefGoogle Scholar
  13. Coble, P. G. (1996). Characterization of marine and terrestrial DOM in sea water using excitation-emission matrix spectroscopy. Marine Chemistry, 52, 325–336.CrossRefGoogle Scholar
  14. Coble, P. G., Del Castillo, C. E., & Avril, B. (1998). Distribution and optical properties of CDOM in the Arabian Sea during the 1995 Southwest Monsoon. Deep-Sea Research II, 45, 2195–2223.CrossRefGoogle Scholar
  15. Coble, P. G., Green, S. A., Blough, N. V., & Gagosian, R. B. (1990). Characterization of dissolved organic matter in the Black Sea by fluorescence spectroscopy. Nature, 348, 432–435.CrossRefGoogle Scholar
  16. Coble, P. G., Schultz, C. A., & Mopper, K. (1993). Fluorescence contouring analysis of DOC intercalibration experimental samples: A comparison of techniques. Marine Chemistry, 41, 173–178.CrossRefGoogle Scholar
  17. Conmy, R. N., Coble, P. G., Chen, R. F., & Gardner, G. B. (2004). Optical properties of colored dissolved organic matter in the Northern Gulf of Mexico. Marine Chemistry, 89, 127–144.CrossRefGoogle Scholar
  18. Cuny, P., Marty, J., Chiavérini, J., Vescovali, I., Raphel, D., & Rontani, J. (2002). Deep-Sea Research II, 49, 1987–2005.CrossRefGoogle Scholar
  19. De Souza Sierra, M. M., Donard, O. F. X., & Lamotte, M. (1997). Spectral identification and behaviour of dissolved organic fluorescent material during estuarine mixing processes. Marine Chemistry, 58, 51–58.CrossRefGoogle Scholar
  20. Del Vecchio, R., & Blough, N. V. (2002). Photobleaching of chromophoric dissolved organic matter in natural waters: Kinetics and modeling. Marine Chemistry, 78, 231–253.CrossRefGoogle Scholar
  21. Derbalah, A. S. H., Nakatani, N., & Sakugawa, H. (2003). Distribution, seasonal pattern, flux and contamination source of pesticides and nonylphenol residues in Kurose River water, Higashi–Hiroshima, Japan. Geochemical Journal, 37, 217–232.Google Scholar
  22. Fetzner, S. (1998). Bacterial degradation of pyridine, indole, quinoline, and their derivatives under different redox conditions. Applied Microbiology and Biotechnology, 49, 237–250.CrossRefGoogle Scholar
  23. Fu, P. Q. (2004). Dissolved organic matter in natural aquatic environments and its complexation with metal ions: A study based on fluorescence spectroscopy. PhD thesis. Graduate School of the Chinese Academy of Sciences. Guiyang, China, pp. 56–87.Google Scholar
  24. Gao, H., & Zepp, R. G. (1998). Factors influencing photoreactions of dissolved organic matter in a coastal river of the southern United States. Environmental Science and Technology, 32, 2940–2946.CrossRefGoogle Scholar
  25. Hayakawa, K. (2004). Seasonal variations and dynamics of dissolved carbohydrates in Lake Biwa. Organic Geochemistry, 35, 169–179.CrossRefGoogle Scholar
  26. Hayase, K., Yamamoto, M., Nakazawa, I., & Tsubota, H. (1987). Behavior of natural fluorescence in Sagami Bay and Tokyo Bay, Japan-vertical and lateral distributions. Marine Chemistry, 20, 265–276.CrossRefGoogle Scholar
  27. IPCC. (1996). In J. T. Houghton, L. G. M. Filho, B. A. Calander, N. Harris, A. Kattenberg, & K. Maskell (Eds.), Climate change 1995: The science of climate change (pp. 572–573). New York: Cambridge University Press.Google Scholar
  28. Ittekkot, V., Safiullah, S., Mycke, B., & Seifert, R. (1985). Seasonal variability and geochemical significance of organic matter in the River Ganges, Bangladesh. Nature, 317, 800–802.CrossRefGoogle Scholar
  29. Keiber, D. J., McDaniel, J., & Mopper, K. (1989). Photochemical source of biological substrates in sea water: Implications for carbon cycling. Nature, 341, 637–639.CrossRefGoogle Scholar
  30. Komada, T., Schofield, O. M. E., & Reimers, C. E. (2002). Fluorescence characteristics of organic matter released from coastal sediments during resuspension. Marine Chemistry, 79, 81–97.CrossRefGoogle Scholar
  31. Kortelainen, P. (1999). Sources of aquatic organic carbon. In J. Keskitalo & P. Eloranta (Eds.), Limnology of humic waters (pp. 43–49). Leiden: Backhuys.Google Scholar
  32. Kotoda, K., & Mizuyama, T. (1984). Water balance. In S. Horie (Eds.), Lake Biwa (pp. 165–174). The Netherlands: Junk.Google Scholar
  33. Kowalczuk, P., Cooper, W. J., Whitehead, R. F., Durako, M. J., & Sheldon, W. (2003). Characterization of CDOM in an organic-rich river and surrounding coastal ocean in the South Atlantic Bight. Aquatic Sciences, 65, 384–401.CrossRefGoogle Scholar
  34. Kowalczuk, P., Stoń-Egiert, J., Cooper, W. J., Whitehead, R. F., & Durako, M. J. (2005). Characterization of chromophoric dissolved organic matter (CDOM) in the Baltic Sea by excitation emission matrix fluorescence spectroscopy. Marine Chemistry, 96, 273–292.CrossRefGoogle Scholar
  35. Kristensen, E., & Holmer, M. (2001). Decomposition of plant materials in marine sediment exposed to different electron acceptors (O2, \( {\text{NO}}^{{\text{ - }}}_{{\text{3}}} \), and \( {\text{SO}}^{{{\text{2 - }}}}_{{\text{4}}} \)), with emphasis on substrate origin, degradation kinetics, and the role of bioturbation. Geochimica et Cosmochimica Acta, 65(3), 419–433.CrossRefGoogle Scholar
  36. Lytle, C. R., & Perdue, E. M. (1981). Free, proteinaceous, and humic-bound amino acids in river water containing high concentrations of aquatic humus. Environmental Science and Technology, 15(2), 224–228.CrossRefGoogle Scholar
  37. Malcolm, R. L. (1985). Geochemistry of stream fulvic and humic substances. In G. R. Aiken, D. M. Mcknight, R. L. Wershaw, & P. MacCarthy (Eds.), Humic substances in soil, sediment, and water: Geochemistry, isolation, and characterization (pp. 181–209). New York: Wiley.Google Scholar
  38. Manahan, S. E. (1999). Environmental chemistry (pp. 147–183). New York: Lewis.Google Scholar
  39. Marañòn, E., Cermeño, P., Fernández, E., Rodrìguez, J., & Zabala, L. (2004). Significance and mechanisms of photosynthetic production of dissolved organic carbon in a coastal eutrophic ecosystem. Limnology and Oceanography, 49, 1652–1666.CrossRefGoogle Scholar
  40. McKnight, D. M., Boyer, E. W., Westerhoff, P. K., Doran, P. T., Kulbe, T., & Andersen, D. T. (2001). Spectrofluorometric characterization of dissolved organic matter for indication of precursor organic material and aromaticity. Limnology and Oceanography, 46, 38–48.CrossRefGoogle Scholar
  41. Medina-Sánchez, M. J., Villar-Argaiz, M., & Carrillo, P. (2006). Solar radiation-nutrient interaction enhances the resource and predation algal control on bacterioplankton: A short-term experimental study. Limnology and Oceanography, 51, 913–924.CrossRefGoogle Scholar
  42. Mopper, K., & Schultz, C. A. (1993). Fluorescence as a possible tool for studying the nature and water column distribution of DOC components. Marine Chemistry, 41, 229–238.CrossRefGoogle Scholar
  43. Mopper, K., & Zhou, X. (1990). Hydroxyl radical photoproduction in the sea and its potential impact on marine processes. Science, 250, 661–664.CrossRefGoogle Scholar
  44. Mopper, K., Zhou, X., Kieber, R. J., Kieber, D. J., Sikorski, R. J., & Jones, R. D. (1991). Photochemical degradation of dissolved organic carbon and its impact on the oceanic carbon cycle. Nature, 353, 60–62.CrossRefGoogle Scholar
  45. Moran, M. A., Sheldon, W. M. Jr., & Zepp, R. G. (2000). Carbon loss and optical property changes during long-term photochemical and biological degradation of estuarine dissolved organic matter. Limnology and Oceanography, 45, 1254–1264.CrossRefGoogle Scholar
  46. Moran, M. A., & Zepp, R. G. (1997) Role of photoreactions in the formation of biologically labile compounds from dissolved organic matter. Limnology and Oceanography, 42, 1307–1316.CrossRefGoogle Scholar
  47. Mostofa, K. M. G., Honda, Y., & Sakugawa, H. (2005a). Dynamics and optical nature of dissolved organic matter in river waters in Hiroshima Prefecture, Japan. Geochemical Journal, 39, 257–271.CrossRefGoogle Scholar
  48. Mostofa, K. M. G., Yoshioka, T., Konohira, E., & Tanoue, E. (in press). Photodegradation of fluorescent dissolved organic matter in river waters. Geochemical Journal.Google Scholar
  49. Mostofa, K. M. G., Yoshioka, T., Konohira, E., Tanoue, E., Hayakawa, K., & Takahashi, M. (2005b). Three-dimensional fluorescence as a tool for investigating the dynamics of dissolved organic matter in the Lake Biwa watershed. Limnology, 6, 101–115.CrossRefGoogle Scholar
  50. Nagata, T., & Kirchman, D. L. (1996). Bacterail degradation of protein adsorbed to model submicron particles in seawater. Marine Ecology Progress Series, 132, 241–248.Google Scholar
  51. Nakane, K., Kohno, T., Horikoshi, T., & Nakatsubo, T. (1997). Soil carbon cycling at a black spruce (Picea mariana) forest stand in Saskatchewan, Canada. Journal of Geophysical Research, 102(D24), 28, 785–28, 793.Google Scholar
  52. Ogawa, H., & Tanoue, E. (2003). Dissolved organic matter in oceanic waters. Journal of Oceanography, 59, 129–147 (review).CrossRefGoogle Scholar
  53. Parlanti, E., Worz, K., Geoffroy, L., & Lamotte, M. (2000). Dissolved organic matter fluorescence spectroscopy as a tool to estimate biological activity in a coastal zone submitted to anthropogenic inputs. Organic Geochemistry, 31, 1765–1781.CrossRefGoogle Scholar
  54. Peuravuori, J., & Pihlaja, K. (1999). Some approaches for modelling of dissolved aquatic organic matter. In J. Keskitalo & P. Eloranta (Eds.), Limnology of humic waters (pp. 11–39). Leiden: Backhuy.Google Scholar
  55. Rontani, J.-F. (2001). Visible light-dependent degradation of lipidic phytoplanktonic components during senescence: A review. Photochemistry, 58, 187–202.CrossRefGoogle Scholar
  56. Rosenstock, B., & Simon, M. (2001). Sources and sinks of dissolved free amino acids and protein in a large and deep mesotrophic lake. Limnology and Oceanography, 50, 90–101.Google Scholar
  57. Schwede-Thomas, S. B., Chin, Y., Dria, K. J., Hatcher, P., Kaiser, E., & Sulzberger, B. (2005). Characterizing the properties of dissolved organic matter isolated by XAD and C-18 solid phase extraction and ultrafiltration. Aquatic Sciences, 67, 61–71.CrossRefGoogle Scholar
  58. Skoog, A., Wedborg, M., & Fogelqvist, E. (1996). Photobleaching of fluorescence and the organic carbon concentration in a coastal environment. Marine Chemistry, 55, 333–345.CrossRefGoogle Scholar
  59. Stedmon, C. A., & Markager, S. (2005a). Resolving the variability in dissolved organic matter fluorescence in a temperate estuary and its catchment using PARAFAC analysis. Limnology and Oceanography, 50, 686–697.CrossRefGoogle Scholar
  60. Stedmon, C. A., & Markager, S. (2005b). Tracing the production and degradation of autochthonous fractions of dissolved organic matter by fluorescence analysis. Limnology and Oceanography, 50, 1415–1426.CrossRefGoogle Scholar
  61. Stedmon, C. A., Markager, S., & Bro, R. (2003). Tracing dissolved organic matter in aquatic environments using a new approach to fluorescence spectroscopy. Marine Chemistry, 82, 239–254.CrossRefGoogle Scholar
  62. Sugiyama, Y., Anegawa, A., Inokuchi, H., & Kumagai, T. (2005). Distribution of dissolved organic carbon and dissolved fulvic acid in mesotrophic Lake Biwa, Japan. Limnology, 6, 161–168.CrossRefGoogle Scholar
  63. Sugiyama, Y., Sugiyama, M., & Hori, T. (2000). Environmental chemistry of rivers and lakes, part V: A comparative study of the chemical and physicochemical characteristics of organic carbon dissolved in river and lake waters. Limnology, 1, 171–176.CrossRefGoogle Scholar
  64. Tanoue, E. (2000). Proteins in the sea-synthesis. In N. Handa, E. Tanoue, & T. Hama (Eds.), Dynamics and characterization of marine organic matter (pp. 383–463). Tokyo: TERRAPUB.Google Scholar
  65. Thurman, E. M. (1985). Humic substances in groundwater. In G. R. Aiken, D. M. McKnight, R. L. Wershaw, & P. MacCarthy (Eds.), Humic substances in soil, sediment, and water: Geochemistry, isolation, and characterization (pp. 87–103) New York: Wiley.Google Scholar
  66. Tranvik, L. J. (1992). Allochthonous dissolved organic matter as an energy source for pelagic bacteria and the concept of the microbial loop. Hydrobiologia, 229, 107–114.Google Scholar
  67. Uchida, M., Nakatsubo, T., Horikoshi, T., & Nakane, K. (1998). Contribution of micro-organisms to the carbon dynamics in black spruce (Picea mariana) forest soil in Canada. Ecological Research, 13, 17–26.CrossRefGoogle Scholar
  68. Uchida, M., Nakatsubo, T., Kasai, Y., Nakane, K., & Horikoshi, T. (2000). Altitude differences in organic matter mass loss and fungal biomass in a subalpine coniferous forest, Mr. Fuji, Japan. Arctic, Antarctic, and Alpine Research, 32(3), 262–269.CrossRefGoogle Scholar
  69. Volk, C. J., Volk, C. B., & Kaplan, L. A. (1997). Chemical composition of biodegradable dissolved organic matter in streamwater. Limnology and Oceanography, 42(1), 39–44.CrossRefGoogle Scholar
  70. Wu, F. C., Mills, R. B., Evans, R. D., & Dillon, P. J. (2005). Photodegradation-induced changes in dissolved organic matter in acidic waters. Canadian Journal of Fisheries Aquatic Sciences, 62, 1019–1027.CrossRefGoogle Scholar
  71. Wu, F. C., Tanoue, E., & Liu, C. Q. (2003). Fluorescence and amino acid characteristics of molecular size fractions of DOM in the waters of Lake Biwa. Biogeochemistry, 65, 245–257.CrossRefGoogle Scholar
  72. Yamashita, Y., & Tanoue, E. (2003a). Chemical characterization of protein-like fluorophores in DOM in relation to aromatic amino acids. Marine Chemistry, 82, 255–271.CrossRefGoogle Scholar
  73. Yamashita, Y., & Tanoue, E. (2003b). Distribution and alteration of amino acids in bulk DOM along a transect from bay to oceanic waters. Marine Chemistry, 82, 145–160.CrossRefGoogle Scholar
  74. Yoshioka, T., Mostofa, K. M. G., Konohira, E., Tanoue, E., Hayakawa, K., Takahashi, M. et al. (2007). Distribution and characteristics of molecular size fractions of freshwater dissolved organic matter in watershed environments: Its implication to degradation. Limnology, 8(1), 29–44.Google Scholar

Copyright information

© Springer Science+Business Media B.V. 2007

Authors and Affiliations

  • Khan M. G. Mostofa
    • 1
    • 2
    Email author
  • Takahito Yoshioka
    • 1
    • 3
  • Eiichi Konohira
    • 1
    • 4
  • Eiichiro Tanoue
    • 1
    • 4
  1. 1.Institute for Hydrospheric Atmospheric SciencesNagoya UniversityNagoyaJapan
  2. 2.C/o-Prof. Fengchang Wu, Graduate School of Chinese Academy of Sciences, Institute of GeochemistryThe Chinese Academy of SciencesGuiyangChina
  3. 3.Field Science Education and Research CenterKyoto UniversityKitashirakawa Oiwake-cho, Sakyo-ku, KyotoJapan
  4. 4.Graduate School of Environmental StudiesNagoya UniversityNagoyaJapan

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