, Volume 20, Issue 1, pp 109–120 | Cite as

Comparison between humic-like peaks in excitation-emission matrix spectra and resin-fractionated humic substances in aquatic environments

  • Kazuhiro KomatsuEmail author
  • Akio Imai
  • Nobuyuki Kawasaki
Research paper


The intensity of the 340/430-nm peak in the three-dimensional excitation-emission matrix spectra of water samples has been used as an index of the concentration of aquatic humic substance (AHS). However, whether this peak corresponds uniquely to AHS has not been definitively verified. Therefore, in this study, our objectives were: (1) to determine whether the 340/430-nm peak in the spectra of lake and river water samples does, in fact, correspond uniquely to AHS; (2) to determine what type of dissolved organic matter (DOM), in terms of hydrophobicity, accounts for the peak; and (3) to determine the advisability of using excitation-emission matrix spectroscopy to rapidly estimate AHS concentrations. We found that the 340/430-nm peak originates not only from the AHS fraction of DOM but also from a portion of the hydrophilic fraction. By analyzing the quantitative relationship between AHS concentration and 340/430-nm peak intensity for DOM samples, we found the intensity can be used to estimate AHS concentration in lake water when the concentration is strongly affected by influent river water or when the ratio of ultraviolet (UV) absorbance to dissolved organic carbon concentration is relatively high.


Dissolved organic matter Aquatic humic substances Hydrophilic fraction Column-capacity factor 



This work was financially supported by the Environment Research and Technology Development Fund of the Ministry of the Environment, Japan (5-1304); by Grants-in-Aid (nos. 17310013, 17760443, and 21241008) from the Scientific Research Fund of the Ministry of Education, Culture, Sports Science and Technology, Japan; by Kankyo-Gijutsu Research Funds (Development of Chromatography System with Organic Carbon Detection for Evaluating Characteristics and Reactivity of Dissolved Organic Matter in Aquatic Systems) from the Ministry of the Environment, Japan; and by Japan Science and Technology Agency (JST)/Japan International Cooperation Agency (JICA), Science and Technology Research Partnership for Sustainable Development (SATREPS) through the project for Continuous Operation System for Microalgae Production Optimized for Sustainable Tropical Aquaculture (COSMOS). 

Supplementary material

10201_2018_555_MOESM1_ESM.doc (40 kb)
Supplementary material 1 (DOC 40 kb)


  1. Amy GL, Sierka RA, Bedessem J, Price D, Tan L (1992) Molecular-size distributions of dissolved organic-matter. J Am Water Works Assoc 84(6):67–75CrossRefGoogle Scholar
  2. Baghoth SA, Sharma SK, Amy GL (2011) Tracking natural organic matter (NOM) in a drinking water treatment plant using fluorescence excitation-emission matrices and PARAFAC. Water Res 45(2):797–809CrossRefGoogle Scholar
  3. Buffle J, Delandoety P, Zumstein J, Haerdi W (1982) Analysis and characterization of natural organic matters in freshwaters. I. Study of analytical techniques. Schweizerische Zeitschrift Fur Hydrologie Swiss J Hydrol 44:325–362Google Scholar
  4. Burdige DJ, Kline SW, Chen W (2004) Fluorescent dissolved organic matter in marine sediment pore waters. Mar Chem 89:289–311CrossRefGoogle Scholar
  5. Chen W, Westerhoff P, Leenheer JA, Booksh K (2003) Fluorescence excitation-emission matrix regional integration to quantify spectra for dissolved organic matter. Environ Sci Technol 37:5701–5710CrossRefGoogle Scholar
  6. Chu WH, Gao NY, Deng Y, Krasner SW (2010) Precursors of dichloroacetamide, an emerging nitrogenous DBP formed during chlorination or chloramination. Environ Sci Technol 44:3908–3912CrossRefGoogle Scholar
  7. Coble PG, Green SA, Blough NV, Gagosian RB (1990) Characterization of dissolved organic matter in the Black Sea by fluorescence spectroscopy. Nature 348(29):432–435CrossRefGoogle Scholar
  8. Determann S, Reuter R, Wagner P (1994) Fluorescent matter in the eastern Atlantic Ocean. Part 1: method of measurement and near-surface distribution. Deep Sea Res Part I Oceanogr Res Pap 41(4):659–675CrossRefGoogle Scholar
  9. Dilling J, Kaiser K (2002) Estimation of the hydrophobic fraction of dissolved organic matter in water samples using UV photometry. Water Res 36(20):5037–5044CrossRefGoogle Scholar
  10. Ertel JR, Hedges JI, Devol AH, Richey JE (1986) Dissolved humic substances of the Amazon River system. Limnol Oceanogr 31:739–754CrossRefGoogle Scholar
  11. Ewald M, Bellin C, Berger P, Weber JH (1983) Corrected fluorescence spectra of fulvic acids isolated from soil and water. Environ Sci Technol 17:501–504CrossRefGoogle Scholar
  12. Fellman JB, D’Amore DV, Hood E (2008) An evaluation of freezing as a preservation technique for analyzing dissolved organic C, N and P in surface water samples. Sci Total Environ 392:305–312CrossRefGoogle Scholar
  13. Fellman JB, Hood E, D’Amore DV, Edwards RT, White D (2009) Seasonal changes in the chemical quality and biodegradability of dissolved organic matter exported from soils to streams in coastal temperate rainforest watersheds. Biogeochemistry 95:277–293CrossRefGoogle Scholar
  14. Fukushima M, Takamura N, Sun LW, Kagawa M, Matsushige K, Xie P (1999) Changes in the plankton community following introduction of filter-feeding planktivorous fish. Freshw Biol 42(4):719–735CrossRefGoogle Scholar
  15. George FV, Mark BD (1991) Chemical characteristics and acidity of soluble organic substances from a northern hardwood forest floor, central Maine, USA. Geochim Cosmochim Acta 55:3611–3625CrossRefGoogle Scholar
  16. Imai A, Fukushima T, Matsushige K, Inoue T, Ishibashi T (1998) Fractionation of dissolved organic carbon from the waters of Lake Biwa and its inflowing rivers. Jpn J Limnol 59:53–68 (in Japanese with English abstract) CrossRefGoogle Scholar
  17. Imai A, Fukushima T, Matsushige K, Kim YH (2001) Fractionation and characterization of dissolved organic matter in a shallow eutrophic lake, its inflowing rivers, and other organic matter sources. Water Res 35(17):4019–4028CrossRefGoogle Scholar
  18. Imai A, Matsushige K, Nagai T (2003) Trihalomethane formation potential of dissolved organic matter in a shallow eutrophic lake. Water Res 37(17):4284–4294CrossRefGoogle Scholar
  19. Nippon-Kagaku-kai (1977) Structure of organic compounds II. In: Shin-Jikken-Kagaku-Kouza, vol 13. Maruzen, Tokyo (in Japanese) Google Scholar
  20. Leenheer JA (1981) Comprehensive approach to preparative isolation and fractionation of dissolved organic carbon from natural waters and wastewaters. Environ Sci Technol 15(5):578–587CrossRefGoogle Scholar
  21. Malcolm RL (1990) The uniqueness of humic substances in each of soil, stream and marine environments. Anal Chim Acta 232(1):19–30CrossRefGoogle Scholar
  22. Matthews BJH, Jones AC, Theodorou NK, Tudhope AW (1996) Excitation-emission-matrix fluorescence spectroscopy applied to humic acid bands in coral reefs. Mar Chem 55:317–332CrossRefGoogle Scholar
  23. Mayer LM, Schick LL, Lober TC III (1999) Dissolved protein fluorescence in two Maine estuaries. Mar Chem 64:171–179CrossRefGoogle Scholar
  24. Meyers SJ, Hedges JI (1986) Molecular evidence for a terrestrial component of organic matter dissolved in seawater. Nature 321:61–63CrossRefGoogle Scholar
  25. Monteith DT, Stoddard JL, Evans CD, de Wit HA, Forsius M, Hogasen T, Wilander A, Skjelkvale BL, Jeffries DS, Vuorenmaa J, Keller B, Kopacek J, Vesely J (2007) Dissolved organic carbon trends resulting from changes in atmospheric deposition chemistry. Nature 450(7169):537–540CrossRefGoogle Scholar
  26. Mopper K, Schultz CA (1993) Fluorescence as a possible tool for studying the nature and water column distribution of DOC components. Mar Chem 41:229–238CrossRefGoogle Scholar
  27. Mostofa KMG, Yoshioka T, Konohira E, Tanoue E, Hayakawa K, Takahashi M (2005) Three-dimensional fluorescence as a tool for investigating the dynamics of dissolved organic matter in the Lake Biwa watershed. Limnology 6:101–115CrossRefGoogle Scholar
  28. Nagai T, Imai A, Matsushige K, Fukushima T (2006) Effect of iron complexation with dissolved organic matter on the growth of cyanobacteria in a eutrophic lake. Aquat Microb Ecol 44:231–239CrossRefGoogle Scholar
  29. Opsahl S, Benner R (1997) Distribution and cycling of terrigenous dissolved organic matter in the ocean. Nature 386:480–482CrossRefGoogle Scholar
  30. Sadiq R, Rodriguez MJ (2004) Disinfection by-products (DBPs) in drinking water and predictive models for their occurrence: a review. Sci Total Environ 321:21–46CrossRefGoogle Scholar
  31. SanClements MD, Oelsner GP, McKnight DM, Stoddard JL, Nelson SJ (2012) New insights into the source of decadal increases of dissolved organic matter in acid-sensitive lakes of the northeastern United States. Environ Sci Technol 46(6):3212–3219CrossRefGoogle Scholar
  32. Sheng GP, Yu HQ (2006) Characterization of extracellular polymeric substances of aerobic and anaerobic sludge using three-dimensional excitation and emission matrix fluorescence spectroscopy. Water Res 40(6):1233–1239CrossRefGoogle Scholar
  33. Shirai M, Ohtake A, Sano T, Matsumoto S, Sakamoto T, Sato A, Aida T, Hanada K, Shimada T, Suzuki M, Nakano M (1991) Toxicity and toxins of natural blooms and isolated strains of Microcystis spp. (cyanobacteria) and improved procedure for purification of cultures. Appl Environ Microbiol 57(4):1241–1245Google Scholar
  34. Stedmon CA, Markager S (2005) Resolving the variability in dissolved organic matter fluorescence in a temperate estuary and its catchment using PARAFAC analysis. Limnol Oceanogr 50(2):686–697CrossRefGoogle Scholar
  35. Stedmon CA, Markager S, Bro R (2003) Tracing dissolved organic matter in aquatic environments using a new approach to fluorescence spectroscopy. Mar Chem 82:239–254CrossRefGoogle Scholar
  36. Thomas JD (1997) The role of dissolved organic matter, particularly free amino acids and humic substances, in freshwater ecosystems. Freshw Biol 38:1–36CrossRefGoogle Scholar
  37. Thurman EM (1985) Organic geochemistry of natural waters. Martinus Nijhoff/Dr W. Junk Publishers, DordrechtCrossRefGoogle Scholar
  38. Thurman EM, Malcolm RL (1981) Preparative isolation of aquatic humic substances. Environ Sci Technol 15(4):463–466CrossRefGoogle Scholar
  39. Wang ZW, Wu ZC, Tang SJ (2009) Characterization of dissolved organic matter in a submerged membrane bioreactor by using three-dimensional excitation and emission matrix fluorescence spectroscopy. Water Res 43(6):1533–1540CrossRefGoogle Scholar
  40. Westerhoff P, Chen W, Esparza M (2001) Fluorescence analysis of a standard fulvic acid and tertiary treated wastewater. J Environ Qual 30:2037–2046CrossRefGoogle Scholar
  41. Worrall F, Harriman R, Evans CD, Watts CD, Adamson J, Neal C, Tipping E, Burt T, Grieve I, Monteith D, Naden PS, Nisbet T, Reynolds B, Stevens P (2004) Trends in dissolved organic carbon in UK rivers and lakes. Biogeochemistry 70(3):369–402CrossRefGoogle Scholar
  42. Yamashita Y, Tanoue E (2003) Chemical characterization of protein-like fluorophores in DOM in relation to aromatic amino acids. Mar Chem 82:255–271CrossRefGoogle Scholar
  43. Yang X, Shang C, Lee W, Westerhoff P, Fan C (2008) Correlations between organic matter properties and DBP formation during chloramination. Water Res 42(8–9):2329–2339CrossRefGoogle Scholar
  44. Zhang T, Lu J, Ma J, Qiang Z (2008) Fluorescence spectroscopic characterization of DOM fractions isolated from a filtered river water after ozonation and catalytic ozonation. Chemosphere 71(5):911–921CrossRefGoogle Scholar

Copyright information

© The Japanese Society of Limnology 2018

Authors and Affiliations

  • Kazuhiro Komatsu
    • 1
    Email author
  • Akio Imai
    • 1
  • Nobuyuki Kawasaki
    • 2
  1. 1.National Institute for Environmental StudiesTsukubaJapan
  2. 2.Faculty of Engineering and Life SciencesUniversiti SelangorBestari JayaMalaysia

Personalised recommendations