Environmental Chemistry Letters

, Volume 17, Issue 4, pp 1857–1866 | Cite as

Isolation and characterization of hydrophilic dissolved organic matter in waters by ion exchange solid phase extraction followed by high resolution mass spectrometry

  • Wei Wang
  • Chen He
  • Yuan Gao
  • Yahe Zhang
  • Quan ShiEmail author
Original Paper


Dissolved organic matter (DOM) is a complex substance occurring in marine and freshwater environments. DOM has many functions that modify physical, chemical and biological processes in ecological systems. Solid-phase extraction (SPE) is widely used for the separation of DOM. However, a part of strongly hydrophilic compounds are lost using classical SPE separation. In this article, the strong hydrophilic components, which cannot be extracted by the hydrophobic reverse phase SPE, were further extracted in a natural organic matter sample by ion exchange SPE cartridges to obtain hydrophilic acid (HIA), hydrophilic neutral (HIN), and hydrophilic base (HIB) fractions. The extracts were characterized by three-dimensional excitation–emission matrix fluorescence spectroscopy and negative-ion electrospray Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). The results revealed that the hydrophilic components were significantly different from the hydrophobic components in molecular composition. Hydrophilic components were identified as tryptophan-like and tyrosine-like compounds by three-dimensional fluorescence spectra. The HIA fraction contains mainly tannic acid-like compounds with high O/C ratio; the HIB fraction contains mainly amide-like compounds; and the HIN fraction contains mainly lignin and lipids.


Dissolved organic matter Hydrophilic Solid-phase extraction Three-dimensional excitation–emission matrix Fourier transform ion cyclotron resonance mass spectrometry 



Dissolved organic matter


Solid-phase extraction


Three-dimensional excitation–emission matrix


Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry


Hydrophobic substance


Hydrophilic acid


Hydrophilic neutral


Hydrophilic base


Double-bond equivalent


Total organic matter


Proton nuclear magnetic resonance


Kendrick mass defect



This work was supported by the National Key Research and Development Program of China (2018YFA0605800).


  1. Baker A (2002) Fluorescence excitation-emission matrix characterization of river waters impacted by a tissue mill effluent. Environ Sci Technol 36(7):1377. CrossRefGoogle Scholar
  2. Chen J, LeBoeuf EJ, Dai S, Gu B (2003) Fluorescence spectroscopic studies of natural organic matter fractions. Chemosphere 50(5):639–647. CrossRefGoogle Scholar
  3. Cilenti A, Provenzano MR, Senesi N (2005) Characterization of dissolved organic matter from saline soils by fluorescence spectroscopy. Environ Chem Lett 3(2):53–56. CrossRefGoogle Scholar
  4. Coble PG (1996) Characterization of marine and terrestrial DOM in seawater using excitation-emission matrix spectroscopy. Mar Chem 51(4):325–346. CrossRefGoogle Scholar
  5. Dai J-Y, Zhou J-M, Qin S-P (2004) Binding of pyrene to dissolved organic matters: fractionation and characterization. J Environ Sci (China) 16(6):928–933Google Scholar
  6. Dittmar T, Koch B, Hertkorn N, Kattner G (2008) A simple and efficient method for the solid-phase extraction of dissolved organic matter (SPE-DOM) from seawater. Limnol Oceanogr Methods 6(6):230–235. CrossRefGoogle Scholar
  7. Fang Z, He C, Li Y, Chung KH, Xu C, Shi Q (2017) Fractionation and characterization of dissolved organic matter (DOM) in refinery wastewater by revised phase retention and ion-exchange adsorption solid phase extraction followed by ESI FT-ICR MS. Talanta 162:466–473. CrossRefGoogle Scholar
  8. Filella M (2009) Freshwaters: which NOM matters? Environ Chem Lett 7(1):21–35. CrossRefGoogle Scholar
  9. Fu P, Wu F, Liu CQ, Wei Z, Bai Y, Liao H (2006) Spectroscopic characterization and molecular weight distribution of dissolved organic matter in sediment porewaters from Lake Erhai, Southwest China. Biogeochemistry 81(2):179–189. CrossRefGoogle Scholar
  10. Ilani T, Schulz E, Chefetz B (2005) Interactions of organic compounds with wastewater dissolved organic matter. J Environ Qual 34(2):552–562CrossRefGoogle Scholar
  11. Janhom T, Musikavong C, Wattanachira S, Furumai H (2007) Reactivity and sensitivity of DOM fractions to form THMs in raw water supply and in treated wastewater used for reclaimed water of the northern-region industrial estate Thailand. Southeast Asian Water Environ 2(15):231–246Google Scholar
  12. Jansson M (1998) Nutrient limitation and bacteria–phytoplankton interactions in humic lakes. Springer, BerlinCrossRefGoogle Scholar
  13. Kim S, Kramer RW, Hatcher PG (2003) Graphical method for analysis of ultrahigh-resolution broadband mass spectra of natural organic matter, the van Krevelen diagram. Anal Chem 75(20):5336–5344. CrossRefGoogle Scholar
  14. Leenheer JA (1981) Comprehensive approach to preparative isolation and fractionation of dissolved organic carbon from natural waters and wastewaters. Environ Sci Technol 15(5):578–587. CrossRefGoogle Scholar
  15. Leenheer JA, Wershaw RL, Brown GK, Reddy MM (2003) Characterization and diagenesis of strong-acid carboxyl groups in humic substances. Appl Geochem 18(3):471–482. CrossRefGoogle Scholar
  16. Li HY, Minor EC (2015) Dissolved organic matter in Lake Superior: insights into the effects of extraction methods on chemical composition. Environ Sci Process Impacts 17(10):1829–1840. CrossRefGoogle Scholar
  17. Li YY, Xu CM, Chung KH, Shi Q (2015) Molecular characterization of dissolved organic matter and its subfractions in refinery process water by Fourier transform ion cyclotron resonance mass spectrometry. Energy Fuels 29(5):2923–2930. CrossRefGoogle Scholar
  18. Li Y, Harir M, Uhl J, Kanawati B, Lucio M, Smirnov KS, Koch BP, Schmitt-Kopplin P, Hertkorn N (2017) How representative are dissolved organic matter (DOM) extracts? A comprehensive study of sorbent selectivity for DOM isolation. Water Res 116(2):316–323. CrossRefGoogle Scholar
  19. Quan S, Na P, Long H, Cui D, Guo X, Long Y, Chung KH, Zhao S, Xu C, Chang SH (2013) Characterization of middle-temperature gasification coal tar. Part 3: molecular composition of acidic compounds. Energy Fuels 27(1):108–117. CrossRefGoogle Scholar
  20. Raeke J, Lechtenfeld OJ, Wagner M, Herzsprung P, Reemtsma T (2016) Selectivity of solid phase extraction of freshwater dissolved organic matter and its effect on ultrahigh resolution mass spectra. Environ Sci Process Impacts 18(7):918–927. CrossRefGoogle Scholar
  21. Seitz WR (1981) Fluorescence methods for studying speciation of pollutants in water Fluorescence quenching yields information on the binding of metal ions to humic substances. Fluorescence polarization may be used to study the conformation of humics and the binding of orga. Trends Anal Chem 1(4):79–83. CrossRefGoogle Scholar
  22. Sleighter RL, Hatcher PG (2011) Fourier transform mass spectrometry for the molecular level characterization of natural organic matter: instrument capabilities, applications, and limitations. InTech, RijekaGoogle Scholar
  23. Stücheli PE, Niggemann J, Schubert CJ (2018) Comparison of different solid phase extraction sorbents for the qualitative assessment of dissolved organic nitrogen in freshwater samples using FT-ICR-MS. J Limnol. CrossRefGoogle Scholar
  24. Trubetskaya OE, Richard C, Trubetskoj OA (2016) High amounts of free aromatic amino acids in the protein-like fluorescence of water-dissolved organic matter. Environ Chem Lett 14(4):495–500. CrossRefGoogle Scholar
  25. VanLoon GW, Duffy SJ (2017) Environmental chemistry: a global perspective. Oxford University Press, OxfordGoogle Scholar
  26. Waska H, Koschinsky A, Chancho MJR, Dittmar T (2015) Investigating the potential of solid-phase extraction and Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) for the isolation and identification of dissolved metal-organic complexes from natural waters. Mar Chem 173:78–92. CrossRefGoogle Scholar
  27. Wolfe MF, Olsen HE, Tjeerdema RS (1996) Induction of stress proteins in Isochrysis galbana exposed to crude oil and chemically dispersed crude oil preparation. Mar Environ Res 42(1):405. CrossRefGoogle Scholar
  28. Wu FC, Evans RD, Dillon PJ, Cai YR (2007a) Rapid quantification of humic and fulvic acids by HPLC in natural waters. Appl Geochem 22(8):1598–1605. CrossRefGoogle Scholar
  29. Wu FC, Kothawala DN, Evans RD, Dillon PJ, Cai YR (2007b) Relationships between DOC concentration, molecular size and fluorescence properties of DOM in a stream. Appl Geochem 22(8):1659–1667. CrossRefGoogle Scholar
  30. Zhao ZY, Gu JD, Fan XJ, Li HB (2006) Molecular size distribution of dissolved organic matter in water of the Pearl River and trihalomethane formation characteristics with chlorine and chlorine dioxide treatments. J Hazard Mater 134(1):60–66. CrossRefGoogle Scholar
  31. Zhou LX, Yang H, Shen QR, Wong MH, Wong JWC (2000) Fractionation and characterization of dissolved organic matter derived from sewage sludge and composted sludge. Environ Technol Lett 21(7):765–771. CrossRefGoogle Scholar

Copyright information

© Springer Nature Switzerland AG 2019

Authors and Affiliations

  1. 1.State Key Laboratory of Heavy Oil ProcessingChina University of PetroleumBeijingPeople’s Republic of China

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