Skip to main content

Advertisement

Log in

Chemical composition of dissolved organic matter from various sources as characterized by solid-state NMR

  • Research Article
  • Published:
Aquatic Sciences Aims and scope Submit manuscript

Abstract

This study used solid-state nuclear magnetic resonance techniques to characterize the chemical compositions of DOM from various sources and thereby explore the linkages of river DOM to its potential point and nonpoint sources. DOM samples were isolated from two streams draining watersheds of different land uses, landfill leachates of two ages, sequential (raw, facility- and wetland-treated) wastewaters in a wastewater treatment plant. Two sampling sites along the Missouri River were located upstream and downstream of the outlet of a tributary, to which the stream waters, landfill leachates, and wastewater effluents were discharged. Compared with the chemical composition of the stream DOM from a cropland-dominated watershed, the stream DOM from a grass/forestland-dominated watershed comprised 14 % more alkyl carbons (C), but ~5 % less O-alkyl C. The two leachate DOM samples from landfill cells of two ages showed similar area fractions of the carbon types, and their spectra exhibited a characteristic alkyl C peak at 37 ppm, potentially a molecular signature of the DOM of landfill leachate source. The DOM from the treated wastewater had slightly (~4 %) less alkyl C than that from the raw wastewater, and the DOM from the wetland-treated wastewater displayed decreased O-alkyl C but increased alkyl C, both to a small degree (by ~4 %), compared to the DOM in the facility-treated wastewater. The chemical composition of DOM in the Missouri River was affected by the local organic inputs, with the DOM from downstream the outlet displaying ~11 % higher alkyl C.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  • Arnold WA, Longnecker K, Kroeger KD, Kujawinski EB (2014) Molecular signature of organic nitrogen in septic-impacted groundwater. Environ Sci Processes Impacts 16:2400–2407

    Article  CAS  Google Scholar 

  • Bianchi TS, Filley T, Dria K, Hatcher PG (2004) Temporal variability in sources of dissolved organic carbon in the lower Mississippi River. Geochim Cosmochim Acta 68:959–967

    Article  CAS  Google Scholar 

  • Cao X, Olk DC, Chappell M, Cambardella CA, Miller LF, Mao J (2011) Solid-state NMR analysis of soil organic matter fractions from integrated physical–chemical extraction. Soil Sci Soc Am J 75:1374–1384

    Article  CAS  Google Scholar 

  • Chai X, Hao Y, Liu G, Zhao X, Zhao Y (2013) Spectroscopic studies of the effect of aerobic conditions on the chemical characteristics of humic acid in landfill leachate and its implication for the environment. Chemosphere 91:1058–1063

    Article  CAS  Google Scholar 

  • Chang H, Chen C, Wang G (2013) Characteristics of C-, N-DBPs formation from nitrogenen-riched dissolved organic matter in raw water and treated wastewater effluent. Water Res 47:2729–2741

    Article  CAS  PubMed  Google Scholar 

  • Dignac MF, Ginestet P, Audic JM, Derenne S, Largeau C (2000) Changes in the organic composition of wastewater during biological treatment as studied by NMR and IR spectroscopies. Water Sci Technol 43:51–58

    Google Scholar 

  • Dixon WT (1982) Spinning-sideband-free and spinning-sideband-only NMR spectra in spinning samples. J Chem Phys 77:1800–1809

    Article  CAS  Google Scholar 

  • Duan S, Bianchi TS, Sampere TP (2007) Temporal variability in the composition and abundance of terrestrially-derived dissolved organic matter in the lower Mississippi and Pearl Rivers. Mar Chem 103:172–184

    Article  CAS  Google Scholar 

  • Fang X, Chua T, Schmidt-Rohr K, Thompson ML (2010) Quantitative 13C NMR of whole and fractionated Iowa Mollisols for assessment of organic matter composition. Geochim Cosmochim Acta 74:584–598

    Article  CAS  Google Scholar 

  • Greenwood PF, Berwick LJ, Croué JP (2012) Molecular characterisation of the dissolved organic matter of wastewater effluents by MSSV pyrolysis GC–MS and search for source markers. Chemosphere 87:504–512

    Article  CAS  PubMed  Google Scholar 

  • Hanley KW, Wollheim WM, Salisbury J, Huntington T, Aiken G (2013) Controls on dissolved organic carbon quantity and chemical character in temperate rivers of North America. Global Biogeochem Cycles 27:492–504

    Article  CAS  Google Scholar 

  • Hernes PJ, Spencer RG, Dyda RY, Pellerin BA, Bachand PAM, Bergamaschi BA (2013) DOM composition in an agricultural watershed: assessing patterns and variability in the context of spatial scales. Geochim Cosmochim Acta 121:599–610

    Article  CAS  Google Scholar 

  • Hertkorn N, Harir M, Koch BP, Michalke B, Schmitt-Kopplin P (2013) High-field NMR spectroscopy and FTICR mass spectrometry: powerful discovery tools for the molecular level characterization of marine dissolved organic matter. Biogeosciences 10:1583–1624

    Article  CAS  Google Scholar 

  • Hua B, Dolan F, McGhee C, Clevenger TE, Deng B (2007) Water-source characterization and classification with fluorescence EEM spectroscopy: PARAFAC analysis. Int J Environ Anal Chem 87:135–147

    Article  CAS  Google Scholar 

  • Huang W, Chen RF (2009) Sources and transformations of chromophoric dissolved organic matter in the Neponset River Watershed. J Geophys Res 114:G00F05

    Google Scholar 

  • Hudson N, Baker A, Reynolds D (2007) Fluorescence analysis of dissolved organic matter in natural, waste and polluted waters: a review. River Res Appl 23:631–649

    Article  Google Scholar 

  • Huo S, Xi B, Yu H, He L, Fan S, Liu H (2008) Characteristics of dissolved organic matter (DOM) in leachate with different landfill ages. J Environ Sci 20:492–498

    Article  CAS  Google Scholar 

  • Kang K, Shin H, Park H (2002) Characterization of humic substances present in landfill leachates with different landfill ages and its implications. Water Res 36:4023–4032

    Article  CAS  PubMed  Google Scholar 

  • Kögel-Knabner I (2002) The macromolecular organic composition of plant and microbial residues as inputs to soil organic matter. Soil Biol Biochem 34:139–162

    Article  Google Scholar 

  • Leenheer JA, Croue J (2003) Characterizing dissolved aquatic organic matter. Environ Sci Technol 37:18A–26A

    Article  CAS  PubMed  Google Scholar 

  • Leenheer JA, Nanny MA, McIntyre C (2003) Terpenoids as major precursors of dissolved organic matter in landfill leachates, surface water, and groundwater. Environ Sci Technol 37:2323–2331

    Article  CAS  PubMed  Google Scholar 

  • Li J, Wen Y, Zhou Q, Xingjie Z, Yang S, Lin T (2008) Influence of vegetation and substrate on the removal and transformation of dissolved organic matter in horizontal subsurface-flow constructed wetlands. Biores Technol 99:4990–4996

    Article  CAS  Google Scholar 

  • Mahieu N, Olk DC, Randall EW (2002) Multinuclear magnetic resonance analysis of two humic acid fractions from lowland rice soils. J Environ Qual 31:421–430

    Article  CAS  PubMed  Google Scholar 

  • Mao J, Chen N, Cao X (2011) Characterization of humic substances by advanced solid state NMR spectroscopy: demonstration of a systematic approach. Org Geochem 42:891–902

    Article  CAS  Google Scholar 

  • Mao J, Kong X, Schmidt-Rohr K, Pignatello JJ, Perdue EM (2012) Advanced solid-state NMR characterization of marine dissolved organic matter isolated using the coupled reverse osmosis/electrodialysis method. Environ Sci Technol 46:5806–5814

    Article  CAS  PubMed  Google Scholar 

  • Mopper K, Stubbins A, Ritchie JD, Bialk HD, Hatcher PG (2007) Advanced instrumental approaches for characterization of marine dissolved organic matter: extraction techniques, mass spectrometry, and nuclear magnetic resonance spectroscopy. Chem Rev 107:419–442

    Article  CAS  PubMed  Google Scholar 

  • Nanny MA, Ratasuk N (2002) Characterization and comparison of hydrophobic neutral and hydrophobic acid dissolved organic carbon isolated from three municipal landfill leachates. Water Res 36:1572–1584

    Article  CAS  PubMed  Google Scholar 

  • Nebbioso A, Piccolo A (2013) Molecular characterization of dissolved organic matter (DOM): a critical review. Anal Bioanal Chem 405:109–124

    Article  CAS  PubMed  Google Scholar 

  • Papenguth HW, Kirkpatrick RJ, Montez B, Sandberg PA (1989) 13C MAS NMR spectroscopy of inorganic and biogenic carbonates. Ame Mineralogist 74:1152–1158

    CAS  Google Scholar 

  • Regnier P, Friedlingstein P, Ciais P, Mackenzie FT, Gruber N, Janssens IA, Goulven G, Laruelle GG, Lauerwald R, Luyssaert S, Andersson AJ, Arndt S, Arnosti C, Borges AV, Dale AW, Gallego-Sala A, Goddéris Y, Goossens N, Hartmann J, Heinze C, Ilyina T, Joos F, LaRowe DE, Leifeld J, Meysman FJR, Munhoven G, Raymond PA, Spahni R, Suntharalingam P, Thullner M (2013) Anthropogenic perturbation of the carbon fluxes from land to ocean. Nat Geosci 6:597–607

    Article  CAS  Google Scholar 

  • Schlesinger WH, Melack JM (1981) Transport of organic carbon in the world’s rivers. Tellus 33:172–187

    Article  CAS  Google Scholar 

  • Serkiz SM, Perdue EM (1990) Isolation of dissolved organic matter from the Suwannee river using reverse osmosis. Water Res 24:911–916

    Article  CAS  Google Scholar 

  • Sherrod A, Dunn G, Peterson GA, Kolberg RL (2002) Inorganic carbon analysis by modified pressure-calcimeter method. Soil Sci Soc Am J 66:299–305

    Article  CAS  Google Scholar 

  • Smernik RJ, Oades JM (1999) Effects of added paramagnetic ions on the 13C CP/MAS NMR spectrum of a de-ashed soil. Geoderma 89:219–248

    Article  CAS  Google Scholar 

  • Spencer RM, Butler KD, Aiken GR (2012) Dissolved organic carbon and chromophoric dissolved organic matter properties of rivers in the USA. J Geophys Res 117:G03001

    Google Scholar 

  • Stubbins A, Robert G, Spencer RM, Chen H, Hatcher PG, Mopper K, Hernes PJ, Mwamba VL, Mangangu AM, Wabakanghanzi JN, Six J (2010) Illuminated darkness: molecular signatures of Congo River dissolved organic matter and its photochemical alteration as revealed by ultrahigh precision mass spectrometry. Limnol Oceanogr 55:1467–1477

    Article  CAS  Google Scholar 

  • Thomas JD (1997) The role of dissolved organic matter, particularly free amino acids and humic substances, in freshwater ecosystems. Freshwater Biol 38:1–36

    Article  CAS  Google Scholar 

  • Thorn KA (1994) Nuclear-magnetic-resonance studies of fulvic and humic acids from the Suwannee River. In: Averett RC, Leenheer JA, KcKnight DM, Thorn KA (eds) Humic substances in the Suwannee River, Georgia: interactions, properties, and proposed structures; United States Geological Suvery water-supply report, vol 2373. US Geological Survey, Denver, CO, pp 141–182

    Google Scholar 

  • Thurman EN (1985) Organic geochemistry of natural waters. Nijhoff and W. Junk Publishers, Dordrecht

    Book  Google Scholar 

  • US Environmental Protection Agency (USEPA) (2011) Total maximum daily load: Hinkson Creek, Boone County, Missouri. US Environmental Protection Agency, Kansas City, KS

  • Wei L, Zhao Q, Xue S, Jia T, Tang F, You P (2009) Behavior and characteristics of DOM during a laboratory-scale horizontal subsurface flow wetland treatment: effect of DOM derived from leaves and roots. Ecol Eng 35:1405–1414

    Article  Google Scholar 

  • Weishaar JL, Aiken GR, Bergamaschi BA, Fram MS, Fugii R, Mopper K (2003) Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic carbon. Environ Sci Technol 37:4702–4708

    Article  CAS  PubMed  Google Scholar 

  • Williams CJ, Yamashita Y, Wilson HF, Jaffe R, Xenopoulos MA (2010) Unraveling the role of land use and microbial activity in shaping dissolved organic matter characteristics in stream ecosystems. Limnol Oceanogr 55:1159–1171

    Article  CAS  Google Scholar 

  • Wilson HF, Xenopoulos MA (2009) Effects of agricultural land use on the composition of fluvial dissolved organic matter. Nat Geosci 2:37–41

    Article  CAS  Google Scholar 

  • Xu Y, Yue D, Zhu Y, Nie Y (2006) Fractionation of dissolved organic matter in mature landfill leachate and its recycling by ultrafiltration and evaporation combined processes. Chemosphere 64:903–911

    Article  CAS  PubMed  Google Scholar 

  • Yamashita Y, Kloeppel BD, Knoepp J, Zausen GL, Jaffe R (2011) Effects of watershed history on dissolved organic matter characteristics in headwater streams. Ecosystems 14:1110–1122

    Article  CAS  Google Scholar 

  • Yang L, Hong H, Guo W, Huang J, Li Q, Yu X (2012) Effects of changing land use on dissolved organic matter in a subtropical river watershed, southeast China. Reg Environ Change 12:145–151

    Article  Google Scholar 

Download references

Acknowledgments

The authors would like to thank Dr. Klaus Schmidt-Rohr at Brandeis University for his advice on NMR analysis and the manuscript. This project was funded by the USDA-NIFA Capacity Building Grant Program through the Grant No. 2010-38821-21558 to Lincoln University of Missouri, University of Missouri, and Old Dominion University.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Jingdong Mao.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhou, Z., Hua, B., Cao, X. et al. Chemical composition of dissolved organic matter from various sources as characterized by solid-state NMR. Aquat Sci 77, 595–607 (2015). https://doi.org/10.1007/s00027-015-0405-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00027-015-0405-8

Keywords

Navigation