Free Standard AU & NZ Shipping For All Book Orders Over $80!
Register      Login
Environmental Chemistry Environmental Chemistry Society
Environmental problems - Chemical approaches
RESEARCH ARTICLE

Molecular-scale investigation of soil fulvic acid and water-extractable organic matter by high-resolution mass spectrometry and 1H NMR spectroscopy

Ruixia Han A B , Jitao Lv https://orcid.org/0000-0003-1872-3832 A C , Lei Luo A , Bei Wen A and Shuzhen Zhang A B
+ Author Affiliations
- Author Affiliations

A State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, PO Box 2871, Beijing 100085, China.

B University of Chinese Academy of Sciences, Beijing 100049, China.

C Corresponding author. Email: jtlv@rcees.ac.cn

Environmental Chemistry 16(2) 92-100 https://doi.org/10.1071/EN18124
Submitted: 8 June 2018  Accepted: 17 December 2018   Published: 21 January 2019

Environmental context. Notwithstanding the environmental and geochemical significance of soil dissolved organic matter (DOM), its molecular components are still not well characterised. This study investigates chemical similarities and differences between two widely used forms of soil DOM: water-extractable organic matter and fulvic acids. The findings will guide appropriate extraction and purification protocols in future studies related to soil DOM.

Abstract. Dissolved organic matter (DOM) is the most active fraction of soil organic matter (SOM), which has both environmental and geochemical importance. However, the extraction of DOM from soils is still ambiguous. Instead, operational concepts, such as fulvic acid (FA) and water-extractable organic matter (WEOM), are widely used in practice. In this study, the molecular components of FA and WEOM extracted from two standard soils were investigated by using electrospray ionisation coupled with Fourier-transform ion cyclotron resonance mass spectrometry and proton nuclear magnetic resonance (1H NMR) spectroscopy to clarify the molecular similarities and differences between them. The results revealed that WEOM and FA shared many of the same molecules, which accounted for 64 % and 82 % of the total numbers of molecules for WEOM and FA respectively. However, WEOM displayed higher chemical and molecular diversities than FA. Detailed analysis revealed that the extraction and desalination procedure of FA led to the loss of lignin, protein and carbohydrate compounds, but induced preferential release of some tannin-like molecules from the aggregate- or organic mineral-associated SOM. Based on the results of the present study, water extraction combined with desalination through a functionalised styrene divinylbenzene polymer-based solid phase extraction is more reliable to retain the molecular diversity of soil DOM.


References

Chen Y, Senesi N, Schnitzer M (1977). Information provided on humic substances by E4/E6 ratios. Soil Science Society of America Journal 41, 352–358.
Information provided on humic substances by E4/E6 ratiosCrossref | GoogleScholarGoogle Scholar |

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. Limnology and Oceanography, Methods 6, 230–235.
A simple and efficient method for the solid-phase extraction of dissolved organic matter (SPE-DOM) from seawaterCrossref | GoogleScholarGoogle Scholar |

Fang K, Yuan D, Zhang L, Feng L, Chen Y, Wang Y (2015). Effect of environmental factors on the complexation of iron and humic acid. Journal of Environmental Sciences 27, 188–196.
Effect of environmental factors on the complexation of iron and humic acidCrossref | GoogleScholarGoogle Scholar |

Feng X, Simpson AJ, Simpson MJ (2005). Chemical and mineralogical controls on humic acid sorption to clay mineral surfaces. Organic Geochemistry 36, 1553–1566.
Chemical and mineralogical controls on humic acid sorption to clay mineral surfacesCrossref | GoogleScholarGoogle Scholar |

Filella M (2009). Freshwaters: which NOM matters?. Environmental Chemistry Letters 7, 21–35.
Freshwaters: which NOM matters?Crossref | GoogleScholarGoogle Scholar |

Fox PM, Nico PS, Tfaily MM, Heckman K, Davis JA (2017). Characterization of natural organic matter in low-carbon sediments: extraction and analytical approaches. Organic Geochemistry 114, 12–22.
Characterization of natural organic matter in low-carbon sediments: extraction and analytical approachesCrossref | GoogleScholarGoogle Scholar |

Galindo C, Del Nero M (2014). Molecular level description of the sorptive fractionation of a fulvic acid on aluminum oxide using electrospray ionization Fourier transform mass spectrometry. Environmental Science & Technology 48, 7401–7408.
Molecular level description of the sorptive fractionation of a fulvic acid on aluminum oxide using electrospray ionization Fourier transform mass spectrometryCrossref | GoogleScholarGoogle Scholar |

Guigue J, Mathieu O, Lévêque J, Mounier S, Laffont R, Maron PA, Navarro N, Chateau C, Amiotte-Suchet P, Lucas Y (2014). A comparison of extraction procedures for water-extractable organic matter in soils. European Journal of Soil Science 65, 520–530.
A comparison of extraction procedures for water-extractable organic matter in soilsCrossref | GoogleScholarGoogle Scholar |

Hayes M, Malcolm RL (2001). Considerations of compositions and aspects of the structures of humic acids. In ‘Humic substances and chemical contaminants’. (Eds CE Clapp, MHB Hayes, N Senesi, PR Bloom, PM Jardine) pp. 3–40. (Soil Science Society of America: Madison, WI).

He W, Chen M, Park JE, Hur J (2016). Molecular diversity of riverine alkaline-extractable sediment organic matter and its linkages with spectral indicators and molecular size distribution. Water Research 100, 222–231.
Molecular diversity of riverine alkaline-extractable sediment organic matter and its linkages with spectral indicators and molecular size distributionCrossref | GoogleScholarGoogle Scholar | 27192357PubMed |

International Humic Substances Society (2018). Elemental compositions and stable isotopic ratios of IHSS samples. Available at http://humic-substances.org/elemental-compositions-and-stable-isotopic-ratios-of-ihss-samples/ [verified 4 January 2019]

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. Analytical Chemistry 75, 5336–5344.
Graphical method for analysis of ultrahigh-resolution broadband mass spectra of natural organic matter, the van Krevelen diagramCrossref | GoogleScholarGoogle Scholar | 14710810PubMed |

Koch BP, Dittmar T (2006). From mass to structure: an aromaticity index for high-resolution mass data of natural organic matter. Rapid Communications in Mass Spectrometry 20, 926–932.
From mass to structure: an aromaticity index for high-resolution mass data of natural organic matterCrossref | GoogleScholarGoogle Scholar |

Kujawinski EB, Vecchio RD, Blough NV, Klein GC, Marshall AG (2004). Probing molecular-level transformations of dissolved organic matter: insights on photochemical degradation and protozoan modification of DOM from electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Marine Chemistry 92, 23–37.
Probing molecular-level transformations of dissolved organic matter: insights on photochemical degradation and protozoan modification of DOM from electrospray ionization Fourier transform ion cyclotron resonance mass spectrometryCrossref | GoogleScholarGoogle Scholar |

Leenheer JA, Croué JP (2003). Characterizing aquatic dissolved organic matter. Environmental Science & Technology 37, 18A–26A.
Characterizing aquatic dissolved organic matterCrossref | GoogleScholarGoogle Scholar |

Leenheer JA, Rostad CE, Gates PM, Furlong ET, Ferrer I (2001). Molecular resolution and fragmentation of fulvic acid by electrospray ionization/multistage tandem mass spectrometry. Analytical Chemistry 73, 1461–1471.
Molecular resolution and fragmentation of fulvic acid by electrospray ionization/multistage tandem mass spectrometryCrossref | GoogleScholarGoogle Scholar | 11321295PubMed |

Lehmann J, Kleber M (2015). The contentious nature of soil organic matter. Nature 528, 60–68.

Leinweber P, Schulten HR, Körschen M (1995). Hot water extracted organic matter: chemical composition and temporal variations in a long-term field experiment. Biology and Fertility of Soils 20, 17–23.
Hot water extracted organic matter: chemical composition and temporal variations in a long-term field experimentCrossref | GoogleScholarGoogle Scholar |

Li Y, Harir M, Lucio M, Kanawati B, Smirnov K, Flerus R, Koch BP, Schmitt-Kopplin P, Hertkorn N (2016). Proposed guidelines for solid phase extraction of Suwannee River dissolved organic matter. Analytical Chemistry 88, 6680–6688.
Proposed guidelines for solid phase extraction of Suwannee River dissolved organic matterCrossref | GoogleScholarGoogle Scholar | 27176119PubMed |

Lusk MG, Toor GS (2016). Dissolved organic nitrogen in urban streams: biodegradability and molecular composition studies. Water Research 96, 225–235.
Dissolved organic nitrogen in urban streams: biodegradability and molecular composition studiesCrossref | GoogleScholarGoogle Scholar | 27058880PubMed |

Luster J, Lloyd T, Sposito G (1996). Multi-wavelength molecular fluorescence spectrometry for quantitative characterization of copper(II) and aluminum(III) complexation by dissolved organic matter. Environmental Science & Technology 30, 1565–1574.
Multi-wavelength molecular fluorescence spectrometry for quantitative characterization of copper(II) and aluminum(III) complexation by dissolved organic matterCrossref | GoogleScholarGoogle Scholar |

Lv J, Zhang S, Wang S, Luo L, Cao D, Christie P (2016a). Molecular-scale investigation with ESI-FT-ICR-MS on fractionation of dissolved organic matter induced by adsorption on iron oxyhydroxides. Environmental Science & Technology 50, 2328–2336.
Molecular-scale investigation with ESI-FT-ICR-MS on fractionation of dissolved organic matter induced by adsorption on iron oxyhydroxidesCrossref | GoogleScholarGoogle Scholar |

Lv J, Zhang S, Luo L, Cao D (2016b). Solid-phase extraction-stepwise elution (SPE-SE) procedure for isolation of dissolved organic matter prior to ESI-FT-ICR-MS analysis. Analytica Chimica Acta 948, 55–61.
Solid-phase extraction-stepwise elution (SPE-SE) procedure for isolation of dissolved organic matter prior to ESI-FT-ICR-MS analysisCrossref | GoogleScholarGoogle Scholar | 27871610PubMed |

Marschner B, Kalbitz K (2003). Controls of bioavailability and biodegradability of dissolved organic matter in soils. Geoderma 113, 211–235.
Controls of bioavailability and biodegradability of dissolved organic matter in soilsCrossref | GoogleScholarGoogle Scholar |

McDonald S, Pringle JM, Bishop AG, Prenzler PD, Robarbs K (2007). Isolation and seasonal effects on characteristics of fulvic acid isolated from an Australian floodplain river and billabong. Journal of Chromatography A 1153, 203–213.
Isolation and seasonal effects on characteristics of fulvic acid isolated from an Australian floodplain river and billabongCrossref | GoogleScholarGoogle Scholar | 17010354PubMed |

McKee GA, Hatcher PG (2015). A new approach for molecular characterization of sediments with Fourier transform ion cyclotron resonance mass spectrometry: extraction optimisation. Organic Geochemistry 85, 22–31.
A new approach for molecular characterization of sediments with Fourier transform ion cyclotron resonance mass spectrometry: extraction optimisationCrossref | GoogleScholarGoogle Scholar |

Mopper K, Stubbins A, Ritchie JD, Bialk HM, Hatcher PG (2007). Advanced instrumental approaches for characterization of marine dissolved organic matter: extraction techniques, mass spectrometry, and nuclear magnetic resonance spectroscopy. Chemical Reviews 107, 419–442.
Advanced instrumental approaches for characterization of marine dissolved organic matter: extraction techniques, mass spectrometry, and nuclear magnetic resonance spectroscopyCrossref | GoogleScholarGoogle Scholar | 17300139PubMed |

Nkhili E, Guyot G, Vassal N, Richard C (2012). Extractability of water-soluble soil organic matter as monitored by spectroscopic and chromatographic analyses. Environmental Science and Pollution Research International 19, 2400–2407.
Extractability of water-soluble soil organic matter as monitored by spectroscopic and chromatographic analysesCrossref | GoogleScholarGoogle Scholar | 22249424PubMed |

Ohno T, Parr TB, Gruselle MC, Fernandez IJ, Sleighter RL, Hatcher PG (2014). Molecular composition and biodegradability of soil organic matter: a case study comparing two new England forest types. Environmental Science & Technology 48, 7229–7236.
Molecular composition and biodegradability of soil organic matter: a case study comparing two new England forest typesCrossref | GoogleScholarGoogle Scholar |

Ohno T, Sleighter RL, Hatcher PG (2016). Comparative study of organic matter chemical characterization using negative and positive mode electrospray ionization ultrahigh-resolution mass spectrometry. Analytical and Bioanalytical Chemistry 408, 2497–2504.
Comparative study of organic matter chemical characterization using negative and positive mode electrospray ionization ultrahigh-resolution mass spectrometryCrossref | GoogleScholarGoogle Scholar | 26869345PubMed |

Perminova IV, Dubinenkov IV, Kononikhin AS, Konstantinov AI, Zherebker AY, Andzhushev MA, Lebedev VA, Bulygina E, Holmes RM, Kostyukevich YI, Popov IA, Nikolaev EN (2014). Molecular mapping of sorbent selectivities with respect to isolation of Arctic dissolved organic matter as measured by Fourier transform mass spectrometry. Environmental Science & Technology 48, 7461–7468.
Molecular mapping of sorbent selectivities with respect to isolation of Arctic dissolved organic matter as measured by Fourier transform mass spectrometryCrossref | GoogleScholarGoogle Scholar |

Qualls RG, Haines BL (1992). Biodegradability of dissolved organic matter in forest throughfall, soil solution, and stream water. Soil Science Society of America Journal 56, 578–586.
Biodegradability of dissolved organic matter in forest throughfall, soil solution, and stream waterCrossref | GoogleScholarGoogle Scholar |

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. Environmental Science: Processes & Impacts 18, 918–927.
Selectivity of solid phase extraction of freshwater dissolved organic matter and its effect on ultrahigh resolution mass spectraCrossref | GoogleScholarGoogle Scholar |

Reemtsma T, These A, Linscheid M, Leenheer J, Spitzy A (2008). Molecular and structural characterization of dissolved organic matter from the deep ocean by FTICR-MS, including hydrophilic nitrogenous organic molecules. Environmental Science & Technology 42, 1430–1437.
Molecular and structural characterization of dissolved organic matter from the deep ocean by FTICR-MS, including hydrophilic nitrogenous organic moleculesCrossref | GoogleScholarGoogle Scholar |

Riedel T, Biester H, Dittmar T (2012). Molecular fractionation of dissolved organic matter with metal salts. Environmental Science & Technology 46, 4419–4426.
Molecular fractionation of dissolved organic matter with metal saltsCrossref | GoogleScholarGoogle Scholar |

Rossel PE, Bienhold C, Boetius A, Dittmar T (2016). Dissolved organic matter in pore water of Arctic Ocean sediments: environmental influence on molecular composition. Organic Geochemistry 97, 41–52.
Dissolved organic matter in pore water of Arctic Ocean sediments: environmental influence on molecular compositionCrossref | GoogleScholarGoogle Scholar |

Schmidt F, Koch BP, Witt M, Hinrichs KU (2014). Extending the analytical window for water-soluble organic matter in sediments by aqueous Soxhlet extraction. Geochimica et Cosmochimica Acta 141, 83–96.
Extending the analytical window for water-soluble organic matter in sediments by aqueous Soxhlet extractionCrossref | GoogleScholarGoogle Scholar |

Seifert AG, Roth VN, Dittmar T, Gleixner G, Breuer L, Houska T, Marxsen J (2016). Comparing molecular composition of dissolved organic matter in soil and stream water: Influence of land use and chemical characteristics. The Science of the Total Environment 571, 142–152.
Comparing molecular composition of dissolved organic matter in soil and stream water: Influence of land use and chemical characteristicsCrossref | GoogleScholarGoogle Scholar | 27470673PubMed |

Senesi N, Miano T, Provenzano MR, Brunetti G (1991). Characterization, differentiation, and classification of humic substances by fluorescence spectroscopy. Soil Science 152, 259–271.
Characterization, differentiation, and classification of humic substances by fluorescence spectroscopyCrossref | GoogleScholarGoogle Scholar |

Shin HS, Monsallier JM, Choppin GR (1999). Spectroscopic and chemical characterizations of molecular size fractionated humic acid. Talanta 50, 641–647.
Spectroscopic and chemical characterizations of molecular size fractionated humic acidCrossref | GoogleScholarGoogle Scholar | 18967755PubMed |

Spencer RGM, Guo W, Raymond PA, Dittmar T, Hood E, Fellman J, Stubbins A (2014). Source and biolability of ancient dissolved organic matter in glacier and lake ecosystems on the Tibetan Plateau. Geochimica et Cosmochimica Acta 142, 64–74.
Source and biolability of ancient dissolved organic matter in glacier and lake ecosystems on the Tibetan PlateauCrossref | GoogleScholarGoogle Scholar |

Stevenson FJ (1994). ‘Humus chemistry: genesis, composition, reactions, 2nd edn.’ (John Wiley & Sons: New York, NY).

Sun SQ, Cai HY, Chang SX, Bhatti JS (2015). Sample storage-induced changes in the quantity and quality of soil labile organic carbon. Scientific Reports 5, 17496
Sample storage-induced changes in the quantity and quality of soil labile organic carbonCrossref | GoogleScholarGoogle Scholar | 26617054PubMed |

Swift RS (1996). Organic matter characterization. In ‘Methods of soil analysis. Part 3 – chemical methods, vol. 5’. (Ed. DL Sparks) pp. 1011–1069. (Soil Science Society of America: Madison, WI)

Tfaily MM, Chu RK, Tolić N, Roscioli KM, Anderton CR, Paša-Tolić L, Robinson EW, Hess NJ (2015). Advanced solvent based methods for molecular characterization of soil organic matter by high resolution mass spectrometry. Analytical Chemistry 87, 5206–5215.
Advanced solvent based methods for molecular characterization of soil organic matter by high resolution mass spectrometryCrossref | GoogleScholarGoogle Scholar | 25884232PubMed |

Tfaily MM, Chu RK, Toyoda J, Tolić N, Robinson EW, Paša-Tolić L, Hess NJ (2017). Sequential extraction protocol for organic matter from soils and sediments using high resolution mass spectrometry. Analytica Chimica Acta 972, 54–61.
Sequential extraction protocol for organic matter from soils and sediments using high resolution mass spectrometryCrossref | GoogleScholarGoogle Scholar | 28495096PubMed |

Thurman EM, Malcolm RL (1981). Preparative isolation of aquatic humic substances. Environmental Science & Technology 15, 463–466.
Preparative isolation of aquatic humic substancesCrossref | GoogleScholarGoogle Scholar |

Vergnoux A, Rocco RD, Domeizel M, Guiliano M, Doumenq P, Théraulaz F (2011). Effects of forest fires on water extractable organic matter and humic substances from Mediterranean soils: UV–vis and fluorescence spectroscopy approaches. Geoderma 160, 434–443.
Effects of forest fires on water extractable organic matter and humic substances from Mediterranean soils: UV–vis and fluorescence spectroscopy approachesCrossref | GoogleScholarGoogle Scholar |

Watanabe A, Itoh K, Arai S, Kuwatsuka S (1994). Comparison of the composition of humic and fulvic acids prepared by the IHSS method and NAGOYA method. Soil Science and Plant Nutrition 40, 601–608.
Comparison of the composition of humic and fulvic acids prepared by the IHSS method and NAGOYA methodCrossref | GoogleScholarGoogle Scholar |

Zark M, Dittmar T (2018). Universal molecular structures in natural dissolved organic matter. Nature Communications 9, 3178
Universal molecular structures in natural dissolved organic matterCrossref | GoogleScholarGoogle Scholar | 30093658PubMed |

Zsolnay Á (2003). Dissolved organic matter: artefacts, definitions, and functions. Geoderma 113, 187–209.
Dissolved organic matter: artefacts, definitions, and functionsCrossref | GoogleScholarGoogle Scholar |