Skip to main content

Molecular Properties and Functions of Humic Substances and Humic-Like Substances (HULIS) from Biomass and Their Transformation Products

  • Chapter
  • First Online:
Analytical Techniques and Methods for Biomass

Abstract

Agricultural and biorefinery byproducts should be regarded as important sources of chemicals and materials, instead of being disposed or burnt. Humic substances (HS) and humic-like substances (HULIS) isolated by such materials may be employed as plant biostimulants, due to their surprising bioactivity on plant development, either after their direct extraction from such byproducts or after composting them. In order to shed light on both the biological activity of HS and HULIS on plant physiology and on soil carbon dynamics, a number of analytical chemical techniques have been employed, thus, providing a detailed insight on their molecular nature. This chapter is intended to provide a comprehensive overview of the more advanced chemical techniques applied in the chemical characterization of HS and HULIS structure, such as GC-MS, NMR, HPSEC, EPR and thermal analyses. Each of these tools provides different but incomplete information on HS and HULIS molecular composition, due to both the intrinsic limitation of each technique and the large molecular heterogeneity and structural complexity of HS and HULIS. Thus, in order to elucidate the chemical nature of such substrates, the various analytical tools should be always exploited concomitantly and critically discussed, thus, offering a comprehensive understanding of HS and HULIS at a molecular level. Achieving this purpose will also allow to efficaciously exploit HS and HULIS as plant biostimulants in sustainable agriculture and/or biomass-based material chemistry.

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

Access this chapter

Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 84.99
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 109.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 109.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

References

  • Abbasi PA, Al-Dahmani J, Sahin F et al (2002) Effect of compost amendments on disease severity and yield of tomato in conventional and organic production systems. Plant Dis 86:156–161

    Article  Google Scholar 

  • Abbt-Braun G, Frimmel FH, Schulten HR (1989) Structural investigations of aquatic humic substances by pyrolysis-field ionisation mass spectrometry and pyrolysis-gas chromatography/mass spectrometry. Water Res 23:1579–1591

    Article  Google Scholar 

  • Abu-Rukah Y, Al-Kofahi O (2001) The assessment of the effect of landfill leachate on ground-water quality — a case study El-Akader landfill site-north Jordan. J Arid Environ 49:615–630

    Article  Google Scholar 

  • Alberts JJ, Schindler JE, Miller RW (1974) Elemental mercury evolution mediated by humic acid. Science 184:895–896

    Article  Google Scholar 

  • Amir S, Hafidi M, Lemee L et al (2006) Structural characterization of humic acids, extracted from sewage sludge during composting, by thermochemolysis–gas chromatography–mass spectrometry. Process Biochem 41:410–422

    Article  Google Scholar 

  • Amir S, Jouraiphy A, Meddich A et al (2010) Structural study of humic acids during composting of activated sludge-green waste: Elemental analysis, FTIR and 13C NMR. J Hazard Mater 177:524–529

    Article  Google Scholar 

  • Argyropoulos DS (2010) Heteronuclear NMR Spectroscopy of Lignins. In: Heitner C, Dimmel DR, Schmidt JA (eds) Lignin and lignans: advances in chemistry. Taylor and Francis Group LLC, Boca Raton, FL, pp 245–265

    Chapter  Google Scholar 

  • Bakhmutov VI (2004) Practical NMR relaxation for chemists. Wiley & Sons Chichester, West Sussex, England

    Book  Google Scholar 

  • Bartoszek M, Polak J, Sułkowski WW (2008) NMR study of the humification process during sewage sludge treatment. Chemosphere 73:1465–1470

    Article  Google Scholar 

  • Bell NGA, Michalchuk AAL, Blackburn JWT et al (2015) Isotope-filtered 4D NMR spectroscopy for structure determination of humic substances. Angew Chem Int Ed Engl 54:8382–8385

    Article  Google Scholar 

  • Blanco MJ, Almendros G (1997) Chemical transformation, phytotoxicity and nutrient availability in progressive composting stages of wheat straw. Plant Soil 196:15–25

    Article  Google Scholar 

  • Blodig W, Smith AT, Winterhalter K et al (1999) Evidence from spin-trapping for a transient radical on tryptophan residue 171 of lignin peroxidase. Arch Biochem Biophys 370:86–92

    Article  Google Scholar 

  • Bollag JM (1992) Enzymes catalyzing oxidative coupling reactions of pollutants. In: Sigel H, Sigel A (eds) Metal ions in biological systems. Marcel-Dekker, New York, pp 205–217

    Google Scholar 

  • Bronick CJ, Lal R (2005) Soil structure and management: a review. Geoderma 124:3–22

    Article  Google Scholar 

  • Busato JG, Canellas LP, Rumjanek VM et al (2005) Rev Bras Ciênc Solo 29:945–953

    Article  Google Scholar 

  • Campanella L, Tomasetti M, Piccolo A (1990) TG and IR analysis of different extracts of soil humic acids. Termochim Acta 170:67–80

    Article  Google Scholar 

  • Canellas LP, Olivares FL (2014) Physiological responses to humic substances as plant growth promoter. Chem Biol Technol Agric 1:3

    Article  Google Scholar 

  • Canellas LP, Piccolo A, Dobbss LB et al (2010) Chemical composition and bioactivity properties of size-fractions separated from a vermicompost humic acid. Chemosphere 78:457–466

    Article  Google Scholar 

  • Challinor JM (1989) A pyrolysis-derivatisation-gas chromatography technique for the structural elucidation of some synthetic polymers. J Anal Appl Pyrol 16:323–333

    Article  Google Scholar 

  • Challinor JM (2001) Review: the development and applications of thermally assisted hydrolysis and methylation reactions. J Anal Appl Pyrol 61:3–34

    Article  Google Scholar 

  • Christoforidis KC, Un S, Deligiannakis Y (2007) High-field 285 GHz electron paramagnetic resonance study of indigenous radicals of humic acids. J Phys Chem A 111:11860–11866

    Article  Google Scholar 

  • Cole EB (1997) Electrospray ionization mass spectrometry. In: Wiley & Sons (ed) Fundamentals, instrumentation and applications. Wiley & Sons, New York, NY

    Google Scholar 

  • Conte P, Piccolo A (1999) Conformational arrangement of dissolved humic substances. Influence of solution composition on the association of humic molecules. Environ Sci Technol 33:1682–1690

    Article  Google Scholar 

  • Conte P, Spaccini R, Smejkalova D, Nebbioso A, Piccolo A (2007) Spectroscopic and conformational properties of size-fractions separated from a lignite humic acid. Chemosphere 69:1032–1039

    Article  Google Scholar 

  • Cozzolino A, Piccolo A (2002) Polymerization of dissolved humic substances catalyzed by peroxidase. Effects of pH and humic composition. Org Geochem 33:281–294

    Article  Google Scholar 

  • Cozzolino A, Conte P, Piccolo A (2001) Conformational changes of soil humic substances induced by some hydroxy-, cheto-, and sulphonic acids. Soil Biol Biochem 33:563–571

    Article  Google Scholar 

  • DeForest PR, Tebbet IR, Larsen AK (1994) Pyrolisys Gas Chromatography in Forensic Science. In: Tebbett I (ed) Gas chromatography in forensic science. Prentice Hall, Oltd Tappan, NJ, pp 165–1850

    Google Scholar 

  • Deiana S, Gessa C, Manunza B et al (1990) Analytical and spectroscopic characterization of humic acids extracted from sewage sludge, manure, and worm compost. Soil Sci 150:419–424

    Article  Google Scholar 

  • del Río JC, Rencoret J, Prinsen P et al (2012) Structural characterization of wheat straw lignin as revealed by analytical pyrolysis, 2D-NMR, and reductive cleavage methods. J Agric Food Chem 60:5922–59350

    Article  Google Scholar 

  • Dobbss LB, Canellas LP, Olivares FL et al (2010) Bioactivity of chemically transformed humic matter from vermicompost on plant root growth. J Agric Food Chem 58:3681–3688

    Article  Google Scholar 

  • Doty FD, Entzminger G, Yang AY (1998) Magnetism in high-resolution NMR probe design: HR MAS. Concept Magnetic Res 10:239–260

    Article  Google Scholar 

  • Drosos M (2009) Isolation and physical-chemical characterization of humic and fulvic acids from Greek soils/lignite/compost. Ph.D. thesis, University of Ioannina, Greece, p 116

    Google Scholar 

  • Drosos M, Jerzykiewicz M, Louloudi M (2011) Progress towards synthetic modelling of humic acid: peering into the physicochemical polymerization mechanism. Colloids Surf A Physicochem Eng Asp 389:254–265

    Article  Google Scholar 

  • Duer MJ (2002) Solid-state NMR Spectroscopy: Principles and Applications, first ed., Blackwell Science, Oxford

    Google Scholar 

  • Ertani A, Francioso O, Tugnoli V et al (2011) Effect of commercial lignosulfonate-humate on Zea mays metabolism. J Agric Food Chem 59:11940–11948

    Article  Google Scholar 

  • Fernández-Gómez MJ, Nogales R, Plante A et al (2015) Application of a set of complementary techniques to understand how varying the proportion of two wastes affects humic acids produced by vermicomposting. Waste Manage 35:81–88

    Article  Google Scholar 

  • Ferreira AJ, Nascimento RO, Martin-Neto L (2001) Hydrophobic interactions between spin-label 5-SASL and humic acid as revealed by ESR spectroscopy. Environ Sci Technol 35:761–765

    Article  Google Scholar 

  • Francioso O, Ferrari E, Saladini M, Montecchio D, Gioacchini P, Ciavatta C (2007) TG–DTA, DRIFT and NMR characterisation of humic-like fractions from olive wastes and amended soil. J Hazard Mat 149:408–417

    Google Scholar 

  • Fuentes M, Baigorri R, González-Vila FJ et al (2010) Pyrolysis–gas chromatography/mass spectrometry identification of distinctive structures providing humic character to organic materials. J Environ Qual 39:1486–1497

    Article  Google Scholar 

  • Fukushima M, Yamamoto M, Komani T et al (2009) Studies of structural alterations of humic acids from conifer bark residue during composting by pyrolysis-gas chromatography/mass spectrometry using tetramethylammonium hydroxide (TMAH-py-GC/MS). J Anal Appl Pyrol 86:200–206

    Article  Google Scholar 

  • Garbin JR, Milori DMBP, Simões ML et al (2007) Influence of humic substances on the photolysis of aqueous pesticide residues. Chemosphere 66:1692–1698

    Article  Google Scholar 

  • Giannakopoulos E, Christoforidis KC, Tsipis A et al (2005) Influence of Pb(II) on the radical properties of humic substances and model compounds. J Phys Chem A 109:2223–2232

    Article  Google Scholar 

  • Giannakopoulos E, Stathi P, Dimos K et al (2006) Adsorption and radical stabilization of humic-acid analogues and Pb2+ on restricted phylomorphous clay. Langmuir 22:6863–6873

    Article  Google Scholar 

  • Giannakopoulos E, Drosos M, Deligiannakis Y (2009) A humic-acid-like polycondensate produced with no use of catalyst. J Colloid Interface Sci 336:59–66

    Article  Google Scholar 

  • Gil AM, Lopes MH, Pascoal Neto C et al (1999) Very high-resolution 1H MAS NMR of a natural polymeric material. Solid State Nucl Mag 15:59–67

    Article  Google Scholar 

  • Goñi MA, Hedges JI (1992) Lignin dimers: structures, distribution, and potential geochemical applications. Geochim Cosmochim Acta 56:4025–4043

    Article  Google Scholar 

  • Grasset L, Vlčková Z, Kučerík J et al (2010) Characterization of lignin monomers in low rank coal humic acids using the derivatization/reductive cleavage method. Org Geochem 41:905–909

    Article  Google Scholar 

  • Guerra A, Filipponen I, Lucia L et al (2006) Comparative evaluation of three lignin isolation protocols for various wood species. J Agric Food Chem 54:9705

    Google Scholar 

  • Haider K, Martin JP (1967) Synthesis and transformation of phenolic compounds by Epicoccum nigrum in relation to humic acid formation. Soil Sci Soc Am Proc 31:766–772

    Article  Google Scholar 

  • Hatcher PG, Clifford DJ (1994) Flash pyrolysis and in situ methylation of humic acids from soil. Org Geochem 21:1081–1092

    Article  Google Scholar 

  • Hayes MHB, Stacey M, Swift RS (1972) Degradation of humic acid in a sodium sulphide solution. Fuel 51:211–213

    Article  Google Scholar 

  • He Z, Olk DC, Cade-Menum BJ (2011) Forms and lability of phosphorus in humic acid fractions of hord silt loam soil. Soil Sci Soc Am J 75:1712–1722

    Article  Google Scholar 

  • Hedenstrom M, Wiklund-Lindstrom S, Oman T et al (2009) Identification of lignin and polysaccharide modifications in populus wood by chemometric analysis of 2D NMR spectra from dissolved cell walls. Mol Plant 2:933–942

    Article  Google Scholar 

  • Hmid A, Mondelli D, Fiore S, Dumontet S (2014) Production and characterization of biochar from three-phase olive mill waste through slow pyrolysis. Biomass Bioenerg 71:330–339

    Article  Google Scholar 

  • Holtman K, Chang H-M, Jameel H et al (2003) Elucidation of lignin structure through degradative methods: comparison of modified DFRC and thioacidolysis. J Agric Food Chem 51:3535–3540

    Article  Google Scholar 

  • Hon DNS (1992) Electron Spin Resonance (ESR) Spectroscopy. In: Lin SY, Dence CW (eds) Methods in lignin chemistry. Springer, Berlin, pp 274–287

    Chapter  Google Scholar 

  • Ikeda T, Holtman K, Kadla JF et al (2002) Studies on the effect of ball milling on lignin structure using a modified DFRC method. J Agric Food Chem 50:129–135

    Article  Google Scholar 

  • Ishida Y, Katagiri M, Ohtani H (2009) Reaction efficiency of organic alkalis with various classes of lipids during thermally assisted hydrolysis and methylation. J Chromatogr A 1216:3296–3299

    Article  Google Scholar 

  • Jacobsen NE (2007) NMR spectroscopy explained – simplified theory, applications and examples for organic chemistry and structural biology. Wiley & Sons, Hoboken, NJ

    Google Scholar 

  • Janoš P (2003) Separation methods in the chemistry of humic substances. J Chromatogr A 983:1–18

    Article  Google Scholar 

  • Jezierski A, Czechowski F, Jerzykiewicz M et al (2000a) Electron paramagnetic resonance (EPR) studies on stable and transient radicals in humic acids from compost, soil, peat and brown coal. Spectrochim Acta Mol Biomol Spectrosc 56:379–385

    Article  Google Scholar 

  • Jezierski A, Czechowski F, Jerzykiewicz M et al (2000b) EPR investigations of structure of humic acids from compost, soil, peat and soft brown coal upon oxidation and metal uptake. Appl Magn Res 18:127–136

    Article  Google Scholar 

  • Jindo K, Martim SA, Navarro EC et al (2012) Root growth promotion by humic acids from composted and non-composted urban organic wastes. Plant Soil 353:209–220

    Article  Google Scholar 

  • Jouraiphy A, Amir S, Winterton P et al (2008) Structural study of the fulvic fraction during composting of activated sludge-plant matter: elemental analysis, FTIR and 13C NMR. Bioresource Technol 99:1066–1077

    Article  Google Scholar 

  • Kamiya M, Kameyama K (1998) Photochemical effects of humic substances on the degradation of organophosphorus pesticides. Chemosphere 36:2337–2344

    Article  Google Scholar 

  • Keeler C, Kelly EF, Maciel GE (2006) Chemical–structural information from solid-state 13C NMR studies of a suite of humic materials from a lower montane forest soil, Colorado, USA. Geoderma 130:124–140

    Article  Google Scholar 

  • Kelleher BP, Simpson AJ (2006) Humic substances in soils: are they really chemically distinct? Environ Sci Technol 40:4605–4611

    Article  Google Scholar 

  • Kossa WC, MacGee J, Ramachandran JS, Webber AJ (1979) Pyrolytic methylation/gas chromatography. A short review. J Chromatogr Sci 17:177–187

    Article  Google Scholar 

  • Larter SR, Horsfield B (1993) Determination of structural components of kerogens by the use of analytical pyrolysis methods. In: Engel MH, Macko SA (eds) Organic geochemistry. Principles and applications. Plenum, New York, NY, pp 271–288

    Chapter  Google Scholar 

  • Lattao C, Birdwell J, Wang JJ, Cook RL (2008) Studying organic matter molecular assemblage within a whole organic soil by nuclear magnetic resonance. J Environ Qual 37:1501–1509

    Article  Google Scholar 

  • Le Brech Y, Delmotte L, Raya J et al (2015) High resolution solid state 2D NMR analysis of biomass and biochar. Anal Chem 87:843–847

    Article  Google Scholar 

  • Lehmann J, Kuzyakov Y, Pan G, Ok Y-S (2015) Biochars and the plant-soil interface. Plant Soil 395:1–5

    Article  Google Scholar 

  • Lehtonen T, Peuravuori J, Pihlaja K (2003) Comparison of quaternary methyl-, ethyl- and butylammonium hydroxides as alkylating reagents in pyrolysis-GC/MS studies of aquatic fulvic acid. J Anal Appl Pyrol 68–69:315–329

    Article  Google Scholar 

  • Leinweber P, Schulten HR, Horte C (1992) Differential thermal analysis, thermogravimetry and pyrolysis-field ionisation mass spectrometry of soil organic matter in particle-size fractions and bulk soil sample. Thermochim Acta 194:175–187

    Article  Google Scholar 

  • Levitt M (2008) Spin dynamics: basics of nuclear magnetic resonance, 2nd edn. Wiley & Sons, Chichester

    Google Scholar 

  • Li M, Mazzei P, Cozzolino V et al (2015) Optimized procedure for the determination of P species in soil by liquid-state 31P-NMR spectroscopy. Chem Biol Technol Agric 2:7

    Article  Google Scholar 

  • Liitia T, Maunu SL, Sipil J, Hortling B (2002) Application of solid-state 13CNMR spectroscopy and dipolar dephasing technique to determine the extent of condensation in technical lignins. Solid State Nucl Mag 21:171–186

    Article  Google Scholar 

  • Lin CSK, Pfaltzfraff LA, Herrero-Davila L et al (2013) Food waste as a valuable resource for the production of chemicals, materials and fuels. Current situation and global perspective. Energ Environ Sci 6:426–464

    Article  Google Scholar 

  • Liptaj T, Barancikova G, Pronayova N (2005) Application of 31P nuclear magnetic resonance for study of phosphorus structural types in humic acids. Agriculture (Bratislava, Slovakia) 51:423–428

    Google Scholar 

  • Lovley DR, Coates JD, Blunt-Harris EL et al (1996) Humic substances as electron acceptors for microbial respiration. Nature 382:445–448

    Article  Google Scholar 

  • Lu F, Ralph J (1996) Reactions of lignin model β-aryl ethers with acetyl bromide. Holzforschung 50:360–364

    Article  Google Scholar 

  • Lu F, Ralph J (1997a) Derivatization followed by reductive cleavage (DFRC method), a new method for lignin analysis: protocol for analysis of DFRC monomers. J Agric Food Chem 45:2590–2592

    Article  Google Scholar 

  • Lu F, Ralph J (1997b) The DFRC method for lignin analysis. Part 1. A new method for β-aryl ether cleavage: lignin model studies. J Agric Food Chem 45:4655–4660

    Article  Google Scholar 

  • Lu F, Ralph J (2003) Non-degradative dissolution and acetylation of ball-milled plant cell walls: high-resolution solution-state NMR. Plant J 35:535–544

    Article  Google Scholar 

  • Mao JD, Schmidt-Rohr K (2004) Separation of aromatic-carbon 13C NMR signals from di-oxygenated alkyl bands by a chemical-shift-anisotropy filter. Solid State Nucl Mag 26:36–45

    Article  Google Scholar 

  • Mao JD, Xing B, Schmidt-Rohr K (2001) New structural information on a humic acid from two-dimensional 1H-13C correlation solid-state nuclear magnetic resonance. Environ Sci Technol 35:1928–1934

    Article  Google Scholar 

  • Mao JD, 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  Google Scholar 

  • Marchesini A, Allievi L, Comotti E, Ferrari A (1988) Long-term effects of quality-compost treatment on soil. Plant Soil 106:253–261

    Article  Google Scholar 

  • Martin JP, Haider K, Wolf D (1972) Synthesis of phenols and phenolic polymers by Hendersonula toruloidea in relation to humic acid formation. Soil Sci Am Proc 36:311–315

    Article  Google Scholar 

  • Martin JP, Haider K, Saiz-Jimenez C (1974) Sodium amalgam reductive degradation of fungal and model phenolic polymers soil humic acids and simple phenolic compounds. Soil Sci Am Proc 38:760–765

    Article  Google Scholar 

  • Martin AR, Martins MA, da Silva ORRF, Mattoso LHC (2010) Studies on the thermal properties of sisal fiber and its constituents. Thermochim Acta 506:14–19

    Article  Google Scholar 

  • Maunu SL (2002) NMR studies of wood and wood products. Prog Nucl Magn Reson Spectrosc 40:151–174

    Article  Google Scholar 

  • Mazzei P, Piccolo A (2012) Quantitative evaluation of noncovalent interactions between glyphosate and dissolved humic substances by NMR spectroscopy. Environ Sci Technol 46:5939–5946

    Article  Google Scholar 

  • Mazzei P, Piccolo A (2015) Interactions between natural organic matter and organic pollutants as revealed by NMR spectroscopy. Magn Reson Chem 53:667–678

    Article  Google Scholar 

  • McBeath AV, Smernik RJ, Krull ES, Lehmann J (2014) The influence of feedstock and production temperature on biochar carbon chemistry: a solid-state 13C NMR study. Biomass Bioenerg 60:121–129

    Article  Google Scholar 

  • McIntyre C, Jardine DR, McRae C (2001) Electrospray mass spectrometry of aquatic fulvic acids. Rapid Commun Mass Spectrom 15:1974–1975

    Article  Google Scholar 

  • Mitchell PJ, Simpson AJ, Soong R, Simpson MJ (2015) Shifts in microbial community and water-extractable organic matter composition with biochar amendment in a temperate forest soil. Soil Biol Biochem 81:244–254

    Google Scholar 

  • Moldoveanu SC (ed) (1998) Analytical pyrolysis of natural organic polymers. Elsevier, Amsterdam, NL

    Google Scholar 

  • Morris KF, Cutak BJ, Dixon AM, Larive CK (1999) Analysis of diffusion coefficient distributions in humic and fulvic acids by means of diffusion ordered NMR spectroscopy. Anal Chem 71:5315–5321

    Article  Google Scholar 

  • Nebbioso A, Piccolo A (2009) Molecular rigidity and diffusivity of Al3+ and Ca2+ humates as revealed by NMR spectroscopy. Environ Sci Technol 43:2417–2424

    Article  Google Scholar 

  • Nebbioso A, Piccolo A (2011) Basis of a humeomics science: chemical fractionation and molecular characterization of humic biosuprastructures. Biomacromolecules 12:1187–1199

    Article  Google Scholar 

  • Nebbioso A, Piccolo A (2012) Advances in humeomic: enhanced structural identification of humic molecules after size fractionation of a soil humic acid. Anal Chim Acta 720:77–90

    Article  Google Scholar 

  • Nebbioso A, Piccolo A, Spiteller M (2010) Limitations of electrospray ionization in the analysis of a heterogeneous mixture of naturally occurring hydrophilic and hydrophobic compounds. Rapid Commun Mass Spectrom 24:3163–3170

    Article  Google Scholar 

  • Nebbioso A, Mazzei P, Savy D (2014) Reduced complexity of multidimensional and diffusion NMR spectra of soil humic fractions as simplified by humeomics. Chem Biol Technol Agr 1:24

    Article  Google Scholar 

  • Nebbioso A, Vinci G, Drosos M et al (2015) Unveiling the molecular composition of the unextractable soil organic fraction (humin) by humeomics. Biol Fertil Soils 51:443–451

    Article  Google Scholar 

  • Nuzzo A, Scherman OA, Mazzei P, Piccolo A (2014) pH-controlled release of auxin plant hormones from cucurbit[7]uril macrocycle. Chem Biol Technol Agr 1:2

    Article  Google Scholar 

  • Ohno T, He Z, Sleighter RL, Honeycutt CW, Hatcher PG (2010) Ultrahigh resolution mass spectrometry and indicator species analysis to identify marker components of soil- and plant biomass-derived organic matter fractions. Environ Sci Technol 44:8594–8600

    Article  Google Scholar 

  • Paul A, Stösser R, Zehl A et al (2006) Nature and abundance of organic radicals in natural organic matter: effect of pH and irradiation. Environ Sci Technol 40:5897–5903

    Article  Google Scholar 

  • Peacock AD, Macnaughton SJ, Cantu J et al (2001) Soil microbial biomass and community composition along an anthropogenic disturbance gradient within a long-leaf pine habitat. Ecol Indic 1:113–121

    Article  Google Scholar 

  • Pfeifer T, Uwe K, Hoffmann R, Spiteller M (2001) Characterisation of humic substances using atmospheric pressure chemical ionisation and electrospray ionisation mass spectrometry combined with size-exclusion chromatography. J Chromatogr A 926:151–159

    Article  Google Scholar 

  • Piccolo A (1988) Characteristics of soil humic substances extracted with some organic and inorganic solvents and purified by the HCl-HF treatment. Soil Sci 146:418–426

    Article  Google Scholar 

  • Piccolo A (2002) The supramolecular structure of humic substances. A novel understanding of humus chemistry and implications in soil science. Adv Agron 75:57–134

    Article  Google Scholar 

  • Piccolo A, Spiteller M (2003) Electrospray ionization mass spectrometry of terrestrial humic substances and their size-fractions. Anal Bioanal Chem 377:1047–1059

    Article  Google Scholar 

  • Piccolo A, Campanella L, Petronio BM (1990) 13C-NMR spectra of humic substances extracted with different mechanisms. Soil Sci Soc Am J 54:750–755

    Article  Google Scholar 

  • Piccolo A, Nardi S, Concheri G (1996) Macromolecular changes of soil humic substances induced by interactions with organic acids. Eur J Soil Sci 47:319–328

    Article  Google Scholar 

  • Piccolo A, Conte P, Cozzolino A (1999) Effects of mineral and monocarboxylic acids on the molecular association of dissolved humic substances. Eur J Soil Sci 50:687–694

    Article  Google Scholar 

  • Piccolo A, Cozzolino A, Conte P, Spaccini R (2000) Polymerization of humic substances by an enzyme-catalyzed oxidative coupling. Naturwissenschaften 87:391–394

    Article  Google Scholar 

  • Piccolo A, Conte P, Cozzolino A (2001) Chromatographic and spectrophotometric properties of dissolved humic substances compared with macromolecular polymers. Soil Sci 166:174–185

    Article  Google Scholar 

  • Piccolo A, Conte P, Trivellone E et al (2002) Reduced heterogeneity of a lignite humic acid by preparative HPSEC following interaction with an organic acid. Characterization of size-separates by PYR-GC-MS and 1H-NMR spectroscopy. Environ Sci Technol 36:76–84

    Article  Google Scholar 

  • Piccolo A, Conte P, Spaccini R, Chiarella M (2003) Effects of some dicarboxylic acids on the association of dissolved humic substances. Biol Fertil Soils 37:255–259

    Google Scholar 

  • Piccolo A, Conte P, Tagliatesta P (2005) Increased conformational rigidity of humic substances by oxidative biomimetic catalysis. Biomacromolecules 6:351–358

    Article  Google Scholar 

  • Piccolo A, Spiteller M, Nebbioso A (2010) Effects of sample properties and mass spectroscopic parameters on electrospray ionization mass spectra of size-fractions from a soil humic acid. Anal Bioanal Chem 397:3071–3078

    Article  Google Scholar 

  • Plancque G, Amekraz B, Moulin V et al (2001) Molecular structure of fulvic acids by electrospray with quadrupole time-of-flight mass spectrometry. Rapid Commun Mass Spectrom 15:827–835

    Article  Google Scholar 

  • Plant AF, Fernández JM, Leifeld J (2009) Application of thermal analysis techniques in soil science. Geoderma 153:1–10

    Article  Google Scholar 

  • Pöerschmann J (2000) Gas Chromatography. In: Wilson ID (ed) Encyclopedia of separation science. Elsevier, Amsterdam, pp 3026–3032

    Chapter  Google Scholar 

  • Popa VI, Dumitru M, Volfa I, Anghel N (2008) Lignin and polyphenols as allelochemicals. Ind Crops Prod 27:144–149

    Article  Google Scholar 

  • Preston CM, Nault JR, Trofymow JA (2009) Chemical changes during 6 years of decomposition of 11 litters in some Canadian forest sites. Part 2. 13C abundance, solid-state 13C NMR spectroscopy and the meaning of “lignin”. Ecosystems 12:1078–1102

    Article  Google Scholar 

  • Ralph J, Lu F (1998) The DFRC method for lignin analysis. 6. A simple modification for identifying natural acetates on lignins. J Agric Food Chem 46:4616–4619

    Article  Google Scholar 

  • Reemtsma T, These A (2003) On-line coupling of size exclusion chromatography with electrospray ionization-tandem mass spectrometry for the analysis of aquatic fulvic and humic acids. Anal Chem 75:1500–1507

    Article  Google Scholar 

  • Reemtsma T, These A, Venkatachari P et al (2006) Identification of fulvic acids and sulfated and nitrated analogues in atmospheric aerosol by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Anal Chem 78:8299–8304

    Article  Google Scholar 

  • Rencoret J, Gutierrez A, Nieto L et al (2011) Lignin composition and structure in young versus adult Eucalyptus globulus plants. Plant Physiol 155:667–682

    Article  Google Scholar 

  • Rex RW (1960) Electron paramagnetic resonance studies of stable free radicals in lignins and humic acids. Nature 188:1185–1186

    Article  Google Scholar 

  • Saiz-Jimenez C (1996) The chemical structure of humic substances. Recent advances. In: Picco A (ed) Humic substances in terrestrial ecosystems. Elsevier, Amsterdam

    Google Scholar 

  • Savy D, Piccolo A (2014) Physical–chemical characteristics of lignins separated from biomasses for second-generation ethanol. Biomass Bioenerg 62:58–67

    Article  Google Scholar 

  • Savy D, Mazzei P, Drosos M et al (2015a) Molecular composition of water-soluble lignins separated from different non-food biomasses. Fuel Process Technol 131:175–181

    Article  Google Scholar 

  • Savy D, Mazzei P, Roque R et al (2015b) Structural recognition of lignin isolated from bioenergy crops by subcritical water:ethanol extraction. Fuel Process Technol 138:637–644

    Article  Google Scholar 

  • Savy D, Cozzolino V, Nebbioso A et al (2015c) Water-soluble lignins from different biomasses for energy stimulate the early development of maize (Zea mays, L.). Molecules 20:19958–19970

    Article  Google Scholar 

  • Savy D, Cozzolino V, Nebbioso A et al (2016) Humic-like bioactivity on emergence and early growth of maize (Zea mays L) of water-soluble lignins isolated from biomass for energy. Plant Soil 402:221–233. doi:10.1007/s11104-015-2780-2

    Article  Google Scholar 

  • Shindo H, Huang PM (1982) Role of Mn(IV) oxide in abiotic formation of humic substances in the environment. Nature 298:363–365

    Article  Google Scholar 

  • Simpson AJ (2001) Multidimensional solution state NMR of humic substances: a practical guide and review. Soil Sci 166:795–809

    Article  Google Scholar 

  • Simpson AJ, Kingery WL, Shaw D et al (2001) The application of 1H HR-MAS NMR spectroscopy for the study of structures and associations of organic components at the solid-aqueous interface of a whole soil. Environ Sci Technol 35:3321–3325

    Article  Google Scholar 

  • Simpson AJ, Tseng LH, Simpson MJ et al (2004) The application of LC-NMR and LC-SPE-NMR to compositional studies of natural organic matter. Analyst 129:1216–1222

    Article  Google Scholar 

  • Simpson AJ, Simpson MJ, Smith E, Kelleher BP (2007) Microbially derived inputs to soil organic matter: are current estimates too low? Environ Sci Technol 41:8070–8076

    Article  Google Scholar 

  • Simpson AJ, McNally DJ, Simpson MJ (2011) NMR spectroscopy in environmental research: From molecular interactions to global processes. Prog Nucl Magn Reson Spectrosc 58:97–175

    Article  Google Scholar 

  • Smejkalova D, Piccolo A. (2008) Aggregation and disaggregation of humic supramolecular assemblies by nmr diffusion ordered spectroscopy (DOSY-NMR). Environ Sci Technol 42: 699–706.

    Google Scholar 

  • Šmejkalová D, Spaccini R, Piccolo A (2008) Multivariate analysis of CPMAS 13C-NMR spectra of soils and humic matter as a tool to evaluate organic carbon quality in natural systems. Eur J Soil Sci 59:496–504

    Article  Google Scholar 

  • Spaccini R, Piccolo A (2007) Molecular characterization of compost at increasing stages of maturity. 1. Chemical fractionation and infrared spectroscopy. J Agric Food Chem 55:2293–2302

    Article  Google Scholar 

  • Spaccini R, Piccolo A (2009) Molecular characteristics of humic acids extracted from compost at increasing maturity stages. Soil Biol Biochem 41:1164–1172

    Article  Google Scholar 

  • Spaccini R, Piccolo A (2013) Effects of field managements for soil organic matter stabilization on water-stable aggregates distribution and aggregate stability in three agricultural soils. J Geochem Explor 129:45–51

    Article  Google Scholar 

  • Spaccini R, Mazzei P, Squartini A, Giannattasio M, Piccolo A (2012) Molecular properties of a fermented manure preparation used as field spray in biodynamic agriculture. Environ Sci Pollut Res 19:4214–4225

    Article  Google Scholar 

  • Steelink C, Tollin G (1962) Stable free radicals in soil humic acid. Biochim Biophys Acta 59:25–34

    Article  Google Scholar 

  • Stenson AC, Landing WM, Marshall AG, Cooper WT (2002) Ionization and fragmentation of humic substances in electrospray ionization Fourier transform-ion cyclotron resonance mass spectrometry. Anal Chem 74:4397–4409

    Article  Google Scholar 

  • Stenson AC, Marshall AG, Cooper WT (2003) Exact masses and chemical formulas of individual Suwannee River fulvic acids from ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectra. Anal Chem 75:1275–1284

    Article  Google Scholar 

  • Striegel A, Yau WW, Kirkland JJ, Bly DD (eds) (2009) Modern size exclusion chromatography: practice of gel permeation and gel filtration chromatography, 2nd edn. Wiley, New York, NY

    Google Scholar 

  • Sunda WG, Kieber DJ (1994) Oxidation of humic substances by manganese oxides yields low-molecular-weight organic substrates. Nature 367:62–65

    Article  Google Scholar 

  • Tanczos I, Schoflinger M, Schmidt H, Balla J (1997) Cannizzaro reaction of aldehydes in TMAH thermochemolysis. J Anal Appl Pyrol 42:21–31

    Article  Google Scholar 

  • Tohmura S, Argyropoulos DS (2001) Determination of arylglycerol-β-aryl ethers and other linkages in lignins using DFRC/31P NMR. J Agric Food Chem 49:536–542

    Article  Google Scholar 

  • Vane CH, Martin SC, Snape CE, Abbott GD (2001) Degradation of lignin in wheat straw during growth of the oyster mushroom (Pleurotus ostreatus) using off-line thermochemolysis with tetramethylammonium hydroxyde and solid state 13C NMR. J Agric Food Chem 49:709–2716

    Article  Google Scholar 

  • Wang MC, Huang PM (1986) Humic macromolecule Interlayering in nontronite through interaction with phenol monomers. Nature 323:529–531

    Article  Google Scholar 

  • Wang MC, Huang PM (1989) Abiotic ring cleavage of pyrogallol and the associated reactions as catalyzed by a natural soil. Sci Total Environ 81:501–510

    Article  Google Scholar 

  • Wang MC, Huang PM (2003) Cleavage and polycondensation of pyrogallol and glycine catalyzed by natural soil clays. Geoderma 112:31–50

    Article  Google Scholar 

  • Wang TSC, Kao MM, Huang PM (1980) The effect of pH on the catalytic synthesis of humic substances by illite. Soil Sci 129:333–338

    Article  Google Scholar 

  • Weber J, Karczewska A, Drozd J et al (2007) Agricultural and ecological aspects of a sandy soil as affected by the application of municipal solid waste composts. Soil Biol Biochem 39:1294–1302

    Article  Google Scholar 

  • You TT, Mao J, Yuan T et al (2013) Structural elucidation of the lignins from stems and foliage of Arundo donax Linn. J Agric Food Chem 61:5361–5370

    Article  Google Scholar 

  • Zakzeski J, Bruijnincx PCA, Jongerius AL et al (2010) The catalytic valorization of lignin for the production of renewable chemicals. Chem Rev 110:3552–3599

    Article  Google Scholar 

  • Zang X, van Heemst JDH, Dria KJ et al (2000) Encapsulation of protein in humic acid from a histosol as an explanation for the occurrence of organic nitrogen in soil and sediment. Org Geochem 31:679–695

    Article  Google Scholar 

  • Zhang D, Pan G, Wu G et al (2014) Biochar helps enhance maize productivity and reduce greenhouse gas emissions under balanced fertilization in a rainfed low fertility inceptisol. Chemosphere 142:106–113

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Alessandro Piccolo .

Editor information

Editors and Affiliations

Rights and permissions

Reprints and permissions

Copyright information

© 2016 Springer International Publishing Switzerland

About this chapter

Cite this chapter

Savy, D. et al. (2016). Molecular Properties and Functions of Humic Substances and Humic-Like Substances (HULIS) from Biomass and Their Transformation Products. In: Vaz Jr., S. (eds) Analytical Techniques and Methods for Biomass. Springer, Cham. https://doi.org/10.1007/978-3-319-41414-0_4

Download citation

  • DOI: https://doi.org/10.1007/978-3-319-41414-0_4

  • Published:

  • Publisher Name: Springer, Cham

  • Print ISBN: 978-3-319-41413-3

  • Online ISBN: 978-3-319-41414-0

  • eBook Packages: EnergyEnergy (R0)

Publish with us

Policies and ethics