Log in

Soil pyrogenic organic matter characterisation by spectroscopic analysis: a study on combustion and pyrolysis residues

  • Impact of Natural and Anthropogenic Pyrogenic Carbon in Soils and Sediments
  • Published:
Journal of Soils and Sediments Aims and scope Submit manuscript

Abstract

Purpose

Pyrogenic organic matter (PyOM) in the soil of a maritime pine forest in Central Italy, formed during a fire of high severity, was characterised by Fourier transform infrared (FT-IR) and 13C nuclear magnetic resonance (NMR). Furthermore, soil samples from burnt and unburnt sampling sites and natural charcoal collected from the ground were characterised after progressive heating under air and nitrogen atmosphere. The aim was to better understand the role fire plays on PyOM formation and oxidation.

Materials and methods

The top 10 cm of mineral soil and the above-lying charcoal particles were collected soon after the fire. Sampling was also performed on an adjacent unburnt portion of the forest. The bulk soil organic matter (SOM), its extractable fraction and charcoal particles were investigated by FT-IR and 13C NMR spectroscopies. They also underwent thermogravimetric analysis under air or N2, stop** the thermal reactions at the end of the first exothermic reaction in the range 350–500 °C.

Results and discussion

The NMR investigation clearly revealed a significant enrichment in aromatic and alkyl C in the burnt soil compared to the unburnt one. Several clues led to hypothesise that SOM was not exposed to extreme heating during the fire, notwithstanding the high fire severity estimated by a vegetation-based visual scale. In the thermal treatment mimicking fire, charcoal lost much of its mass and carbon content. However, at 500 °C, it still maintained a significant recalcitrant fraction. Nitrogen concentration in the bulk soil increased after heating, particularly under air condition. This phenomenon could be due to the formation of heterocyclic nitrogen compounds in the charred material.

Conclusions

In the study area, PyOM is rich in aliphatic compounds presumably because of the understory sclerophyllous vegetation typically found in Mediterranean environments. A large fraction of the charcoal released to the soil during the fire is sensitive to oxidation by subsequent fires. On the other hand, charcoal preserves a significant fraction of C, the most recalcitrant one, with expected long residence time in soil. PyOM formed under high oxygen availability is richer in N than that formed in inert atmosphere, which might make PyOM more susceptible to biochemical degradation.

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

Access this article

Subscribe and save

Springer+ Basic
EUR 32.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or Ebook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price includes VAT (Germany)

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  • Almendros G, Knicker H, González-Vila FJ (2003) Rearrangement of carbon and nitrogen forms in peat after progressive thermal oxidation as determined by solid-state 13C- and 15N-NMR spectroscopy. Org Geochem 34:1559–1568

    Article  CAS  Google Scholar 

  • Almendros G, Martin F, González-Vila FJ (1988) Effects of fire on humic and lipid fractions in a Dystric Xerochrept in Spain. Geoderma 42:115–127

  • Benzing-Purdie L, Ripmeester JA, Preston CM (1983) Elucidation of the nitrogen forms in melanoidins and humic acid by nitrogen-15 cross polarization-magic angle spinning nuclear magnetic resonance spectroscopy. J Agr Food Chem 31:913–915

    Article  CAS  Google Scholar 

  • Certini G (2014) Fire as a soil-forming factor. Ambio 43:191–195

    Article  Google Scholar 

  • Certini G, Nocentini C, Knicker H, Arfaioli P, Rumpel C (2011) Wildfire effects on soil organic matter quantity and quality in two fire-prone Mediterranean pine forests. Geoderma 167:148–155

    Article  Google Scholar 

  • Dai KH, Johnson CE (1999) Applicability of solid-state 13C CP/MAS NMR analysis in Spodosols: chemical removal of magnetic materials. Geoderma 93:289–310

    Article  CAS  Google Scholar 

  • DeBano LF (2000) The role of fire and soil heating on water repellency in wildland environments: a review. J Hydrol 231–232:195–206

    Article  Google Scholar 

  • De la Rosa JM, González-Pérez JA, González-Vázquez R, Knicker H, López-Capel E, Manning DAC, González-Vila FJ (2008) Use of pyrolysis/GC–MS combined with thermal analysis to monitor C and N changes in soil organic matter from a Mediterranean fire affected forest. Catena 74:296–303

    Article  Google Scholar 

  • Doerr SH, Shakesby RA, Walsh RPD (2000) Soil water repellence: its causes, characteristics and hydro-geomorphological significance. Earth-Sci Rev 51:33–65

    Article  Google Scholar 

  • El-Hendawy ANA (2006) Variation in the FTIR spectra of a biomass under impregnation, carbonization and oxidation conditions. J Anal Appl Pyrol 75:159–166

    Article  CAS  Google Scholar 

  • Francioso O, Montecchio D, Gioacchini P, Cavani L, Ciavatta C, Trubetskoj O, Trubetskaya O (2009) Structural differences of Chernozem soil humic acids SEC-PAGE fractions revealed by thermal (TG-DTA) and spectroscopic (DRIFT) analyses. Geoderma 152:264–268

    Article  CAS  Google Scholar 

  • Francioso O, Sanchez-Cortes S, Bonora S, Roldán ML, Certini G (2011) Structural characterization of charcoal size-fractions from a burnt Pinus pinea forest by FT-IR, Raman and surface-enhanced Raman spectroscopies. J Mol Struct 994:155–162

    Article  CAS  Google Scholar 

  • Fuente E, Menendez JA, Diez MA, Suarez D, Montes-Moran MA (2003) Infrared spectroscopy of carbon materials: a quantum chemical study of model compounds. J Phys Chem B 107:6350–6359

    Article  CAS  Google Scholar 

  • González-Pérez JA, González-Vila FJ, Almendros G, Knicker H (2004) The effect of fire on soil organic matter—a review. Environ Int 30:855–870

    Article  Google Scholar 

  • Knicker H (2007) How does fire affect the nature and stability of soil organic nitrogen and carbon? A review. Biogeochemistry 85:91–118

    Article  CAS  Google Scholar 

  • Knicker H (2010) “Black nitrogen”—an important fraction in determining the recalcitrance of charcoal. Org Geochem 41:947–950

    Article  CAS  Google Scholar 

  • Knicker H (2011) Pyrogenic organic matter in soil: its origin and occurrence, its chemistry and survival in soil environments. Quatern Int 243:251–263

    Article  Google Scholar 

  • Knicker H, Almendros G, González-Vila FJ, González-Pérez JA, Polvillo O (2006) Characteristic alterations of quantity and quality of soil organic matter caused by forest fires in continental Mediterranean ecosystems: a solid-state 13C NMR study. Eur J Soil Sci 57:558–569

    Article  CAS  Google Scholar 

  • Knicker H, González-Vila FJ, Polvillo O, González JA, Almendros G (2005a) Fire-induced transformation of C- and N- forms in different organic soil fractions from a Dystric Cambisol under a Mediterranean pine forest (Pinus pinaster). Soil Biol Biochem 37:701–718

    Article  CAS  Google Scholar 

  • Knicker H, Hilscher A, Gonzàlez-Vila F, Almendros G (2008) A new conceptual model for the structural properties of char produced during vegetation fires. Org Geochem 39:935–939

    Article  CAS  Google Scholar 

  • Knicker H, Totsche KU, Almendros G, González-Vila FJ (2005b) Condensation degree of burnt peat and plant residues and the reliability of solid-state VACP MAS 13C NMR spectra obtained from pyrogenic humic material. Org Geochem 36:1359–1377

    Article  CAS  Google Scholar 

  • IUSS Working Group WRB (2014) World Reference Base for Soil Resources 2014. International soil classification system for naming soils and creating legends for soil maps. World Soil Resources Reports No. 106. FAO, Rome

  • Lozano E, Jiménez-Pinilla P, Mataix-Solera J, Arcenegui V, Bárcenas GM, González-Pérez JA, García-Orenes F, Torres MP, Mataix-Beneyto J (2013) Biological and chemical factors controlling the patchy distribution of soil water repellency among plant species in a Mediterranean semiarid forest. Geoderma 207–208:212–220

    Article  Google Scholar 

  • Mastrolonardo G, Certini G, Krebs R, Forte C, Egli M (2013) Effects of fire on soil organic matter quality along an altitudinal sequence on Mt. Etna, Sicily. Catena 110:133–145

    Article  CAS  Google Scholar 

  • Mastrolonardo G, Francioso O, Di Foggia M, Bonora S, Rumpel C, Certini G (2014) Application of thermal and spectroscopic techniques to assess fire-induced changes to soil organic matter in a Mediterranean forest. J Geochem Explor 143:174–182

    Article  CAS  Google Scholar 

  • McKissock I, Gilkes RJ, van Bronswijk W (2003) The relationship of soil water repellency to aliphatic C and kaolin measured using DRIFT. Aust J Soil Res 41:251–265

  • Moriondo M, Good P, Durao R, Bindi M, Giannakopoulos C, Corte-Real J (2006) Potential impact of climate change on fire risk in the Mediterranean area. Clim Res 31:85–95

    Article  Google Scholar 

  • Nguyen BT, Lehmann J, Hockaday WC, Joseph S, Masiello CA (2010) Temperature sensitivity of black carbon decomposition and oxidation. Environ Sci Technol 44:3324–3331

    Article  CAS  Google Scholar 

  • Nyquist RA (2001) Interpreting infrared, raman, and nuclear magnetic resonance spectra. Academic, San Diego

    Google Scholar 

  • Nocentini C, Certini G, Knicker H, Francioso O, Rumpel C (2010) Nature and reactivity of charcoal produced and added to soil during wildfire are particle-size dependent. Org Geochem 41:682–689

    Article  CAS  Google Scholar 

  • Parson A, Robichaud PR, Lewis SA, Napper C, Clark JT (2010) Field guide for map** post-fire soil burn severity. Gen Tech Rep RMRS-GTR-243. US Dept of Agriculture, Forest Service, Rocky Mountain Research Station. Fort Collins, CO

  • Pausas JG, Llovet J, Rodrigo A, Vallejo R (2008) Are wildfires a disaster in the Mediterranean basin?—A review. Int J Wildland Fire 17:713–723

    Article  Google Scholar 

  • Pituello C, Francioso O, Simonetti G, Pisi A, Torreggiani A, Berti A, Morari F (2014) Characterization of chemical-physical, structural and morphological properties of biochars from biowastes produced at different temperatures. J Soil Sediments. doi:10.1007/s11368-014-0964-7 (this issue)

    Google Scholar 

  • Preston CM, Newman RH (1995) A long-term effect of N fertilization on the 13C CPMAS NMR of de-ashed soil humin in a second-growth Douglas-fir stand of coastal British Columbia. Geoderma 68:229–241

    Article  CAS  Google Scholar 

  • Quideau S, Chadwick O, Benesi A, Graham R, Anderson M (2001) A direct link between forest vegetation type and soil organic matter composition. Geoderma 104:41–60

    Article  CAS  Google Scholar 

  • Rao CNR (1963) Chemical applications of infrared spectroscopy. Academic, New York

    Google Scholar 

  • Rumpel C, Rabia N, Derenne S, Quenea K, Eusterhues K, Kögel-Knabner I, Mariotti A (2006) Alteration of soil organic matter following treatment with hydrofluoric acid (HF). Org Geochem 37:1437–1451

    Article  CAS  Google Scholar 

  • Santin C, Knicker H, Fernandez S, Menendez-Duarte R, Alvarez M (2008) Wildfires influence on soil organic matter in an Atlantic mountainous region (NW of Spain). Catena 74:286–295

  • Schmidt MWI, Noack AG (2000) Black carbon in soils and sediments: analysis, distribution, implications, and current challenges. Global Biogeochem Cy 14:777–793

    Article  CAS  Google Scholar 

  • Shakesby RA (2011) Post-wildfire soil erosion in the Mediterranean: review and future research directions. Earth-Sci Rev 105:71–100

    Article  Google Scholar 

  • Skjemstad J, Clarke P, Taylor J, Oades J, Newman R (1994) The removal of magnetic materials from surface soils—a solid state 13C CP/MAS NMR study. Aust J Soil Res 32:1215–1229

  • Skjemstad JO, Clarke P, Taylor JA, Oades JM, McClure SG (1996) The chemistry and nature of protected carbon in soil. Aust J Soil Res 34:251–271

  • Stoffyn-Egli P, Potter TM, Leonard JD, Pocklington R (1997) The identification of black carbon particles with the analytical scanning electron microscope: methods and initial results. Sci Total Environ 198:211–223

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Giovanni Mastrolonardo.

Additional information

Responsible editor: José M. De la Rosa

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Mastrolonardo, G., Francioso, O., Di Foggia, M. et al. Soil pyrogenic organic matter characterisation by spectroscopic analysis: a study on combustion and pyrolysis residues. J Soils Sediments 15, 769–780 (2015). https://doi.org/10.1007/s11368-014-1034-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11368-014-1034-x

Keywords

Navigation