Carbon and nitrogen molecular composition of soil organic matter fractions resistant to oxidation
Katherine Heckman A C , Dorisel Torres B , Christopher Swanston A and Johannes Lehmann B
+ Author Affiliations
- Author Affiliations
A USDA Forest Service, Northern Research Station, 410 MacInnes Drive, Houghton, MI 49931, USA.
B Soil and Crop Sciences, Cornell University, Ithaca, NY 14853, USA.
C Corresponding author. Email: kaheckman@fs.fed.us
Soil Research 55(8) 809-818 https://doi.org/10.1071/SR16182
Submitted: 12 July 2016 Accepted: 20 May 2017 Published: 23 June 2017
Abstract
The methods used to isolate and characterise pyrogenic organic carbon (PyC) from soils vary widely, and there is little agreement in the literature as to which method truly isolates the most chemically recalcitrant (inferred from oxidative resistance) and persistent (inferred from radiocarbon abundance) fraction of soil organic matter. In addition, the roles of fire, fuel type and soil morphology in the preservation of PyC are not yet defined. In an attempt to elucidate the importance of oxidative recalcitrance, fuel type and soil morphology to the persistence of soil organic matter, we examined two strongly contrasting soils using a variety of PyC isolation techniques coupled with quantifications of the molecular structure and mean residence time of the isolated organic materials. Surface and subsurface soil samples were examined from a Red Chromosol soil and a Black Vertosol soil. The δ13C values suggest that PyC in the Red Chromosol was sourced from eucalyptus, whereas PyC in the Black Vertosol was formed from grass. Soils were sieved at 53 µm, treated with hydrofluoric acid to remove organics associated with mineral surfaces, then subjected to three common ‘PyC isolation’ treatments: chromic acid, photo-oxidation and chromic acid followed by photo-oxidation. Molecular structure of the organic residues remaining after each treatment was quantified by solid-state 13C cross polarisation magic angle spinning nuclear magnetic resonance and near edge X-ray absorption fine structure spectroscopy, and the mean residence time of the organic residues was estimated based on radiocarbon abundance. In all cases, treatment with chromic acid followed by photo-oxidation isolated the smallest proportion of organic matter (5–10% of <53 µm C) which also had the longest mean residence time (estimated 600–3460 years). Additionally, molecular structure measurements indicated that this fraction was not composed solely of aromatic compounds, suggesting a non-homogenous source for the most oxidative-resistant fraction of soil organic matter.
Additional keywords: chromic acid, photo-oxidation, pyrogenic carbon, soil organic matter.
References
Bird MI, Wynn JG, Saiz G, Wurster CS, McBeath A (2015) The pyrogenic carbon cycle. Annual Review of Earth and Planetary Sciences 43, 273–298.| The pyrogenic carbon cycle.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2MXhsVGns7nP&md5=5b05edeeb7123a816d53b4b3ade25a4cCAS |
Cheng CH, Lehmann J, Engelhard M (2008) Natural oxidation of black carbon in soils: changes in molecular form and surface charge along a climosequence. Geochimica et Cosmochimica Acta 72, 1598–1610.
| Natural oxidation of black carbon in soils: changes in molecular form and surface charge along a climosequence.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXivFOjurg%3D&md5=a4589522145259cddebcfc6cb20bdb7fCAS |
Cohen-Ofri I, Weiner L, Boaretto E, Mintz G, Weiner S (2006) Modern and fossil charcoal: aspects of structure and diagenesis. Journal of Archaeological Science 33, 428–439.
| Modern and fossil charcoal: aspects of structure and diagenesis.Crossref | GoogleScholarGoogle Scholar |
Czimczik CI, Masiello CA (2007) Controls on black carbon storage in soils. Global Biogeochemical Cycles 21, GB3005.
| Controls on black carbon storage in soils.Crossref | GoogleScholarGoogle Scholar |
Davis JC, Proctor ID, Southon JR, Caffee MW, Heikkinen DW, Roberts ML, Moore TL, Turteltaub KW, Nelson DE, Loyd DH, Vogel JS (1990) LLNL/US AMS facility and research program. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms 52, 269–272.
| LLNL/US AMS facility and research program.Crossref | GoogleScholarGoogle Scholar |
Gonçalves CN, Dalmolin RSD, Dick DP, Knicker H, Klamt E, Kögel-Knabner I (2003) The effect of 10% HF treatment on the resolution of CPMAS 13C NMR spectra and on the quality of organic matter in Ferralsols. Geoderma 116, 373–392.
| The effect of 10% HF treatment on the resolution of CPMAS 13C NMR spectra and on the quality of organic matter in Ferralsols.Crossref | GoogleScholarGoogle Scholar |
González-Pérez J, González-Vila FJ, Almendros G, Knicker H (2004) The effect of fire on soil organic matter—a review. Environment International 30, 855–870.
| The effect of fire on soil organic matter—a review.Crossref | GoogleScholarGoogle Scholar |
Graetz RD, Skjemstad JO (2003) The charcoal sink of biomass burning on the Australian continent. Atmospheric Research Technical Paper 64. CSIRO, Aspendale, Victoria, Australia. Available at http://www.cmar.csiro.au/e-print/open/graetz_2003a.pdf [verified 5 June 2017].
Hammes K, Schmidt MWI, Smernik RJ, Currie LA, Ball WP, Nguyen TH, Louchouarn P, Houel S, Gustafsson Ö, Elmquist M, Cornelissen G, Skjemstad JO, Masiello CA, Song J, Peng P, Mitra S, Dunn JC, Hatcher PG, Hockaday WC, Smith DM, Hartkopf-Fröder C, Böhmer A, Lüer B, Huebert BJ, Amelung W, Brodowski S, Huang L, Zhang W, Gschwend PM, Xanat Flores-Cervantes D, Largeau C, Rouzaud J-N, Rumpel C, Guggenberger G, Kaiser K, Rodionov A, Gonzalez-Vila FJ, Gonzalez-Perez JA, de la Rosa JM, Manning DAC, López-Capél E, Ding L (2007) Comparison of quantification methods to measure fire-derived (black/elemental) carbon in soils and sediments using reference materials from soil, water, sediment and the atmosphere. Global Biogeochemical Cycles 21, GB3016. https://doi.org/10.1029/2006GB002914
Heymann K, Lehmann J, Solomon D, Schmidt MWI, Regier T (2011) C 1s K-edge near-edge X-ray absorption fine structure (NEXAFS) spectroscopy for characterizing the functional group chemistry of black carbon. Organic Geochemistry 42, 1055–1064.
| C 1s K-edge near-edge X-ray absorption fine structure (NEXAFS) spectroscopy for characterizing the functional group chemistry of black carbon.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhtFWktL3P&md5=0a4bc7f36c8d3d4baaa05aa523d86127CAS |
Hogg AG, Hua Q, Blackwell PG, Buck CE, Guilderson TP, Heaton TJ, Niu M, Palmer JG, Reimer PJ, Reimer RW, Turney CSM, Zimmerman SRH (2013) SHCal 13 southern hemisphere calibration, 0–50,000 years cal BP. Radiocarbon 55, 1–15.
Isbell RF (2002). ‘The Australian soil classification.’ Revised edn. (CSIRO Publishing: Collingwood, Victoria)
Knicker H (2007) How does fire affect the nature and stability of soil organic nitrogen and carbon? A review. Biogeochemistry 85, 91–118.
| How does fire affect the nature and stability of soil organic nitrogen and carbon? A review.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXntlajs7c%3D&md5=937ac840ff684eb236495cd3e11f1d9fCAS |
Knicker H (2011a) Pyrogenic organic matter in soil: its origin and occurrence, its chemistry and survival in soil environments. Quaternary International 243, 251–263.
| Pyrogenic organic matter in soil: its origin and occurrence, its chemistry and survival in soil environments.Crossref | GoogleScholarGoogle Scholar |
Krull ES, Swanston CW, Skjemstad JO, McGowan JA (2006) Importance of charcoal in determining the age and chemistry of organic carbon in surface soils. Journal of Geophysical Research 111, G04001.
| Importance of charcoal in determining the age and chemistry of organic carbon in surface soils.Crossref | GoogleScholarGoogle Scholar |
Lagercrantz C, Yhland M (1963) Photo-induced free radical reactions in the solutions of some tars and humic acids. Acta Chemica Scandinavica 17, 1299–1306.
| Photo-induced free radical reactions in the solutions of some tars and humic acids.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaF3sXksleisLs%3D&md5=eaa3887000429f50ad9f84fb386e7b44CAS |
Leavitt SW, Follett RF, Paul EA (1996) Estimation of slow- and fast-cycling soil organic carbon pools from 6N HCl hydrolysis. Radiocarbon 38, 231–239.
| Estimation of slow- and fast-cycling soil organic carbon pools from 6N HCl hydrolysis.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2sXitVejtrc%3D&md5=11b73d16e0e51ff6c571a36542f365d5CAS |
Leinweber P, Kruse J, Walley FL, Gillespie A, Eckhardt K-U, Blyth RIR, Regier T (2007) N K-edge XANES: an overview of reference compounds used to identify ‘unknown’ organic nitrogen in environmental samples. Journal of Synchrotron Radiation 14, 500–511.
| N K-edge XANES: an overview of reference compounds used to identify ‘unknown’ organic nitrogen in environmental samples.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXht1ehtL%2FI&md5=5bbb464a8462ee772b44945c038639e3CAS |
Martel YA, Paul EA (1974) The use of radiocarbon dating of organic matter in the study of soil genesis. Soil Science Society of America Proceedings 38, 501–506.
| The use of radiocarbon dating of organic matter in the study of soil genesis.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE2cXksFaltrc%3D&md5=b050f30fcc98aaa2f523e4a200ea88c0CAS |
Masiello CA, Druffel ERM (1998) Black carbon in deep-sea sediments. Science 280, 1911–1913.
| Black carbon in deep-sea sediments.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXjvFyqurk%3D&md5=5e7d397b6e80391aac547bd64881fd56CAS |
Nelson PN, Baldock JA (2005) Estimating the molecular composition of a diverse range of natural organic materials from solid-state 13C NMR and elemental analysis. Biogeochemistry 72, 1–34.
| Estimating the molecular composition of a diverse range of natural organic materials from solid-state 13C NMR and elemental analysis.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXksVWks7c%3D&md5=b3b40b4949a8a8b8e7d47550e57342bbCAS |
Ravel B, Newville M (2005) ATHENA, ARTEMIS, HEPHAESTUS: data analysis for x-ray absorption spectroscopy using IFEFFIT. Journal of Synchrotron Radiation 12, 537–541.
| ATHENA, ARTEMIS, HEPHAESTUS: data analysis for x-ray absorption spectroscopy using IFEFFIT.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXltlCntLo%3D&md5=53690957a72470fc222fb4a690741002CAS |
Regier T, Krochak J, Sham TK, Hu YF, Thompson J, Blyth RIR (2007) Performance and capabilities of the Canadian Dragon: The SGM beamline at the Canadian Light Source. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment 582, 93–95.
Reimer PJ, Brown TA, Reimer RW (2004) Discussion: reporting and calibration of post-bomb C-14 data. Radiocarbon 46, 1299–1304.
| Discussion: reporting and calibration of post-bomb C-14 data.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXpsVams7k%3D&md5=6386757ed7629304f9d039c619e557fbCAS |
Schmidt MWI, Noack AG (2000) Black carbon in soils and sediments: analysis, distribution, implication, and current challenges. Global Biogeochemical Cycles 14, 777–793.
| Black carbon in soils and sediments: analysis, distribution, implication, and current challenges.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXmsVymt7s%3D&md5=e421026dbf1278b2cdc1531067ac643cCAS |
Schmidt MWI, Skjemstad JO, Czimczik CI, Glaser B, Prentice KM, Gelinas Y, Kuhlbusch TAJ (2001) Comparative analysis of black carbon in soils. Global Biogeochemical Cycles 15, 163–167.
| Comparative analysis of black carbon in soils.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXisVCht7Y%3D&md5=90422ee8805b39ec70f257445ce0382bCAS |
Senesi N, Schnitzer M (1977) Effects of pH, reaction time, chemical reduction and irradiation on the ESR spectra of fulvic acid. Soil Science 123, 224–234.
| Effects of pH, reaction time, chemical reduction and irradiation on the ESR spectra of fulvic acid.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE2sXktVCls7Y%3D&md5=c242dd126b39f2e568f624bc5dbf324dCAS |
Skjemstad JO, Janic LJ, Head MJ, McClure SG (1993) High energy ultraviolet photo-oxidation: a novel technique for studying physically protected organic matter in clay- and silt-sized aggregates. Journal of Soil Science 44, 485–499.
| High energy ultraviolet photo-oxidation: a novel technique for studying physically protected organic matter in clay- and silt-sized aggregates.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2cXktlCjt7g%3D&md5=a94b01deaf7c8eda90037220b50d8fb9CAS |
Skjemstad JO, Clarke P, Taylor JA, Oades JM, McClure SG (1996) The chemistry and nature of protected carbon in soil. Soil Research 34, 251–271.
Skjemstad JO, Reicosky DC, Wilts AR, McGowan JA (2002) Charcoal carbon in U.S. agricultural soils. Soil Science Society of America Journal 66, 1249–1255.
| Charcoal carbon in U.S. agricultural soils.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XlslOrtr0%3D&md5=6284e164acf48fe5a6ec3a42a09e7df4CAS |
Skjernstad JO, Taylor JA, Smernik RJ (1999) Estimation of charcoal (char) in soils. Communications in Soil Science and Plant Analysis 30, 2283–2298.
| Estimation of charcoal (char) in soils.Crossref | GoogleScholarGoogle Scholar |
Slawinska D, Slawinska J, Sarna T (1975) The effect of light on the ESR spectra of humic acids. Journal of Soil Science 26, 93–99.
| The effect of light on the ESR spectra of humic acids.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE2MXlsVKntLw%3D&md5=74dcdc173dafb13605a337eb990c7527CAS |
Solomon D, Lehmann J, Kinyangi J, Liang B, Hanley K, Heymann K, Wirick S, Jacobsen C (2009) Carbon (1s) NEXAFS spectroscopy of biogeochemically relevant organic reference compounds. Soil Science Society of America Journal 73, 1817–1830.
| Carbon (1s) NEXAFS spectroscopy of biogeochemically relevant organic reference compounds.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXhsVSku7rN&md5=36154e26a3e65af7142b93d11e95580fCAS |
Song J, Peng P, Huang W (2002) Black Carbon and Kerogen in soils and sediments. 1. Quantification and characterization. Environmental Science & Technology 36, 3960–3967.
| Black Carbon and Kerogen in soils and sediments. 1. Quantification and characterization.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38Xmt1Slu7c%3D&md5=c20cab72846e2f34ada62d9f7ea0e36dCAS |
Stuiver M, Polach HA (1977) Discussion: reporting of 14C data. Radiocarbon 19, 355–363.
| Discussion: reporting of 14C data.Crossref | GoogleScholarGoogle Scholar |
Torn MS, Lapenis AG, Timofeev A, Fischer ML, Babikov BV, Harden JW (2002) Organic carbon and carbon isotopes in modern and 100-year-old-soil archives of the Russian steppe. Global Change Biology 8, 941–953.
| Organic carbon and carbon isotopes in modern and 100-year-old-soil archives of the Russian steppe.Crossref | GoogleScholarGoogle Scholar |
Trumbore SE (1993) Comparison of carbon dynamics in tropical and temperate soils using radiocarbon measurements. Global Biogeochemical Cycles 7, 275–290.
| Comparison of carbon dynamics in tropical and temperate soils using radiocarbon measurements.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2cXnsFek&md5=72df84d80850c8081146ea655b9e57b9CAS |
Vogel JS, Southon JR, Nelson DE (1987) Catalyst and binder effects in the use of filamentous graphite for AMS. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms 29, 50–56.
| Catalyst and binder effects in the use of filamentous graphite for AMS.Crossref | GoogleScholarGoogle Scholar |
Wilson MA (1987) ‘NMR techniques and applications in geochemistry and soil chemistry.’ (Elsevier: New York)
Wojdyr M (2010) Fityk: a general-purpose peak fitting program. Journal of Applied Crystallography 43, 1126–1128.
| Fityk: a general-purpose peak fitting program.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXhtFOqsbbK&md5=266f7e68eadd79591c34f23676dbaa33CAS |
Zepp RG, Wolfe NL, Baughman GL, Hollis RC (1977) Singlet oxygen in natural waters. Nature 267, 421–423.
| Singlet oxygen in natural waters.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE1cXktlSmsL0%3D&md5=c6e3ac43115acd8539891199737b2570CAS |
Zubavichus Y, Fuchs O, Weinhardt L, Heske C, Umbach E, Denlinger JD, Grunze M (2004) Soft X-ray-induced decomposition of amino acids: an XPS, mass spectrometry, and NEXAFS study. Radiation Research 161, 346–358.
| Soft X-ray-induced decomposition of amino acids: an XPS, mass spectrometry, and NEXAFS study.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXhvFertbw%3D&md5=fe299f79cd28a0221480403298a6e8aeCAS |
Zubavichus Y, Shaporenko A, Grunze M, Zharnikov M (2005) Innershell absorption spectroscopy of amino acids at all relevant absorption edges. The Journal of Physical Chemistry A 109, 6998–7000.
| Innershell absorption spectroscopy of amino acids at all relevant absorption edges.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXmtlGrsbs%3D&md5=fbe8bcbbe8665ea7a8aa80decd840de5CAS |
