, Volume 144, Issue 3, pp 291–304 | Cite as

Thermal oxidation of carbon in organic matter rich volcanic soils: insights into SOC age differentiation and mineral stabilization

  • Katherine E. GrantEmail author
  • Valier V. Galy
  • Oliver A. Chadwick
  • Louis A. Derry


Radiocarbon ages and thermal stability measurements can be used to estimate the stability of soil organic carbon (OC). Soil OC is a complex reservoir that contains a range of compounds with different sources, reactivities, and residence times. This heterogeneity can shift bulk radiocarbon values and impact assessment of OC stability and turnover in soils. Four soil horizons (Oa, Bhs, Bs, Bg) were sampled from highly weathered 350 ka Pololu basaltic volcanics on the Island of Hawaii and analyzed by Ramped PyrOX (RPO) in both the pyrolysis (PY) and oxidation (OX) modes to separate a complex mixture of OC into thermally defined fractions. Fractions were characterized for carbon stable isotope and radiocarbon composition. PY and OX modes yielded similar results. Bulk radiocarbon measurements were modern in the Oa horizon (Fm = 1.013) and got progressively older with depth: the Bg horizon had an Fm value of 0.73. Activation energy distributions (p(E)) calculated using the ‘rampedpyrox’ model yielded consistent mean E values of 140 kJ mol−1 below the Oa horizon. The ‘rampedpyrox’ model outputs showed a mostly bimodal distribution in the p(E) below the Oa, with a primary peak at 135 kJ mol−1 and a secondary peak at 148 kJ mol−1, while the Oa was dominated by a single, higher E peak at 157 kJ mol−1. We suggest that mineral-carbon interaction, either through mineral surface-OC or metal-OC interactions, is the stabilization mechanism contributing to the observed mean E of 140 kJ mol−1 below the Oa horizon. In the Oa horizon, within individual RPO analyses, radiocarbon ages in the individual thermal fractions were indistinguishable (p > 0.1). The flat age distributions indicate there is no relationship between age and thermal stability (E) in the upper horizon (> 25 cm). Deeper in the soil profile higher µEf values were associated with older radiocarbon ages, with slopes progressively steepening with depth. In the deepest (Bg) horizon, there was the largest, yet modest change in Fm of 0.06 (626 radiocarbon years), indicating that older OC is slightly more thermally stable.


Soil organic carbon (SOC) Ramped pyrolysis/oxidation (RPO) Radiocarbon 



We would like to thank the staff at NOSAMS for their generous laboratory help and guidance, especially A. Mchnicol, M. Lardie Gaylord, and A. Gagnon. K. Grant would like to thank J. Hemingway for his assistance with the RPO instrument and help with the ‘rampedpyrox’ code, and Gregg McElwee for assistance with ICP instrumentation at Cornell. Marc Kramer helped with field sampling and interpretation of soil organic C properties in the soil horizon.


This work was partially supported by the Cornell University Atkinson Center Small Grant program and by NSF EAR 1660923 (Derry, PI). KEG was supported by the Cross-Scale Biogeochemistry and Climate – National Science Foundation Integrative Graduate Education and Research Traineeship grant#DGE-1069193 and the Cornell Graduate Fellowship.

Supplementary material

10533_2019_586_MOESM1_ESM.docx (65 kb)
Supplementary material 1 (DOCX 66 kb)


  1. Barre P, Plante AF, Cecillon L, Lutfalla S, Baudin F, Bernard S, Christensen BT, Eglin T, Fernandez JM, Houot S, Katterer T, Le Guillou C, Macdonald A, van Oort F, Chenu C (2016) The energetic and chemical signatures of persistent soil organic matter. Biogeochemistry 130(1–2):1–12CrossRefGoogle Scholar
  2. Bianchi TS, Galy V, Rosenheim BE, Shields M, Cui XQ, Van Metre P (2015) Paleoreconstruction of organic carbon inputs to an oxbow lake in the Mississippi River watershed: effects of dam construction and land use change on regional inputs. Geophys Res Lett 42(19):7983–7991CrossRefGoogle Scholar
  3. Bradford MA, Wieder WR, Bonan GB, Fierer N, Raymond PA, Crowther TW (2016) Managing uncertainty in soil carbon feedbacks to climate change. Nat Clim Change 6(8):751–758CrossRefGoogle Scholar
  4. Buettner SW, Kramer MG, Chadwick OA, Thompson A (2014) Mobilization of colloidal carbon during iron reduction in basaltic soils. Geoderma 221–222:139–145CrossRefGoogle Scholar
  5. Chadwick OA, Gavenda RT, Kelly EF, Ziegler K, Olson CG, Elliott WC, Hendricks DM (2003) The impact of climate on the biogeochemical functioning of volcanic soils. Chem Geol 202(3–4):195–223CrossRefGoogle Scholar
  6. Chadwick OA, Kelly EF, Hotchkiss SC, Vitousek PM (2007) Precontact vegetation and soil nutrient status in the shadow of Kohala Volcano, Hawaii. Geomorphology 89(1–2):70–83CrossRefGoogle Scholar
  7. Chorover J, Amistadi MK, Chadwick OA (2004) Surface charge evolution of mineral-organic complexes during pedogenesis in Hawaiian basalt. Geochim Cosmochim Acta 68:4859–4876CrossRefGoogle Scholar
  8. Davidson EA, Janssens IA (2006) Temperature sensitivity of soil carbon decomposition and feedbacks to climate change. Nature 440(7081):165–173CrossRefGoogle Scholar
  9. Feng WT, Plante AF, Six J (2013a) Improving estimates of maximal organic carbon stabilization by fine soil particles. Biogeochemistry 112(1–3):81–93CrossRefGoogle Scholar
  10. Feng X, Vonk JE, Van Dongen BE, Gustafsson Ö, Semiletov IP, Dudarev OV, Wang Z, Montluçon DB, Wacker L, Eglinton TI (2013b) Differential mobilization of terrestrial carbon pools in Eurasian Arctic river basins. Proc Natl Acad Sci USA 110(35):14168–14173CrossRefGoogle Scholar
  11. Giambelluca TW, Nullet MA, Schroeder TA (1986) Rainfall atlas of Hawai’i. Department of Land and Natural Resources, Hawai’iGoogle Scholar
  12. Giambelluca TW, Chen Q, Frazier AG, Price JP, Chen Y-L, Chu PS, Eischeid K, Delparte DM (2013) Online rainfall atlas of Hawai‘i. Bull Am Meteorol Soc 94:313–316CrossRefGoogle Scholar
  13. Gu BH, Schmitt J, Chen Z, Liang LY, McCarthy JF (1995) Adsorption and desorption of different organic-matter fractions on iron-oxide. Geochim Cosmochim Acta 59(2):219–229CrossRefGoogle Scholar
  14. Hemingway JD (2016) rampedpyrox: open-source tools for thermoanalytical data analysis. Accessed 5 Aug 2018
  15. Hemingway JD, Galy VV, Gagnon AR, Grant KE, Rosengard SZ, Soulet G, Zigah PK, McNichol AP (2017a) Assessing the blank carbon contribution, isotope mass balance, and kinetic isotope fractionation of the ramped pyrolysis/oxidation instrument at NOSAMS. Radiocarbon 59(1):179–193CrossRefGoogle Scholar
  16. Hemingway JD, Rothman DH, Rosengard SZ (2017b) Galy VV (2017b) Technical note: an inverse method to relate organic carbon reactivity to isotope composition from serial oxidation. Biogeosciences 14:5099–5114CrossRefGoogle Scholar
  17. Hemingway JD, Hilton RG, Hovius N, Eglinton TI, Haghipour N, Wacker L, Chen M-C, Galy VV (2018) Microbial oxidation of lithospheric organic carbon in rapidly eroding tropical mountain soils. Science 360(6385):209–212CrossRefGoogle Scholar
  18. Hemingway JD, Rothman DH, Grant KE, Rosengard SZ, Eglinton TI, Derry LA, Galy VV (2019) Mineral protection regulates the global preservation of natural organic carbon. Nature 570(7760):228CrossRefGoogle Scholar
  19. Jackson RB, Lajtha K, Crow SE, Hugelius G, Kramer MG, Pineiro G (2017) The ecology of soil carbon: pools, vulnerabilities, and biotic and abiotic controls. Annu Rev Ecol Evol Syst 48(48):419–445CrossRefGoogle Scholar
  20. Kaiser K, Guggenberger G (2003) Mineral surfaces and soil organic matter. Eur J Soil Sci 54(2):219–236CrossRefGoogle Scholar
  21. Kleber M, Mikutta R, Torn, Jahn R (2005) Poorly crystalline mineral phases protect organic matter in acid subsoil horizons. Eur J Soil Sci 56(6):717–725Google Scholar
  22. Kramer MG, Sanderman J, Chadwick OA, Chorover J, Vitousek PM (2012) Long-term carbon storage through retention of dissolved aromatic acids by reactive particles in soil. Glob Change Biol 18(8):2594–2605CrossRefGoogle Scholar
  23. Kurtz AC, Derry LA, Chadwick OA, Alfano MJ (2000) Refractory element mobility in volcanic soils. Geology 28(8):683–686CrossRefGoogle Scholar
  24. Kurtz AC, Derry LA, Chadwick OA (2001) Accretion of Asian dust to Hawaiian soils: isotopic, elemental, and mineral mass balance. Geochim et Cosmochim Acta 65:1971–1983CrossRefGoogle Scholar
  25. Lehmann J, Kleber M (2015) The contentious nature of soil organic matter. Nature 528(7580):60–68CrossRefGoogle Scholar
  26. Leifeld J, von Lutzow M (2014) Chemical and microbial activation energies of soil organic matter decomposition. Biol Fertil Soils 50(1):147–153CrossRefGoogle Scholar
  27. Lopez-Capel E, Krull ES, Bol R, Manning DAC (2008) Influence of recent vegetation on labile and recalcitrant carbon soil pools in central Queensland, Australia: evidence from thermal analysis-quadrupole mass spectrometry-isotope ratio mass spectrometry. Rapid Commun Mass Spectrom 22(11):1751–1758CrossRefGoogle Scholar
  28. Marin-Spiotta E, Chadwick OA, Kramer M, Carbone (2011) Carbon delivery to deep mineral horizons in Hawaiian rain forest soils. J. Geophys. Res. Google Scholar
  29. Marín-Spiotta E, Gruley KE, Crawford J, Atkinson EE, Miesel JR, Greene S, Cardona-Correa C, Spencer RGM (2014) Paradigm shifts in soil organic matter research affect interpretations of aquatic carbon cycling: transcending disciplinary and ecosystem boundaries. Biogeochemistry 117(2–3):279–297CrossRefGoogle Scholar
  30. McNichol AP, Osborne EA, Gagnon AR, Fry B, Jones GA (1994) TIC, TOC, DIC, DOC, PIC, POC—unique aspects in the preparation of oceanographic samples for C-14 AMS. Nucl Instrum Methods Phys Res Sect B 92(1–4):162–165CrossRefGoogle Scholar
  31. Mikutta R, Kleber M, Torn MS, Jahn R (2006) Stabilization of soil organic matter: association with minerals or chemical recalcitrance? Biogeochemistry 77(1):25–56CrossRefGoogle Scholar
  32. Mikutta R, Schaumann GE, Gildemeister D, Bonneville S, Bonneville S, Kramer MG, Chorover J, Chadwick OA, Guggenberger G (2009) Biogeochemistry of mineral-organic associations across a long-term mineralogical soil gradient (0.3–4100 kyr), Hawaiian Islands. Geochim et Cosmochim Acta 73(7):2034–2060CrossRefGoogle Scholar
  33. Ohno T, Heckman KA, Plante AF, Fernandez IJ, Parr TB (2017) 14 C mean residence time and its relationship with thermal stability and molecular composition of soil organic matter: a case study of deciduous and coniferous forest types. Geoderma 308:1–8CrossRefGoogle Scholar
  34. Plante AF, Fernandez JM, Leifeld J (2009) Application of thermal analysis techniques in soil science. Geoderma 153(1–2):1–10CrossRefGoogle Scholar
  35. Plante AF, Beaupre SR, Roberts ML, Baisden T (2013) Distribution of radiocarbon ages in soil organic matter by thermal fractionation. Radiocarbon 55(2–3):1077–1083CrossRefGoogle Scholar
  36. Rasmussen C, Torn MS, Southard RJ (2005) Mineral assemblage and aggregates control carbon dynamics in a California Conifer forest. Soil Sci Soc Am J 69(6):1711CrossRefGoogle Scholar
  37. Rosenheim BE, Galy V (2012) Direct measurement of riverine particulate organic carbon age structure. Geophys Res Lett. Google Scholar
  38. Rosenheim BE, Day MB, Domack E, Schrum H, Benthien A, Hayes JM (2008) Antarctic sediment chronology by programmed-temperature pyrolysis: methodology and data treatment. Geochem, Geophys, Geosyst. Google Scholar
  39. Rothman DH, Forney DC (2007) Physical model for the decay and preservation of marine organic carbon. Science 316(5829):1325–1328CrossRefGoogle Scholar
  40. Schmidt MW, Torn MS, Abiven S, Dittmar T, Guggenberger G, Janssens IA, Kleber M, Kogel-Knabner I, Lehmann J, Manning DA, Nannipieri P, Rasse DP, Weiner S, Trumbore SE (2011) Persistence of soil organic matter as an ecosystem property. Nature 478(7367):49–56CrossRefGoogle Scholar
  41. Schreiner KM, Bianchi TS, Rosenheim BE (2014) Evidence for permafrost thaw and transport from an Alaskan North Slope watershed. Geophys Res Lett 41(9):3117–3126CrossRefGoogle Scholar
  42. Soulet G, Skinner LC, Beaupre SR, Galy V (2016) A note on reporting of reservoir C-14 disequilibria and age offsets. Radiocarbon 58(1):205–211CrossRefGoogle Scholar
  43. Thompson A, Chadwick OA, Boman S, Chorover J (2006a) Colloid mobilization during soil iron redox oscillations. Environ Sci Technol 40(18):5743–5749CrossRefGoogle Scholar
  44. Thompson A, Chadwick OA, Rancourt DG, Chorover J (2006b) Iron-oxide crystallinity increases during soil redox oscillations. Geochim Cosmochim Acta 70(7):1710–1727CrossRefGoogle Scholar
  45. Torn MS, Trumbore SE, Chadwick OA, Vitousek PM, Hendricks DM (1997) Mineral control of soil organic carbon storage and turnover. Nature 389(6647):170–173CrossRefGoogle Scholar
  46. Trumbore S (2009) Radiocarbon and soil carbon dynamics. Annu Rev Earth Planet Sci 37:47–66CrossRefGoogle Scholar
  47. Vetter L, Rosenheim BE, Fernandez A, Tornqvist TE (2017) Short organic carbon turnover time and narrow C-14 age spectra in early Holocene wetland paleosols. Geochem Geophys Geosyst 18(1):142–155CrossRefGoogle Scholar
  48. Williams EK, Rosenheim BE (2015) What happens to soil organic carbon as coastal marsh ecosystems change in response to increasing salinity? an exploration using ramped pyrolysis. Geochem Geophys Geosyst 16(7):2322–2335CrossRefGoogle Scholar
  49. Williams EK, Rosenheim BE, McNichol AP, Masiello CA (2014) Charring and non-additive chemical reactions during ramped pyrolysis: applications to the characterization of sedimentary and soil organic material. Org Geochem 77:106–114CrossRefGoogle Scholar
  50. Williams EK, Fogel ML, Berhe AA, Plante AF (2018) Distinct bioenergetic signatures in particulate versus mineral-associated soil organic matter. Geoderma 330:107–116. CrossRefGoogle Scholar
  51. Zhang XW, Bianchi TS, Cui XQ, Rosenheim BE, Ping CL, Hanna AJM, Kanevskiy M, Schreiner KM, Allison MA (2017) Permafrost organic carbon mobilization from the watershed to the Colville River delta: evidence from C-14 ramped pyrolysis and lignin biomarkers. Geophys Res Lett 44(22):11491–11500CrossRefGoogle Scholar

Copyright information

© Springer Nature Switzerland AG 2019

Authors and Affiliations

  1. 1.Department of Earth and Atmospheric SciencesCornell UniversityIthacaUSA
  2. 2.Department of Marine Chemistry and GeochemistryWoods Hole Oceanographic InstitutionWoods HoleUSA
  3. 3.Department of GeographyUniversity of CaliforniaOaklandUSA

Personalised recommendations