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RESEARCH ARTICLE

Measuring organic carbon in Calcarosols: understanding the pitfalls and complications

Aaron Schmidt A , Ronald J. Smernik A C and Therese M. McBeath A B
+ Author Affiliations
- Author Affiliations

A School of Agriculture, Food and Wine and Waite Research Institute, The University of Adelaide, Waite Campus, Urrbrae, SA 5064, Australia.

B CSIRO Sustainable Agriculture Flagship, CSIRO Ecosystem Sciences, PMB 2, Glen Osmond, SA 5064, Australia.

C Corresponding author. Email: ronald.smernik@adelaide.edu.au

Soil Research 50(5) 397-405 https://doi.org/10.1071/SR12134
Submitted: 25 November 2011  Accepted: 24 May 2012   Published: 20 July 2012

Abstract

The measurement of soil organic carbon (OC) is important for assessing soil condition and improving land management systems, as OC has an important role in the physical, chemical, and biological fertility of soil. The OC contents of Calcarosols often appear high compared with other Australian soil types with similar fertility. This may indicate either systematic overestimation of OC in Calcarosols or the existence of a mechanism of OC stabilisation specific to carbonate-rich soils. This study compares three dry combustion techniques (dry combustion with correction for carbonate-C determined separately, dry combustion following sulfurous acid treatment, and dry combustion following treatment with hydrofluoric acid) and two wet oxidation techniques (Walkley–Black and Heanes) for the measurement of soil OC content, to determine which method is best for Calcarosols. Nine calcareous and nine non-calcareous soils were analysed. Of the methods, dry combustion with carbonate-C correction and dry combustion following sulfurous acid pre-treatment were found to be unsuitable for highly calcareous soils. Dry combustion with carbonate-C correction was unsuccessful primarily due to incomplete conversion of carbonate to CO2 under the combustion conditions used. However, even if this problem could be overcome, the method would still not be suitable for highly calcareous soils since it would involve the measurement of a relatively small value (OC) as the difference of two much larger values (total C and carbonate-C). Sulfurous acid pre-treatment was unsuitable because it did not remove 100% of carbonate present. Although the remaining dry combustion technique (i.e. following hydrofluoric acid treatment) did not have such problems, it did give very different (and much lower) OC estimations than the two wet oxidation techniques for the highly calcareous soils. These results are consistent with carbonate minerals interacting with and stabilising a substantial quantity of soluble OC. This has implications for the way OC levels should be measured and interpreted in Calcarosols, in terms of both fertility and C stabilisation and sequestration.

Additional keywords: calcareous, stabilisation, dry combustion, wet oxidation, Walkley–Black, HF treatment.


References

Allison LE, Moodie CD (1965) Carbonate: volumetric calcimeter method. In ‘Methods of soil analysis. Part 2. Chemical and microbiological methods’. (Ed. CA Black) pp. 1389. (American Society of Agronomy: Madison, WI)

Batlle-Aguilar J, Brovelli A, Porporato A, Barry DA (2011) Modelling soil carbon and nitrogen cycles during land use change. A review. Agronomy for Sustainable Development 31, 251–274.
Modelling soil carbon and nitrogen cycles during land use change. A review.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXosVWjurg%3D&md5=cdcfccf5c804543183d8622a08f08caaCAS |

Bertrand I, Holloway RE, Armstrong RD, McLaughlin MJ (2003) Chemical characteristics of phosphorus in alkaline soils from southern Australia. Australian Journal of Soil Research 41, 61–76.
Chemical characteristics of phosphorus in alkaline soils from southern Australia.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXitVygsrg%3D&md5=da41618ef0122ff0753f302ea4f4d3e6CAS |

Bisutti I, Hilke I, Raessler M (2004) Determination of total organic carbon – an ovrview of current methods. Trends in Analytical Chemistry 23, 716–726.
Determination of total organic carbon – an ovrview of current methods.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXhtVCmtbbO&md5=6d9133644a93808ed29c06a3e8a910c8CAS |

Brye KR, Slaton NA (2003) Carbon and nitrogen storage in a Typic Albaqualf as affected by assessment method. Communications in Soil Science and Plant Analysis 34, 1637–1655.
Carbon and nitrogen storage in a Typic Albaqualf as affected by assessment method.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXksFeru7k%3D&md5=fc281a756c1e51a63122894915585914CAS |

Caughey ME, Barcelona MJ, Powell RM, Cahill RA, Grøn C, Lawrenz D, Meschi PL (1995) Interlaboratory study of a method for determining nonvolatile organic carbon in aquifer materials. Environmental Geology 26, 211–219.
Interlaboratory study of a method for determining nonvolatile organic carbon in aquifer materials.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK28XmtVKrsg%3D%3D&md5=80063cbb25ffb1529b85f51d42045f7bCAS |

Chatterjee A, Lal R, Wielopolski L, Martin MZ, Ebinger MH (2009) Evaluation of different soil carbon determination methods. Critical Reviews in Plant Sciences 28, 164–178.
Evaluation of different soil carbon determination methods.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXktFClsrc%3D&md5=be3826c51779726e9a8f8d1df03c6f71CAS |

Chave KE (1965) Carbonates: Association with organic matter in surface seawater. Science 148, 1723–1724.
Carbonates: Association with organic matter in surface seawater.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaF2MXksVCrurk%3D&md5=c293a3f3981740a7f30332a75c324ddcCAS |

Chichester FW, Chaison JRF (1992) Analysis of carbon in calcareous soils using a two temperature dry combustion infrared instrumental procedure. Soil Science 153, 237–241.
Analysis of carbon in calcareous soils using a two temperature dry combustion infrared instrumental procedure.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK38XitlCms7Y%3D&md5=4dd7610751d6559f141862ca385a0dc0CAS |

Fernandes M, Krull E (2008) How does acid treatment to remove carbonates affect the isotopic and elemental composition of soils and sediments? Environmental Chemistry 5, 33–39.
How does acid treatment to remove carbonates affect the isotopic and elemental composition of soils and sediments?Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXitlagsbk%3D&md5=e9c02eaf293e2aefbe17b66f6bbd834eCAS |

Gibbs RJ (1977) Effect of combustion temperature and time, and of the oxidation agent used in organic carbon and nitrogen analyses of sediments and dissolved organic material. Journal of Sedimentary Petrology 47, 547–550.

Gordon J, Carriker MR (1980) Sclerotized protein in the shell matrix of a bivalve mollusc. Marine Biology 57, 251–260.
Sclerotized protein in the shell matrix of a bivalve mollusc.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL3cXmtFyhsrw%3D&md5=072bee4fadc2a9834e4673cafd8110baCAS |

Grünewald G, Kaiser K, Jahn R, Guggenberger G (2006) Organic matter stabilization in young calcareous soils as revealed by density fractionation and analysis of lignin-derived constituents. Organic Geochemistry 37, 1573–1589.
Organic matter stabilization in young calcareous soils as revealed by density fractionation and analysis of lignin-derived constituents.Crossref | GoogleScholarGoogle Scholar |

Grünewald G, Kaiser K, Jahn R (2008) Hydrotalcite—A potentially significant sorbent of organic matter in calcareous alkaline soils. Geoderma 147, 141–150.
Hydrotalcite—A potentially significant sorbent of organic matter in calcareous alkaline soils.Crossref | GoogleScholarGoogle Scholar |

Heanes DL (1984) Determination of total organic-C in soils by an improved chromic acid digestion and spectrophotometric procedure. Communications in Soil Science and Plant Analysis 15, 1191–1213.
Determination of total organic-C in soils by an improved chromic acid digestion and spectrophotometric procedure.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL2cXmt12itL8%3D&md5=0f3a9b7361981a4a5d4ce181fd234098CAS |

Heron G, Barcelona MJ, Andersen ML, Christensen TH (1997) Determination of nonvolatile organic carbon in aquifer solids after carbonate removal by sulfurous acid. Ground Water 35, 6–11.
Determination of nonvolatile organic carbon in aquifer solids after carbonate removal by sulfurous acid.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2sXislaisQ%3D%3D&md5=27c0ae36bac860257db9b9da294e8835CAS |

Hockaday WC, Masiello CA, Randerson JT, Smernik RJ, Baldock JA, Chadwick OA, Harden JW (2009) Measurement of soil carbon oxidation state and oxidative ratio by 13C nuclear magnetic resonance. Journal of Geophysical Research 114, G02014
Measurement of soil carbon oxidation state and oxidative ratio by 13C nuclear magnetic resonance.Crossref | GoogleScholarGoogle Scholar |

Holloway RE, Bertrand I, Frischke AJ, Brace DM, McLaughlin MJ, Shepperd W (2001) Improving fertiliser efficiency on calcareous and alkaline soils with fluid sources of P, N and Zn. Plant and Soil 236, 209–219.
Improving fertiliser efficiency on calcareous and alkaline soils with fluid sources of P, N and Zn.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXptlKhurc%3D&md5=227a6f22fd73b1ef73be6506f9f69af1CAS |

Ingalls AE, Aller RC, Lee C, Wakeham SG (2004) Organic matter diagenesis in shallow water carbonate sediments. Geochimica et Cosmochimica Acta 68, 4363–4379.
Organic matter diagenesis in shallow water carbonate sediments.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXovVSgtLg%3D&md5=ce06c5c3bf5d45772e6d3432bb192453CAS |

Isbell RF (2002) ‘The Australian Soil Classification.’ (CSIRO Publishing: Melbourne)

Jacob DE, Soldati AL, Wirth R, Huth J, Wehrmeister U, Hofmeister W (2008) Nanostructure, composition and mechanisms of bivalve shell growth. Geochimica et Cosmochimica Acta 72, 5401–5415.
Nanostructure, composition and mechanisms of bivalve shell growth.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXht1yrs7rP&md5=a01e1823326edbc7b8b207537608d3c3CAS |

Kerven GL, Menzies NW, Geyer MD (2000) Soil carbon determination by high temperature combustion—a comparison with dichromate oxidation procedures and the influence of charcoal and carbonate carbon on the measured value. Communications in Soil Science and Plant Analysis 31, 1935–1939.
Soil carbon determination by high temperature combustion—a comparison with dichromate oxidation procedures and the influence of charcoal and carbonate carbon on the measured value.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXmvVGlsLs%3D&md5=092e1e1353297ddd917621f7e0f24893CAS |

Kowalenko CG (2001) Assessment of Leco CNS-2000 analyzer for simultaneously measuring total carbon, nitrogen and sulphur in soil. Communications in Soil Science and Plant Analysis 32, 2065–2078.
Assessment of Leco CNS-2000 analyzer for simultaneously measuring total carbon, nitrogen and sulphur in soil.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXns1Wlsbo%3D&md5=54971c23db691df7a751e90b7d46b7b2CAS |

Lettens S, De Vos B, Quataert P, van Wesemael B, Muys B, van Orshoven J (2007) Variable carbon recovery of Walkley-Black analysis and implications for national soil organic carbon accounting. European Journal of Soil Science 58, 1244–1253.
Variable carbon recovery of Walkley-Black analysis and implications for national soil organic carbon accounting.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXitVWmsQ%3D%3D&md5=604e793ffcf95a833431f37959b1b6dcCAS |

Manlay RJ, Feller C, Swift MJ (2007) Historical evolution of soil organic matter concepts and their relationships with the fertility and sustainability of cropping systems. Agriculture, Ecosystems & Environment 119, 217–233.
Historical evolution of soil organic matter concepts and their relationships with the fertility and sustainability of cropping systems.Crossref | GoogleScholarGoogle Scholar |

Matejovic I (1997) Determination of carbon and nitrogen in samples of various soils by the dry combustion. Communications in Soil Science and Plant Analysis 28, 1499–1511.
Determination of carbon and nitrogen in samples of various soils by the dry combustion.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2sXnsVCltbg%3D&md5=14193f2c99595db0ae873a0059a8861fCAS |

McBeath TM, Armstrong RD, Lombi E, McLaughlin MJ, Holloway RE (2005) Responsiveness of wheat (Triticum aestivum) to liquid and granular phosphorus fertilisers in southern Australian soils. Australian Journal of Soil Research 43, 203–212.
Responsiveness of wheat (Triticum aestivum) to liquid and granular phosphorus fertilisers in southern Australian soils.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXivVOjurc%3D&md5=992d229d9a73a70c3486ac3265e514d7CAS |

Merry RH, Spouncer LR (1988) The measurement of carbon in soils using a microprocessor-controlled resistance furnace. Communications in Soil Science and Plant Analysis 19, 707–720.
The measurement of carbon in soils using a microprocessor-controlled resistance furnace.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL1cXktlOitbc%3D&md5=5ee4cfb8b7a127aabab1d9ca9f92a1b6CAS |

Mikhailova EA, Noble RRP, Post CJ (2003) Comparison of soil organic carbon recovery by Walkley-Black and dry combustion methods in the Russian Chernozem. Communications in Soil Science and Plant Analysis 34, 1853–1860.
Comparison of soil organic carbon recovery by Walkley-Black and dry combustion methods in the Russian Chernozem.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXltlGlsrw%3D&md5=d91ed22820f26d0799955b81157830e8CAS |

Morse JW, Arvidson RS, Lüttge A (2007) Calcium carbonate formation and dissolution. Chemical Reviews 107, 342–381.
Calcium carbonate formation and dissolution.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXhtVOmsbc%3D&md5=24a2b77d3e73fcb539373c065ed150c2CAS |

Nelson DW, Sommers LE (1996) Total carbon, organic carbon, and organic matter. In ‘Methods of soil analysis. Part 3. Chemical methods’. (Ed. DL Sparks) pp. 961–1010. (Soil Society of America and American Society of Agronomy: Madison, WI)

Rayment GE, Higginson FR (1992) ‘Australian laboratory handbook of soil and water chemical methods.’ (Inkata Press: Melbourne)

Santi C, Certini G, D’Acqui LP (2006) Direct determination of organic carbon by dry combustion in soils with carbonates. Communications in Soil Science and Plant Analysis 37, 155–162.
Direct determination of organic carbon by dry combustion in soils with carbonates.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28XksF2isQ%3D%3D&md5=bbe425a161d93636e2ab218177bc23cfCAS |

Schmidt MWI, Knicker H, Hatcher PG, Kogel-Knabner I (1997) Improvement of 13C and 15N CPMAS NMR spectra of bulk soils, particle size fractions and organic material by treatment with 10% hydrofluoric acid. European Journal of Soil Science 48, 319–328.
Improvement of 13C and 15N CPMAS NMR spectra of bulk soils, particle size fractions and organic material by treatment with 10% hydrofluoric acid.Crossref | GoogleScholarGoogle Scholar |

Skjemstad JO, Clarke P, Taylor JA, Oades JM, Newman RH (1994) The removal of magnetic materials from surface soils. A solid state 13C CP/MAS n.m.r. study. Australian Journal of Soil Research 32, 1215–1229.
The removal of magnetic materials from surface soils. A solid state 13C CP/MAS n.m.r. study.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2MXis1Git7c%3D&md5=67ad8b122ad4848c723ec645cc4f063fCAS |

Skjemstad JO, Janik LJ, Taylor JA (1998) Non-living soil organic matter: what do we know about it? Australian Journal of Experimental Agriculture 38, 667–680.
Non-living soil organic matter: what do we know about it?Crossref | GoogleScholarGoogle Scholar |

Soil Survey Staff (1999) ‘Soil Taxonomy.’ 2nd edn (United States Department of Agriculture, Natural Resources Conservation Service: Washington, DC)

Soon YK, Aboud S (1991) A comparison of some methods for soil organic carbon determination. Communications in Soil Science and Plant Analysis 22, 943–954.
A comparison of some methods for soil organic carbon determination.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3MXltlCqtro%3D&md5=5cad9d955d67ca09737caf8b0cca1de3CAS |

Suess E (1970) Interaction of organic compounds with calcium carbonate—I. Association phenomena and geochemical implications. Geochimica et Cosmochimica Acta 34, 157–168.
Interaction of organic compounds with calcium carbonate—I. Association phenomena and geochemical implications.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE3cXpt1emsg%3D%3D&md5=7ee6655ab12178c59f09b4b56e12682eCAS |

Telek G, Marshall N (1974) Using a CHN analyzer to reduce carbonate interference in particulate organic carbon analyses. Marine Biology 24, 219–221.
Using a CHN analyzer to reduce carbonate interference in particulate organic carbon analyses.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE2cXktFKmu7w%3D&md5=9da31edb83e2eb8e7e8e94c4987a9462CAS |

Walkley A, Black IA (1934) An examination of the Degtjareff method for determining soil organic matter, and a proposed modification of the chromic acid titration method. Soil Science 37, 29–38.
An examination of the Degtjareff method for determining soil organic matter, and a proposed modification of the chromic acid titration method.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaA2cXitlGmug%3D%3D&md5=fc64e31f35bd31ad014c98e8c0a3d186CAS |

Wright AF, Bailey JS (2001) Organic carbon, total carbon, and total nitrogen determinations in soils of variable calcium carbonate contents using a Leco CN-2000 dry combustion analyzer. Communications in Soil Science and Plant Analysis 32, 3243–3258.
Organic carbon, total carbon, and total nitrogen determinations in soils of variable calcium carbonate contents using a Leco CN-2000 dry combustion analyzer.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XhtFOhtg%3D%3D&md5=09f84c786ff6b122ae4ccd5bf8ea15efCAS |