Detection of Biochar Carbon by Fluorescence and Near-Infrared-Based Chemometrics

  • Minori UchimiyaEmail author
  • Alan J. Franzluebbers
  • Zhongzhen Liu
  • Marshall C. Lamb
  • Ronald. B. Sorensen


Large-scale biochar field trials have been conducted worldwide to test for “carbon negative strategy” in the event of carbon credit and if other subsidies become enacted in the future. Once amended to the soil, biochar engages in complex organo-mineral interactions, fragmentation, transport, and other aging mechanisms exhibiting interactions with treatments including the irrigation and fertilizer application. As a result, quantitative tracing of biochar carbon relying on the routinely measured soil parameters, e.g., total/particulate organic carbon, poses a significant analytical uncertainty. This study utilized two biochar field trial sites to calibrate for the biochar carbon structure and quantity based on the infrared- and fluorescence-based chemometrics: (1) slow pyrolysis biochar pellets on kaolinitic Greenville fine sandy loam in Georgia and (2) fast pyrolysis biochar powder on Crider silt loam in Kentucky. Partial least squares-based calibration was constructed to predict the amount of solvent (toluene/methanol)-extractable fluorescence fingerprint (290/350 nm excitation and emission peak) attributed to biochar based on the comparison with the authentic standard. Near-infrared-based detection was sensitive to the C–H and C–C bands, as a function of biochar loading and the particulate organic carbon content (< 53 μm) of the bulk soil. Developed chemometrics could be used to validate tarry carbon structures intrinsic to biochar additives, as the impact of biochar additives on soil chemical properties (pH, electric conductivity, and dissolved organic carbon) becomes attenuated over time.


Thermochemical conversion Biomass Black carbon Clay Humic substance 


Supplementary material

10498_2018_9347_MOESM1_ESM.doc (2.6 mb)
Supplementary material 1 (DOC 2692 kb)


  1. Allen RM, Laird DA (2013) Quantitative prediction of biochar soil amendments by near-infrared reflectance spectroscopy. Soil Sci Soc Am J 77:1784–1794CrossRefGoogle Scholar
  2. Andrade CR, Trugilho PF, Hein PRG, Lima JT, Napoli A (2012) Near infrared spectroscopy for estimating eucalyptus charcoal properties. J Near Infrared Spectrosc 20:657–666CrossRefGoogle Scholar
  3. ASTM D5159 (2014) Standard guide for dusting attrition of granular activated carbon. American Society for Testing and Materials, West ConshohockenGoogle Scholar
  4. Bednarz CW, Harris GH, Shurley WD (2000) Agronomic and economic analyses of cotton starter fertilizers. Agron J 92:766–771CrossRefGoogle Scholar
  5. Brewer CE, Schmidt-Rohr K, Satrio JA, Brown RC (2009) Characterization of biochar from fast pyrolysis and gasification systems. Environ Prog Sustain Energy 28:386–396CrossRefGoogle Scholar
  6. Brewer CE, Unger R, Schmidt-Rohr K, Brown RC (2011) Criteria to select biochars for field studies based on biochar chemical properties. Bioenergy Res 4:312–323CrossRefGoogle Scholar
  7. Christensen JH, Hansen AB, Mortensen J, Andersen O (2005) Characterization and matching of oil samples using fluorescence spectroscopy and parallel factor analysis. Anal Chem 77:2210–2217CrossRefGoogle Scholar
  8. Davis-Carter JG, Shuman LM (1993) Influence of texture and pH of kaolinitic soils on zinc fractions and zinc uptake by peanuts. Soil Sci 155:376–384CrossRefGoogle Scholar
  9. Faber NM, Bro R (2002) Standard error of prediction for multiway PLS: 1. Background and a simulation study. Chemom Intell Lab Syst 61:133–149CrossRefGoogle Scholar
  10. Fu H, Liu H, Mao J, Chu W, Li Q, Alvarez PJJ, Qu X, Zhu D (2016) Photochemistry of dissolved black carbon released from biochar: reactive oxygen species generation and phototransformation. Environ Sci Technol 50:1218–1226CrossRefGoogle Scholar
  11. Fukushi K, Sakai H, Itono T, Tamura A, Arai S (2014) Desorption of intrinsic cesium from smectite: inhibitive effects of clay particle organization on cesium desorption. Environ Sci Technol 48:10743–10749CrossRefGoogle Scholar
  12. Gimbert LJ, Haygarth PM, Beckett R, Worsfold PJ (2005) Comparison of centrifugation and filtration techniques for the size fractionation of colloidal material in soil suspensions using sedimentation field-flow fractionation. Environ Sci Technol 39:1731–1735CrossRefGoogle Scholar
  13. Hanke UM, Reddy CM, Braun ALL, Coppola AI, Haghipour N, McIntyre CP, Wacker L, Xu L, McNichol AP, Abiven S, Schmidt MWI, Eglinton TI (2017) What on earth have we been burning? Deciphering sedimentary records of pyrogenic carbon. Environ Sci Technol 51:12972–12980CrossRefGoogle Scholar
  14. Ishii SKL, Boyer TH (2012) Behavior of reoccurring PARAFAC components in fluorescent dissolved organic matter in natural and engineered systems: a critical review. Environ Sci Technol 46:2006–2017CrossRefGoogle Scholar
  15. Jaffé R, Ding Y, Niggemann J, Vähätalo AV, Stubbins A, Spencer RGM, Campbell J, Dittmar T (2013) Global charcoal mobilization from soils via dissolution and riverine transport to the oceans. Science 340:345–347CrossRefGoogle Scholar
  16. Jonker MT, Koelmans AA (2002) Extraction of polycyclic aromatic hydrocarbons from soot and sediment: solvent evaluation and implications for sorption mechanism. Environ Sci Technol 36:4107–4113CrossRefGoogle Scholar
  17. Kusumo BH, Arbestain MC, Mahmud AF, Hedley MJ, Hedley CB, Pereira RC, Wang T, Singh BP (2014) Assessing biochar stability indices using near infrared spectroscopy. J Near Infrared Spectrosc 22:313–328CrossRefGoogle Scholar
  18. Laird DA, Fleming P, Davis DD, Horton R, Wang B, Karlen DL (2010) Impact of biochar amendments on the quality of a typical midwestern agricultural soil. Geoderma 158:443–449CrossRefGoogle Scholar
  19. Leblanc J, Uchimiya M, Ramakrishnan G, Castaldi MJ, Orlov A (2016) Across-phase biomass pyrolysis stoichiometry, energy balance, and product formation kinetics. Energy Fuel 30:6537–6546CrossRefGoogle Scholar
  20. Lehmann J (2007) A handful of carbon. Nature 447:143–144CrossRefGoogle Scholar
  21. Major J, Lehmann J, Rondon M, Goodale C (2010) Fate of soil-applied black carbon: downward migration, leaching and soil respiration. Glob Change Biol 16:1366–1379CrossRefGoogle Scholar
  22. McNeil VH, Cox ME (2000) Relationship between conductivity and analysed composition in a large set of natural surface-water samples, Queensland, Australia. Environ Geol 39:1325–1333CrossRefGoogle Scholar
  23. Metrohm AG (2013) A guide to near-infrared spectroscopic analysis of industrial manufacturing processes, Herisau, Switzerland.
  24. Miller RW, Donahue RL (1990) Soils: an introduction to soils and plant growth. Prentice Hall, Englewood CliffsGoogle Scholar
  25. Mochidzuki K, Soutric F, Tadokoro K, Antal MJ Jr, Tóth M, Zelei B, Várhegyi G (2003) Electrical and physical properties of carbonized charcoals. Ind Eng Chem Res 42:5140–5151CrossRefGoogle Scholar
  26. Morita S (2004–2005) 2Dshige 1.3. Kwansei-Gakuin University. Accessed 18 May 2018
  27. Murphy KR, Stedmon CA, Graeber D, Bro R (2013) Fluorescence spectroscopy and multi-way techniques. PARAFAC Anal Methods 5:6557–6566CrossRefGoogle Scholar
  28. National Academy of Sciences (2018) Science breakthroughs to advance food and agricultural research by 2030. The National Academies Press, Washington, DC. Accessed 9 Oct 2018
  29. Noda I (2018) Chapter 2—advances in two-dimensional correlation spectroscopy (2DCOS). In: Laane J (ed) Frontiers and advances in molecular spectroscopy. Elsevier, Amsterdam, pp 47–75CrossRefGoogle Scholar
  30. Noda I, Dowrey AE, Marcott C, Story GM, Ozaki Y (2000) Generalized two-dimensional correlation spectroscopy. Appl Spectrosc 54:236A–248ACrossRefGoogle Scholar
  31. Pignatello JJ, Uchimiya M, Abiven S, Schmidt MWI (2015) Evolution of black carbon properties in soil. In: Lehmann J, Joseph S (eds) Biochar for environmental management: science, technology, and implementation. Taylor & Frances, London, pp 195–234Google Scholar
  32. Sainju UM, Whitehead WF, Singh BP (2003) Cover crops and nitrogen fertilization effects on soil aggregation and carbon and nitrogen pools. Can J Soil Sci 83:155–165CrossRefGoogle Scholar
  33. Siebers N, Abdelrahman H, Krause L, Amelung W (2018) Bias in aggregate geometry and properties after disintegration and drying procedures. Geoderma 313:163–171CrossRefGoogle Scholar
  34. Sigmund G, Huber D, Bucheli TD, Baumann M, Borth N, Guebitz GM, Hofmann T (2017) Cytotoxicity of biochar: a workplace safety concern? Environ Sci Technol Lett 4:362–366CrossRefGoogle Scholar
  35. Sorensen RB, Lamb MC (2016) Crop yield response to increasing biochar rates. J Crop Improv 30:703–712CrossRefGoogle Scholar
  36. Stedmon CA, Bro R (2008) Characterizing dissolved organic matter fluorescence with parallel factor analysis: a tutorial. Limnol Oceanogr Methods 6:572–579CrossRefGoogle Scholar
  37. Uchimiya M (2014) Influence of pH, ionic strength, and multidentate ligand on the interaction of CdII with biochars. ACS Sustain Chem Eng 2:2019–2027CrossRefGoogle Scholar
  38. Uchimiya M, Ohno T, He Z (2013a) Pyrolysis temperature-dependent release of dissolved organic carbon from plant, manure, and biorefinery wastes. J Anal Appl Pyrol 104:84–94CrossRefGoogle Scholar
  39. Uchimiya M, Orlov A, Ramakrishnan G, Sistani K (2013b) In situ and ex situ spectroscopic monitoring of biochar’s surface functional groups. J Anal Appl Pyrol 102:53–59CrossRefGoogle Scholar
  40. Uchimiya M, Hiradate S, Antal MJ (2015) Influence of carbonization methods on the aromaticity of pyrogenic dissolved organic carbon. Energy Fuel 29:2503–2513CrossRefGoogle Scholar
  41. Uchimiya M, Liu Z, Sistani K (2016) Field-scale fluorescence fingerprinting of biochar-borne dissolved organic carbon. J Environ Manag 169:184–190CrossRefGoogle Scholar
  42. Uchimiya M, Pignatello JJ, White JC, Hu S, Ferreira PJ (2017) Structural transformation of biochar black carbon by C60 superstructure: environmental implications. Sci Rep 7:11787CrossRefGoogle Scholar
  43. Wang C, Walter MT, Parlange JY (2013) Modeling simple experiments of biochar erosion from soil. J Hydrol 499:140–145CrossRefGoogle Scholar
  44. Wetzel DL (1983) Near-infrared reflectance analysis. Anal Chem 55(12):1165A–1176ACrossRefGoogle Scholar
  45. Yi P, Pignatello JJ, Uchimiya M, White JC (2015) Heteroaggregation of cerium oxide nanoparticles and nanoparticles of pyrolyzed biomass. Environ Sci Technol 49:13294–13303CrossRefGoogle Scholar
  46. Zhang W, Niu J, Morales VL, Chen X, Hay AG, Lehmann J, Steenhuis TS (2010) Transport and retention of biochar particles in porous media: effect of pH, ionic strength, and particle size. Ecohydrology 3:497–508CrossRefGoogle Scholar

Copyright information

© © Springer Nature B.V. 2019

Authors and Affiliations

  • Minori Uchimiya
    • 1
    Email author
  • Alan J. Franzluebbers
    • 2
  • Zhongzhen Liu
    • 1
    • 3
  • Marshall C. Lamb
    • 4
  • Ronald. B. Sorensen
    • 4
  1. 1.USDA-ARS Southern Regional Research CenterNew OrleansUSA
  2. 2.USDA-ARS Plant Science Research UnitRaleighUSA
  3. 3.Institute of Agricultural Resources and EnvironmentGuangdong Academy of Agricultural SciencesGuangdongChina
  4. 4.USDA-ARS National Peanut Research LaboratoryDawsonUSA

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