Assessment of the surface chemistry of wood-derived biochars using wet chemistry, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy
R. Calvelo Pereira A C , M. Camps Arbestain A , M. Vazquez Sueiro A and J. A. Maciá-Agulló B
+ Author Affiliations
- Author Affiliations
A New Zealand Biochar Research Centre, Soil and Earth Sciences Group, Institute of Agriculture and Environment, Massey University, Private Bag 11222, Palmerston North 4442, New Zealand.
B Instituto Universitario de Tecnología Química CSIC-UPV, Universidad Politécnica de Valencia, Av. De los Naranjos s/n, 46022, Valencia, Spain.
C Corresponding author. Email: R.Calvelopereira@massey.ac.nz
Soil Research 53(7) 753-762 https://doi.org/10.1071/SR14194
Submitted: 29 July 2014 Accepted: 13 April 2015 Published: 27 October 2015
Abstract
In order to understand the reactivity of biochar in soil, we thoroughly examined the carbonaceous surface of different biochars, paying particular attention to the distribution of oxygen-containing functional groups. Biochar was produced from pine, poplar and willow at two different temperatures (400 and 550°C) and characterised using elemental analysis and wet chemistry (Boehm and potentiometric titrations, cation-exchange capacity (CEC) measurement). In addition, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses were performed on both untreated and acid-washed biochar samples. Qualitative relationships were observed between data generated from the titration methods under investigation and XPS analyses, both describing the general distribution of oxygen-containing surface functional groups. Total acidity of biochar ranged widely, between 32 and 1067 mmol kg–1, and was mostly attributed to the presence of hydroxyl or phenol groups. The number of functional groups containing oxygen decreased with increasing pyrolysis temperature, mainly because of a decrease in the content of phenol groups. A quantitative comparison of titrations and CEC (i.e. biochar’s ion-exchange capacity) measurements was compromised by a masking effect caused by the biochar’s inorganic fraction (<8%). An acid-washing step with nitric acid was shown not to alter the biochar surface systematically. The use of potentiometric titrations with an acid-washing pretreatment proved to be suitable to quantify biochar acidic functional groups, and hence biochar acidity.
Additional keywords: acidity, aromaticity, potentiometric titrations, spectroscopy, surface functional groups.
References
Artz RRE, Chapman SJ, Jean Robertson AH, Potts JM, Laggoun-Défarge F, Gogo S, Comont L, Disnar J-R, Francez A-J (2008) FTIR spectroscopy can be used as a screening tool for organic matter quality in regenerating cutover peatlands. Soil Biology & Biochemistry 40, 515–527.| FTIR spectroscopy can be used as a screening tool for organic matter quality in regenerating cutover peatlands.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXhtlajsL7P&md5=ef784a70fa9950d9598d031898591728CAS |
Atkinson C, Fitzgerald J, Hipps N (2010) Potential mechanisms for achieving agricultural benefits from biochar application to temperate soils: a review. Plant and Soil 337, 1–18.
| Potential mechanisms for achieving agricultural benefits from biochar application to temperate soils: a review.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXhsVWmtb3J&md5=88da5593dd6ce38d632215aa26e706abCAS |
Bandosz TJ, Jagiello J, Schwarz JA (1992) Comparison of methods to assess surface acidic groups on activated carbons. Analytical Chemistry 64, 891–895.
| Comparison of methods to assess surface acidic groups on activated carbons.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK38XhsF2msLw%3D&md5=951cab997b0714bc5e98ad72c00fa46eCAS |
Biniak S, Szymański G, Siedlewski J, Światkowski A (1997) The characterization of activated carbons with oxygen and nitrogen surface groups. Carbon 35, 1799–1810.
| The characterization of activated carbons with oxygen and nitrogen surface groups.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXnt1Wlsw%3D%3D&md5=a7f81fb2cd544cf69c3e73edf147b510CAS |
Blakemore LC, Searle PL, Daly BK (1987) ‘Methods for chemical analysis of soils.’ NZ Soil Bureau Scientific Report 80, Lower Hutt. (NZ Soil Bureau, Department of Scientific and Industrial Research: Lower Hutt, New Zealand)
Boehm HP (2002) Surface oxides on carbon and their analysis: a critical assessment. Carbon 40, 145–149.
| Surface oxides on carbon and their analysis: a critical assessment.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXptFCht7s%3D&md5=725c02b0759354a7a3ceeca95e7342e4CAS |
Calvelo Pereira R, Kaal J, Camps Arbestain M, Pardo Lorenzo R, Aitkenhead W, Hedley M, Macías F, Hindmarsh J, Maciá-Agulló JA (2011) Contribution to characterisation of biochar to estimate the labile fraction of carbon. Organic Geochemistry 42, 1331–1342.
| Contribution to characterisation of biochar to estimate the labile fraction of carbon.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhsVWktrzL&md5=9c8f35ea97b32666e58092f24f451f82CAS |
Calvelo Pereira R, Camps Arbestain M, Kaal J, Vazquez Sueiro M, Sevilla M, Hindmarsh J (2014) Detailed carbon chemistry in charcoals from pre-European Māori gardens of New Zealand as a tool for understanding biochar stability in soils. European Journal of Soil Science 65, 83–95.
| Detailed carbon chemistry in charcoals from pre-European Māori gardens of New Zealand as a tool for understanding biochar stability in soils.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2cXnt1egtg%3D%3D&md5=72d1407c3aafff22332f2e730caa4559CAS |
Cheng C-H, Lehmann J, Engelhard MH (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=1ff342736b3fca9efd0792a13c96f8d1CAS |
Chun Y, Sheng G, Chiou CT, Xing B (2004) Compositions and sorptive properties of crop residue-derived chars. Environmental Science & Technology 38, 4649–4655.
| Compositions and sorptive properties of crop residue-derived chars.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXlvVOlsLo%3D&md5=53551ebf1686afd588ed62a552681395CAS |
Cooke JD, Hamilton-Taylor J, Tipping E (2007) On the acid−base properties of humic acid in soil. Environmental Science & Technology 41, 465–470.
| On the acid−base properties of humic acid in soil.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28Xht1OmsL%2FI&md5=c1f0844c8bf75d8e7522fca5abd24cd6CAS |
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.
| Applicability of solid-state 13C CP/MAS NMR analysis in Spodosols: chemical removal of magnetic materials.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXns12m&md5=61ba0402376f99f697a2ba167aed66b0CAS |
Essington ME (2004) ‘Soil and water chemistry. An integrative approach.’ (CRC Press: Boca Raton, FL)
Glaser B, Balashov E, Haumaier L, Guggenberger G, Zech W (2000) Black carbon in density fractions of anthropogenic soils of the Brazilian Amazon region. Organic Geochemistry 31, 669–678.
| Black carbon in density fractions of anthropogenic soils of the Brazilian Amazon region.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXmsFSqu78%3D&md5=4621903ba6d9b5467156d365a0cb169dCAS |
Goertzen SL, Thériault KD, Oickle AM, Tarasuk AC, Andreas HA (2010) Standardization of the Boehm titration. Part I. CO2 expulsion and endpoint determination. Carbon 48, 1252–1261.
| Standardization of the Boehm titration. Part I. CO2 expulsion and endpoint determination.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXnt1arsQ%3D%3D&md5=cdcbae54551f46961e8c183255ad4e95CAS |
Hina K, Bishop P, Arbestain MC, Calvelo-Pereira R, Maciá-Agulló JA, Hindmarsh J, Hanly JA, Macías F, Hedley MJ (2010) Producing biochars with enhanced surface activity through alkaline pretreatment of feedstocks. Australian Journal of Soil Research 48, 606–617.
| Producing biochars with enhanced surface activity through alkaline pretreatment of feedstocks.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXht1Sru7nK&md5=f069201288524b5234e72fdd8a64c3caCAS |
Jeffery S, Bezemer TM, Cornelissen G, Kuyper TW, Lehmann J, Mommer L, Sohi SP, van de Voorde TFJ, Wardle DA, van Groenigen JW (2015) The way forward in biochar research: targeting trade-offs between the potential wins. GCB Bioenergy 7, 1–13.
| The way forward in biochar research: targeting trade-offs between the potential wins.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2cXitFGku7nJ&md5=9f62ecbe19d93342dc37c0733383045eCAS |
Joseph SD, Camps Arbestain M, Lin Y, Munroe P, Chia CH, Hook J, Van Zwieten L, Kimber S, Cowie A, Singh BP, Lehmann J, Foidl N, Smernik RJ, Amonette JE (2010) An investigation into the reactions of biochar in soil. Australian Journal of Soil Research 48, 501–515.
| An investigation into the reactions of biochar in soil.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXht1Sru7bM&md5=9daf8a9f04eea02dc32da4ee0be9c23eCAS |
Knicker H, Hilscher A, González-Vila FJ, Almendros G (2008) A new conceptual model for the structural properties of char produced during vegetation fires. Organic Geochemistry 39, 935–939.
| A new conceptual model for the structural properties of char produced during vegetation fires.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXovFOltL4%3D&md5=9d209bb079d90a9eba2902158ea5bc09CAS |
Kwon S, Pignatello JJ (2005) Effect of natural organic substances on the surface and adsorptive properties of environmental black carbon (char): pseudo pore blockage by model lipid components and its implications for N2-probed surface properties of natural sorbents. Environmental Science & Technology 39, 7932–7939.
| Effect of natural organic substances on the surface and adsorptive properties of environmental black carbon (char): pseudo pore blockage by model lipid components and its implications for N2-probed surface properties of natural sorbents.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXhtVWhs7jO&md5=b414e1bd219273eda43d93eab782cf37CAS |
László K, Tombácz E, Josepovits K (2001) Effect of activation on the surface chemistry of carbons from polymer precursors. Carbon 39, 1217–1228.
| Effect of activation on the surface chemistry of carbons from polymer precursors.Crossref | GoogleScholarGoogle Scholar |
Lehmann J (2007) Bio-energy in the black. Frontiers in Ecology and the Environment 5, 381–387.
| Bio-energy in the black.Crossref | GoogleScholarGoogle Scholar |
Liang B, Lehmann J, Solomon D, Kinyangi J, Grossman J, O’Neill B, Skjemstad JO, Thies J, Luizao FJ, Petersen J, Neves EG (2006) Black carbon increases cation exchange capacity in soils. Soil Science Society of America Journal 70, 1719–1730.
| Black carbon increases cation exchange capacity in soils.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28Xpsl2lsbo%3D&md5=4b23acbe97059601e412f91a79e289aeCAS |
Lopez-Ramon MV, Stoeckli F, Moreno-Castilla C, Carrasco-Marin F (1999) On the characterization of acidic and basic surface sites on carbons by various techniques. Carbon 37, 1215–1221.
| On the characterization of acidic and basic surface sites on carbons by various techniques.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXkt12jtrg%3D&md5=70557613efa330e2843f4ffecaeaf917CAS |
Matsue N, Wada K (1985) A new equilibration method for cation-exchange capacity measurement. Soil Science Society of America Journal 49, 574–578.
| A new equilibration method for cation-exchange capacity measurement.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL2MXktlKlsbY%3D&md5=78dcc6f81768c4630c207d505dc75578CAS |
Moreno-Castilla C, López-Ramón MV, Carrasco-Marín F (2000) Changes in surface chemistry of activated carbons by wet oxidation. Carbon 38, 1995–2001.
| Changes in surface chemistry of activated carbons by wet oxidation.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXmsFyks7o%3D&md5=6625f00f6dd919c333cf7726d1631463CAS |
Mukherjee A, Zimmerman AR, Harris W (2011) Surface chemistry variations among a series of laboratory-produced biochars. Geoderma 163, 247–255.
| Surface chemistry variations among a series of laboratory-produced biochars.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXnt1amsrg%3D&md5=972bad836ed27980a236692adc0fcc11CAS |
Nagodavithane CL, Singh B, Fang Y (2014) Effect of ageing on surface charge characteristics and adsorption behaviour of cadmium and arsenate in two contrasting soils amended with biochar. Soil Research 52, 155–163.
| Effect of ageing on surface charge characteristics and adsorption behaviour of cadmium and arsenate in two contrasting soils amended with biochar.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2cXltFehuro%3D&md5=edc8e8ea1aaff50cd2f3345ccd1ea033CAS |
Petit C, Seredych M, Bandosz TJ (2009) Revisiting the chemistry of graphite oxides and its effect on ammonia adsorption. Journal of Materials Chemistry 19, 9176–9185.
| Revisiting the chemistry of graphite oxides and its effect on ammonia adsorption.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXhsFSgtrnP&md5=a07ab6b07fb625c0c777c4d12470c716CAS |
Pradhan BK, Sandle NK (1999) Effect of different oxidizing agent treatments on the surface properties of activated carbons. Carbon 37, 1323–1332.
| Effect of different oxidizing agent treatments on the surface properties of activated carbons.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXkt12jt7k%3D&md5=6f6259f0c9908b968ee50f2e99f91800CAS |
Rayment GE, Lyons DJ (2011) ‘Soil chemical methods – Australasia.’ (CSIRO Publishing: Melbourne)
Ritchie JD, Perdue EM (2008) Analytical constraints on acidic functional groups in humic substances. Organic Geochemistry 39, 783–799.
| Analytical constraints on acidic functional groups in humic substances.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXmt1eis7g%3D&md5=ea9acc0fe44d4b3e3072da0a03e7d384CAS |
Rutherford DW, Wershaw RL, Reeves JB, Survey G (2008) ‘Development of acid functional groups and lactones during the thermal degradation of wood and wood components.’ (US Geological Survey: Reston, VI, USA)
Schmidt M, Knicker H, Hatcher P, 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 |
Singh B, Singh BP, Cowie AL (2010) Characterisation and evaluation of biochars for their application as a soil amendment. Soil Research 48, 516–525.
| Characterisation and evaluation of biochars for their application as a soil amendment.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXht1Sru7nJ&md5=ec763488e76207385f6e3752b1fefb33CAS |
Singh B, Fang Y, Cowie BCC, Thomsen L (2014) NEXAFS and XPS characterisation of carbon functional groups of fresh and aged biochars. Organic Geochemistry 77, 1–10.
| NEXAFS and XPS characterisation of carbon functional groups of fresh and aged biochars.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2cXhs1ehsLfK&md5=ecc77537d8237f43c582c4c0a5a95a8cCAS |
Spokas KA (2010) Review of the stability of biochar in soils: predictability of O : C molar ratios. Carbon Management 1, 289–303.
| Review of the stability of biochar in soils: predictability of O : C molar ratios.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXhsFGrs7fO&md5=937e51156e5060c2f626f4ab9560a962CAS |
Tatzber M, Stemmer M, Spiegel H, Katzlberger C, Haberhauer G, Gerzabek M (2007) An alternative method to measure carbonate in soils by FT-IR spectroscopy. Environmental Chemistry Letters 5, 9–12.
| An alternative method to measure carbonate in soils by FT-IR spectroscopy.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXislygt78%3D&md5=a49aad26ad97bf85aed22d294e8bc198CAS |
Uchimiya M, Lima IM, Klasson KT, Wartelle LH (2010) Contaminant immobilization and nutrient release by biochar soil amendment: roles of natural organic matter. Chemosphere 80, 935–940.
| Contaminant immobilization and nutrient release by biochar soil amendment: roles of natural organic matter.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXptVCns78%3D&md5=39c4abbd069e82ba6537a62f4ecce7deCAS | 20542314PubMed |
Verheijen FGA, Jeffery S, Bastos AC, van der Velde M, Diafas I (2009) ‘Biochar application to soils. A critical scientific review of effects on soil properties, processes and functions.’ EUR 24099 EN. (Office for the Official Publications of the European Communities: Luxembourg)
Wang S, Wang K, Liu Q, Gu Y, Luo Z, Cen K, Fransson T (2009) Comparison of the pyrolysis behavior of lignins from different tree species. Biotechnology Advances 27, 562–567.
| Comparison of the pyrolysis behavior of lignins from different tree species.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXntVyqsLk%3D&md5=6a58b4b19daa10ea66bc4d3961f14983CAS | 19393737PubMed |
Wang T, Camps-Arbestain M, Hedley M (2013) Predicting C aromaticity of biochars based on their elemental composition. Organic Geochemistry 62, 1–6.
| Predicting C aromaticity of biochars based on their elemental composition.Crossref | GoogleScholarGoogle Scholar |
Yao FX, Camps Arbestain M, Virgel S, Blanco F, Arostegui J, Maciá-Agulló JA, Macías F (2010) Simulated geochemical weathering of a mineral ash-rich biochar in a modified Soxhlet reactor. Chemosphere 80, 724–732.
| Simulated geochemical weathering of a mineral ash-rich biochar in a modified Soxhlet reactor.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXptVCmtb4%3D&md5=9ccf509d69265e6a5c1896fd13459413CAS | 20542316PubMed |
Zachara JM, Cowan CE, Resch CT (1991) Sorption of divalent metals on calcite. Geochimica et Cosmochimica Acta 55, 1549–1562.
| Sorption of divalent metals on calcite.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3MXkvFGqurY%3D&md5=bc1eb2710a2974d1f1952d2e17e9c2b5CAS |
