Jeffrey L. Smith a, * , Harold P. Collins b,1 , Vanessa L. Bailey c, 2 a USDA-ARS, Washington State University, 215 Johnson Hall, Pullman, WA 99164, USA b USDA-ARS, Vegetable and Forage Crops Research Unit, 24106N Bunn Rd, Prosser, WA 99350, USA c Microbiology/Biological Sciences Division, Pacic Northwest National Laboratory, 902 Battelle Boulevard, MSIN J4-18, Richland, WA 99352, USA a r t i c l e i n f o Article history: Received 4 March 2010 Received in revised form 8 September 2010 Accepted 9 September 2010 Available online 24 September 2010 Keywords: Biochar Carbon sequestration Soil respiration v 13 C a b s t r a c t The low temperature pyrolysis of organic material produces biochar, a charcoal like substance. Biochar is being promoted as a soil amendment to enhance soil quality, it is also seen as a mechanism of long-term sequestration of carbon. Our experiments tested the hypothesis that biochar is inert in soil. However, we measured an increase in CO 2 production from soils after biochar amendment which increased with increasing rates of biochar. The v 13 C signature of the CO 2 evolved in the rst several days of the incu- bation was the same as the v 13 C signature of the biochar, conrming that biochar contributed to the CO 2 ux. This effect diminished by day 6 of the incubation suggesting that most of the biochar C is slowly decomposing. Thus, aside from this short-term mineralization increasing soil C with young biochar may indeed be a long-term C storage mechanism. Published by Elsevier Ltd. Recently there has been increasing interest in low temperature pyrolysis of organic materials to produce a charcoal product termed biochar. It has been postulated that biochar is an inert substance that could be a benecial soil amendment for increasing soil quality and a permanent mechanismfor carbon (C) sequestration to reduce CO 2 enrichment of the atmosphere from anthropogenic activities (Laird, 2008; Novak et al., 2009). Biochar is not a precisely dened material since process conditions and feedstocks can inuence the characteristics of the nal biochar product, where slow pyrolysis properties tend to be similar, fast pyrolysis chars are a more chemically heterogeneous group (Amonette et al., 2008). Beyond pure chemistry biochar is thought to have some common features regardless of feedstock source or synthesis, in particular, potential soil quality benets which include increases in the water holding capacity, cation exchange capacity, and C content of amended soils (Lehmann et al., 2008). In addition, biochar may enhance soil fertility (Van Zwieten et al., 2010) and soil aggregation (Novotny et al., 2009). An auxiliary benet may be the suppression of N 2 O production from biochar amended soils (Singh et al., 2010). Generally, biochar additions to soil may increase the soil C and N pools but the accompanying N addition may have little added benet for plant nutrition (Granatstein et al., 2009). Several ques- tions remain to be addressed: what is the inuence of biochar on biological activity (Kolb et al., 2009) or soil processes (Granatstein et al., 2009) and is biochar truly inert in soil? We hypothesized that biochar is not totally inert in soil and thus contributes to CO 2 ux when added to soil. A C 4 biochar and historically C 3 soils were used to follow soil organic matter decomposition to CO 2 . The young biochar was produced from a switchgrass (Panicum virgatum) feedstock that was processed at a pyrolysis temperature of 500
C in a lowoxygen environment for 2 h. The biochar product had the following chemical characteristics: pH 9.7, 52%C, 1.6%N and v 13 C of 12.57&. Typically, switchgrass loses 45% of the original C and 65% of original Nduring pyrolysis (Granatstein et al., 2009). The young biochar contained 40% volatile (low vapor pressure compounds) (Spokas et al., 2010) matter and was dominated by aromatic ring structures followed by aliphatic and to a lesser extent carbonylic functional groups as determined by NMR (Amonette et al., 2008). The soluble C concentration of the water extracted biochar was 3.4 mg-C/g biochar and the N .075 mg-N/g biochar (0.03 NH 4
and 0.15 NO 3
mg-N/g biochar). By FTIR analysis the
soluble C and N were dominated by aromatic (amide and methyl), aliphatic and carboxylate groups. We used two Washington State, USA soils to test our hypothesis, a Shano silt loam (Coarse-silty, mixed, superactive, mesic Xeric Haplocambids) and a Walla Walla silt loam (Coarse-silty, mixed, superactive, mesic Typic Haploxerolls). The soils were collected from the 0e5 cm depth, put through a 2 mm sieve and used eld * Corresponding author at: Tel.: 1 509 335 7648; fax: 1 509 335 3842. E-mail addresses: jlsmith@wsu.edu (J.L. Smith), hal.collins@ars.usda.gov (H.P. Collins), vanessa.bailey@pnl.gov (V.L. Bailey). 1 Tel.: 1 509 786 9250. 2 Tel.: 1 509 371 6965. Contents lists available at ScienceDirect Soil Biology & Biochemistry j ournal homepage: www. el sevi er. com/ l ocat e/ soi l bi o 0038-0717/$ e see front matter Published by Elsevier Ltd. doi:10.1016/j.soilbio.2010.09.013 Soil Biology & Biochemistry 42 (2010) 2345e2347 moist (adjusted to 0.03 MPa where needed). The Shano silt loam has a pH of 5.4, 0.64%C, 0.08%N and a v 13 C of 21.4 &. The Walla Walla silt loam has a pH of 7.1, 1.27%C, 0.12%N and a v 13 C of 21.2&. We amended 25 g aliquots of each soil with biochar at rates equivalent to 0, 11.2, 22.4 and 44.8 Mg/ha. Biochar plus sand was used as a secondary control. The amended soils were incubated at 0.03 MPa moisture potential in closed containers with a 1 NNaOH trap for collecting CO 2 . Total CO 2 was determined by titration of these traps at 2, 6, 10, 17, 28, 35, 42, 49 days. Before the titration trapped CO 2 was precipitated with SrCl 2 to form a precipitate that combusts at a temperature less than 1100
C. The residual Sr 13 CO 3 left after the titration was dried and the v 13 C of the 13 CO 2 evolved was determined by isotope ratio mass spectrometry (IRMS). The cumulative CO 2 evolved after biochar addition is shown in Fig. 1. Both soils showed an increase in CO 2 production with increased biochar additions. The Walla Walla soil experienced larger increases (Fig. 1b) than the Shano soil. CO 2 production in the Shano soil (Fig. 1a) did not differ signicantly at the 2 intermediate rates of biochar addition. In contrast these biochar amendment rates in the Walla Walla soil (Fig. 1b) did generate signicantly different rates of CO 2 evolution, and the lowest rate was not signicantly different than the control. However, in both soils the increases were mostly during the rst few days of incubation, thereafter the rates of CO 2 production were similar (slopes of the lines from 10 to 50 days). The CO 2 signature of the evolved CO 2 from decomposition is shown in Fig. 2. After 2 days the CO 2 evolved from the highest biochar addition had a similar signature to that of pure biochar, approximately 13&. After 4 days both soils continued to show a signicant biochar inuence in the CO 2 evolved from decompo- sition. By day 6 there was no signicant difference in the CO 2 signature between the control soil (0 biochar additions) and the other 3 biochar soil additions (Fig. 2). This was consistent from day 6 to day 50 of the incubation (data not shown). These experiments provide strong evidence that young biochar is not inert but provides signicant amounts of labile C that is readily available to soil microorganisms for use as an energy source within a relatively short timeframe. The soluble C concentration of the biochar was 3.4 mg-C/g biochar. The rates applied would equal 350e1250 mg soluble C/g soil which could easily account for the difference between the highest rate of biochar addition and the control (Fig. 1). We conclude that there is a distinct labile C pool associated with young biochar that may be signicant in the short-term. It is likely that a fraction of the condensates from the bio-oil formed during pyrolysis absorbed to the biochar during cooling. These conden- sates are likely the source of the labile C pool and thus do not originate from the stable carbonized components of the biochar. Since only about 10e20% of the soluble component is mineralized to CO 2 it is probable that the aromatic and aliphatic compounds may precipitate forming larger more complex molecules. In the long-term, we suggest these materials would be resistant to decomposition and would become part of the slow to resistant C pools in soils. Thus the claims in the literature and popular press that the greenhouse effect of increased CO 2 could be reduced by converting organic material to biochar and used as a soil amend- ment may have merit. Acknowledgements This work was supported in part by the US Department of Energy, Ofce of Science, Ofce of Biological and Environmental Research, Climate Change Research Division under contract DE- AC05-76RL01830 to Pacic Northwest National Laboratory. References Amonette, J.E., Dai, S.S., Hu, Y., Schlekewey, N., Shaff, Z., Russell, C.K., Burton, S.D., Arey, B.W., 2008. An exploration of the physico-chemical diversity of a suite of biochars. Eos Transactions, AGU 89 (53) Fall Meeting Supplement, Abstract B31G-0379. Granatstein, D., Kruger, C., Collins, H., Galinato, S., Garcia-Perez, M., Yoder, J., 2009. Use of Biochar From the Pyrolysis of Waste Organic Material as a Soil Amendment. Final Project Report. Center for Sustaining Agriculture and Natural Resources, Washington State University, Wenatchee, WA, USA, 167 pp. Kolb, S.E., Fermanich, K.J., Dornbush, M.E., 2009. Effect of charcoalquantity on microbial biomass and activity in temperate soils. Soil Science Society of America Journal 73, 1173e1181. 0 50 100 150 200 250 300 350 0 10 20 30 40 50 60 O C g u 2 l i o s g / C - 0 11.2 22.4 44.8 0 50 100 150 200 250 300 350 0 10 20 30 40 50 60 Days l i o s g / C - 2 O C g u Mg/ha a b Fig. 1. Cumulative CO 2 evolved during a 50 day incubation after addition of biochar. a) Shano silt loam soil, b) Walla Walla silt loam soil (mean and standard error). -22 -20 -18 -16 -14 -12 -10 0 2 4 6 8 d 3 1 O C 2 0 11.2 22.4 44.8 -22 -20 -18 -16 -14 -12 -10 0 2 4 6 8 Days d 3 1 O C 2 a b Mg/ha Fig. 2. The v 13 C signature of the CO 2 evolved during the rst 6 days of soil incubation. a) Shano silt loam soil, b) Walla Walla silt loam soil (mean and standard error). J.L. Smith et al. / Soil Biology & Biochemistry 42 (2010) 2345e2347 2346 Laird, D.A., 2008. The charcoal vision: a winewinewin scenario for simultaneously producing bioenergy, permanently sequestering carbon, while improving soil and water quality. Agronomy Journal 100, 178e181. Lehmann, J., Skjemstad, J., Sohi, S., Carter, J., Barson, M., Falloon, P., Coleman, K., Woodbury, P., Krull, E., 2008. Australian climate-carbon cycle feedback reduced by soil black carbon. Nature Geoscience 1, 832e835. Novak, J.M., Busscher, W.J., Laird, D.A., Ahmedna, M., Watts, D.W., Niandou, M., 2009. Impact of biochar amendment on fertility of a southeastern coastal plain soil. Soil Science 174, 105e112. Novotny, E.H., Hayes, M.H.B., Madari, B.E., Bonagamba, T.J., deAzevedo, E.R., de Souza, A.A., Song, G.X., Nogueira, C.M., Mangrich, A.S., 2009. Lessons from the Terra Preta de Indios of the Amazon region for the utilisation of charcoal for soil amendment. Journal of the Brazilian Chemical Society 20, 1003e1010. Singh, B.P., Hatton, B.J., Singh, B., Cowie, A.L., Kathuria, A., 2010. Inuence of bio- chars on nitrous oxide emission and nitrogen leaching from two contrasting soils. Journal of Environmental Quality 39, 1224e1235. Spokas, K.A., Baker, J.M., Reicosky, D.C., 2010. Ethylene: potential key for biochar amendment impacts. Plant Soil 333, 443e452. Van Zwieten, L., Kimber, S., Morris, S., Chan, K.Y., Downie, A., Rust, J., Joseph, S., Cowie, A., 2010. Effects of biochar from slow pyrolysis of papermill waste on agronomic performance and soil fertility. Plant and Soil 327, 235e246. J.L. Smith et al. / Soil Biology & Biochemistry 42 (2010) 2345e2347 2347
A Comparison of Producer Gas, Biochar, and Activated Carbon From Two Distributed Scale Thermochemical Conversion Systems Used To Process Forest Biomass