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    Elsevier Editorial System(tm) for Bioresource TechnologyManuscript Draft

    Manuscript Number:

    Title: Influence of Pyrolysis Temperature on Cadmium and Zinc Sorption Capacity of Sugarcane Straw-Derived Biochar

    Article Type: Original research paper

    Keywords: Heavy metals; Biomass; Tropical soils; Adsorption

    Corresponding Author: Dr. Leonidas Carrijo Azevedo Melo,

    Corresponding Author's Institution: Universidade Federal de Viosa

    First Author: Leonidas Carrijo Azevedo Melo

    Order of Authors: Leonidas Carrijo Azevedo Melo; Aline R Coscione; Cleide A Abreu; Aline P Puga;Otvio A Camargo

    Abstract: The effect of pyrolysis temperature (400, 500, 600 and 700 oC) on the characteristics andmetal sorption capacity of sugarcane straw derived-biochar (BC) was investigated. By increasing thepyrolysis temperature there was a reduction in the O/C and H/C molar ratios. Sorption capacity ofbiochar pyrolyzed at 700 C was nearly four-times greater than that produced at 400 C. In the Entisolmixture there was an increase up to seven-fold in the sorption of both Cd and Zn, while in the Oxisolmixture there was a maximum 20% increase in sorption, compared to the control. For remediationpurposes of Cd and Zn contaminated substrates the use of higher pyrolysis temperature biochars arerecommended due to their higher metal sorption capacity.

    S gg t d R i L M

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    Suggested Reviewers: Lena Ma

    All authors are in agreement with the submission of the manuscript. Also, themanuscript is original work and has not been submitted earlier to BITE or to any other

    journal. In this work it is described a detailed characterization and the utilization, asmetal sorbent, of biochar produced from sugar cane residues. It was found that byincreasing the pyrolytic temperature the sorption of zinc and cadmium was enhancedgreatly both in aqueous solution and in soils. The sugarcane industry produces a hugeamount of biomass that can be used to generate electricity as well as biochar. Therefore,such results may help to encourage the use of this type of biomass for a different use,i.e. as metal sorbent with potential to reclaim areas contaminated by heavy metals.Subject Classification number 40: BIOMASS & FEEDSTOCK UTILIZATION

    Cover Letter

    http://popupclassificationdetail%28185%29/http://popupclassificationdetail%28185%29/
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    HIGHLIGHTS

    Pyrolysis temperature affected the physicochemical properties of biochar.

    Higher pyrolysis temperature increased the capacity of biochar to sorb Cd and Zn.

    The effect of biochar in the sorption of Cd and Zn is pronounced in sandy soils.

    *Highlights (for review)

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    Influence of Pyrolysis Temperature on Cadmium and Zinc Sorption1

    Capacity of Sugarcane Straw-Derived Biochar2

    3Lenidas C. A. Melo, a,* Aline R. Coscione, b Cleide A. Abreu, b Aline P. Puga b and Otvio4A. Camargo b 5a Departamento de Solos, Universidade Federal de Viosa, CEP 36570-000, Viosa, MG, Brazil. 6*Corresponding author: Tel.: +55 31 3899 1048; Fax.: +55 31 3899 2648. E-mail adress:[email protected] 8

    b Centro de Solos e Recursos Ambientais, Instituto Agronmico de Campinas, CEP 13020 902, Campinas, SP,9 Brazil.10

    11

    ABSTRACT12

    The effect of pyrolysis temperature (400, 500, 600 and 700 oC) on the characteristics and13

    metal sorption capacity of sugarcane straw derived-biochar (BC) was investigated. By14

    increasing the pyrolysis temperature there was a reduction in the O/C and H/C molar ratios.15

    Sorption capacity of biochar pyrolyzed at 700 C was nearly four-times greater than that16

    produced at 400 C. In the Entisol mixture there was an increase up to seven-fold in the17

    sorption of both Cd and Zn, while in the Oxisol mixture there was a maximum 20%18

    *ManuscriptClick here to view linked References

    mailto:[email protected]:[email protected]://ees.elsevier.com/bite/viewRCResults.aspx?pdf=1&docID=41629&rev=0&fileID=1034748&msid={7255CC8D-5649-42D3-8955-49CDB686BBC5}http://ees.elsevier.com/bite/viewRCResults.aspx?pdf=1&docID=41629&rev=0&fileID=1034748&msid={7255CC8D-5649-42D3-8955-49CDB686BBC5}mailto:[email protected]
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    chemical quality (Maia et al. 2011) and/or enhance carbon sequestration (Lehmann et al.28

    2006). Most recently biochar has been considered as an option for remediation of heavy29

    metals and organic pollutants contaminated soils, as reviewed by Beesley et al. (2011).30

    Chemically, biochar is difficult to define due to the wide variety of biomass and31

    charring conditions used in its production, which results in materials with a wide range of32

    final characteristics (Lehmann and Joseph 2009). By increasing the pyrolysis temperature,33

    there is a gradual increase in the aromaticity of the plant biomass, forming a continuum 34

    from partially charred plant materials, to charcoal, soot and ultimately graphite (Preston and35

    Schmidt 2006). In the range of temperature that biochar is produced (usually < 700 C),36

    after an extensive characterization of grass and wood based biochar, Keiluweit et al. (2010)37

    proposed a categorization based on its chemical and physical states during pyrolysis: (i)38

    transition chars the crystalline character of the feedstock is preserved; (ii) amorphous39

    chars - heat-altered molecules and incipient aromatic polycondensates are randomly mixed;40

    (iii) composite chars - poorly ordered graphene stacks embedded in amorphous phases; and41

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    in the environment that could an advantage to avoid field re-applications. Another51

    mechanism of stability is the formation of mineral-biochar complexes related to increasing52

    surface oxidation of the biochars during the aging, as observed by Lin et al. (2012) after53

    incubation of an Fe rich soil (ferrosol) with biochars produced at 550 C.54

    Chen et al. (2011) verified that corn straw-derived biochar pyrolyzed at 600 C55

    adsorbed about twice as much of Cu(II) and Zn(II) from aqueous solution, as compared to a56

    hardwood-derived biochar pyrolyzed at 450 C. On the other hand, Cao et al. (2009)57

    observed that manure-derived biochar produced at 200 C (BC200) showed higher Pb58

    sorption than the biochar formed at 350 C (BC350). This was mainly attributed to the59

    precipitation of lead with soluble P, which was higher in BC200 than in BC350. Such60

    research findings show that the use of biochar as metal sorbent depends strongly on the61

    feedstock and pyrolysis conditions, and should be evaluated case-by-case.62

    In Brazil, the sugarcane processing facilities convert the feedstock (sugarcane) into63

    a variety of products such as sugar, bioethanol, electricity, and other by-products (Cavalett64

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    sorption capacity is sought for future application of biochar to reclaim Zn contaminated73

    mine soils.74

    75

    2. Material and Methods76

    77

    Sugarcane straw was collected in a field experiment, just after the harvest of78

    sugarcane. The material was oven-dried at 60 C for 24h and placed in a pyrolyzer, sealed79

    and heated to 400, 500, 600 and 700 C at the rate of 10 C/min. The desired temperature80

    was held for about one hour (slow pyrolysis), after which the pyrolysed material was left to81

    slowly cool down to room temperature. The weights of the starting biomass and of the82

    resulting material (biochar - BC) were recorded to determine the BC yield. Biochar was83

    ground to pass a stainless steel sieve (< 0.5 mm) and used for characterization and84

    subsequent experimentation. A clay-rich Oxisol and an Entisol were used in the batch85

    sorption experiments.86

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    and two portions of 20 mL of the acetate solution. The excess solution (non-adsorbed96

    NH 4+) was washed out with three portions of 30 mL of isopropyl alcohol. The biochar was97

    rinsed with four portions of 50 mL of 1M KCl solution and the rinsate was collected and98

    brought to the final volume of 250 mL and the NH 4+ was determined by the Kjeldahl99

    method.100

    Prior to the analysis of the point of zero charge (pH pzc ), the ash of biochar samples101

    was removed by washing with 0.1 M HCl (27 g L -1) by constant stirring for 1 h, then the102

    material was rinsed three times with distilled deionized water (DDW) and dried overnight103

    at 80 C (Uchimiya et al. 2011b). The pH pzc was determined as described by Yang et al.104

    (2004). In 60 mg of BC were added 20 mL of 0.01M CaCl 2 solution previously adjusted105

    with diluted HCl or NaOH solutions to pH 4, 6, 8 and 10. After shaking for 24 h the pH106

    was measured and when the final pH was equal to the initial pH (line 1:1) it was considered107

    as pH pzc . The CHN elemental composition was determined in an elemental analyzer (Perkin108

    Elmer series II 2400). The oxygen contents were estimated by mass difference, i.e. 100% -109

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    119

    2.2 FT-IR and thermal analysis120

    121

    Surface functional groups of BC were analyzed by Fourier transform-infrared122

    spectroscopy (FT-IR, Spectrum One, Perkin Elmer), in the range of 4000 to 450 cm -1, by123

    using 20 scans/min at 4 cm -1 resolution. Measurements were performed in pellets of BC124

    blended with KBr.125

    Thermogravimetric analysis of BC was performed in a TGA 2050 TA Instrument.126

    The measurements were obtained under N 2 atmosphere from room temperature up to 950127

    C at a heating rate of 20 C/min. Samples mass varying from 5.1 to 5.7 mg were used.128

    129

    2.3 Scanning Electron Microscopy130

    131

    Analysis of Scanning Electron Microscope (SEM) was carried out using a LEO Evo132

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    extracted with a 1 M KCl solution and measured by titration with a 0.025 M NaOH142

    solution. Phosphorus, Ca, Mg and K were extracted by ionic exchange resin and determined143

    by ICP OES. The cation exchange capacity (CEC) was calculated as the sum of cations (Ca144

    + Mg + K + H + Al). Total acidity (H+Al) was estimated at pH 7.0 with buffer SMP145

    solution. Available sulfur was extracted by Ca(H 2PO 4)2 0.01 M and determined146

    turbidmetrically, after reaction with BaCl 2.2H 2O. Soil available concentrations of Cu, Fe,147

    Mn and Zn were extracted with DTPA pH 7.3 (Lindsay and Norvell, 1978). Boron was148

    extracted by hot water and determined colorimetrically. For a more detailed149

    characterization of these soils see Melo et al. (2011).150

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    2.5 Batch sorption experiments151

    152

    Sorption experiments were carried out following the procedures described by153

    Uchimiya et al. (2011c), with modifications. Briefly, 0.2 g of BC or 2.0 g of soil + BC154

    mixture (1.8 g of Oxisol or Entisol + 0.2 g of BC) were weighted into 50 mL centrifuge155

    tubes, in duplicate. Then, 20 mL of synthetic rainwater (SR - obtained by addition of 10156

    mM H 2SO 4 in deionized water until pH 4.5 was reached) were added to the sample and157

    shaken horizontally for 24 h at 100 oscillations/min. After, 200 L of a 0.2 M stock158

    solution of Cd or Zn were added in order to reach a final concentration of 2 mM and the159

    tubes were shaken for another 24 h, and subsequently filtered. In the equilibrium solution160

    Cd or Zn were measured by ICP-OES. Control treatments were achieved by using blank161

    reagents in all batch procedures. Tests of sorption using longer times (i.e. 48 h and 96 h)162

    were performed and showed no significant difference (data not shown), confirming the163

    duration (24 h) was adequate for equilibration.164

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    pH and electrical conductivities was observed, probably reflecting the greater ash content174

    of biochar obtained at higher pyrolysis temperatures.175

    The cation exchange capacity (CEC) reduced, while the increase of the carbon176

    content corresponded to a decrease of O and H was observed at higher pyrolysis177

    temperatures. Consequently there was a reduction in the O/C and H/C molar ratios. The178

    reduction in CEC is probably related to loss of O containing functional groups. Such179

    findings are in agreement with other authors (Singh et al., 2010; Mukherjee et al. 2011;180

    Uchimiya et al. 2011a; Song and Guo 2012) that also observed similar results for the effect181

    of temperature on these biochar parameters, produced from various biomasses suggesting182

    that variations in these parameters with temperature occurs regardless of the parent biomass183

    and seems to be a general rule. 184

    The molar ratios obtained from the elemental analysis are commonly used to185

    determine the degree of aromaticity (H/C) and polarity (O/C) of coal and have been used186

    for biochar characterization (Uchimiya et al. 2011a) since by increasing the pyrolysis187

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    expected to be more available. The relatively high levels of Ca, Mg and K in all BCs tested197

    are due to the sugarcane straw s initial composition, which is rich in such elements, mainly198

    K (Oliveira et al., 2002). It should be noted that since this BC presents alkaline reaction199

    (pH ranging from 8.6 to 10.1) and is rich in nutrients, such factors indicate its good200

    potential for reclaiming contaminated land, since it could act as a metal immobilizer and a201

    nutrient supplier, allowing the growth of plants in bare soils. Such characteristics make this202

    particular biochar an attractive option for this purpose. Al-Wabel et al. (2013) verified203

    enrichment of 232%, 199% and 304% for Ca, Mg, K, respectively, for biochar produced204

    from conocarpus wastes at 800 C. They concluded that such an increase in alkaline205

    elements could be responsible for liming effects induced by biochar pyrolyzed at high206

    temperatures.207

    The FTIR spectra revealed in all cases bands at the region of 3500 to 3400 cm -1,208

    which relates to stretches of hydroxyl groups and indicates hydrogen bonds (Figure 1). The209

    bands between 2900 and 2800 cm -1 are related to the elongation of CH aliphatic chains.210

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    decrease in the intensity of the peaks of different groups, which is consistent with the lower219

    O contents of biochars at higher temperatures.220

    The mass loss at different TGA stages analysis of the biochar samples are presented221

    in Table 2. For all samples considered the stage 1, around 100 C, was observed and it is222

    consistent with the loss of water (moisture) from samples. With the increase of furnace223

    temperatures occurred a plateau until around 380 C (400 BC) and 450 C (700 BC), in224

    which no effective loss of mass was observed. After, at stage 3 there was a sudden drop, of225

    approximately 50% sample weight loss, up to 640 C. An exception here is the BC700, in226

    which the mass loss is relatively low (23.7%) at stage 3, as compared to biochar samples227

    obtained at lower temperatures. The mass loss at this range of temperature is related to the228

    decomposition of organic remaining content of the BC samples, including cellulose and229

    hemicellulose. The latter starts to decompose from 220 C up to 315 C, and it is followed230

    by cellulose decomposition (Yang et al. 2007).231Finally, a loss of approximately 20% of samples mass that has occurred between232

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    Furthermore, the surface properties of materials are also important to explain its240

    reactivity. In general, the surface morphology of the sugarcane straw biochar samples,241

    despite the temperature it is produced at, showed an irregular amorphous surface with a242

    porous structure (Figure 2). This effect could be the result of melting and fusion process of243

    the lignin and other small molecules compounds, such as pectin and inorganic compounds,244

    as was described by Liu et al. (2010) in pinewood biochar produced at 300 C and 700 C.245

    246

    3.2 Adsorption of Cd and Zn in soils247

    248

    The Oxisol and the Entisol used for experimentation were slightly acidic and had249

    contrasting characteristics, mainly governed by the clay content/fraction (63% for the250

    Oxisol x 6% for the Entisol), CEC and organic matter content (Table 3). The lower251

    available P and micronutrient (i.e. Cu, Fe, Mn and Zn) contents in the Oxisol as compared252

    to the Entisol, indicate a naturally higher sorption capacity of the Oxisol.253

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    removal from aqueous solution with biochar produced from a giant Miscanthus at higher263

    pyrolysis temperature. Jiang et al. (2012) observed that the application of rice straw derived264

    biochar in an Ultisol increased soil pH, making the surface charge more negative, and265

    significantly reduced the acid soluble Cu(II) and Pb(II). They also found that the functional266

    groups (i.e. -COOH e -OH) of the biochar formed stable complexes mainly with Cu(II),267

    enhancing greatly its adsorption.268

    Interesting results were found when biochar was mixed into the soils, as related to269

    Cadmium (Cd) or Zinc (Zn) sorption (Figures 3B and 3C). The addition of 10% BC to the270

    Oxisol increased the adsorption of either Cd or Zn up to 20%, as compared to the control.271

    As discussed above the Oxisol is clay-rich and naturally exhibits a relatively high sorption272

    capacity. Even so, BC played a role to increase metal sorption capacity in this soil. When273

    BC was applied to the Entisol there was an increase up to seven-fold the sorption of both274

    cations, as compared to the control (without BC). Uchimiya et al. (2011c) also found275

    similar results for Cu retention in two soils (Norfolk and San Joaquin), with distinct276

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    functional groups that are able to retain cationic metals. On the other hand, results from286

    Uchimiya et al. (2011a) show that biochar formed at lower temperature (350 C) was more287

    effective to retain heavy metals in an acidic and eroded soil than biochar formed at higher288

    temperatures. They concluded that surface functional groups of biochars (which govern289

    pH pzc and VM and oxygen contents) control their ability to retain heavy metals in the soil 290

    Therefore; they stated that biochar selection for soil amendment must be made case-by-291

    case based on the biochar characteristics, soil property, and the target function . In this292

    particular case, the pH pzc of the BC at 350 C was the only one unit below the equilibrium293

    pH. The higher is the difference between pH pzc and equilibrium pH the higher are expected294

    to be the electrostatic interactions between cationic metal species and negatively charged295

    surfaces (Uchimiya et al. 2011a), which in our case is for BC at 700 C, helping to explain296

    its higher metal sorption.297

    Uchimiya et al. (2012), however, found that BC poultry litter pyrolyzed at 350 C298

    was better to retain and stabilize Pb in a contaminated soil than the BC produced at 650 C.299

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    increased the capacity of sugarcane straw-derived biochar to sorb Cd and Zn. The effect of309

    biochar in the sorption of Cd and Zn is much more pronounced in sandy soils with low310

    natural ability to retain metal pollutants than in clayey soils. The specific intention being311

    the application of sugarcane straw-derived biochars to Zn contaminated mine soils higher312

    pyrolytic temperatures are recommended.313

    314

    Acknowledgments315

    316

    The authors are grateful for the financial support of the So Paulo Research317Foundation FAPESP (Grant. No. 2011/12346-3) and for the postdoctoral fellowship318

    (Grant. No. 2011/02844-6) for the first author. We also are grateful to Prof. J.O. Brito319

    (Esalq/USP) for kindly provide the biochar for the study and Dr. Luke Beesley (The James320

    Hutton Institute) for the helpful comments on the article.321

    322

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    Cavalett, O., Junqueira, T.L., Dias, M.O.S., Jesus, C.D.F., Mantelatto, P.E., Cunha, M.P.,333

    Franco, H.C.J., Cardoso, T.F., Maciel Filho, R., Rossell, C.E. V., Bonomi, A., 2011.334 Environmental and economic assessment of sugarcane first generation biorefineries in335Brazil. Clean Technol. Environ. Policy 14, 399 410.336

    Chen, X., Chen, G., Chen, L., Chen, Y., Lehmann, J., McBride, M.B., Hay, A.G., 2011.337Adsorption of copper and zinc by biochars produced from pyrolysis of hardwood and338corn straw in aqueous solution. Bioresour. Technol. 102, 8877 8884.339

    Ferreira-Leito, V., Gottschalk, L.M.F., Ferrara, M.A., Nepomuceno, A.L., Molinari,340H.B.C., Bon, E.P.S., 2010. Biomass residues in Brazil: availability and potential uses.341Waste Biomass Valorization 1, 65 76.342

    Fuertes, A.B., Arbestain, M.C., Sevilla, M., Maci-Agull, J.A., Fiol, S., Lpez, R.,343Smernik, R.J., Aitkenhead, W.P., Arce, F., Macias, F., 2010. Chemical and structural344

    properties of carbonaceous products obtained by pyrolysis and hydrothermal345carbonisation of corn stover. Aust. J. Soil Res. 48, 618 626.346

    Jiang, J., Xu, R., Jiang, T., Li, Z., 2012. Immobilization of Cu(II), Pb(II) and Cd(II) by the347addition of rice straw derived biochar to a simulated polluted Ultisol. J. Hazard. Mater.348229-230, 145 150.349

    Keiluweit, M., Nico, P.S., Johnson, M.G., Kleber, M., 2010. Dynamic molecular structure350of plant biomass-derived black carbon (biochar). Environ. Sci. Technol. 44, 1247 3511253.352

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    from pinewood pyrolysis and hydrothermal treatment. Fuel 89, 510 514.367

    Maia, C.M.B.F., Madari, B.E., Novotny, E.H., 2011. Advances in biochar research in368Brazil. Dynamic Soil, Dynamic Plant 5 (Special Issue 1), 53-58.369

    Melo, L.C.A., Alleoni, L.R.F., Carvalho, G., Azevedo, R.A., 2011. Cadmium- and barium-370toxicity effects on growth and antioxidant capacity of soybean (Glycine max L.)371

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    Nutr. Soil Sci. 174, 847 859.373

    Mukherjee, a., Zimmerman, a. R., Harris, W., 2011. Surface chemistry variations among a374series of laboratory-produced biochars. Geoderma 163, 247 255.375

    Oliveira, M.W., Trivelin, P.C.O., Boareto, A.E., Muraoka, T., Mortatti, J., 2002. Leaching376of nitrogen , potassium , calcium and magnesium in a sandy soil cultivated with377sugarcane. Pesqui. Agropecu. Bras. 37, 861 868.378

    Preston, C.M., Schmidt, M.W.I., 2006. Black (pyrogenic) carbon: a synthesis of current379knowledge and uncertainties with special consideration of boreal regions.380Biogeosciences 3, 397 420.381

    Quirk, R.G., Zwieten, L., Kimber, S., Downie, A., Morris, S., Rust, J., 2012. Utilization of382 biochar in sugarcane and sugar-industry management. Sugar Tech 14, 321 326.383

    Raij, B. van, Andrade, J.C., Cantarella,H., Quaggio, J.A., 2001. Chemical analysis to384evaluate the fertility of tropical soils (in Portuguese), Instituto Agronmico de385

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    Uchimiya, M., Klasson, K.T., Wartelle, L.H., Lima, I.M., 2011c. Influence of soil398

    properties on heavy metal sequestration by biochar amendment: 1. Copper sorption399 isotherms and the release of cations. Chemosphere 82, 1431 1437.400

    Uchimiya, M., Wartelle, L.H., Klasson, K.T., Fortier, C. a, Lima, I.M., 2011a. Influence of401 pyrolysis temperature on biochar property and function as a heavy metal sorbent in402soil. J. Agric. Food Chem. 59, 2501 2510.403

    Wu, W., Yang, M., Feng, Q., McGrouther, K., Wang, H., Lu, H., Chen, Y., 2012. Chemical404

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    Yang, H., Yan, R., Chen, H., Lee, D.H., Zheng, C., 2007. Characteristics of hemicellulose,407cellulose and lignin pyrolysis. Fuel 86, 1781 1788.408

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    Figure 1. FTIR spectra of sugarcane straw derived biochar pyrolyzed at four temperatures.424

    425

    Figure 2. Scanning Electron Microscope (SEM) images of biochar. The images show426

    biochars produced at 400C (a; c) and 700C (b; d), at 200x (a; b) and 1000x magnification427

    (c; d).428

    429

    Figure 3. Adsorption of Cadmium and Zinc in biochars prepared at different temperatures430

    (A); and adsorption of Cadmium (B) or Zinc (C) in an Oxisol and an Entisol alone or mixed431

    with 10 % (w/w) biochar pyrolyzed at different temperatures. *Fig. B has the same legend432

    as Fig. C433

    434Table 1435Characterization of the Biochar436Parameter Pyrolysis Temperature (C)

    400 500 600 700

    Yield (%, w/w) 45 38 35 31EC (mS cm -1) 3.3 3.8 3.4 5.1

    pH H2O 8.6 9.8 9.7 10.1

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    123456

    789

    10111213141516171819202122232425

    26272829303132333435363738

    Table 2440

    Temperature range and mass loss for TGA in biochar samples441 Samples Stage 1 Stage 2 Stage 3 Stage 4 Totalmassloss(%)

    Temp.range(C)

    Massloss(%)

    Temp.range(C)

    Massloss(%)

    Temp.range(C)

    Massloss (%)

    Temp.range(C)

    Massloss(%)

    BC400 < 96 2.4 96-378 6.1 378-641 45.5 641-950 24.1 78.1BC500 < 99 2.2 99-410 5.7 410-677 50.1 677-950 23.4 81.3BC600 < 96 2.0 96-439 4.3 439-683 44.8 683-950 24.5 75.6BC700 < 114 3.2 114-451 3.5 451-648 23.7 648-950 29.8 60.2

    442443

    Table 3444Characterization of the soils used in the sorption experiment445Soil pH SOM CEC Al Ca Mg K

    CaCl 2 (g kg- ) ----------------------------mmol c kg

    - ----------------------------Oxisol 5.7 0.0 37 2 94 7 - 39 2 26 2 1.4 0.1Entisol 5.2 0.2 23 2 69 4 1.4 0.1 28 1 1.9 0.8 0.6 0.1

    P S Cu Fe Mn Zn B----------------------------------------------------mg kg - -------------------------------------------------------

    Oxisol 3.9 0 60 3 0.7 0.1 39 1 14 2 0.5 0.1 0.3 0Entisol 173 6 15 1 3.0 0.1 130 13 28 1 11 0.1 1.0 0Values are mean (n = 3) standard deviation. SOM = Soil Organic Matter; CEC = Cation Exchange Capacity; - not446detected 447

    448449450451

    Figure

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    Wavenumber (cm -1)

    5001000150020002500300035004000

    BC 400

    BC 500

    BC 600

    BC 700

    O-H3430

    C=C

    C-H aliphatic

    Absorbance

    C-H 2C-O-C

    C-Haromatic

    29182850

    16181438

    1112

    874-810

    g

    Figure

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    200 m

    b

    100 m

    a

    20 m

    dc

    20 m

    Figure

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    T t t

    Adsorbed metal (mg g

    -1)

    O x i s o lE n t i s o l

    S 4 0 0 5 0 0 6 0 0 7 0 0

    0 .0

    0 .5

    1 .0

    1 .5

    2 .0

    2 .5

    3 .0Z i n c

    b

    a a a a

    c

    b b b

    a

    T r e a t m e n t s

    Adsorbed metal (mg g

    -1)

    S 4 0 0 5 0 0 6 0 0 7 0 00 .0

    0 .5

    1 .0

    1 .5

    2 .0

    2 .5

    3 .0C a d m i u m

    b

    a a a a

    c

    b a b a b

    a

    P y r o l y s i s te m p e r a t u r e ( C )

    4 0 0 5 0 0 6 0 0 7 0 0

    Adsorbed metal (mg g

    -1)

    0

    4

    8

    1 2

    1 6

    2 0

    C d

    Z n

    b

    b

    b

    b

    b

    b

    a

    a


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