CSIRO PUBLISHING

www.publish.csiro.au/journals/ajsr Australian Journal of Soil Research, 2010, 48, 516–525

Characterisation and evaluation of biochars for their application

as a soil amendment

Balwant Singh A,D, Bhupinder Pal Singh B, and Annette L. Cowie C

A
Faculty of Agriculture, Food and Natural Resources, The University of Sydney, Sydney, NSW 2006, Australia.
B
Forest Science Centre, Industry and Investment NSW, PO Box 100, Beecroft, NSW 2119, Australia.
C
National Centre for Rural Greenhouse Gas Research, University of New England, Armidale, NSW 2351,
Australia.
D
Corresponding author. Email: [email protected]

Abstract. Biochar properties can be significantly influenced by feedstock source and pyrolysis conditions; this warrants
detailed characterisation of biochars for their application to improve soil fertility and sequester carbon. We characterised 11
biochars, made from 5 feedstocks [Eucalyptus saligna wood (at 4008C and 5508C both with and without steam activation);
E. saligna leaves (at 4008C and 5508C with activation); papermill sludge (at 5508C with activation); poultry litter and cow
manure (each at 4008C without activation and at 5508C with activation)] using standard or modified soil chemical
procedures. Biochar pH values varied from near neutral to highly alkaline. In general, wood biochars had higher total C,
lower ash content, lower total N, P, K, S, Ca, Mg, Al, Na, and Cu contents, and lower potential cation exchange capacity
(CEC) and exchangeable cations than the manure-based biochars, and the leaf biochars were generally in-between.
Papermill sludge biochar had the highest total and exchangeable Ca, CaCO3 equivalence, total Cu, and potential CEC, and
the lowest total and exchangeable K. Water-soluble salts were higher in the manure-based biochars, followed by leaf,
papermill sludge, and wood biochars. Total As, Cd, Pb, and polycyclic aromatic hydrocarbons in the biochars were either
very low or below detection limits. In general, increase in pyrolysis temperature increased the ash content, pH, and surface
basicity and decreased surface acidity. The activation treatment had a little effect on most of the biochar properties. X-ray
diffraction analysis showed the presence of whewellite in E. saligna biochars produced at 4008C, and the whewellite was
converted to calcite in biochars formed at 5508C. Papermill sludge biochar contained the largest amount of calcite. Water-
soluble salts and calcite interfered with surface charge measurements and should be removed before the surface charge
measurements of biochar. The biochars used in the study ranged from C-rich to nutrient-rich to lime-rich soil amendment,
and these properties could be optimised through feedstock formulation and pyrolysis temperature for tailored soil
application.

Additional keywords: carbon sequestration, soil fertility, pyrolysis, Boehm titrations, heavy metals, surface acidity.

Introduction research has focused on energy and fuel quality of the

Increasing atmospheric CO2 is an important global issue of the biochar product, and the agronomic impacts of biochar have
21st century, and long-term storage of carbon in soil is been largely disregarded (Horne and Williams 1996; Tsai et al.
considered an important option to mitigate the increasing 2006). The influence of biochar on soil properties is likely to
level of CO2 in the atmosphere (Lal 2009). Since the vary significantly between different biochars because biochar
discovery of so-called Terra Preta, the highly fertile soil properties are governed by the biomass source and the pyrolysis
enriched with charred biomass in the Amazon (Sombroek conditions such as temperature and activation treatment (Chan
1966; Glaser et al. 2001), biochar has emerged as a viable et al. 2007, 2008; Gaskin et al. 2008; Chan and Xu 2009; Novak
option for sequestering carbon in soil (Lehmann et al. 2006). et al. 2009; Nguyen et al. 2010). Indeed, the limited published
Biochar application also possesses potential for (i) enhancing research to date has highlighted significant differences in the
soil fertility and consequently agricultural productivity properties of biochar produced from different feedstocks and
(Lehmann et al. 2006; Chan et al. 2007, 2008; Steiner et al. under different pyrolysis conditions (Shinogi et al. 2003; Chan
2007), (ii) improving nutrient- and water-use efficiencies (Glaser et al. 2007, 2008; Gaskin et al. 2008). This limits our ability to
et al. 2002), and (iii) mitigating emissions of N2O (Singh et al. evaluate potential benefits to soil from biochar application.
2010). Additionally, plants native to Australia growing on nutrient-
Biochar has been produced from a wide variety of organic poor soils produce nutrient-poor tissues (Orians and Milewski
materials including forestry and crop residues, papermill sludge, 2007), and thus biochar produced from nutrient-poor feedstock
and poultry waste (Chan and Xu 2009). Most of the early may have limited soil fertility benefits. However, such

CSIRO 2010 10.1071/SR10058 0004-9573/10/070516

Evaluation of biochars for soil amendment Australian Journal of Soil Research 517

information is not available for many plant-based feedstocks Total C and N concentrations were determined by dry
used for making biochar in Australia. combustion using a Vario Max CNS analyser. Concentrations
In view of escalating public interest in the application of of the other major and trace elements were determined by
biochar, there is a need for systematic studies of the relationship digesting biochar samples in a mixture of nitric acid (HNO3)
between biomass type, pyrolysis conditions, and chemical and perchloric acid (HClO4) (Miller 1998), and these are
composition of biochars. Agronomic responses to biochar termed total element concentration in biochars. The digests
application are likely to be influenced by several aspects of were analysed for various elements using a Varian Vista
chemical composition of the biochar: the total and available AX inductively coupled plasma-atomic emission
plant nutrients, the liming equivalence, the presence of toxic spectrophotometer. Available phosphorus (Olsen P) was
constituents, and the surface properties of biochar. It is not clear extracted by shaking 1 g biochar with 50 mL of 0.5 M
whether the methods commonly used to assess these properties NaHCO3 (pH 8.5) for 1 h, and P concentration in the solution
in soils will be applicable for biochar characterisation. The was determined by the ascorbic acid method.
objectives of this study were to determine the effects of
feedstock, pyrolysis temperature, and activation on chemical CaCO3 equivalence of biochars
properties of biochar and to evaluate some routine soil analysis The CaCO3 equivalence of biochars was determined using the
procedures for the characterisation of biochars. rapid titration method, involving shaking 2 or 4 g biochar with
100 mL of 1 M HCl for 2 h (Rayment and Higginson 1992). We
Materials and methods also determined the CaCO3 equivalence of biochars from the
volume of 0.5 M HCl added to biochar–water suspension to bring
Biochars
the equilibrium solution pH to 7.0. The detailed procedure for
For this study, 11 biochars were produced from 5 feedstocks: this acid treatment is described below in Boehm titrations.
Eucalyptus saligna wood (47.9% C, ~0.03% N), E. saligna
leaves (50.1% C, 1.33% N), paper sludge (33.5% C, 0.20% N), Polycyclic aromatic hydrocarbons
poultry litter (poultry manure on rice hull, 39.3% C, 6.09% N), Polycyclic aromatic hydrocarbons (PAHs) in biochars were
and cow manure (20% C, 1.96% N). The biochars were analysed at the Australian Government National Measurement
produced using slow pyrolysis by BEST Energies, Inc. Institute, Pymble (NSW), after extraction with dichloromethane
(Daisy Reactor, Sydney). The wood biochars were produced using soxhlet apparatus for 12 h. The extract was concentrated
at 4008C or 5508C with and without steam activation, and the by Kuderna Danish apparatus then analysed by GC-MS in SIM
leaf biochars at 4008C or 5508C with activation only. The mode. The column used was a DB-5-ms (30 m by 0.25 mm by
papermill sludge was produced at 5508C with activation, and 0.25 mm) with GC oven ramp from 408C to 3208C. The mass
the biochars from poultry litter and cow manure were produced spectrometer was set to SIM mode, and the PAHs were
each at 4008C without steam activation and 5508C with steam quantified using the internal standard method in accordance
activation. The biochars were pyrolysed at 5 108C/min heating with EPA 8270C method for determination of semi-volatile
rate and 40 min residence time, and N2 was then added into the organic compounds by GC-MS.
reactor during the cooling-off period to maintain the inert
environment. Boehm titrations
The oxygen-containing acidic and basic surface functional
Chemical analyses groups of biochar were determined using the Boehm titration
The biochars were homogenised and ground to <2 mm for the method (Boehm 1994). Boehm titration results can be affected
majority of analyses. For total elemental analyses including C by the presence of water-soluble salts and carbonates in
and N, biochar samples were ground to <100 mm. At least 3 biochar (Contescu et al. 1997, 1998) and these components
replicates were used for each analysis, and in some analyses 4 should be removed before the titrations. Biochar–water mixtures
replicates were used. Biochar pH and electrical conductivity (1 : 5) were neutralised to pH 7.0  0.02 by incremental
(EC) were measured using 1 : 5 solid : solution ratio after shaking additions of 0.5 M HCl followed by overnight shaking. The
for 30 min in deionised water. Expecting high amounts of water- desired pH was obtained after 3–4 weeks, and finally
soluble salts in some biochars, EC was also measured after biochars were repeatedly washed until free of Cl– as detected
shaking biochar–water mixtures (1 : 5 solid : solution ratio) for by AgNO3 and dried at 508C. For each biochar sample, 4 sets
24 h. Ash contents of biochars were determined by dry weighing 0.3 g were mixed separately with 30 mL of 0.25 M
combustion in a muffle furnace at 5508C for 2 h, and also at NaOH, 0.05 M NaOH, 0.05 M NaHCO3, and 0.05 M HCl. Biochar
7008C until a constant weight was obtained. suspensions were shaken in tightly closed containers for 44 h
Exchangeable cations of the original untreated biochar and then filtered using a glass fibre filter paper. A volume of
samples were measured using 1 M ammonium acetate (pH 7) the filtered basic or acid solution was added with excess 0.05 M
and silver thiourea methods as described by Rayment and HCl and then back-titrated to pH 7 with 0.1 M NaOH using an
Higginson (1992). The potential CEC of the original biochars automatic Metrohm titrator. Surface acidity and basicity were
and the biochar samples after removing water-soluble salts and calculated on the basis of the assumption that 0.05 M NaHCO3
carbonates was measured using the silver thiourea method neutralises carboxyl groups only (the strongest acid fraction),
(Rayment and Higginson 1992). Water-soluble salts and 0.05 M NaOH neutralises acidic groups including carboxyl,
carbonates were removed by an acid treatment procedure as lactones, and phenols, 0.25 M NaOH neutralises total acidity
described below in Boehm titrations. (carboxyl, lactones, phenols, carbonyls, and any other acidic
518 Australian Journal of Soil Research B. Singh et al.

species), and HCl neutralises all basic groups including The EC values (30 min equilibration) of the biochars were
ketones, pyrones, and chromens (Boehm 1994; Chun et al. significantly different for the feedstocks used in the study
2004). (Table 1). The biochars produced from wood and paper
sludge had low EC values (0.09 0.44 dS/m), whereas poultry
X-ray diffraction analysis and cow manure biochars showed very high EC values
(6.32 9.64 dS/m). Pyrolysis temperature treatment
Ground powdered biochar samples were filled into Al-holders to
significantly increased the EC values of eucalyptus leaf and
obtain random powder X-ray diffraction patterns. The scans
manure biochars but had no significant effect on the wood
were collected from 3–758 on a GBC MMA diffractometer using
biochar. The EC values increased substantially for most
monochromatised CoKa radiation (35 kV, 28.5 mA) and a step
biochars with increased equilibration time from 30 min to
size of 0.028 2q and scan speed of 1.08 2q/min. The minerals
24 h; however, the sequence for the biochar EC values did
were identified by comparing d-spacings in the diffraction
not change.
patterns to the ICDD–PDF mineral database.
The biochar ash content at 5508C varied from 32 to 762 g/kg
and was significantly lower for the wood or leaf biochars than
Statistical analysis the poultry and cow manure biochars (Table 1). Increasing the
Least significant differences (l.s.d.) at P = 0.05 between ashing temperature from 5508C to 7008C caused a substantial
properties of biochars were determined by general analysis of decrease in the ash content of the paper sludge biochar, whereas
variance using GENSTAT 12.1 (Payne et al. 2009). Correlations the decreases were relatively small for the other biochars.
between biochar properties were also calculated using this The CaCO3 equivalence of biochars varied from –9.2 to
software. 409.3 g/kg, with the lowest values for the wood biochars
followed by cow manure, eucalyptus leaf, and poultry litter
Results biochars; paper sludge biochar had the highest CaCO3
equivalence (Table 1). The CaCO3 equivalence for the high-
General properties of biochars temperature biochars was higher than for the low-temperature
Biochar pH (H2O) varied significantly among feedstocks, biochars. The CaCO3 equivalence values determined by slow
ranging from 6.93 to 10.26 (Table 1). Higher pyrolysis titration to pH 7 were approximately half of the values obtained
temperature increased the pH of most biochars except the by the rapid titration method, and there was a strong linear
cow manure biochar, where it remained virtually the same. correlation (r2 = 0.99) between the values obtained using the two
The steam activation treatment increased the pH of wood methods (Fig. 1).
biochars at both temperatures. Biochar pH values measured
in 0.01 M CaCl2 solution (data not presented here) were lower
(0.22 1.32 unit) than the corresponding water pH values, Total carbon and nutrient contents of biochars
especially for the wood and paper sludge biochars, which had The total C content of the biochars varied widely, with average
lower levels of soluble salts (Table 1). values ranging from 165 to 836 g/kg. The eucalyptus wood and

Table 1. Mean (þs.e.) for pH, electrical conductivity (EC), ash content, total carbon and nitrogen contents, and CaCO3 equivalence in the
11 biochars

Biochar treatment pH EC (1 : 5) (dS/m) Ash content (g/kg) Total C Total N CaCO3A

(1 : 5 H2O) 30 min 24 h 5508C 7008C (g/kg) (g/kg)
E. saligna wood
4008C, activated 7.67 ± 0.10 0.13 ± 0.01 0.44 ± 0.01 42 ± 4 37 ± 2 694.0 ± 5.1 2.1 ± 0.2 –3.4 ± 0.9
5508C, activated 9.49 ± 0.04 0.17 ± 0.01 0.26 ± 0.01 44 ± 6 55 ± 7 792.2 ± 4.7 2.3 ± 0.2 4.1 ± 0.03
4008C, non-activated 6.93 ± 0.02 0.09 ± 0.01 0.27 ± 0.01 32 ± 2 35 ± 1 697.4 ± 4.3 2.1 ± 0.2 –9.2 ± 0.04
5508C, non-activated 8.82 ± 0.01 0.16 ± 0.02 0.32 ± 0.01 44 ± 13 33 ± 1 836.1 ± 7.6 2.6 ± 0.2 7.2 ± 1.8
E. saligna leaves
4008C, activated 9.17 ± 0.05 1.44 ± 0.23 3.52 ± 0.15 99 ± 1 40 ± 1 662.8 ± 2.9 16.4 ± 0.5 15.4 ± 1.0
5508C, activated 9.88 ± 0.01 2.27 ± 0.15 4.18 ± 0.02 117 ± 8 92 ± 3 719.8 ± 5.3 17.0 ± 0.2 72.0 ± 2.8
Paper sludge
5508C, activated 9.22 ± 0.02 0.44 ± 0.01 0.68 ± 0.01 654 ± 5 475 ± 6 315.9 ± 1.6 2.1 ± 0.1 409.3 ± 27.5
Poultry litter
4008C, non-activated 9.20 ± 0.02 6.32 ± 0.06 9.27 ± 0.02 423 ± 36 346 ± 1 431.1 ± 6.8 51.8 ± 0.3 58.2 ± 2.4
5508C, activated 10.26 ± 0.01 7.64 ± 0.07 10.17 ± 0.03 459 ± 2 444 ± 1 413.2 ± 1.8 37.9 ± 0.1 86.3 ± 0.9
Cow manure
4008C, non-activated 9.03 ± 0.01 9.18 ± 0.14 12.28 ± 0.19 703 ± 4 704 ± 7 175.0 ± 1.5 13.5 ± 0.1 34.8 ± 2.1
5508C, activated 8.94 ± 0.02 9.64 ± 0.08 10.97 ± 0.12 762 ± 6 757 ± 5 165.3 ± 2.5 11.4 ± 0.2 42.7 ± 4.1
l.s.d. (P = 0.05) 0.11 0.29 0.24 36 18 6.5 0.3
A
Rapid titration.
Evaluation of biochars for soil amendment Australian Journal of Soil Research 519

250 the values for the leaf biochars were intermediate (Table 2). The
trend in total S and Mg was quite similar to P and K, except that
the values for these elements were higher in the paper sludge
CaCO 3 (g/kg) neutralised to pH 7

200 biochar than the wood biochars. Calcium content was the highest
in the paper sludge; most other biochars contained similar
amounts of Ca, apart from poultry litter biochar which had
150 intermediate values (Table 2).

Trace nutrient and non-essential elements contents

100
of biochars
y = 0.52x + 1.767 The Al content was low in the eucalyptus feedstock biochars
50 R 2 = 0.99 and high in cow manure and papermill sludge biochars (Table 3).
The poultry manure biochars contained intermediate levels of
Al. Total Na contents were lowest in the eucalyptus wood
0
biochars (<750 mg/kg), intermediate in the papermill sludge
–5 95 195 295 395 495 biochar, and highest (4100–5800 mg/kg) in the eucalyptus
CaCO3 (g/kg) rapid titration
leaf and the manure-based biochars. Total Zn in the wood
and poultry litter biochars was significantly higher than in the
Fig. 1. Relationship between CaCO3 equivalence (g/kg) of biochars other biochars (Table 3). The lowest Zn content was observed
determined by rapid titration with 1 M HCl and slow titration to pH 7 by in the eucalyptus leaf biochars (<150 mg/kg). The biochars
0.5 M HCl. produced from the eucalyptus feedstocks contained similar
and significantly lower Cu content than the other biochars.
leaf biochars had the highest total C content and cow manure The highest Cu content was found in the papermill sludge
biochars the lowest. For the wood and leaf biochars, the C values biochar (~150 mg/kg). Nickel content in the biochars varied
increased upon increase in pyrolysis temperature, whereas the between 4 and 26 mg/kg; the low-temperature wood biochars
reverse trend was found for the poultry litter and cow manure contained the lowest Ni and cow manure biochars had the
biochars. highest Ni contents (Table 3). Arsenic, Cd, and Pb contents
Total N content was the highest in the poultry litter biochars in the biochars were either very low or below the detection
followed by eucalyptus leaves, and cow manure biochars. The limits.
wood and paper sludge biochars had the lowest N contents with Available P was quite low in the wood (<5 mg/kg) and
values ranging from 2.1 to 2.6 g/kg on a dry-weight basis. papermill (7.9 mg/kg) biochars. The eucalyptus leaf biochars
Overall, eucalyptus feedstock biochars had high C and low N contained intermediate levels of available P (60–120 mg/kg).
contents, whereas manure-based biochars had low C and high N Both poultry and cow manure biochars had very high available
contents. P values (1555–2446 mg/kg), and in the poultry manure
Total P and K contents were low in the eucalyptus wood and biochars available P increased from 1756 to 2446 mg/kg with
paper sludge biochars and high in the manure-based biochars; increased pyrolysis temperature whereas the values were

Table 2. Mean (þs.e.) for total phosphorus, sulfur, calcium, potassium, and magnesium contents (mg/kg) in the 11 biochars

Biochar treatment P K S Ca Mg
E. saligna wood
4008C, activated 127 ± 8 1756 ± 200 127 ± 33 17 994 ± 590 911 ± 184
5508C, activated 160 ± 4 1907 ± 60 165 ± 30 17 914 ± 637 927 ± 23
4008C, non-activated 127 ± 4 1428 ± 19 278 ± 42 11 236 ± 239 666 ± 12
5508C, non-activated 217 ± 3 2358 ± 27 488 ± 36 21 263 ± 576 1085 ± 17
E. saligna leaves
4008C, activated 2077 ± 51 12 816 ± 339 910 ± 22 17 144 ± 469 4657 ± 144
5508C, activated 2673 ± 90 14 923 ± 368 992 ± 31 20 522 ± 537 5420 ± 150
Paper sludge
5508C, activated 378 ± 1 520 ± 26 1591 ± 16 179 535 ± 8232 2825 ± 107
Poultry litter
4008C, non-activated 5763 ± 120 24 851 ± 1376 4900 ± 455 33 352 ± 948 6835 ± 210
5508C, activated 6042 ± 499 22 983 ± 2013 5122 ± 493 39 847 ± 5720 7466 ± 939
Cow manure
4008C, non-activated 4359 ± 47 26 429 ± 3468 4526 ± 75 17 518 ± 493 10 699 ± 218
5508C, activated 4927 ± 128 23 075 ± 1860 3737 ± 458 18 810 ± 606 11 823 ± 91
l.s.d. (P = 0.05) 276 2380 419 5198 529
520 Australian Journal of Soil Research B. Singh et al.

Table 3. Mean (þs.e.) for total aluminium, sodium, copper, zinc, and nickel contents (mg/kg) in the 11 biochars

Biochar treatment Al Na Zn Cu Ni
E. saligna wood
4008C, activated 55 ± 7 655 ± 137 1312 ± 69 13 ± 3 5±1
5508C, activated 111 ± 1 610 ± 74 1599 ± 116 15 ± 2 14 ± 1
4008C, non-activated 103 ± 7 412 ± 106 1661 ± 47 21 ± 2 4±1
5508C, non-activated 190 ± 4 727 ± 90 1366 ± 22 16 ± 1 23 ± 1
E. saligna leaves
4008C, activated 153 ± 9 5080 ± 253 117 ± 24 13 ± 1 6±1
5508C, activated 229 ± 11 5691 ± 78 142 ± 30 17 ± 2 8±1
Paper sludge
5508C, activated 27 876 ± 1124 1226 ± 51 845 ± 73 154 ± 8 9±0
Poultry litter
4008C, non-activated 1246 ± 89 5498 ± 120 1449 ± 73 59 ± 2 9±1
5508C, activated 1357 ± 177 5777 ± 499 1642 ± 79 84 ± 28 12 ± 2
Cow manure
4008C, non-activated 34 026 ± 1586 4095 ± 47 557 ± 75 51 ± 1 22 ± 3
5508C, activated 37 321 ± 1908 4700 ± 127 622 ± 197 52 ± 15 26 ± 4
l.s.d. (P = 0.05) 1395 322 148 17 3

similar for the low- and high-temperature cow manure biochars CEC was the highest for the high-temperature poultry litter
(1555–1700 mg/kg). biochar and lowest for the eucalyptus feedstock biochars, except
for the high-temperature activated wood biochar.
Exchangeable (and soluble) K, Mg, and Na were much
Surface charge properties of biochars higher in the poultry and cow manure biochars than the other
Potential CEC values of the original biochars (untreated and biochars. Exchangeable Mg and Na were the lowest in the wood
unwashed) and acid-treated and -washed biochars, as biochars. Exchangeable K was the lowest in the wood and paper
determined using the silver thiourea method, are presented in sludge biochars. Exchangeable Ca was the highest in the paper
Table 4. For the acid-washed biochar samples, the eucalyptus sludge biochar and was also higher in the high-temperature
feedstock biochars had low CEC values, whereas papermill wood and cow manure biochars than the other biochars
sludge and the low-temperature cow manure biochars had (Table 4). Both silver thiourea and ammonium acetate
high CEC values. In the case of original biochar samples, removed exchangeable (and soluble) cations with similar

Table 4. Mean cation exchange capacity (þs.e., mmolc/kg) of the biochars after removing soluble salts and carbonates
(CECAW) and the original biochars (CECO) as measured by the silver thiourea method
Exchangeable plus soluble cation values (mmolc/kg) for the original biochar samples are also given

Biochar treatment CECAW CECO Exchangeable cations

Ca Mg Na K
E. saligna wood
4008C, activated 47.3 ± 4.7 134.4 ± 3.7 40.1 ± 2.7 1.2 ± 0.2 13.0 ± 0.6 3.3 ± 0.4
5508C, activated 39.0 ± 1.0 272.1 ± 25.5 138.4 ± 11.4 2.0 ± 0.1 11.4 ± 0.2 7.3 ± 0.1
4008C, non-activated 39.1 ± 2.8 73.0 ± 3.2 27.7 ± 1.1 1.3 ± 0.1 4.9 ± 0.1 3.1 ± 0.3
5508C, non-activated 34.8 ± 2.5 91.2 ± 8.5 90.0 ± 3.6 1.3 ± 0.1 8.6 ± 0.2 4.8 ± 0.2
E. saligna leaves
4008C, activated 77.7 ± 5.3 71.0 ± 1.3 47.1 ± 2.9 20.5 ± 0.8 58.2 ± 0.8 72.2 ± 2.9
5508C, activated 57.4 ± 6.0 127.6 ± 12.3 77.9 ± 1.3 25.5 ± 3.8 65.0 ± 0.9 89.0 ± 1.7
Paper sludge
5508C, activated 212.1 ± 16.7 227.1 ± 10.9 193.7 ± 15.5 24.5 ± 0.9 21.6 ± 2.5 0.7 ± 0.0
Poultry litter
4008C, non-activated 172.9 ± 3.7 145.1 ± 15.4 28.5 ± 1.3 46.1 ± 2.9 100.1 ± 1.1 360.0 ± 12.3
5508C, activated 104.9 ± 2.8 451.5 ± 16.3 27.9 ± 1.0 111.8 ± 7.9 108.2 ± 1.5 417.5 ± 36.4
Cow manure
4008C, non-activated 208.8 ± 7.2 221.9 ± 5.5 39.9 ± 0.3 54.0 ± 0.6 125.8 ± 1.4 475.1 ± 8.3
5508C, activated 127.3 ± 3.1 286.3 ± 28.5 121.2 ± 1.3 107.8 ± 2.4 93.9 ± 0.6 407.6 ± 10.4
l.s.d. (P = 0.05) 9.3 43.0 17.9 8.5 3.3 36.1
Evaluation of biochars for soil amendment Australian Journal of Soil Research 521

efficiency, as indicated by a good correlation between the sums for the total surface basicity of biochars. The carboxyl group also
of cations measured using these 2 methods (Fig. 2). decreased at higher temperature for most biochars, and the
activated low-temperature wood biochar had higher carboxyl
Surface acidic and basic functional groups of biochars groups than its non-activated counterpart. The high-temperature
The quantities of the carboxyl groups, the combined acidity of cow manure biochar had the highest surface basicity and the
the 3 functional groups (carboxyls + lactones + phenols), total low-temperature cow manure biochar had the highest surface
surface acidity (carboxyls + lactones + phenols + additional acidity. Overall, the papermill sludge and manure-based
acidic species), and surface basicity of the biochars are biochars had higher surface basicity than the eucalyptus
presented in Table 5. The total and combined surface acidity biochars.
of the 3 functional groups was higher in the low-temperature
than the high-temperature biochars; the reverse trend was found X-ray diffraction analysis
800 There was no difference in the mineral composition of activated
and non-activated low-temperature biochars made from
eucalyptus wood and leaves. The major crystalline phase in
Sum of cations, NH4OAc (mmolc /kg)

700
the 3 biochars produced from eucalyptus feedstocks at 4008C
600 was whewellite (calcium oxalate, Ca(C2O4).H2O), and these 3
biochars produced similar diffraction patterns (Fig. 3a). The
500 XRD patterns of these biochars also showed a broad hump with
centroid at ~3.8 Å, which indicates the presence of a largely
400 poorly crystalline, carbon-rich phase in these samples. Increase
in pyrolysis temperature to 5508C resulted in the loss of
300 whewellite structure, and calcite (CaCO3) formed in all 3
y = 0.95x + 54 eucalyptus feedstock biochars (Fig. 3b). Sylvite (KCl) was
200
R 2 = 0.96 also identified in leaf biochars at 5508C (XRD pattern not
shown). There was no difference in the XRD patterns of
100
manure-based biochars produced at 4008C and 5508C. Cow
0
manure biochars showed distinct peaks for quartz, kaolinite,
0 100 200 300 400 500 600 700 800 albite, sylvite, and calcite (Fig. 3c). Sylvite, quartz, and calcite
were the main phases in the poultry manure, and a broad hump
Sum of cations, AgTh (mmol c /kg)
with centroid at ~3.8 Å was also present (Fig. 3d). In the
Fig. 2. Relationship between sum of cations (mmolc/kg) of the original papermill sludge biochar, calcite was the predominant
biochars extracted by 1 M ammonium acetate (pH 7) and 0.01 M silver crystalline phase and a small amount of kaolinite was also
thiourea. present in this sample (Fig. 3e).

Table 5. Oxygenated acidic and basic functional groups (mean þ s.e., mmolc/g C) of biochars, after removing
soluble salts and carbonates, as determined by Boehm titrations

Biochar treatment Carboxyl Carboxyl + lactonic Total acidity Total basicity

+ phenolic
E. saligna wood
4008C, activated 0.83 ± 0.11 2.68 ± 0.14 5.71 ± 0.76 0.60 ± 0.16
5508C, activated 0.20 ± 0.08 0.65 ± 0.15 1.58 ± 0.13 0.35 ± 0.07
4008C, non-activated 0.26 ± 0.05 3.14 ± 0.09 6.07 ± 0.58 0.38 ± 0.08
5508C, non-activated 0.17 ± 0.05 0.53 ± 0.17 1.49 ± 0.55 0.31 ± 0.09
E. saligna leaves
4008C, activated 0.63 ± 0.11 2.67 ± 0.17 5.34 ± 0.73 0.93 ± 0.05
5508C, activated 0.24 ± 0.08 0.93 ± 0.13 2.39 ± 0.61 1.06 ± 0.11
Paper sludge
5508C, activated 0.43 ± 0.11 0.86 ± 0.10 3.27 ± 0.21 7.66 ± 1.66
Poultry litter
4008C, non-activated 0.83 ± 0.15 3.23 ± 0.14 5.10 ± 0.30 4.29 ± 0.23
5508C, activated 0.26 ± 0.09 1.20 ± 0.09 1.67 ± 0.05 2.20 ± 0.10
Cow manure
4008C, non-activated 2.01 ± 0.24 5.15 ± 0.09 8.08 ± 0.79 6.46 ± 0.27
5508C, activated 1.00 ± 0.24 2.12 ± 0.24 3.42 ± 0.40 10.28 ± 0.39
l.s.d. (P = 0.05) 0.39 0.42 1.52 1.54
522 Australian Journal of Soil Research B. Singh et al.

1200 1200
(a) Wh Ca
(b)
1000 1000
Wh Ca

800 800

600 Wh 600
Al Ca
Al Ca
400 400 Ca Ca

200 200

0 0

3000 400
(c) Qu (d) Qu
Sy
2500
300 Qu
Ca
2000
Intensity

1500 200 Ca Sy
Qu Sy
Qu Ca Qu
1000
100
Sy Sy
500 Hm Qu
Qu Qu
Ka Ka Ka Qu
0
0 5 15 25 35 45 55 65

3000
(e) Ca
2500

2000

1500

1000

Ca Ca Ca Ca Ca
500 Ca
Ka Ca

0
5 15 25 35 45 55 65
Degree two-theta (CoKα)

Fig. 3. Random powder X-ray diffraction patterns of selected biochars: (a) Eucalyptus saligna wood 4008C non-activated biochar;
(b) Eucalyptus saligna wood 5508C non-activated biochar; (c) cow manure, 5508C, activated biochar; (d) poultry litter, 5508C, activated
biochar; and (e) paper sludge, 5508C, activated biochar. Wh, Whewellite; Al, aluminium from holder; Ca, calcite; Ka, kaolinite; Qu, quartz; Hm,
hematite; Sy, sylvite.

Discussion grouped into 2 broad categories: (a) plant-based biochars,

This study has shown that feedstock type and pyrolysis made from eucalyptus wood and leaf materials, possessing
temperature can influence the measured chemical properties high C, low contents of total N, P, K, S, Ca, Mg, Al, Na,
of biochars. The influence of the steam activation treatment, and Cu, and low CEC and exchangeable cations values; and
which was evaluated for the wood biochars, on the chemical (b) manure-based biochars, made from poultry litter and cow
properties was relatively small. These results are consistent with manure, showing an opposite trend to the plant-based biochars
earlier studies (Gaskin et al. 2008; Novak et al. 2009), which for these properties. The papermill sludge biochar does not fit in
found that the chemical composition and nutrient concentrations either of the categories; it contained substantially higher calcite
of feedstocks and pyrolysis temperature can strongly influence content than other biochars as confirmed by the XRD and
biochar properties. The biochars used in this study can be chemical analyses. Calcite was probably added during the
Evaluation of biochars for soil amendment Australian Journal of Soil Research 523

paper-making process and it remained unaffected during the wood biochars. Such high pH values have been reported for
pyrolysis process so was inherited by the biochar. biochars (Gaskin et al. 2008) and the high pH has been attributed
Because of their low ash contents, a greater accumulation of to hydrolysis of salts of Ca, Mg, and K (Tyron 1948). The
the initial feedstock C and N was observed in the wood and leaf increase in pH of the wood biochars upon steam activation
biochars during the pyrolysis process compared with the treatment, however, is not supported by ash, alkaline elements,
manure-based and papermill sludge biochars (Table 1). These and calcite contents of biochars (Tables 1–3). The extremely
results are consistent with the study of Gaskin et al. (2008), who high pH value of some biochars is possibly due to the presence of
also found higher C content in the plant-based biochars carbonate and biocarbonate of Na in the biochars. High pH and
(e.g. peanut hulls, pine chips) than the manure-based (poultry the presence of calcite is a useful attribute of biochars for
litter) biochar. The mineral components in the feedstocks are neutralising soil acidity (Glaser et al. 2002). The papermill
mostly non-volatile in nature (Knicker 2007; Gaskin et al. 2008) sludge biochar particularly possesses high liming value and
and it is likely that the disproportionate loss of volatile (C, H, O, can effectively ameliorate soil acidity (Van Zwieten et al.
and N) v. non-volatile components during pyrolysis of ash-rich 2010); other studies have reported an increase in soil pH
papermill sludge and manure-based feedstocks caused a following application of alkaline biochars (e.g. Chan et al.
decrease or no change in the C and N contents in the 2007; Novak et al. 2009). Extremely high EC values
biochars compared with the original feedstock. In fact, the particularly for manure feedstock biochars confirm the
high temperature pyrolysis led to a further decrease in the C presence of high amount of water-soluble salts in these biochars.
and N contents of the manure-based biochars, but a reverse trend The substantial decrease in the ash content of the papermill
was found in the plant-based biochars. sludge biochar with increased ashing temperature from 5508C to
The degree of aromaticity has been shown to increase with 7008C could be due to the loss of CO2 from structural
increasing charring temperature (Baldock and Smernik 2002; disintegration of calcite, which is a major component in the
Nguyen et al. 2010); hence, the C-rich biochars made at high biochar. Thermal decomposition of calcite commences at
temperature may have greater soil C-sequestration value than the ~6008C and is complete at 8508C when it is converted to
low-temperature biochars (Singh and Cowie 2008). On the other CaO (Rodriguez-Navarro et al. 2009).
hand, manure-based biochars, e.g. poultry litter biochar, The higher potential CEC values for the untreated biochars
especially synthesised at low temperature, may comprise a compared with the acid-washed and salt-free biochars
considerable proportion of aliphatic C and low proportion of (Table 4) suggest that the CEC was overestimated due to the
aromatic aryl C (McBeath and Smernik 2009). Because of this, presence of water-soluble salts of common cations or indirectly
and their high nutrient content, the manure-based biochars may by increased pH of the solution during extraction of biochars.
mineralise and release nutrients more rapidly in soil than the The overestimation of potential CEC by the silver thiourea
plant-based biochars rich in condensed aromatic structures method in the original biochar could be due to the
(Singh and Cowie 2008; Novak et al. 2009). precipitation of Ag2S at pH >8.0. Fresh biochars produced
For organic substrates, a C : N ratio <20 : 1 is generally taken from plant biomass do not contribute much CEC, and
as a predictor of N mineralisation, and for values >30 : 1 an relatively higher CEC values for manure and papermill
initial net immobilisation of N is expected (Stevenson and Cole sludge biochars were possibly due to the presence of clay
1999). Using this criterion, increased N availability is expected minerals in these biochars. The general decrease in CEC of
only from application of cow manure and poultry litter biochars biochars pyrolysed at 4008C compared to 5508C is consistent
(C : N <15) to soil. However, the relatively recalcitrant nature of with the published data (Guo and Rockstraw 2007; Gaskin et al.
C in other biochars may fail to enhance microbial activity (due to 2008).
low C availability) and, hence, may not induce N immobilisation The acidic functional groups on biochar surfaces contribute
in soil. Indeed, higher availability of N in Terra Preta soil to the CEC value of biochars (Cheng et al. 2006, 2008). In our
compared to an adjacent Ferrosol was observed by Lehmann study, the acidic functional groups’ values were generally
et al. (2003). The relatively high levels of total and available P in similar within each of the low and high pyrolysis temperature
the poultry and cow manure biochars, with available P categories for various feedstocks, except for the cow manure
constituting >30–56% of the total P in these biochars, biochars, which had higher amounts of the acidic functional
indicate that they are a good source of P in soil. groups than the other biochars (Table 5). The potential CEC of
The high levels of K, S, and Mg in the manure-based biochars the acid-washed cow manure biochars was also higher than the
(Table 2) are consistent with the results of Gaskin et al. (2008), other biochars. In contrast to factors such as steam activation and
who reported much higher K and Mg in poultry litter biochar feedstock type, pyrolysis temperature had a major influence on
than in the biochars made from peanut hull and pine chips. The the amounts of acidic functional groups; consistent with the
quantities of non-essential and toxic trace elements are well potential CEC of the acid-washed biochars, except for the
below the ecological investigation levels, and similarly the wood biochars, these groups decreased significantly at 5508C
PAHs values are well below (<0.5 mg/kg) the health compared with 4008C pyrolysis temperature (Tables 4 and 5).
investigation levels (NEPM 1999), which make these The carboxylic functional groups have the lowest pK values
biochars safe for soil application. and contribute most to the CEC among the organic acidic
The relatively high pH of the manure-based, papermill functional groups (Boehm 1994). In the biochar studied here,
sludge, and leaf biochars could have resulted from the carboxyl groups were not a major component of the total
presence of greater quantities of salts of alkali and alkaline surface acidity and there was an increase in the carboxyl
elements (Na, K, Ca, Mg) and calcite in these biochars than the groups upon activation of low-temperature wood biochar
524 Australian Journal of Soil Research B. Singh et al.

(Table 5). This suggests that activation may be a useful approach information about their mineralogical composition and
to increase the carboxylic groups and consequently their transformation in mineral phases at different pyrolysis
contribution to CEC. The decrease in surface acidity and CEC temperatures, and it should be used in combination with the
at higher pyrolysis temperature may limit the ability of high- other chemical and spectroscopic methods for biochar
temperature biochars to increase nutrient cation retention characterisation.
capacity of soil, compared with low-temperature biochars, at
least in the short term (Liang et al. 2006; Novak et al. 2009).
Conclusions
However, acidic functional groups, especially the carboxyl
group, can increase considerably following oxidation of In addition to carbon sequestration potential, biochars prepared
biochar in soil (Cheng et al. 2006). The development of from eucalypt, manure, and papermill sludge feedstocks through
appreciable amount of negative charge on biochars may slow pyrolysis are potential sources of nutrient elements, and
take months to years before it generates high CEC in the range leaf, manure-based, and paper-sludge biochars possess good to
found in Terra Preta (Glaser et al. 2002; Cheng et al. 2008). The very high liming potential. The biochars contain negligible
presence of surface basicity (Table 5) suggests that fresh levels of toxic elements and PAHs; therefore, they do not
biochars will also have some capacity to retain anions in soil; possess soil contamination risk for these compounds.
however, the surface basicity may decrease and eventually Feedstock source and/or pyrolysis temperature significantly
disappear with progressive oxidation of biochar (Cheng et al. influence charge properties and the contents of C, nutrients,
2008). and liming potential of biochars. It is thus important to
The analyses of fresh biochars indicate that eucalyptus characterise biochars in relation to their properties, thereby
biochars generally, and in particular eucalyptus wood allowing users to select the most suitable biochar for a
biochars, have low nutrient contents and higher C contents specific soil application; for example, nutrient-rich and high
than the manure-based biochars. The mineral nutrient CEC biochars could potentially be applied to degraded, nutrient-
composition of eucalyptus wood biochars was comparable poor soil, or biochars with high acid-neutralising capacity could
with biochars made from a woody feedstock such as be applied to alleviate soil acidity. However, further research on
pinechips (Gaskin et al. 2008). These results are contrary to the forms and bioavailability of nutrients present in biochar is
the observation made by Orians and Milewski (2007) that required. Due to the presence of water-soluble salts and calcite,
Australian native plants growing on nutrient-poor soils some of the routinely used laboratory procedures for soil
produce nutrient-poor tissues. analysis are not suitable for biochar characterisation.
One of the aims of this study was to evaluate the suitability of
standard soil analytical methods to characterise biochars. We Acknowledgements
found that the routinely used shaking time of 30 min for
We thank Tshewang Namgay, Irshad Bibi, Nabeel Niazi, Kamaljeet Kaur,
measuring EC underestimated the soluble salt content of
Cheryl Poon, and Blake Hatton for their assistance in the laboratory analyses,
many biochars tested in this study. The presence of soluble and Peter Geelan-Small for his advice on statistical analysis.
salts in biochars interfered particularly with the measurement of
surface charge properties, so ideally soluble salts should be
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