CSIRO PUBLISHING

Soil Research, 2014, 52, 155–163

http://dx.doi.org/10.1071/SR13187

Effect of ageing on surface charge characteristics and

adsorption behaviour of cadmium and arsenate in two
contrasting soils amended with biochar

Chamali Laksala Nagodavithane A, Balwant Singh A,B, and Yunying Fang A

A
Department of Environmental Sciences, Faculty of Agriculture and Environment, The University of Sydney,
NSW 2006, Australia.
B
Corresponding author. Email: balwant.singh@sydney.edu.au

Abstract. Biochar has been recognised as an effective amendment for the remediation of contaminated soils; however,
there is limited knowledge on the effects of biochar ageing in soil on its adsorption behaviour for cationic and anionic
species. Biochars are considered to develop negative charge from oxidation with ageing, which may create additional
interaction mechanisms for adsorption processes. In the present study, surface charge characteristics and cadmium (Cd) and
arsenate (AsO43–) adsorption behaviour of aged biochar were investigated in two soils with variable charge, an Oxisol and
an Inceptisol, by comparing (i) unamended soils, and soils amended with (ii) fresh biochar (4508C) and (iii) biochar (4508C)
aged for 12 months, applied at a rate of 2% w/w. Surface charge characteristics were assessed using the ‘index’ ion
adsorption method, with a LiCl electrolyte. Batch adsorption studies were conducted using fresh and aged soil–biochar
mixtures. In contrast to previous studies, the results provided no evidence of an increase in cation exchange capacity as a
consequence of biochar ageing. There was an increase in Cd adsorption in the presence of aged biochar in both soil types
compared with unamended soils and soils amended with fresh biochar. Results also indicated an increase in AsO43–
adsorption in the Inceptisol amended with aged biochar, whereas a decrease in AsO43– adsorption was observed in the
Oxisol amended with aged biochar. Overall, the study has highlighted that adsorption behaviour of aged biochar varies
depending on the ion it interacts with, soil properties and solution pH.

Additional keywords: black carbon, heavy metal contamination, organic matter.

Received 26 June 2013, accepted 4 October 2013, published 27 February 2014

Introduction
Biochar is a solid material derived from the carbonisation of
biomass, and it has received increased research focus over
recent years. Biochar is distinguished from other charred
products along the black carbon continuum with respect to its
intended usage, which is primarily for soil application and as a
form of storage of atmospheric carbon in soil (Kookana et al.
2011). Incorporation of biochar into the soil profile has produced
various agronomic and environmental benefits, including
improvements to soil properties and crop yield (Kimetu et al.
2008; Novak et al. 2009), enhanced nutrient retention (Laird
et al. 2010), and reduced availability of heavy metals in soils
(Cao et al. 2009; Namgay et al. 2010).
Biochar properties are influenced by various parameters,
notably the conditions of pyrolysis, and the feedstock source
(Novak et al. 2009; Singh et al. 2010). The agronomic and
environmental benefits of biochar are also likely to vary
depending on the biochar properties and soil type into which
it has been amended (Novak et al. 2009; Singh et al. 2010; Van
Zwieten et al. 2010; Kookana et al. 2011). Although biochar is
regarded as being chemically and biologically recalcitrant in
nature, it is subject to a geochemical weathering process, termed
‘ageing’, once added to the soil (Cheng et al. 2006; Hale et al.
2011; Joseph et al. 2010). The key contributors to biochar
ageing are sorption of environmental constituents, primarily
natural organic matter (OM), and oxidation through both
abiotic and biotic mechanisms (Cheng et al. 2006, 2008;
Cheng and Lehmann 2009; Zimmerman 2010).
Studies on biochar ageing are scarce; however, useful
insights can be gained from the ageing of other carbonised
materials (e.g. activated carbon), which have been studied more
extensively. Cheng and Lehmann (2009) examined the ageing of
black carbon and reported marked differences in the surface
properties of historic black carbon samples, notably an increase
in oxygen (O) concentration and the concomitant reduction in
carbon (C) content, compared with present-day black carbon
samples. It has been postulated that the C that is oxidised first
is more likely to be aliphatic and closer to the external surface
of the particle, a view supported by other authors (Liang et al.
2006; Zimmerman 2010). A hallmark of the surface chemistry
of aged black carbon is the formation of O-containing functional
groups, especially carboxylic and phenolic functional groups,
which in turn provide sites for increased negative charge (Cheng
et al. 2006, 2008; Cheng and Lehmann 2009). A concomitant

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156 Soil Research
reduction in surface positive charge has also been observed.
Evidence suggests that the organic functional groups and
adsorption sites present on the surface of biochar may
influence its cation exchange capacity (CEC) (Cheng et al.
2006, Cheng et al. 2008; Liang et al. 2006; Cheng and
Lehmann 2009) and, in turn, play a crucial role in the
formation of biochar–trace element complexes (Lee et al. 2010).
Cadmium (Cd) and arsenic (As) were chosen for evaluation
of the adsorption characteristics of soil–biochar systems; the
common ionic species (Cd2+; arsenate, AsO43–) of these
elements are adsorbed through inner-sphere complex
formation on variable-charge surfaces, and may provide
additional information about the role of aged biochar in the
adsorption of environmentally important ionic species. In the
agricultural context, heavy metal contamination is a serious
problem, particularly in areas closer to industrial and mining
sites, or peri-urban agricultural areas. Heavy metals enter the soil
environment by various pathways, and once in the soil, they are
readily taken up by plants (Namgay et al. 2010; Singh 2001).
Cadmium is a cationic heavy metal that is highly toxic even
at low concentrations and is a common contaminant in
agricultural soils (Kachenko and Singh 2006; Singh 2001).
Soil contamination by AsO43–, an anionic species, is also a
major environmental threat, due to its high toxicity to plants,
animals and humans at elevated concentrations (Hartley and
Lepp 2008). The adsorption of heavy metals from the soil
environment thus plays a critical role in reducing ecological
and human health risks associated with heavy metal
contamination. Of the numerous soil remediation methods,
the addition of OM to soil offers a promising approach to
immobilising most trace elements. However, a shortcoming is
that once the OM decomposes, the adsorbed metals may be
released back into the soil (van Herwijnen et al. 2007). Biochar
is an alternative that may prove effective in adsorbing trace
elements from the soil, by forming complexes with metal
ions (Lee et al. 2010; Namgay et al. 2010). Due to the
highly recalcitrant nature of biochar, it is likely that the
biochar–trace element complexes formed will be more stable
than OM–trace element complexes (Namgay et al. 2010).
The adsorption capacity of biochar has been well
documented and is reviewed elsewhere (Kookana et al.
2011). However, a gap exists in our understanding of biochar
ageing and the way in which ageing may affect the adsorption
behaviour of biochar. In this study, the effect of biochar
ageing was investigated, by examining (i) surface charge
characteristics and (ii) adsorption behaviour of Cd and
AsO43–, in two contrasting soils.
Materials and methods
Soil and biochar
Two contrasting Australian soils, an Oxisol (Soil Taxonomy,
Soil Survey Staff 2010) or Ferrosol (ASC, Isbell 2002) from
Wollongbar (288500 S, 1538250 E), New South Wales, and an
Inceptisol or Tenosol, from Wongan Hills (358890 S, 1168380 E),
Western Australia. Biochar samples were sourced from a long-
term incubation experiment on the interaction of biochar in
different soil types (Fang et al. 2014). Six different soil systems
were studied: (i) Oxisol without amendment, (ii) Oxisol
C. L. Nagodavithane et al.
amended with fresh biochar, (iii) Oxisol amended with
biochar and aged for 12 months, (iv) Inceptisol without
amendment, (v) Inceptisol amended with fresh biochar, and
(vi) Inceptisol amended with biochar and aged for 12 months.
In soil samples amended with fresh biochar, the biochar had
been added to the two soils and was immediately oven-dried in
order to remove the moisture content. In soils amended with
biochar and aged for 12 months (referred to as aged biochar), the
biochar had been incubated in the two soils at 408C at 70%
water-holding capacity for 12 months.
The biochar was produced from a Eucalyptus salinga wood
feedstock source that had been grown for 2 years under an
environment of elevated CO2 (Keith et al. 2011). The biochar
was produced at 4508C by slow pyrolysis (5–108C per min
heating rate, 40 min residence time) at Pacific Pyrolysis Pty Ltd,
Somersby, NSW. The biochar was ground to <2 mm before
being incorporated into the soil and was applied at a rate of 2%
w/w, which approximately corresponds to a field application
rate of 40 t ha–1. Soil samples were homogenously mixed with
the biochar. Important properties of the soil and biochar are
presented in Table 1.
Samples of fresh biochar, unamended soils, or soils amended
with biochar were suspended in 0.01 M Ca(NO3)2 using a
sample : solution ratio of 1 : 10, to determine extractable Cd
and As. Extractable Cd and As concentrations in the solution
were below their detection limit of 20 and 100 mg L–1,
respectively.
Surface charge characteristics
Surface charge characteristics of soil and soil–biochar mixtures
were assessed using the ‘index’ or ‘indifferent’ ion adsorption
method with a LiCl electrolyte (Chorover et al. 2004). The
method involved three main steps, as briefly described below:
1. Soil–biochar slurries, saturated with decreasing
concentrations of LiCl (1, 0.2, and 0.01 M) were prepared
using a soil : solution ratio of 1 : 5.
2. Approximately 0.3 g of Oxisol–biochar slurry and 0.8 g of
Inceptisol–biochar slurry, on a dry-weight basis, were
transferred to pre-weighed 50-mL centrifuge tubes; 20 mL
of 0.01 M LiCl was added to the tubes and the solution pH
was adjusted across a pH range of 3–7 in increments of 0.5.
Equilibrium pH was measured immediately following
centrifugation and the concentrations of Li and Cl in the
supernatant were measured.
3. Ammonium nitrate (20 mL, 1 M) was added to the centrifuge
tubes and shaken for 1 h to displace the Li and Cl ions
adsorbed by the soil or soil–biochar mixtures. The
procedure was repeated twice and the extracts were
pooled. The concentration of Li and Cl ions extracted by
1 M ammonium nitrate solution was measured using a
Varian SpectrAA 220FS atomic absorption spectrometer
(AAS) (Agilent Technologies Inc., Santa Clara, CA, USA)
and a Metrohm Tiamo 1.3 ion analyser (Metrohm AG,
Herisau, Switzerland), respectively.
The adsorption of Li and Cl ions was calculated using the
following equation:
K or Cl ¼ nLi ðor nCl Þ  Mentr mLi or ðMentr mCl Þ
Surface charge properties of aged biochars
Table 1. Soil and biochar properties (Fang et al. 2014; Keith et al. 2011)
Property Oxisol
pH (1 : 5 H2O) 5.70
EC (1 : 5, mS/m) 15.0
Clay (%) 44
CEC (mmolc kg–1) 119.9
Total C (%) 4.39
Specific surface area (m2 g–1) – –
Pore volume (%) – –
Minerals in the clay fraction (<2 mm) Goethite 20–40%
Gibbsite 20–40%
Kaolinite 20–40%
Hematite 5–20%
Anatase 5–20%
Hydroxy-interlayered vermiculite  5%
where nLi or nCl was the Li and Cl extracted in 1 M ammonium
nitrate, Mentr denotes the mass of entrained solution left in the
centrifuge tube before ammonium nitrate replacement, and mLi
or mCl denotes the concentration of Li or Cl ions in the
supernatant.
Adsorption studies
To elucidate the adsorption capacity of aged biochar, we
compared soil, soil amended with fresh biochar and soil
amended with aged biochar. Batch experiments were
conducted under ambient laboratory conditions, at the pH of
the soil or soil–biochar mixture, and two replicates were used for
each adsorbate.
For Cd experiments, separate 1-g samples of Inceptisol or
Inceptisol amended with biochar were used. Due to the higher
absorption capacity of the Oxisol than the Inceptisol, as
determined through a preliminary study, only 0.5-g samples
of the Oxisol soil systems were used. Cadmium solutions
were prepared using Cd(NO3)2, ranging from 0 to 2  10–4 M
in a background solution of 0.01 M Ca(NO3)2. Cadmium
concentration in the initial and final equilibrium solutions was
measured using AAS. All calculations were based on an oven-
dried soil mass.
A second batch experiment was conducted to investigate the
effect of an aged biochar on AsO43– adsorption in the soils, using
1-g soil and soil–biochar samples. A preliminary study identified
the Inceptisol as having an extremely low AsO43– adsorption
capacity compared with the Oxisol. The initial As concentration
range was varied for the two soil types (As of 0–5 and 0–100 mg
mL–1 for Inceptisol and Oxisol, respectively) to account for the
marked difference in their adsorption capacities. Arsenic
solutions were prepared from AR-grade Na2HAsO4.7H2O
in a background solution of 0.01 M Ca(NO3)2. Arsenate
concentration in the initial and final equilibrium solutions was
measured with a Varian Model 720 inductively coupled plasma
optical-emission spectrometer.
Cadmium and AsO43– adsorption data were fitted to the non-
linear form of the Freundlich and Langmuir equations. The
Freundlich equation can be expressed as:
x ¼ kF C n
Soil Research 157
Inceptisol Biochar 4508C
5.60 8.64
8.2 89.4
1.3 –
24.4 11.4
0.95 67.4
191
57
Kaolinite 60%
Quartz 5%
Illite 5%
where x is the amount adsorbed (mmol kg–1), C is the equilibrium
concentration (mmol L–1), kF is a Freundlich coefficient
(mmol1 – n Ln kg–1) reflecting the number of adsorption sites,
and n (L mmol–1) relates to the type of adsorption sites at which
adsorption occurs.
The Langmuir equation may be expressed as:
bkL C
x¼
1 þ kL C
where C is the equilibrium concentration (mmol L–1), x is the
amount adsorbed (mmol kg–1), kL is a constant related to bonding
energy (L kg–1), and b is the maximum amount of adsorbate that
can be adsorbed (mmol kg–1).
Results
Surface charge characteristics
Investigating any changes in the surface charge properties
following biochar ageing may explain trends observed in the
adsorption studies. The results of the surface charge analysis are
presented in Fig. 1. In each of the soil systems, the CEC was
found to be pH-dependent, with an increase in CEC with
increasing equilibrium pH (Fig. 1a, c). However, there were
no significant alterations in the CEC of soil–biochar mixtures
following ageing in both soil types. Systematic differences were
not observed in CEC between the unamended soil and the soils
amended with fresh and aged biochar. The results for anion
exchange capacity (AEC), in contrast to the CEC, were not
affected by pH (Fig. 1b, d). Across the equilibrium pH range,
a relatively constant AEC was observed, with only minor
fluctuations in Cl– ion concentration. The AEC value was
significantly lower than the corresponding CEC value over
the entire pH range; thus, a point of zero net charge (PZNC)
could not be derived.
Cadmium adsorption
Cadmium adsorption onto soil and soil–biochar mixtures
increased with increasing equilibrium Cd concentration for
both soil–biochar systems; however, at the same equilibrium
concentration the adsorption was >3 times greater for the Oxisol
systems than the corresponding Inceptisol systems (Fig. 2). For
both soils, there was an increase in the amount of Cd adsorbed in
158 Soil Research C. L. Nagodavithane et al.

Oxisol Oxisol + biochar Oxisol + biochar Inceptisol Inceptisol + biochar Inceptisol + biochar
(fresh) (aged) (fresh) (aged)

35 10
(a) (c)
CEC (mmolc kg–1) 8
25
6

4
15
2

5 0

0.004 0.003
(b) (d )
AEC (mmolc kg–1)

0.003
0.002

0.002

0.001
0.001

0.000 0.000
3 4 5 6 7 3 4 5 6 7

Equilibrium solution pH

Fig. 1. Surface charge characteristics of the Oxisol and Inceptisol soil systems: (a) cation exchange capacity
and (b) anion exchange capacity of the Oxisol (unamended soil), Oxisol amended with fresh biochar and
Oxisol amended with biochar and aged for 12 months, and (c) cation exchange capacity and (d) anion
exchange capacity of the Inceptisol (unamended soil), Inceptisol amended with fresh biochar and Inceptisol
amended with biochar and aged for 12 months.

6000 1600
(a) (b)
Cd sorbed (µmoles kg–1)

5000
1200
4000

3000 800

2000
Oxisol 400 Inceptisol
1000 Oxisol + biochar (fresh) Inceptisol + biochar (fresh)
Oxisol + biochar (aged) Inceptisol + biochar (aged)
0 0
0 50 100 150 0 50 100 150
Equilibrium concentration (µmol L–1)

Fig. 2. Cadmium adsorption isotherms for the Oxisol and Inceptisol soil systems: (a) Oxisol (unamended
soil), Oxisol amended with fresh biochar and Oxisol amended with biochar and aged for 12 months, and (b)
Inceptisol (unamended soil), Inceptisol amended with fresh biochar and Inceptisol amended with biochar and
aged for 12 months. Plotted values are averages of the two replicates.

the following order: soil < soil amended with fresh biochar < soil
amended with aged biochar.
The Cd adsorption capacity of the various soil systems was
quantified by applying the non-linear form of the Freundlich and
Langmuir equations to the adsorption data. The coefficients,
along with the R2 and Akaike information criterion (AIC) values
are shown in Table 2. The AIC is considered a better measure
of the fit than the correlation coefficient, R2, for the non-linear
Freundlich and Langmuir functions (Akaike 1981). In a
qualitative sense, the Freundlich kF and the Langmuir b
coefficients essentially describe similar adsorption parameters
(Singh and Gilkes 1991). The Cd adsorption capacity of
the soils, as indicated by the Langmuir maximum, b, was
significantly greater across the Oxisol soil systems than the
Inceptisol systems, hence providing evidence of the higher Cd
adsorption capacity of the Oxisol. This is consistent with the kF
values, indicating a larger number of adsorption sites available
for Cd adsorption in the Oxisol than the Inceptisol soil systems.
Across both soil types, the values of the kF and b coefficients
were higher in the soil amended with aged biochar than in the
unamended soil and the soil amended with fresh biochar. This
implies that ageing of biochar creates more adsorption sites and
Surface charge properties of aged biochars Soil Research 159

Table 2. Freundlich and Langmuir coefficients for the cadmium adsorption data for the six soil and soil–biochar systems
Regression coefficients and Akaike information criterion (AIC) for the two equations are provided

Soil system Freundlich equation Langmuir equation

KF (±s.e.) n (±s.e.) R2 AIC KL (±s.e.) b (±s.e.) R2 AIC
(mmol1–nLn kg–1) (L mmol–1) (L kg–1) (mmol kg )–1

Oxisol 286.1 ± 77.6 0.52 ± 0.06 0.96 100.5 0.020 ± 0.004 4608 ± 377 0.98 93.5
Oxisol + biochar (fresh) 289.2 ± 96.3 0.56 ± 0.08 0.95 105.1 0.017 ± 0.005 5995 ± 771 0.97 100.0
Oxisol + biochar (aged) 491.2 ± 85.8 0.52 ± 0.04 0.98 102.1 0.024 ± 0.002 7472 ± 320 0.99 90.6
Inceptisol 46.1 ± 10.7 0.59 ± 0.05 0.98 77.7 0.010 ± 0.001 1511 ± 115 0.99 70.7
Inceptisol + biochar (fresh) 46.5 ± 10.8 0.65 ± 0.05 0.98 79.1 0.009 ± 0.002 2006 ± 241 0.99 76.9
Inceptisol + biochar (aged) 58.3 ± 8.7 0.67 ± 0.03 0.99 76.5 0.008 ± 0.001 2865 ± 255 0.99 74.5

30 000 160
As sorbed (µmoles kg–1)

(a) (b)

120
20 000

80
10 000
Oxisol
40 Inceptisol
Oxisol + biochar (fresh)
Inceptisol + biochar (fresh)
Oxisol + biochar (aged)
Inceptisol + biochar (aged)
0 0
0 100 200 300 400 500 0 10 20 30 40 50 60 70

Equilibrium concentration (µmol L–1)

Fig. 3. Arsenate adsorption isotherms for the Oxisol and Inceptisol soil systems: (a) Oxisol (unamended
soil), Oxisol amended with fresh biochar and Oxisol amended with biochar and aged for 12 months, and (b)
Inceptisol (unamended soil), Inceptisol amended with fresh biochar and Inceptisol amended with biochar and
aged for 12 months. Plotted values are averages of the two replicates.

increases maximum Cd adsorption. Comparison of the
coefficient for bonding energy, kL, reveals a higher bonding
energy in the Oxisol soil systems than the Inceptisol systems.
However, within each soil type, the addition of biochar appeared
to have no major effect on this parameter. The Oxisol soil
systems apparently have a lower n coefficient value than the
Inceptisol soil systems, suggesting that different types of
adsorption sites may be present in the two different soil
types. On average, the equilibrium solution pH increased by
0.14 and 0.48 pH units for the fresh and aged biochar systems
of the Oxisol, and the corresponding increases for the Inceptisol
systems were 0.59 and 0.69 pH units.
Arsenate adsorption
The adsorption isotherms for the AsO43– experiments are
presented in Fig. 3. The results demonstrate a different
adsorption pattern for AsO43– compared with Cd, in both soil
types. In the Oxisol system, AsO43– adsorption onto soil and
soil–biochar mixtures increased with increasing equilibrium
AsO43– concentration (Fig. 3a); this trend began to plateau at
higher equilibrium AsO43– concentrations (~250 mmol L–1). For
the unamended Oxisol and Oxisol amended with fresh
biochar, the difference in the AsO43– adsorption behaviour
was negligible, with data points overlapping across the
equilibrium concentration range. In the presence of aged
biochar, a reduction in AsO43– adsorption is evident, with the
reduction in the kF and b values from 4064 to 3608 mmol1 – n Ln
kg–1, and 28 630 to 26 870 mmol kg–1, respectively, compared
with the unamended soil.
Figure 3b shows the AsO43– adsorption data for the Inceptisol
soil systems, where a nearly linear relationship exists between
equilibrium AsO43– concentration and AsO43– adsorbed over
the concentration range studied. For the Inceptisol, only the
Freundlich equation provided a valid fit for the data for the three
systems (Table 3); thus, the Langmuir equation parameters will
not be used for comparison between the soil systems. There were
only minor differences in the AsO43– adsorption behaviour of
the unamended Inceptisol and the Inceptisol amended with fresh
biochar, a trend that was also observed in the Oxisol systems.
However, in contrast to the Oxisol systems, the Inceptisol
amended with aged biochar had a higher AsO43– adsorption
capacity than the unamended soil and the soil amended with
fresh biochar. This finding is quantified by the higher kF value
(Table 3) in the Inceptisol amended with aged biochar than in
the two other Inceptisol soil systems. The extremely low AsO43–
adsorption capacity of the Inceptisol soil systems is apparent by
the 1000–3000 fold reduction in the KF values in the Inceptisol
systems relative to the Oxisol systems. The higher n coefficient
value of the Inceptisol, compared with the Oxisol soil systems,
suggests that different types of AsO43– adsorption sites may be
present in the two different soil types. Similar to the Cd
adsorption experiments, a small increase (0.33–0.56 pH units)
in the equilibrium solution pH was observed following the
160 Soil Research
Table 3. Freundlich and Langmuir coefficients for the arsenate adsorption data for the six soil and soil–biochar systems
Regression coefficients and Akaike information criterion (AIC) for the two equations are provided
Soil system Freundlich equation
KF (±s.e.) n (±s.e.) R2
(mmol1–n Ln kg–1) (L mmol–1)
Oxisol 4064 ± 220 0.33 ± 0.01 0.99
Oxisol + biochar (fresh) 4037 ± 306 0.33 ± 0.01 0.99
Oxisol + biochar (aged) 3608 ± 221 0.33 ± 0.01 0.99
Inceptisol 2.65 ± 1.09 0.93 ± 0.11 0.95
Inceptisol + biochar (fresh) 1.49 ± 0.73 1.08 ± 0.13 0.95
Inceptisol + biochar (aged) 3.78 ± 0.72 0.89 ± 0.05 0.99
AsO43– adsorption in the soil–biochar systems, except for the
freshly amended Oxisol where pH remained similar to the
unamended soil.
Discussion
Surface charge characteristics
This study is one of the first to document the effects of biochar
ageing on surface charge characteristics and adsorption
behaviour. Our results do not show evidence of an increase
in CEC with biochar ageing, which contrasts with previous
findings (Cheng et al. 2006, 2008; Liang et al. 2006; Cheng and
Lehmann 2009). In a key study by Cheng and Lehmann
(2009), techniques of X-ray photoelectron spectroscopy and
Fourier-transform infrared spectroscopy were used to examine
aged black carbon samples, showing an increase in O
concentration and a concomitant reduction in C content
compared with present-day black carbon samples.
Furthermore, the authors noted the formation of O-containing
functional groups, notably carboxylic and phenolic groups,
which provided sites for increased negative charge, while a
reduction in surface positive charge and a lower PZNC was also
observed (Cheng et al. 2006, 2008). Nguyen and Lehmann
(2009) also reported an increase in CEC in corn black
carbon after ageing for 1 year, which was well correlated
with the increase in O/C values. In their study, black carbon
decomposition was investigated using corn stover residue and
oakwood-derived black carbon, produced at 350 and 6008C,
respectively, and incubated with pure white sand.
Our results are, however, inconsistent with previous findings,
and we propose a range of explanations to account for the
observed differences. The biochar used in the present study
had been aged for a relatively short period of 1 year, and perhaps
limited oxidation of biochar has occurred in the soil systems
investigated here. It has been suggested that a certain period
may be required for the development of functional groups
and for the penetration of oxidation into the interior domain
of the biochar particles (Cheng et al. 2006, 2008). The historical
black carbon samples used in the study by Cheng et al. (2008)
had been aged for 130 years and showed much greater oxidation
than black carbon aged for 12 months.
It is also plausible that the development of surface negative
charge is influenced by the nature of the soil system. In the study
by Nguyen and Lehmann (2009), for example, black carbon was
incubated with pure sand, whereas in the present study the soil
C. L. Nagodavithane et al.
Langmuir equation
AIC KL (±s.e.) (L kg–1) b (±s.e.) R2 AIC
(mmol kg–1)
158.9 0.025 ± 0.006 28630 ± 1558 0.97 182.5
165.9 0.027 ± 0.006 27990 ± 1425 0.97 181.9
159.5 0.021 ± 0.005 26870 ± 1417 0.97 181.1
68.0 0.003 ± 0.004 797 ± 908 0.96 106.8
69.1 – – – –
58.6 0.004 ± 0.002 813 ± 351 0.99 58.0
system was characterised by variable charge. The interactive
processes that take place in variable charge systems are likely
to differ from that of pure systems (Naidu et al. 1997). The
negatively charged surfaces developed on biochar with ageing
may have formed direct or indirect surface complexes with
variable-charge minerals. This interaction may have masked
the negative charge on biochar surfaces, which was thus not
detected using the cation exchange procedure employed in our
study. Finally, the interaction of biochar with soil minerals may
have led to a decrease in oxidation, which has been observed in
C mineralisation experiments of soil–biochar mixtures (Fang
et al. 2014).
It is notable that there was a rapid mineralisation of biochar-C
during the initial stages (up to ~8 weeks) of the incubation in
both soils, and 2.29 and 1.47% of the biochar-C was mineralised
during the 12 months of incubation, from the Inceptisol and
Oxisol, respectively (Fang et al. 2014). Obviously, the oxidation
of the labile C of the biochar in the two soils did not produce
any negative charge on the biochar surfaces. The interactions
of iron (Fe) and aluminium (Al) oxides with soil OM may also
have masked the presence of positive charge in the soil–biochar
mixtures, particularly in the Oxisol.
Adsorption studies
The Oxisol soil systems had a greater adsorption capacity for
both Cd and AsO43– compared with the Inceptisol soil systems.
This result was not unexpected, considering the marked
difference in soil composition between the two soil types
(Table 1). Iron and Al oxides have been implicated in Cd
adsorption, and have been identified as having high affinity
for metal cations (Benjamin and Leckle 1982). The Oxisol
contains a large proportion (15% dithionite-extractable Fe) of
Fe oxides, namely goethite and hematite, as well as the Al
hydroxide gibbsite (Table 1). The absence of these minerals and
considerably lower clay content in the Inceptisol explain the
much lower Cd adsorption capacity of this soil compared with
the Oxisol. Similarly, AsO43– adsorption in soils has been
correlated with Al and Fe oxide content (Zhang and Selim
2005). In particular, Fe oxides have been extensively studied
as a suitable amendment for AsO43– immobilisation due to the
preferential attachment of AsO43– to Fe oxides in soil solution
(Hartley and Lepp 2008; Kumpiene et al. 2008; Niazi et al.
2011) via ligand exchange mechanisms (Zhang and Selim
2005). Furthermore, AsO43– has been found to bind more
Surface charge properties of aged biochars
strongly to clayey soils than to sandy soils (Kumpiene et al.
2008).
The higher percentage of OM (4.39%) in the Oxisol than the
Inceptisol (0.95%) may further contribute to the greater Cd
adsorption in the Oxisol. Early studies demonstrated the
chelating ability of soil OM to trace metals (McLaren and
Crawford 1973). It has been reported that increasing addition
of OM to soil leads to increased adsorption of Cd, which has
been attributed to the high CEC of soil OM (Eriksson 1988;
Bradl 2004). The role of OM in AsO43– immobilisation has been
controversial, with varied results reported (Kumpiene et al.
2008). The varying effect of OM on As mobility is believed
to stem from the pH of the soil system and the properties of OM.
The addition of fresh biochar in both soil types led to an
enhanced Cd adsorption. These results are consistent with
previous findings, demonstrating the adsorption capacity of
biochar for heavy metals (Cao et al. 2009; Namgay et al.
2010). The novel finding, however, was that the presence of
aged biochar led to a further increase in Cd adsorption in both
soil types. It has been proposed that the adsorption mechanism
is related to an increase in CEC and soil pH due to biochar
amendments (Liang et al. 2006; Kumpiene et al. 2008). The
liming potential of biochar has been identified in previous
studies (Chan et al. 2008). However, in the present study,
only a slight increase in pH was observed with biochar
amendments. It is therefore unlikely that the pH played a
major role in the increased Cd adsorption observed in the
presence of fresh and aged biochar.
The CEC serves as an indicator of biochar oxidation upon
ageing, whereby any changes to the value may signify new or
additional interaction mechanisms for adsorption processes
(Hale et al. 2011). However, based on the findings of our
surface charge study, the mechanism of CEC cannot explain
our adsorption data for aged biochar. Rather, we suggest that Cd
adsorption occurred via specific adsorption to biochar surfaces.
Harvey et al. (2011) suggested that Cd2+ adsorption on biochar
occurs predominantly via two distinct cation-p bonding
mechanisms involving Cd2+-p bonding with soft ligands (e.g.
C = O) or electron-rich domains on aromatic structures. The
contributions of these mechanisms to Cd2+ sorption on biochar
can exceed three times that expected for ion exchange; such
adsorption processes are probably responsible for the increased
Cd2+ adsorption in the biochar-amended soil systems in our
study, as there was no change in the CEC of the soil from biochar
addition. Harvey et al. (2011) also concluded that biochar CEC
may be a poor indicator of the sorption capacity of metals. It is
also possible that interaction of soil minerals, particularly Fe and
Al oxides, with aged biochar creates additional available sites for
Cd adsorption, on either the minerals or the biochar surfaces.
Surface metal OH groups present on Fe and Al oxides are able to
form stable complexes with Cd ions (McBride 1989). The
specific adsorption of Cd onto metal oxides involves covalent
and ionic bonding, via inner sphere complex formation, which
differs from electrostatic attraction mechanisms that operate in
the cation exchange process (Christensen and Huang 1999).
Thus, Cd can be adsorbed onto Fe and Al oxides surfaces even
when these minerals carry a net positive charge.
The results for the AsO43– adsorption study suggest that
negatively charged ionic species may interact differently with
Soil Research 161
aged biochar than do cationic trace elements, depending on the
soil type. In the Inceptisol soil systems, there was an increase in
the AsO43– adsorbed in the presence of aged biochar. We know
of no studies that have investigated AsO43– adsorption onto aged
biochar surfaces; however, researchers have investigated the
use of unaged biochar as a tool for remediating AsO43–-
contaminated soils. Namgay et al. (2010) observed significant
reductions in the concentration of AsO43– in maize shoots in a
biochar-amended sandy soil, which was largely attributed to the
adsorption of AsO43– onto the biochar surfaces. Those authors
also observed a small increase in phosphate-extractable As in
the biochar-amended soil compared with the control (Namgay
et al. 2010). Indeed, a strong adsorption of AsO43– to OM has
been reported, whereby compost addition was found to reduce
AsO43– accumulation in crops (Cao and Ma 2004). However, it
should be noted that in the present study, there were minimal
effects of fresh biochar on AsO43– adsorption compared with the
unamended soil systems. This result is in agreement with Hartley
et al. (2009), who observed negligible effects of biochar on
As mobility. We hypothesise that the presence of aged biochar
produces complex physicochemical changes within the soil
matrix, which leads to enhanced AsO43– adsorption; the
actual mechanism could not be ascertained due to the small
adsorption capacity of the soil–biochar systems in the Inceptisol.
It is also possible that dissolved organic C from biochar formed
complexes with AsO43– in soil solution, and such complexes
were then preferentially adsorbed onto biochar surfaces; this
effect will be more pronounced in the Inceptisol, with much
lower organic C content than the Oxisol. The small changes in
solution pH might not be the main driver for the differences
in the adsorption behaviour of the two soils after biochar
amendment.
In contrast to the Inceptisol soil systems, there was a
reduction in AsO43– adsorbed in the Oxisol amended with
aged biochar compared with the unamended soil and the soil
amended with fresh biochar. This implies that the difference in
soil composition between the two soil types is likely to play a
role in the adsorption behaviour of AsO43– to aged biochar
surfaces. Aged black carbon has been found to retain Fe on
particle surfaces once in contact with soils (Nguyen et al.
2009). The adsorption of organic molecules onto positively
charges surfaces of Fe and Al oxides has been shown to
decrease the adsorption sites available for anions (Gu et al.
1995; Van Ranst et al. 1998). Additionally, the adsorption of
organic compounds such as humic acid and fulvic acid has
been shown to decrease arsenate adsorption by competition
(Weng et al. 2012). An array of OM and minerals can be
found on the surfaces of aged biochar. Electron microprobe
analysis of a greenwaste biochar identified a high concentration
of clay minerals, consisting of different combinations of
Al, Si, C, Fe and Ti, and trace amounts of Mg, Mn, K, Na, P
and S, which were not observed in the fresh biochar (Joseph
et al. 2010). Thus, competitive adsorption between anions such
as phosphate (PO43–) and AsO43– may also be a contributing
factor to the decreased AsO43– adsorption (Hartley et al. 2009;
Lin et al. 2008). Alternatively, it is also possible that the
chemical interaction of aged biochar with Fe and Al oxides
reduces the AsO43– adsorption characteristics of biochar
amended Oxisol.
162 Soil Research
Environmental relevance
The application of biochar has been proposed in the remediation
of contaminated soils. Most studies have shown promising
results, demonstrating the adsorption capacity of biochar on
environmental contaminants including heavy metals (Cao et al.
2009; Namgay et al. 2010) and pyrene (Hale et al. 2011). The
present study sought to determine whether the adsorption
capacity of biochar could be sustained after ageing for
1 year. Our results suggest that aged biochar may be a useful
tool to remediate contaminated soils; however, the benefit it
offers may depend on the nature of the interacting ionic species
and the soil type. Indeed, in the case of Cd, the results were
encouraging, whereby biochar ageing led to an enhanced
adsorption of Cd, across both soil types, compared with the
unamended soil and the soil amended with fresh biochar. On
the other hand, the results for AsO43– suggest that the efficacy of
aged biochar to adsorb anionic trace elements from the soil may
be limited to sandy soils.
The effect of biochar ageing on adsorption behaviour
warrants further investigation. In particular, the impact of the
ageing period and the evaluation of adsorption mechanisms of
cationic and anionic trace elements should be investigated.
Furthermore, field experiments are necessary to confirm the
laboratory results, and to examine the influence of aged
biochar on plant uptake of trace elements. Nevertheless, this
study is a step forward in understanding the adsorption dynamics
of aged biochar in soils.
Acknowledgements
We thank the financial support from the Australian Government under its
Climate Change Research Program. We express our sincere thanks to Tom
Savage (The University of Sydney) for the ICP-OES analysis; Michael
Turner (The University of Sydney) for assistance with AAS and the titration
procedure; and Floris Van Ogtrop (The University of Sydney) for the expert
advice in applying the non-linear fits using R program.
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