Environ Sci Pollut Res (2018) 25:25638–25647

DOI 10.1007/s11356-017-8551-2

ENVIRONMENTAL FUNCTIONS OF BIOCHAR

Adsorption of ammonium in aqueous solutions by pine sawdust

and wheat straw biochars
Hye In Yang 1,2 & Kangyi Lou 1 & Anushka Upamali Rajapaksha 3 & Yong Sik Ok 4 &
Anthony O. Anyia 5 & Scott X. Chang 1

Received: 5 August 2016 / Accepted: 1 February 2017 / Published online: 22 February 2017
# Springer-Verlag Berlin Heidelberg 2017

Abstract Ammonium (NH4+) is a common form of reactive
nitrogen in wastewater, and its discharge to water bodies can
lead to eutrophication. This study was conducted to under-
stand NH4+ adsorption mechanisms of pine sawdust and
wheat straw biochars in aqueous solutions and the factors
affecting NH 4 + removal. Biochars were produced by
pyrolysing pine sawdust at 300 °C (PS300) and 550 °C
(PS550) and wheat straw at 550 °C (WS550). Pseudo-
second-order and Redlich-Peterson models best fitted the ad-
sorption data. The PS300 showed the highest NH4+ adsorption
capacity (5.38 mg g−1), followed by PS550 (3.37 mg g−1) and
WS550 (2.08 mg g−1). Higher H/C and O/C ratios of PS300
(0.78 and 0.32, respectively) indicated the greater presence of
functional groups on the biochar’s surface as compared to
PS550 (0.35 and 0.10, respectively) and WS550 (0.36 and
0.08, respectively), resulting in different NH4+ adsorption
through electrostatic interactions. The dominant mechanism
for NH4+ adsorption by the biochars was likely chemical
Responsible editor: Philippe Garrigues
* Scott X. Chang
scott.chang@ualberta.ca
1
Department of Renewable Resources, University of Alberta, 442
Earth Sciences Building, Edmonton, AB T6G 2E3, Canada
2
Department of Rural and Biosystems Engineering, Chonnam
National University, Gwangju 61186, Republic of Korea
3
Department of Basic Sciences, Faculty of Health Sciences, The Open
University of Sri Lanka, Nawala, Nugegoda 10250, Sri Lanka
4
Korea Biochar Research Center & School of Natural Resources and
Environmental Science, Kangwon National University,
Chuncheon 24341, Republic of Korea
5
Aquatic and Crop Resource Development Portfolio, National
Research Council of Canada, Ottawa, ON K1N 5A2, Canada
bonding and electrostatic interaction of NH4+ with the surface
functional groups. Lower pyrolysis temperature resulted in a
higher NH4+ adsorption capacity by the pine sawdust biochar.
At the same pyrolysis temperature (550 °C), the biochar made
with pine sawdust as the feedstock had a higher NH4+ adsorp-
tion capacity than biochar made from wheat straw. We con-
clude that biochars can be efficient absorbents for NH4+ re-
moval from wastewater, and the removal efficiency can be
optimised by selecting different feedstocks or the pyrolysis
condition for biochar production.
Keywords Black carbon . Charcoal . Ammonium
adsorption . Kinetics . Isotherm . Wastewater treatment
Introduction
Ammonium (NH4+) is one of the common forms of reactive
nitrogen (N) in water and wastewater (Cui et al. 2016).
Pollution of NH4+ mainly originates from the discharge of
NH4+ in municipal sewage, wastewater from fertiliser facto-
ries and agricultural wastewater. High levels of NH4+ in water
bodies accelerate eutrophication that depletes dissolved oxy-
gen and substantially contribute to toxicity on aquatic organ-
isms (Ismail and Hameed 2014). Ammonium nitrogen (NH4+-
N) is the primary form of N pollution (reactive N), and remov-
al of NH4+ in wastewater often involves biological systems
using the nitrification-denitrification process. Ammonium is
converted to nitrate (NO3−) and the N gas is produced as the
final conversion product (Thornton et al. 2007). However,
biological processes for removing NH4+ can be slow and dif-
ficult to deal with when the ammonium concentration in
wastewater suddenly increases (Jorgensen and Weatherly
2003).
Environ Sci Pollut Res (2018) 25:25638–25647
Adsorption is considered to be an effective water treatment
technique as it is cost-effective, straightforward and efficient
in removing pollutants (Inyang et al. 2016; Rajapaksha et al.
2016). Different adsorbents such as activated carbon and ze-
olites were reported to be effective in adsorbing contaminants
in wastewater, but limitations exist because the cost of activat-
ed carbon is high, and the availability of zeolites is limited
(Ahmad et al. 2012; Wahab et al. 2010; Wang and Peng 2010).
Biochar has gained global interest in environmental sci-
ences due to its cost-effectiveness as an adsorbent, as well as
the benefits in long-term carbon storage (Lehmann and Joseph
2009; Mohan et al. 2014; Ok et al. 2015). Biochar production
involves thermal decomposition of biomass rich in carbon
such as leaves, manure and agricultural residues under a
low-oxygen condition (Lehmann and Joseph 2009; Yao
et al. 2012). In this manner, waste materials can be converted
into stabilised carbon as biochar, thereby reducing carbon
emission to the atmosphere. Also, it has been reported that
biochar, with its high cation exchange capacity, is effective
in adsorbing cations (Cao et al. 2009). Studies have found that
biochar effectively removes organic and inorganic contami-
nants in water through sorption (Ahmad et al. 2014; Tan et al.
2015; Lou et al. 2016b; Rajapaksha et al. 2016). Furthermore,
biochar produced from a range of feedstocks has been shown
to mitigate nutrient loss from agricultural soils by reducing
nitrogen leaching and increasing NH4+ sorption (Ding et al.
2010; Hollister et al. 2013; Zheng et al. 2013). In addition,
nitrogen-loaded biochar could also be added to the soil as a
fertiliser (Hina et al. 2013; Wu et al. 2013). However, research
on removing nutrients such as NH4+ from aqueous environ-
ments such as wastewater by biochar adsorption is limited.
Plant-based waste materials such as sawdust, wood chips
and agricultural wastes are produced from the forest products
and agriculture industries, and these wastes incur disposal
cost. Utilising waste materials has economic advantages of
obtaining low-cost feedstocks for biochar production and re-
ducing waste disposal costs. It also offers an environmental
advantage of reusing and minimising wastes. One example of
such waste materials which can be utilised as a cost-effective
feedstock for biochar production is pine sawdust. Wheat straw
is an agricultural by-product that is abundantly available and
can be utilised as a biochar feedstock. Studies on adsorption
capacity and adsorption mechanism of NH4+ on sawdust and
straw biochars in aqueous solutions and the effects from op-
eration conditions (e.g., pH, application rate and competing
ions) are limited (Chun et al. 2004; Hina et al. 2013).
The objectives of this study were to (i) investigate the
effects of pyrolysis temperature and feedstock types on
NH4+ adsorption from aqueous solutions by biochars,
(ii) evaluate the mechanisms of NH4+ adsorption by bio-
chars and (iii) examine how biochar application rate and
environmental conditions including pH and competing
ions affect the adsorption capacity of biochars to provide
25639
practical implications for wastewater treatment by biochar
with different properties.
Materials and methods
Preparation of biochar and aqueous solutions containing
NH4+
The pine sawdust biochars were produced at the pyrolysis
temperature of 300 °C (PS300) and 550 °C (PS550) and the
wheat straw biochar was pyrolysed at 550 °C (WS550). The
production of the pine sawdust biochar was described in Lou
et al. (2016a), and the production of the wheat straw biochar
was provided by Alberta Innovates Technology Futures.
Briefly, PS300 and PS550 were produced in a pyrolyser
(N11/H Nabertherm, Germany) at 300 and 550 °C, respective-
ly. The WS550 was produced in a batch-type carboniser
(Alberta Innovates Technology Futures, Prototype 1.0) at
500–550 °C.
The cation exchange capacity (CEC) of biochar was mea-
sured using a modified NH4+-acetate compulsory displace-
ment method (Rajkovich et al. 2012). Briefly, 1.0 g of each
biochar sample was saturated with 50 mL of 1 N ammonium
acetate at pH 7 and shaken in a shaker for 16 h. Then, the
sample was filtered and washed with a 50-mL ammonium
acetate. The samples were then washed with 30 mL of ethanol
three times. Then, 50 mL of 2 N potassium chloride (KCl)
solution was added to the biochar and the samples were shak-
en for 16 h to replace the adsorbed NH4+ with K+ ions. The
samples were filtered, and a second aliquot of 50 mL of 2 N
KCl solution was used to wash the biochar. The extracted
NH4+ concentration was determined colorimetrically using
the indophenol blue method with the absorbance read at
636 nm (USEPA 1993).
An NH4+-N stock solution of 100 mg N L−1 was prepared
with ammonium sulphate ((NH4)2SO4, Certified A.C.S.,
Fisher Scientific). Then, the stock solution was used to pre-
pare NH4+-N solutions of varying concentrations between 10
and 100 mg L−1 by dilution. The solution pH was adjusted
using HCl (0.1 N) and NaOH (0.1 N) solutions. Adsorption
batch experiments were conducted to study the effects of bio-
char application rate, pH, contact time and the presence of
competing ions on NH4+ adsorption. All preparations and ex-
periments were conducted at room temperature (approximate-
ly 20 °C).
Effects of biochar application rate, pH, initial NH4+
concentration and competing ions on NH4+ adsorption
The influence of biochar application rate on NH4+ adsorption
was investigated by treating 20 mL of NH4+-N solutions
(40 mg N L−1) at different biochar application rates (1, 2, 3,
25640
5 and 7 g L−1); the initial NH4+ concentration of 40 mg N L−1
is typical of municipal wastewaters (Bolan et al. 2004). The
pH was adjusted to 7.0 for consistency and the samples were
shaken for 24 h in a mechanical shaker.
To investigate the effect of initial NH4+ concentration,
3 g L−1 of biochar was applied in NH4+ solutions of varying
concentrations (0, 10, 20, 30, 50, 70 and 100 mg N L−1) at
adjusted pH of 7.0. The samples were shaken in a mechanical
shaker for 24 h. The effect of contact time on NH4+ removal
was studied by applying 3 g L−1 of biochar in 20 mL of
40 mg N L−1 solutions. The samples were then adjusted to
pH 7 and shaken in a mechanical shaker for 0, 1, 2, 4, 6, 12, 24
and 48 h to determine at which time equilibrium was reached.
The effect of pH on NH4+ adsorption was studied over a pH
range of 3.0–10.0 in 1.0 pH unit increments, with the biochar
application rate of 3 g L−1 and NH4+ solution of 40 mg N L−1.
The samples were shaken for 24 h, and the pH values of the
samples were readjusted to the initial pH values.
Competing ions effect on biochar NH4+ adsorption was
investigated by preparing solutions containing sodium (Na+),
potassium (K+), calcium (Ca2+) and magnesium (Mg2+) using
NaCl, KCl, CaCl2 and MgCl2, respectively. These ions were
selected because they are commonly present in various types
of wastewater including municipal and industrial wastewater
and compete with NH4+ for adsorption sites (Jorgensen and
Weatherly 2003). A 10-mL 80 mg L−1 NH4+-N solution and a
10-mL solution containing one of the competing cations at
80 mg L−1 concentration were mixed and reacted with
3 g L−1 of biochar. The initial concentrations of NH4+-N and
each of the competing cations were thus 40 mg L−1. The
samples were adjusted to pH 7 and shaken in a mechanical
shaker (200 rpm) for 24 h. A 0.45-μm membrane was used to
filter the samples. The filtrate NH4+-N concentration was de-
termined colorimetrically using the indophenol blue method
with the absorbance read at 636 nm (USEPA 1993). All the
samples in the above experiments were run in triplicates.
Kinetic study
Ammonium adsorption by biochar was observed over 48 h to
establish the time taken to reach equilibrium and to determine
the adsorbed quantity of NH4+ at equilibrium. To understand
the mechanisms of NH4+ adsorption by pine sawdust and
wheat straw biochars, pseudo-first-order and pseudo-second-
order kinetic models were used to model the data. The pseudo-
first-order equation and its linearised form are given as fol-
lows (Ho and McKay 1998; Rajapaksha et al. 2011)
dq
¼ k 1 ðqe −qt Þ ð1Þ
dt
k1t
logðqe −qt Þ ¼ logqe − ð2Þ
2:303
Environ Sci Pollut Res (2018) 25:25638–25647
where qe is the amount adsorbed (mg g−1), qt is the amount
adsorbed at time t (h) and k1 is the pseudo-first-order rate
constant (h−1). The values of k1 and qe were obtained from
the slope and intercepts of the plots of log(qe − qt) against t.
The pseudo-second-order equation and its linear form are
given as follows (Ho and McKay 1999; Rajapaksha et al.
2011)
dq
¼ k 2 ðqe −qt Þ2 ð3Þ
dt
t 1 t
¼ þ ð4Þ
qt k 2 q2e qe
where qe is the amount adsorbed (mg g−1), qt is the amount
adsorbed at time t (h) and k2 is the pseudo-second-order rate
constant (g mg−1 h−1). Plots of qt against t were presented, and
t
k2 and qe values were obtained from the slope and intercepts.
Isotherm study
Adsorption isotherms are used to describe how adsorbates
interact with adsorbents at equilibrium (Mittal et al. 2010).
Langmuir, Freundlich, Temkin and Redlich-Peterson isotherm
models were used to analyse the experimental data. The
Langmuir isotherm is expressed as
ðkqm C e Þ
qe ¼ ð5Þ
ð1 þ k  C e Þ
where qe is the amount of adsorbate adsorbed at equilibrium
(mg g−1), qm is the maximum adsorption capacity (mg g−1), Ce
is the equilibrium concentration of the adsorbate (mg L−1) and
k is the Langmuir constant (L mg−1).
A dimensionless separation factor (R) expresses Langmuir
isotherm and can be calculated as (Weber and Chakravorti
1974)
1
R¼ ð6Þ
1 þ kC 0
where k is the Langmuir constant and C0 is the initial adsor-
bate concentration. The separation factor indicates the iso-
therm as unfavourable (R > 1), linear (R = 1), favourable
(0 < R < 1) or irreversible (R = 0).
The Freundlich model equation is stated as
qe ¼ KC e n ð7Þ
where qe is the amount of adsorbate adsorbed at equilibrium
(mg g−1), Ce is the equilibrium concentration of the adsorbate
(mg L−1), K is the Freundlich constant indicating adsorption
capacity and n is adsorption intensity.
The Temkin model assumes that indirect interactions
among adsorbates lead to a linear decrease in the heat
of adsorption with coverage (Kavitha and Namasivayam
Environ Sci Pollut Res (2018) 25:25638–25647 25641

2006; Zhang et al. 2011). The equation is expressed as
follows
qe ¼ B1 lnðK t C e Þ
RT
B1 ¼
b moval of oxygen-containing functional groups results in de-
where R is the gas constant (8.31 J mol−1 K−1), T is the abso-
lute temperature (K), b is a constant related to the heat of
adsorption, qe is the amount of adsorbate adsorbed at equilib-
rium (mg g−1), Kt is the equilibrium constant (L mg−1), which
corresponds to the maximum binding energy, and Ce is the
equilibrium concentration of the adsorbate (mg L−1).
The Redlich-Peterson model is expressed as
AC e
qe ¼
1 þ BC ge
where qe is the amount of adsorbate adsorbed at equilibrium
(m g−1), A (L g−1) and B (L mg−1) are Redlich-Peterson iso-
therm constants, Ce is the equilibrium concentration of the
adsorbate (mg L−1) and g (0 < g < 1) is the Redlich-Peterson
constant. When g is equal to 1, Eq. 10 converts to the
Langmuir form (Han et al. 2009). When g is equal to 0, it is
simplified to Henry’s law equation, and when the value of
BC ge is much larger than 1, the equation becomes Freundlich
equation (Yao et al. 2010).
pyrolysis temperature tend to have lower CEC values because
they lose their surface functional groups (Silber et al. 2010).
The carbon (C) content was the highest for WS550 (86.97%),
ð8Þ
followed by PS550 (78.0%) and PS300 (62.7%). As the py-
rolysis temperature increases, C content increases but the re-
ð9Þ
creased hydrogen (H) and oxygen (O) contents (Chun et al.
2004). The H/C ratio for PS300, PS550 and WS550 was 0.78,
0.35 and 0.36, respectively. The highest H/C ratio of PS300
indicated that PS300 had a relatively lower aromatic structure
and may have more adsorption sites due to more organic C
being retained (Cui et al. 2016; Lou et al. 2016b). The O/C
ratio was also the highest for PS300 (0.32) as compared to
PS550 (0.1) and WS550 (0.08), indicating that PS300 had
greater oxygen-containing functional groups on its surface
ð10Þ
and, therefore, remained hydrophilic and polar (Wang et al.
2015a; Cui et al. 2016; Lou et al. 2016b). The surface area was
the largest for PS550 (189.2 m2 g−1), followed by WS550
(55.24 m2 g−1) and PS300 (<1 m2 g−1). PS300 had the lowest
surface area, but with its higher CEC and H/C and O/C ratios,
it was more favourable for NH4+ adsorption than the other two
biochars.
Effect of application rate, pH and competing ions on NH4+
adsorption

As the application rate of biochars increased from 1 to 7 g L−1,

Results and discussion
Biochar characteristics
The pH of PS300 was low (4.92), and the pH values of PS550
and WS550 were higher (8.16 and 10.13, respectively)
(Table 1). At low pyrolysis temperature, the biochar’s pH
was low because of the production of organic acids and phe-
nolic substances, whereas at a high pyrolysis temperature
(>300 °C), pH of the biochar increased because of alkali salts
that separated from the feedstock material (Chen et al. 2011).
The biochars’ CEC values were 6.05 (PS550), 29.04 (PS300)
and 30.46 cmol kg−1 (WS550). Biochar produced at high
the NH4+-N removal efficiency increased from 10.2 to 19.5,
6.9 to 28.6 and 1.0 to 7.7% for PS300, PS550 and WS550,
respectively (Fig. 1). Such increases in the NH4+-N removal
efficiency may be caused by an increase in the total adsorptive
surface resulting in an increased availability of adsorptive sites
(Zhou et al. 2015). The total amount of NH4+-N removed or
the removal efficiency can be expected to continuously in-
crease as the application rate increases until the adsorption
sites are saturated (Ihsanullah et al. 2015). As the biochar
application rate increased, the amount of NH4+ adsorbed per
unit mass of biochar decreased from 4.07 to 1.11 and 2.74 to
1.63 mg N g−1 for PS300 and PS550, respectively (Fig. 1).
However, NH4+ adsorption of WS550 increased from 0.39 to
0.73 mg N g−1 as the application rate increased from 1 to

Table 1 Physical and chemical

properties of pine sawdust Biochar pH CEC %C %H %O %N H/C O/C Surface area
biochar produced at 300 °C (cmol kg−1) (m2 g−1)
(PS300) and 550 °C (PS550) and
wheat straw biochar produced at PS300a 4.92 29.04 62.7 4.1 27.1 0.34 0.78 0.32 <1
550 °C (WS550) PS550a 8.16 6.05 78.0 2.3 10.2 0.57 0.35 0.10 189.2
WS550b 10.13 30.46 87.0 2.6 8.9 1.32 0.36 0.08 55.2
a
Data including pH, %C, %H, %O, %N, H/C, O/C and surface area obtained from Lou et al. (2016a)
b
Data including pH, %C, %H, %O, %N, H/C, O/C and surface area obtained from Dugdug et al. (personal
communication)
25642 Environ Sci Pollut Res (2018) 25:25638–25647

3 g L−1 and decreased to 0.44 mg N g−1 as the application rate
increased further to 7 g L−1 (Fig. 1). The decrease in NH4+
adsorption per unit mass of biochar may be attributed to a
lower NH4+ ion concentration to biochar adsorption sites ratio
resulting from the increased amount of biochar added to the
solution (Zhang et al. 2011). As a result, less NH4+ was dif-
fused onto the surface and more adsorption sites on the bio-
char remained unsaturated on a per unit mass basis even
though the total amount of adsorbate removed increased. For
WS550, the slight increase in NH4+ adsorption with the initial
increase in biochar application rate may be attributed to its low
surface functional groups and thus low adsorption sites and
5 30
4.5 qe (mg g-1)
4
% adsorbed
25
3.5
20
adsorption capacity compared to the other two biochars. The
adsorbate to adsorption site ratio for WS550 may not have
decreased as much as PS300 or PS550. However, as more
biochar was added, the number of adsorption site increased,
eventually resulting in less NH4+ ions diffusing onto the bio-
char surface, thereby decreasing NH4+ adsorption per unit
mass of biochar. Possible aggregation of biochar particles un-
der higher biochar application rates may have reduced the
adsorption sites and the total surface area, decreasing the ad-
sorption capacity (Limousin et al. 2007; Zhang et al. 2011).
Kizito et al. (2015) also observed the same effect using wood
and rice husk biochars.
The pH significantly affected the NH4+-N removal by bio-
char, as increasing pH increased the NH4+ adsorption capacity
(Fig. 2). The adsorption capacity was the lowest at pH 3 for
PS300, PS550 and WS550 (2.41, 0.01 and 0.51 mg g−1, re-
spectively) and the highest at pH 9 for PS300 and PS550 (6.26

% Removal
and 3.12 mg g−1, respectively). Ammonium adsorption did
qe (mg g-1)

3
2.5 15 not reach the maximum for WS550 in the pH range of 3–10.
2 Below pH 7, higher concentrations of H+ ions led to compe-
10
1.5 tition between NH4+ and H+ for adsorption sites on biochar
1
5 surface, thereby reducing the adsorption of NH4+. As pH in-
0.5 creased above 7, the H+ concentration decreased and more
0 0 NH4+ ions were adsorbed. When pH >9.5, NH4+ ions can
0 2 4 6 8
react with OH− ions to form NH3, causing the NH4+ concen-
4.5 35 tration in the aqueous solution to decrease thereby decreasing
4 qe (mg g-1)
30
the amount of NH4+ adsorption (Ismail and Hameed 2014).
3.5 % adsorbed Therefore, a slight alkaline solution will be the most suitable
3
25 for NH4+ adsorption.
The presence of competing ions including Na+, K+, Ca2+
% Removal
qe (mg g-1)

2.5 20
and Mg2+ decreased NH4+ adsorption capacity of PS300
2 15 (Fig. 3), with the NH4+ adsorption higher in the control solu-
1.5
10
tion (3.53 mg g−1) as opposed to those containing one of the
1 cations (3.04 to 3.26 mg g−1). Ammonium adsorption capacity
5 for PS300 was higher in solutions containing monovalent cat-
0.5
0 0 ions (Na+ and K+) than that containing divalent cations (Ca2+
0 2 4 6 8 and Mg2+), illustrating that the divalent cations were stronger
4.5 30
7
4 qe (mg g-1) 25 6
3.5
3 % adsorbed 20 5
% Removal
qe (mg g-1)

qe (mg g-1)

2.5 4
15
2 PS300
3 PS550
1.5 10
2 WS550
1
5
0.5 1
0 0 0
0 2 4 6 8 0 2 4 6 8 10 12
Application rate (g L-1) pH
Fig. 1 Effect of biochar application rate on NH4+ adsorption by pine Fig. 2 Sorption-edge experiment on the effect of pH on NH4+ adsorption
sawdust biochar produced at 300 °C (PS300) and 550 °C (PS550) and by pine sawdust biochar produced at 300 °C (PS300) and 550 °C (PS550)
wheat straw biochar produced at 550 °C (WS550) (pH = 7; contact and wheat straw biochar produced at 550 °C (WS550) (biochar
time = 24 h) application rate = 3 g L−1; contact time = 24 h)
Environ Sci Pollut Res (2018) 25:25638–25647
4 5
3.5
3 3.5
2.5
qe (mg g-1)
2 PS300
1.5 PS550
WS550
1
0.5
0 Fig. 4 Effect of contact time on NH4+ adsorption by pine sawdust
Na+ K+ Ca2+ Mg2+ NH4+
Competing ions
Fig. 3 The effect of competing ions, Na+, K+, Ca2+ and Mg2+, on NH4+
adsorption by pine sawdust biochar produced at 300 °C (PS300) and
550 °C (PS550) and wheat straw biochar produced at 550 °C (WS550)
(pH = 7; biochar application rate = 3 g L−1; contact time = 24 h)
competitors for the adsorption sites and the divalent cations
occupied more adsorption sites due to its divalent charge.
Ammonium adsorption for PS550 and WS550 mostly non-
significantly decreased in the solution with competing ions.
One of the mechanisms for NH4+ adsorption by biochar is
electrostatic attraction between the cations and the oppositely
charged functional groups (Ahmad et al. 2014). Therefore, all
coexisting cations had a negative effect on NH4+ adsorption of
the biochar as they competed for adsorption sites. Other stud-
ies also have shown that the presence of cations in aqueous
solutions reduced NH4+ adsorption capacity of biochar and
other adsorbents such as zeolites (Zhang et al. 2011; Kizito
et al. 2015). For instance, Kizito et al. (2015) reported that
NH4+ adsorption rates by wood and rice husk biochar were
lower in digestate slurry as compared to those in a pure NH4+-
N solution, due to the competition of NH4+ with the cations in
the slurry.
Adsorption kinetics and effect of contact time
The NH4+ adsorption process was time-dependent for all test-
ed biochars. A rapid removal of NH4+ occurred during the
initial 1 h. The adsorption rate then decreased gradually until
it almost reached equilibrium around 12 h and became stable
after 24 h (Fig. 4). A high number of unoccupied adsorption
sites and a high-solute concentration gradient at the beginning
of adsorption process promoted the rapid initial uptake (Zhang
et al. 2011). Further, the initial interaction of NH4+ ions with
negatively charged surface anion groups such as carboxylate
(COO−) and hydroxyl (OH−) groups also contributed to the
fast adsorption (Ismail and Hameed 2014; Wahab et al. 2010).
The slower adsorption rate that followed after the first 1 h
indicated an ionic balance between the aqueous solution and
the adsorbent (Kizito et al. 2015). Other studies have also
found rapid NH4+ adsorption during the first 1 to 2 h which
slowed and became stable after 10 to 24 h or even after 4 h
25643
4.5
4
PS300
qe (mg g-1)
3
PS550
2.5
2
WS550
1.5
1
0.5
0
0 10 20 30 40 50 60
Time (h)
biochar produced at 300 °C (PS300) and 550 °C (PS550) and wheat
straw biochar produced at 550 °C (WS550) (pH = 7; NH 4 +
concentration = 40 mg L−1; biochar application rate = 3 g L−1)
(Liu et al. 2013a; Liu et al. 2013b; Gao et al. 2015). The
adsorption sites eventually became saturated, and equilibrium
was reached (Karadag et al. 2006). The correlation coeffi-
cients obtained from the pseudo-first-order model were low
for PS300 and PS550 (0.66 and 0.52, respectively) and higher
for WS550 (0.95). However, the calculated values for NH4+
removal capacities (qe1, cal) for all three biochars were not
consistent with the experimental (qe, exp) values (Table 2).
The pseudo-first-order model is applicable at the beginning
of adsorption (20–30 min), and it provides a better fit at high
initial adsorbate concentration (Azizan 2004; Ismail and
Hameed 2014). Therefore, the pseudo-first-order model did
not represent the experimental data very well.
The pseudo-second-order model resulted in a better fit for
the experimental data. The graph plotted between t/qt and time
(Fig. 5) showed good linearity, and high R2 values were ob-
tained (Table 2). The calculated adsorption capacities (qe, cal)
of the three biochars all closely matched their corresponding
experimental adsorption capacities (qe, exp) (Table 2). The
pseudo-second-order model is applicable over the entire peri-
od of the adsorption experiment (Ismail and Hameed 2014).
Therefore, the pseudo-second-order model best fitted the ex-
perimental data, suggesting that chemisorption was the rate-
limiting step that involved ion exchange and valency forces
through electron sharing between the adsorbent and the adsor-
bate (Ho 2006).
Adsorption isotherm
The NH 4 + adsorption data were fitted to Langmuir,
Freundlich, Temkin and Redlich-Peterson isotherm models.
Parameters and the coefficients of determination (R2) of each
isotherm model are given in Table 3. The Redlich-Peterson
model resulted in higher R2 values for the three biochars (0.97,
0.98 and 0.89 for BC300, BC550 and WS550, respectively)
compared to the other three models. The Langmuir and
Temkin model fittings of the adsorption data were not as close
as that of the Redlich-Peterson model (Table 3). The Temkin
model is suitable for modelling gas phase equilibrium and
25644 Environ Sci Pollut Res (2018) 25:25638–25647

Table 2 Kinetic parameters for

NH4+ adsorption by pine sawdust Experimental Pseudo-first-order model Pseudo-second-order model
biochar produced at 300 °C
(PS300) and 550 °C (PS550) and qexp (mg g−1) qe1, cal (mg g−1) k1 (h−1) R2 qe2, cal (mg g−1) k2 (g mg−1 h−1) R2
wheat straw biochar produced at
550 °C (WS550) (pH = 7; biochar PS300 4.66 1.04 0.12 0.66 4.67 0.68 1.00
application rate = 3 g L−1) PS550 1.27 0.43 0.15 0.52 1.29 1.62 1.00
WS550 0.82 0.56 0.14 0.96 0.84 0.72 1.00

may not appropriately represent liquid-phase adsorption (Foo The maximum NH4+ adsorption capacity given by the
and Hameed 2010). The Freundlich model exhibited the same Langmuir model was 5.38, 3.37 and 2.08 mg g−1 for PS300,
R2 values as the Redlich-Peterson model for BC300 and PS550 and WS550, respectively. For comparison, NH4+ ad-
BC550, but a lower R2 value for WS550 (0.75). The isotherm sorption capacities of adsorbents such as clinoptilolites, saw-
model fitting for WS550 was relatively poor because there dust, various biosorbents and biochars made from various
was little change in the amount of NH 4+ adsorbed by feedstocks reported in the literature are given in Table 4, indi-
WS550 at lower NH 4 + initial concentrations (10– cating that the maximum NH4+ adsorption capacities of those
30 mg L−1). Ammonium adsorption by the other two biochars absorbents were similar. However, a few studies reported sig-
increased with initial concentrations to fit the isotherm curve. nificantly higher NH4+ adsorption capacities of biochars com-
The Redlich-Peterson model is an improvement over pared to the NH4+ adsorption capacities found in this study
Langmuir and Freundlich models and has both features of and a few similar studies using biochars. For instance, Kizito
the two models (Behnamfard and Salarirad 2009; Han et al. et al. (2016) reported NH4+ adsorption capacity of hardwood
2009). The BC ge values at different equilibrium NH4+ concen- and corncob biochars to be over 114.7 and 104.8 mg g−1,
trations for the three biochars ranged from 7.48 to 96.03, respectively, in a flow system study using biochar beds. Gao
which were well over 1. Therefore, it approached Freundlich et al. (2015) also reported that NH4+ adsorption capacities of
model, indicating a multi-layer adsorption on a heterogeneous peanut shell, corncob and cotton stalk biochars to be over
surface (Foo and Hameed 2010; Yao et al. 2010). 200 mg g−1. The initial NH4+ concentration used in those
The k values given by the Langmuir model for PS300, studies were 500 mg L−1 which was much higher than that
PS550 and WS550 were 0.026, 0.1 and 0.025 L mg−1, respec- used in this study. The adsorption values obtained in this
tively. When the Langmuir isotherm was expressed by the study, especially that of PS300, were comparable to or higher
dimensionless separation factor R for each biochar, R was
between 0 and 1, suggesting that the adsorption was Table 3 Isotherm parameters for ammonium adsorption by pine
sawdust biochar produced at 300 °C (PS300) and 550 °C (PS550) and
favourable. In addition, the adsorption is deemed favourable
wheat straw biochar produced at 550 °C (WS550) (pH = 7; biochar
if the n value in the Freundlich model is between 0.1 and 1 application rate = 3 g L−1; contact time = 24 h)
(Zhang et al. 2011). The n values obtained were 0.51, 0.29 and
0.47 for PS300, PS550 and WS550, respectively. Thus, both PS300 PS550 WS550
the Langmuir and Freundlich isotherm models confirmed that Langmuir
NH4+ adsorption by the three biochars were effective. qm (mg g−1) 5.38 3.37 2.08
k (L mg−1) 0.026 0.1 0.025
70 R2 0.94 0.83 0.61
60
y = 1.192x + 1.984 Freundlich
R² = 0.997
K (mg g−1) 0.4 0.87 0.18
50
y = 0.777x + 0.373 n 0.51 0.09 0.47
t/qt (h g mg-1)

R² = 0.999
40 R2 0.97 0.98 0.75
PS300
30 Temkin
PS550
y = 0.214x + 0.067
B1 1.06 0.64 0.36
20 WS550
R² = 0.999 Kt (L mg−1) 0.33 1.56 0.47
10
R2 0.92 0.95 0.68
0 Redlich-Peterson
0 10 20 30 40 50 60
A (L g−1) 1.32 3.53 0.55
Time (h)
B (L mg−1) 2.82 4.00 4.93
Fig. 5 Pseudo-second-order plot for NH4+ adsorption by pine sawdust
biochar produced at 300 °C (PS300) and 550 °C (PS550) and wheat straw g 0.52 0.71 0.41
biochar produced at 550 °C (WS550) (pH = 7; biochar application R2 0.97 0.98 0.89
rate = 3 g L−1)
Environ Sci Pollut Res (2018) 25:25638–25647 25645

Table 4 Maximum adsorption

capacities (mg g−1) of various Adsorbents Adsorption capacities Source
adsorbents for NH4+ (mg g−1)

Clinoptilolite 5.2–8.1 Karadag et al.(2006)

Zeolite 5.22 Liang and Ni (2009)
Strawberry leaf powder 3.9–7.7 Liu et al. (2010a)
Strawberry stem 4.62 Liu et al. (2010b)
Boston ivy stem 5.01 Liu et al. (2010b)
Sawdust 1.7 Wahab et al. (2010)
Posidonia oceanica fibres 1.9 Jellali et al. (2011)
Biochar made from Salix rosthornii 3.3–7.4 Zeng et al. (2013)
Biochar made from Thalia dealbata 7.5–17.6 Zeng et al. (2013)
Biochar made from Vetiveria zizanioides 1.9–4.4 Zeng et al. (2013)
Biochar made from Phragmites spp. 2.2–5.4 Zeng et al. (2013)
Maple wood biochar 0.73–5.44 Wang et al. (2015b)
Oak wood sawdust biochar 5.3–32.0 Wang et al. (2015a)
Giant reed biochar 1.2–1.5 Hou et al. (2016)
Southern magnolia leaves 6.22 Liu et al. (2010b)
Maple wood biochar 0.46–0.87 Wang et al. (2016)

than biochars made from different feedstocks and other adsor-
bents reported in the literature, indicating that the biochars
have considerable potential to adsorb NH 4+ (Table 4).
Higher adsorption capacity of PS300 compared to PS550
and WS550 is in agreement with a study by Wang et al.
(2015a), which reported that biochars produced at 300 °C
yielded a higher NH4+ adsorption capacity than biochars pro-
duced at higher pyrolysis temperature (600 °C). In another
study, Zeng et al. (2013) tested biochars derived from four
herbaceous plants at 500, 600 and 700 °C, and half of the
biochars’ adsorption capacities were below 5 mg g−1.
Possible mechanisms for NH4+ adsorption
Ammonium adsorption by biochar may involve several
adsorbent-adsorbate interactions such as electrostatic attrac-
tion, ion exchange, surface complexation and physical adsorp-
tion (Tan et al. 2015). Ion exchange contributes to the adsorp-
tion, and biochars with high CEC resulted in relatively high
NH4+ adsorption capacity (Cui et al. 2016), with CEC as the
potential dominant factor influencing the NH4+ adsorption
capacity of biochars (Zeng et al. 2013, Gai et al. 2014).
However, WS550 and PS300 in this study had similar CECs
(30.46 and 29.04 cmol kg−1, respectively) but different ad-
sorption capacities (2.08 and 5.38 mg g−1, respectively).
Jassal et al. (2015) reported that the NH4+ adsorption capaci-
ties of poultry litter biochar, spruce-pine-fir chip biochar and
the mix of the two did not correspond to their CEC values.
They found that NH4+ adsorption exceeded the CEC of the
biochars and suggested physical entrapment of NH4+ ions as
the main mechanism of adsorption (Jassal et al. 2015). Since
NH4+ adsorption capacities of the biochars used in this study
did not exceed the CEC values, physical entrapment is likely
not the dominant mechanism for NH4+ adsorption.
Also, PS300 had the highest adsorption capacity but had
the lowest surface area (<1 m2 g−1), while PS550 and WS550
had higher surface areas (189.2 and 55.2 m2 g−1, respectively)
but had lower NH4+ adsorption capacities. This indicates that
large surface area did not necessarily result in more adsorption
of NH4+ on the biochar surfaces. Therefore, physical adsorp-
tion did not play a significant role in NH4+ adsorption by the
pine sawdust and wheat straw biochars, similar to the findings
by Kizito et al. (2015) on wood and rice husk biochars. Kizito
et al. (2015) also suggested that chemical interaction between
NH4+ and biochar surface with various functional groups in-
fluenced NH4+ adsorption.
The chemical properties of the functional groups on bio-
chars’ surface influence NH4+ adsorption more than physical
properties such as surface area (Spokas et al. 2012). Higher H/
C and O/C ratios suggest more presence of functional groups
and presents a possibility of chemical bonding of polar com-
pounds such as NH4+ (Jassal et al. 2015). High O/C ratios also
indicate high biochar surface polarity, which can result in
higher NH4+ adsorption through electrostatic interaction (Gai
et al. 2014; Takaya et al. 2016). Removal of hydrogen and
oxygen-containing functional groups at high pyrolysis tem-
perature results in a higher surface area but low H/C and O/
C ratios for biochars (Gai et al. 2014). The highest H/C and O/
C ratios were found in PS300, which corresponded to its high
NH4+ adsorption capacity, while PS550 and WS550 produced
25646
at higher pyrolysis temperatures exhibited lower H/C and O/C
ratios and correspondingly lower NH4+ adsorption capacities.
This illustrates that pyrolysis temperature and feedstock types
affect NH4+ adsorption. The PS300 biochar may have retained
more cellulose chains and lignin functional groups such as
alcohols, acids and hydroxides from its wood-derived feed-
stock (Abdolali et al. 2014). Surface complexes formation
with oxygen-containing groups such as carboxyl and carbonyl
groups may also have enhanced NH4+ adsorption by the bio-
chars (Cui et al. 2016). Further studies on the analysis of
different feedstocks’ characteristics and how they may affect
NH4+ adsorption efficiency of biochars would be beneficial.
The dominant mechanism for NH4+ adsorption by the three
biochars studied is likely chemical bonding and electrostatic
interaction with functional groups rather than physical adsorp-
tion or ion exchange.
Conclusions
The three biochars (PS300, PS550 and WS550) were effective
for NH4+ removal from aqueous solutions; their adsorption
capacities were affected by pH, competing ions and biochar
application rate, showing a competitive adsorption capacity to
existing adsorbents. The pseudo-second-order kinetic model
and Redlich-Peterson isotherm model best fitted adsorption
data obtained for the biochars used in this study. Chemical
bonding and polar interaction of NH4+ and the surface func-
tional groups are likely the primary influence on NH4+ adsorp-
tion on the biochars. Pine sawdust biochar produced at the
lower pyrolysis temperature (300 °C) had the highest H/C
and O/C ratios and NH4+ adsorption capacity. In contrast,
wheat straw biochar pyrolysed at the higher temperature
(550 °C) had low H/C and the lowest O/C ratio and the lowest
NH4+ adsorption capacity. We conclude that biochar is an
effective absorbent for removing NH4+ from wastewater,
and it is possible to design pyrolysis conditions or select dif-
ferent feedstock types to optimise the adsorption of NH4+ by
biochars.
Acknowledgements This study was conducted with financial support
from an NSERC CREATE Grant that supported the Land Reclamation
International Graduate School (LRIGS) and partially supported by an
NSERC Discovery grant.
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