J Soils Sediments

DOI 10.1007/s11368-015-1219-y

BIOCHAR FOR A SUSTAINABLE ENVIRONMENT

Effect of low energy-consuming biochars in combination

with nitrate fertilizer on soil acidity amelioration and maize
growth
Khalid Mehmood 1,2 & Jiu-yu Li 1 & Jun Jiang 1 & M. M. Masud 1,2 & Ren-kou Xu 1

Received: 15 May 2015 / Accepted: 24 July 2015

# Springer-Verlag Berlin Heidelberg 2015

Abstract
Purpose We evaluated the ameliorative effects of crop straw
biochars either alone or in combination with nitrate fertilizer
on soil acidity and maize growth.
Materials and methods Low energy-consuming biochars
were prepared from canola and peanut straws at 400 C for
2 h. Incubation experiment was conducted to determine application rate of biochars. Afterward, maize crop was grown in
pots for 85 days to investigate the effects of 1 % biochars
combined with nitrate fertilizer on soil pH, exchangeable
acidity, and maize growth in an Ultisol collected from
Guangdong Province, China.
Results and discussion Application of 0.5, 1.0, and 1.5 %
either canola straw biochar (CSB) or peanut straw biochar
(PSB) increased soil pH by 0.15, 0.27, 0.34, and 0.30, 0.58,
0.83 U, respectively, after 65-day incubation. Soil pH was
increased by 0.49, 0.72, 0.78, and 0.88 U when 1 % CSB or
PSB was applied in combination with 100 and 200 mg N/kg
of nitrate, respectively, after maize harvest in greenhouse pot
experiment. These low-cost biochars when applied alone or in
combination with nitrate not only reduced soil exchangeable
acidity, but also increased Ca2+, Mg2+, K+, Na+, and base
saturation degree of the soil. A total of 49.91 and 80.58 %
decreases in exchangeable acidity were observed when 1 %
CSB and PSB were incubated with the soil for 65 days,

compared to pot experiment where 71.35, 78.64, 80.2, and

81.77 % reductions of exchangeable acidity were observed
when 1 % CSB and PSB were applied in combination with
100 and 200 mg N/kg of nitrate, respectively. The higher
contents of base cations (Ca2+, Mg2+, K+, Na+) in biochars
also influenced the plant growth. The higher biomass in
CSB-treated pots was attributed to the higher K content compared to PSB. The higher percent reduction in exchangeable
Al3+ by applying 1 % CSB combined with 200 mg N/kg of
nitrate consistently produced maximum biomass (129.65 g/pot)
compared to 100 mg N/kg of nitrate and 1 % PSB combined
with 100 and 200 mg N/kg of nitrate. The exchangeable Al3+
mainly responsible for exchangeable acidity was decreased
with the application of biochars and nitrate fertilizer. A highly
significant negative relationship was observed between soil
exchangeable Al3+ and plant biomass (r2 =0.88, P<0.05).
Conclusions The biochars in combination with nitrate fertilizer
are cost-effective options to effectively reduce soil acidity and
improve crop growth on sustainable basis.

Responsible editor: Yong Sik Ok

Soil acidification is a serious problem in tropical and subtropical regions of China and around the world. Removal
of crop residues for energy production negatively affected
soil acidity which was manifested as aluminum and manganese toxicity, thus reducing soil fertility and plant growth
(Lal et al. 2007). Lime and gypsum were used traditionally
to ameliorate soil acidity, but the lack of these ameliorants
in many areas limited their wide use, especially in many
developing countries (Sun et al. 2000). To overcome the

* Ren-kou Xu
rkxu@issas.ac.cn
1

State Key Laboratory of Soil and Sustainable Agriculture,

Institute of Soil Science, Chinese Academy of Sciences,
P.O. Box 821, Nanjing, China

University of Chinese Academy of Sciences, Beijing 100049, China

Keywords Amelioration of soil acidity . Biochar .

Rhizosphere alkalization . Maize . Nitrate fertilizer . Ultisol

1 Introduction

J Soils Sediments

deleterious effect of soil acidity on plant growth and restoring

the productivity of acid soils, enhanced attention was paid to
alternatives or complementary methods to combat soil acidity.
Recently, biochar, a significant carbonaceous component
arising from the incomplete combustion of various organic
precursors such as crop residues, has attained utmost importance as potential amendment for soils (Novak et al. 2009).
Moreover, agronomic performances of biochars were variable, hosting a positive or negative impact on yield of different
crops and plants in a wide range of soil types (Zhu et al. 2014).
Positive effects were mainly attributed to supply of important
nutrients like K, P, Ca, and Mg (Zhu et al. 2014), improved N
use efficiency (Clough and Condron 2010), and reduced ammonium depletions along with N2O soil emissions (Atkinson
et al. 2010). Application of biochars compared to direct incorporation of crop residues had long-lasting effects on soil fertility, thereby enhanced nutrient retention capacity of added
fertilizers (Rengel et al. 2000; Xu et al. 2006), and thus reduced the fertilizer requirements. Hence, biochar application
to soils could be one of the suitable options to increase agricultural productivity on sustainable basis. Incorporation of
biochar increased soil pH, electrical conductivity (EC), cation
exchange capacity (CEC) of acidic soils due to large amount
of negative charge on its surface and consequently adsorption
capacity of the soils for selected nutrients (Gaskin et al. 2008;
Novak et al. 2009).
The functional groups on biochar formed surface complexes with aluminum cations and alleviated aluminum phytotoxicity in acidic soils (Qian et al. 2013). Significant increases in exchangeable base cations and reductions in exchangeable acidity and Al saturation were observed as application rate of biochar increased, but there were no further
effects on soil pH. The lack of change in soil pH at the higher
application rate of biochar may be due to the displacement of
exchangeable acidity and the high buffering capacity of biochar, thereby retarding a further liming effect (Wang et al.
2014). Ammonification of organic N consumed protons and
caused soil pH to increase, whereas nitrification of ammonium
released protons and caused soil pH to decrease. Biochar negative charge sites can adsorb H+, and decarboxylation processes can neutralize soil acidity. However, the physical and chemical characteristics of biochars are influenced by the properties
of the feedstock and pyrolysis conditions, such as temperature
and furnace residence time (Gaskin et al. 2008). The type and
forms of available nutrients can also affect soil properties, as
nitrogen transformation has effects on the soil pH fluctuation
(Xu and Coventry 2003). The magnitude of pH change depends on overall cation-anion relationship; therefore, the type
of charge excreted by plant roots mainly depends on the form
of nitrogen that is available to the plants. Thus, the plants
supplied with the nitrate form of N-fertilizers can result in
alkalization in the rhizosphere, and the supply of ammonium
can lead to acidification of rhizosphere or exacerbate acidity

of an acid soil. A supply of nitrate can stimulate root growth

and N capture, resulting in rhizosphere alkalization in acidic
subsoil (Weligama et al. 2010).
Application of biochar pyrolyzed at low temperature was
more suitable for agricultural use as it containd greater quantities of functional groups and had a higher exchange capacity
(Novak et al. 2009). The liming effects of biochars varied with
pyrolysis temperatures and duration (Yuan et al. 2011a, b).
The role of biochar in ameliorating acidity and its influence
on soil fertility have been proved, but its massive use is limited
due to time and energy required for biochar preparation. The
present study explored the liming potential of low energyconsuming biochars (low temperature and less furnace residence time) alone, and in combination with mineral fertilizer in an incubation and greenhouse pot experiment. We
ascertained that investigation regarding rhizosphere
alkalization through nitrate uptake combined with biochars
should lead to better understanding about the role of biochars in soil acidity amelioration.

2 Materials and methods

2.1 Biochar preparation
Locally available canola (Brassica campestris L.) and peanut
(Arachis hypogaea L.) straws were collected after crop harvest
from suburb of Nanjing, China. The feed stocks were air-dried
at room temperature and milled to pass through a 1-mm sieve.
Powered residues were then placed in ceramic crucibles,
each covered with fitting lid and pyrolyzed under the
oxygen-limited conditions in a muffle furnace (RH Corp.,
Nanjing, China). Furnace temperature was ramped at
20 C/min and held at 400 C for different residence
times (1, 2, 3, and 4 h). Biochars prepared at different
residence times were allowed to cool to the room temperature and then ground to pass through 0.3-mm sieve. The
production rate of biochar was calculated using the following
equation: production rate (%)=(MBiochar /MPlant material)100,
where M is the mass. The pH and alkalinity of biochars prepared for 14-h furnace residence time were measured. The
biochar prepared for 2-h residence times was further analyzed
for soluble and exchangeable base cations.
2.2 Physical and chemical properties of biochars
The biochar samples were thoroughly mixed with deionized
water at 1:5 w/w ratio, and pH was then measured using an
Orion 720 pH meter (Thermo Fisher Scientific, Waltham,
MA, USA). The alkalinity of the biochars was determined
by acidbase titration method (Yuan et al. 2011a). A mass of
0.5 g of the biochar samples (0.3-mm sieve) was placed in
50-mL plastic bottles. Then, 20.0 mL of deionized water was

J Soils Sediments

added to each bottle, stirred on a magnetic stirrer for 2 h at

25 C. The samples were then titrated with 0.1 M HCl at 25 C
to the end point at pH 2.0 using an automatic titration instrument (TIM854, Radiometer, UK) with magnetic stirring. The
alkalinity is equal to the amount of HCl consumed during the
titration.
The CECs of the biochars were measured by a modified
NH4-acetate compulsory displacement method (Gaskin et al.
2008). Of the biochars, 0.2 g was leached with 20 mL of
deionized water five times, and the leachates were collected
together. The K+, Na+, Ca2+, and Mg2+ in the leachates were
determined as the soluble base cations of the biochars. After
the fifth run of the leaching with deionized water, the biochars
were leached with 20 mL of 1 M Na-acetate (pH 7) five times,
and the leachates were collected together. The K+, Ca2+, and
Mg2+ in the leachates were determined as the exchangeable
base cations. The biochar samples were then washed with
20 mL of ethanol five times to remove the excessive Na+.
Afterward, the Na+ on the exchangeable sites of the biochars
was displaced by 20 mL of 1 M NH4-acetate (pH 7) five times,
and the CEC of the biochars was calculated from the Na+
displaced by NH4+. The contents of K+ and Na+ in the leachates were determined by flame photometry (FP640, Shanghai
Aopu Analytical Instruments Co., Ltd, China) and Ca2+ and
Mg2+ by atomic absorption spectrometry (AAS) (nov AA350,
analytikjenaAG, Germany).
2.3 Soil
The acidic Ultisol (U.S. Soil Taxonomy; Ferrali-Haplic
Acrisol in the WRB Taxonomy) used in the experiments
was collected from cropland of Gongdong Province, China
(23 10 N, 113 30 E). The sample was taken from the topsoil
(015 cm), air-dried, and ground to pass a 2-mm sieve. Soil
texture was sandy clay loam. The soil pH was 4.68 as determined in a 1:2.5 soil/water suspension. Soil organic matter as
determined by the dichromate method was 11.45 g/kg. The
soil CEC as determined by ammonium acetate method was
81.2 mmolc/kg, and soil exchangeable H+, Al3+, K+, Na+,
Ca2+, and Mg2+ were 2.83, 29.99, 0.18, 0.38, 9.45, and
5.29 mmolc/kg, respectively.
2.4 Incubation experiment
Air-dried soil samples of 300 g were placed in plastic cups,
and each biochar was added at the rate of 0.5, 1.0, and 1.5 %.
Soils and biochars were thoroughly mixed, and then wetted
with deionized water to 70 % of field water-holding capacity
of the soil. All cups were covered with plastic film, and a small
hole was made to allow gaseous exchange but to minimize
moisture loss, and then incubated at 25 C. The cups were
weighed every 3 days with water added to maintain a constant
moisture content throughout the experimental period. Soils

were subsampled after 5, 10, 15, 20, 25, 35, 45, and 65 days,
and the fresh soil samples were used to determine the pH.
There were three replicates for each treatment with control
having no biochar. After 65-day incubation, the soil samples
were removed from the cups, air-dried, and ground to pass a
0.3-mm sieve for further analysis.
2.5 Greenhouse pot experiment
Air dried 2-mm sieved soils and biochars from the bulk used
in the incubation experiment were also used in greenhouse pot
experiment. A basal dose of KH2PO4 at the rate of 280 mg/kg
was applied to all pots to meet the requirements of P and K
based on the dose of the fertilizer used in south of China.
Soils after through mixing with biochars and nitrate-N in
the form of Ca(NO3)2 were filled in plastic pots at the rate
of 5 kg/pot. The treatments comprised of the following:
(1) control, (2) 100 mg N/kg, (3) 200 mg N/kg, (4)
100 mg N/kg+1 % canola straw biochar (CSB), (5)
200 mg N/kg+1 % CSB, (6) 100 mg N/kg+1 % peanut
straw biochar (PSB), and (7) 200 mg N/kg+1 % PSB.
Locally grown seeds of Zhengdan-958 maize variety were
grown in plastic trays in laboratory, and seedlings were
transferred into pots at the rate of 10 plants/pot. Water
was added to maintain field water-holding capacity level
throughout the experiment.
At the end of the pot experiment (85 days), the whole
shoots and roots were harvested by removing them from the
individual pots. The plants were washed with deionized water,
oven-dried at 70 C to a constant weight, and then weighed to
determine the dry matter yield. Soil samples were collected,
air-dried, and ground to pass a 0.3-mm sieve for further
analyses.
2.6 Soil analysis
After crop harvest, the pH of soil samples from pot experiment
was determined in a 1:2.5 soil/water suspension. The exchangeable H+ and Al3+ of the soil samples were extracted with
1.0 M KCl, and then titrated by 0.01 M NaOH to pH 7.0 (Pansu
and Gautheyrou 2006). Soil exchangeable base cations were
extracted with 1.0 M ammonium acetate (pH 7.0) (Pansu and
Gautheyrou 2006), and then, Ca2+ and Mg2+ were measured
using AAS and K+ and Na+ with flame photometry. The soil
NH4+-N and (NO3+NO2)-N were extracted with 2.0 M KCl
using a 1:5 soil to solution ratio (Pansu and Gautheyrou 2006),
and their concentrations were determined by the continuous
flow analytical system (Skalar San++, The Netherlands).
2.7 Statistical analysis
SPSS 15.0 (SPSS Inc., Chicago, IL, USA) was used for the
statistical analysis of the data obtained. All the results were

J Soils Sediments

provided as the average of the three replicates with the standard error. Multifactorial ANOVA analysis was undertaken to
figure out the interactive effects of N-fertilizer and biochars on
soil acidity and maize growth. Pearson correlation between
maize biomass and exchangeable Al3+ was performed at P
0.05. Significant effects for various treatments were detected
using t test (Landau and Everitt 2004).

3 Results and discussion

3.1 Chemical compositions and properties of biochars
The properties of biochars produced by pyrolyzing feedstock
for different residence times are presented in Table 1. It is
evident from the results that by increasing the furnace residence time, the pH and alkalinity of biochars increased,
whereas the production rate decreased. The relatively low
yield of biochars compared to previous studies (Peng et al.
2011) was because oxygen was not completely limited during
pyrolysis of biomass in the present study. PSB had higher pH
and greater alkalinity than CSB. The pH and production rate
of biochars with the furnace residence time of 2 h were similar
to biochars with the furnace residence time of 3 h, and the
alkalinity of the former was slightly lower than the latter
(Table 1). The preparation of biochars at higher temperatures
not only consumed more energy, but also caused nutrient
losses. It was evidently reported that N loss from biochars
increased when the temperature was raised above 400 C
(Lang et al. 2005). The decreases in volatile matter, EC, and
CEC of biochar were noticed with the increase in pyrolysis
temperature from 400600 C (Mndez et al. 2013).
Moreover, application of biochar pyrolyzed at low temperature was more suitable for agricultural use as it contained
greater quantities of functional groups (Novak et al. 2009).
Therefore, for the current incubation and pot experiments,
the biochars were pyrolyzed at low residence time of 2 h at
400 C.
The C and N contents, soluble and exchangeable base cations, and CEC of the biochars produced for 2 h are presented
in Table 2. PSB had higher N content and base cations than
CSB whereas CSB had greater CEC than PSB confirming the
Table 1 Properties of biochar
pyrolyzed at 400 C for different
residence time

Residence time (h)

1
2
3
4

previous report (Yuan and Xu 2012) that biochars prepared

from legume straws had higher CEC than non-legume straws.
Biochars generally have several fold higher CEC than
soils and can be used as suitable amendment for tropical
and subtropical soils having CEC less than 10 cmolc/kg
(Li et al. 2012). The feedstock affected the properties of
biochars as K and Na contents were greater in CSB while
Ca and Mg contents were higher in PSB. Both the biochars had abundant soluble and exchangeable base cations.
The components in feedstock responsible for alkalinity
were concentrated in biochars during pyrolysis process
and radially available to make exchange reactions.
3.2 Changes in soil pH during incubation
The changes in soil pH during incubation with different application rates of CSB and PSB are presented in Fig. 1. Initially,
there was a sharp increase in soil pH with the incorporation of
biochars; however, fluctuation was noted up to 25 days, and
afterward, there was slight change throughout the incubation
period. In control (without biochars), an increase in soil pH
was also observed in the beginning and then pH declined till
end of the incubation. PSB increased the pH significantly
higher than CSB. The significant rise in pH might be attributed to high total nitrogen content of PSB and alkalinity of the
biochars. At initial days of incubation, mineralization of organic N consumed protons and led to an increase in soil pH,
while nitrification of NH4+ decreased pH due to release of
protons afterward (Xu and Coventry 2003). The alkalinity of
biochars and mineralization of organic N at the early stage of
the incubation were two factors that contributed to the rise
in soil pH for the treatments with biochars added, whereas
subsequent nitrification of NH4+-N at later stage would
have contributed to the soil pH decline. The alkalinity
was the main factor for the increase in soil pH for the
treatments with biochars added. The greater alkalinity of
PSB led to much greater increase in soil pH compared to
CSB at similar application rates (Fig. 1 and Table 2), which was
consistent with our previous report (Yuan and Xu 2012). After
65-day incubation, increase in the soil pH ranged from 0.15 to
0.83 U by biochar incorporation compared to control. The rise
in soil pH was consistent with the increase in application rates

Production rate (%)

pH

CSB

PSB

CSB

PSB

CSB

PSB

42.3
35.4
35.2
33.5

45.4
40.8
40.5
38.1

7.48
7.72
7.65
7.92

9.07
9.28
9.33
9.69

49.3
101.0
104.4
121.7

293.6
425.4
435.5
510.3

CSB canola straw biochar, PSB peanut straw biochar

Alkalinity (cmol/kg)

J Soils Sediments
Table 2
Biochar

Some chemical properties of biochars produced at 400 C for 2 h

Total C (%)

Total N (%)

Soluble base cations (cmol/kg)

Exchangeable base cations (cmol/kg)

Ca2+

Mg2+

K+

Na+

Ca2+

Mg2+

K+

CEC (cmolc/kg)

CSB

60.8

1.12

17.2

3.2

56.3

18.3

69.5

9.7

27.7

133.5

PSB

50.6

2.74

22.9

18.8

41.9

2.9

88.1

40.7

20.2

108.9

CSB canola straw biochar, PSB peanut straw biochar

exchangeable Al3+ which transformed to Al-OH and precipitated as Al hydroxides. Thus, the decrease of Al3+ being active
species of soil Al reduced potential toxicity of Al3+, imparting
amelioration effects on acidic soils.
The high concentration of base cations contained in the
feed stocks were retained in biochars after pyrolysis (Wang
et al. 2009), which were readily available to make exchange
reactions with soil particles; thus, incorporation of biochars
led to the increase in exchangeable base cations of the
soil. The increase in each base cation in the soil after
biochar incorporation was consistent with corresponding
base cations in biochar samples. The greater increase in
soil Ca2+ content after application of PSB was due to its higher
content of Ca2+ (22.9 cmol/kg) than CSB (17.7 cmol/kg).
Similarly, higher Mg2+ concentration in CSB was revealed by
higher Mg2+ contents in the soil with CSB applied. Higher
exchangeable K+ and Na+ contents in the biochars increased
soil contents of K+ and Na+ many folds after the biochars
incorporated into the soil. About 5, 11, and 16 time increases
in soil exchangeable K+ were noticed by applying 0, 1, and
1.5 % CSB, and 4, 10, and 15 time increases in soil exchangeable K+ were observed by applying the same rates of PSB
(Tables 2 and 3). Similarly, Na+ contents were increased by
29, 36, and 42 times by applying CSB and 3, 7, and 10 times
by applying PSB at the same rates. It suggested that application
of biochars to soil could increase nutrient cations many folds
and thus improved soil fertility.

of the biochars. When 0.5, 1.0, and 1.5 % of CSB and PSB
were incorporated, the increases in soil pH were 0.15, 0.27,
0.34, 0.30, 0.58, and 0.83 U, respectively.
3.3 Effect of biochars on soil exchangeable acidity
and exchangeable base cations
Soil acidity is manifested mainly by exchangeable Al3+ while
exchangeable H+ has less contribution to overall acidity in
highly acidic soils (Yu 1997). It is evident from the results in
Table 3 that incorporation of biochars decreased soil exchangeable acidity, whereas exchangeable base cations and
base saturation were increased, confirming the results presented in previous reports (Steiner et al. 2008). The percent decreases in exchangeable acidity compared to control were
25.4, 49.9, 61.7 % by applying CSB at application rates of
0.5, 1.0, and 1.5 %, and 60.1, 80.6, and 82.1 % by applying
PSB at the same rate. The percent decrease in exchangeable
acidity due to the addition of PSB was significantly higher
than CSB and the two higher rates, i.e., 1 and 1.5 % were
statistically at par. The higher reduction in exchangeable
acidity by PSB was comparable to its higher alkalinity
(425.42 cmol/kg) than CSB (101.04 cmol/kg) (Table 2).
Previous investigations (Masud et al. 2014a; Zhu et al. 2014)
also supported the evidence that leguminous materials are
better choice to be used as amendments for acidic soils. The
reduction in exchangeable acidity indicated hydrolysis of
6.0

Fig. 1 Changes in soil pH by

applying different rates of canola
straw biochar (CSB) and peanut
straw biochar (PSB) during
65-day incubation

Control

0.5% CSB

1.0% CSB

0.5% PSB

1.0% PSB

1.5% PSB

1.5% CSB

Soil pH

5.5

5.0

4.5

10

20

30

40

Incubation days

50

60

70

J Soils Sediments
Table 3
Treatment

Control

Chemical properties of the soil amended with different rates of biochars after 65-day incubation
Application Exchangeable acidity (mmol/kg)
rate (%)
H+
Al3+
Acidity

Exchangeable base cations (mmol/kg)

Ca2+

Mg2+

K+

Na+

ECEC (mmolc/kg) Base

saturation (%)

2.7a

28.0a

30.7a

9.6e

5.3f

0.2d

0.4e

46.2d

33.6e

Canola straw biochar 0.5

1.0

2.0b
1.6c

20.9b
13.8c

22.9b
15.4c

12.5e
23.6c

5.6f
7.1e

0.8c
1.8b

4.9c
6.1b

46.7d
54.0c

51.0d
71.5c

1.5
Peanut straw biochar 0.5

1.1d
2.2b

10.7d
10.1d

11.8d
12.3d

24.6c
17.9d

8.7d
15.7c

2.8a
0.7c

7.2a
0.6e

55.2c
47.1d

78.7b
74.0c

1.0

2.1b

3.9e

6.0e

35.9b

27.2b

1.7b

1.2de

71.9b

91.7a

1.5

1.5c

4.0e

5.5e

50.5a

38.2a

2.7a

1.8e

98.6a

94.4a

Within the columns, means (n=3) followed by the same letter are not significantly different at P<0.05

The alkaline nature and high CEC of the biochars contributed to soil negative charge and thereby increased soil effective cation exchange capacity (ECEC). The increment trend in
ECEC followed the increasing biochar application rates
(Table 3). When the biochars were incorporated into the acidic
soils, base cations exchanged with exchangeable Al3+ and H+
on soil negative charge sites and thus decreased soil exchangeable acidity. In addition to increase in soil exchangeable base
cations, higher increase in soil ECEC was induced by application of PSB compared to CSB due to more increase in soil
pH by PSB. The negative charge on biochars was mainly
from the dissociation of acidic function groups, and the
dissociation of the functional groups increased with rising
pH. Thus, the biochars contributed more negative charges
to the soil at higher pH (Fig. 1 and Table 3). Moreover,
the nutrient retention and increase in base saturation were
1 to 3 times higher in biochar applied treatments compared to control (Table 3). This increase in base saturation
also improved soil fertility, which supported the findings
of other reports (Steiner et al. 2008).
3.4 Changes in soil pH and exchangeable acidity
after 85-day greenhouse pot experiment
The nitrate-N fertilizers applied alone or in combination with
biochars increased soil pH after maize harvest in greenhouse
pot experiment (Fig. 2). Sole application of nitrate 100 mg
N/kg and 200 mg N/kg was found to have a significant
(P<0.05) increase in the soil pH by 0.12 and 0.20 U over
control, whereas there was non-significant difference between
the two N treatments. The combined application of nitrate
with biochars significantly increased soil pH. The increases
in soil pH by applying 1 % CSB along with 100 mg and
200 mg N/kg were 0.49 and 0.72 U, respectively, compared
to 0.78 and 0.88 U increase caused by 1 % PSB biochar
combined with same amounts of nitrate, respectively, indicating the superiority of PSB in terms of reducing soil acidity.
Application of N in the form of nitrate enhanced soil pH,

which was due to more anion uptake and release of hydroxyl

ions by plant roots. Maintaining optimum nitrate nutrition
may enable the plant to protect its most essential root zone
from the adverse effects of strong acidity by locally raising the
rhizosphere pH (Gijsman 1990). The combined application of
nitrate and biochar was more effective in increasing soil pH
compared to sole application of nitrate, suggesting that overall
pH increase was not only due to biochars but also contributed
by nitrate-N. The alkalinity in biochars induced greater ameliorative effect on soil acidity, and hydroxyl release by roots
had caused more alkalization. By comparing the results of
incubation study with pot experiment, it was evident that the
increases in soil pH by 1 % CSB and PSB at the end of 65-day
incubation were 0.27 and 0.58 U, respectively (Fig. 1). In pot
experiment 1 % CSB when applied in combination with 100
and 200 mg N/kg, the increases in pH were 0.49 and 0.72 U,
whereas 0.79 and 0.80 U when 1 % PSB was applied along
with 100 and 200 mg N/kg, respectively. The pH enhancement in greenhouse experiment by combined application of
the biochars with nitrate confirmed the root zone alkalization
due to nitrate uptake and hydroxyl release by maize plants
(Weligama et al. 2010). The maximum pH was observed in
the pots treated with PSB combined with 200 mg N/kg of
nitrate, followed by 100 mg N/kg+1 % PSB. Increase in pH
by CSB was lower than PSB at both rates of applied nitrate.
The higher increase in soil pH by application of PSB was
consistent with its alkalinity content (425.42 cmol/kg) than
CSB (101.04 cmol/kg). Application of nitrate fertilizer
combined with biochars had two simultaneous neutralization effects, due to biochar alkalinity, and secondly
contributed through biological amelioration by hydroxyl
release from maize roots due to nitrate uptake by the
plant (Masud et al. 2014b). Thus, the biochars in combination with nitrate despite of removing paddock were
capable to maintain higher soil pH (Fig. 2).
In contrast to increase in soil pH by nitrate and biochars, a
decrease in soil exchangeable acidity was also observed
(Fig. 2). When nitrate-N was applied alone, a significant

J Soils Sediments
30
Exchageable Acidity (mmol/kg)

Fig. 2 Changes in soil pH and

exchangeable acidity after crop
harvest in 85-day greenhouse pot
experiment with application of
sole nitrate (100 and 200 mg
N/kg) and in combination with
1 % canola straw biochar (CSB)
or peanut straw biochar (PSB).
Bars sharing the same letter are
not significantly different at
P<0.05

25

20

15

10

5
0
6.0

5.5

ab

Soil pH

c
5.0

e
4.5

4.0
Control

100 mg/kg

200 mg/kg

100 mg/kg
+1% CSB

200 mg/kg
+1% CSB

100 mg/kg
+1% PSB

200 mg/kg
+1% PSB

biochars with mineral nitrate fertilizer caused higher reduction

in soil exchangeable acidity.

decrease in exchangeable acidity was noticed (P<0.05). The

combined use of nitrate with the biochars caused a further
drastic reduction in exchangeable acidity. About 34-fold decrease in exchangeable acidity was noticed in the treatments
with 1 % biochars combined with nitrate compared to single
nitrate applications (Fig. 2). The highest decrease in exchangeable acidity was observed in the treatment supplied
with 200 mg N/kg+1 % PSB, which was not significantly
different from 100 mg N/kg+1% PSB and 200 mg N/kg+1%
CSB. Hence, consistent with pH increase, combined use of

3.5 Soil exchangeable base cations, contents

of (NO3+NO2) and NH4+ and maize biomass in 85-day
greenhouse pot experiment
The post-harvest soil analysis showed that sole N application
in the form of calcium nitrate significantly increased soil Ca2+
contents (P<0.05) (Table 4), whereas did not significantly

Table 4 Exchangeable base cations, contents of (NO3+NO2)-N and NH4+-N of the soil and maize biomass after 85-day greenhouse pot experiment
with application of sole nitrate (100 and 200 mg N/kg) and in combination with 1 % canola straw biochar (CSB) or peanut straw biochar (PSB)
Treatment

Control
100 mg N/kg
200 mg N/kg
100 mg N/kg+1
200 mg N/kg+1
100 mg N/kg+1
200 mg N/kg+1

NO3+NO2

Exchangeable base cations

% CSB
% CSB
% PSB
% PSB

Ca2+
(mmol/kg)

Mg2+

8.5d
26.9b
37.4a
20.1c
25.9b
19.3c
28.3b

5.2d
5.3d
5.5d
8.3b
7.0c
19.9a
19.7a

K+

Na+

NH4+

Total
(mg/kg)

0.2c
0.3c
0.3c
0.5a
0.5a
0.4b
0.4b

0.4c
0.5b
0.4c
0.7a
0.7a
0.4c
0.4c

Maize biomass

14.3d
32.9c
43.6b
29.6c
34.0c
40.0b
48.8a

51.3b
61.7b
96.1a
57.1b
52.6b
46.2b
42.6b

Within the columns, means (n=3) followed by the same letter are not significantly different at P<0.05

(g/pot)
6.5b
8.4b
11.6a
7.6b
8.4b
7.5b
8.6b

28.1e
45.5d
49.5d
114.8b
129.7a
99.6c
95.7c

J Soils Sediments
Table 5 ANOVA analysis showing interaction between nitrate and
biochar for pH, exchangeable acidity, exchangeable base cations, and
maize biomass after 85-day pot experiment with application of sole
nitrate (100 and 200 mg N/kg) and in combination with 1 % canola
straw biochar or peanut straw biochar
Treatments

pH Exchangeable Exchangeable base Maize

acidity
cations
biomass

NO3-N

**

**

**

**

Biochar
** **
NO3-N X Biochar NS **

**
NS

**
NS

NS non-significant
**Highly significant at P0.01
*Significant at P0.05

influenced the contents of Mg2+, K+, and Na+ compared to

control. The results suggested that biochar incorporation with
nitrate enhanced the exchange reactions of the base cations from
amendments with soil exchangeable Al3+ and H+ and thus increased soil exchangeable base cations (Table 4). This process
also contributed to the decrease of soil exchangeable acidity,
similar to the role of organic matter application that lowered
the exchangeable Al3+ content of acidic soils (Hue and Amien
1989; Naramabuye and Haynes 2006). The biochar used in
present study was pyrolyzed at 400 C for 2 h and had ample
oxygen-containing functional groups that formed complexes
with Al3+, thereby decreased exchangeable Al3+ and increased
exchangeable base cations (Tables 3 and 4). Therefore, nitrate
application alone and in combination with biochars not only
ameliorated soil acidity, but also supplied Ca2+, Mg2+, K+, and
Na+ to the soil. The higher Mg2+ in PSB (Table 2) increased soil
Mg2+ content, whereas higher content of K+ in CSB increased
K+ content in the soil (Table 4). These nutrient contents in biochars laid strong influence on plant biomass. Application of
CSB enhanced the K supply in the soil and increased the plant

Correlations

160
140
120

Biomass (g/pot)

Fig. 3 Relationship between

maize biomass and exchangeable
Al3+ (Exc. Al3+) after 85-day
greenhouse pot experiment with
application of sole nitrate (100
and 200 mg N/kg) and in
combination with 1 % canola
straw biochar (CSB) or peanut
straw biochar (PSB)

biomass over PSB. Thus, in spite of lower alkalinity, the increased

K supply by CSB considerably improved the crop growth.
There was no significant difference in contents of (NO3+
NO2)-N and NH4+-N among the treatments except for the
sole application of 200 mg N/kg (Table 4). The higher N
contents retained in 200 mg N/kg treatment were probably
due to either increased supply of nitrate or the inability of
weakly grown plants to uptake N in highly acidic conditions.
Two factorial ANOVA (Table 5) showed highly significant
interactions among nitrate-N levels and biochar types for pH,
exchangeable acidity, exchangeable base cations, and plant
biomass with respect to control (P<0.05). The interaction between nitrate and biochars was also highly significant for exchangeable acidity, significant for pH and plant biomass, but
non-significant for exchangeable base cations at P0.05.
Ammonification of organic N consumed protons and caused
soil pH to increase, whereas nitrification of ammonium released
protons and caused the soil pH to decrease (Tong and Xu 2012),
which resulted soil acidification and probably affected crop
growth. Application of biochars to the soil had several benefits depending upon their properties. Incorporation of charcoal amendments into a highly weathered soil improved Nfertilizer use efficiency due to charcoals high CEC (Steiner
et al. 2008). Biochars high porosity accompanied by high
surface areas contributed to nutrient adsorption (Ahmad et al.
2014). Similarly, biochar application increased soil pH, organic
carbon, total N, and thus rice productivity (Zhang et al. 2012).
Moreover, it was suggested that biochar application improved
the soil aggregation and enhanced physiochemical and biological properties of the soil (Awad et al. 2013). The results presented in this study suggested that agronomic properties of
biochars could be enhanced by combining with proper mineral
fertilizer to ensure sustainable agriculture in soils of tropical
and subtropical regions. The soils in these regions were deficient in Ca2+, Mg2+, and K+ due to extensive leaching.

100
80

Exc. Al3+

Biomass

-.882**
.000
21

Exc. Al3+ Pearson Correlation

Sig. (2-tailed)
N

21

Biomass Pearson Correlation

Sig. (2-tailed)
N

-.882**
.000
21

1
21

** Correlation is significant at the 0.01 level (2-tailed).

60
40
20
0

10

15

Exchangeable Al3+(mmol/kg)

20

25

30

J Soils Sediments

3.6 Relationship between maize biomass

and exchangeable Al3+
The exchangeable Al3+ which is mainly responsible for exchangeable acidity in acidic soils decreased significantly by
application of nitrate and crop straw biochars. The consistent
decrease in exchangeable Al3+ increased the plant biomass. A
highly significant negative relationship between exchangeable
Al3+ and maize biomass (R2 =0.080**) was found (P<0.05).
A similar relationship between maize biomass and soil exchangeable Al3+ was reported previously in 46-day pot experiment (Zhu et al. 2014). Therefore, we concluded that application of biochar in combination with nitrate fertilizer could
reduce soil acidity and Al toxicity, and thus improved crop
growth in acidic soils (Fig. 3).

4 Conclusions
The properties of biochars mainly depended on type of feedstock, pyrolysis temperatures, and furnace residence times.
Crop residues after crop harvest if pyrolyzed for 2 h and incorporated into soils along with nitrate fertilizers could be an
efficient and low-cost amendment for acidic soils. It is imperative to measure the properties of straw-derived biochars before use. However, alkaline nature of biochars had the ability
to decrease soil exchangeable acidity and thus increase soil
pH, exchangeable base cations, and base saturation of acidic
soils. The combined application of biochars with nitrate fertilizer
would provide simultaneous neutralization effects, due to biochar alkalinity and hydroxyl release from plant roots through
nitrate uptake. The biochars in combination with nitrate despite
of removing paddock were capable of maintaining higher soil
pH and improving fertility status of acidic soils. We concluded
that application of biochars combined with nitrate fertilizers
could ensure sustainable agriculture in tropical and subtropical
regions, where mostly soils are acidic and normally deficient
in Ca2+, Mg2+, and K+ due to extensive leaching.
Acknowledgments This study was supported by the National Key Basic
Research Program of China (2014CB441003) and the National Natural
Science Foundation of China (41230855). The CAS-TWAS Presidents
Fellowship for PhD studies in China was also gratefully acknowledged.

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