This article was downloaded by: [Moskow State Univ Bibliote]

On: 16 August 2013, At: 09:21

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

Archives of Agronomy and Soil Science

Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gags20

Effect of biochar on chemical

properties of acidic soil
a a a
Rajesh Chintala , Javier Mollinedo , Thomas E. Schumacher ,
a b
Douglas D. Malo & James L. Julson
a
Department of Plant Science, South Dakota State University,
Brookings, SD, USA
b
Department of Agricultural & Biosystems Engineering, South
Dakota State University, Brookings, SD, USA
Accepted author version posted online: 05 Apr 2013.Published
online: 28 May 2013.

To cite this article: Archives of Agronomy and Soil Science (2013): Effect of biochar
on chemical properties of acidic soil, Archives of Agronomy and Soil Science, DOI:
10.1080/03650340.2013.789870

To link to this article: http://dx.doi.org/10.1080/03650340.2013.789870

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.

This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &
 Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions
Downloaded by [Moskow State Univ Bibliote] at 09:21 16 August 2013
 Archives of Agronomy and Soil Science, 2013
http://dx.doi.org/10.1080/03650340.2013.789870

Effect of biochar on chemical properties of acidic soil

Rajesh Chintalaa*, Javier Mollinedoa, Thomas E. Schumachera, Douglas D. Maloa and
James L. Julsonb
a
Department of Plant Science, South Dakota State University, Brookings, SD, USA; bDepartment of
Agricultural & Biosystems Engineering, South Dakota State University, Brookings, SD, USA
(Received 31 October 2012; final version received 21 March 2013)
Downloaded by [Moskow State Univ Bibliote] at 09:21 16 August 2013

The effect of biochar addition on the chemical properties of acidic soil such as soil pH,
electrical conductivity (EC), cation exchange capacity (CEC), and exchangeable acid-
ity were investigated to determine the liming potential of biochars. This study was
conducted by incubating acidic soil (clayey, smectitic, acid, mesic, shallow, Aridic
Ustorthent) of pH < 4.80 with biochars for 165 days. The biochars were produced from
two biomass feedstocks such as corn stover (Zea mays L.) and switchgrass (Panicum
virgatum L.) using microwave pyrolysis (at 650°C). Corn stover biochar, switchgrass
biochar, and lime (calcium carbonate) were applied at four rates (0, 52, 104, and
156 Mg ha−1) to acidic soil. Amendment type, application rate, and their interaction
had significant effects (p < 0.05) on soil pH, EC, and CEC of acidic soil. Exchangeable
acidity was significantly affected by amendment type. Application of corn stover
biochar had shown a relatively larger increase in soil pH than switchgrass biochar at
all application rates. The ameliorating effect of biochars on chemical properties of
acidic soil was consistent with their chemical composition.
Keywords: Grummit soil; soil pH; exchangeable acidity; CEC; phosphorus; corn
stover biochar; switchgrass biochar; EC; Aridic Ustorthent

Introduction
Hydrogen (H+) and aluminum (Al3+) ion dominance in the soil exchangeable complex
causes acidity which limits crop yield and utilization of many essential nutrients by plants
(Black 1993; Chintala et al. 2012a). Liming to remediate acidic soils has a longer history
than the use of any other forms of soil amendments (McLean 1971). Liming has shown
the synergistic interaction with applied nutrients (through fertilizers) and increased the
nutrient uptake by plants (Chintala et al. 2012b). Liming results in changes in the
chemical and physical properties of soil that improve conditions for plant growth
(Menzies et al. 1994). There has been increased interest on alternative liming agents
with multiple benefits such as pyrolytic biochars which can be used to improve soil
fertility and to store carbon (C) in the soil (Steiner et al. 2007; Nguyen & Lehmann 2009;
Yuan & Xu 2011).
The thermal conversion of biomass (pyrolysis) in a low or no oxygen environment
produces high carbonaceous biochar material or charcoal with unique characteristics
(Gaskin et al. 2008). Biochars are highly recalcitrant with carbon sequestration benefit
(Lehmann 2007; Rebecca 2007) and can influence soil pH (Xu et al. 2006). It was observed
that application of biochars to acidic soil increases its sorption capacity for nutrients (Sohi

*Corresponding author. Email: rajesh.chintala@sdstate.edu

© 2013 Taylor & Francis

 2 R. Chintala et al.

et al. 2010) and reduces the exchangeable acidity (Van Zwieten et al. 2009). Higher
pyrolytic temperature (>400°C) was observed to produce biochars with alkaline pH
(Novak et al. 2009). Several studies have already observed the beneficial effects of biochar
on soil quality and fertility parameters. Before applying these biochars to acidic soils as
amendment, it will be necessary to analyze their composition and liming potential.
The physical and chemical characteristics of any amendment determine its effective-
ness as liming agent (Barber 1984). The ameliorating ability of biochars can be varied due
to differences in their physical and chemical properties. These biochar properties are
influenced by pyrolytic parameters and feedstock type (Lei et al. 2009). The liming effect of
any amendment can be determined by studying soil indices such as soil pH and exchangeable
acidity (Wong & Swift 1995; Wang et al. 2009). Liming potential of a material can also be
predicted by its properties such as calcium carbonate equivalence (Mokolobate & Haynes
2002) and ash alkalinity (Noble et al. 1996). Little information is available on the liming
Downloaded by [Moskow State Univ Bibliote] at 09:21 16 August 2013

potential of biochars produced from various pyrolytic processes using different biomass
feedstocks and their associated reaction mechanisms to reduce soil acidity. It was hypothe-
sized that biochars produced from microwave pyrolysis using corn stover and switchgrass
had a permanent ameliorating effect on chemical properties of acidic soil. The ameliorating
effect of biochars on acidic soil was assumed to be consistent with their composition and
properties which depend on biomass feedstock type and pyrolytic conditions. The objective
of this study was to determine the biochar induced changes on selected chemical properties of
acidic soil such as soil pH, exchangeable acidity, and cation exchange capacity (CEC).

Materials and methods

Soil and biochar materials
Acidic soil (0–15 cm) was collected from cultivated Entisol (clayey, smectitic, acid,
mesic, shallow Aridic Ustorthents) belonging to the Grummit soil series (located at 44°
18′ 2.52″ N and 103° 20′ 33.39″ W) (U.S. Department of Agriculture 2005). Soil was air-
dried, crushed, and passed through a 2-mm sieve before chemical characterization. pH
(1:15) was determined by glass membrane electrode (Rayment & Higginson 1992).
Electrical conductivity (EC) was measured by using a conductivity meter (Rhoades
1996). Soil texture was determined by the pipette method (Sternberg & Creager 1961).
Total carbon (C) and total nitrogen (N) were analyzed by Elementar Vario MAX CNS
analyzer (Elementar Analysensysteme GmbH, Hanau, Germany) (Chintala, Clay, et al.
2013); Olsen-extractable phosphorus (Olsen-P) was determined according to Olsen et al.
(1954) and CEC by the ammonium acetate method (Chapman 1965). All determinations
were done to samples from three replications.
Biochar materials were by-products of bio-oil production from two feedstocks such as
corn stover (Zea mays L.) and switchgrass (Panicum virgatum L.) using microwave
pyrolysis at 650°C with residence time of 18 min. The biochars were homogenized,
ground to pass through <0.2 mm, and analyzed for chemical properties such as pH, EC,
proton consumption capacity, calcium carbonate (CaCO3) content, total C and N, and base
cations. The proton consumption capacity was determined by titrating with 0.05 M
sulfuric acid to pH 4.0 (Wong et al. 2000). CaCO3 content was measured with the
calcimeter method (Sherrod et al. 2002). Biochar samples were digested with nitric
acid to determine P and base cations (Ca, Mg, K, and Na) using Inductively Coupled
Plasma Atomic Emission Spectroscopy (ICP-OES) (Varian, Mulgrove, Australia) (U.S.
Environmental Protection Agency 1998).
 Archives of Agronomy and Soil Science 3

Incubation experiment
Air-dried soil samples of 200 g were placed in plastic cups, and lime (finely
powdered CaCO3), and each biochar type (switchgrass and corn stover) were added at
0 g kg−1 (0 Mg ha−1), 20 g kg−1 (52 Mg ha−1), 40 g kg−1 (104 Mg ha−1), and 60 g kg−1
(156 Mg ha−1), respectively. The biochar rates per hectare were calculated using tillage
depth of 0.2 m and bulk density of 1300 kg m−3. The soil and biochar were mixed
thoroughly and then wetted with deionized water to 70% of field water holding capacity
of the soil (Naeth et al. 1991). 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 constant 25°C. The cups were weighed every three days and water was added to
maintain constant moisture content throughout the experiment. The soils were sub-
sampled at 0, 15, 30, 45, 60, 75, 90, 105, 120, 135, 150, and 165 days from the
Downloaded by [Moskow State Univ Bibliote] at 09:21 16 August 2013

initiation of incubation. The incubation study was carried out (for 165 days) until the
steady state was achieved in chemical properties of soil-amendment mixtures. These soil
samples were air-dried, and ground to pass a 2-mm sieve. Later, these soil samples were
used to determine the soil pH, EC, exchangeable acidity, and CEC. Soil exchangeable
acidity (H+ and Al3+) was extracted with 1.0 M KCl, and then titrated by 0.25 M NaOH
to pH 7.0 (Farina & Channon 1991). CEC of the soil samples was measured by
ammonium acetate method. Samples from soil-amendment mixtures were treated with
1 N NH4OAc (pH 7.0) to replace all exchangeable base cations (Ca, Mg, K, Na) with
ammonium ion (NH4+). The sorbed NH4+ (indicator ion) was replaced from sorption
places with K+ by using 1 M KCl solution. The concentration of replaced NH4+ in
solution was measured to calculate CEC by capturing NH3 in saturated H3BO3 and
titrated with 0.1 N HCl in the presence of mixed indicator (Chapman 1965). Solution
and sample mixtures were filtered using Whatman no. 42 filter paper (with reten-
tion: >2.5 µm) to avoid losses of samples during the chemical procedure. Three
replications were used for each treatment and controls had no incorporated biochar.

Statistical analysis
A one-way analysis of variance was performed for each incubation time interval to
determine significant differences between treatments. The significant effects for various
treatments were determined by using a t-test (Steel & Torrie 1980; Tukey 1994).

Results and discussion

Characterization of soil and biochar materials
The texture of the acidic soil was a clay loam (35.8% clay; 44.4% sand; 19.8% silt), with an
initial pH of 4.78, 93 μS cm−1 EC, 3.5 cmolc kg−1 exchangeable acidity, 3.26 cmolc kg−1
exchangeable Al, 0.02 g kg−1 total nitrogen, 0.24 g kg−1 total carbon, 5.06 cmolc kg−1 exchange-
able Ca, 0.42 cmolc kg−1 exchangeable Mg, and 0.61 cmolc kg−1 exchangeable K. Selected
chemical properties of biochars were determined and presented in Table 1. Overall, the biochars
have high pH, CaCO3 content, and base cation concentrations, which are essential chemical
properties to determine their liming potential. The pyrolytic process of biomass feedstocks was
attributed to lead to higher concentration of elements in biochar materials. Corn stover biochar
was found to have significantly higher pH, EC, and CaCO3 content compared with switchgrass
biochar. Therefore, corn stover biochar had relatively higher proton consumption capacity due to
the higher base cation concentration and CaCO3 content. The presence of higher soluble salts in
the biochars resulted in higher EC values. The cations on biochar surface may not be strongly
 4 R. Chintala et al.

Table 1. Chemical properties of biochars with standard errors.

Chemical properties Corn stover biochar Switchgrass biochar

pH 11.42 ± 0.10a 10.45 ± 0.15b

EC (μS cm−1) 3000 ± 60a 890 ± 20b
Proton consumption capacity (cmolc kg−1) 59.1 ± 3.21a 25.0 ± 1.75b
CaCO3 (g kg−1) 2.5 ± 0.52a 2.0 ± 0.36b
Ca (g kg−1) 7.51 ± 0.24a 7.12 ± 0.17a
Mg (g kg−1) 5.34 ± 0.88a 5.25 ± 0.51a
K (g kg−1) 21.4 ± 2.75a 2.70 ± 0.13b
Na (g kg−1) 6.95 ± 0.41a 6.76 ± 0.62a
Total P (g kg−1) 1.99 ± 0.14a 1.89 ± 0.05a
Total N (g kg−1) 12.3 ± 1.02b 16.4 ± 1.72a
Total C (g kg−1) 750 ± 24.6b 784 ± 21.1a
Downloaded by [Moskow State Univ Bibliote] at 09:21 16 August 2013

Note: Different letters within the row represent significant differences by Tukey’s test at α = 0.05.

bound by electrostatic forces and dissolve as soluble salts. Total N and C were significantly
higher in switchgrass biochar than corn stover biochar. The plant-based biochars had shown
higher total C and N compared to animal-based biochars in previous studies (Gaskin et al. 2008).
But the base cation concentration was not significantly different (p < 0.05) in biochars except K.
After incorporation of these highly alkaline biochars with high base cation concentration, these
base cations can be released into the soil solution and the acidity can be reduced through proton
consumption reactions in the soil. The composition and properties of biochars varied signifi-
cantly with biomass feedstock despite similar pyrolytic conditions which was also observed in
previous studies (Chintala, Schumacher, et al. Forthcoming 2013). The biomass feedstock type
and pyrolytic conditions can directly influence the heterogeneous composition of biochar
surface and its reactivity with ionic species of soil solution (Lua & Yang 2004; Amonette &
Joseph 2009). The characterization of biochars is the key to understand their potential as
agricultural amendments.

Amendment type versus chemical properties of acidic soil during incubation time
Analysis of variance showed that amendment type, application rate, incubation time, and the
interaction of amendment type and application rate had significant effects (p < 0.05) on
chemical properties of the acidic soil such as soil pH, EC, and CEC. Exchangeable acidity
was significantly affected by only amendment type and incubation time (Table 2). There was

Table 2. Effects of amendment type, application rate, and incubation time on chemical properties
of acidic soil.

Amendment Application Incubation Amendment type ×

type rate time Application rate

Soil chemical property p-value

Soil pH <0.0001 <0.0001 <0.0001 0.0016

Electrical conductivity (EC) <0.0001 <0.0001 0.0163 0.0022
Exchangeable acidity <0.0001 0.9011 <0.0001 0.8566
Cation exchange capacity <0.0001 <0.0001 0.0045 0.0031
(CEC)
 Archives of Agronomy and Soil Science 5

significantly larger change in chemical properties of soil-amendment mixtures in the first two
weeks of incubation time and later the properties would tend to more or less plateau.
Soil pH, EC, and CEC were significantly increased by all amendments at different
rates over incubation time compared to control treatment. There was a significant decrease
in exchangeable acidity with the application of biochars and lime. Higher soil pH values
were obtained with corn stover biochar as compared to switchgrass biochar at all
application rates (Figures 1(a)–(c)). Application of biochars and lime (finely powdered
CaCO3) caused the highest increase in soil pH within the first 15 days of incubation.
There was no significant difference in soil pH values of lime treatments (52, 104, and
156 Mg ha−1). Based on our study, the soil seems to need a lime rate less than 52 Mg ha−1
(20 g kg−1 of soil) to neutralize its acidity.
Exchangeable acidity (sum of exchangeable H+ and Al3+) was significantly decreased
by biochars and lime during incubation (Figures 2(a)–(c)). A relatively higher rate of
Downloaded by [Moskow State Univ Bibliote] at 09:21 16 August 2013

decrease was observed with in the first 15 days of incubation and continued to decrease
in later part of incubation period. The initial rate of decrease in exchangeable acidity was
relatively higher in lime treatments followed by cornstover biochar and switchgrass biochar.
There was no significant difference in exchangeable acidity values among lime treatments.
EC values were also increased at a higher rate for all three amendments with in the
first 15 days of incubation and started to stabilize in the later part of incubation period

0 Mg ha–1
–1
52 Mg ha
104 Mg ha–1
156 Mg ha–1
(a) (b) (c)
8 8
7.5 8
7.5
7.5
7 7
7
6.5 6.5 6.5
pH

pH

6 6
pH

6
5.5 5.5 5.5
5 5 5
4.5 4.5 4.5
4 4 4
0 30 60 90 120 150 180 0 30 60 90 120 150 180 0 30 60 90 120 150 180
Incubation time (days) Incubation time (days) Incubation time (days)

Figure 1. Effect of (a) corn stover biochar, (b) switchgrass biochar, and (c) lime on pH of an acidic
soil in dependence on amount and incubation time. Each data point represents the mean of three
replications with standard error.

0 Mg ha–1
52 Mg ha–1
104 Mg ha–1
(a) (b) (c)
156 Mg ha–1
Exchangeable acidity (cmolc kg–1)
Exchangeable acidity (cmolc kg–1)
Exchangeable acidity (cmolc kg–1)

4 4 4
3.5 3.5 3.5
3 3 3
2.5 2.5 2.5
2 2 2
1.5 1.5 1.5
1 1 1
0.5 0.5 0.5
0 0 0
0 30 60 90 120 150 180 0 30 60 90 120 150 180 0 30 60 90 120 150 180

Incubation time (days) Incubation time (days) Incubation time (days)

Figure 2. Effect of (a) corn stover biochar, (b) switchgrass biochar, and (c) lime on exchangeable
acidity of an acidic soil in dependence on amount and incubation time. Each data point represents
the mean of three replications with standard error.
 6 R. Chintala et al.

0 Mg ha–1
52 Mg ha–1
–1
(b) (c) 104 Mg ha
(a) 156 Mg ha–1
20 20
20 18 18

CEC (cmolc kg )

CEC (cmolc kg )
–1

–1
18 16 16
CEC (cmolc kg )
–1

16 14 14
14 12 12
12
10 10
10
8 8
8
6 6 6
0 30 60 90 120 150 180 0 30 60 90 120 150 180 0 30 60 90 120 150 180
Incubation time (days) Incubation time (days) Incubation time (days)

Figure 3. Effect of (a) corn stover biochar, (b) switchgrass biochar, and (c) lime on electrical
Downloaded by [Moskow State Univ Bibliote] at 09:21 16 August 2013

conductivity (EC) of an acidic soil in dependence on amount and incubation time. Each data point
represents the mean of three replications with standard error.

(Figure 3(a)–(c)). The relatively higher EC was attained in lime treatments of all applica-
tion rates followed by corn stover biochar and switchgrass biochar. Application of all
amendment types at all application rates had significantly increased EC of soil compared
to control treatment. CEC was also significantly increased for all amendments over the
incubation period (Figures 4(a)–(c)). Biochar treatments showed significantly higher CEC
compared to lime treatments. Significant higher CEC values were observed in corn stover
biochar treatments compared to switchgrass biochar treatments. CEC was observed to
increase continuously over incubation time in all treatments of three amendments. The
increase of soil pH, EC, and CEC of acidic soil can be attributed to alkalinity, CaCO3
content, proton consumption capacity, and base cation concentration of the biochars.

Application rate of amendment versus chemical properties of acidic soil during

incubation time
Increase in biochar application rate (from 0 to 156 Mg ha−1) had shown a significant
increase in soil pH, EC, and CEC, but lime did not show any significant difference in soil
pH and EC as application rate increased from 52 to 156 Mg ha−1 (20–60 g kg−1 of soil)
(Figure 5). Mean EC values of corn stover and switchgrass biochar treatments were not

0 Mg ha–1
52 Mg ha–1
104 Mg ha–1
156 Mg ha–1
(a) (b) (c)
20 20 20
18 18 18
CEC (cmolc kg–1)

CEC (cmolc kg–1)

CEC (cmolc kg–1)

16 16 16
14 14 14
12 12 12
10 10 10
8 8 8
6 6
6
0 30 60 90 120 150 180 0 30 60 90 120 150 180 0 30 60 90 120 150 180
Incubation time (days) Incubation time (days) Incubation time (days)

Figure 4. Effect of (a) corn stover biochar, (b) switchgrass biochar, and (c) lime on cation
exchange capacity (CEC) of an acidic soil in dependence on amount and incubation time. Each
data point represents the mean of three replications with standard error.
 Archives of Agronomy and Soil Science 7

(a) (b)
8 4

Exchangeable acidity (cmolc kg–1)

corn stover biochar
7.5 3.5
switchgrass biochar
7 3 lime
6.5 2.5
pH

6 2
5.5 1.5
5 1
4.5 0.5
4 0
0 25 50 75 100 120 150 175 0 25 50 75 100 120 150 175
Downloaded by [Moskow State Univ Bibliote] at 09:21 16 August 2013

Application rate (Mg ha–1) Application rate (Mg ha–1)

(d) (c)
800
22
Cation exchange capacity (cmolc kg–1)

700
20
600 18
EC (µS cm–1)

500 16
400 14
300 12
200 10
100 8
0 6
0 25 50 75 100 120 150 175 0 25 50 75 100 120 150 175
Application rate (Mg ha–1) Application rate (Mg ha–1)

Figure 5. Chemical properties of the acidic soil in dependence on amendment rate. Each data point
represents the mean of three replications with standard error.

significantly different. The increase in soil CEC values of soil was significantly higher in
corn stover biochar at all application rates followed by switchgrass biochar and lime
treatments. Exchangeable acidity was significantly decreased to a very low level at the
rate of 52 Mg ha−1 (20 g kg−1soil) in all three amendments. There was no significant
difference in exchangeable acidity values as application rate of amendment increased from
52 to 156 Mg ha−1 (Figure 2). Differences in properties of biochars such as alkalinity,
proton consumption capacity, and base cation concentration are the major causes of
difference in the response of chemical properties at different application rates.

Liming effect of biochars on chemical properties of acidic soil

Biochars at all application rates significantly increased soil pH, EC, and CEC and
decreased the exchangeable acidity when compared with control treatments (Table 3).
Soil pH was significantly increased by 0.73, 0.99, and 1.36 units with the application of
corn stover biochar at 52, 104, and 156 Mg ha−1, respectively, whereas the switchgrass
biochar application increased soil pH by 0.49, 0.74, and 0.91 units at application rates of
 8 R. Chintala et al.

Table 3. Effect of biochars on chemical properties of the acidic soil with standard errors.

Exchangeable
acidity CEC
Treatment pH EC (μS cm−1) (cmolc kg−1) (cmolc kg−1)

Control (0 Mg ha−1) 4.78 ± 0.04a 92.8 ± 1.01a 3.54 ± 0.32d 7.86 ± 0.24a
Corn stover biochar 5.51 ± 0.02c 113 ± 3.00b 0.24 ± 0.05b 14.71 ± 0.58d
(52 Mg ha−1)
Corn stover biochar 5.77 ± 0.06c 130 ± 8.32c 0.07 ± 0.02a 17.33 ± 0.96e
(104 Mg ha−1)
Corn stover biochar 6.14 ± 0.01d 240 ± 10.0e 0.02 ± 0.01a 19.04 ± 0.86f
(156 Mg ha−1)
Switchgrass biochar 5.27 ± 0.04b 110 ± 2.08b 0.44 ± 0.07c 12.44 ± 0.68c
(52 Mg ha−1)
Downloaded by [Moskow State Univ Bibliote] at 09:21 16 August 2013

Switchgrass biochar 5.52 ± 0.03c 140 ± 5.50d 0.07 ± 0.02a 14.87 ± 0.23d
(104 Mg ha−1)
Switchgrass biochar 5.69 ± 0.10c 146 ± 5.68d 0.01 ± 0.01a 17.51 ± 0.69e
(156 Mg ha−1)
Lime (52 Mg ha−1) 7.49 ± 0.08e 706 ± 6.00f 0.01 ± 0.00a 10.41 ± 1.17b
Lime (104 Mg ha−1) 7.51 ± 0.01e 700 ± 13.01f 0.01 ± 0.00a 12.12 ± 1.42c
Lime (156 Mg ha−1) 7.58 ± 0.01e 713 ± 6.08f 0.01 ± 0.00a 12.09 ± 1.71c

Note: Different letters in the same column represent significant differences by Tukey’s test at α = 0.05.

52, 104, and 156 Mg ha−1, respectively. The rate of pH increase was significantly higher
in corn stover biochar compared to switchgrass biochar. Lime treatments showed no
significant difference in soil pH which was increased by 2.71, 2.73, and 2.80 units at
lime application rates of 52, 104, and 156 Mg ha−1, respectively. The unit pH change can
be predicted per unit increase or decrease in application rate of biochar using Equations
(1) and (2).

Δ soil pH ¼ 0:120 þ 0:21  CS (1)

Δ soil pH ¼ 0:089 þ 0:015  SC (2)

where CS is the corn stover biochar (Mg ha−1) and SC is the switchgrass biochar
(Mg ha−1). The unit increase in soil pH per unit increase in application rate was
significantly higher in corn stover biochar than switchgrass biochar. Switchgrass biochar
was required at higher quantity to obtain specific soil pH when compared with corn stover
biochar. Yuan and Xu (2011) also observed a significant linear correlation between soil
pH and the alkalinity of nine biochar types which were produced from legume and non-
legume materials. The release of base cations and the higher CaCO3 content of biochars
can increase the pH and decrease the Al saturation of acid soil during incubation. The
incorporation of coal-ash to eroded Palouse soil at the rate of 110 Mg ha−1 had increased
the pH 6.0–6.8 (Cox et al. 2001). Application of charcoals from burned biomass had
demonstrated well their ability to raise soil pH in previous studies (Sanchez et al. 1983;
Kishimoto & Sugiura 1985; Mbagwu & Piccolo 1997).
Exchangeable acidity was significantly decreased by all three amendments. But there
was no significant difference among application rates of three amendments. The propor-
tion of decrease in exchangeable acidity was significantly higher for lime treatment
 Archives of Agronomy and Soil Science 9

(99.5%) at application rate of 52 Mg ha−1 followed by corn stover biochar (93%) and
switchgrass biochar (87.4%). The higher CaCO3 content and proton consumption capacity
of corn stover biochar seems to be the cause for relatively higher increase in soil pH and
decrease in exchangeable acidity when compared with switchgrass biochar. As the soil pH
increases the soluble and exchangeable Al3+ precipitates as insoluble hydroxyl Al-species
(Ritchie 1994). Apart from increase in soil pH, the incorporation of biochars can release
their base cations into acidic soil which can participate in exchange reactions and replace
the exchangeable Al3+ and H+ on the soil surface and decrease the soil exchangeable
acidity (Warnock et al. 2007; Chan et al. 2008; Yuan et al. 2011).
EC was significantly increased with application of biochars and lime by the end of
incubation time. Lime treatments were found to increase EC at highest level and with no
significant difference among application rates. The rate of increase in EC at application
rate of 52 Mg ha−1 was very high for lime treatment and did not significantly increase as
Downloaded by [Moskow State Univ Bibliote] at 09:21 16 August 2013

application rate increased. Corn stover biochar significantly increased EC of acidic soil by
21%, 40%, and 83% as application rate increased from 52, 104, and 156 Mg ha−1,
respectively, whereas the switchgrass biochar had increased the EC of soil by 19%,
51%, and 57% at application rates of 52, 104, and 156 Mg ha−1, respectively. There
was no significant difference in EC values at 52, 104, and 156 Mg ha−1 of biochar
treatments. Application rate of 156 Mg ha−1 (60 g kg−1) had shown significantly different
EC values for corn stover biochar and switchgrass biochar. Incorporation of biochars into
acidic soil caused an increase in EC due to the release of weakly bound nutrients (cations
and anions) of biochars into the soil solution, which are available for plant uptake (Glaser
et al. 2000; Gundale & DeLuca 2007; Chan et al. 2008).
Biochars at all application rates had significantly higher CEC values when compared
with lime treatments despite higher pH values. Corn stover biochar had increased the CEC
values by 87%, 120%, and 142% and switchgrass biochar by 58%, 89%, and 122% at
application rates 52, 104, and 156 Mg ha−1, respectively, whereas lime treatments had
increased CEC of soil by 32%, 54%, and 53% as application rate increased from 52, 104,
and 156 Mg ha−1, respectively, when compared with control treatment. The increase of
soil pH due to the application of biochars makes the soil surface more negative (Steiner
et al. 2007). CEC of soils had increased by 50% with the addition of charcoal materials
(Mbagwu & Piccolo 1997). The increased CEC of soil–biochar mixtures may be due to
slow oxidation of biochar material as the result of biotic and abiotic factors during
incubation which can oxygenate the functional groups of biochar surface and enhance
the formation of organo-mineral complexes (Ma et al. 1979; Glaser 1999; Glaser et al.
2001). The charge density per unit surface of biochar is generally high and its incorpora-
tion can increase the cation sorption of soils (Liang et al. 2006). In another study,
Chintala, Mollinedo, et al. (Forthcoming 2013) observed the decrease of point of zero
charge on biochar materials due to oxidation induced by acid treatment which would
increase the negative charge on the surface of biochar materials.

Conclusion
In this study, the biochars were by-products of bio-oil production from corn stover, switch-
grass, and Ponderosa pine wood residue using microwave pyrolysis unlike previously
published studies. The characteristics and reactivity of biochars with soil are highly hetero-
geneous with batches of production using similar feedstock and pyrolytic conditions and the
findings of a study could not be applied universally to all biochar materials. In conclusion,
this incubation study demonstrated the effectiveness of biochars in ameliorating acidity
 10 R. Chintala et al.

which increased the soil pH, EC, and CEC and decreased the exchangeable acidity. Corn
stover biochar was found to have significantly better liming potential than switchgrass
biochar. The liming potential of biochar can be attributed to their alkalinity, proton
consumption capacity/acid neutralization capacity, and base cation concentration. The
incorporation of these highly carbonaceous biochar materials can induce ameliorating
changes to chemical properties of acidic soils and improve the bioavailability of plant
essential nutrients. Future research needs to evaluate the liming effect of biochars on acidic
soils and their practical management (timing and application methods) and economic
viability under field conditions. This type of studies at different locations with different
feedstocks and pyrolytic process will help to design biochar materials as liming amend-
ments for farmers to reclaim acidic soils with specific guidelines.
Downloaded by [Moskow State Univ Bibliote] at 09:21 16 August 2013

Acknowledgment
This project was supported by Agriculture and Food Research Initiative Competitive Grant no.
2011-67009-30076 from the USDA National Institute of Food and Agriculture.

References
Amonette JE, Joseph S. 2009. Characteristics of biochar: microchemical properties. Chapter 3. In:
Lehmann J, Joseph S, editors. Biochar for environmental management science and technology.
London: Earthscan; p. 33–52.
Barber SA. 1984. Liming materials and practices. In: Adams F, editor. Soil acidity and liming.
Madison (WI): ASA, CSSA, SSSA; p. 171–209.
Black AC. 1993. Soil fertility evaluation and control. Boca Raton (FL): Lewis Publishers.
Chan KY, Van Zwiete L, Meazaros I, Downie A, Joseph S. 2008. Poultry litter biochars as a soil
amendments. Aust J Soil Res. 46:437–444.
Chapman HD. 1965. Cation exchange capacity. In: Black CA, editor. Methods of soil analysis Part
2, No. 9 in the series Agronomy. Madison (WI): American Society of Agronomy; p. 891–901.
Chintala R, Clay DE, Schumacher TE, Malo DD, Julson J. 2013. Optimization of oxygen para-
meters for analyzing carbon and nitrogen in biochar materials. Anal Lett. 46:532–538.
Chintala R, McDonald LM, Bryan WB. 2012a. Effect of soil water and nutrients on productivity of
Kentucky bluegrass system in acidic soils. J Plant Nutr. 35:288–303.
Chintala R, McDonald LM, Bryan WB. 2012b. Optimization of water potential and nutrient levels
for Kentucky bluegrass-white clover mixture on acidic soils. Biotechnol Agron Soc Environ.
16:167–177.
Chintala R, Mollinedo J, Schumacher TE, Malo DD, Papiernik S, Clay DE, Kumar S, Gulbrandson
DW. Forthcoming 2013. Nitrate sorption and desorption by biochars produced from microwave
pyrolysis. Microporous Mesoporous Mater (in press).
Chintala R, Schumacher TE, Malo DD, Clay DE, Clay SA, McDonald LM, Julson J. Forthcoming
2013. Phosphorus sorption and availability in biochars and soil-biochar mixtures. CLEAN (in
press).
Cox D, Bezdicek D, Fauci M. 2001. Effects of compost, coal ash, and straw amendments on
restoring the quality of eroded Palouse soil. Biol Fertil Soils. 33:365–372.
Farina MPW, Channon PA. 1991. Field comparison of lime requirement indices for maize. Plant
Soil. 134:127–135.
Gaskin JW, Steiner C, Harris K, Das KC, Bibens B. 2008. Effect of low-temperature pyrolysis
conditions on biochar for agricultural use. Trans Am Soc Agric Biol Eng. 51:2061–2069.
Glaser B. 1999. Eigenschaften und Stabilität des Humuskörpers der Indianerschwarzerden
Amazoniens. Bayreuther Bodenkundliche Berichte, Vol. 68. Bayreuth: Institute of Soil
Science and Soil Geography, University of Bayreuth.
Glaser B, Balashov E, Haumaier L, Guggenberger G, Zech W. 2000. Black carbon in density
fractions of anthropogenic soils of the Brazilian Amazon region. Org Geochem. 31:669–678.
 Archives of Agronomy and Soil Science 11

Glaser B, Haumaier L, Guggenberger G, Zech W. 2001. The Terra Preta phenomenon – a model for
sustainable agriculture in the humid tropics. Naturwissenschaften. 88:37–41.
Gundale MJ, DeLuca TH. 2007. Charcoal effects on soil solution chemistry and growth of
Koeleria macrantha in the Ponderosa Pine/Douglas-fir ecosystem. Biol Fertil Soils.
43:303–311.
Kishimoto S, Sugiura G. 1985. Charcoal as a soil conditioner. Int Achieve Future. 5:12–23.
Lehmann J. 2007. Bio-energy in the black. Front Ecol Environ. 5:381–387.
Lei H, Ren S, Julson J. 2009. The effects of reaction temperature and time and particle size of corn
stover on microwave pyrolysis. Energ Fuel. 23:3254–3261.
Liang BL, Solomon J, Kinyangi D, Grossman J, O’Neill J, Skjemstad B, Thies JO, Petersen FJ,
Neves J. 2006. Black carbon increases cation exchange capacity in soils. Soil Sci Soc Am J.
70:1719–1730.
Lua AC, Yang T. 2004. Effects of vacuum pyrolysis conditions on the characteristics of activated
carbons derived from pistachio-nut shells. J Colloid Interface Sci. 276:364–372.
Ma YJ, Li SG, Wang ZQ. 1979. Effect of weathered coal on the colloidal property of soils (in
Downloaded by [Moskow State Univ Bibliote] at 09:21 16 August 2013

Japanese). Tu Jang Hsueh Pao. 16:22–28.

Mbagwu JSC, Piccolo A. 1997. Effects of humic substances from oxidized coal on soil chemical
properties and maize yield. In: Drozd J, Gonet SS, Senesi N, Weber J, editors. The role of humic
substances in the ecosystems and in environmental protection. Wroclaw: IHSS, Polish Society
of Humic Substances; p. 921–925.
McLean EO. 1971. Potentially beneficial effects from liming: chemical and physical. Soil Crop Sci
Soc Fla Proc. 31:189–196.
Menzies NW, Bell LC, Edwards DG. 1994. Exchange and solution phase chemistry of acid, highly
weathered soils.1. Characterstics of soils and effect of lime and gypsum amendments. Aust J
Soil Res. 32:251–267.
Mokolobate MS, Haynes RJ. 2002. Comparative liming effect of four organic residues applied to an
acid soil. Biol Fertil Soils. 35:79–85.
Naeth MA, Bailey AW, Chanasyk DS, Pluth DJ. 1991. Water holding capacity of litter and soil
organic matter in mixed prairie and fescue grassland ecosystems of Alberta. J Range Manage.
44:13–17.
Nguyen BT, Lehmann J. 2009. Black carbon decomposition under varying water regimes. Org
Geochem. 40:846–853.
Noble AD, Zenneck I, Randall PJ. 1996. Leaf litter ash alkalinity and neutralization of soil acidity.
Plant Soil. 179:293–302.
Novak JM, Busscher WJ, Laird DL, Ahmedna M, Watts DW, Niandu MAS. 2009. Impact of biochar
amendment on fertility of a southeastern coastal plain soil. Soil Sci. 174:105–112.
Olsen SR, Cole CV, Watanabe FS, Dean LA. 1954. Estimation of available phosphorus in soils by
extraction with sodium bi-carbonate. USDA Circular 939. Washington (DC): U.S. Department
of Agriculture; 1–19.
Rayment GE, Higginson FR. 1992. Australian laboratory handbook of soil and water chemical
methods. Melbourne: Inkata Press; p. 330.
Rebecca R. 2007. Rethinking biochar. Environ Sci Technol. 41:6032–6033.
Rhoades JD. 1996. Salinity: electrical conductivity and total dissolved solids. In: Sparks DL, editor.
Methods of soil analysis, Part 3. Chemical methods. Madison (WI): Soil Science Society of
America; p. 417–435.
Ritchie GSP. 1994. Role of dissolution and precipitation of minerals in controlling soluble alumi-
num in acid soils. Adv Agron. 53:47–83.
Sanchez PA, Villachia JH, Bandy DE. 1983. Soil fertility dynamics after clearing tropical rainforest
in Peru. Soil Sci Soc Am J. 47:1171–1178.
Sherrod LA, Dunn G, Peterson GA, Kolberg RL. 2002. Inorganic carbon analysis by modified
pressure-calcimeter method. Soil Sci Soc Am J. 66:299–305.
Sohi SP, Krull E, Lopez-Capel E, Bol R. 2010. A review of biochar and its use and function in soil.
Adv Agron. 105:47–82.
Steel RGW, Torrie JH. 1980. Principles and procedures of statistics: a biometrical approach. 2nd ed.
New York (NY): McGraw-Hill Book Co.
Steiner C, Teixeira WG, Lehmann J, Nehls T, de Macedo JLV, Blum WEH, Zech W. 2007. Long
term effects of manure, charcoal, and mineral fertilization on crop production and fertility on a
highly weathered central Amazonian upland soil. Plant Soil. 291:275–290.
 12 R. Chintala et al.

Sternberg RW, Creager JS. 1961. Comparative efficiencies of size analysis by hydrometer and
pipette methods. J Sediment Petrol. 31:96–100.
Tukey JW. 1994. The collected works of John W. Tukey VIII. Multiple comparisons: 1948–1983.
New York (NY): Chapman and Hall.
U.S. Department of Agriculture, Natural Resources Conservation Service. 2005. National soil
survey handbook, title 430-VI; [cited 2012 Jan 1]. Available from: http://soils.usda.gov/
technical/handbook/.
U.S. Environmental Protection Agency. 1998. Microwave assisted acid digestion of sediments,
sludges, soils, and oils, Method 3051a. Washington (DC): Office of Solid Waste and
Emergency Response, U.S. Government Printing Office.
Van Zwieten L, Singh B, Joseph S, Kimber S, Cowie A, Chan Y. 2009. Biochar and emissions of
non-CO2 greenhouse gases from soil. In: Lehmann J, Joseph S, editors. Biochar for environ-
mental management: science and technology. London: Earthscan; p. 227–249.
Wang N, Li JY, Xu RK. 2009. Use of various agricultural by-products to study the pH effects in an
acid tea garden soil. Soil Use Manage. 25:128–132.
Downloaded by [Moskow State Univ Bibliote] at 09:21 16 August 2013

Warnock DD, Lehmann J, Kuyper TW, Rillig MC. 2007. Mycorrhizal responses to biochar in soil—
concepts and mechanisms. Plant Soil. 300:9–20.
Wong MTF, Gibbs P, Nortcliff S, Swift RS. 2000. Measurement of the acid neutralizing capacity of
agroforestry tree prunings added to tropical soils. J Agric Sci. 134:269–276.
Wong MTF, Swift RS. 1995. Amelioration of aluminium phytotoxicity with organic matter. In: Date
RA, Grundon NJ, Rayment GE, Probert ME, editors. Plant-soil interactions at low pH: princi-
ples and management. Dordrecht: Kluwer; p. 41–45.
Xu JM, Tang C, Chen ZL. 2006. The role of plant residues in pH change of acid soils differing in
initial pH. Soil Biol Biochem. 38:709–719.
Yuan JH, Xu RK. 2011. The amelioration effects of low temperature biochar generated from nine
crop residues on an acidic Ultisol. Soil Use Manage. 27:110–115.
Yuan JH, Xu RK, Zhang H. 2011. The forms of alkalis in the biochar produced from crop residues at
different temperatures. Bioresour Technol. 102:3488–3497.