Microporous and Mesoporous Materials 179 (2013) 250257

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Microporous and Mesoporous Materials

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Nitrate sorption and desorption in biochars from fast pyrolysis

Rajesh Chintala a,, Javier Mollinedo a, Thomas E. Schumacher a, Sharon K. Papiernik b, Douglas D. Malo a,
David E. Clay a, Sandeep Kumar a, Dylan W. Gulbrandson a
a
Department of Plant Science, South Dakota State University, Brookings, SD, USA
b
USDA-ARS, Brookings, SD, USA

a r t i c l e i n f o a b s t r a c t

Article history: Increasing the nitrate (NO 3 ) sorption capacity of Midwestern US soils has the potential to reduce nitrate
Received 13 February 2013 leaching to ground water and reduce the extent of the hypoxia zone in the Gulf of Mexico. The objective
Received in revised form 1 April 2013 of this study was to determine the sorption and desorption capacity of non-activated and chemically acti-
Accepted 27 May 2013
vated biochars from microwave pyrolysis using selected biomass feedstocks of corn stover (Zea mays L.),
Available online 14 June 2013
Ponderosa pine wood chips (Pinus ponderosa Lawson and C. Lawson), and switchgrass (Panicum virgatum
L.). Surface characteristics such as surface area and net surface charge have shown signicant effects on
Keywords:
nitrate sorption and desorption in biochars. Freundlich isotherms performed well to t the nitrate sorp-
Nitrate retention
Nitrate release
tion data (R2 > 0.95) of biochars when compared to Langmuir isotherms. Nitrate sorption and desorption
Biochars was signicantly inuenced by solution pH and presence of highly negative charged potential ions such
Surface charge as phosphate (PO3 2
4 ) and sulfate (SO4 ) in aqueous solution. Chemical activation with concentrated HCl
Point of zero net charge had signicant effect on surface characteristics of biochars and enhanced the nitrate sorption capacity.
The rst order model t the nitrate desorption kinetics of biochars with a high coefcient of determina-
tion (R2 > 0.95) and low standard error (SE).
2013 Elsevier Inc. All rights reserved.

1. Introduction
In Midwestern US agriculture, ammonium (NH 4 ) based fertiliz-
ers are routinely applied to meet the nitrogen (N) requirement of
agricultural crops. Nitrogen fertilizers generally undergo chemical
transformations such as ammonication, nitrication, de-nitrica-
tion, nitrogen xation, and immobilization in soil [1,2]. Nitrica-
tion is one of the quickest reaction pathways. It results in the
formation of nitrate ion, which is plant available but also highly
mobile due to its weak afnity to form surface complexes and
therefore prone to leaching [35] or is subject to denitrication.
Increasing nitrate concentrations in surface and groundwater re-
sources across the world have been attributed to agricultural and
industrial inputs [6,7]. Several nitrate removal technologies have
been developed such as anion exchange [8], biological denitrica-
tion [9], chemical denitrication [10,11], catalytic denitrication
[12], reverse osmosis [13], and electrodialyis [14]. These available
physico-chemical and biological technologies may be expensive,
generate additional by-products and toxic wastes, and have limited
applicability in large scale remediation scenarios [15]. For instance,
chemical denitrication (reduction) using reductants such as zero-
valent iron (ZVI) have been extensively used to reduce nitrate
Corresponding author. Address: SNP 247, Box 2140C, South Dakota State
University, Brookings, SD 57006, USA. Tel.: +1 6056884547.
E-mail address: rajesh.chintala@sdstate.edu (R. Chintala).
(NO 3 ) in ground water. But this process requires reduced pH and
produces ammonia as by-product [16]. Biological denitrication
is slow and inefcient to remove nitrate from highly concentrated
systems, and also requires additional organic substrates as electron
donors [17]. Reverse osmosis and ion exchange resins are not eco-
nomical for large scale nitrate removal. Ion exchange resins are not
selective and also retain other anions (such as SO2 4 and HCO 3)
which cause the disequlibrium in the ionic composition of soil
and water systems and also release chloride (Cl) ions during the
exchange process [18]. Among these nitrate removal technologies,
adsorption has been found less expensive and more effective in re-
moval of nitrate from water systems. Adsorption technologies have
evolved as highly efcient remediation tools with lesser energy in-
put to produce sorbent materials; adsorption is easy to apply at
large scales [15].
Control of nitrate mobility at its source would eliminate the
need for remediation. Various sorbents have been identied which
have potential to reduce of nitrate ion mobility in soil and water
ecosystems [19,20]. The success of adsorption techniques depends
on the selection of appropriate sorbents, their removal efcacy,
and economic feasibility. Sorbents (either naturally available or
synthetically produced) to remove nitrate from water and waste
water systems include functionalized mesoporous siliceous and
non-siliceous materials [2123], metal organic frame works
[24], mesoporous carbon materials [25], red mud [26], agricul-
tural waste [27,28], polypropylene-g-N,N-dimethylaminoethyl

1387-1811/$ - see front matter 2013 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.micromeso.2013.05.023
 R. Chintala et al. / Microporous and Mesoporous Materials 179 (2013) 250257
methacrylate [29], poly (dimethylaminoehtyl methacrylate/2-hy-
droxy ethyl methacrylate) [30], poly (dimethyl diallyl ammonium
chloride)/polyacrylamide [31], sepiolite [19], bentonite [32,33],
slag [19], activated carbon [19,34], chitin and chitosan derivatives
[35,36], and MII-Al-Cl layered double hydroxides [37,38]. In recent
years, the depletion of petroleum oil reserves and growing demand
for energy across the world has initiated the development of sus-
tainable alternative energy technologies based on renewable bio-
mass. Biochar is the by-product of biomass conversion using
pyrolysis to produce bio-oil and syngas. The scientic community
has found opportunities to develop these biochar materials as cli-
mate change mitigation tools due to their ability to store carbon
in soil for long periods. Biochar based materials have the potential
to sorb anionic nutrients such as nitrogen (N) and phosphorus (P)
from aqueous solutions [39]. Several studies have described that
biochars can also supply nutrients to crop plants and reduce the
leaching of nutrients in soil [40,41]. Unlike other existing nitrate
removal sorbents, biochar can be produced by a simple, cost effec-
tive process and its application to agricultural lands may improve
soil quality and health.
The sorption capacity of highly carbon rich biochars have been
found to be excellent due to their unique surface characteristics
such as high surface area, pore volume, and surface functional
groups [42]. The surface area and porosity of biochars can be en-
hanced by either physical or chemical activation methods [43].
The activation of biochars from agricultural products has been in-
creased in recent years due to its use in environmental pollution
control [44,45]. Among the activation methods, chemical activa-
tion is more economical with higher yield at lower temperature
and less production of burn-off char [46]. Slowing the rate at which
of nitrate is leached from surface to subsurface soils could improve
water quality and reduce greenhouse gas generation. The sorption
capacity of soils is critical along with the water ow to determine
the leaching rate of nitrate in soil. Cation transport is slowed by
sorption on soils with negative charge, while anion transport is slo-
wed by sorption on positively charged soil particles [47]. Most
Midwestern United States soils have relatively low anion sorption
capacity. For example, the anion exchange capacity of Kranzburg
silty clay loam soil (ne-silty, mixed, superactive, frigid, Aeric Cal-
ciaquoll) was ranged from 0.25 to 0.27 cmolc kg1. This relatively
minor anion sorption capacity must be compared with the soil
cation exchange capacities that ranged from 27.9 to 33.127
cmolc kg1 [47].
Batch experiments are often used to quantify the ionic retention
of biochar and other sorbents [48]. The determination of sorption
coefcients (Kd) and sorption maxima (qmax) of these sorbents help
in developing them as remediation tools to control contaminant
transport in soil and water eco-systems. In this context, it is impor-
tant to investigate the interaction of biochar-based sorbents from
agricultural products with highly mobile anionic nutrient such as
nitrate is essential. Therefore this study was designed with the
following objectives: (1) determine the surface characteristics of
non-activated and activated biochars produced from microwave
pyrolysis using corn stover (Zea mays L.), Ponderosa pine (Pinus
ponderosa Lawson and C. Lawson) wood residue, and switchgrass
(Panicum virgatum L.); and (2) determine the nitrate sorption and-
desorption potential of non-activated and activated biochars.
2. Materials and methods
2.1. Production of non-activated and activated biochar materials
Using corn stover, Ponderosa pine wood chips and switchgrass
as feedstocks, three biochars were formed as co-products of bio-
oil production using microwave pyrolysis at 650 C and residence
251
time of 18 min. These biochars were activated by heating with con-
centrated hydrochloric acid (HCl). Air dried biochar (25 g) was
placed in a conical ask covered with a watchglass and treated
with 250 ml of concentrated HCl. The biochar mixed with concen-
trated HCl was heated on hot plate at 200 C (placed in laboratory
hood) for 24 h. After heating, the biochars were washed with
deionized water four times and then washed with 1% sodium
bicarbonate (NaHCO3) solution (1:500 solid-solution ratio) four
times to remove acid residues. Later the biochar materials were
washed with deionized water several times until the pH of the
supernatant was 7.0. The washed biochars were oven dried at
105 5 C for 8 h and considered as acid activated biochars [49].
These non-activated and activated biochar materials were homog-
enized and ground to pass through a 0.2 mm sieve and used for
characterization and batch studies.
2.2. Characterization of non-activated and activated biochar materials
Specic surface area of biochars, were determined using the io-
dine absorption method [50]. The biochar acidity, pH, and EC (elec-
trical conductivity) were measured at 1:1 water to solid ratio after
shaking for 30 min in deionized water [51]. The cation exchange
capacity (CEC) of biochar samples were measured using 1 M
ammonium acetate (CH3COONH4) at pH 7.0 [51]. The quantitative
analysis of volatile organic compounds (VOCs) in biochar samples
were determined [52]. Total carbon and total nitrogen were ana-
lyzed by Elementar Vario MAX CNS analyzer [53]. Biochar samples
were wet digested using concentrated nitric acid (HNO3) in a pres-
surized (200 psi) microwave oven (MARS 5, CEM Corp., USA)
[54,55] equipped with teon closed vessels. The wet digested sam-
ples were diluted with distilled water to measure nutrient compo-
sition (total P, Ca, Mg, Na, and K) using Inductively Coupled Plasma
Atomic Emission Spectroscopy (ICP-AES) (Varian, Australia) [56].
All these determinations were conducted in four separate biochar
samples from different pyrolysis runs.
2.3. Infrared spectroscopic analysis of non-activated and activated
biochars
Infrared spectrums were recorded for biochar samples using
Fourier Transform Infrared Spectroscopy (Thermo Scientic NICO-
LET 6700 FT-IR spectrometer). Samples were prepared and pressed
into pellets using 10 wt% potassium bromide (KBr). The spectrum
had wave number (cm1) on x-axis and transmittance (%) on y-axis
with resolution using 40 scans. The peaks of the spectrum were
studied to understand the surface functionality of non-activated
and activated biochar samples.
2.4. Surface charge characteristics of non-activated and activated
biochars
The point of zero net charge (PZNC) was measured by determin-
ing the cation exchange capacity (CEC) and anion exchange capac-
ity (AEC) simultaneously at eight pH values (pH 210) [57]. The
PZNC was the pH at which CEC and AEC were equal on sorbent sur-
face. Biochar samples were initially saturated with 0.01 M KCl and
the pH was adjusted with 1 M HCl and 1 M KOH. For the pH adjust-
ment, biochar samples (10 g) were weighed in triplicate. These bio-
char samples were suspended in 100 ml of 0.01 M KCl to prepare
subsequent pH levels. These biochar suspensions were adjusted
to different pH by adding predetermined amounts of 1 M HCl
and 1 M KOH. These predetermined quantities were calculated
by using regression equations tted to the potentiometric titration
curves of these biochar materials. The biochar samples were sha-
ken for 12 h and the pH was measured every day until the pH val-
ues were constant. Then suspensions were ltered and washed
252 R. Chintala et al. / Microporous and Mesoporous Materials 179 (2013) 250257
with ethanol and dried to obtain biochar samples of different pH
levels to use for determining PZNC. Later, 0.5 M NaNO3 was used
as an extractant to exchange K+ and Cl from surface of samples
to determine CEC and AEC. Potassium (K) was analyzed using
Flame Atomic Absorption Spectroscopy (GBC Avanta Corp., USA)
and the Cl ion was determined using Flow Injection Analysis
(Quick Chem FIA+, 8000 series, Latchat Instruments, USA). The
CEC (K+) and the AEC (Cl) were calculated using Eqs. (1) and (2).
1
CEC cmolc kg 0:1C 2 V 2  C 1 V 1 =39W 1 24 h on a reciprocating shaker. Samples from four replications
1
AEC cmolc kg 0:1C 2 V 2  C 1 V 1 =35:5W 2 ashless lter paper (with retention: >2.5 lm) and analyzed for des-
+ 
where C1 = K or Cl concentration in supernatant solution of
0.01 M KCl (mg L1), V1 = volume of entrained solution in the bio-
char sediment (mL), C2 = K+ or Cl concentration in the displacing
solution of 0.5 M NaNO3 (mg L1), V2 = total volume of displacing
solution of 0.5 M NaNO3 (mmol L1), 39 = atomic weight of K+,
35.5 = atomic weight of Cl, and W = oven dried sample weight (g).
2.5. Nitrate sorption isotherms for non-activated and activated
biochars
All biochar materials were adjusted to pH 4.0 0.1 after saturat-
ing with K+ or Cl using KCl solution [57]. This process was done to
maximize the nitrate sorption and remove other competitive an-
ions from biochar surface. Nitrate sorption isotherms were deter-
mined for biochars produced from the previous process. Biochar
samples (0.5 g) were placed in a 50-mL centrifuge tube. A 20-mL
solution of 0.01 M calcium chloride (CaCl2) containing 0, 0.16,
0.32, 0.64, 1.29, and 1.61 mmol L1 of nitrate (NO 3 ) were added
along with two drops of chloroform to inhibit microbial growth.
The samples were equilibrated in an end-over-end shaker at room
temperature for 24 h and then centrifuged (with xed-angle rotor)
for 5 min, producing a clear supernatant. The supernatant was l-
tered using ashless lter paper with retention: >2.5 lm (Whatman
42, Whatman Corp., Kent, UK) and then analyzed for nitrate using
Flow Injection Analysis (Quick Chem FIA+, 8000 series, Latchat
Instruments, USA). Sorbed nitrate was calculated as the difference
between equilibrium nitrate concentration (after shaking) and ini-
tial nitrate concentration of solution. Adjustable parameters for
Freundlich (Eq. (3)) and Langmuir (Eq. (4)) were determined by
non-linear regression using Proc NLIN [58]:
Freundlich equation q K f c1=n
Langmuir equation q K L bc=1 K L c 4
where q = sorbed nitrate (mmol kg1), c = nitrate concentration in
the equilibrium solution (mmol L1), Kf = Freundlich partitioning
coefcient, 1/n = sorption intensity, b = adsorption maxima
(mmol kg1 of nitrate), and KL = parameter related to binding en-
ergy (L kg1).
2.6. Effect of solution pH and competitive anions
The pH of the initial nitrate solution of 1.29 m mmol L1 was
adjusted to obtain a range in solution pH from 4.0 to 9.0 [57]. This
pH adjusted nitrate solution was added to biochar (adjusted to pH
4.0 0.1) to study the effect of solution pH on nitrate sorption. The
inuence of competitive anions such as phosphate and sulfate on
nitrate sorption was also investigated by adding 0.01 M KH2PO4
and K2SO4 solutions (1.29 mmol L1 of phosphate and sulfate) in
separate centrifuge tubes. Biochar (0.5 g) sample (with pH 4.0)
was added to 20 mL of pH adjusted nitrate solutions with other
competitive ions (with pH 4.0) into centrifuge tubes. Sorption of
nitrate was determined using the procedure described above.
2.7. Desorption of nitrate from non-activated and activated biochars
Desorption of nitrate was determined in biochar samples (at the
end of the sorption experiment using an initial nitrate concentra-
tion of 1.29 mmol L1. After equilibration and sorbed nitrate con-
centrations were determined, samples were extracted with 50 mL
of deionized water (a 1:50 solid to solution ratio) at two pH levels
4.0 and 9.0 to study the pH effect on desorption. The tubes with
sample and extractant (deionized water) were then shaken for
were then centrifuged, supernatant solutions were ltered using
orbed nitrate concentration as described above. The desorbed ni-
trate was calculated as percentage using equation (Eq. (5)).
Desorption % desorbed nitrate adsorbed nitrate  100 5
Desorption kinetics were studied by successive measurement of
nitrate concentration at different agitation times. Following the
sorption step, deionized water (20 ml) with pH levels of 4.0 and
9.0 was added to 0.5 g of nitrate treated biochar samples in centri-
fuge tube. Samples were equilibrated on reciprocating shaker at
27 1 C for periods of 15,30,45,60, 75, and 90 min. At the end of
each agitation period the supernatant solutions were collected to
measure nitrate concentrations. Then fresh deionized water
(20 ml) was added to continue to measure nitrate desorption at
longer agitation times. The rst order kinetic model was tted to
the data using equation (Eq. (6)).
lnP0  Pt a  K d t 6
1
where Pt = desorbed nitrate at time t (mmol kg ), P0 = desorbed ni-
trate at equilibrium (mmol kg1), Kd = kinetic constant (h1),
t = time (min), and a = constant.
The goodness of t for this kinetic model was determined by
evaluating its coefcient of determination (R2) and standard error
of estimate (SE). A one-way analysis of variance (ANOVA) was per-
formed using the SAS Statistical Package, version 9.2 to determine
the effect of treatments on characterization, nitrate sorption, and
desorption. TukeyKramer multiple comparisons analysis was
done to determine the signicant differences (p 6 0.05 level) be-
tween treatments [59].
3. Results and discussion
3
3.1. Characterization of non-activated and activated biochars
The physical and chemical properties of non-activated biochars
varied signicantly with biomass feedstocks (p < 0.05) (Table 1).
Corn stover (CSB) and switchgrass biochars (SGB) exhibited signif-
icantly higher pH, EC, CEC, PZNC, VOCs, total nitrogen, and base
cation concentration (Ca, Mg, K, and Na) than Ponderosa pine wood
residue biochar (PWRB), whereas PWRB had higher surface area
and total carbon content. The alkaline nature of CSB and SGB
may be due to high base cation concentration which may partici-
pate in proton consuming reactions [60]. The presence of soluble
salts caused higher EC values for these plant based biochars. CEC
of CSB and SGB was signicantly higher than PWRB due to their
high pH and negative surface charge potential. The source of this
surface charge potential may be due to the amphoteric nature of
oxygenated functional groups present in VOCs [61]. CSB and SGB
had signicantly higher VOC concentrations than PWRB.
The chemical activation (with conc. HCl) of these three biochars
signicantly increased their surface area and CEC, but decreased
chemical properties such as pH, EC, PZNC, VOCs, total carbon,
and base cation concentration. (Table 1). Surface area of SGB and
CSB was increased by 12 times whereas PWRB increased by 9 times
 R. Chintala et al. / Microporous and Mesoporous Materials 179 (2013) 250257 253

Table 1
Physical and chemical properties of biochars produced from fast pyrolysis at 650 C of corn stoverb (CSB), switchgrass (SGB), and Ponderosa pine wood residue (PWRB). Values are
means of four samples with standard errors. Different letters within the row represent signicant differences by Tukeys test at a = 0.05.

Properties CSB PWRB SGB

Non-activated Activated Non-activated Activated Non-activated Activated
Specic surface area (m2 g1) 43.4 2.5f 513 21b 52.1 4.1d 456 15c 48.0 2.6e 582 23a
pH 10.5 0.04a 8.16 0.10c 7.85 0.02f 7.05 0.11e 9.73 0.24b 7.75 0.10d
EC (lS cm1) 3000 61a 140 21e 200 22c 110 15f 890 21b 152 16d
CEC (cmolc kg1) 41.6 5e 134 11b 32.5 3f 115 7c 43.1 2d 149 8a
PZNC 6.67 0.15b 4.63 0.13d 5.75 0.03c 3.04 0.07e 7.08 0.44a 4.92 0.14d
VOC (g kg1) 206 21a 58.5 8e 125 11c 45.1 6f 184 15b 59.1 7d
Total N (g kg1) 13.5 0.3b 12.8 0.1b 4.82 0.1c 4.94 0.03c 15.8 0.7a 15.2 0.5a
Total C (g kg1) 742 10d 726 13e 845 30a 801 14b 763 22c 720 17c
Ca (g kg1) 7.82 0.25a 6.12 0.55c 2.62 0.16d 1.25 0.09e 7.04 0.22b 5.82 0.61c
Mg (g kg1) 5.61 0.26a 4.33 0.15c 0.86 0.31e 0.26 0.03f 5.18 0.06b 4.15 0.05d
K (g kg1) 23.5 2.6a 15.6 1.4b 1.55 0.03e 0.92 0.07f 2.92 0.05c 1.72 0.11d
Na (g kg1) 0.86 0.06a 0.64 0.01c 0.62 0.03c 0.45 0.05d 0.75 0.05b 0.60 0.08c

CSB, Corn stover biochar; PWRB, Ponderosa pine wood residue biochar; SGB, Switchgrass biochar.

Fig. 1. ac FTIR sepctra of non-activated and activated biochars. KBr pellet 10 wt%.

after chemical activation. Biochars may undergo decomposition VOCs, and soluble salts and decreasing pH, EC, PZNC, and total
during the acid activation process and subsequent washing with carbon. For example, the activation may have had a catalytic effect
NaHCO3 solution, resulting in loss of base cation concentration, on the cleavage of bond linkages in hemicellulose and cellulose,
254 R. Chintala et al. / Microporous and Mesoporous Materials 179 (2013) 250257

Fig. 2. ac pH-dependent CEC and AEC of biochars within the pH investigated (2.0 6 pH 6 9.0). Symbols represent data SE. Each data point is average of four replications.

Table 2
Freundlich and Langmuir nitrate sorption parameters with standard errors for biochars. Different letters in the same column represent signicant differences by Tukeys test at
a = 0.05.
Biochar Freundlich Langmuir
Kf 1/n R2 KL b R2
CSB Non-activated 384 21e 0.77 0.07b 0.99 0.95 0.06d 620 26e 0.73
Activated 456 28c 0.60 0.03e 0.99 1.59 0.05b 702 35b 0.90
PWRB Non-activated 158 17f 0.65 0.02c 0.99 0.41 0.04f 184 13f 0.95
Activated 437 26d 0.65 0.08d 0.99 1.09 0.04c 696 24c 0.84
SGB Non-activated 447 44b 0.92 0.12a 0.99 0.92 0.05e 625 35d 0.80
Activated 576 31a 0.57 0.08f 0.99 1.76 0.06a 800 35a 0.92

CSB, corn stover biochar; PWRB, Ponderosa pine wood residue biochar; SGB, switchgrass biochar. Kf and KL are expressed in L kg1 and b is in mmol L1.

increasing the internal pore volume. The acid treatment may have
oxidized the carbon and made walls of pores thinner, increasing
both the micro-porosity and surface area of biochars [62]. The in-
creased surface area would also inuence the sorption of ions
which may also result high CEC. Similar changes in pH, EC, and
ash fraction were observed for pecan shell-based granular carbon
following activation with phosphoric acid (H3PO4) [63]. Changes
in surface properties due to the activation process are expected
to inuence the adsorptive efciency of biochars and their ionic
retention mechanism in soil.
3.2. Infrared spectroscopic analysis of non-activated and activated
biochars
The baseline corrected FT-IR spectra of non-activated and acti-
vated biochars were shown the vibrational mode of surface func-
tional groups (Fig. 1ac). The composition of functional groups in
biochars produced from herbaceous feedstocks (CSB and SGB)
was similar. Non-activated and activated biochars of CSB and
SGB had shown CN stretch (23002360 cm1), C@O stretch
(17251735 cm1), CAO stretch (11001124 cm1), and aromatic
 R. Chintala et al. / Microporous and Mesoporous Materials 179 (2013) 250257 255

CAH vibrational band (700713 cm1). PWRB was recorded

with bands of CN stretch (23502352 cm1), CAO stretch
(10911100 cm1), and aromatic CAH (740743 cm1) in both
non-activated and activated biochars. Chemical activation signi-
cantly decreased the absorbence of FT-IR bands of all functional
groups. The acid-base properties of these functional groups on bio-
char develop surface charge and result in electrostatic attraction
for opposite charged ions in soil solution.

3.3. pH-dependent surface charge characteristics of biochars

Surface charge of three biochars was found to be variable with

pH (Fig. 2ac). All three biochars exhibited a wide range of CEC and
AEC values as pH increased from 2 to 10. The CEC increased signif-
icantly (p < 0.05) with increasing pH in all biochars, but AEC de-
creased with increasing pH. The CEC and AEC of CSB and SGB
were relatively higher than PWRB at all pH. Each unit increase in
pH caused a higher increase of CEC for SGB (3.88 cmol kg1) than
for CSB (3.41 cmol kg1) and PWRB (2.91 cmol kg1). AEC was de-
creased by an average of 1.74, 2.33, and 2.84 cmol kg1 in SGB,
CSB, and PWRB respectively, per unit increase in pH. The PZNC Fig. 3. Quantity of nitrate sorbed per kilogram of biochar (q) across a range of
equilibrium nitrate solution concentrations at pH = 4.0 0.1 for non-activated and
was also signicantly higher for SGB (7.08) than CSB (6.51) and
activated biochars produced from corstover (CSB), Ponderosa pine wood residue
PWRB (5.75). The pH of all the biochars was higher than their PZNC (PWRB), and switchgrass (SGB). Lines represent Freundlich isotherms. Each data
values, implying an overall negative surface charge potential. The point was mean of four replications.
variable surface charge of biochars and their anion exchange
capacity may be caused by the protonation of functional groups
which can be inuenced by the pH and ionic strength of aqueous
solution. The sorption studies were conducted using biochars ad-
justed to pH 4.0 where the net surface charge of biochars was po-
sitive according to their PZNC. The information related to surface
charge and composition would be extremely critical to determine
the utility of these biochars as sorbents to remove anions such as
nitrate from solutions.

3.4. Nitrate sorption in non-activated and activated biochars

Freundlich and Langmuir isotherm models were used to t the

equilibrium and sorbed concentration of nitrate in biochars and
activated biochars for both non-activated and activated biochars
(Table 2). Coefcients of determination (R2 value) were higher for
Freundlich isotherms for both non-activated and activated bioch-
ars when compared to the Langmuir isotherm. The better t of
the Freundlich isotherm model suggests heterogeneity of sorption
sites on the biochar surface which is not restricted to monolayer
formation (Fig. 3). Nitrate sorption at the biochar surface may be
mainly due to electrostatic interaction (outer-sphere complexation Fig. 4. Effect of solution pH on nitrate sorption (q sorbed nitrate concentration) in
mechanism) and to a lesser extent ionic exchange mechanism. non-activated and activated biochars produced from corstover (CSB), Ponderosa
There was a signicant difference in sorption potential of biochars pine wood residue (PWRB), and switchgrass (SGB). The initial nitrate concentration
of solution was 1.29 mmol L1 at pH ranged from 4.0 0.1 to 9.0 .1. Values are the
due to biomass feedstock type and activation. Among non-
mean of four samples. Error bars indicate standard error of the mean.
activated biochars, SGB was found to have the highest sorption
capacity (highest Kf) followed by CSB and PWRB. The higher nitrate
sorption observed for SGB and CSB possibly due to their higher
PZNC, VOCs, and base cation concentration providing a greater po- sorption in activated biochars may be mainly due to increased sur-
sitive charge on surface functional groups. The higher base cation face area.
concentration also may facilitate divalent cation bridging with
negatively charged nitrate ions. 3.5. Effect of solution pH and competitive anions on nitrate sorption of
The acid activation (with conc. HCl) signicantly increased the non-activated and activated biochars
sorption capacity of all biochars. A greater increase in nitrate sorp-
tion was observed in activated PWRB (440%) followed by activated Solution pH had a signicant effect on nitrate sorption of non-
biochars of CSB (240%) and SGB (200%). The acid activation greatly activated and activated biochars (Fig. 4). As the solution pH in-
increased the surface area of all biochars, providing more space for creased from 4.0 to 9.0, the nitrate sorption signicantly decreased
sorption of ions. CEC was also increased in biochars due to in- (p < 0.05). The decrease in nitrate sorption per unit increase in
creased surface area during acid activation. Despite may chemical solution pH was higher in activated biochars than non-activated
changes induced by acid activation (decrease in pH, EC, PZNC, biochars. The oxygenated functional groups of biochar undergo
VOCs, and base cation concentration, Table 1), the increased nitrate protonation and de-protonation reactions as aqueous solution pH
256 R. Chintala et al. / Microporous and Mesoporous Materials 179 (2013) 250257

Table 3
First order kinetic equations for nitrate sorption on biochars at pH 4.0 and initial
nitrate solution concentration of 1.29 mmol L1. Different letters in the same column
represent signicant differences by Tukeys test at a = 0.05.

Biochar type a Kd  102 SE R2

CSB non-activated 4.35c 2.78b 0.05 0.97
CSB activated 5.05b 2.81b 0.08 0.99
PWRB non-activated 3.61d 3.48a 0.07 0.95
PWRB activated 5.09b 3.52a 0.05 0.97
SGB non-activated 4.38c 2.79b 0.03 0.96
SGB activated 5.33a 2.83b 0.09 0.98

CSB, corn stover biochar; PWRB, Ponderosa pine wood residue biochar; SGB,
switchgrass biochar.

sorption sites towards more highly negatively charge potential an-

Fig. 5. Effect of competitive ion concentration in solution on nitrate sorption by
non- activated and activated biochars from corstover (CSB), Ponderosa pine wood
residue (PWRB), and switchgrass (SGB). The initial nitrate concentration of solution
was 1.29 mmol L1 at pH 4.0 0.1. Values are the mean of four samples. Error bars
indicate standard error of mean.
ions such as phosphate and sulfate. This phenomenon was ob-
served to be more predominant with activated biochars which
may be due to their higher surface area and greater sorption capac-
ity. The decrease in nitrate sorption was higher in CSB (71.3%) and
SGB (74.2%) than PWRB (57.6%) among non-activated biochars in
the presence of phosphate ion. When phosphate was present, the
% decrease in nitrate sorption (75%) was the same for all activated
biochars. Sulfate ion had a lesser effect on nitrate sorption, about
3854%. In the presence of sulfate ion, the decrease in nitrate sorp-
tion was greater for CSB and SGB than for PWRB in activated and
non-activated biochars.

changes. As the solution pH decreases, the positive charge on the

biochar surface increases due to protonation reactions which in-
creased the electrostatic attraction between the biochar surface
and negatively charged nitrate ions. Anion exchange also took
place between the anions on the biochar surface and nitrate ions
by breaking up of electrostatic interactions. The functional groups
on the biochar surface undergo dissociation (deprotonation) and
develop negative charge as the solution pH increases above the
PZNC of biochars. The competition for sorption sites from OH ions
then increases which may hinder nitrate sorption.
The presence of competitive anions such as phosphate and sul-
fate in solution signicantly decreased nitrate sorption on non-
activated and activated biochars (Fig. 5). The decrease in nitrate
sorption was signicantly higher in activated biochars than non-
activated biochars in presence of both phosphate and sulfate ions.
The decrease in nitrate sorption may be due to the preference of
3.6. Desorption of nitrate from non-activated and activated biochars
The desorption (%) of sorbed nitrate (at initial nitrate concentra-
tions of 0.16, 0.64, and 1.29 mmol L1) was signicantly higher in
activated biochars than non-activated biochars at both pH 4.0 and
9.0 (Fig. 6a and b). Nitrate desorption was signicantly higher at
pH 9.0 than 4.0 and showed hysteresis. As the initial nitrate concen-
tration increased, nitrate desorption also increased. Higher nitrate
concentration may translate to lower bond energy and more
exchangeable ions (nitrate more easily desorbed). Nitrate desorp-
tion was signicantly higher at pH 9.0 than 4.0. The surface of bio-
char may develop negative charge as the pH increased over PZNC
which may repel the negatively charged nitrate ions. Moreover,
the OH concentration in solution may also increase at high pH
and displace nitrate ions from sorption sites. Both non-activated

Fig. 6. a and b Desorption of nitrate on biochars and activated biochars from corstover (CSB), Ponderosa pine wood residue (PWRB), and switchgrass (SGB). The initial nitrate
concentration of solution was 1.29 mmol L1 at two pH levels (4.0 0.1 and 9.0 0.1). Values are mean of four samples. Error bars indicate standard error of mean.
 R. Chintala et al. / Microporous and Mesoporous Materials 179 (2013) 250257
and activated CSB and SGB showed signicantly higher desorption
than PWRB at both pH 4.0 and 9.0. Nitrate desorption of non-
activated and activated biochars followed rst order kinetics with
higher coefcients of determination (R2) and low standard error
(SE) (Table 3). Acid activation did not affect rst order rate con-
stants (Kd). But nitrate desorption was complete (equal to nitrate
released at equilibrium) in approximately 58 min for non-activated
and activated biochars of CSB and SGB and 54 min for PWRB which
were not signicantly different.
4. Conclusions
Our results demonstrate strong sorption potential of selected
biochars to remove anionic nutrient such as nitrate from aqueous
solution. The nitrate sorption capacity of biochars was observed
to depend on surface properties of biochar (surface area and sur-
face charge), solution pH, and presence of competitive ions with
high negative potential. Surface charge of biochars was found to
be pH dependent due to the amphoteric nature of surface func-
tional groups. Study of surface characteristics is essential to under-
stand the potential of biochars as soil amendments at the eld
scale or use biochars as remediation tool. Acid activation of bioch-
ars tremendously increased the biochar surface area and the po-
tential to sorb nitrate ions. Acid activation seems to be efcient
in increasing the sorbing potential of biochars that can immobilize
nitrate ions. In higher nitrate concentration systems, the activated
biochars have greater utility in reducing the availability of nitrate
ions for biological de-nitrication and also mitigating the eutrophi-
cation. Biochars may also increase the residence time of highly mo-
bile nitrate ions and make them more available for plant and
nutrient utilization under conditions of limited N availability. Ni-
trate desorption was higher for chemically-activated biochars
and increased solution pH. Feedstock inuenced nitrate sorption
and desorption by biochar.
Acknowledgments
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.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.micromeso.2013.
05.023.
References
[1] D.A. Martens, W. Dick, Biol. Fertil. Soils 38 (2003) 144153.
[2] R.A. Ortega, D.G. Westfall, G.A. Peterson, Commun. Soil Sci. Plant Anal. 36
(2005) 28752887.
[3] R.L. Partt, Chemical properties of variable charge soils, in: B.K.G. Theng (Ed.),
Soils with Variable Charge. New Zealand Society of Soil Science, Offset
Publications, Palmerston North, New Zealand, 1980, pp. 167194.
[4] M. Chabani, A. Amrane, A. Bensmaili, Desalination 197 (2006) 117123.
[5] X. Xu, B.Y. Gao, Q.Y. Yue, Q.Q. Zhang, Bioresour. Technol. 101 (2010) 8558
8564.
[6] Z. Li, Micropor. Mesopor. Mater. 61 (2003) 181188.
[7] M. Islam, R. Patel, J. Hazard. Mater. 169 (2009) 524531.
[8] A. Pintar, J. Batista, J. Levec, Chem. Eng. Sci. 56 (2001) 15511559.
[9] B. Moreno, M.A. Gomez, A. Ramos, J. Gonzalez-Lopez, E. Hontoria, J. Hazard.
Mater. 127 (2005) 180186.
[10] M. Kumar, S. Chakraborty, J. Hazard. Mater. 135 (2006) 112121.
[11] Y.H. Huang, T.C. Zhang, J. Environ. Eng. 128 (2002) 604610.
[12] A. Pintar, J. Batista, Appl. Catal., B 63 (2006) 150159.
[13] J.J. Schoeman, A. Steyn, Desalination 15 (2003) 1526.
[14] A. Elmidaoui, M.A. Menkouchi Sahli, M. Tahaikt, L. Chay, M. Taky, M. Elmghari,
M. Hafsi, Desalination 153 (2002) 389397.
257
[15] A. Bhatnagar, M. Sillanpaa, Chem. Eng. J. 168 (2011) 493504.
[16] L.F. Cheng, R. Muftikian, Q. Fernando, N. Korte, Chemosphere 35 (1997) 2689
2695.
[17] F. Thalasso, A. Vallecillo, P. Garcia-Encina, F. Fdz-Polanco, Water Res. 31 (1997)
5566.
[18] C.T. Matos, A.M. Sequeira, S. Velizarov, J.G. Crespo, M.A.M. Reis, J. Hazard.
Mater. 166 (2009) 428434.
[19] N. Ozturk, T.E. Bektas, J. Hazard. Mater. 112 (2004) 155162.
[20] Y. Wang, B.Y. Gao, W.W. Yue, Q.Y. Yue, J. Environ. Sci. 19 (2007) 13051310.
[21] A. Vinu, K.Z. Hossain, K. Ariga, J. Nanosci. Nanotech. 5 (2005) 347375.
[22] S. Hamoudi, R. Saad, K. Belkacemi, Ind. Eng. Chem. Res. 46 (2007) 88068812.
[23] K. Ariga, A. Vinu, Y. Yamauchi, Q. Ji, J.P. Hill, Bull. Chem. Soc. Jpn. 85 (2012) 1
32.
[24] N. Stock, S. Biswas, Chem. Rev. 112 (2012) 933969.
[25] A. Vinu, M. Miyahara, V. Sivamurugan, T. Mori, K. Ariga, J. Mater. Chem. 15
(2005) 51225127.
[26] Y. Cengeloglu, A. Tor, M. Ersoz, G. Arslan, Sep. Purif. Technol. 51 (2006) 374
378.
[27] U.S. Orlando, A.U. Baes, W. Nishijima, M. Okada, Bioresour. Technol. 83 (2002)
195198.
[28] P.C. Mishra, R.K. Patel, J. Environ. Manage. 90 (2009) 519522.
[29] M.F.A. Taleb, G.A. Mahmoud, S.M. Elsigeny, E.S.A. Hegazy, J. Hazard. Mater. 159
(2008) 372379.
[30] Y. Tian, Chin. Chem. Lett. 19 (2008) 11111114.
[31] Y. Zheng, A. Wang, J. Chem. Eng. Data 55 (2010) 34943500.
[32] C.J. Mena-Duran, M.R.S. Kou, T. Lopez, J.A. Azamar-Barrios, D.H. Aguilar, M.I.
Dominguez, J.A. Odriozola, P. Quintana, Appl. Surf. Sci. 253 (2007) 57625766.
[33] K.G. Bhattacharyya, S.S. Gupta, Adv. Colloid Interface Sci. 140 (2008) 114131.
[34] A. Khani, M. Mirzaei, Comparative study of nitrate removal from aqueous
solution using powder activated carbon and carbon nanotubes, in: 2nd
International IUPAC Conference on Green Chemistry, Russia, 2008 pp. 1419.
[35] A. Bhatnagar, M. Sillanpaa, Adv. Colloid Interface Sci. 152 (2009) 2638.
[36] S. Chatterjee, D.S. Lee, M.W. Lee, S.H. Woo, J. Hazard. Mater. 166 (2009) 508
513.
[37] K. Hosni, E. Srasra, Inorg. Mater. 44 (2008) 742749.
[38] M. Islam, R. Patel, Desalination 256 (2010) 120128.
[39] M. Zhang, B. Gao, Y. Yao, Y. Xue, M. Inyang, Chem. Eng. J. 210 (2012) 2632.
[40] J. Lehmann, J. Pereira da Silva, C. Steiner, T. Nehls, W. Zech, B. Glaser, Plant Soil
249 (2003) 343357.
[41] J. Major, M. Rondon, D. Molina, S.J. Riha, J. Lehmann, Plant Soil 333 (2010) 117
128.
[42] G.N. Kasozi, A.R. Zimmerman, P. Nkedi-Kizza, B. Gao, Environ. Sci. Technol. 44
(2010) 61896195.
[43] I.A.W. Tan, A.L. Ahmad, B.H. Hameed, J. Hazard. Mater. 154 (2008) 337346.
[44] R.L. Tseung, S.K. Tseng, J. Hazard. Mater. 136 (2006) 671680.
[45] F.C. Wu, R.L. Tseng, R.S. Juang, Sep. Purif. Technol. 47 (2005) 1019.
[46] C.K. Sing, J.N. Sahu, K.K. Mahalik, C.R. Mohanty, R.B. Mohan, B.C. Meikap, J.
Hazard. Mater. 153 (2008) 221228.
[47] D.E. Clay, Z. Zheng, Z. Lui, S.A. Clay, T.P. Trooien, J. Environ. Qual. 33 (2004)
338342.
[48] K. Jaafari, T. Ruiz, S. Elmaleh, J. Coma, K. Benkhouja, Chem. Eng. J. 99 (2004)
153160.
[49] K. Ramakrishnan, C. Namasivayam, J. Environ. Eng. Manage. 19 (2009) 173
178.
[50] ASTM, Standard Test Method for Carbon Black-Iodine Absorption, ASTM
D1510-09A, American Society for Testing and Materials, West Conshohocken,
PA, 2009.
[51] G.E. Rayment, F.R. Higginson, Australian Laboratory Handbook of Soil and
Water Chemical Methods, Inkata Press, Melbourne, 1992. p. 330.
[52] ASTM, Standard Test Method for the Analysis of Wood Charcoal (D176284),
2007.
[53] R. Chintala, D.E. Clay, T.E. Schumacher, D.D. Malo, J. Julson, Anal. Lett. 46
(2013) 532538.
[54] J.K. Friel, C.S. Skinner, S.E. Jackson, H.P. Longerich, Analyst 115 (1990) 269273.
[55] V.D. Zheljazkov, N.E. Nielson, Plant Soil 178 (1996) 5966.
[56] US, Environmental Protection Agency, Microwave Assisted Acid Digestion of
Sediments, Sludges, Soils, and Oils, Method 3051a. Ofce of Solid Waste and
Emergency Response, US Government Printing Ofce, Washington, DC, 1998.
[57] L.W. Zelazny, H.E. Liming, A.N. Van Wormhoudt, Charge analysis of soils and
anion exchange, in: D.L. Sparks (Ed.), Methods of Soil Analysis. Part 3. SSSA
Book Ser. 5, SSSA, Madison, WI, 1996, pp. 12311253.
[58] SAS Institute, SAS Stat., vols. 12. Release 8.2., Cary, NC, 2003.
[59] R.G.W. Steel, J.H. Torrie, Principles and Procedures of Statistics: A Biometrical
Approach, second ed., McGraw-Hill Book Co., New York, 1980.
[60] J.W. Gaskin, C. Steiner, K. Harris, K.C. Das, B. Bibens, Trans. ASABE 51 (2008)
20612069.
[61] K.A. Spokas, J.M. Novak, C.E. Stewart, K.B. Cantrell, M. Uchimiya, M.G. Dusaire,
K.S. Ro, Chemosphere 85 (2011) 869882.
[62] C. Moreno-Castilla, M.A. Ferro-Garcia, J.P. Joly, I. Bautista-Toledo, F. Carrasco-
Marin, J. Rivera-Utrilla, Langmuir 11 (1996) 43864392.
[63] R.R. Bansode, J.N. Losso, W.E. Marshall, R.M. Rao, R.J. Portier, Bioresour.
Technol. 94 (2004) 129135.