Environmental Technology & Innovation 10 (2018) 16–26

Contents lists available at ScienceDirect

Environmental Technology & Innovation

journal homepage: www.elsevier.com/locate/eti

Effect of feed source and pyrolysis conditions on properties

and metal sorption by sugarcane biochar
Amir Hass a, *, Isabel M. Lima b
a
Agricultural and Environmental Research Station, West Virginia State University, Institute, WV 25112, United States
b
Commodity Utilization Research Group, USDA, Agricultural Research Service, Southern Regional Research Center, New Orleans, LA
70124, United States

highlights

• Aged sugarcane bagasse produces biochar of high metal sorption capacity.

• Biochar ash content play a significant role in metal sorption by sugarcane bagasse.
• Acid-washing drastically decreased activated biochar Cu sorption capacity.
• Copper sorption was inversely related to biochar oxygen content and O/C molar ratio.

article info a b s t r a c t
Article history: Sugarcane biomass from different feed sources of sugar mill operation were used in
Received 4 October 2017 producing biochar at different temperatures (350, 500, 650, and 800 ◦ C) with/out steam
Received in revised form 10 January 2018 activation at 800 ◦ C. Feed sources included fresh cane-trash, fresh bagasse, and old bagasse
Accepted 13 January 2018
collected from a pile left outside the plant for several years. Biochar yield and composition
Available online 3 February 2018
were determined and metal sorption capacity evaluated. Pyrolysis more than doubled
biochar ash content which was 2 to 3 times higher for fresh cane trash and old bagasse
Keywords:
Langmuir sorption isotherm than for fresh bagasse biochars. On the other hand, surface area of fresh bagasse activated
Cane trash biochars (493 m2 g−1 ) nearly doubled that of the old bagasse (262 m2 g−1 ), or fresh cane
Ash content trash (204 m2 g−1 ) biochars. Cadmium sorption capacity increased upon activation and was
Steam activation an order of magnitude higher for old bagasse biochars than for fresh bagasse or fresh cane
Sugarcane bagasse trash biochars across production temperatures (ranging from 43.4 mg g−1 to 63.8 mg g−1
Biochar compared to 0.35 mg g−1 to 0.47 mg g−1 , or 4.35 mg g−1 to 6.29 mg g−1 , respectively).
Maximum sorption capacity for Cd and Cu was highly correlated with biochar ash content,
while that of Pb correlated with biochar surface area and total sulfur content. Cu sorption
capacity inversely correlated with O/C ratio and reduced significantly upon acid washing
of activated 500 ◦ C old bagasse biochar (from 32.2 mg g−1 to 14.3 mg g−1 ). Ash content
seemed to play a decisive role in metal sorption capacity of sugarcane bagasse biochars.
Overall, old sugarcane bagasse feedstock demonstrated best performance in producing
biochars of higher metal sorption capacity compared to fresh cane-trash or fresh bagasse.
© 2018 Elsevier B.V. All rights reserved.

* Corresponding author.
E-mail address: amirhass@wvstateu.edu (A. Hass).

https://doi.org/10.1016/j.eti.2018.01.007
2352-1864/© 2018 Elsevier B.V. All rights reserved.
 A. Hass, I.M. Lima / Environmental Technology & Innovation 10 (2018) 16–26 17

1. Introduction

Intensive agronomic production systems and expansion of urban landscapes, both ubiquitous to population and economic
growth, adversely affects landscape hydrology and natural system filtration capacity and ability to sustain ecosystem
services, such as clean water. Engineered runoff management practices can alleviate such impact by removing pollutants
from runoff water. Yet, inasmuch as such systems performing well as physical filtration systems, a more specific and selective
composition is required for more efficient and effective removal of dissolved components (Davis et al., 2009, 2012; Smith
and Livingston, 2013). Use of selective sorbents in the engineered soil media of runoff management practices will improve
the system efficiency.
Biochar, a carbon-rich solid produced via pyrolysis of biomass showed to remove excess nutrients, heavy metals,
pesticides, and other synthetic organics from water, with feedstock and pyrolysis conditions to significantly affect biochar
pollutants removal efficiency (Ahmad et al., 2014; Lima and Marshall, 2005, 2007; Trakal et al., 2011; Uchimiya et al., 2010).
Produced from agronomic waste streams, biochar is proposed as a cost-effective source for bulk sorbent material for such
non-point-source large-scale systems. Biomass residue from sugarcane operations can serve as a low-cost feedstock for
such applications (Ding et al., 2014; Mohan et al., 2014). Biochar efficacy as metal sorbent depends on biochar feedstock
and pyrolysis conditions (Lima et al., 2009; Asuquo et al., 2017; Li et al., 2017). Hence, proper selection of feedstock and
pyrolysis conditions is important in order to maximize sugarcane biochar performance. The objective of this study was to
investigate different available feed sources along sugarcane harvesting and milling operations for their potential conversion
into biochars and activated biochars. Furthermore, different pyrolysis conditions were applied in order to investigate
their role in conjunction with the different properties of the original feedstock in the final physico-chemical and sorption
properties of the biochars. Their composition and metal sorption characteristics were analyzed and compared in order to
determine role of feedstock and pyrolysis conditions and activation step in the overall biochar performance as metal sorbent.

2. Materials and methods

2.1. Sample collection and preparation

Two types of sugarcane bagasse material, old and fresh were collected from Cora Texas Sugar Mill (White Castle, LA).
The fresh bagasse was collected the same day it was generated and the old bagasse was collected from a bagasse pile left
outside for several years. Additionally, a sample of fresh cane trash material was collected from a mechanical de-trasher
system installed to separate and remove incoming trash (mostly leafy material) from the billeted sugarcane prior to sugar
extraction. All three materials were air dried in a greenhouse prior to grinding to pass 2-mm sieve using a Retsch 2000
cutting mill. Select properties of the different feed sources are provided in Table S1.
The different feed sources were pyrolyzed in a Lindberg bench furnace equipped with a retort (Lindberg/Blue M, Type
51662-HR, Watertown, WI, USA). Samples were placed in a ceramic evaporating dish in the furnace chamber and pyrolyzed
at the peak temperature for one hour under a flow of nitrogen gas set at a flow rate of 1.6 L min−1 . Four pyrolysis temperatures
were studied from 350 ◦ C to 800 ◦ C with 150 ◦ C increments and a 6 ◦ C min−1 ramp rate up to the final temperature. A sample
of old bagasse was also pyrolyzed at 300 ◦ C. Biochars were allowed to cool down to room temperature overnight in the retort
under a flow of nitrogen gas.
Half of the biochar samples were further activated by steam upon completion of the 60-min pyrolysis, by continued
heating to 800 ◦ C at the same temperature ramping rate, and after reaching 800 ◦ C injecting distilled water into the nitrogen
gas flow at a rate of 3 ml min−1 for 45 min using a peristaltic pump. As before, samples were allowed to cool down overnight
under a flow of nitrogen. Samples of the activated and non-activated old bagasse that were pyrolyzed at 500 ◦ C were either
(a) used as is (unwashed) or, (b) acid-washed with 0.1 N HCl (2% w/v ratio) for 1 h with two subsequent water rinses (2%
w/v ratio), and dried overnight at 90 ◦ C. One mL aliquot of the acid-washed suspensions were drawn using a disposable
syringe and filtered through a 0.22 µm Millipore filter (Millipore Corp., Bedford, MA) prior to dilution and analysis. Leachate
elemental composition was analyzed using inductively coupled plasma, atomic emission spectroscopy (ICP-AES; Leeman
Labs, Hudson, NH, USA).

2.2. Physical and chemical measurements, yield, and surface area

Biochars and feedstocks were evaluated for select properties including biochar yield, surface area (data reported as
average of duplicate samples), and elemental and proximate analyses. Elemental analysis was conducted on a single
composite sample. Prior to all measurements, biochar and activated biochar samples were ground to particle size <100
µm. Surface area measurements were obtained from duplicate analysis of nitrogen adsorption isotherms at 77 ◦ K using
Nova 2200e Surface Area Analyzer (Quantachrome Corp., Boynton Beach, FL). Specific surface areas (BET, Brunauer–Emmett–
Teller) were calculated from adsorption isotherms using the BET equation. The micropore size distributions were calculated
using t-plots derived from the Nova 2200e software. Micropores are those having less than 2 nm in diameter and referred
herein as inner surface area, while remaining surface area is herein referred to as outer surface area.
Ultimate analysis (CHNSO) was determined by dry combustion/TCD (CHN); percent sulfur content was determined by
O2 flask combustion/titration and percent oxygen content was determined by pyrolysis/gravimetric determination (Micro-
Analysis, Inc., Wilmington, DE). Proximate analysis (ASTM method D5142-09) was performed using Thermo-Gravimetric
Analyzer (TGA701, LECO, St. Joseph, MI) to determine moisture, ash, volatile matter, and fixed carbon (results reported as
average of triplicate samples).
18 A. Hass, I.M. Lima / Environmental Technology & Innovation 10 (2018) 16–26

2.3. Sorption assays

Sorption assays were conducted in triplicate for the following metals and biochars: cadmium on 350 ◦ C, 500 ◦ C, and
650 ◦ C old bagasse activated and non-activated biochars, and for 350 ◦ C and 650 ◦ C activated and non-activated fresh cane
trash and fresh bagasse biochars; Cu and Pb on 350 ◦ C, 500 ◦ C, and 650 ◦ C old bagasse biochars. Copper sorption assay was
conducted also for acid-washed old bagasse 500 ◦ C biochars. Equilibrium sorption assays were carried out by adding 0.250 g
of biochar sample to 25 mL of either one of three single metal ion solutions using a 150 mL beaker. Solutions of CuCl2 ·2H2 O
and Pb(NO3 )2 were obtained from Fisher scientific (Fair Lawn, NJ), and Cd(NO3 )2 was obtained from EM Science (Cherry Hill,
NJ). Single metal ion solutions were made at the following concentrations: 0.48, 4.8, 24, 48, 96 and 480 mg L−1 metal ion in
a 0.07M sodium acetate/0.03M acetic acid buffer, pH 4.8. The pH of the equilibrium slurry was recorded using Thermo Orion
pH meter (Beverly, MA). For any given experiment, pH varied between 4.5 and 5.5. Beakers were covered with parafilm and
the slurry was stirred with Teflon coated magnetic stir-bars for 24 h at 300 rpm using a multiple stirrer (VarioMAC Multipoint
HP 15, H+P Labortechnik GmbH, Germany). Beakers of metal solutions without biochar samples were used as control. An
aliquot of each suspension was filtered, acidified (4% v/v nitric acid; Ultrapure, ICP grade), and diluted prior to determination
of metal concentrations using ICP-AES (above).
Maximum adsorption capacity (qmax ) and adsorption affinity constant (b) were calculated by fitting the data to the non-
linear Langmuir adsorption model, as follows:
qmax bCe
qe = (1)
1 + bCe
where qe is the amount of solute adsorbed per unit weight of adsorbent (mg g−1 ) at solute equilibrium concentration Ce
(mg L−1 ); qmax is the adsorbent maximum sorption capacity, corresponding to a monolayer coverage of the sorbent, and b
is an equilibrium constant related to free energy of adsorption (L mg−1 ). The non-linear least squares regression method of
Marquardt was implemented using Sigma Plot v.11.0 (SPSS Inc. Chicago, IL) and correlation coefficient (r 2 ) and probability
value (p-value) representing ‘‘goodness of fit’’ of the Langmuir model were obtained.

2.4. Statistical analysis

Treatment effects and multiple comparison analysis among treatments (feedstock, pyrolysis temperature, activation), and
correlation analysis among measured parameters and biochar feedstock, pyrolysis temperature, and steam activation were
conducted using Proc GLM and Tukey Honest Significant Difference, and Pearson correlations, respectively, all at p = 0.05,
using SAS 9.4 (SAS Inc. Cary, NC). Correlation between metal sorption capacities and biochar parameters (ash, total, inner, and
outer surface areas, and N, O, S content) were conducted for the complete data sets as well as for activated and non-activated
subsets across temperatures and feedstocks.

3. Results and discussion

3.1. Yield

Biochar yield, determined as percent of initial biomass (on dry weight basis), decreased with increase in pyrolysis
temperature, and remained relatively constant at pyrolysis temperatures above 500 ◦ C (Fig. S1). Overall, average biochar
yield across production temperatures was 42 ± 1.8%, 37 ± 2.0%, and 27 ± 2.0% for fresh cane trash, old bagasse, and fresh
bagasse biochars, respectively (n = 4). Biochar yield decreased with increase in feedstock oxygen and carbon contents
while increasing with feedstock ash content (Table S1). This is an expected trend given that feedstock ash content act
more conservatively compared to carbon and oxygen that volatilized to different degrees under the pyrolysis conditions.
Additionally, it has been reported that inorganic compounds, found indigenously within biomass, promote formation of
gaseous species and biochar at the expense of bio-oil yield (Sekiguchi and Shafizadeh, 1984). This corroborates with the fact
that the presence of certain minerals in the biochar (e.g. with particular emphasis on potassium), has been linked to higher
yields (Jensen et al., 2001; Fahmi et al., 2007) by acting as catalysts and influencing rate of degradation during carbonization
reactions. Indeed, Lima and White (2016) reported 45.5 g kg−1 and 7.02 g kg−1 of potassium respectively in sugarcane
trash and bagasse materials. Percent yield of activated biochars was lower compare to their non-activated counterparts
as additional carbon and volatile compounds are further lost upon activation. Overall, average activated biochar yield was
36 ± 0.4%, 32 ± 1.5%, and 23 ± 0.5% across all four pyrolysis temperatures for fresh cane trash, old bagasse, and fresh bagasse
biochars, respectively (n = 4; Fig. S1).

3.2. Surface area

Biochar surface area was peak temperature, activation, and feedstock dependent. Total surface area of non-activated
biochars increased with increase in peak temperature across feedstock, with old bagasse biochars having a higher surface
area compared to the other feedstock biochars (Table 1; Fig. 1B). Biochar inner surface area was nearly zero for non-activated
biochars of all feedstock at peak production temperature below 800 ◦ C, and followed the order: old bagasse (50 m2 g−1 ) ≫
 A. Hass, I.M. Lima / Environmental Technology & Innovation 10 (2018) 16–26 19

Table 1
Surface area of biochars produced at different temperatures from different feedstock and with/out steam activation (values within row or column following
by the same lowercase or uppercase letters, respectively, are not significantly different at p < 0.05).
Pyrolysis temperature (◦ C) Old bagasse Fresh bagasse Fresh cane trash
Non-act Activated Non-act Activated Non-act Activated
Total surface area (m2 g−1 )
350 1.99 (0.01)c C 253 (0.75)b A 2.10 (0.04)c B 466 (49.3)a A 2.60 (0.33)c C 182 (8.82)b B
500 26.8 (0.64)d BC 255 (4.31)b A 7.11 (1.11)d B 530 (1.44)a A 8.17 (0.68)d B 207 (6.31)c AB
650 57.1 (4.3)d AB 284 (27.5)b A 21.5 (11.2)d AB 497 (5.74)a A 8.86 (0.20)d B 217 (8.64)c A
800 106 (24.7)c A 256 (7.48)b A 30.6 (0.56)d A 479 (39.0)a A 25.4 (2.22)d A 208 (1.60)b AB
Inner surface area (m2 g−1 )
350 0.00 (0.00)c A 202 (1.44)b A 0.73 (0.28)c A 390 (48.16)a A 0.13 (0.00)c A 125 (4.82)b B
500 0.00 (0.00)d A 205 (5.93)b A 0.00 (0.00)d A 446 (0.70)a A 2.64 (0.19)d A 146 (3.46)c A
650 4.47 (6.32)d A 224 (22.6)b A 0.00 (0.00)d A 414 (4.93)a A 0.00 (0.00)d A 155 (5.53)c A
800 50.3 (25.0)c A 210 (5.12)b A 1.79 (2.27)c A 401 (31.8)a A 5.02 (7.10)c A 154 (0.80)b A
Outer surface area (m2 g−1 )
350 2.0 (0.01)d C 50 (0.61)c A 1.4 (0.32)d B 76 (1.17)a B 2.5 (0.33)d A 57 (4.00)b A
500 27 (0.64)d B 53 (1.63)c A 7.1 (1.11)e AB 83 (0.72)a A 5.5 (0.88)e A 61 (2.85)b A
650 53 (2.07)b A 60 (4.90)b A 22 (11.3)c AB 84 (0.81)a A 8.9 (0.20)c A 62 (3.11)b A
800 56 (0.30)b A 46 (2.36)b A 29 (2.82)c A 79 (1.48)a B 13 (5.60)d A 54 (0.80)b A

Fig. 1. Total, inner, and outer surface area of activated (A) and non-activated (B) biochars from different feedstocks (values are average of biochars from all
peak production temperatures of a given feedstock, n = 4; bars with the same lowercase letter within the same surface type are not significantly different
at p < 0.05; vertical lines represent one standard error).

fresh cane trash (5.0 m2 g−1 ) > fresh bagasse (1.8 m2 g−1 ), at 800 ◦ C (Table 1). Steam activation increased biochar total surface
area by 10 to 100 fold, with fresh bagasse feedstock resulting in much higher total surface area among activated biochars
across all peak production temperatures, following the order: fresh bagasse (493 ± 27 m2 g−1 ) ≫ old bagasse (262 ± 15 m2
g−1 ) > fresh cane trash (204 ± 15 m2 g−1 ), (Fig. 1A). The increase in total surface area was associated with a marked increase
in biochar inner surface area, accounting for 71%, 80%, and 84% of total surface area of cane trash, and old and fresh bagasse
activated biochars, respectively (Table 1).
In general, outer surface area increased with pyrolysis temperature and was highest for old bagasse biochars, with
56 ± 0.3 m2 g−1 at 800 ◦ C peak production temperature. Outer surface area increased upon activation independent of
pyrolysis temperature (Table 1) averaging 52 ± 5.9 m2 g−1 , 80 ± 3.7 and 59 ± 3.7 m2 g−1 respectively for old bagasse,
fresh bagasse and fresh cane trash activated biochars. Highest increase in outer surface area upon activation was observed
for fresh bagasse biochars (Table 1). The increase in total, inner, and outer surface areas were all negatively correlated with
biochar N, H, O, and S content (data not shown) suggesting relatively higher loss of moieties containing these elements with
increase in production temperature.
Acid washing of old bagasse biochars produced at 500 ◦ C reduced the surface area of non-activated biochar (from
26.8 ± 0.6 down to 19.9 ± 1.1 m2 g−1 ), but had no effect on the total surface area of activated biochar (255 ± 4, and 243 ± 20
m2 g−1 for the as-is, and the acid-washed 500 ◦ C old bagasse activated biochars, respectively). Overall, the surface analysis
results suggests that there was limited contribution from acid-soluble mineral phases to biochar surface area; that much
of the increase in surface area upon steam activation was due to creation and/or exposure of inner pore surfaces; and that
surface area of activated fresh bagasse biochars far exceeds that of other feedstocks biochars.
20 A. Hass, I.M. Lima / Environmental Technology & Innovation 10 (2018) 16–26

Table 2
Proximate analysis results for biochars produced at different temperatures from different feedstock and with/out steam activation (all results are on dry
weight basis; values within row or column following by the same lowercase or uppercase letter, respectively, are not significantly different at p < 0.05).
Pyrolysis temperature (◦ C) Old bagasse Fresh bagasse Fresh cane trash
Non-act Activated Non-act Activated Non-act Activated
Ash content (%)
350 32 (0.9)c B 63 (1.0)a A 14 (0.5)e B 24 (0.8)d A 42 (1.5)b D 61 (1.9)a A
500 46 (4.5)b A 58 (0.2)a A 19 (2.3)c A 23 (1.9)c A 48 (1.3)b C 61 (2.9)a A
650 53 (6.0)a A 58 (1.0)a A 18 (1.0)b A 22 (0.4)b A 53 (0.9)a B 60 (1.2)a A
800 52 (3.4)b A 58 (5.1)ab A 21 (1.5)c A 26 (2.7)c A 60 (3.9)ab A 64 (2.7)a A
Volatile matter (%)
350 35 (0.2)b A 4.3 (0.1)d A 38 (1.1)a A 5.1 (0.4)d A 29 (0.8)c A 4.8 (0.3)d A
500 18 (0.4)a B 4.6 (0.3)d A 16 (0.3)b B 5.0 (0.4)d A 14 (0.2)c B 5.1 (0.6)d A
650 11 (0.3)a C 4.6 (0.4)b A 8.4 (1.3)b C 4.7 (0.4)b A 10 (1.7)a C 5.4 (0.2)b A
800 4.7 (0.7)a D 4.1 (0.4)a A 5.6 (1.2)b D 5.0 (0.5)a A 5.5 (0.9)a D 4.8 (0.2)a A
Fixed carbon (%)
350 32 (1.0)cd B 33 (1.00)cd A 48 (1.3)b C 71 (0.8)a A 29 (1.4)d B 34 (1.9)c A
500 36 (4.1)c AB 38 (0.1)c A 65 (2.2)b B 72 (2.2)a A 38 (1.5)c A 34 (3.0)c A
650 37 (6.2)b AB 38 (1.2)b A 74 (1.80)a A 73 (0.8)a A 37 (2.4)b A 35 (1.3)b A
800 43 (2.7)b A 38 (5.5)bc A 74 (0.8)a A 69 (3.2)a A 34 (3.2)c A 31 (2.5)c A

3.3. Proximate and ultimate analysis

Biochar proximate analysis showed that feedstock, pyrolysis peak temperature, and steam activation, all affected ash,
volatile matter, and fixed carbon content (Table 2). Feedstock ash content followed the order: fresh cane trash (23 ± 1.0%)
> old bagasse (15 ± 1.7%) > fresh bagasse (5.1 ± 0.2%). These differences are likely due to higher degree of decomposition
(in the case of the old bagasse), and mineral impurities, and lower proportion of fibrous and higher proportion of plant parts
of higher mineral content such as leafy material (in the case of fresh cane trash). Ash content of fresh bagasse in this study
was within the range of previously published work (2.1%–7.0%; Filho and Badr, 2004; and Lee et al., 2013, and citations
therein). Biochar ash content increased with increase in production temperature and was similar among old bagasse and
fresh cane trash, both being 2 to 2.5 times greater than fresh bagasse biochars throughout production temperatures (Table 2).
As expected, fixed carbon content also increased with pyrolysis temperature, as an indicator of aromaticity development.
Steam activation further increased biochars ash content at all production temperatures by 2 to 4 times their initial content
in the feedstock, averaging 62 ± 3%, 59 ± 3%, and 22 ± 7% in fresh cane trash, and in old and fresh bagasse, respectively
(Table 2). Unlike non-activated biochars, ash content of activated biochars was inversely correlated with biochar total, inner,
and outer surface area (r 2 = −0.981, p < 0.0001; r 2 = −0.974, p < 0.0001; r 2 = −0.920, p < 0.0001, all respectively).
This is likely due to the differences in specific particle densities between the ash and carbon matrices as well as precipitating
mineral phases in a sintering like process, blocking biochar porosity. Ash content in activated biochars was also negatively
correlated with total and fixed carbon content.
Elemental composition of biochars changed with increase in pyrolysis temperature and upon activation (Table S2; Fig. S2).
Biochar carbon content was significantly different among feedstock across production temperature and activation, following
the order: fresh bagasse ≫ old bagasse >fresh cane trash (n = 4; Fig. S2A). As total sulfur content was only moderately
affected by pyrolysis temperature (Table S2), that of oxygen, hydrogen, and nitrogen decreased sharply upon activation
and with increase in peak production temperature of non-activated biochars across feedstock, while being much lower and
independent of production temperature upon activation (Fig. S2B–S2D). As much of these changes occurred below 650 ◦ C,
increase in pyrolysis temperature from 650 ◦ C to 800 ◦ C brought little change in biochar O, H, or N content (Fig. S2).
A Van Krevelen diagram (H/C vs. O/C molar ratios plot) for all non-activated biochars and feedstocks was further
constructed and presented in Fig. S3. Higher values of H/C and O/C suggest proportionally higher content of aliphatic and
oxidized substances, while lower ratios are indicative of proportionally higher content of aromatic and reduced substances,
all respectively. Similarly to their elemental content behavior upon activation, all H/C and O/C molar ratios of activated
biochars were low irrespectively of pyrolysis production temperature or feedstock (see inset in Fig. S3). The increase in
pyrolysis temperature progressively changes biochar composition as aliphatic and short chain organic acids such as acetic,
formic, and propionic acids are removed (or otherwise recovered in the bio-oil fraction in fast pyrolysis operations; Mahfud et
al., 2008; Mullen and Boateng, 2008; Yanik et al., 2007). The removal of oxygen bearing functional groups showed to increase
with increase in pyrolysis temperature according to the sequence: carboxylic (at 300 ◦ C to 400 ◦ C); lactone, phenol, and
carbonyl (at 400 ◦ C to 700 ◦ C); and anhydride, ether, and quinone groups at temperatures above ca 700 ◦ C (Figueiredo et al.,
1999). Concomitant to the increase in pyrolysis temperature and elimination of these functional groups (as well as aliphatic,
cellulose, hemicellulose, and lignin carbon forms), there is a consistent shift of the remaining carbon into condensed aromatic
structures (Al-Wabel et al., 2013; Kim et al., 2012).
 A. Hass, I.M. Lima / Environmental Technology & Innovation 10 (2018) 16–26 21

3.4. Metal sorption

Biochars adsorption capacity (qmax ) and affinity (b) towards Cd, Cu, and Pb are presented in Table 3. Sorption capacity
of activated biochars was higher than that of non-activated biochars across metals and pyrolysis temperatures. Cadmium
sorption was low among non-activated biochars following the order: fresh cane trash (4.60 mg g−1 ) >fresh bagasse (0.33 mg
g−1 ) >old bagasse (0.00 mg g−1 ) at low temperature (350 ◦ C), with the sorption capacity of old bagasse biochar increasing
with increase in pyrolysis temperature, while that of fresh bagasse and fresh cane trash decreased (Table 3). The increase in
Cd sorption on the old bagasse biochars with increase in pyrolysis temperature is likely related to the corresponding increase
in biochar (inner) surface area for this feed source (Table 1). Similar range of Cd sorption capacities were reported earlier for
other biomass feedstock biochars, ranging from 3.4 mg g−1 for wood (type not specified) and 4.5 mg g−1 for coconut shell at
700 ◦ C (Lima et al., 2009), to 5.4 mg g−1 for oak bark biochar as summarized recently by Li et al. (2017, and citation therein).
On the other hand, biochars produced from animal wastes such as broiler cake or litter and from dairy, pig, and cow manures
(and of higher ash content) resulted in higher Cd sorption capacity (31.9 mg g−1 to 118 mg g−1 ; Kolodynska et al., 2012; Li
et al., 2017; Lima et al., 2009), while that made from low-ash raw or modified carbon nanotubes ranged from 1.1 mg g−1 to
11.0 mg g−1 (Rao et al., 2007), and that from activated carbon ranging between 4.29 mg g−1 and 16.2 mg g−1 ( Asuquo et al.,
2017 and citation therein).
Upon activation Cd sorption capacity increased by an order of magnitude for old bagasse while having much modest
impact on biochars of fresh bagasse or fresh cane trash feedstock (Table 3). The increase in Cd sorption capacity correlated
with inner surface area of non-activated biochars (r 2 = 0.807; p = 0.0282) but not with activated biochars. Overall, old
bagasse biochars Cd sorption capacity increased by steam activation as biochar surface area increased (Table 1, and Table 3).
However, and while surface area of fresh bagasse activated biochars increased to nearly twice as much as their old bagasse
counterparts (averaging 498 ± 32 m2 g−1 vs. 264 ± 62 m2 g−1 across pyrolysis temperatures, respectively), the sorption
capacity of the activated old bagasse biochars was much higher (52 ± 17 mg g−1 vs. 0.410 ± 0.089 mg g−1 , across pyrolysis
temperatures, respectively). In fact, Cd sorption capacity of the activated old bagasse biochars was 10 times higher than that
of fresh cane trash activated biochar, which itself was 10 or 20 times higher than that of activated fresh bagasse biochars
(see 350 ◦ C and 650 ◦ C activated biochars, Table 3). Furthermore, the sharp increase in total surface area of fresh bagasse
biochar upon activation (averaging across pyrolysis temperatures: 10.2 ± 10.1 m2 g−1 for non-activated up to 498 ± 32 m2
g−1 for activated fresh biochars) did not result in a corresponding increase in Cd sorption capacity (averaging across pyrolysis
temperatures: 0.410 ± 0.089 mg g−1 vs. 0.163 ± 0.231 mg g−1 , respectively). The increase in cadmium sorption capacity by
old bagasse biochars followed the increase in biochar ash content, which was significantly higher for old bagasse compared
to fresh bagasse biochars (Table 2). Overall, Cd sorption capacity was correlated with biochar ash content (r 2 = 0.563;
p = 0.0362) across production temperatures and feedstocks, and was significantly higher for the old bagasse compared
to the other feedstocks, following the order: old bagasse (51.60 mg g−1 ) ≫ fresh cane trash (5.32 mg g−1 ) >fresh bagasse
(0.41 mg g−1 ). Noteworthy, inasmuch as the fresh cane trash biochars had similar ash content as that from old bagasse
(Table 2) they did not exhibit the same increase in sorption capacity as did old bagasse biochars (Table 3). This might be
related to the biodegradation and aging effect of the old bagasse and the association of the metals therein compared to
the fresh cane trash. Metals in the latter are in association within cell structure and function ( Hshieh and Richards, 1989;
Vassilev et al., 2012) while that in the field-aged bagasse might be in a more conducive geochemical form (if not already in)
for development of discrete mineral phase ash concretion of higher ability to interact with the introduced heavy metals. In
fact, such off-white concretions 2–3 mm in size were observed in all of the activated old bagasse biochars, and to a lesser
degree in the non-activated old bagasse biochars produced at above 500 ◦ C.
Biochar Cu sorption capacity increased with increase in pyrolysis temperature. At 650 ◦ C, Cu sorption capacity of the
biochar was not significantly different from that of 350 ◦ C activated biochar from where Cu sorption capacity decreased as
pyrolysis temperature of activated biochar increased (Table 3). Copper sorption capacity of 650 ◦ C biochar, and that of all
activated biochars, was higher than reported for biochars of other plant biomasses such as Miscanthus (15.4 mg g−1 and
8.87 mg g−1 for non-activated and activated 500 ◦ C biochars, respectively; Shim et al., 2015), and hardwood or corn straw
produced at 450 ◦ C and 600 ◦ C (ranging from 6.79 mg g−1 to 12.5 mg g−1 ; Li et al., 2017, and references therein). Tested
on animal waste-derived biochars, Lima et al. (2009) reported similar values for broiler cake and litter produced at 700 ◦ C
and 800 ◦ C (57.8 mg g−1 and 36.9 mg g−1 , and 66.7 mg g−1 and 43.2 mg g−1 , respectively), while recording no measurable
sorption on coal, wood, or coconut shell biochars. Biniak et al. (1999) estimated Cu sorption capacity of de-ashed (treated with
concentrated HF and HCl), heat-treated (at 1000 ◦ C) activated biochar at 27.3 mg g−1 . While attributing much of the sorption
mechanisms to d-π dipole–dipole interactions between graphene-like char surface and the metal ion, and to spontaneous
electrochemical reduction of CuII , they also attributed some 16% of the sorbed metal to CuOH− , Cu(OH)2 and hydrated Cu
complexes at the carbon surface (Biniak et al., 1999).
Copper sorption capacity of old bagasse 350 ◦ C and 500 ◦ C biochars increased nearly 10 fold upon activation, from 0.65
mg g−1 and 3.88 mg g−1 to 40.5 mg g−1 and 32.2 mg g−1 , all respectively (Table 3). This can be attributed to the similar
increase in biochar surface area of those biochars upon activation (1.99 mg g−1 to 253 m2 g−1 , and 26.8 mg g−1 to 255
m2 g−1 , all respectively, Table 1). Similarly to Cd, Cu sorption capacity was correlated with inner surface area and for non-
activated biochars only (r 2 = 0.997, p = 0.0474). Cu sorption capacity was also positively correlated with ash and negatively
correlated with oxygen content across feedstocks, pyrolysis temperatures, and activation (r 2 = 0.856, p = 0.0297; and, r 2
= −0.875, p = 0.0226; all respectively). On the other hand, the fact that Cu sorption capacity of 650 ◦ C non-activated
 22
Table 3

A. Hass, I.M. Lima / Environmental Technology & Innovation 10 (2018) 16–26

Fitting parameters of Langmuir sorption isotherms for biochar maximum sorption capacity (qmax ) and sorption affinity (b) for cadmium, copper, and lead (also included are the model goodness-of-fit
correlation coefficient [r2 ] and the probability value parameters).

Non-activated biochar Activated biochar

Pyrolysis 350 500 500-AW 650 350 500 500-AW 650
temperature (C◦ )
Feedstock type Old Fresh Fresh cane Old Old Old Fresh Fresh cane Old Fresh Fresh cane Old Old Old Fresh Fresh cane
bagasse bagasse trash bagasse bagasse bagasse bagasse trash bagasse bagasse trash bagasse bagasse bagasse bagasse trash
Cd
qmax (mg g−1 ) 0.00 0.33 4.60 0.00 7.09 0.00 0.03 63.8 0.35 6.29 43.4 47.6 0.47 4.35
b (L mg−1 ) 0.0000 0.542 0.0063 0.0000 0.0409 0.0000 0.1411 0.0238 0.0072 0.0132 0.0741 0.0347 0.0076 0.0142
r2 – 0.6313 0.999 – 0.8611 – 0.996 0.874 0.991 0.942 0.8467 0.8937 0.927 0.993
P-value – 0.0328 <0.0001 – 0.072 – 0.002 0.0018 0.0004 0.0013 0.0268 0.0152 0.0021 <0.0001
Cu
qmax (mg g−1 ) 0.65 3.88 –a 39.8 40.5 32.2 14.3 23.0
b (L mg−1 ) 0.0554 0.0008 0.0004 0.0027 0.0033 0.0008 0.0068
r2 0.9771 0.9976 0.9987 0.9473 0.958 0.9976 0.9034
P-value <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001
Pb
qmax (mg g−1 ) 2.63 3.92 0.70 6.49 7.65 8.70
b (L mg−1 ) 0.0084 0.0013 0.0098 0.0051 0.0040 0.0040
r2 0.9384 0.9532 0.833 0.9921 0.9936 0.9937
P-value <0.0001 <0.0001 0.0016 <0.0001 <0.0001 <0.0001
a
Sorption data did not obey Langmuir isotherm pattern—see text for discussion.
 A. Hass, I.M. Lima / Environmental Technology & Innovation 10 (2018) 16–26 23

Fig. 2. Cu sorption capacity (qmax ) and oxygen (A) and ash (B) content of old bagasse biochars (arrows point to the direction of increase in pyrolysis
temperature of activated [solid line], and non-activated [dissected line] biochars; solid regression line are exponential fit for all observations).

old bagasse biochar was not different from that of 350 ◦ C activated counterpart (39.8 mg g−1 vs. 40.5 mg g−1 , respectively;
Table 3) was surprising, as the surface area of the latter increased by nearly 5 times (57 ± 4 mg g−1 vs. 253 ± 1 m2 g−1 ,
respectively; Table 1). Furthermore, Cu sorption capacity increased amid decrease in oxygen content in both activated and
non-activated biochars (Fig. 2A), while increasing with increase in biochar ash content in both activated and non-activated
biochars (Fig. 2B). These observations suggest that biochar Cu sorption capacity is building up with increase in pyrolysis
temperature and while sustained at high activation temperature, remained somewhat unaffected by the marked increase
in surface area or loss of oxygen. This implies that biochar ash content might have a significant role in biochar Cu sorption
capacity, and that further study into biochar ash composition and mineralogy is needed.
In an effort to assess the role of ash content on Cu sorption, the old bagasse 500 ◦ C activated and non-activated
biochars were further acid-washed and sorption assays conducted on the acid-washed biochars to evaluate the acid-washing
treatment impact on Cu sorption capacity. Acid washing reduced biochar ash content by 34% and 27% for the non-activated
and activated old bagasse biochars, respectively (from 46 ± 4% to 31 ± 2%, and from 58 ± 0.22% to 42 ± 3%, all respectively).
Acid washing also decreased biochar total surface area by 26% and 5% for non-activated and activated biochars respectively
(data not shown). The treatment also reduced oxygen content in non-activated biochar but not in the activated biochar (Table
S2), resulting in a decrease in O/C mole ratio in the non-activated biochar from 0.130 to 0.080, while remaining unchanged
for acid washed and as-is activated biochars (0.037 and 0.036, all respectively). Cu sorption isotherm on the as-is and on
acid-washed old bagasse 500 ◦ C biochars, and the composition of the elements removed from the biochars by the process
are presented in Figs. 3 and 4, respectively. Acid washing decreased Cu sorption by activated biochar by 56%, from 32.2 mg g−1
down to 14.3 mg g−1 , while having minimal effect on non-activated acid-washed biochar (Table 3; Fig. 3). Acid washing of the
non-activated biochar seemed to shift somewhat Cu sorption pattern to where it no longer obeyed Langmuir-like sorption
isotherm (Fig. 3A). This pattern may represent the initial portion of an S-shape sorption isotherm where (organic/inorganic)
soluble ligands released to solution and outcompete with biochar surface for Cu binding at low concentrations (Neal and
Sposito, 1986).
Acid washing was conducted under mild concentration of HCl acid (0.1 N) and therefore was not complete, as only about
one third of the ash was removed in the process as determined by proximate analysis (data not shown). Acid washing was
element selective, removing mostly Ca, and to a lesser degree Al, Fe, Mg, and to even lesser extent other elements (Fig. 4). This
sequence of elements and relative proportions thereof is similar to that reported by Díaz et al. (2015) for sugarcane bagasse
ash composition Si ≫ Ca > Al ≈ K > Fe > P > S > Mg. As for oxygen and O/C ratio, and unlike previous reports (Uchimiya
et al., 2011) we found Cu sorption to negatively correlate with biochar oxygen content (Fig. 2A) or O/C ratio. Furthermore,
Cu sorption onto activated biochar decreased drastically upon acid washing (by 56%; Fig. 3B), amid no change in biochar O/C
ratio.
Lead maximum sorption capacity increased upon activation and with pyrolysis temperature therein, ranging from 0.70
mg g−1 to 3.92 mg g−1 in the non-activated biochars and from 6.49 mg g−1 to 8.70 mg g−1 in the activated biochars (Table 3).
These values are below and along the lower end of previously reported range of sorption capacity for Pb by activated carbons
(ranging between 5.95 mg g−1 to 47.2 mg g−1 , Asuquo et al., 2017, and citation therein). It was however, within the range of
non-modified biomass-derived biochars, ranging from 2.40 mg g−1 to 44.91 mg g−1 (Ifthikar et al., 2017; Li et al., 2017, and
citations therein). Ding et al. (2014) reported Pb sorption capacities of 6.1 mg g−1 to 21 mg g−1 by biochars made from fresh
sugarcane bagasse, with the sorption capacity decreasing with increase in pyrolysis temperature (from 250 ◦ C to 600 ◦ C).
24 A. Hass, I.M. Lima / Environmental Technology & Innovation 10 (2018) 16–26

Fig. 3. Copper sorption on non-activated (A) and activated (B) old bagasse biochar produced at 500 ◦ C used as-is (open circles) or acid washed (0.1 N HCl,
filled circles; vertical lines represent one standard deviation).

Fig. 4. Cumulative amount of elements leached during 0.1 N HCl wash of old bagasse 500 ◦ C activated and non-activated biochars (vertical lines represent
one standard deviation).

The authors attributed Pb removal mechanisms to interaction with surface oxygen functional groups at low temperatures,
to intraparticle diffusion at high temperatures where pore space become more dominant, and to (co)precipitation as lead
phosphate across all pyrolysis temperatures (estimated to account for some 10% of the removed lead; Ding et al., 2014).
Examining biochars produced at different temperatures and from different biomass, Yuan et al. (2011) showed that carbonate
content, as well as total alkalinity and total P content increases with increase in biochar pyrolysis temperature while oxygen
and functional groups thereof, as well as biochar total acidity and negative charge, decreases. Similar trends of decrease in
total acidity, as well as decrease in O/C mole ratio and increase in pHPZC , with increase in pyrolysis temperature was reported
by Uchimiya et al. (2011) for biochar from cottonseed hulls produced at 200–800 ◦ C.
In our study, lead sorption capacity correlated with activated biochar oxygen content (r 2 = 0.999, p = 0.0225), but
unlike Cd and Cu, was not responsive to differences in biochar ash content. Lead sorption capacity on activated biochars did
increase with pyrolysis temperature (Table 3) and was highly correlated with total and inner surface areas (r 2 = 0.894, p =
0.0164; and r 2 = 0.924, p = 0.00855, respectively [both of which were correlated among themselves: r 2 = 0.997,
p < 0.0001]), and with total sulfur content (r 2 = 0.850, p = 0.0322) across all temperatures and activation. The increase in
sorption capacity with pyrolysis temperature may be associated with precipitation of sulfate minerals as well as carbonates.
Zhang et al. (2017) reported high Pb sorption capacity of celery leaves and celery stem derived biochars (ranging from 188
mg g−1 to 304 mg g−1 ), attributing it to precipitation and formation of lead sulfate and carbonate minerals such as anglesite
 A. Hass, I.M. Lima / Environmental Technology & Innovation 10 (2018) 16–26 25

(PbSO4 ), hydrocerussite (2PbCO3 ·Pb(OH)2 ), and leadhillite Pb4 SO4 (CO3 )2 (OH)2 . They further evaluated the impact of the ash
phase on Pb sorption in a similar acid washing assay (as in the assay for Cu in our study) and found a 10-fold decrease in
biochar sorption capacity upon acid washing (Zhang et al., 2017).
Overall, previous findings support the trends found in this study suggesting that multiple and likely simultaneous
mechanisms are involved in metal removal from aqueous solution by biochars, the dominant of which depend on biochar
composition and solution chemistry. Inasmuch as we can only speculate on the mechanisms and solid phases involved in
the sorption process, and as much as correlation not necessarily implies on causation, biochar ash content seemed to play
a significant role in metal sorption by old, field-aged bagasse used in this study. Noteworthy, the similar ash content in the
fresh cane trash did not seem to affect metal sorption capacity by biochars of this feedstock as it did in the old bagasse.
This suggests that all ash (values) are not created equal and that such biochar property, although tempting, may not be
indicative, by itself, for biochar sorption capacity. It is very likely that the ash from the aged bagasse underwent partial
decomposition as it laid in a pile outside the sugar mill. As such, it represents different mineral form and metal composition
along a biochemical–geochemical weathering/decomposition continuum that affected the formation and composition of
biochar mineral phases. Further work is required to fully understand the role of feedstock mineral composition and pyrolysis
conditions on formation of biochar mineral phase and metal retention and solubility.

4. Summary and conclusions

This study summarizes physical and chemical properties and metal sorption capacity by biochars produced at different
temperatures (350, 500, 650, and 800 ◦ C) and with/out steam-activation made from sugarcane harvesting and processing
residues, including old field-aged bagasse, fresh cane trash and fresh bagasse. All non-activated biochars had low surface
areas (averaging 25 ± 30 m2 g−1 , across all feed sources and pyrolysis temperatures) and metal sorption capacities. Steam
activation increased biochar surface area by 10 to 100 fold, with that of fresh bagasse biochar (493 ± 27 m2 g−1 ) being some
2 fold higher than that of old bagasse (262 ± 15 m2 g−1 ), and fresh cane trash (204 ± 15 m2 g−1 ), across all production
temperatures. On the other hand, and while similar among themselves, ash content of old bagasse and fresh cane trash
steam activated biochars (59 ± 3%, and 62 ± 3%, respectively), were nearly three times higher than that of fresh bagasse
activated biochars (22 ± 7%). Cadmium sorption capacities by old bagasse activated biochar produced at 350 ◦ C and at
650 ◦ C were 10 times higher compared to fresh cane trash (63.8 mg g−1 vs. 6.29 mg g−1 , and 47.6 mg g−1 vs. 4.35 mg g−1 , all
respectively), which were some 10 times higher than fresh bagasse biochars (0.35 mg g−1 and 0.47 mg g−1 , for 350 and 650 ◦ C
fresh bagasse activated biochars, respectively). Copper sorption capacity by old bagasse biochars increased with pyrolysis
temperature and at 650 ◦ C was similar to that of 350 ◦ C activated biochar (39.8 mg g−1 and 40.5 mg g−1 , respectively), amid
much higher increase in biochar surface area (from 57.1 m2 g−1 to 284 m2 g−1 , respectively). Acid-washing of old bagasse
500 ◦ C activated and non-activated biochars decreased biochar ash content by some 33%, and reduced Cu sorption capacity
of activated biochar by more than 50%. Overall, Cd and Cu sorption were correlated with ash content and that of Pb with
surface area and S content. This study points out to the dominant role of feedstock mineral composition in biochar metal
sorption capacity and further research is needed to elucidate mechanisms.
The results of this study showed that partially decomposed, old bagasse biomass is preferred over fresh bagasse or fresh
cane trash feedstock in producing biochar for metal sorption purposes. Moreover, production temperature of 350 ◦ C followed
by steam activation was found to be optimal for maximizing biochar metal sorption capacity across the metals tested in this
study.

Acknowledgments

The authors would like to thank the following for their funding and support of this study: USDA ARS Faculty Research
Fellowships for Capacity Building at 1890 Land-Grant Universities, Project No. 6054-41000-110-10S, Accession No. 430309;
USDA McIntyre Stennis Cooperative Forestry Research Program, award No. 2016-32100-08919; to Renee Bigner and USDA
ARS SRRC staff for their technical support and assistant; and to Cora Texas Sugar Mill staff at White Castle, LA for providing
access and feedstock material for the study.

Appendix A. Supplementary data

Supplementary material related to this article can be found online at https://doi.org/10.1016/j.eti.2018.01.007.

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