Journal of Industrial and Engineering Chemistry 22 (2015) 103–109

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Journal of Industrial and Engineering Chemistry

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

Biochar from woody biomass for removing metal contaminants and

carbon sequestration
Tarek M. Abdel-Fattah a,*, Mohamed E. Mahmoud b, Somia B. Ahmed b, Matthew D. Huff c,
James W. Lee c, Sandeep Kumar d
a
Applied Research Center Thomas Jefferson National Accelerator Facility and Department of Molecular Biology and Chemistry, Christopher Newport
University, Newport News, VA 23606, USA
b
Faculty of Sciences, Chemistry Department, Alexandria University, P.O. Box 426, Alexandria 21321, Egypt
c
Department of Chemistry and Biochemistry, Old Dominion University, Norfolk, VA 23529, USA
d
Department of Civil and Environmental Engineering, Old Dominion University, Norfolk, VA 23529, USA

A R T I C L E I N F O A B S T R A C T

Article history: Biochar generated from pinewood via slow pyrolysis was studied for its viability as a soil amendment as
Received 2 December 2013 well as for its absorptive capacity for Mg, Ca, Cr, and Pb in solution. Cation exchange capacity (CEC)
Received in revised form 23 June 2014 measurements showed that the biochar sample has a CEC of roughly double that of the reference soil
Accepted 25 June 2014
sample. A high CEC value indicates that not only can the biochar sample be used as a carbon
Available online 2 July 2014
sequestration agent, but also as a valuable soil amendment for increasing a soil’s natural CEC. Biochar
was characterized using elemental analysis, SEM, BET surface area, FTIR, and XRF. These results showed
Keywords:
that biochar produced via slow pyrolysis possesses several highly beneficial attributes. The metal
Biochar
adsorption characteristics of biochar were studied in presence of various controlling parameters such as
Carbon sequestration
Cation exchange capacity pH, contact time, adsorbent dosage, and interfering species. The results confirmed excellent adsorption
Adsortption capacity values of the biochar for Mg(II), Ca(II), Cr(VI), and Pb(II) by producing 440 (pH 7.0), 120 (pH 7.0),
Isotherm 680 (pH 1.0), and 520 (pH 6.0) mmol g1, respectively. The potential applications of the biochar for
Metal ions. removal of these four metal ions from real water samples were also studied and evaluated.
ß 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Introduction of metal contaminants via adsorption, it is not as ubiquitous as it

might be due to the high cost of production [12].
Much interest has been focused on biochar in an effort to With the recent rapid development of biofuels sector, a greater
provide a means for effective carbon sequestration and environ- interest has been placed into the development of a low cost, yet
mental management. Biochar is defined here as the non-liquefied effective, alternative to activated carbon through the use of biochar
carbonaceous solid product resulting from the thermal decompo- for the removal of heavy metals from aqueous solutions [13]. In
sition of biomass. Biochar has been extensively studied for its recent years, government agencies have sponsored numerous
application in soils as both a beneficial soil amendment in terms of studies and demonstrated projects focusing on the development of
increasing cation exchange, and also as a long term carbon non-food biomass (lignocellulosic) resources to biofuels [14].
sequestration agent. It is also known that biochar helps retain plant During the conversion of lignocellulosic biomass to biofuels,
nutrients that would have otherwise been lost by runoff, which biochar is one of the byproducts recovered at the end of bioenergy
helps maintaining water quality [1]. Several recent studies have cycle. Essentially, all forms of biomass (e.g. forest residue,
been shown that biochar can have high adsorption potential for herbaceous grasses, agricultural residues, food waste, manure,
heavy metals in solution [2–11]. While the use of activated carbon and paper sludge) can be converted to biochar. The effective use of
is well known and has been shown to be very effective at removal biochar for contaminant remediation would enhance the goal of
the green processes by providing opportunity to the long-term
storage of carbon in soil. Historically, biochar has been used for soil
* Corresponding author. Tel.: +1 757 594 7606. amendment. Moreover, biochar helps in improving the water
E-mail address: [email protected] (T.M. Abdel-Fattah). quality by the retention of nutrients and agrochemicals and retards

http://dx.doi.org/10.1016/j.jiec.2014.06.030
1226-086X/ß 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
104 T.M. Abdel-Fattah et al. / Journal of Industrial and Engineering Chemistry 22 (2015) 103–109

the leaching of nutrients from soil, which is one of the causes of is heated for an extended period of time at moderate temperatures
groundwater pollution [1,15]. (400–500 8C) in the absence of oxygen. This paper uses slow
The porous structure, aromatic surface, and the presence of pryrolysis process to produce biochar from pinewood. Biochar was
oxygen functional groups on biochar surface play a crucial role in used to remove a suit of metal contaminants such as Ca, Mg, Cr(VI),
trapping the metal contaminants. These properties provide an and Pb from aqueous solution. Ca and Mg species were studied due
excellent opportunity to adsorb heavy metal ions from the aqueous to their importance in water softening. Cr(VI) and Pb were of
solution [16–18]. Generally, the raw biomass has lower adsorption particular interest and consider rephrasing it for clarity.due to their
capacity. By the esterification of spent grain, the adsorption abundance in wastewater streams, and the effect of biochar can
capacity of spent grain for heavy metal ions (Cu2+, Pb2+, Zn2+, Cd2+, have at mitigating their deleterious effects [42]. The biomass used
and Ag+) was enhanced substantially. The improvements were in this study was woody yard waste, predominately consisting of
mainly due to the formation of ester linkages and grafting of pine branches. The primary objective of this study was to evaluate
carboxyl groups on the spent grain [19]. Heavy metal ions biochar produced via slow pyrolysis for carbon sequestration
particularly at low ion concentration have been reported to adsorb applications and as an absorbent for a suit of metal contaminants.
to raw biomass (e.g. peat, poplar sawdust, and coconut shell) Cation exchange capacity measurements evaluated the biochars
[20,21]. But, the use of raw biomass as an adsorbent has associated usefulness as a soil amendment, and elemental analysis provides
risk of leaching of organic material, affect redox conditions, and some idea of the half-life of the biochar in soil as its use as a long
metal mobilization [5]. Biochar, a refractory organic adsorbent, is term carbon sequestration agent. Batch adsorption studies
useful in avoiding such risks. Besides being free of toxic or provided the insight as the usefulness of biochar in the treatment
carcinogenic compounds, the carbonaceous material is also water- of wastewater with the removal of unwanted metal species. In
wettable. Sorption properties of biochar depend on the method of order to gain a detail understanding of the characteristics of the
its production and also on the starting material. biochar, SEM imaging, BET surface analysis, FTIR, and XRF data
Earlier studies have reported on the use of biochar for removing were studied.
metal contaminants such as lead, mercury, and arsenic from
aqueous solution [22–24]. Biochar derived from dairy manure was Methods and materials
reported to sorb both heavy metals and organics [25]. The lead
adsorption on the biochars was strongly influenced by the solution Materials
pH which is consistent with sorption to surface hydroxyl groups
[26,27]. The adsorption process was a physical endothermic Biochar was prepared using pinewood branches collected locally
process, where irregular surface and oxygen containing groups (without drying) in a custom made oil-drum slow pyrolyzer. The
(carboxyl, lactone, and hydroxyl groups) proved to be beneficial [5]. pyrolyzer consisted of an oil-drum which had been modified to
Biochar produced at high temperature have benefits of high pH, allow for the release of gases generated during the process. The oil-
CEC, and surface area [28]. The higher oxygen content (>20%) in drum was placed in a rectangular cinder block structure which was
biochar produced at lower temperature indicates that the availability then covered with an insulated sheet metal roof with a chimney
of more actives sites and existence of stable carbon–oxygen complex attachment. Fig. 1 shows a photograph of the pyrolyzer prior to
in biochar [3]. The presence of oxygen groups on the surfaces adds synthesis. The biomass was placed inside the oil-drum and then
substantial CEC which can substantially affect soil biogeochemical sealed, ensuring for limited oxygen exposure. Additional biomass
processes. Biochar amended soil was reported to have 5–20% higher was then placed around the reactor and lit on fire, which provided
CEC during a 500 day soil column leaching/incubation study [29]. The the heat for the conversion process. The reactor was then heated by
carboxylic groups available and also formed over time on the surface the biomass until the biomass was consumed over the course of 2 h.
of biochar increased its nutrient holding capacity as well as reduced Once pyrolyzer had cooled, it was opened and the biochar was
leaching of pollutants such as dissolved phosphate and nitrate into collected. The collected biochar samples were then ground and
groundwater and other bodies [30]. sieved (<420 mm) for further analysis.
Biomass pyrolysis with utilization of biochar as a soil The reference soil sample was autoclaved at 120oC for 30 min
amendment is a potentially significant approach for renewable prior to analysis. Additional information pertaining to the soil
energy production and for carbon sequestration at giga tons of sample can be located in the supporting data. All chemicals used in
carbon (GtC) scales. This approach, which was co-initiated by this work were purchased from Aldrich Chemical Company, USA.
Danny Day of Eprida Inc. and one of us (Lee) through a 2002 U.S. Aqueous solutions (0.1 M) of metal ions were prepared in 1.0 L by
provisional patent application followed by a PCT international dissolving the corresponding mass of their salts; lead acetate
patent application, has received some recognition worldwide [31– trihydrate Pb(CH3COO)23H2O (37.93 g), magnesium sulphate
35], especially since certain biochar-related soil research results heptahydrate MgSO47H2O (24.64 g), anhydrous calcium chloride
have also indicated the possibility of using biochar as a soil [(Fig._1)TD$IG] 2 (11.09 g), and sodium chromate tetrahydrate Na2CrO44H2O
CaCl
amendment for carbon sequestration [36–40]. Recently, the
approach of biochar soil application has been discussed at the
United Nations Framework Convention on Climate Change
(UNFCCC) for possible consideration as a potential climate
mitigation technology in accounting carbon credit (International
Biochar Initiative). However, significantly more study is needed
before this approach can be considered for commercial imple-
mentation [41]. One of the R&D needs is to further the scientific
understanding of biochar material physical chemistry with respect
to specific biomass and pyrolysis conditions in relation to the
envisioned mission of biochar soil application and carbon
sequestration to help control climate change.
The conversion of biomass to biochar can be accomplished in
several ways including slow pyrolysis, flash pyrolysis, and
hydrothermal conversion. Slow pyrolysis occurs when biomass Fig. 1. Modified drum type slow pyrolyzer.
 T.M. Abdel-Fattah et al. / Journal of Industrial and Engineering Chemistry 22 (2015) 103–109 105

(23.40 g). The accurate concentrations of these metal ion solutions This mixture was shaken by using an automatic shaker for 30 min,
were determined by complexometric titration with standard EDTA filtered, and washed with 50 mL distilled water. The residual metal
solution (0.01 M) using the appropriate buffer and indicator and/or ion in the filtrate was determined by EDTA titrations and each
atomic absorption analysis. Adjusted acidic and buffer solutions experiment was repeated three times.
(pH 1.0–7.0) were prepared by mixing the appropriate volumes of
1.0 M hydrochloric acid solution and 1.0 M sodium acetate Effect of contact time
trihydrate solution and diluting to 1 L with distilled water and The previously mentioned batch experiment procedure was
the pH-values were adjusted by using the pH-meter. carried out at different shaking time (1, 5, 10, 15, 20, 25, and
30 min) at optimum buffering conditions of each metal biosorp-
Product characterization tion. A 1.0 mL of 0.1 mol L1 metal ion solution was mixed with
50  1 mg of the dry biosorbent and the pH value of this mixture was
Elemental analysis adjusted by adding 9.0 mL of the optimum buffer for each metal ion
Elemental analysis was performed in triplicate, utilizing a CE [47,48]. This mixture was shaken for the selected period of time,
instruments Flash EA1112. Ash content was measured in duplicate filtered, and washed with 50 mL distilled water. The residual metal
via standard procedure provided by National Renewable Energy ion was determined as described above.
Laboratory (NREL) Technical report NREL/TP-510-42622. Moisture
content of the sample was measured at 105 8C by an IR 35 Denver Effect of dosage
Instrument. Similar batch experiments were carried out by using different
biochar dosages, viz. 10.0, 20.0, 30.0, 40.0, and 50.0 mg. The
SEM analysis selected mass was mixed with 1.0 mL of 0.1 mol L1 metal ion
For SEM analysis the biochar sample was placed onto adhesive solution and 9.0 mL of the optimum buffer solution for each metal
carbon tape on an aluminum stub and then coated by a sputter of ion. The sorption mixture was then shaken for 30 min and the
gold. Surface morphology of the sample was then studied using a residual metal ion was determined by EDTA titration [49].
JEOL JSM-6060 LV scanning electron microscopy system.
Effect of initial metal concentration
BET surface area measurement Sorption equilibrium and isotherm studies were evaluated for
BET surface analysis was carried out using a Nova 2200e surface metal ions by varying the initial metal ion concentration. A 1.0 mL
area and pore analyzer (Quantichrome Instruments). The sample solution of 0.01, 0.025, 0.05, 0.1, 0.25, and 0.5 mol L1 metal ion
was degassed at 70 8C for 10 h prior to analysis. Nitrogen was used was used. This solution was mixed with 9.0 mL of the optimum
as the adsorptive gas at 77 K. buffer solution and 50  1 mg of the dry sorbent and shaken for
30 min. The mixture was filtered, washed and the residual metal ion
FTIR analysis concentration was determined by EDTA titrations as described in
Infrared spectra were recorded using a Shimadzu IRPrestige-21 ‘‘Effect of pH’’ section.
FTIR spectrophotometer equipped with ZnSe trough ATR attach-
ment. Spectra were collected over 256 scans, at a resolution of Effect of interfering ion
4 cm1, and over a range of 750–4000 cm1. Removal of metal ions was investigated in presence of other
competing ions with equi-molar concentration. The examined
CEC Analysis solution was prepared by mixing a 1.0 mL of 0.1 mol L1 solution of
CEC refers to the amount of exchangeable cations bound to a the selected metal ion with a 1.0 mL of 0.1 mol L1 of an interfering
sample. CEC is normally reported as molar equivalents of monova- ion. This solution was then mixed with 8.0 mL of optimum pH in a
lent cations per weight of sample. In this study, a modified version of volumetric flask containing 50  1 mg of the dry biosorbent. The
a compulsive barium chloride exchange protocol was used in order mixture was shaken for 30 min, filtered, and washed with 50 mL of
to determine the CEC over a range of pH values [43]. The assay was distilled water. The residual metal content was determined by atomic
performed in duplicate at room temperature for both biochar and absorption spectrophotometer [50,51].
reference soil samples. Aliquots of 0.5 g samples of biochar were
placed into 50 mL centrifuge tubes and subsequently treated with Potential applications of biochar material for removal of metal ions
barium chloride solutions for loading. The initial CEC measurement from real water samples
was taken at a pH of 8.5, at which point the sample is treated with an Real samples of drinking water, sea water, and leather tanning
addition of 0.01 M H2SO4 in order to lower the pH by half units. CEC wastewater were collected and utilized to evaluate the potential
measurements were made at each half pH unit interval. A full applications of biochar material for removal of the examined metal
explanation for the calculation of CEC can be found in the ions. Each sample was first analyzed for the metal content then
supplemental material of the cited resource [44]. either spiked or passed directly into a microcolumn packed with
the biochar material. One liter of each sample was passed
XRF analysis throughout a multi-stages micro-column packed with
X-ray fluorescence (XRF) spectroscopy was performed using a 100  1 mg of the dry biochar under constant flow rate
Bruker S4 Pioneer to determine the elemental composition of the (10 mL min1). The effluent was collected, analyzed to determine
samples. the metal concentrations using atomic absorption analysis. The
percentage extraction of each metal was then calculated [52,53].
Batch adsorption studies
Results and discussion
Effect of pH
All batch sorption experiments were carried out at room Physio-chemical properties
temperature (25  1 8C). Each experiment was performed in a 50 mL
volumetric flask by mixing a 1.0 mL of 0.1 mol L1 metal ion solution Table 1 shows the results for the elemental analysis and ash
with 50  1 mg of the dry sorbent and the pH value of this mixture content assays. The elemental analysis revealed that high amounts
was adjusted by adding 9.0 mL of buffer solution (pH 1.0–7.0) [45,46]. of carbon and oxygen in the biochar. The calculated O/C mol ratio is
106 [(Fig._3)TD$IG]
T.M. Abdel-Fattah et al. / Journal of Industrial and Engineering Chemistry 22 (2015) 103–109

Table 1
Elemental analysis and ash content (wt%) of biochar.

Elements C N H O Ash

Biochar 66.54 0.0 0.96 17.19 18.31

0.19, which gives some idea about the stability of the biochar in the
soil [54]. In general, biochars with an O/C mol ratio above 0.2 have
half lives in soil between 100–1000 years, while biochars with an
O/C mol ratio below 0.2 have half lives in soil longer than 1000
years. This biochar sample therefore lies on the edge of being
classified as having very long term soil stability The ash content of
the biochar is also relatively high, at 18.31 wt%. Ash content is
Fig. 3. FTIR spectra of biochar sample.
important when considering the usage of biochar as soil
[(Fig._4)TD$IG]
amendments for agronomic purposes. Ash content represents
inorganic nutrients vital to plant growth. Conversely, higher ash
content means that competing ions are present in the biochar
sample, which must be considered in the application of biochar for
the removal of metal contaminants.
Fig. 2 shows the SEM images of the biochar samples at two
different magnifications. These images are representative of the
porous structure of the biochar sample. Large channel-like
structures proliferate the surface of the biochar, showing at least
partial retention of the morphology of the initial input biomass.
The porous structure of the biochar is created during pyrolysis by
the production of volatile matter. As the matter escapes, pores and
cracks begin to appear on the surface of the biochar. BET surface
analysis was relatively low (4.587 m2/g). Cumulative surface pore
volume was found to be 0.0119 mL/g, and pore diameter to be
Fig. 4. CEC of biochar and reference soil samples.
62.56 Å, which indicates that the surface has micropores in high
abundance.
Fig. 3 shows the FTIR spectra of the biochar sample. The spectra biochar as an amendment into various soils with inherently varied
suggest the presence of a variety of oxygen functional groups, as native pH values. The high CEC of the sample can be attributed to the
well as aromatic carbon groups. Strong peaks which are high amount of retained oxygen content, as previously published
representative of aromatic C5 5O and C5 5C functional groups at [44]. Higher retained oxygen content presents itself on the biochar as
1400 cm1 as well as a peak at 875 cm1 which correlates with primarily carbonyl, carboxyl, and phenolic groups, all of which in part
aromatic C–H stretching [55]. A wide band of intensity from 1115 facilitate CEC through electrostatic interactions. Furthermore, this
to 1215 cm1 shows aromatic C–O and phenolic O–H functional data shows that the biochar sample has the capability of not only
groups. The spectrum correlates well with the elemental analysis, serving as a long-term carbon sequestration agent, but also has the
which also revealed a relatively high amount of retained oxygen potential to increase soil CEC. Table 2 shows the % inorganic
content. composition of the biochar sample. The large % (27.7) of calcium oxide
CEC and its dependence over a pH range from 5.0 to 8.5 is shown indicates that the biochar can be a valuable soil additive for improving
in Fig. 4. The results show that the biochar synthesized has a the soil’s properties (e.g. neutralizing soil acidity).
relatively high CEC, at 33.048  2.246 cmol kg1 at a pH of 8.5,
which is more than double that of the reference soil at the same pH Sorption studies
(15.328  0.361). These results also reveal that the biochar retains a
high CEC relative to the soil sample over the entire pH range of the Four metal ions, Mg(II), Ca(II), Pb(II), and Cr(VI), were selected
assay. This CEC over such a range of pH is important when considering to study and evaluate the performance of biochar material as
[(Fig._2)TD$IG]

Fig. 2. SEM images of biochar sample at (a) 1500 and (b) 5000 magnifications.
 T.M. Abdel-Fattah et al. / Journal of Industrial and Engineering Chemistry 22 (2015) 103–109 107

Table 2 Table 4
XRF analysis of biochar. Effect of contact time on the mmol g1 and percent extraction values.

Formula Concentration (%) Time (min) Metal sorption capacity in mmol g1 (%)

CaO 27.70 Mg(II) Ca(II) Pb(II) Cr(VI)

K2O 1.87
1 340 (77%) 40 (33%) 140 (27%) 340 (50%)
Fe2O3 1.60
5 360 (82%) 80 (67%) 260 (50%) 480 (71%)
P2O5 0.75
10 360 (82%) 80 (67%) 300 (58%) 600 (91%)
SiO2 0.60
15 360 (82%) 120 (100%) 440 (85%) 660 (97%)
MgO 0.59
20 360 (82%) 120 (100%) 480 (92%) 680 (100%)
MnO 0.36
25 400 (91%) 120 (100%) 520 (100%) 680 (100%)
SrO 0.30
30 440 (100%) 120 (100%) 520 (100%) 680 (100%)
SO3 0.22
Na2O 0.10
BaO 0.07
Al2O3 0.06 Pb(II), and Cr(VI) were characterized to establish 100% extraction at
MoO3 0.05 equilibration time of 15, 25, and 20 min, respectively. Thus, one can
Cl 0.04 conclude from this study that the interaction between biochar
TiO2 0.03
material and heavy metal ions is very fast.
CuO 0.02
ZnO 0.02 The effect of biochar dosage, as an important controlling factor,
on the extraction and removal processes of Mg(II), Ca(II), Pb(II), and
Cr(VI) was also examined by the batch equilibrium technique and
at the optimum buffer condition of each examined metal ion. The
efficient sorbent. The metal uptake properties were investigated mass of biochar was taken in the range of 0.025–0.250 g and the
under the influence of various controlling factors such as the effect results of this study are listed in Table 5. It is evident that the
of pH of metal ion, reaction contact time, biochar dosage, initial maximum values of metal uptake in mmol g1 were detected by
metal ion concentration, and interfering species. using 0.025 g for all metal ions. This behavior may be due to the
The effect of pH of metal ion solutions on the sorption capacity availability of a high number of metal ions compared to the
values of Mg(II), Ca(II), Pb(II), and Cr(VI) was reformed by using pH exposed surface functional groups on the biochar material. A
1.0–7.0 and the results of this study are compiled in Table 3. A general trend of gradual decrease in the mmol g1 metal sorption
gradual increase in the metal sorption capacity values (mmol g1) capacity values upon increasing the sorbent dosage was also
was found upon increasing the pH value of contact solution from observed in Table 5. The minimum values of metal extraction were
1.0 to 7.0 in the case of Mg(II) and Ca(II). The optimum pH values obtained when 0.250 g of biochar was used. In this case, a great
for maximum extraction of Mg(II), Ca(II), and Pb(II) were identified number of sorbent functional groups are available compared to the
as 7.0, 7.0, and 6.0, respectively. In higher pH (6.0–7.0) values, the number of interacting metal ions.
degree of surface protonation of adsorbent material is minimal and The effect of interfering anions and cations in the extraction
this condition allows more and strong binding capability between processes of Mg(II), Ca(II), Pb(II), and Cr(VI) by the biochar material
the target metal ions and the surface functional groups. In addition, was also studied and the results are outlined in Table 6. NaCl,
a good possibility of complex formation between oxygen donor K2SO4, and KNO3 were not characterized by strong interference.
atoms in the form of surface C5 5O, C–O, and phenolic O–H However, CaCl2 was found to highly interfere in the extraction
functional groups with the interacting metal ions such as Mg(II), process of Mg(II) and MgSO4 was identified to highly contribute to
Ca(II), and Pb(II). However, Cr(VI) was found to behave differently
by producing its maximum adsorption capacity value as
680 mmol g1 in acidic pH 1.0. In such low pH value, the surface Table 5
Effect of biochar dosage on the metal sorption values.
of adsorbent is known to be highly protonated and this condition
favors the possible formation of ion-pair interaction mechanism Mass (g) Metal sorption capacity in mmol g1
between the positively charged  functional
 groups and the Mg(II) Ca(II) Pb(II) Cr(VI)
negatively charged chromate CrO2 4 ion.
0.025 440 120 520 680
The effect of shaking time on the metal sorption capacity values
0.050 320 90 310 500
and the percent extraction of Mg(II), Ca(II), Pb(II), and Cr(VI) was also 0.100 270 60 180 300
studied by using the batch equilibrium technique in the optimum pH 0.150 233 47 140 213
7.0, 7.0, 6.0, and 1.0, respectively. The results of this study are listed in 0.200 193 40 100 185
0.250 160 32 80 140
Table 4 and indicate that Mg(II) was highly extracted by the biochar
material after only 1 min of contact time and was identified to
produce 77% extraction. However, a complete extraction of Mg(II)
was obtained after 30 min of contact time. On the other hand, Ca(II), Table 6
Effect of interfering ions on the mmol g1 capacity values.

Table 3 Interfering ion Metal sorption capacity in mmol g1

Effect of pH on the metal sorption capacity values of various metal ions. Mg(II) Ca(II) Pb(II) Cr(VI)

pH Metal sorption capacity in mmol g1 NaCl 400 200 540 615
K2SO4 400 120 480 –
Mg(II) Ca(II) Pb(II) Cr(VI)
KNO3 – – – 688
1 0 0 280 680 NH4Cl 440 120 – 680
2 80 0 280 660 CaCl2 224 – – –
3 200 20 320 520 MgSO4 – 62 – –
4 260 40 400 360 CoCl2 – – 428 –
5 320 40 500 280 NiCl2 – – 435 –
6 420 60 520 120 CuCl2 – – 299 –
7 440 120 500 80 CrCl3 – – – 200
108 T.M. Abdel-Fattah et al. / Journal of Industrial and Engineering Chemistry 22 (2015) 103–109

Table 7
Potential applications of biochar for adsorptive removal of various metal ions from real water matrices.

Sample Metal ion Spiked or First Second Third

detected (mg L1) run (%) run (%) run (%)

Tap water Mg(II) 40.3 (detected) 40.0 68.0 85.1

Ca(II) 80.0 (detected) 44.11 62.5 80.0
Pb(II) 2.0 (spiked) 91.6 – –

Sea water Mg(II) 1250.0 (detected) 55.7 76.5 86.8

Ca(II) 399.00 (detected) 19.8 40.0 71.2
Pb(II) 2.5 (spiked) 55.7 76.5 71.0
Cr(VI) 2.7 (spiked) 70.0 75.0 83.0

Leather tanning wastewater Cr(VI) 2.6 (detected) 76.0 81.0 84.0

the removal of Ca(II) by the biochar. CuCl2 was found to exhibit Ms. Doris Hamill (NASA Langley Center) and the friends at City of
high interference in the extraction process of Pb(II) as compared to Hampton Master Gardeners for arranging the slow pyrolysis
NaCl, K2SO4, CoCl2, and NiCl2 as listed in Table 6. In the case of demonstration at Hampton, VA and sharing the part of biochar for
Cr(VI), only CrCl3 was found to exhibit high interference. this research study. This research was also supported, in part, by
Extraction and adsorptive removal of Mg(II), Ca(II), Pb(II), and the 2013 Old Dominion University Multidisciplinary Seed Funding
Cr(VI) from real water samples such as drinking water, sea water, Program (Grant No. 533571) (Lee and Kumar). The authors would
and leather tanning wastewater were performed by using a also like to extend our thanks to Drs. Richard Gregory, Thomas
multistage microcolumn technique [45–49]. The results of this Sprinkle, and Wei Cao Applied Research Center at Old Dominion for
study are listed in Table 7 and show the percent extraction values their assistance in obtaining FT-IR spectra and SEM images.
after each step. The real concentrations of metal ions in the
selected water samples were determined before running on the
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