Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467

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Journal of the Taiwan Institute of Chemical Engineers

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

Efficient removal of lead from aqueous solution by urea-functionalized

magnetic biochar: Preparation, characterization and mechanism study
Xiaohui Zhou, Yaochi Liu∗, Jianjun Zhou, Jing Guo, Jialin Ren, Fang Zhou
College of Chemistry and Chemical Engineering, Central South University, 410083 Changsha, China

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

Article history: A novel urea-functionalized magnetic biochar (MBCU) was prepared, characterized and evaluated for re-
Received 3 February 2018 moval of lead (II) from aqueous solution. The results of SEM, BET, XPS, FTIR, VSM and Zeta-potential
Revised 8 April 2018
exhibited a successful fabrication of MBCU. The magnetism magnitude of magnetic biochar could si-
Accepted 13 April 2018
multaneously affect the adsorption and recovery efficiency of lead (II) on magnetic biochar. Hence, the
Available online 5 July 2018
optimum mass ratio range of MBCU was determined to be 1.7:1–2.3:1, which could guarantee high re-
Keywords: moval (> 73.14%) and recovery (> 78.35%) efficiency. The experimental results indicated that the adsorp-
Magnetic biochar tion isotherm and kinetics were well described by the Sips model and pseudo-second-order model, re-
Separation spectively. The maximum adsorption capacity of lead (II) on MBCU was 188.18 mg/g at 323 K. Five-cycle
Modification reusability tests demonstrated MBCU could be effectively recovered and repeatedly used with a small
Palm fiber adsorption loss (< 20%). Mechanism study demonstrated that the adsorption process involved in elec-
Lead (II)
trostatic interaction, ion exchange and complexation. The unique features of its outstanding adsorption
performance, reusability and separation efficiency suggested that the magnetic biochar can be potentially
applied in elimination of lead (II) from wastewater.
© 2018 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction terials have been designed and conducted as adsorbents to elim-

inate lead from wastewater in both academic research and in-
Due to the rapid development of industrialization, water pol- dustrial application [12]. While the activated carbon, ion-exchange
lution by heavy metals is a global issue owing to its high toxi- resins, natural clay has impeded the wide application of adsorption
city, carcinogenicity, wide sources and non-biodegradable proper- owing to its expensive produce cost [13,14]. Biochar is black carbon
ties. Most seriously, it can cause continuous threat to the envi- which is the pyrolytic product of biomass under oxygen-limited
ronment and human health and has become more serious than condition. Biochar, as adsorbent, has been received increasing in-
ever before [1,2]. Among these heavy metals, lead deserves spe- terest because of its several potential environmental applications
cial attention, because it’s highly toxic to human beings even in in soil amendment, carbon sequestration and contaminant reme-
small quantity [3]. Lead can be easily accumulated in various in- diation [15,16]. Biochar could immobilize many kinds of contami-
dustrial wastewaters, then assimilated and concentrated in body nants including organic pollutants and heavy metals [17,18]. Hence,
system, causing anaemia, chills, diarrhea and dysfunction of the biochar shows a great potential in the wastewater treatment.
kidney [4,5]. Removal lead from aqueous environments is impor- However, the powered biochars are difficult to be separated
tant and urgent to ensure purified and recycled water. from the aqueous solution due to the small particle sizes and lower
Several methods for lead removal from wastewater have been density, which restricts its further practical industrial application
investigated, including chemical precipitation [6], ion exchange [7], in the wastewater treatment process. A system which can capture
filtration [8], electroplating [9], reverse osmosis [10], and adsorp- the heavy metal ions with great competence and then to isolate
tion [11]. Among these methods, adsorption has been considered to them out with ease is essential [19]. Maybe the magnetic biochar
be the most promising one because of its easy operation, high ef- could achieve the goal. Introducing magnetic compounds to the
ficiency and low cost, which can be used for removal lead at a low biochar enables the magnetic biochar to be effectively separated
content. The widely successful application of adsorption largely de- by magnetic separating technique. It is well known that Fe3 O4
pends on the efficient development of adsorbent, thus diverse ma- process rapidly magnetic responsibility when the external mag-
netic field is applied. However, the magnetization of the biochar
partially reduced its heavy metal adsorption efficiency due to the
∗
Corresponding author.
biochar’s surface pores becoming plugged with iron oxide parti-
E-mail address: liuyaochi72@163.com (Y. Liu). cles. In literatures, many efforts have been devoted to removing

https://doi.org/10.1016/j.jtice.2018.04.018
1876-1070/© 2018 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
458 X. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467

contaminates from aqueous solution by magnetic biochars, which washed with distilled water several times, dried at 323 K for 12 h
was fabricated from various raw materials. For example, the mag- and then stored in polyethylene bag.
netic biochar derived from peanut hull was applied to eliminate
chromium (VI) from wastewater [20]. The waste marine macro- 2.3. Fabrication of magnetic biochar (MBCU)
algal biomass was used as the precursor to fabricate magnetic
biochar for removal cadmium, copper and zinc [21]. But the appli- The pretreated palm fiber was converted into biochar by pyrol-
cation of palm fiber biochar remains limited. The widespread and ysis in a muffle furnace at 400 °C with a heating rate of 10 °C/min
low-cost palm fiber is a common nature vegetable fiber with large under the protection of N2 for 2 h. The pristine biochar was re-
elastic modulus, high strength, highly developed porous and regen- ferred to as BC.
erative nature. Hence, the palm fiber may be the ideal resource to The method to synthesize the magnetic biochar (MBC) was
produce biochar. Lu et al. has testified the pristine biochar for re- based on the previous study by Zhou [24] and it was amended
moval of lead, but achieved adsorption capacity is still unsatisfac- and optimized in this study. As shown in Scheme 1, the procedure
tory [22]. Thus the functional modification of biochar is required was as follows: A certain mass ratio of biochar and Fe3 O4 nano-
to improve the adsorption capacity and selectivity [23]. The urea particles were mixed in 100 mL distilled water and then 5.0 mL
NH2 CONH2 is extensively found in natural products and is an at- of 3-Triethoxysilylpropylamine (TSA) was later added to the solu-
tractive functional moiety. The groups-nitrogen and oxygen of urea tion. The mixture was stirred in an oil bath for 8 h at 323 K. The
can offer multitude of bonding potentials owing to its electron pair, magnetic biochar named as MBC was subsequently washed with
which plays a key role in adsorption of heavy metals. ethanol and distilled water several times after being separated by
To overcome the aforesaid challenges, we prepared a novel a magnet.
magnetic palm fiber biochar via magnetic and functional modifi- Next, 4 mL epichlorohydrin (EC) was dissolved in 100 mL mixed
cation for elimination of lead (II) in aqueous solution. The biochar solvent with acetone/distilled water (V:V = 1:1)solution and 2.0 g
derived from palm fiber was used as the support to load Fe3 O4 of MBC was later added to the media for cross-linking, the mix-
nano-particles on the surface, then the composites were coated a ture was constantly stirred for 12 h in an oil bath at 303 K. Then,
layer of 3-Triethoxysilylpropylamine, which could immobilize the 4.0 g of urea and 50 mL of 1 mol/L NaOH were added into mixture
Fe3 O4 nano-particles sites on the surface of biochar. In order to fur- and stirred in an oil bath at 333 K for 12 h. After being separated
ther increase the adsorption sites and selectivity to lead, the mag- with magnet, the materials were subsequently washed with ace-
netic biochar was modified with urea containing amino groups. tone, ethanol and distilled water and finally oven-dried for 24 h at
The magnetic modified biochar was characterized by SEM, BET, 323 K. The resulting biochar sample was referred as MBCU.
FTIR, XPS, VSM and Zeta potential. The effects of pH, contact time,
and initial concentration of lead on the removal of lead (II) from 2.4. Characterization of biochar
the aqueous solution by the magnetic biochar were investigated.
This work will provide an alternately low cost, high adsorption The surface morphologies of the biochars were analyzed by
and separation efficiency adsorbent for detoxification of lead from scanning electron microscopy measurement (JSM-6360LV, Japan).
wastewater. The functional groups of biochars before and after modification
were measured by a Fourier transform infrared (FTIR) spectroscopy
(Nicolet 6700, USA) using the KBr pellet technique and were exam-
2. Experimental and methods
ined in the 40 0 0–40 0/cm region. The BET surface area (SBET , m2 /g),
total pore volume (VT , m3 /g) and average diameter (Dp , nm) for
2.1. Chemicals and material
the investigated biochar were determined through N2 adsorption/
desorption isotherms at 77 K using a surface area analyzer (Gemini
FeSO4 •7H2 O and FeCl3 •6H2 O were purchased from Sinopharm
Ⅶ2390, USA). The surface chemical composition was confirmed by
Chemical reagent Company. 3-Triethoxysilylpropylamine (TSA),
the X-ray Photoelectron Spectroscopy (ESCALAB 250Xi, USA). The
epichlorohydrin (EC), urea and other chemicals were purchased
Zeta potential was measured at different pH using a Zeta potential
from Honghua Reagent Co. Ltd. (Changsha, China). Lead (II) stock
analyzer (JS94H, China). Magnetic property of the MBCU was de-
solution (500 mg/L) was prepared by dissolving lead nitrate in dis-
termined by magnetization curve using the vibrating sample mag-
tilled water and then diluted to appropriate concentrations. All the
netometer (Lake Shore 7404, USA).
chemicals used in this study were of analytical grade, and dis-
tilled water (18.2 M, 25 °C) from a Milli-Q plus purification sys-
2.5. Batch sorption equilibrium experiments
tem (Millipore) was utilized throughout the experiments for solu-
tion preparation and glassware cleaning. About 50 g of palm fiber
Batch experiments were conducted to examine the adsorption
was purchased from a local market, which is shaped with broom,
efficiency of BC, MBC and MBCU for removal lead (II) from aque-
cut into about 0.5 cm filaments, thoroughly washed with tap water
ous solution. Generally, a certain amount of biochar was mixed
to clear the dust and other adhering impurities, soaked in 10 0 0 mL
with lead (II) solution in a flask. Then the mixture was shaken in
of 1 mol/L NaOH for 12 h, washed with distilled water for several
a thermostatic shaker at 160 rpm at the investigated temperature
times and then dried at 323 K.
for 24 h. After that, the separated solution was drawn out for ab-
sorbance measurement with a UV–vis spectrophotometer (UV759S,
2.2. Preparation of Fe3 O4 nano-particles China).
MBCU adsorbent was used to study the dosage effects on lead
Fe3 O4 nano-particles were prepared by chemical co- removal. The pH values of solution ranging from 2.0 to 8.0 were
precipitation of in Fe3+ /Fe2+ solution. Typically, 2.3967 g of adjusted by 0.01 mol/L HCl and 0.01 mol/L NaOH solution. The
FeSO4 •7H2 O and 4.6634 g of FeCl3 •6H2 O were dissolved in 150 mL equilibrium adsorption isotherms for lead on MBCU were deter-
of distilled water in a flask. The mixture was stirred for 30 min mined using 0.0400 g biochar with 40 ml lead solutions of differ-
under the protection of N2 , then 28%NH3 •H2 O was gradually ent concentrations ranging from 25 to 300 mg/L in a batch of con-
added in the flask, until the pH of the mixture was around 10.0. ical vessels. The adsorption kinetic experiments were conducted at
The suspension was vigorously stirred in an oil bath for 5 h at different time intervals, ranging from 5 to 120 min, with 100 mg/L
353 K. The black precipitate was collected by a magnet and then lead solution at pH 6.5.
 X. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467 459

Scheme 1. The systemic procedure of the magnetic biochar of MBCU.

In order to assess the reusability of the magnetic biochar, functional modification in MBCO, which suggested that the surface
adsorption-desorption experiments were conducted. MBCU with morphology of MBC was hardly influenced by the functional mod-
adsorbed lead was treated by 0.1 mol/L Na2 EDTA for 1 h and ification.
rinsed with distilled water for three times. Afterwards, the des-
orbed biochar was rinsed, dried and added to lead solution 3.1.2. Surface functional groups
(100 mg/L, 40 mL) in a flask again and the experimental condition The surface functional groups are the main chemical factor of
and measurements were the same as adsorption. The adsorption- biochars that affect the heavy metal adsorption. Fig. 2 showed the
desorption process was repeated six cycles. The equilibrium ad- FTIR spectra of BC, MBC and MBCU. The was a strong absorbance
sorption amount Qe (mg/g) was calculated according to the follow- peak appeared at 568/cm and 1110/cm owing to the Fe-O vibra-
ing equations: tion of Fe3 O4 and the Si-O vibration of silane coupling agent, re-
(C0 − Ce ) × V spectively, which indicated that the Fe3 O4 nano-particles and 3-
Qe = (1) Triethoxysilylpropylamine have been successfully loaded on the
m
Where Ce and Co are the equilibrium and the initial concentra- surface of the biochar as demonstrated by the SEM results. The
tions of lead (mg/L), respectively. V is the volume of solution (L) peak at 3427/cm corresponded to the O-H stretching vibration of
and m is the weight of added biochar (g). -OH, which was wider and stronger in MBCU than that of in MBC
due to the existence of hydrogen bond between -OH and -NH2 .
3. Results and discussion The absorbance peak at 1377/cm and 1585/cm were the charac-
teristic peak of -C-O and -C = O, respectively. These observations
3.1. Characterization of the biochars before and after modification confirmed MBC was successfully modified with urea.

3.1.1. Surface morphology 3.1.3. XPS analysis

The surface morphologies of BC, MBC and MBCU were illus- The oxidation states and surface elemental composition of BC
trated in Fig. 1, which showed that BC had a highly developed and MBCU were studied by XPS analysis. Fig. 3a and b showed
porous structure. When comparing the SEM images of BC and MBC, the wide scan spectra of BC and MBCU. Compared to the raw BC,
it was clearly showed that splendent particles appeared on the sur- the new element peaks at 399.76 eV, 711.28 eV and 152.87 eV ap-
face of MBC, which can be attributed to the existence of Fe3 O4 peared in MBCU ascribed to the binding energy of N1s, Fe2p and
nano-particles. Due to the wrinkled surface of BC, the Fe3 O4 nano- Si2s, respectively, which illustrated that the Fe3 O4 nano-particles
particles can be easily loaded into the porous. The porous surface and 3-Triethoxysilylpropylamine has been successfully grafted on
of BC was preserved after magnetization and modification and the the surface of BC and MBC has been successfully modified with
Fe3 O4 nano-particles were not uniformly distributed on the sur- urea as proved in FTIR analysis. The Fe2p peaks at 711.24 eV and
face of BC. Compared with MBC, there was no obvious change after 724.81 eV corresponded to the Fe2p3/2 and Fe2p1/2 spin-orbit peak
460 X. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467

a b c

Fig. 1. The SEM images of BC (a), MBC (b) and MBCU (c).

of the magnetization (emu/g) against the flied strength (Oe). As

shown in the loop seen in Fig. 1S, the magnetization sharply in-
creased with the decrease of the mass ration of BC: Fe3 O4 nano-
particles and the saturation magnetization (Ms ) reached to 10.2,
15.5, 16.9, 20.1, 32.3 emu/g for MBCU(3:1), MBCU(2:1), MBCU(2:1),
MBCU(1:1) and Fe3 O4 nano-particles, respectively, which revealed
that the magnetization of MBCU can be adjusted by the mass ra-
tion of BC: Fe3 O4 nano-particles. The super-paramagnetic behav-
ior was caused by the modification of biochar with Fe3 O4 nano-
particles, which could guarantee the MBCU can be readily recol-
lected from the suspended solution by applying the external mag-
netic field, which makes the repeated use of the MBCU in the real
wastewater treatment process possible.

3.2. Adsorption study

Fig. 2. The FTIR spectra of BC, MBC and MBCU.
3.2.1. Effect of solution pH on lead (II) adsorption
The pH is a pivotal parameter in the adsorption process which
of magnetic compounds, which was an evidence to further verify has been demonstrated in literatures, because it not only affects
the Fe oxides were attached to the biochar matrix. the degree of ionization and speciation of the heavy metals, but
Moreover, the percentage of surface elements composition in also the charges and states of the functional groups of adsorbent.
BC and MBCU were listed in Table 1S. As shown in Table 1S, the To study the influence of pH upon adsorption of lead, the experi-
%C and %O were the highest in BC followed by MBC and MBCU ments were conducted in the pH range of 2–8 and the results were
and the %N was the opposite order. The %Fe detected in BC was shown in Fig. 4b. The adsorption capacity of lead (II) on BC, MBC
negligible, while MBC and MBCU had 17.29% and 16.36% of Fe, re- and MBCU remarkably increased with the increase of pH from 2
spectively. The elements analysis indicated that the N and O ele- to 6.5, after that, it decreased when pH value greater than 6.5,
ments highly increased after magnetic and functional modification which indicated that the adsorption of lead on the biochar was
and the magnetic and functional modification of BC with Fe3 O4 strongly depended on the pH of the system. The Zeta-potential
nano-particles and urea was successful. changes of BC, MBC and MBCU at pH 2–12 were shown in Fig. 4a.
The values of Zeta-potential decreased with the increase of pH and
3.1.4. Elemental composition and porous structure the point of zero charge (PZC) of BC, MBC and MBCU was 3.65,
The specific surface area, total pore volume advantage pore di- 4.00 and 4.72, respectively. When the pH value was less than the
ameter are the physical factors of biochar that affect the heavy PZC, the biochars were protonated and positively charged; when
metal adsorption. It was notable that BC had a high surface are of pH value was more than the PZC, the biochars were negatively
169.73 mg/g, while the MBC has lower surface area of 103.87 mg/g. charged, which was in favor of lead (II) adsorption as lead (II) was
The decrease in the surface area of MBC was expected because the positively charged.
MBC was composed of a high surface area carbonaceous and a low It is well reported in literatures that lead is present in various
surface area of Fe3 O4 , since the Fe3 O4 nano-particles could block forms i.e. Pb2+ , Pb(OH)+ , Pb(OH)2 0 , and Pb(OH)3 − at different pH
some of the pores of the BC. The lower surface area of magnetic values [26]. At relatively low pH, Pb2+ is the predominant form
composites compared to pristine biochar has also been observed in and it would compete with the excess H+ for the adsorption sites
other study [25]. Compared with the MBC, there was little change on the surface of biochar, on the other hand, the surface groups
of MBCU in surface area, which indicated that the functional mod- could be protonated and repel the lead (II), so low uptake capac-
ification had a negligible effect on surface area of biochar. ity was observed at low pH region. Along with the increase of pH
value, the decrease of H+ could reduce the competitive adsorption,
3.1.5. Magnetic properties leading to the increase of adsorption capacity [24]. However, at
The magnetic hysteresis loops of the prepared magnetic pH > 6.5, the lead (II) would hydrolyze and the surface of biochar
biochars and Fe3 O4 nano-particles were obtained from the plot would be covered with the hydrolysis product of lead, which has
 X. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467 461

Fig. 3. XPS spectra of (a) BC, (b) MBCU and (c) MBCU after lead adsorption; (d) XPS of C1s before and after lead (II) adsorption; (e) XPS of O1s before and after lead (II)
adsorption; (f) XPS of N1s before and after lead (II) adsorption.
462 X. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467

Fig. 4. (a) The Zeta potential of BC, MBC and MBCO at different pH. (b) Effect of pH on lead (II) removal by BC, MBC and MBCU (C0 = 100 mg/L, dosage = 1.0 g/L, contact
time = 12 h, adsorption temperature = 293 K).

Fig. 5. Lead (II) removal percentage and adsorption capacity versus MBCU dosage Fig. 6. Effect of the mass ratio of BC: Fe3 O4 nano-particles on the magnetic biochar
(C0 = 100 mg/L, pH = 6.5, contact time = 12 h, adsorption temperature = 293 K). in term of adsorption capacity of lead (II) and recovery efficiency (C0 = 100 mg/L,
pH = 6.5, contact time = 12 h, adsorption temperature = 293 K).

adverse effect on the adsorption process. Therefore, the adsorption

capacity reduced in the pH range from 6.5 to 8 and the maximum 3.2.3. Optimum iron loading for magnetization
adsorption capacity of lead (II) on magnetic biochar was observed Though the magnetic biochar could be effectively recovered
at pH 6.5. from aqueous solution, the adsorption efficiency reduced at the
same time due to the pores in the surface of biochar becom-
ing plugged with iron oxide particles. Hence, it is essential to
determine the optimum mass ratio of BC: Fe3 O4 nano-particles
3.2.2. Effect of adsorbent dosage that maximize the magnetic biochar’s separation efficiency without
Adsorbent dosage is a significant impact factor of adsorp- sacrificing its adsorption efficiency. Fig. 6 represents the adsorp-
tion process. It determines the adsorbent-adsorbate equilibrium of tion capacity and recovery efficiency of lead (II) on the magnetic
the adsorption system. The removal efficiency of lead increased biochar from the aqueous solution when the mass ratio of BC:
from 12% to 100% as the adsorbent dosage increased from 0.1 Fe3 O4 nano-particles was 0:1,1:1,1.5:1,2:1,3:1,1:0 to impart magne-
to 1.5 g/L. On the other hand, the maximum adsorption capac- tization. It was clearly observed that the adsorption capacity and
ity of 106.6 mg/g was achieved at the dosage of 0.1 g/L and de- recovery efficiency of the magnetic biochar displayed the opposite
creased with the adsorbent dosage (Fig. 5). MBCU was demon- tendency depending on the mass ratio. The adsorption capacity of
strated with super removal efficiency to lead from aqueous solu- lead (II) on the biochar decreased from 99.89 to 12.91 mg/g as the
tion. This remarkable adsorption performance was due to the ex- mass ratio of BC: Fe3 O4 nano-particles decreased. Contrary to the
istence of abundant active sites and multiple interactions between adsorption capacity, the recovery efficiency of the magnetic biochar
MBCU with lead, namely electrostatic interaction, ion exchange and increased as the mass ratio decreased. Based on the results, it
complexation, which would be discussed in 3.2.8. Thus, all the is essential to determine the optimum mass ratio of BC: Fe3 O4
following adsorption experiments were carried out at adsorbent nano-particles that maximize the magnetic biochar’s separation
dosage of 1.0 g /L, which could guarantee the relatively excellent efficiency without sacrificing its adsorption capacity of lead (II).
adsorption capacity and removal efficiency at the same time. To achieve these controversial purposes, namely high adsorption
 X. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467 463

Fig. 7. (a) The adsorption kinetic plots of BC, MBC and MBCU. (b) Linear fit for pseudo-first-order model of kinetic data. (c) Linear fit for pseudo-second-order model of
kinetic data. (d) Intra-particle diffusion model plot of kinetic data. (C0 = 100 mg/L, dosage = 1.0 g/L, pH = 6.5, adsorption temperature = 293 K).

capacity and recovery efficiency, the optimum mass ratio range process, the pseudo-first-order reported by Lagergren [27] and
was determined to be 1.7:1–2.3:1. At the mass ratio of 2:1, the pseudo-second-order reported by Ho and McKay [28] were em-
magnetic biochar showed a high adsorption capacity of 88.9 mg/g ployed to describe the adsorption kinetic data, given by Eqs.
for lead (II) and recovery efficiency of 97.9% for magnetic biochar. (2) and (3).
Meanwhile, research concerning additive materials which can
maintain the magnetic properties and reinforce the adsorption In(Qe − Qt ) = InQe − k1 t (2)
ability of biochar after magnetization is required in the future.
t 1 1
3.2.4. Adsorption kinetics = + t (3)
Qt k2 Qe 2 Qe
Fig. 7a showed the effects of the modification the adsorption
kinetics of lead (II) by various biochars. It is observed that the ad- Where Qe and Qt (mg/g) are the amounts of lead (II)adsorbed
sorption capacity of lead (II) on BC was biter weaker than MBC, onto magnetic biochar at equilibrium and at time t (min), re-
which may be result from the coating of coupling agent and fill- spectively; k1 (1/min) and k2 (g/(mg•min)) are the rate constant of
ing up with Fe3 O4 nano-particles. In addition, the MBCU modified pseudo-first-order and pseudo-second-order. The plots of log (Qe -
with urea showed the highest adsorption capacity of lead (II). That Qt ) versus t and t/ Qt versus t give the values of k1 and Qe , k2 and
was because the amine groups were introduced to the surface of Qe , respectively. The fitting plots were showed in Fig. 7b and c and
the magnetic biochar, which played an essential role in lead (II) the corresponding fitting parameters were listed in Table 2S. It can
adsorption. be obviously observed that the pseudo -first-order model was not
It is noteworthy that the adsorption capacity of lead (II) was suitable to describe the kinetic profiles, while they were accurately
markedly ascended within the first 5 h for all biochars, and a described by the pseudo-second-order model. The regression coef-
further increase in contact time barely affected the adsorption ficients (R2 > 0.99) obtained from pseudo-second-order non-linear
efficiency, because adsorption equilibrium was reached. To fur- fits was much larger than that of pseudo-first-order non-linear fits.
ther investigate the potential adsorption mechanism of adsorption In addition, the experimental results of adsorbed lead (II) amount
464 X. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467

at equilibrium were in very good agreement with those calcu- Where Ce (mg/L) and Qe (mg/g) are the equilibrium concentra-
lated from the pseudo-second-order model, which indicated that tion of adsorate and the amount of adsorate adsorbed at equilib-
the pseudo-second-order model was more appropriate to describe rium, respectively. Qm (mg/g) denotes the maximum adsorption ca-
the adsorption behavior of lead (II) on biochars. The results sug- pacity. The b (L/mg) related to the heat of adsorption is the Lang-
gested that chemical adsorption of the lead (II) on the MBCU was muir constant. The Kf (mg/g (L/mg)1/n ) related to the relative ad-
dominant. sorption capacity and n related to the intensity of adsorption are
Since the pseudo-first-order and pseudo-second-order model the Freundlich constant, being the latter a measure of the hetero-
were based on the whole adsorption process and could not pro- geneity of surface adsorption sites. All these parameters appeared
vide the control step in different adsorption stages. Hence, the in the Sips equation maintain the same meanings.
kinetic data were also fitted by intra-particle diffusion model The plots of Qe versus Ce of the three isotherm models were
(Eq. (4)) originated from Fick’s second law [29]. It can be seen shown in Fig. 8 and the parameters of mathematical modeling
that the curves present multi linearity shown in Fig. 7d and the were listed in Table 4S. The comparison of regression coefficients
order of diffusion rate constant was kp 1 > kp 2 > kp 3 , implying that for the non-linear plots of Langmuir and Freundlich isotherm in-
intra-particle diffusion did not limit the whole adsorption process dicated that the experimental data was better fitted with the
(Table 3S). Additional, the diffusion rate constant was different for Langmuir equation rather than the Freundlich model. However,
the three biochar and the order was MBCU>MBC>BC, which could the comparison with Sips model revealed that the latter isotherm
be owing to the kinds and amount of functional groups [24].Based could even better fit the experimental data since the R2 was always
on the pore-diffusion theory, the adsorption process can be de- higher than that of Langmuir or Freundlich model. Furthermore,
scribed by three steps [30]: (1) the adsorption happened quickly as Table 4S showed, the saturation adsorption capacities of lead
and could be ascribed to film diffusion (transport of lead (II)from (II) on MBCU were closed to the maximum adsorption capacities
the boundary film to the exterior surface of adsorbent); (2) the obtained from the Sips model at 293, 303, 313, and 323 K. There-
adsorption rate decreased and could be ascribed to intra-particle fore, it can be concluded that the adsorption of lead (II) on MBCU
diffusion (transfer of lead (II) from the surface to the pores of ad- mainly entailed the formation of a superficial monolayer, but there
sorbent); (3) the adsorption equilibrium reached and could be as- was a certain degree of heterogeneity.
cribed to equilibrium stage (adsorption of lead (II) on the interior The separation factor (RL ) is a dimensionless constant, which is
surface of adsorbent was saturated). used to determine whether the adsorption was favorable or not.
The RL is expressed as follows:
Qt = k pi t 1/2 + Ci (4)
1
kpi (mg/(g min−1/2 )) is intra-particle diffusion rate constant of stage RL = (8)
1 + b · C0
i, Ci is a parameter about the thickness of the boundary layer.
Where C0 and b represent the initial concentration of lead (II)
and Sips constant, respectively. The RL value classified the nature of
3.2.5. Adsorption isotherm
adsorption to be irreversible (RL = 0), favorable (0 < RL < 1) and un-
The adsorption isotherm study was performed at different tem-
favorable (RL > 1). For the current adsorption system, the RL values
peratures i.e. 293, 303, 313, 323 K by adjusting initial lead (II) con-
for MBCU were calculated to be 0.022–0.214, 0.015–0.159, 0.010–
centration from 25 to 300 mg/L and the adsorption isotherm curves
0.112 and 0.008–0.094 with initial concentration ranging from 25
were presented in Fig. 8a. It was clearly that the absorbed lead
to 300 mg/L at 293, 303, 313, and 323 K, which indicated that the
(II) on MBCU increased with the increasing of initial lead (II) con-
favorability of the adsorption process as RL was between 0 and
centration and the isotherms were L-type with an initial moderate
1. Furthermore, the adsorption capacity of lead (II) on MBCU in-
slope until reached a plateau value for the higher lead (II) concen-
creased with the increasing of adsorption temperature, which in-
tration.
dicated that the adsorption process was an endothermic reaction
The study of adsorption isotherms is very vital to understand
and higher temperature would benefit to the adsorption. That was
the interaction behavior between adsorbent and heavy metals. It’s
partly because the increase of temperature may cause a swelling
necessary to establish an appropriate correlation of adsorption
effect on pore volume of MBCU, which favored the lead (II) diffu-
equilibrium to optimum the adsorption system for efficient adsorp-
sion both in the boundary layer and internal pores of the MBCU
tion of heavy metals in practical application. For this adsorption
[34].
system, three isotherm models including Langmuir, Freundlich and
The comparison of bibliography evidences the major adsorption
Sips were used to fit the isotherm data. The Langmuir isotherm
capacities found in the present study (Table 1). The results showed
assumes the adsorption occurs in the monolayer way with no
that the maximum adsorption capacity of MBCU was higher than
interaction between the adsorbed molecular [31]. The Freundlich
that of other materials. Moreover, it was worthy to remark the sig-
isotherm assumes the multilayer and non-ideal adsorption on the
nificant capacity of MBCU to remove lead (II) from aqueous so-
heterogeneous surface with a non-uniform distribution of adsorp-
lution, being possible to achieve an adsorption percentage higher
tion activation energy [32]. In between, the Sips isotherm effec-
than 90% when the initial lead (II) concentration was lower than
tively reduces to the Freundlich isotherm at low adsorate concen-
100 mg/L. This result was especially relevant when this magnetic
tration whereas at high adsorate concentration, it displays a mono-
modified material was considered to be applied in practical appli-
layer adsorption characteristic of the Langmuir isotherm [33]. The
cation.
non-linear form of the three isotherms model could be expressed
in Eqs. (5) –(7):
3.2.6. Recycle and desorption of MBCU
Qm · b · Ce The recycle and desorption potential of adsorbents was investi-
Langmuir : Qe = (5)
1 + b · Ce gated to make the adsorption process more economical. 0.1 mol/L
Na2 EDTA was applied as the desorbing solution for the recovery
Freundlich : Qe = KF · Ce n (6) of the lead (II) from the Pb-loaded MBCU. The lead (II) removal
efficiency remained > 80% and the desorption efficiency of each
cycle maintained > 93.1% after six successive cycles, as shown in
Qm · b · Ce n Fig. 9. It was observed that the lead (II) adsorption efficiency only
Sips : Qe = (7)
1 + b · Ce n decreased by 18.7% after six successive cycles compared with the
 X. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467 465

Fig. 8. (a) Adsorption isotherm of lead (II) on MBCU at different temperatures. (b) The non-linear fit of Freundlich isotherm model. (c) The non-linear fit of Langmuir
isotherm model. (d) The non-linear fit of Sips isotherm model. (pH = 6.5, dosage = 1.0 g/L, contact time = 12 h).

Table 1
Comparison of adsorption capacity of lead (II) on different adsorbents.

Adsorbents Conditions Qm (mg/g) Ref.

Biomass fly ash T = 293 K,pH = 5.0,D. = 0.83 g/L 6.30 [35]

L-proline silica gel T = 303 K,pH = 5.5,D. = 2 g/L 22.22 [36]
Agriculture soil T = 293 K,pH = 6.5,D. = 4 g/L 20.16 [37]
NCS/PU/PPG-glu T = 293 K, pH = 6.0, D. = 4 g/L 169.52 [38]
Porous leather particles T = 328 K, pH = 5.0, D. = 2 g/L 31.66 [5]
GO composite T = 298 K, pH = 6.0, D. = 0.25 g/L 72.18 [39]
Activated carbon T = 293 K,pH = 6.0,D. = 1.0 g/L 163.93 [13]
Anaerobic digestion sludge biochar T = 313 K,pH = 6.0,D. = 1.0 g/L 53.96 [26]
40% MnOx-loaded biochar T = 298 K,pH = 5.0,D. = 2.0 g/L 86.50 [40]
MBCU T = 323 K,pH = 6.5,D. = 1.0 g/L 188.18 This study

first cycle, indicating a good regeneration and reusability of MBCU. containing of 100 mg/L Cd(II), Zn(II), Cu(II), Ni(II) and Pb(II). Af-
In addition, the magnetic property of MBCU could effectively pro- ter the adsorption equilibrium was reached, the adsorption capac-
mote the separation process and significantly reduced the loss of ities of these heavy metals were determined and the results were
MBCU with repetitive usage. Therefore, the advantage of magnetic showed in Fig. 2S. It can be seen that the order was Pb(II)> Cd(II)>
property and remarkable reusability for the effectively removal Ni(II)> Cu(II)> Zn (II), which indicated that the MBCU showed high
lead (II) made MBCU as a promising candidate in wastewater selectivity for lead (II). Indeed, the adsorption capacity of Pb(II)
treatment. was 1.5 times higher than that of Cd(II), 4 times for Cu(II), 6 times
for Ni(II) and 3 times for Pb(II), that is, Pb(II) was well-formed
3.2.7. The adsorption selectivity of MBCU into complexes with the functional groups(-NH2-,-C=O and -OH)
To investigate the adsorption selectivity of MBCU for different on the surface of MBCU [26]. The magnetic MBCU produced by
heavy metal ions, the competitive heavy metal adsorption experi- bio-material was able to selectively remove lead (II) from aqueous
ment was carried out at 293 K for 12 h using solutions separately solution. Hence, owing to its availability, selectivity, reusability and
466 X. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467

H+ also competed for the adsorption sites on MBCU with Pb(II) via
ion-exchange. Therefore, the adsorption capacity of Pb(II) on MBCU
was poor at pH < 5.3. When pH was above 5.5 but below 7, the
density of negative increased substantially, resulting in the dra-
matic charge neutralization activity at this stage, which could en-
hance the adsorption process via electrostatic interactions and ion-
exchange. Additionally, the release of cation (ion-exchange) was
also proved by the Pb-O binding energy at ∼138 Ev [42]. Beyond
pH 7.0, the Zeta-potential of MBCU-Pb(II) kept a steady stage, the
adsorption capacity decreased owing to the formation of Pb(OH)2
precipitation. Hence, the possible ion-exchange adsorption mecha-
nism occurred in functional groups of MBCU with lead (II), which
was showed in Eqs. (12) and (13).

Complexation : R–NH2 +Pb(II ) ⇔ R–NH2 –Pb(II ) (9)

R–C = O + Pb(II ) ⇔ R–C = O–Pb(II ) (10)

Fig. 9. The adsorption and desorption efficiency of lead (II) on MBCU in five suc-
cessive regeneration cycles.
R–OH + Pb(II ) ⇔ R–OH–Pb(II ) (11)

efficient separation, the MBCU could be a promising adsorbent for

removal lead (II) from aqueous solution.
Ion–exchange : R–NH3 + +Pb(II ) ⇔ R–NH2 –Pb(II )+H+ (12)
3.2.8. The adsorption mechanism of lead (II) on MBCU
XPS analysis of MBCU and MBCU-Pb(II), as exhibited in  
Fig. 3(c)–(f), provided the further illustration of adsorption mech- (R − OH )2 +Pb(II ) ⇔ R−O− 2 −Pb(II ) + 2H+ (13)
anism of Pb(II) on MBCU. The C1s of MBCU was deconvoluted
into five components: C-H at 283.86 eV, C-C/C=C at 284.61 eV, C- Where R represented the other component of MBCU. In conclu-
N at 285.31 eV, C-O at 286.40 eV and 287.82 eV. Although the C1s sion, Pb (II) adsorption experiments and XPS analysis coindicated
of MBCU after Pb (II) adsorption exhibited the same functionali- the adsorption mechanism of Pb (II) on MBCU could be involved
ties as the MBCU, there was a certain degree of the binding en- in chemical adsorption including electrostatic interaction, ion ex-
ergy after Pb (II) adsorption. Compared with MBCU spectrum, the change and complexation. The ion exchange was occurred between
four components of O1s corresponded to O-H at 532.88 eV, O = C Pb (II) with the protons in the functional groups of MBCU. The
at 531.49 eV, O-C at 530.44 eV and O-Si at 529.76 eV shifted to electrostatic interaction of the deprotonated functional groups en-
532.91 eV, 531.52 eV, 530.50 eV and 529.87 eV, respectively. Two hanced adsorption of Pb (II). The N atoms in −NH2 groups and
major peaks in N1s at 401.87 and 399.74 eV could be attributed to O atoms in -OH, and –C = O could donate their electrons to form
the N-C and N-H, respectively. After adsorption Pb (II), the peak of coordination complexes or covalent binding with Pb (II). More-
N-C and N-H shifted to 402.06 and 399.84 eV, respectively, which over, MBCU showed multi-porous structure with high surface area,
implied that the lone pairs of electron in N and O was shared with which offered tremendous adsorption sites. Together with the mul-
Pb(II), leading to the decrease of electron density and the increase tiple chemical interactions, MBCU could be considered as a supe-
of binding energy of nitrogen and oxygen atoms[24]. It mainly re- rior adsorbent to remove Pb (II) from wastewater.
sulted from the formation of complexation between Pb(II) and ni-
trogen, oxygen atoms of the functional groups [41]. The possible
adsorption complexation mechanism of Pb(II) on MBCU was pre- Conclusion
sented by the formation of the complexation shown in Eqs. (9)–
(11). A novel urea-functionalized magnetic biochar (MBCU) was syn-
Meanwhile, the final pH of the solution after adsorption equi- thesized via magnetic and functional modification for remove of
librium and the Zeta-potential change of MBCU and MBCU-Pb(II) lead (II) from aqueous solution. The results of SEM, BET, XPS, FTIR,
were shown in Fig. 3S (a) and (b). It is remarkable that the pH vari- VSM and Zeta-potential indicated that the Fe3 O4 nano-particles
ation during Pb(II) adsorption was not varying significantly: at low and urea were successfully grafted on the surface of biochar. The
pH (below pH 5.5), a slight increase of the equilibrium pH (below experimental results exhibited the adsorption isotherm can be well
0.37 pH unit) was observed, while above pH 5.5, the equilibrium fitted by Sips model and the adsorption kinetic data was fitted
pH tended to slightly decrease (variation being less than 0.22 pH well with pseudo-second-order model. The maximum adsorption
unit), which indicated that the grafting of functional groups con- capacities of lead (II) on MBCU calculated from the Sip model were
tributed to smooth this pH variation effect. Compared with MBCU, 154.95, 166.78, 175.36 and 188.18 mg/g at 293, 303, 313 and 323 K,
the pH at PZC and Zeta-potential of MBCU-Pb(II) transferred to a respectively, which was higher than that of other adsorbents pub-
higher value and more positive direction, because the formation of lished in references. The lead (II) removal efficiency of MBCU re-
ionic bonds in the complexes of MBCU with Pb(II)(e.g., MBCU•NH2 - mained > 80% and the desorption efficiency maintained > 93.1% af-
Pb(II), MBCU•C = O-Pb(II) and MBCU•OH-Pb(II)) brought more pos- ter five adsorption/desorption cycles. The saturation magnetization
itive charge to the surface of MBCU. For MBCU-Pb(C), at pH below of MBCU reached to 16.9 emu/g, which could guarantee the MBCU
5.3, the density of positive charge was high, because the –NH2 on could be easily and effectively separated from the solution by ap-
MBCU was protonated at low pH, resulting in the formation of – plying the external magnetic field. The sustainable and low-cost
NH3 + . Then, –NH3 + enhanced the electrostatic repulsion between magnetic adsorbent MBCU has great potential to be a promising
the positively charged Pb(II) and MBCU, besides, the abundant candidate for lead (II) removal.
 X. Zhou et al. / Journal of the Taiwan Institute of Chemical Engineers 91 (2018) 457–467 467

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Universities of Central South University (No. 1053320171391) and sorbent modified with amino siloxane for fast removal of Pb(II) from aqueous
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[21] Son EB, Poo KM, Chang JS, Chae KJ. Heavy metal removal from aqueous
solutions using engineered magnetic biochars derived from waste marine
Supplementary material associated with this article can be macro-algal biomass. Sci Total Environ 2018;615:161–8.
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