Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 582–591

Contents lists available at ScienceDirect

Chemical Engineering Research and Design

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

A comparative study of arsenic(V), tetracycline and

nitrate ions adsorption onto magnetic biochars and
activated carbon

Guangcai Tan a,b , Yi Mao a,c , Hongyuan Wang d , Nan Xu a,∗

a Shenzhen Engineering Research Center for Nanoporous Water Treatment Materials, School of Environment and
Energy, Peking University Shenzhen Graduate School, Shenzhen 518055, China
b Department of Civil and Environmental Engineering, Louisiana State University, Baton Rouge, LA 70803, USA
c UCD Dooge Centre for Water Resource Research, School of Civil, Structural and Environmental Engineering,

University College Dublin, Belfield, Dublin 4, Ireland

d Key Laboratory of Nonpoint Source Pollution Control, Ministry of Agriculture, Institute of Agricultural Resources

and Regional Planning, Chinese Academy of Agricultural Sciences, Beijing 100081, China

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

Article history: The removal of contaminants in co-solute systems is a pressing issue. Herein, the adsorp-
Received 19 November 2019 tion capacities of magnetic biochars and activated carbon were investigated and compared
Received in revised form 9 April for various aqueous anions, including As(V), tetracycline (TC) and NO3 − , existed alone or
2020 as a mixture. One-step (pre-treating biomass with FeCl3 before pyrolysis (FB)) and two-
Accepted 9 May 2020 step (pyrolysing biomass before modification with FeCl3 (BF)) magnetization methods were
Available online 23 May 2020 applied to synthesize magnetic biochars. Magnetic activated carbon (AF) was also prepared
with the two-step magnetization method. FB presented the highest adsorption capacities for
Keywords: As(V) and NO3 − respectively at 6.77 and 6.31 mg g−1 . AC (612.38 mg g−1 ) showed the highest
Biochar adsorption capacity for TC, which decreased by 189.76% after magnetization. Magnetiza-
As(V) tion was proved to be a promising method to improve the adsorption of both As(V) and
Tetracycline NO3 − on adsorbents through enhanced electrostatic attraction, while the adsorption of TC
Nitrate depended mainly on high specific surface area of the adsorbent. Results from competitive
Co-adsorption adsorption in the co-solute systems suggested that FB had a great potential for applica-
tion in the co-contaminated environment (heavy metal and inorganic anions), and AF could
be a promising adsorbent to remediate multiple-contaminated environment (i.e. organic
pollution and heavy metal/inorganic anions).
© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
Arsenic (As) contamination in surface water or groundwater is
a global health concern because of its various kinds of toxici-
ties including epidemiological, cytotoxic and genotoxic effects
(Mangwandi et al., 2016; Islam et al., 2018a,b; Song et al., 2019).
In the northwest of China, high levels of As (up to 1.35 mg L−1 )
in groundwater have been detected as early as the 1950s (Guo
∗
Corresponding author.
E-mail address: xunan@pkusz.edu.cn (N. Xu).
https://doi.org/10.1016/j.cherd.2020.05.011
0263-8762/© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
et al., 2001; Fujino et al., 2004). Zhang et al. (2002) reported
that the average As content in groundwater was more than
0.2 mg L−1 in Hetao area (northwest of China) which signifi-
cantly exceeded the permissible limits set by the World Health
Organization (WHO) (10 ␮g L−1 in drinking water) (Xia et al.,
2014). As(V) accounted for a greater percentage in the total
arsenic, nearly 30% in average (in the range of 9–90%) (Xia
et al., 2014). In the rural areas contaminated by As, the antibi-
otic pollution in groundwater also existed due to the frequent
use of domestic and livestock wastewater containing antibi-
otics for irrigation of farmland (Fytianos and Christophoridis,
2004; Wang et al., 2015; Islam et al., 2019). Different kinds of
 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 582–591
antibiotics (e.g. tetracycline (TC), lincomycin and sul-
famethoxazole) and their metabolites have been detected in
groundwater in the northern China (Hu et al., 2010). The spread
of antibiotics residues can potentially induce adverse effects
on ecosystem such as acute and chronic toxicity and prop-
agation of antibiotic resistance in microbes (Li et al., 2016).
Besides, with the unbalanced and/or excessive application of
fertilizers, nitrate (NO3 − ) was widely detected in groundwater
due to its high solubility (Kilpimaa et al., 2014; Xu et al., 2016).
Chen et al. reported that the average NO3 − content in ground-
water was as high as 12.15 ± 12.92 mg L−1 in Ningxia (Hetao
area, northwest of China) (Chen et al., 2016), indicating the
potential health risk (Divband Hafshejani et al., 2016). Besides,
heavy metals, organic chemicals and inorganic anions were
often detected simultaneously in wastewater and surface
water (Lian et al., 2013). Therefore, it is a pressing issue to
investigate the removal of contaminants in co-solute systems.
As an organic carbon-rich material, biochar is synthe-
sized through pyrolyzing biomass under an oxygen-limited
environment (Lehmann and Joseph, 2015). Because of its abun-
dant oxygen functional groups and high surface-to-volume
ratio, biochar has been successfully used for treatment of
organically and inorganically contaminated water, which is
beneficial to both wastewater treatment and greenhouse gas
mitigation (Xu et al., 2015; Wang et al., 2017; Wu et al., 2019;
Tan et al., 2019b). However, the raw biochar was reported to be
less efficient for treatment of anionic contaminants including
As(V), TC (at high pH) and NO3 − due to its negatively charged
surface and limited functional groups (Tan et al., 2016b). In
addition, the powdered biochar is difficult to be separated
after application in aqueous solution. In order to overcome
these drawbacks, magnetic modification was employed to pro-
duce Fe2 O3 /biochar composites (Zhang et al., 2013; Zhu et al.,
2014a). Zhang et al. (2013) reported that magnetic biochar can
be prepared directly from FeCl3 treated biomass through pyrol-
ysis, which showed excellent adsorption capacity for arsenic
in water compared to the raw one. However, little information
was documented about the performance of magnetic biochar
in the adsorption of organic pollutant (e.g. TC) and inorganic
anions (e.g. NO3 − ), and the competitive adsorption among
them is even less studied. Activated carbon is also a kind of
adsorbent which has been widely used in wastewater reme-
diation owing to its large specific surface area. Therefore, it
is worthwhile to compare the adsorption ability of magnetic
biochars with that of magnetic activated carbon.
Herein, for the first time, we investigated and compared
the adsorption capacities of magnetic biochars and activated
carbon for various aqueous anions, As(V), TC and NO3 − , in
single/binary-mixture systems. Both biochar and activated
carbon were produced from corn-straw. Magnetic biochars
and magnetic activated carbon were produced using fer-
ric chloride. These adsorbents were used to evaluate the
adsorption of individual As(V), TC and NO3 − , as well as their
binary mixtures. The main objectives were to: (1) investi-
gate and compare the adsorption capacities of the adsorbents
for As(V), TC and NO3 − , and reveal the effects of magne-
tization on the adsorption performance; (2) investigate the
competitive adsorption in binary-mixture systems among
As(V), TC and NO3 − ; and (3) investigate the mechanisms for
the competitive adsorption of As(V), TC and NO3 − onto these
adsorbents.
583
2. Materials and methods
2.1. Preparation of the adsorbents
Air-dried corn straw (Zea mays L.) was washed three times
using ultrapure water (18.2 M cm) firstly, and then oven-dried
(80 ◦ C) for 12 h. Biochar (BC) was produced using slow pyrolysis
at 600 ◦ C in a furnace (Olympic 1823HE, USA) under N2 envi-
ronment for 1.5 h. For synthesis of activated carbon (AC), dried
corn straw was firstly impregnated in phosphoric acid (85%)
for 24 h, then dried for 4 h at 105 ◦ C in an oven, and pyrolyzed
under the same condition as for producing BC.
Two synthesis methods were applied to prepare two dif-
ferent kinds of magnetic biochars (Zhang et al., 2013; Baig
et al., 2014; Tan et al., 2016b). In the first method (two-step
procedure), the magnetic biochar was produced with BC as the
precursor. Briefly, 5 g of BC was suspended in FeCl3 solutions
(dissolving 40 g of FeCl3 ·6H2 O in 500 mL of ultrapure water) for
24 h under continuous agitation using a magnetic stirrer, and
then oven-dried (105 ◦ C) for 12 h under air. Therefore, the mag-
netic biochar synthesized with this method was termed as BF.
In the second method, one-step procedure was applied, dur-
ing which dried corn straw was immersed into the same FeCl3
solution for 24 h, and then oven-dried (105 ◦ C) for 12 h under
air. The pre-treated corn straw was pyrolyzed in a furnace at
the same condition as for producing BC. Therefore, the mag-
netic biochar synthesized with the one-step procedure was
termed as FB. As the corn straw needs to be firstly activated
by phosphoric acid to produce AC, only the two-step procedure
was employed to produce magnetic activated carbon with AC
as the precursor, referred as AF. All the five kinds of adsorbents
were thoroughly washed with ultrapure water and sieved to
get <1 mm sized particle before being used for the following
experiments.
2.2. Characterization of adsorbents
The CHNOS analyzer (Thermo Flash 2000, USA) was used to
measure the contents of different elements (C, H, O, N) in
the adsorbents. Surface structural characteristics of the adsor-
bents were examined by a NOVA 2000 sorptiometer (Quan-
tachrome Instruments, USA). The Brunauer–Emmett–Teller
(BET) method was used to measure the pore volume and
total surface area. The Barrett–Joiner–Halenda (BJH) method
was used to determine the pore size distributions. A scan-
ning electron microscope (SEM, Hitachi S4800, Japan) coupled
with an energy dispersive X-ray spectroscopy (EDS, Oxford
Instruments, USA) was used to examine the morphology and
elemental composition of adsorbents. The spectral properties
of adsorbents were examined by a Fourier transform infrared
(FT-IR) spectrometer (Nicolet Magna-IR 750, USA). The crystal
structure of the adsorbents was evaluated through Powder X-
ray diffraction (XRD) (X’Pert Pro, PANalytical, Netherland). The
X-ray photoelectron spectroscopy (XPS) of the adsorbents was
obtained using a PHI 5100 series ESCA spectrometer (Perkin
Elmer, USA). Magnetic properties were obtained on a vibrating
sample magnetometer (VSM, Lake Shore 7410, USA). The ther-
mal stability of adsorbents was examined by a Mettler Toledo’s
TGA/DSC analyzer (TGA/SDTA851, USA). Zeta potential (ZP)
of the adsorbents was determined following the procedures
described in our previous work (Tan et al., 2016a).
584 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 582–591
2.3. Adsorption experiments
2.3.1. Chemicals
Sodium arsenate dibasic heptahydrate (Na2 HAsO4 ·7H2 O) and
potassium nitrate (KNO3 ) were purchased from Fisher Sci-
entific (USA). TC hydrochloride (>98%) was purchased from
Aldrich Chemical Co. (USA). The chemicals used in the
present study were of analytical grade and dissolved in ultra-
pure water. The stock solutions of As(V) (1000 mg L−1 ), TC
(1000 mg L−1 ) as well as NO3 − (1000 mg L−1 ) were prepared and
stored at 4 ◦ C.
2.3.2. Effect of pH
All the adsorption experiments were performed through a
batch equilibrium method. The effects of pH on the adsorp-
tion of As(V) (5 mg L−1 ), TC (100 mg L−1 ) and NO3 − (10 mg L−1 )
onto these adsorbents were examined at five different pH val-
ues (3, 5, 7, 9, and 11). The pH was adjusted with HCl and NaOH
solutions.
2.3.3. Adsorption kinetics for As(V), TC and NO3 −
According to the tentative experiments and previous studies
(Tofighy et al., 2012; Peng et al., 2014; He et al., 2018), 40 mg L−1
As(V), 400 mg L−1 TC and 30 mg L−1 NO3 − were used in kinetic
experiments. In detail, 0.05 g adsorbent samples were added
into 60 mL As(V) solution (40 mg L−1 ) in a conical flask (500 mL)
with cover. The HCl and NaOH solutions were used to adjust
the initial solution pH to 6.0 ± 0.1. All the conical flasks were
then shaken at 110 rpm and 25 ± 1 ◦ C on a water bath shaker
in the dark. Similarly, the adsorption kinetics for TC and NO3 −
were conducted with 60 mL corresponding solution (at 400 and
30 mg L−1 , respectively) and 0.05 g adsorbent samples under
the same experimental conditions. At appropriate time inter-
vals, one milliliter solution was sampled for analysis of As(V),
TC and NO3 − concentration. Kinetic data were fitted using
different kinetic models (the details were given in Supplemen-
tary Materials).
2.3.4. Adsorption isotherms for As(V), TC and NO3 −
Adsorption isotherms experiments for As(V) were conducted
by adding 0.05 g adsorbent into 60 mL As(V) solutions (the con-
centrations were ranging from 2 to 60 mg L−1 ) in the conical
flasks. Then 50 mg L−1 of TC or 30 mg L−1 of NO3 − was addi-
tionally spiked, respectively, so as to investigate the effect of
TC or NO3 − on As(V) adsorption. The initial solution pH was
adjusted to 6.0 ± 0.1 using HCl and NaOH solutions. The con-
ical flasks were shaken at 110 rpm and 25 ± 1 ◦ C on a water
bath shaker for 24 h in the dark. Similar to As(V), adsorp-
tion isotherms of TC and NO3 − were conducted by adding
0.05 g adsorbent samples into 60 mL corresponding working
solutions in the conical flasks at different concentrations rang-
ing from 20 to 400 and 0.5 to 50 mg L−1 , respectively. Then
30 mg L−1 of As(V) or NO3 − was additionally spiked, respec-
tively, so as to investigate the effect of As(V) or NO3 − on TC
adsorption. Similarly, 30 mg L−1 of As(V) or 50 mg L−1 TC was
additionally spiked, respectively, so as to investigate the effect
of As(V) or TC on NO3 − adsorption. All the adsorption exper-
iments were conducted in triplicate, and the average values
were reported. Control experiments with no adsorbents were
carried out simultaneously under the same conditions, indi-
cating that the pollutants removal was negligible. Isotherm
data were fitted with different isotherm models (the details
were described in Supplementary Materials).
2.3.5. Analytical methods
The supernatant of each sample at a given time interval
was firstly centrifuged and then filtered. The concentra-
tions of As(V) were analyzed using an inductively coupled
plasma-atomic emission spectrometry (ICP-AES, Perkin–Elmer
Plasma 3200, USA). The high-performance liquid chromato-
graph (Agilent 1100, USA) coupled with a UV detector at 355 nm
absorbing wavelength was used to determine the concentra-
tions of TC. The targeted compound was separated on an
Agilent Eclipse Plus C18 column (4.6 × 250 mm, 5 ␮m) using a
binary mobile phase of CH3 CN and 0.01 mol L−1 NaH2 PO4 of
20:80 (v/v). The flow rate was 1.0 mL min−1 with the injection
volume of 10 ␮L, and the retention time for TC was 3.9 min. The
ion chromatograph (ICS90, Dionex Inc., USA) equipped with a
conductivity detector was used to analyze the concentrations
of NO3 − .
3. Results and discussion
3.1. Characterization of adsorbents
Table 1 presents the physico-chemical properties of the five
adsorbents. After magnetization, both the ratios of (O + N)/C
and O/C obviously increased for FB, BF and AF as compared
to BC and AC, respectively, suggesting the increase of O-
containing groups. The BET surface area of FB (115.43 m2 g−1 )
was more than twice that of BC (56.18 m2 g−1 ), which could
be attributed to the reaction between iron particle and car-
bonaceous compound during the pyrolysis in the one-step
procedure (Zhang et al., 2013). However, the surface area of
BF (48.43 m2 g−1 ) and AF (217.87 m2 g−1 ) decreased in compari-
son with BC (85.06 m2 g−1 ) and AC (563.93 m2 g−1 ), respectively.
This could be due to the blockage of internal pores by the sur-
face complex of iron in the two-step procedure (Baig et al.,
2014). Meanwhile, the total pore volume and mesopore volume
increased for FB and decreased for BF compared to BC, and
also decreased for AF in comparison with AC. In addition, the
average pore size of FB, BF and AF increased compared to BC
and AC, respectively. The N2 adsorption–desorption isotherms
and pore size distribution are exhibited in Figs. S1 and S2,
respectively.
Fig. S3 shows the XRD patterns of the adsorbents. For the
magnetic adsorbents (FB, BF and AF), the sharp and strong
reflection peaks indicated the as-prepared iron oxides were
well crystallized within the biochar or activated carbon matrix.
Maghemite (␥-Fe2 O3 ) was found as the major crystalline phase
for the magnetic adsorbents (Zhang et al., 2013; Wang et al.,
2014). Fig. S4 shows the SEM images and the corresponding
EDS spectra of the adsorbents. Element analysis from EDS sug-
gested that FB (22.79%) had the highest iron weight, followed
by BF (14.35%) and AF (9.91%). As a result, FB possessed the
highest residual mass (>35%) during TGA, indicating its higher
stability than BF and AF (Fig. S5). High-resolution XPS spectra
of magnetic adsorbents in the Fe2p region are shown in Fig. S6.
The two bands at 710.43 and 723.76 eV were always present in
the spectra for FB, BF and AF, which were attributed to the
peaks of Fe3+ including Fe 2p3/2 and Fe 2p1/2 (Zhang et al.,
2013). The magnetic properties of FB, BF and AF are shown in
Fig. S7. The saturation magnetization of FB was 17.5 emu g−1 ,
the highest among the magnetic adsorbents, suggesting the
easiest separation of FB from the aqueous solution with exter-
nal magnetic field. These results further demonstrated that
biochar and activated carbon were successfully magnetized.
 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 582–591 585

Table 1 – Elemental compositions, atomic ratios and porous characterization of the biochar (BC), magnetic biochars (FB,
BF), activated carbon (AC) and magnetic activated carbon (AF).
BC FB BF AC AF

C (%) 85.06 56.27 64.13 75.81 53.24

H (%) 0.84 0.76 1.11 1.01 1.32
O (%) 4.14 10.47 8.29 10.89 14.95
N (%) 0.61 0.45 0.67 0.75 0.52
H/C 0.0099 0.0135 0.0173 0.0133 0.0248
O/C 0.0487 0.1861 0.1293 0.1436 0.2808
(O + N)/C 0.0558 0.1941 0.1397 0.1535 0.2906
BET surface area (m2 g−1 ) 56.18 115.43 48.41 563.93 217.87
Total pore volume (cm3 g−1 ) 0.0313 0.0693 0.0159 1.0872 0.4287
Mesopore volume (2–10 nm) (cm3 g−1 ) 0.0128 0.0160 0.0032 0.0728 0.0428
Average pore size (nm) 3.33 5.42 5.18 2.26 3.47

Fig. 1 – The effects of pH values on As(V), tetracycline (TC) and NO3 − adsorption by the biochar (BC), magnetic biochars (FB,
BF), activated carbon (AC) and magnetic activated carbon (AF) (T = 25 ◦ C, adsorbent dosage = 0.05 g).

Fig. S8 shows the FTIR patterns of the adsorbents. For all the
five adsorbents, visible bands appeared around 3400, 1580,
1380 and 1080 cm−1 , corresponding to the vibration peaks of
OH, C C, -COOH and C-O, respectively (Baig et al., 2014; He
et al., 2018; Tan et al., 2019a). The intensity of OH and C O
peaks slightly increased for FB, BF and AF in comparison with
BC and AC, respectively. In addition, the band around 580 cm−1
was assigned to Fe O vibration in the magnetic adsorbents
(Lim et al., 2009; Baig et al., 2014). These results indicated
that the functional groups on the surface of adsorbents were
altered after magnetization and the oxygen-containing groups
were increased (i.e. OH and C O). Fig. S9 depicts the zeta
potentials of adsorbents. The zeta potentials of all magnetic
adsorbents obviously shifted toward higher pH in comparison
with BC and AC, indicating the increase of positive charges at
the surface of FB, BF and AF. Therefore, these magnetic adsor-
bents could have higher adsorption capacity for the anionic
pollutants due to the electrostatic interaction.
3.2. Effects of solution pH on As(V), TC and NO3 −
adsorption
The amounts of As(V) retained by the adsorbents at differ-
ent pH values are shown in Fig. 1a. The As(V) adsorption
decreased with increasing solution pH for all the adsorbents
especially at pH > 7, which was consistent with the results of
Baig et al. (2014) and Zhou et al. (2017). According to He et al.
(2018), the predominant AS(V) species were H2 AsO4 − at pH < 7
and HAsO4 2− at pH > 7. The zeta potentials of adsorbents
gradually changed from positive at low pH to negative at
high pH, except for BC. As a result, these adsorbents could
adsorb negatively charged As(V) species at low pH, while
there was electrostatic repulsion between the As(V) species
and the negatively charged adsorbents at high pH. Although
BC was generally negatively charged at pH 3–11, some of the
functional groups could be protonated and thus positively
charged. Thereby, BC had a relatively higher As(V) adsorption
at low pH. Similarly, the NO3 − adsorption also decreased with
increasing solution pH for all the adsorbents (Fig. 1c), which
was similar with the result of Usman et al. (2016). At low pH,
there were more positively charged sites on the surface of
adsorbents due to the reduction of negative charges by the
excessive protons in solution (Usman et al., 2016).
As an amphoteric molecule, TC has three pKa values (3.3,
7.7 and 9.7). The predominant species of TC will be H4 TC+
at pH < 3.3, H3 TC at 3.3 < pH < 7.7, H2 TC− at 7.7 < pH < 9.7, and
HTC2− at pH > 9.0, respectively (Liu et al., 2012; Zhu et al.,
2014a). Fig. 1b presents the effect of pH on TC adsorption.
Similar to the findings of Zhao et al. (2011) and Lian et al.
(2013), the adsorption of TC on all the adsorbents gradu-
ally increased in this study with the increase of pH, and
reached the maximum level at pH 7, except for BC. For FB, BF,
AC and AF, electrostatic repulsion would occur between the
adsorbents and cationic TC at acidic pH. With the increase
of pH, TC molecules gradually became neutral or negatively
charged through deprotonation, resulting in higher adsorption
affinity with the adsorbents through electrostatic attractions.
However, when pH further increased, the adsorbents became
negatively charged, resulting in electrostatic repulsion with
anionic TC and therefore the decline in adsorption. Regarding
BC, the adsorption of TC slightly decreased with the increase
in solution pH from 3 to 11, attributed to the negatively charged
surface of BC that exhibited higher adsorption affinity with
cationic TC at low pH.
586 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 582–591

Fig. 2 – Adsorption kinetics and isotherms of As(V) with/without 50 mg L−1 TC or 30 mg L−1 NO3 − onto the biochar (BC),
magnetic biochars (FB, BF), activated carbon (AC) and magnetic activated carbon (AF) (solid lines represent Langmuir model
and dashed lines represent Freundlich model in adsorption isotherm, T = 25 ◦ C, adsorbent dosage = 0.05 g).

Table 2 – Kinetic parameters for As (V), TC and NO3 − adsorption onto the biochar (BC), magnetic biochars (FB, BF),
activated carbon (AC) and magnetic activated carbon (AF).
Model Parameters 30 mg L−1 As (V) 400 mg L−1 TC 30 mg L−1 NO3 −

BC FB BF AC AF BC FB BF AC AF BC FB BF AC AF

Pseudo first qe (mg g−1 ) 0.797 5.790 3.225 1.054 1.974 12.038 42.519 37.054 535.82 192.26 0.567 5.285 2.642 0.845 1.131
order
k1 (h−1 ) 0.022 0.256 0.156 0.105 0.132 0.011 0.015 0.011 0.00238 0.0031 0.040 0.092 0.016 0.043 0.070
R2 0.623 0.877 0.888 0.624 0.924 0.952 0.901 0.982 0.984 0.981 0.753 0.968 0.749 0.776 0.729
Pseudo qe (mg g−1 ) 0.822 5.901 4.371 1.332 3.586 12.024 41.165 35.745 546.913 189.815 0.59 5.469 2.795 0.897 1.189
second order
k2 (g mg−1 h−1 ) 0.030 0.066 0.040 0.070 0.034 0.0014 5 × 10−4 6 × 10−4 6 × 10−6 2 × 10−5 0.12 0.031 0.011 0.079 0.095
R2 0.803 0.990 0.983 0.855 0.991 0.908 0.885 0.853 0.926 0.902 0.915 0.968 0.839 0.953 0.939

Table 3 – Adsorption isotherm parameters for As (V) in single solute or co-solute system with tetracycline (50 mg L−1 ) or
NO3 − (30 mg L−1 ) onto the biochar (BC), magnetic biochars (FB, BF), activated carbon (AC) and magnetic activated carbon
(AF).
Model Parameters Single-solute Co-solute (with 50 mg L−1 TC) Co-solute (with 30 mg L−1 NO3 − )

BC FB BF AC AF BC FB BF AC AF BC FB BF AC AF

Langmuir Qm (mg g−1 ) 1.14 6.77 4.20 1.59 2.70 0.94 5.76 3.44 1.54 2.57 0.97 6.43 4.01 1.33 2.52
KL (L mg−1 ) 0.057 0.120 0.075 0.045 0.067 0.045 0.114 0.052 0.040 0.052 0.035 0.098 0.056 0.048 0.045
R2 0.987 0.986 0.963 0.988 0.975 0.965 0.989 0.958 0.990 0.985 0.969 0.986 0.959 0.978 0.990
Freundlich KF (mg g−1 )(mg L−1 )−n 0.276 1.805 1.226 0.281 1.094 0.159 1.422 0.732 0.244 0.788 0.117 1.474 0.931 0.223 0.659
1/n 0.497 0.409 0.441 0.529 0.460 0.542 0.409 0.497 0.546 0.519 0.599 0.436 0.479 0.528 0.537
R2 0.952 0.981 0.957 0.953 0.972 0.936 0.939 0.972 0.964 0.946 0.946 0.967 0.972 0.916 0.966

3.3. Adsorption kinetics and capacity
3.3.1. As(V) removal in a monocomponent solution
Fig. 2a presents the adsorption kinetics of As(V), and the
parameters obtained from pseudo-first-order and pseudo-
second-order models are listed in Table 2. Rapid adsorption
of As(V) was observed within the first 3 h, especially on
magnetic adsorbents, and then quick approaching to the
equilibrium. For all the adsorbents, the R2 values of the
pseudo-first-order model (0.623–0.924) were lower than those
of the pseudo-second-order model (0.803–0.991). The results
suggested that the number of active sites on the surface of
adsorbents played a key role in the reaction rate and chemi-
cal adsorption was the rate-limiting step (Zhou et al., 2017).
Fig. 2b shows the adsorption isotherms of As(V). Table 3
gives the correlation coefficients and adsorption constants
determined from Langmuir and Freundlich isotherms. The
Langmuir model described the adsorption of As(V) on the
adsorbents better than the Freundlich model, suggesting that
As(V) was adsorbed through monolayer adsorption onto the
surface of the adsorbent. According to the Langmuir model,
the maximum adsorption capacities of FB (6.77 mg g−1 ) and BF
(4.20 mg g−1 ) increased by 4.94 and 2.68 times in comparison
with BC (1.14 mg g−1 ), respectively. Similarly, the adsorption
capacity of AF (2.70 mg g−1 ) increased by 70% in compari-
son with AC (1.59 mg g−1 ). These results indicated that ferric
chloride magnetization was an effective way to improve the
removal of aqueous As(V). Besides, the maximum adsorption
capacity of FB was much higher than that of many previously
reported Fe-impregnated adsorbents (Table S1), suggesting
that the produced magnetic biochar can be an efficient adsor-
bent to remove aqueous As(V).
3.3.2. TC removal in a monocomponent solution
Fig. 3a presents the effect of contact time on TC adsorption by
various adsorbents. Table 2 presents the parameters obtained
from pseudo-first-order and pseudo-second-order models.
Unlike As(V), it took nearly 7 d for the TC adsorption to reach
 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 582–591 587

Fig. 3 – Adsorption kinetics and isotherms of tetracycline (TC) with/without 30 mg L−1 As(V) or 30 mg L−1 NO3 − onto the
biochar (BC), magnetic biochars (FB, BF), activated carbon (AC) and magnetic activated carbon (AF) (solid lines represent
Langmuir model and dashed lines represent Freundlich model in adsorption isotherm, T = 25 ◦ C, adsorbent dosage = 0.05 g).

Table 4 – Adsorption isotherm parameters for TC in single solute or co-solute system with As (V) (30 mg L−1 ) or NO3 −
(30 mg L−1 ) onto the biochar (BC), magnetic biochars (FB, BF), activated carbon (AC) and magnetic activated carbon (AF).
Model Parameters Single-solute Co-solute (with 30 mg L−1 As (V)) Co-solute (with 30 mg L−1 NO3 − )

BC FB BF AC AF BC FB BF AC AF BC FB BF AC AF

Langmuir Qm (mg g−1 ) 12.24 49.57 44.07 612.38 211.34 8.77 42.59 34.15 562.46 191.32 9.64 45.55 38.39 578.49 196.48
KL (L mg −1 ) 0.066 0.037 0.019 0.076 0.047 0.024 0.026 0.017 0.066 0.037 0.044 0.025 0.017 0.066 0.039
R2 0.976 0.963 0.968 0.935 0.935 0.926 0.958 0.978 0.978 0.953 0.952 0.959 0.951 0.977 0.958
Freundlich KF (mg g−1 )(mg L−1 )−n 4.276 8.674 5.032 131.39 46.63 1.122 5.882 3.231 95.01 35.846 2.007 6.364 3.689 95.04 37.15
1/n 0.180 0.269 0.359 0.311 0.265 0.303 0.326 0.381 0.355 0.291 0.216 0.305 0.379 0.358 0.285
R2 0.963 0.987 0.967 0.938 0.942 0.968 0.978 0.930 0.932 0.909 0.966 0.959 0.952 0.939 0.916

equilibrium. Fig. 3b presents the adsorption isotherms of TC,
and the Langmuir and Freundlich model fittings. The best-fit
model parameters can be found in Table 4. Both isotherms
can well describe the equilibrium data, indicating that the
TC adsorption on the adsorbents included not only mono-
layer physical adsorption process but also some chemical
interactions (Liu et al., 2012). According to the Langmuir
model (Table 4), the maximum adsorption capacities of FB
(49.56 mg g−1 ) and BF (44.07 mg g−1 ) increased by 3.05 and
2.60 times in comparison with BC (12.24 mg g−1 ). However,
the adsorption capacity of AF (211.34 mg g−1 ) decreased by
1.90 times in comparison with AC. The adsorption capacity
of AC (612.38 mg g−1 ) was comparable and even higher than
that of many other similar adsorbents (Table S1). Neverthe-
less, the use of phosphoric acid (85%) should be taken into
consideration when employing the produced AC.
3.3.3. NO3 − removal in a monocomponent solution
Fig. 4a presents the adsorption kinetics of NO3 − on the five
adsorbents, and parameters fitted with the kinetic models are
presented in Table 2. The apparent adsorption equilibrium was
reached in approximately 4 h, the pseudo-second-order model
gave the best fitting. Similar to As(V), the result indicated
that chemical adsorption could be the rate-limiting step. The
adsorption isotherms data were evaluated using the Langmuir
and Freundlich models (Fig. 4b), and the calculated parameters
are listed in Table 5. The adsorption of NO3 − tended to increase
with ascending NO3 − concentration until equilibrium was
achieved. The Langmuir maximum NO3 − adsorption capacity
on FB amounted to 6.31 mg g−1 , followed by BF (3.48 mg g−1 ),
AF (2.06 mg g−1 ), AC (1.28 mg g−1 ) and BC (0.82 mg g−1 ). The
order was similar to that for the As(V) adsorption, suggesting
that similar mechanism was involved and ferric chloride
magnetization was an efficient way to improve NO3 − adsorp-
tion as well. Additionally, the maximum adsorption capacity
of FB was much higher than that of many other adsorbents
(Table S1). Taking into account the high NO3 − adsorption
capacity and facile preparation method, the magnetic biochar
can be an excellent alternative to remove aqueous NO3 − .
3.4. Competitive adsorption
As shown in Figs. 2–4, the adsorption isotherms of As(V),
TC and NO3 − in the co-solute systems were shifted down-
ward compared to their corresponding isotherms in the single
solute systems, indicating the presence of competitive adsorp-
tion between different anionic pollutants. Under the condition
of 50 mg L−1 TC, the As(V) adsorption capacities decreased
by 17.54%, 14.92%, 18.09%, 3.14% and 4.81%, while the NO3 −
adsorption capacities decreased by 17.5%, 16.32%, 20.98%,
7.81% and 10.19% for BC, FB, BF, AC and AF, respectively, com-
pared to the single solute system. As shown in the graphical
illustration of postulated adsorption mechanisms (Fig. 5), in
a co-solute system, the adsorbed TC on the surface of adsor-
bents may block the access of As(V) and NO3 − to the surface
because of its large molecular size, thus suppress the adsorp-
tion of As(V) and NO3 − . Besides, as a kind of bulky molecule, TC
can induce a marked pore filling effect when being adsorbed
on carbonaceous material (Zhu et al., 2014b), thereby decrease
the adsorption of As(V) and NO3 − .
Under the condition of 30 mg L−1 NO3 − , the As(V) adsorp-
tion capacities decreased by 14.91%, 5.02%, 4.52%, 16.35% and
6.67% for BC, FB, BF, AC and AF, respectively, compared to the
single solute system. On the other hand, the NO3 − adsorption
capacities were inhibited by 24.39%, 18.07%, 26.44%, 35.94%
and 27.67% in the presence of 30 mg L−1 As(V) for BC, FB, BF,
588 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 582–591

Fig. 4 – Adsorption kinetics and isotherms of NO3 − with/without 30 mg L−1 As(V) or 50 mg L−1 tetracycline (TC) onto the
biochar (BC), magnetic biochars (FB, BF), activated carbon (AC) and magnetic activated carbon (AF) (solid lines represent
Langmuir model and dashed lines represent Freundlich model in adsorption isotherm, T = 25 ◦ C, adsorbent dosage = 0.05 g).

Table 5 – Adsorption isotherm parameters for NO3 − in single solute or co-solute system with As (V) (30 mg L−1 ) or TC
(50 mg L−1 ) onto the biochar (BC), magnetic biochars (FB, BF), activated carbon (AC) and magnetic activated carbon (AF).
Model Parameters Single-solute Co-solute (with 30 mg L−1 As (V)) Co-solute (with 50 mg L−1 TC)

BC FB BF AC AF BC FB BF AC AF BC FB BF AC AF
−1
Langmuir Qm (mg g ) 0.82 6.31 3.48 1.28 2.06 0.62 5.17 2.56 0.82 1.49 0.66 5.28 2.75 1.18 1.85
KL (L mg−1 ) 0.125 0.502 0.224 0.098 0.102 0.070 0.283 0.163 0.102 0.074 0.073 0.338 0.198 0.097 0.066
R2 0.997 0.946 0.970 0.994 0.973 0.975 0.916 0.973 0.972 0.991 0.930 0.954 0.986 0.977 0.963
Freundlich KF (mg g−1 )(mg L−1 )−n 0.156 2.272 0.927 0.208 0.354 0.075 1.537 0.576 0.138 0.195 0.082 1.816 0.933 0.184 0.238
1/n 0.398 0.291 0.338 0.433 0.421 0.487 0.336 0.377 0.423 0.471 0.480 0.312 0.280 0.434 0.488
R2 0.946 0.962 0.970 0.936 0.976 0.912 0.975 0.963 0.911 0.984 0.842 0.944 0.929 0.890 0.932

Fig. 5 – Graphical illustration of postulated mechanisms for the competitive adsorption of As(V), tetracycline (TC) and NO3 −
on magnetic adsorbent (e.g. FB) surface.

AC and AF, respectively. Compared to others, FB showed a
much smaller decrease in the adsorption capacities for As(V)
and NO3 − in the co-solute system, indicating its great poten-
tial for application in the co-contaminated environment with
heavy metals and inorganic anions. Besides, NO3 − imposed
less impact on the As(V) removal, especially for FB, BF and AF.
This could be attributed to the stronger electrostatic attrac-
tion of As(V) with Fe-adsorbent than that of NO3 − (An et al.,
2011; He et al., 2018). For the same reason, TC exerted stronger
inhibitory effect on NO3 − adsorption than on As(V) adsorption.
Under the condition of 30 mg L−1 As(V), the TC adsorp-
tion capacities decreased by 28.43%, 14.06%, 22.51%, 8.15% and
9.47% for BC, FB, BF, AC and AF, respectively, compared to the
single solute system. Similarly, the TC adsorption capacities
decreased by 21.24%, 8.09%, 12.89%, 5.53% and 7.03% for BC, FB,
BF, AC and AF, respectively, when 30 mg L−1 NO3 − was spiked.
The presence of either As(V) or NO3 − inhibited the adsorption
of TC in a co-solute system compared to the single system. In
addition, As(V) exerted stronger negative effect on TC adsorp-
tion than NO3 − . This could be firstly due to the formation of
 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 582–591
strong inner-sphere complexes between As(V) and the func-
tional groups on the adsorbent surface, which results in the
blockage to the pores. Secondly, the electrostatic interaction
of As(V) with the adsorption sites of adsorbent was much
stronger than that of NO3 − , because multivalent anion with
higher charge density was more readily adsorbed in compari-
son with monovalent anion (Divband Hafshejani et al., 2016).
Thirdly, As(V) of larger aqueous ionic radius induced stronger
steric repulsion than NO3 − , and thus stronger inhibitory effect
on the adsorption of TC (He et al., 2018). It is noteworthy that
AC and AF showed a much smaller decrease in the adsorption
capacity for TC in the co-solute system. Due to its relatively
higher adsorption capacities for As(V) and NO3 − , AF could be
a promising adsorbent to remediate the aquatic environment
with multiple contaminants.
3.5. Adsorption mechanisms
It has been reported that the adsorption of As(V) was primarily
influenced by two factors: the As(V) speciation and the surface
charge of the adsorbent (Zhang et al., 2013; Wang et al., 2014).
As the adsorption kinetics and isotherms were conducted at
pH 6, As(V) mainly existed as HAsO4 2− under this circum-
stance, and generally FB, BF, AC and AF were all positively
charged. Besides, some functional groups on the surface of
biochar were positively charged because they could be pro-
tonated at pH 6. As a result, electrostatic attractions were
present between all the five adsorbents and As(V). In partic-
ular, the positive iron oxide particles on FB, BF and AF could
act as efficient adsorption sites for As(V) in aqueous solution.
The adsorption capacity for As(V) increased with ascending
iron ratio among FB, BF and AF, suggesting that the electro-
static anionic attraction on the H2 + –O–Fe-adsorbent played a
key role in As(V) adsorption (Usman et al., 2016). Neither the
XRD nor the XPS analyses of Fe2p showed obvious change for
the post-adsorption adsorbents compared to the original ones
(Figs. S3 and S6). These results demonstrated that As(V) in
the initial solution was only loaded onto the surface of the
adsorbents, and electrostatic attractions could be the main
mechanism for the As(V) removal. Similar to As(V), FB showed
the highest adsorption capacity for NO3 − and followed by
BF and AF, indicating that the elevated amount of iron can
adsorb more negatively charged NO3 − through electrostatic
attraction. In addition, as shown in Fig. S9 (pHpzc ), there were
more surface positive charges on FB, followed by BF and AF,
which could provide more surface functional groups and con-
sequently a higher affinity for NO3 − . AC exhibited higher NO3 −
adsorption, 1.39 times that of BC. This could be due to the
surface positive charges as well as high specific surface area.
Unlike As(V) and NO3 − , TC was primarily present as
zwitterion at pH 6, therefore hydrophobic effect could play
an important role in TC removal (Lian et al., 2013). Gen-
erally, as the specific surface area decreased in the order
of AC > AF > FB > BC > BF (Table 1), the maximum adsorption
capacities of these adsorbents for TC also decreased except
for BF and BC (Fig. 3). Larger surface areas can provide a
larger number of active adsorption sites for TC molecules
(Zhu et al., 2014b). Besides, the more porous and aromatic
structure of AC was more beneficial for TC removal, which
favored both specific interaction and hydrophobic effect (Zhu
et al., 2014b). Although the specific surface area of BF was
slightly lower than that of BC, the adsorption capacity of BF
for TC was much higher. One possible reason could be the
large average pore size in BF which favored the diffusion of
589
TC into the inner pore network (Table 1). Some other factors
can also influence TC adsorption such as electrostatic attrac-
tion and functional groups. Compared to BC, there were more
O-containing functional groups on the surface of FB, BF and
AF after magnetization (Fig. S8). The functional groups can
facilitate the formation of hydrogen bonds with TC molecules,
therefore improve the adsorption of TC (Jing et al., 2014). The
surficial Fe may also play a part in TC adsorption through
surface reactions and ion exchange (e.g. cation bridging and
complexation) (MacKay and Vasudevan, 2012; Lian et al., 2013).
Additionally, both biochar and activated carbon possessed
short stacks of small graphite-like sheets arranged in disor-
dered form (Liu et al., 2012). Due to the electron-withdrawing
ability of ketone groups, the TC molecules could act as
effective ␲-electron-acceptors. While the adsorbents could be
␲-electron-donors because of the polarized ␲-electron-rich
graphite surface. Therefore, the ␲–␲ electron donor-acceptor
(EDA) interaction could be formed between the TC molecules
and the adsorbents (Fig. 5) (Zhu et al., 2014a). Van der Waals
forces can also exist between the graphite surface of adsor-
bents and TC (Zhao et al., 2011; Liu et al., 2012). On the other
hand, according to the FTIR spectra (Fig. S8), several func-
tional groups (i.e. C O and Fe O) showed variations among
post-adsorption samples, suggesting that As(V), TC and NO3 −
would compete for finite adsorption sites in a co-solute system
(Fig. 5). In addition, they will repulse each other in a co-solute
system as anions. Therefore, their adsorption affinity to the
adsorbent would be significantly inhibited.
4. Conclusions
Magnetic biochar synthesized from one-step method showed
the highest As(V) and NO3 − adsorption capacities, which were
5.94 and 7.69 times that of the pristine biochar, respectively.
Competitive adsorption among As(V), TC and NO3 − occurred
on all adsorbents as they could all be anions. One-step mag-
netization of biochar was an efficient way to improve the
adsorption capacities of As(V) and NO3 − , showing a great
potential for application in the co-contaminated environment
with heavy metals and inorganic anions. Activated carbon
revealed the highest adsorption capacity for TC which was
decreased after magnetization. However, magnetic activated
carbon could still be a promising adsorbent to remediate the
aquatic environment with multiple contaminants.
Conflict of interest
None declared.
Acknowledgements
The study was supported by the National Natural Science
Foundation of China (41301311, 51579003), and the Shenzhen
Municipal Development and Reform Commission (Shenzhen
Engineering Research Center for Nanoporous Water Treat-
ment Materials, and Discipline construction of watershed
ecological engineering).
Appendix A. Supplementary data
Supplementary material related to this article can be
found, in the online version, at https://doi.org/10.1016/
j.cherd.2020.05.011.
590 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 582–591

References biomass and its application in removal of tetracycline from

aqueous solution. Bioresour. Technol. 121, 235–240.
MacKay, A.A., Vasudevan, D., 2012. Polyfunctional ionogenic
An, B., Liang, Q., Zhao, D., 2011. Removal of arsenic(V) from spent
compound sorption: challenges and new approaches to
ion exchange brine using a new class of starch-bridged
advance predictive models. Environ. Sci. Technol. 46,
magnetite nanoparticles. Water Res. 45, 1961–1972.
9209–9223.
Baig, S.A., Zhu, J., Muhammad, N., Sheng, T.T., Xu, X.H., 2014.
Mangwandi, C., Suhaimi, S.N.A., Liu, J.T., Dhenge, R.M., Albadarin,
Effect of synthesis methods on magnetic Kans grass biochar
A.B., 2016. Design, production and characterisation of
for enhanced As(III, V) adsorption from aqueous solutions.
granular adsorbent material for arsenic removal from
Biomass Bioenergy 71, 299–310.
contaminated wastewater. Chem. Eng. Res. Des. 110, 70–81.
Chen, J., Wu, H., Qian, H., 2016. Groundwater nitrate
Peng, L., Ren, Y., Gu, J., Qin, P., Zeng, Q., Shao, J., Lei, M., Chai,
contamination and associated health risk for the rural
L.J.E.S., Research, P., 2014. Iron improving bio-char derived
communities in an agricultural area of Ningxia, Northwest
from microalgae on removal of tetracycline from aqueous
China. Exposure Health 8, 349–359.
system. Environ. Sci. Pollut. Res. 21, 7631–7640.
Divband Hafshejani, L., Hooshmand, A., Naseri, A.A.,
Song, X., Zhang, Y., Luo, X., Chen, P., Liu, J., 2019. 2D magnetic
Mohammadi, A.S., Abbasi, F., Bhatnagar, A., 2016. Removal of
scallion sheathing-based biochar composites design and
nitrate from aqueous solution by modified sugarcane bagasse
application for effective removal of arsenite in aqueous
biochar. Ecol. Eng. 95, 101–111.
solutions. Chem. Eng. Res. Des. 152, 384–392.
Fujino, Y., Guo, X., Liu, J., You, L., Miyatake, M., Yoshimura, T.,
Tan, G., Mao, Y., Wang, H., Junaid, M., Xu, N., 2019a. Comparison
Japan Inner Mongolia Arsenic Pollution Study G, 2004. Mental
of biochar-and activated carbon-supported zerovalent iron for
health burden amongst inhabitants of an arsenic-affected
the removal of Se(IV) and Se(VI): influence of pH, ionic
area in Inner Mongolia, China. Soc. Sci. Med. 59, 1969–1973.
strength, and natural organic matter. Environ. Sci. Pollut. Res.
Fytianos, K., Christophoridis, C., 2004. Nitrate, arsenic and
26 (21), 21609–21618.
chloride pollution of drinking water in Northern Greece.
Tan, G., Sun, W., Xu, Y., Wang, H., Xu, N., 2016a. Sorption of
Elaboration by applying GIS. Environ. Monit. Assess. 93, 55–67.
mercury (II) and atrazine by biochar, modified biochars and
Guo, X., Fujino, Y., Kaneko, S., Wu, K., Xia, Y., Yoshimura, T., 2001.
biochar based activated carbon in aqueous solution.
Arsenic Contamination of Groundwater and Prevalence of
Bioresour. Technol. 211, 727–735.
Arsenical Dermatosis in the Hetao Plain Area, Inner Mongolia,
Tan, G., Wang, H., Xu, N., Junaid, M., Liu, H., Zhai, L., 2019b.
China, Molecular Mechanisms of Metal Toxicity and
Effects of biochar application with fertilizer on soil microbial
Carcinogenesis. Springer, pp. 137–140.
biomass and greenhouse gas emissions in a peanut cropping
He, R., Peng, Z., Lyu, H., Huang, H., Nan, Q., Tang, J., 2018.
system. Environ. Technol., 1–11.
Synthesis and characterization of an iron-impregnated
Tan, X.F., Liu, Y.G., Gu, Y.L., Xu, Y., Zeng, G.M., Hu, X.J., Liu, S.B.,
biochar for aqueous arsenic removal. Sci. Total Environ. 612,
Wang, X., Liu, S.M., Li, J., 2016b. Biochar-based
1177–1186.
nano-composites for the decontamination of wastewater: a
Hu, X., Zhou, Q., Luo, Y., 2010. Occurrence and source analysis of
review. Bioresour. Technol. 212, 318–333.
typical veterinary antibiotics in manure, soil, vegetables and
Tofighy, M.A., Mohammadi, T.J.C.E.R., Design, 2012. Nitrate
groundwater from organic vegetable bases, northern China.
removal from water using functionalized carbon nanotube
Environ. Pollut. 158, 2992–2998.
sheets. Chem. Eng. Res. Des. 90, 1815–1822.
Islam, M.A., Ali, I., Karim, S.M.A., Hossain Firoz, M.S., Chowdhury,
Usman, A.R., Ahmad, M., El-Mahrouky, M., Al-Omran, A., Ok, Y.S.,
A.-N., Morton, D.W., Angove, M.J., 2019. Removal of dye from
Sallam, A., El-Naggar, A.H., Al-Wabel, M.I., 2016. Chemically
polluted water using novel nano manganese oxide-based
modified biochar produced from conocarpus waste increases
materials. J. Water Process. Eng. 32, 100911.
NO3 − removal from aqueous solutions. Environ. Geochem.
Islam, M.A., Morton, D.W., Johnson, B.B., Mainali, B., Angove, M.J.,
Health 38, 511–521.
2018a. Manganese oxides and their application to metal ion
Wang, B., Wang, Z., Jiang, Y., Tan, G., Xu, N., Xu, Y., 2017.
and contaminant removal from wastewater. J. Water Process.
Enhanced power generation and wastewater treatment in
Eng 26, 264–280.
sustainable biochar electrodes based bioelectrochemical
Islam, M.A., Morton, D.W., Johnson, B.B., Pramanik, B.K., Mainali,
system. Bioresour. Technol. 241, 841–848.
B., Angove, M.J., 2018b. Metal ion and contaminant sorption
Wang, H., Zhang, D., Mou, S., Song, W., Al-Misned, F.A., Mortuza,
onto aluminium oxide-based materials: a review and future
M.G., Pan, X., 2015. Simultaneous removal of tetracycline
research. J. Environ. Chem. Eng. 6, 6853–6869.
hydrochloride and As(III) using poorly-crystalline manganese
Jing, X.-R., Wang, Y.-Y., Liu, W.-J., Wang, Y.-K., Jiang, H., 2014.
dioxide. Chemosphere 136, 102–110.
Enhanced adsorption performance of tetracycline in aqueous
Wang, S., Gao, B., Zimmerman, A.R., Li, Y., Ma, L., Harris, W.G.,
solutions by methanol-modified biochar. Chem. Eng. J. 248,
Migliaccio, K.W., 2014. Removal of arsenic by magnetic biochar
168–174.
prepared from pinewood and natural hematite. Bioresour.
Kilpimaa, S., Runtti, H., Kangas, T., Lassi, U., Kuokkanen, T., 2014.
Technol. 175C, 391–395.
Removal of phosphate and nitrate over a modified carbon
Wu, P., Ata-Ul-Karim, S.T., Singh, B.P., Wang, H., Wu, T., Liu, C.,
residue from biomass gasification. Chem. Eng. Res. Des. 92,
Fang, G., Zhou, D., Wang, Y., Chen, W., 2019. A scientometric
1923–1933.
review of biochar research in the past 20 years (1998–2018).
Lehmann, J., Joseph, S., 2015. Biochar for Environmental
Biochar 1, 23–43.
Management: Science, Technology and Implementation.
Xia, S., Shen, S., Xu, X., Liang, J., Zhou, L., 2014. Arsenic removal
Routledge.
from groundwater by acclimated sludge under
Li, A., Pi, S., Wei, W., Chen, T., Yang, J., Ma, F., 2016. Adsorption
autohydrogenotrophic conditions. J. Environ. Sci. 26, 248–255.
behavior of tetracycline by extracellular polymeric substrates
Xu, N., Tan, G., Wang, H., Gai, X., 2016. Effect of biochar additions
extracted from Klebsiella sp. J1. Environ. Sci. Pollut. Res. 23,
to soil on nitrogen leaching, microbial biomass and bacterial
25084–25092.
community structure. Eur. J. Soil Biol. 74, 1–8.
Lian, F., Song, Z., Liu, Z., Zhu, L., Xing, B., 2013. Mechanistic
Xu, N., Zhang, B., Tan, G., Li, J., Wang, H., 2015. Influence of
understanding of tetracycline sorption on waste tire powder
biochar on sorption, leaching and dissipation of bisphenol A
and its chars as affected by Cu(2+) and pH. Environ. Pollut.
and 17␣-ethynylestradiol in soil. Environ. Sci. Process. Impact
178, 264–270.
17, 1722–1730.
Lim, S.-F., Zheng, Y.-M., Chen, J.P., 2009. Organic arsenic
Zhang, H., Ma, D.S., Hu, X.X., 2002. Arsenic pollution in
adsorption onto a magnetic sorbent. Langmuir 25, 4973–4978.
groundwater from Hetao Area, China. Environ. Geol. 41,
Liu, P., Liu, W.J., Jiang, H., Chen, J.J., Li, W.W., Yu, H.Q., 2012.
638–643.
Modification of bio-char derived from fast pyrolysis of
 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 582–591
Zhang, M., Gao, B., Varnoosfaderani, S., Hebard, A., Yao, Y., Inyang,
M., 2013. Preparation and characterization of a novel magnetic
biochar for arsenic removal. Bioresour. Technol. 130, 457–462.
Zhao, Y., Geng, J., Wang, X., Gu, X., Gao, S., 2011. Tetracycline
adsorption on kaolinite: pH, metal cations and humic acid
effects. Ecotoxicology 20, 1141–1147.
Zhou, Z., Liu, Y.-g., Liu, S.-b., Liu, H.-y., Zeng, G.-m., Tan, X.-f.,
Yang, C.-p., Ding, Y., Yan, Z.-l., Cai, X.-x., 2017. Sorption
performance and mechanisms of arsenic(V) removal by
591
magnetic gelatin-modified biochar. Chem. Eng. J. 314, 223–231.
Zhu, X., Liu, Y., Qian, F., Zhou, C., Zhang, S., Chen, J., 2014a.
Preparation of magnetic porous carbon from waste hydrochar
by simultaneous activation and magnetization for
tetracycline removal. Bioresour. Technol. 154, 209–214.
Zhu, X., Liu, Y., Zhou, C., Luo, G., Zhang, S., Chen, J., 2014b. A
novel porous carbon derived from hydrothermal carbon for
efficient adsorption of tetracycline. Carbon 77, 627–636.