Science of The Total Environment
Science of The Total Environment
Science of The Total Environment
H I G H L I G H T S G R A P H I C A L A B S T R A C T
a r t i c l e i n f o a b s t r a c t
Article history: In this study, the effect factors and mechanisms of doxycycline hydrochloride (DOX) adsorption on copper nitrate
Received 6 January 2017 modified biochar (Cu-BC) was investigated. Cu-BC absorbent was synthesized through calcination of peanut
Received in revised form 2 March 2017 shells biomass at 450 °C and then impregnation with copper nitrate. The Cu-BC has exhibited excellent sorption
Accepted 9 March 2017
efficiency about 93.22% of doxycycline hydrochloride from aqueous solution, which was double higher than that
Available online xxxx
of the unmodified biochar. The experimental results suggest that the adsorption efficiency of DOX on the Cu-BC is
Editor: D. Barcelo dominated by the strong complexation, electrostatic interactions between DOX molecules and the Cu-BC sam-
ples. Comprehensively considering the cost, efficiency and the application to realistic water, the Cu-BC hold
Keywords: the significant potential for enhancing the effectiveness to remove DOX from water.
Biochar © 2017 Elsevier B.V. All rights reserved.
DOX
Adsorption
Copper modification
Water treatment
1. Introduction
Abbreviations: DOX, doxycycline hydrochloride; BC, biochar; Cu-BC, copper nitrate
modified biochar; SEM, scanning electron microscopy; XRD, X-ray diffraction; XPS, X-ray Modern society is confronted with a challenge of antibiotics contam-
Photoelectron Spectrometer; FTIR, Fourier transform infrared spectrophotometer.
⁎ Corresponding authors at: College of Environmental Science and Engineering, Hunan
inants, which is harmful to the human health and environment
University, Changsha 410082, PR China. (Kummerer, 2009). Antibiotics are widely applied to improve the
E-mail addresses: whxu@hnu.edu.cn (W. Xu), liuyunguo@hnu.edu.cn (Y. Liu). human health, prevent and treat infections of plants and animals, as
http://dx.doi.org/10.1016/j.scitotenv.2017.03.087
0048-9697/© 2017 Elsevier B.V. All rights reserved.
Please cite this article as: Liu, S., et al., Facile synthesis of Cu(II) impregnated biochar with enhanced adsorption activity for the removal of
doxycycline hydrochloride from..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.03.087
2 S. Liu et al. / Science of the Total Environment xxx (2017) xxx–xxx
well as promote the animal husbandry growth (Martinez, 2009). How- experiments. All chemicals employed in the experiments were pur-
ever, some studies indicated that about 30–90% of antibiotics were chased at analytic purity and used.
weakly absorbed and released into the environment as the parent com-
pound (Gao et al., 2012; Liu et al., 2011). The related research pointed
2.2. Preparation of sorbents
out that the antibiotics had been detected potable in surface water
and ground water (Ternes, 1998). However, antibiotics in traditional
Peanut shells were first washed with high purified water, dried and
wastewater sewage treatment plants are removed with low efficiency
shattered to pieces. BC was obtained by pyrolyzing the feedstock in a
which resulted in higher antibiotic resistance (Ling et al., 2013). DOX,
lab-scale tubular reactor (SK-G08123K, China) at 450 °C in a flow of
an effective road-spectrum antibiotic, it is used to treat a number of dif-
N2 for 2 h. The BC were modified as follows: 1 g prepared BC and 2 g
ferent bacterial infections which could keep bacteria from reproducing
Cu(NO3)2·2H2O was mixed with 100 mL high purified water in a
and synthesizing protein (Phaechamud and Charoenteeraboon, 2008;
200 mL conical flask and then it was shaken in a temperature controlled
Vargas-Estrada et al., 2008). Their complicated structures and variable
shaker (SHZ-88, Shanghai) at 150 rpm at 25 °C for 16 h. Then the mod-
physicochemical properties caused their complex behavior in the envi-
ified BC was filtered and washed with purified water by vacuum filtra-
ronment. Developing an efficient, sustainable and economically feasible
tion until the pH close to neutral. Finally the sorbent was reserved in
adsorbent is an effective way to remove the antibiotics pollutants from
desiccators before used.
waste water. Some studies have shown that graphene (Gao et al., 2012),
mesoporous silica (Zhang et al., 2015), montmorillonite (Zhao et al.,
2012) and carbon nanotubes (Kim et al., 2014; Tang et al., 2014; 2.3. Characterization methods
Zhang et al., 2016) were effective and widely used as sorbent for remov-
ing contaminant. However their high cost and complicated process lim- The morphology of adsorbent was characterized which was used to
ited their application. BC and activated carbon are the preferred compare the structure and surface characteristics of the materials by a
adsorbent for the removal of contaminant from water. They have field-emission scanning electron microscopy (JEOL JSM-6700. Japan).
some favorable physical/chemical surface characteristics such as exten- The X-ray diffraction (XRD) patterns of samples were obtained using
sive surface area and well-developed pore structure (Ahmed et al., an X-ray diffractometer (Rigaku D/max-2500, Japan), with Cu Kα radi-
2015; Li et al., 2013b; Sun et al., 2013). The raw materials for activated ation (λ = 1.541 Å) over the 2θ range of 10–80°. The elemental compo-
carbon production are mostly obtained from coal and timber which sition of the samples was examined using an ESCALAB 250Xi X-ray
are nonrenewable and relatively expensive. Nevertheless, BC is the py- Photoelectron Spectrometer (XPS) (Thermo Fisher, USA). Surface or-
rolytic product of various waste biomass sources (i.e. forest energy, ganic functional groups of BC were analyzed by a Fourier transform in-
crop straw, livestock manure, living garbage), which is more environ- frared spectrophotometer (FTIR) (Nicolet, 6700 spectrometer, USA).
mentally and economically viable (Tan et al., 2015; Wang et al., 2013; Spectra were obtained at the 4000–400 cm−1 region. The surface charge
Yao et al., 2011). Therefore, BC is a feasible substitute for activated car- of the samples was determined by measuring the zeta potential using an
bon that is widely employed in removing contaminants from aqueous electroacoustic spectrometer (Zetasizer Nano-ZS90, Malvern) under a
solution. Numerous studies have shown that metallic catalysts modified solution pH varying from 2.0 to 11.0.
biochar can enhance the capacity and selectivity for pollutant removal.
Wang et al. (Wang et al., 2016) synthesized Ni and Mn oxides biochar
and the results showed that the adsorption capacity of the modified 2.4. Adsorption batch experiment
BC was increased compared with the pristine biochar. Hu et al. (Hu et
al., 2015) studied iron-impregnated biochar and the results indicated To avoid photodegradation, all sample flasks or tubes were wrapped
that the specific surface areas of the biochar was decreased through by aluminum-foil in all the batch experiments. A stock solution
iron impregnation, which caused much better sorption of As. Fang et (1000 mg/L) of DOX was always freshly prepared by dissolving 0.2 g
al. (Fang et al., 2014) used Mg modified corn biochar to remove P, and of DOX into 1000 mL distilled water during all the experiments. Differ-
obtained the predictive effect. ent DOX concentrations used in batch experiments were obtained
In this work, biochar was derived from peanut shell in a N2 atmo- through diluting the stock solution. 20 mg/L was the initial concentra-
sphere at 450 °C without oxidation and then impregnated with Cu(II). tion of DOX solution. The batch experiments for sorption of DOX were
Cu(II) has a significant tendency to form complexes in solution with carried out in 100 mL conical flasks containing 0.10 g of Cu-BC and
various functional groups present in organic matter, i.e. \\COOH and 50 mL DOX solution, then shaken with a speed of 150 rpm for 24 h at
\\OH. Selecting DOX as a target pollutant, we investigated the sorption 25 °C. The DOX solution pH was adjusted by adding negligible volumes
performance of Cu-BC by batch of experiments. The main goals of this of 0.1 M NaOH or HCl. At predetermined time, the mixture was drawn
work were to: (1) synthesize and characterize the Cu-BC, (2) test the and separated by filtration. The remaining concentration of DOX in the
effects of the solution pH and ionic strength on DOX adsorption, adsorp- supernatant was determined on a UV–vis spectrophotometer (UV-
tion kinetics, adsorption isotherms and the DOX removal ability of the 2550, SHIMADZU, Japan) at wavelength (kmax) of 351 nm (Alkhraisat
Cu-BC, (3) analyze the sorption mechanism of DOX onto the Cu-BC et al., 2010) using calibration curve. Adsorption efficiency E (%) and
under different physical and chemical conditions. the adsorption capacity qe (mmol/kg) of DOX were calculated using
the following equations:
Please cite this article as: Liu, S., et al., Facile synthesis of Cu(II) impregnated biochar with enhanced adsorption activity for the removal of
doxycycline hydrochloride from..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.03.087
S. Liu et al. / Science of the Total Environment xxx (2017) xxx–xxx 3
3.1. Characterization
Please cite this article as: Liu, S., et al., Facile synthesis of Cu(II) impregnated biochar with enhanced adsorption activity for the removal of
doxycycline hydrochloride from..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.03.087
4 S. Liu et al. / Science of the Total Environment xxx (2017) xxx–xxx
Fig. 3. XPS spectra of (a) C1s, (b) N1s, (c) O1s and (d) Cu2p of Cu-BC.
initial concentration of 20 mg/L. In short, Cu-BC exhibited excellent might come from both cationic (amine) and anionic (hydroxyl or car-
sorption efficiency compared with pristine biochar. boxyl) groups in their molecules. According to the zeta potential-pH
profiles, the sorption efficiency of DOX increased quickly at pH b 4.0,
3.3. Effect of pH on the DOX adsorption slowly at pH 4.0–8.0, and decreased rapidly at pH N 8.0. These
phenomena might be attributed to the strong electrostatic
The solution pH is an important factor to investigate the adsorption interactions between DOX molecules and Cu-BC adsorbent
process, because it can affect the sorption characteristics and the degree surfaces. The maximum adsorption efficiency (93.22%) was
of ionization and speciation of the sorbent (Kołodyńska et al., 2012). occurred at pH 8.0, because of the difference between positive and
The experiment investigated the effect of pH ranged from 2.0–11.0 on negative surface charges reached the largest value of charge. Thus,
sorption. Zeta potential of two samples and DOX sorption efficiency pH = 8.0 was the optimal pH for the adsorption experiments. And the
under different pH are measured and illustrated in Fig. 6. The tested ma- electrostatic interaction might be a major factor controlling the adsorp-
terials showed amphoteric properties: The properties of Cu-BC and DOX tion process.
Fig. 4. FTIR spectra of (a) BC, (b) Cu-BC and (c) Cu-BC after DOX adsorption. Fig. 5. The comparison of adsorption efficiency on BC and Cu-BC under 298 K.
Please cite this article as: Liu, S., et al., Facile synthesis of Cu(II) impregnated biochar with enhanced adsorption activity for the removal of
doxycycline hydrochloride from..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.03.087
S. Liu et al. / Science of the Total Environment xxx (2017) xxx–xxx 5
t 1 t
pseudo‐second‐order : ¼ þ ð4Þ
qt k2 qe 2 qe
qe ¼ kp t 0:5 þ C ð5Þ
Table 1
Pseudo-first-order and pseudo-second-order kinetic models of DOX adsorption on the
Cu-BC.
qe,1 K1 R2 qe,2 K2 R2
Fig. 7. Kinetics of DOX sorption onto Cu-BC: (a) pseudo-first-order and pseudo-second- (mmol/kg) (1/min) (mmol/kg) (kg/mmol min)
order sorption kinetics; (b) intra-particle diffusion kinetics (C0(DOX) = 20 mg/L, pH =
18.764 18.073 0.107 0.929 18.916 0.001 0.993
8.0 ± 0.2, t = 24 h, T = 298 K).
Please cite this article as: Liu, S., et al., Facile synthesis of Cu(II) impregnated biochar with enhanced adsorption activity for the removal of
doxycycline hydrochloride from..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.03.087
6 S. Liu et al. / Science of the Total Environment xxx (2017) xxx–xxx
298 52.374 0.124 0.959 103.014 0.295 0.906 1.513 10.160 0.958 298 8.190 −2.029 68.136 13.957
318 69.065 0.108 0.956 141.203 0.309 0.792 1.117 14.383 0.907 308 8.373 −2.144
338 93.498 0.079 0.965 183.728 0.356 0.838 0.214 17.230 0.940 318 8.461 −2.237
Please cite this article as: Liu, S., et al., Facile synthesis of Cu(II) impregnated biochar with enhanced adsorption activity for the removal of
doxycycline hydrochloride from..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.03.087
S. Liu et al. / Science of the Total Environment xxx (2017) xxx–xxx 7
4. Conclusions
showed that the equilibrium sorption efficiency was influenced by the Acknowledgments
existence of cations. Na+, K+ promoted the adsorption of DOX while
the Ca2+, Mg2+, Mn2+ inhibited. The effect of promotion/inhibition en- This research was financially supported by the National Natural
hanced with the increase of concentration. Obviously, the effect of the Science Foundation of China (Grant Nos. 51609268, 51108167 and
divalent cations were higher than monovalent cations, and the adsorp- 51521006), and the Hunan Provincial Innovation Foundation for Post-
tion efficiency of Na+, K+ was little difference, which suggested that graduate (Grant Nos. CX2015B090 and CX2016B135).
DOX adsorption onto Cu-BC was little sensitive to the with the same
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Please cite this article as: Liu, S., et al., Facile synthesis of Cu(II) impregnated biochar with enhanced adsorption activity for the removal of
doxycycline hydrochloride from..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.03.087