Chemosphere 164 (2016) 32e40

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Chemosphere
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Adsorption of arsenic, phosphorus and chromium by bismuth

impregnated biochar: Adsorption mechanism and depleted adsorbent
utilization
Ningyuan Zhu a, b, Tingmei Yan a, *, Jun Qiao a, Honglei Cao a, b
a
Institute of Soil Science, Chinese Academy of Sciences, No. 71 East Beijing Road, Nanjing 210008, China
b
Graduate School of the Chinese Academy of Sciences, Beijing 100039, China

h i g h l i g h t s

Bismuth activated carbons derived from wheat straw were fabricated.

Bismuth particles grown within biochar matrix.

BiBC500 showed high adsorption capacity to arsenic, phosphorus and chromium.

Adsorption mechanisms of arsenic, phosphorous and chromium were illustrated.

Phosphate depleted material could photodegrade dye pollutant.

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

Article history: Bismuth impregnated biochar were synthesized to deal with wastewater pollution. Nitrogen adsorption-
Received 20 April 2016 desorption isotherms, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy
Received in revised form (FTIR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to determine the
25 July 2016
characteristics of adsorbents and explore the main adsorption mechanism. Results showed that bismuth
Accepted 7 August 2016
Available online 28 August 2016
particle was carried successfully within the biochar matrix, making contributions to creating micropore
and boost specific surface area. The loaded bismuth, served as the adsorption site, rather than the specific
Handling Editor: X. Cao surface area played an important role in arsenic and phosphorus adsorption. Batch adsorption experi-
ments demonstrated a fit Langmuir model for arsenic (As) and phosphorus (P) and a suitable Freundlich
Keywords: model for chromium (Cr). Thermodynamic parameters depicted the endothermic nature and the
Bismuth spontaneous process for phosphate and arsenic adsorption. Besides, this contaminant-loaded carbon
Activated carbon adsorbent was further applied for the removal of methylene blue from aqueous solution.
Adsorption mechanism © 2016 Elsevier Ltd. All rights reserved.
Depleted adsorbents

1. Introduction environment and human beings because of their high toxicity, non-
biodegradation and accumulation through food chain. Thus, the
The continuous growth of population, increasing reinforcement World Health Organization recommended that the maximum
of agricultural activities and rapid development of urbanization and permissible limit for arsenic should be 10 mg L1 while the
industrialization worsen water quality of our water resources maximum limit for chromium be 0.05 mg L1 in drinking water (Liu
which is the most essential component for life (Ali, 2012). The et al., 2008; Tang et al., 2014; Wang et al., 2010).
excessive input of phosphorus in surface water worsened eutro- Therefore, it is very imperative to deal with contaminated
phication and algae blooms as well as deteriorated the quality of wastewater prior to its discharge into soil and water environment.
the groundwater severely. Heavy metals, especially the chromium Many researchers have explored various methods such as chemical
and arsenic, are more problematic and threatening to ecological precipitation, gravity separation, solvent extraction, reverse
osmosis, ion-exchange, electrocoagulation and electrodialysis,
flotation and adsorption for removing phosphate or heavy mental
irons from sewage system (Hua et al., 2012). For instance, Afkhami
* Corresponding author.
et al. synthesized DNPH (nano-alumina modified with 2,4-
E-mail address: [email protected] (T. Yan).

http://dx.doi.org/10.1016/j.chemosphere.2016.08.036
0045-6535/© 2016 Elsevier Ltd. All rights reserved.
 N. Zhu et al. / Chemosphere 164 (2016) 32e40 33

dinitrophenylhydrazine) with a satisfying adsorption capacity to- and then dried at 105  C. The biochar precursors were then heated
ward Pb (II), Cr (III) and Cd (II) ions in a multiple-metal solution, to setting temperature (400, 500 and 600  C) and finally main-
indicating that DNPH is a promising adsorbent for heavy mental tained for 60 min in a furnace with the heating rate of 10  C min1
treatment (Afkhami et al., 2010). Nevertheless, few researches under nitrogen flow. Finally, the biochar materials were washed
developed effective, efficient, economical and eco-friendly mate- with 0.01 M NaHCO3 solution and distilled water for three times.
rials or methods for reduction of arsenic, phosphate and chromium Activated carbons were labelled as BiBC400, BiBC500 and BiBC600
pollutant which are more difficult to be removed because of their while the control labelled as CBC400, CBC500 and CBC600.
anion form (Alemayehu et al., 2011; Onnby et al., 2014). In addition,
the removal efficiency of As (III) is much lower than As (V) for 2.2. Characterization of adsorbents
adsorption process was unable to act on the uncharged form of As
(III) especially at environmentally relevant pH (Sun et al., 2013). Porosity and surface characteristics were measured by N2
But, arsenite is more toxic, soluble, and mobile than arsenate. (0.162 nm2) adsorption using a NOVA-2000E (Quantachrome, USA)
Fortunately, metal salt, metal oxides and hydrous metal oxides surface area analyzer. Brunauer-Emmertt-Teller (BET) surface area
such as granular ferric hydroxide (Banerjee et al., 2008), TiO2 (Liu and average pore diameter of the BiBCs and CBCs were determined
et al., 2008), akaganeite (Lazaridis et al., 2005), and Na2SO3/FeSO4 by multipoint BET analysis of adsorption data points with relative
(Pan et al., 2014) have been well explored for arsenic, phosphorus pressures of 0.05e0.3. Surface functional groups were detected by
or chromium treatment. Adsorption is recognized as one of the Fourier transform infrared spectroscopy (FTIR) (Nicolet IS10,
most available option because of its low cost and high efficiency. Thermo Electron Co, USA) at a spectral range of 4000 cm1 to
However, handling and disposal of the waste sludge is still a 400 cm1 with a resolution of 8 cm1. X-ray diffraction (XRD)
cumbersome problem limiting their actual industrial application. patterns of the synthesized biochars were measured by a Siemens
Furthermore, there is still lack of economical way to transform D-501 diffractometer with Ni filter and graphite monochromator.
more agricultural residues like straw resources to valuable and Furthermore, X-ray photoelectron spectroscopy (XPS) and scanning
green by-product whether in production sites or in factory for their electron microscopy (SEM) were used to further investigate the
high-fibre content and low-protein quality. After harvest season, adsorption mechanism and determine its surficial morphology
farmers burn crop stalk in great quantities, causing serious envi- characteristics.
ronmental problems such as haze which may pose a serious threat
to public health. 2.3. Adsorption experiments
Biochar, originated from biomass pyrolysis under oxygen-
limited environment can be used as soil amendment to increase Adsorption experiments were used to reveal the adsorption
soil fertility, double or triple plant yields, fix carbon and cut potential of different biochar samples. Effect of pH on phosphorus,
greenhouse gas emissions in a vast scale. Besides, the chemical arsenic and chromium adsorption was investigated in a conical
modified biochar also adsorb contaminants either by electrostati- flask containing 0.1 g adsorbent and 50 ml of 50 mg L1 adsorbate
cally attractive forces or by ligand exchange mechanism without (phosphate, sodium arsenite and potassium dichromate). The pH
the adverse waste sludge production (Loganathan et al., 2013; level was adjusted at the range of 2e10 with hydrochloric acid and
Marris, 2006). Thus, application of the adsorption methods with sodium hydroxide. To evaluate the stability of the BiBC during those
biochar based adsorbent is a promising way for arsenic, phosphate three adsorbates adsorption process, the desorbed bismuth con-
and chromium treatment. Herein, to enhance the adsorption ability centration from aqueous solution was also analyzed.
of biochar and probe into the rational straw utilization of straw Adsorption dosage experiments were executed by adding 0.01,
resources, bismuth oxide and wheat straw were explored to pre- 0.05, 0.1, 0.25, 0.5, and 1 g sorbent in a conical flask with 50 mL
pare a cost-effective but high efficiency material for wastewater solution under the optimum pH value at initial 50 mg L1 con-
treatment for the first time. The specific objectives of this work centration of phosphate, sodium arsenite or potassium dichromate.
were to: (1) prepare and characterize Bi2O3 impregnated biochar The mixture was agitated at 150 rpm in an orbital shaker (SHA-C) at
composites, (2) test its sorption capacities for As (III), P and Cr (VI), 25  C for 2 h and then placed for 24 h to reach the equilibrium
and (3) investigate the possible mechanisms involved in the As (III), condition.
P and Cr (VI) adsorption. Adsorption kinetics experiments were conducted as follows:
0.1 g bismuth oxide activated carbon was added in 50 mL phos-
2. Materials and methods phate, arsenic or chromium solution with initial concentration of
300, 10, and 20 mg L1 under the optimum pH level, respectively.
2.1. Preparation of adsorbents The sorption amount of phosphorus, arsenic and chromium were
investigated at different time intervals (0, 0.5, 1, 2, 5, 10, 30, 60, and
Bismuth oxide solution (Bi-solution) was prepared by adding 120 min). The mixture was agitated at 200 rpm in an orbital shaker
10 mmol Bi2O3 to 20 ml hydrochloric acid (0.12 mol) and then (SHA-C) at 25  C for 24 h to reach the equilibrium condition.
diluted to 100 ml with distilled water. A stock solution of Adsorption isotherm experiments were conducted as follows:
3000 mg L1 KH2PO4, 200 mg L1 sodium arsenite and 200 mg L1 0.1 g adsorbent was mixed with 50 ml adsorbate solution with
potassium dichromate were prepared in a volumetric flask and concentration ranging from 60 to 1800 mg L1 for phosphate and
diluted to the required concentrations (60e1800 mg L1). Bi2O3, concentration ranging from 5 to 200 mg L1 for potassium di-
KH2PO4, NaAsO2, K2Cr2O7 and other reagents used in this work chromate or sodium arsenite under the optimum pH value in the
were all at analytical grade. centrifuge tube respectively. All the vessels above were shaken at
Wheat straw (WS) was obtained from Wuxi city, Jiangsu prov- 150 rpm in the oscillator for 2 h and then placed in the water bath
ince, China. It was milled and sized into particle with diameters under constant temperature (15, 25 and 45  C) for 24 h to reach
between 0.60 and 0.80 mm. Bismuth oxide activated carbon (BiBC) equilibrium.
and control biochar (CBC) were produced as follow: 10 g WS was Besides, adsorbate saturated materials were prepared by mixing
mixed with 100 ml Bi-solution and hydrochloric acid (0.12 mol) 4 g adsorbent with 2 L 500 mg L1 phosphate or 100 mg L1 sodium
respectively, stirred vigorously at 80  C for 3 h, exposed to ultra- arsenite/potassium dichromate solution under the optimum pH
sonic treatment to get the targeted particles as small as possible value and then named as BiPBC500, BiAsBC500 and BiCrBC500
34 N. Zhu et al. / Chemosphere 164 (2016) 32e40

respectively. Table 1
The concentration of phosphate was determined using double Surface areas and pore volumes of activated carbons.

UVevis spectrophotometer (UV-2450 Shimadzu, Japan) at its Sample SBET (m2/g) SMicro (m2/g) Dp (nm) VMicro (cm3/g) VTotal (cm3/g)
maximum wavelength of 700 nm. Inductive coupled plasma CBC400 6.34 e 7.03 e 0.011
emission spectrometry (ICP) and Inductive coupled plasma emis- CBC500 124.44 46.82 2.58 0.019 0.080
sion spectrometry-mass spectrum (ICP-MS) were used to detect the CBC600 38.49 e 5.54 e 0.053
concentration of arsenic, chromium and the leaching bismuth. BiBC400 87.42 52.15 2.49 0.023 0.054
BiBC500 190.40 124.55 2.00 0.047 0.095
BiBC600 106.70 22.26 2.95 0.010 0.079
3. Results and discussion

3.1. Characteristics of biochar

inhibited the formation of tars which jam up the pores and, thus,
decreased micropore collapse of the samples. The average diameter
3.1.1. Surface area and pore volume
of 2.00 nm indicated that the synthesized BiBC500 was in the
Nitrogen adsorption is a standard procedure for the determi-
micropore region according to the IUPAC classification implying
nation of the porosity of adsorbents. The N2 adsorption-desorption
high adsorption potential. Highly developed micropore structure
isotherms of biochar based materials contained an almost hori-
means high specific surface area and high adsorption potential to
zontal plateau at higher pressures (Fig. 1). According to the IUPAC,
certain substances.
both BiBCs and CBCs exhibited a type I isotherm and a type H4
hysteresis loops, indicating relatively small external surfaces and
highly microporous within the materials. Besides, the isotherm of 3.1.2. Morphology study
CBC400 and CBC600 raised rapidly near P/P0 ¼ 1 demonstrating the The morphology and particle size of the materials were
presence of macropore. analyzed by SEM. The pore structure was observed obviously for
Carbonization temperature had a significant impact upon the the CBC500 and CBC600 (Appendices Fig. 1). However, the pore
pore development and specific surface area of the activated agent structure of CBC500 was inerratic while the pore structure of
(Table 1). With temperature increasing from 400 to 600  C, BET CBC600 was unordered. The surface of CBC400 was rough but
surface areas, pore volumes as well as pore size distribution of all apparently absence of porosity. The flourishing pore structure was
the materials did show a disciplinary change. They increased firstly observed for all the bismuth activated carbon. Besides, when the
and then reduced with the continuously increasing pyrolysis tem- bismuth oxide impregnated biochar precursor was carbonized at
perature. It was known that the BET surface area, pore volume and 400, 500, and 600  C, globular particles were inlaid on the porous
pore size distribution of activated carbons were closely related to surface of biochar, with a diameter between 0.5 and 1 mm (see
the final pyrolysis temperature, raw material and retention time. Appendices Fig. 1). The size of the pores on the surface of biochar
With the same raw material and retention time, increasing decreased with the increasing carbonization temperature. Besides,
carbonization temperature within a certain temperature range in- few larger particle size with an uneven surface was also observed
creases the evolution of volatile matters from the precursor, ben- for the BiBC600. The very small white globular particles were firmly
efits pore development and even creates new pores. This attached within the biochar matrix which may represent the bis-
pyrolyzation effect, when out of the range, will cause the collapse of muth serve as the adsorption site on the surface of activated
micropore and widen a significant amount of micropore to meso- carbon.
pore, quality just drop (Demiral and Gunduzoglu, 2010).
BiBCs had larger BET surface area and pore volume, especially 3.2. The main adsorption mechanism
the micropore area and micropore volume, but a lower average
pore diameter than that of CBCs under the same carbonization BiBC500 was used to investigate the adsorption performance of
temperature (Table 1). This could be attributed to the fact that the bismuth activated carbons because of their high BET surface area
activating agent (bismuth oxide) helped in creating new micropore, and abundant pore volume. The raw biochar (CBC500) removed
negligible phosphorus, arsenic and chromium while BiBC500
showed high adsorption ability to those kinds of anion.

3.2.1. FTIR
FTIR was used to identify the functional groups and the roles
they played during the modification and adsorption procedure
(Fig. 2). Functional groups of BiBC500 were not changed greatly
after being doped with bismuth (Fig. 2b). The new peaks at
513 cm1 and 622 cm1 were observed which demonstrated the
existence of BieO bond on BiBC500 (Fruth et al., 2006). The strong
new band centered at 1027 cm1, 593 cm1 and 536 cm1 were also
noticed (Fig. 2c). Those new peaks were linked with the stretching
vibration of PO4 groups and the bend vibration of O-P-O (Luwang
et al., 2011). The bands at 3435 cm1 which represented the hy-
droxyl groups were all existed in CBC500, BiBC500 BiAsBC500,
BiPBC500 and BiCrBC500. But this peak for BiAsBC500, BiPBC500
and BiCrBC500 was much more intense than BiBC500, implying O-
H of the water molecules were adsorbed on the activated carbon
surface with the adsorption process as well (Xue et al., 2009).
It was reported that the characteristic absorption bands of
adsorbed arsenate was 650e1050 cm1 for As-OH or As-O
Fig. 1. N2 adsorptionedesorption isotherms of various activated carbons. stretching vibration (Hu et al., 2015). Peak at 1045 cm1
 N. Zhu et al. / Chemosphere 164 (2016) 32e40 35

Fig. 3. XRD pattern of a) CBC500, b) BiBC500, c) BiAsBC500, d) BiPBC500 and e)

BiCrBC500.

represented the existence of bismuth structure. Prominent peak

corresponding to P2p and As3d were observed in the surface of
BiPBC500 and BiAsBC500 respectively demonstrating phosphorus
or arsenic was fixed successfully on the material after adsorption.
The binding energy of 134.5 eV demonstrated the PO4 group
structure (Lo et al., 1994). The binding energy was 48.75 suggesting
As (III) oxidation was not happen. XPS investigation also displayed
the major adsorbed chromium was Cr (III) (Fig. 4). This result
demonstrated that reduction of hexavalent chromium was
happened in the process of Cr adsorption.

3.2.3. The mechanism of adsorption of arsenic, phosphorous and

Fig. 2. FTIR graph of a) CBC500, b) BiBC500, c) BiAsBC500, d) BiPBC500 and e) chromium
BiCrBC500. Bismuth, with the electronic configuration of (Xe)
4f145d106s26p3, is one of the most thoroughly investigated main
group elements, which has been known as ‘the wonder metal’
represented a weak AseO bond suggesting As (III) surface complex
owing to the easy involvement in chemical combinations for the
was non protonated (Pena et al., 2006) while peak at 876 cm1
electrons in its p orbital (Sun et al., 2014). Thus, the bismuth
implied the As-OH vibration(Fig. 2d). The FTIR results suggested
impregnated biochar may have the great potential in adsorbing
that electrostatic attraction contributed slightly to As (III) adsorp-
some inorganic anions contaminant through ligand exchange or
tion. However, no any new peak was observed after Cr adsorption
electrostatic incorporation.
(Fig. 2d). The chromium adsorption mechanism should be studied
XPS results demonstrated phosphorus, arsenic and chromium
by other technological means.
were immobilized firmly on the surface of bismuth activated car-
bon. The FTIR detected new peaks after arsenic and phosphorus
3.2.2. XRD study and XPS investigation adsorption suggesting these two species were adsorbed by chem-
There was no obvious peaks found for the raw biochar (Fig. 3a). ical adsorption. The As (V) could be adsorbed through the elec-
Diffraction peaks were observed at 2q ¼ 27.165, 37.949, 39.618, trostatic force (ion-exchange on the protonated surface based on
44.553, 46.007 and 48.689 which were corresponding to 012, 104, Coulombic force) and Lewis acidebase interactions (ligand ex-
110, 015, 113 and 202 planes respectively, marching bismuth change reactions) while the As (III) adsorption was mainly involved
structure (Fig. 3b). Those diffraction peaks could also be observed a Lewis acidebase (ligand exchange) reaction (Munoz et al., 2002).
after arsenic, phosphorus or chromium adsorption. The new XPS results also indicated the adsorbed arsenic was As (III). Thus,
diffraction peaks at 2q ¼ 14.605, 20.068, 25.472, 29.033, 29.504, the main arsenic adsorption mechanism could be attributed to the
31.316 and 41.866 which were assigned to 100, 101, 110, 111, 200, Lewis acidebase reaction between the bismuth atom and arsenite.
102 and 211, respectively (Fig. 3c) demonstrating the existence of Based on the results above, the main phosphorus sorption process
bismuth phosphate compound (Nithya et al., 2015). However, no could be described as follow: bismuth atom was loaded on the
obvious new peaks were found after arsenic or chromium surface of activated carbon, served as the sorption site and then
adsorption, suggesting that there was no crystal generated. become hydroxylated under the acidic condition. Then the hy-
XPS was used to further investigate the mechanism of arsenic, droxylated bismuth attracted phosphate group and formed BiPO4
phosphorus and chromium sorption by the bismuth modified which has been reported as a high effective photocatalyst for
biochars (Fig. 4). Bismuth peaks corresponding to Bi4f were found degradation methylene blue efficiently under the ultraviolet irra-
almost same in the surface of Bi-impregnated biochar and other diation (Pan and Zhu, 2010). This is our ongoing word for the uti-
adsorbed materials. The binding energy of 159.6 and 164.9 eV lization of phosphate exhausted adsorbent. FTIR detected no new
36 N. Zhu et al. / Chemosphere 164 (2016) 32e40

Fig. 4. High-resolution XPS spectra of Bi4f, As3d, P2p and Cr2p.

peaks after Cr adsorption which confirming Cr adsorption was water at various pH (Appendices Fig. 2). In low pH range, the
mainly a physical adsorption process. Previous studies proved that released Bi2þ was less than 0.2 mg/L (at pH 2) and it decreased to
the pristine biochar displayed low adsorption ability to Cr (VI) but 0.01 mg/L (at pH 5). This result manifested that the most of bismuth
high affinity to Cr (III) (Pan et al., 2014). Therefore, the main chro- atoms were firmly loaded within the BiBC matrix. Within the pH
mium adsorption mechanism could be described as follow: Cr (VI) range from 5 to 10, the residual bismuth concentrations were near
was adsorbed by the pronated material through electrostatic phe- zero. The leaching loss amounts of bismuth increased under the
nomenon, then reduced to Cr (III), an easily immobilized form, and presence of chromium. The application of bismuth activated carbon
finally fixed within the biochar matrix. for chromium adsorption should be cautious. There was fewer
The surface of BiAsBC500 became roughly with intensive flake bismuth ions detected in the aqueous solutions under the phos-
around the white particle after arsenic adsorption while the surface phorus or arsenic existence condition, confirming BiBC could be
of BiCrBC500 changed mildly. This result confirmed that bismuth considered as a kind of environmental-friendly material for phos-
played an important role in arsenic sorption but contributed phorus and arsenic pollutant removal.
slightly to chromium adsorption. The acicular crystal structure
which related to bismuth phosphate on the surface of the globular
particle was obvious after phosphate adsorption. Herein, we 3.3.1. Effect of pH and sorbent dosage
concluded that physicochemical actions other than the traditional The effect of initial solution pH was investigated firstly. The
consideration mechanism, namely related to its specific surface removal efficiency of arsenic for BiBC500 went up gradually and
area, contributed mainly to the adsorption to arsenic and phos- then decreased with increasing the initial solution pH level
phorus by the prepared bismuth activated carbon. Still, there was (Appendices Fig. 3). The maximum adsorption efficiency of As (III)
no sufficient information to prove that bismuth made a difference was obtained at pH 9.3 which was coincident with the first disso-
on the chromium reduction process. Therefore, further researches ciation constant of H3AsO3 (pK1 ¼ 9.23). Similar adsorption be-
are still needed to understand the mechanism comprehensively haviors have been reported for As on metal based adsorbents such
and thoroughly. as TiO2 and iron oxides or hydroxide (Liu et al., 2008; Meng et al.,
2000). Arsenous acid is a kind of weak acid (pKa1 ¼ 9.23,
pKa2 ¼ 12.10, and pKa3 ¼ 13.41). Under the acid condition, the
3.3. Adsorption study surface of adsorbent tends to be protonated with one H2O molecule
and one hydrion which hampered the Lewis acidebase reaction
Before evaluation of adsorption potential of the prepared ma- between the active adsorption site and the uncharged species
terial, the leaching risk of bismuth was studied first. Results dis- H3AsO03 (Tripathi et al., 2015).
played that the concentration of residual bismuth ions was low in The adsorption capability of BiBC500 to phosphate was also
 N. Zhu et al. / Chemosphere 164 (2016) 32e40 37

affected by the initial pH dramatically. The maximum removal ef- constant with adsorbent dose increasing meaning a homogeneous
ficiency was obtained at pH 3 and BiBC500 showed considerable surface, the other is to rise with the sorbent dose implying a het-
adsorption ability to phosphate at pH between 2 and 6. Metal ox- erogeneous surface (Tian et al., 2011). BiBC500 had a KD with the
ides possessed strong ability to adsorb negatively charged com- latter form implying a heterogeneous surface of BiBC500
pounds, such as phosphate and arsenite (Yao et al., 2011). With the (Appendices Fig. 4).
change of pH, phosphate acid can dissociated to different anion
species as follows: 3.3.2. Adsorption kinetic
Batch aqueous sorption experiments displayed that BiBC500
H3 PO4 4H2 PO4 þH
þ
pka1 ¼ 2:15 possessed much better phosphorus, arsenic and chromium
H2 PO4 4HPO4 þHþ
2 2
pka2 ¼ 7:20 adsorption capabilities. Three widely used kinetic models (pseudo-
þ first-order, pseudo-second-order and intra-particle-diffusion
HPO2 3
4 4PO4 þH pka3 ¼ 12:33
models) were selected to study the experimental data based on
When the solution pH was at 2, namely pH < pKa1, the phos- three initial solution concentrations to further depict the adsorp-
phate species in solution contained the uncharged H3PO4 which tion process clearly (Calisto et al., 2014). Those modes could be
could strongly be attached onto the sites of BiBC500 by coordina- described as follows in turn:
tion interaction between bismuth atom and phosphate group. The
high adsorption capacity then decreased in the range of pH from 3 lnðqe  qt Þ ¼ ln qe  k1 t (2)
to 6. Under this condition phosphate mainly existed as the form of
monovalent H2PO 4 which could be adsorbed by electrostatic t 1 t
¼ þ (3)
interaction with protonated bismuth atom. However, when pH was qt k2 q2e qe
higher than 7.2, most H2PO 2
4 was transformed to HPO4 because of

concentration of OH . On the other hand, the bismuth was stabi- 1
qt ¼ kp t 2 þ Ci (4)
lized and unlikely protonated under the alkaline condition. Thus,
the binding affinity between phosphate and bismuth was almost
Where t is the adsorption time (min), qt and qe are the amount of
negligible.
adsorbate adsorbed on a given period of time t (mg g1) and at
Chromium adsorption was also affected dramatically by the
equilibrium (mg g1), k1 (1 min1), k2 (g mg1 min1), and kp
initial solution pH (Appendices Fig. 3). Removal efficiency
(mg g1 min1/2) are the adsorption rate constant of the three ki-
decreased with the increasing initial pH value ranging from 2 to 10.
netic model respectively and Ci is a constant in the intra-particle-
The pH level affected the form of Cr (VI) in aqueous solution, which
diffusion equation, corresponding to the thickness of boundary
arose from the hydrolysis reaction of Cr2O2 7 which was expressed
layer.
as follow (Giri et al., 2012):
Arsenic, phosphorus and chromium adsorption process pro-
ceeded very quickly and could attach equilibrium in 120 min
(Fig. 5). All the regression coefficients of the pseudo-second-kinetic
model were higher than that of pseudo-first-kinetic model, and the
experimental qe values were very close to that calculated from the
model (Table 2), suggesting the adsorption process was chemi-
sorption. The intra-particle-diffusion model is always used to
comprehensively illustrate the adsorbate diffusion mechanism and
determine whether intra-particle-diffusion is the rate-limiting
factor controlling the adsorption process especially in a solid-
liquid adsorption system. The determination coefficients of the
whole process were all between 0.920 and 0.941, indicating that the
intra-particle-diffusion model was not the only rate-limiting step, a
multi-step process is expected to work during the entire time range
(Table 2). The linear plot (for phosphate adsorption) did not pass
through the origin and could be divided into two stages according
to the changing phosphate adsorption rate (Fig. 5). The first sharp
region is instantaneous adsorption stage or the transport of phos-
The dominant form of hexavalent chromium at acidic condition phate molecules from the bulk solution to the adsorbent external
was HCrO 4 . The maximum adsorption capacity was obtained at pH
surface driven by the initial phosphate gradients. The second
3, indicating HCrO 4 was easier to be adsorbed over the protonated
potion is the intra-particle-diffusion process, phosphate molecules
surface of adsorbent based on electrostatic phenomenon. transported from external surface into the pores of the BiBC500,
It was obvious that the removal efficiency was enhanced along showing chemical sorption characteristic.
with the increasing sorbent dosage which affected the distribution
coefficient KD. KD was used for describing the binding ability of an 3.3.3. Adsorption isotherm
adsorbate element over adsorbent surface. KD could be calculated The Langmuir, Freundlich isotherm and Temkin models were
by the following equation: used to analyze arsenic phosphorus and chromium adsorption
experimental data (Song et al., 2016; Davis and Di Toro, 2015). The
Langmuir model (i.e. L model) is based on a monolayer adsorption
Ce
KD ¼ (1) assumption and the equation could be expressed in the following
Ca linear form:
Where Ce and Ca are the element concentrations on adsorbents Ce Ce 1
(mg g1) and in aqueous solution (mg L1), respectively. With a ¼ þ (5)
qe Q0 bQ0
certain pH, KD would show two different situations: one is to keep a
38 N. Zhu et al. / Chemosphere 164 (2016) 32e40

Fig. 5. Adsorption kinetics for arsenite, phosphate and dichromate removal.

Table 2
Parameters of adsorption kinetic models for removal of arsenic, phosphorous and chromium.

Adsorbate Pesudo-first-order kinetic model Pesudo-second-order kinetic model Intra-particle-diffusion model

k1 qe R2 k2 qe R2 kp Ci R2

As 0.015 1.91 0.912 0.047 2.23 0.996 0.20 0.22 0.920

P 0.023 106.29 0.966 0.008 131.58 0.982 11.69 2.74 0.941
Cr 0.028 2.60 0.989 0.020 3.27 0.998 0.29 0.13 0.935

Freundlich model (i.e. F model) derived from a multilayer (mg g1) and b (L mg1) were Langmuir constants. Kf (mg g1) and
adsorption condition with an inhomogeneous distribution of heat n were Freundlich constants. A (L mg1) and bT (J g1) were Temkin
of adsorption over the surface. Freundlich equation could be writ- constants. T was absolute temperature and R was universal gas
ten as follows: constant 8.314 J mol1 K1. Results showed that the L model was
mostly suitable for the equilibrium data of arsenic and phosphorus
1 adsorption (r2L > r2T > r2F) assuming a monolayer adsorption pro-
ln qe ¼ ln Kf þ ln Ce (6)
n cess for As and P respectively (Appendices Fig. 5). The maximum
Temkin isotherm (i.e. T model) assumes that the heat of adsorption capacities were 125.40 mg g1 for P and16.21 mg g1 for
adsorption decreases linearly. The equation could be expressed in As (III), which were more excellent than other commonly used
the following form: adsorbents reported in the literature (Qian et al., 2013; Cui et al.,
2013). A dimensionless equilibrium parameter (RL) can be further
RT RT analyzed by the Langmuir equation. The lower RL value means the
qe ¼ lnA þ ln Ce (7)
bT bT more favorable adsorption provided at the range between 0 and 1.
The values of RL were 0.034e0.583 for BiBC500 to arsenic and
Where Ce (mg L1) was the equilibrium concentration, and qe 0.045e0.541for BiBC500 to phosphate in the C0 range of our study,
(mg g1) was the amount of adsorption capacity at equilibrium. Q0 implying a favorable adsorption process to arsenic and phosphate.
 N. Zhu et al. / Chemosphere 164 (2016) 32e40 39

The Temkin plots also had good linearity indicating the strong   
chemical interaction between adsorbate and adsorbent. These re- d ln Cqee
sults illustrated the homogenous distribution of active sites over DHobs ¼ R   (11)
sorbent surface.
d T1
Generally, the Langmuir model is suitable for the uniformly
distributed metal salts, namely, the active sorption site to some
certain contaminants on the surface of activated carbon. The Where qe and Ce were calculated by the Langmuir parameters.
Freundlich model, however, was best fitted to the chromium DHobs can be estimated from the slope of line yields from plots of
sorption data (r2F > r2L > r2T) suggesting a multilayer sorption ln(qe/Ce) versus reciprocal reaction temperature (Liu et al., 2015).
process for chromium. The maximum Cr (VI) adsorption capacity Results showed that adsorption of As needed much more adsorp-
was detected as 12.23 mg g1 in our study. This result also indi- tion heat than phosphate adsorption (Table 3). An increase of DHobs
cated that those active adsorption sites were inoperative to with increasing qe was observed which could contribute to the
chromium. reason that a greater repulsive interaction between the adsorbed As
or P and the free adsorbate in aqueous solution needs to be over-
come at a higher qe (Appendices Fig. 6). Besides, the increasing rate
of change in the DHobs curve (both P and As adsorption) indicated
3.3.4. Thermodynamic parameters that the higher adsorption capacity means the more heat of
The Langmuir model was best fitted for experimental data of P adsorption after adsorbed certain substances.
and As (III) adsorption. The Gibbs free energy equation and the
linearized Van't Hoff equation (i.e., the van't Hoff plot) were then 3.4. Utilization of phosphate depleted adsorbents
used for estimating the thermodynamic parameters of P and As
adsorption, which were expressed as follows: As Bi2O3 and BiPO4 has been reported with an excellent pho-
todegradation ability to organic pollutant such as methylene blue

DG ¼ RTlnK (8) under the ultraviolet light irradiation (Pan and Zhu, 2010). As bio-
char has been reported as a considerable adsorption capacity for
  methylene blue. A dark experiment (without ultraviolet radiation)
DS DH
lnK ¼  (9) was first executed as follow: 0.1 g phosphate saturated material was
R RT
mixed with 50 ml methylene blue solution in a conical flask with
Where DG (kJ mol1) is the change of free energy, DS (kJ mol1) is concentration ranging from 10 to 150 mg L1. Correspondingly,
the change of entropy, T is the absolute temperature, DH (kJ mol1) 0.1 g BiPBC500 was mixed with 50 ml methylene blue solution in a
is the change of enthalpy (integral enthalpy), R is the ideal gas quartz container with concentration ranging from 10 to 150 mg L1.
constant, and K is the dimensionless equilibrium coefficient esti- All the vessels were standing at 25  C for 24 h to reach the equi-
mated from the Langmuir constant (b) as librium sufficiently and then detected the methylene blue con-
centration. Then, the quartz container was placed under ultraviolet
K ¼ bCw (10) irradiation environment at 25  C. The photodegradation methylene
blue amounts was investigated at different time intervals (0.5, 1, 2,
Where Cw is the water concentration (5.56  104 mmol L1). 3, 4 and 5 h). The MB removal efficiency which was enhanced after
Thermodynamic parameters for phosphate and arsenic (III) sufficient UV irradiation especially at a medium concentration
adsorption were summarized in Table 3. The negative values of (Appendices Fig. 7). Obviously, the reaction rates decreased with
free energy change DG demonstrate the spontaneous nature of the increasing of the initial concentration of MB solution. This could
the adsorption process. The DG was within the range of 20 be attributed to the high dye concentration effect which impeded
to 80 kJ mol1, suggesting that chemisorption and phys- the light penetration and resulted in fewer photon reaching to the
isorption coexist in the adsorption process. The positive values in catalyst surface. This results demonstrated BiBC500 could be used
the differential heat of adsorption (DH ) indicate that the for phosphate removal and further make contribution to
adsorption of P or As (III) onto the BiBC500 is an endothermic adsorption-photodegradation of dye.
process. Investigating the enthalpy changes with the amount of
adsorption capacity (qe) would be conducive to comprehend the 4. Conclusion
interaction between adsorbate (P or As) and BiBC500. The
observed molar differential enthalpy (DHobs) of arsenic or phos- Bismuth activated carbons displayed high sorption ability to
phate sorption on bismuth activated carbon were further ob- arsenite, phosphate and dichromate. Bach adsorption experiments
tained from the differential Van't Hoff equation which were reveled the spontaneous nature and endothermic process for P and
expressed as follows: As adsorption. The interaction between phosphate group and bis-
muth particles played a fatal role in phosphate adsorption and
formed bismuth phosphate which could photodegrade MB solu-
tion. Ligand exchange contributed mainly to arsenic removal while
Table 3 electrostatic phenomenon along with the chromium reduction
Parameters of Langmuir isotherms and thermodynamics of As (III) and P adsorption.
played an important role in chromium sorption. This work
Adsorbate Temperature(K) Langmuir parameters Thermodynamics demonstrated that bismuth modified biochar provides an innova-
Q0 b R2 DG DS DH tive and effective way to utilize straw resources by preparing cost-
effective adsorbents for anion pollutants treatment.
P 288 1.18 13.88 0.998 26.47 0.12 6.82
298 1.32 18.86 0.995 27.76
318 1.48 22.84 0.994 29.97 Acknowledgement
As 288 0.182 1.13 0.99 32.48 0.15 11.86
298 0.216 1.31 0.992 34.36 This study was funded by the National Natural Science Foun-
318 0.273 1.5 0.997 37.18
dation of China (41171236), the National Key Technology R&D
40 N. Zhu et al. / Chemosphere 164 (2016) 32e40

Program of China (2012BAD15B03) and the National S&T Major electrochemical-behavior of electroless Ni-P alloys in 3.5 wt.percent Nacl so-
lutions. Surf. Coat. Technol. 67, 27e34.
Project of China (2012ZX07204-003).
Loganathan, P., Vigneswaran, S., Kandasamy, J., 2013. Enhanced removal of nitrate
from water using surface modification of adsorbents e a review. J. Environ.
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dx.doi.org/10.1016/j.chemosphere.2016.08.036. 2998e3004.
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