Chemosphere 202 (2018) 768e776

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Arsenic removal from water and river water by the combined

adsorption - UF membrane process
Linlin Hao a, b, Nannan Wang c, Chang Wang a, Guiju Li a, *
a
College of Marine and Environmental Sciences, Tianjin University of Science & Technology, Tianjin 300457, PR China
b
School of Municipal and Environmental Engineering, Harbin Institute of Technology, Harbin, 150090, PR. China
c
School of Mechanical Engineering, Beijing Institute of Petrochemical Technology, Beijing Key Laboratory of Pipeline Critical Technology and Equipment for
Deepwater Oil & Gas Development, Beijing, 102617, PR China

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 combined adsorption e UF process

is established for arsenic removal.

A newly designed amino-
functionalized coffee cellulose is
synthesized.

The pilot study of arsenic removal
from river water is conducted.

Effects of aeration and UF membrane
on arsenic removal are investigated.

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

Article history: In this study, a pilot-scale adsorption-UF process equipped with an aerated system is established for
Received 2 January 2018 arsenic removal from As-spiked Songhua river water. A newly synthesized amino-functionalized coffee
Received in revised form cellulose adsorbent (PEI-coffee) which is derived from spent coffee powder is fully characterized and
22 March 2018
used for arsenic removal from water. The batch experiments revealed that the adsorption process could
Accepted 23 March 2018
Available online 24 March 2018
be well described by Langmuir model with a maximum adsorption capacity of 13.2 and 46.1 mg/g for
As(III) and As(V), respectively. The negative value of △H and △G indicated the exothermic and spon-
Handling Editor: Tsair-Fuh taneous nature of As adsorption on PEI-coffee. The effects of operating parameters such as pH, initial
concentration and adsorbent dosage, were optimized by response surface methodology (RSM) based on a
Keywords: central composite design (CCD). The combined adsorption - UF process was employed for arsenic
Arsenic removal from As-spiked Songhua river water. It was demonstrated that aeration not only increased the
Adsorption removal efficiency by oxidizing As(III) to As(V), but mitigated the membrane fouling process. Besides of
Cellulose the adsorption process, UF membrane could also reject arsenic through the electrostatic repulsion be-
Membrane
tween arsenic species and membrane surface. After UF filtration, the dissolved As, suspended solids (SS),
River water
and TOC can be effectively eliminated. The saturated adsorbent was regenerated by using an eluting
agent of 10 wt% NaCl and 10 wt% NaOH, the regenerated adsorbent still sustained a very high adsorption
capacity after 6 cycles of adsorption-regeneration process.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction
* Corresponding author. College of Marine and Environmental Sciences, Tianjin
University of Science & Technology, Tianjin 300457, PR China. Intensive research efforts have been pursued to remove arsenic
E-mail addresses: xilan.2009@tust.edu.cn (L. Hao), lgj69@tust.edu.cn (G. Li).

https://doi.org/10.1016/j.chemosphere.2018.03.159
0045-6535/© 2018 Elsevier Ltd. All rights reserved.
 L. Hao et al. / Chemosphere 202 (2018) 768e776
(As) contamination from wastewater or groundwater, but limited
attention is given to arsenic contamination in the natural water
system such as rivers or lakes, which are the important sources to
provide potable water supply to millions of people living in
different countries. Unlike of excessive arsenic in groundwater, the
elevated arsenic concentration in surface waters (such as river or
lakes) was mainly caused by anthropogenic activities, wherein
As(III) and As(V) are always co-existing (Hao et al., 2016). Arsenic
pollution in the natural water sources at elevated concentrations
were well documented in many countries such as America, France,
Bangladesh, China, India and Mexico (Guan et al., 2012; Lee et al.,
2017). The baseline concentrations of arsenic in rivers or lakes
have been reported in the range of 0.1e2.0 mg/L (Rahimsouri and
Modabberi, 2013). Gomati river (Ganga Plain, northern India) had
arsenic concentrations in the range of 1.29e9.62 mg/L due to the
geothermal influence and anthropogenic causes (Singh et al., 2010).
Alpine/Mediterranean Var River water (France) showed arsenic
concentrations in the range of 0.1e263 mg/L (Barats et al., 2014). In
the Stampede and Slate Creek watersheds (Alaska, USA), arsenic
concentrations in stream waters were as high as 239 mg/L in the
year of 2010 (Ritchie et al., 2013). Manchar Lake (Pakistan) was
reported to have arsenic concentrations of around 60.45 mg/L (Arain
et al., 2009). Moreover, water pollution accidents through anthro-
pogenic activities occurred frequently owing to the development of
global economy and urbanization processes (Hu et al., 2016).
Arsenic removal from water can be achieved by conventional
treatment processes such as chemical precipitation, ion exchange
and electro-coagulation (Hering et al., 2017; Nidheesh and Singh,
2017; Smith et al., 2017). Among these possible treatment pro-
cesses, adsorption techniques are extensively studied due to its
high removal efficiency, flexibility, low cost and ease of operation
(Yu et al., 2016). Recently, Membrane separation processes such as:
ultrafiltration (UF), nonofiltration (NF) and reverse osmosis (RO),
have been increasingly used for the treatment of arsenic to
decrease the amount of produced wastewater (S anchez et al., 2016).
A combination of adsorption e UF technique proves to be a
promising technology for separation of arsenic from effluents
(Chen et al., 2016). The use of readily available low-cost adsorbent
in combination with UF is a hybrid approach to concentrate
selectively and to recover valuable metal resources. The advantages
of adsorption -filtration process are the high separation selectivity
due to the use of a selective adsorbent and low energy re-
quirements involved in these processes (Kai et al., 2016).
This work focused on investigation of the adsorption - UF pro-
cess for removal of arsenic from As-spiked Songhua river water
using modified coffee cellulose as an adsorbent. To highlight the
arsenic removal performance, the main operating parameters such
as pH, adsorbent dosage, and initial concentrations, have been
investigated. The thermodynamic and kinetic studies were also
conducted to better understand the properties of the modified
coffee cellulose adsorbent. The aerated stirring method was per-
formed to assess the effect of aeration on the removal efficiency of
total arsenic and membrane fouling.
2. Materials and methods
2.1. Materials
All chemicals are analytical grade and supplied by Shanghai
Chemical Co., Ltd. (China). All solutions are prepared with ultrapure
water of conductivity less than 1 ms/cm. The solution pH is adjusted
by adding 0.1 M H2SO4 and 0.1 M NaOH. The experimental water
samples are collected from Songhua river (Heilongjiang province,
China), and the baseline concentration of arsenic in Songhua river
water is detected to be less than 0.01 mg/L. The stock solutions of
769
As(III) and As(V) of 10 mg/L are prepared by dissolving NaAsO2 and
Na3AsO4$12H2O, respectively, in Songhua river water, and all the
required concentrations are diluted by the real Songhua river water.
A hollow fiber UF membrane is used, which is offered from
Tianjin Motian Membrane Eng. & Tech. Co., Ltd. (China). The char-
acteristic of the membrane is listed in Table S1. The membrane
surface has been modified from hydrophobic to hydrophilic and
carries a great deal of negative charge, which results in low arsenic
affinity on the membrane surface.
2.2. Preparation of the modified coffee cellulose adsorbent
The spent coffee powders were collected from local coffee shops
and washed several times to remove the soluble compounds. 30 g
of spent coffee powder was mixed with 500 mL of NaClO solution
(5%, w/v) in a conical flask overnight, which is called the bleaching
process. The bleaching of the spent coffee was conducted repeat-
edly for several times until the color of the spent coffee powder
changed from black to white. The floating cellulose fibers were
separated by Buchner funnel, and then stirred with 200 mL of 10%
polyethyleneimine (PEI) solution for 2 h. 0.5 mL of 25% glutaralde-
hyde was added dropwise into the flask and kept for 1 h. The final
product was washed with deionized water to remove excess re-
agents, dried in a vacuum oven and designated as PEI-coffee. The
schematic diagram of the synthetic process is shown in Fig. S1.
2.3. Experimental procedure
Adsorption equilibrium: Isothermal adsorption experiments
were conducted in a shaking water bath (150 rpm) with a tem-
perature controller. Batch experiments were performed in Erlen-
meyer flasks (250 mL) containing 1 g/L adsorbent equilibrated with
1, 5, 10, 15, 20, 25, 35, 50 mg/L As(III) or As(V) for 6 h at 20, 30 and
40  C, respectively. Finally, the samples were filtered through a
0.22 mm membrane, and residual arsenic concentration was deter-
mined by using an inductively coupled plasma-optical emission
spectroscopy (ICP-OES).
Kinetic experiment: The experimental procedures for three
consecutive runs were conducted. For the first run, the feeding
arsenic solution of 1 mg/L (0.5 mg/L As(III) þ 0.5 mg/L As(V)), which
was prepared by using real Songhua river water, was added into the
main reactor until the total volume reached 10 L, the adsorbent
dosage was 0.5 g/L. The solution was kept to be stirred by an
aeration pump with a gas flow rate of 0.2 L/min. The UF membrane
module was started to obtain the permeate samples, which are
collected at 1, 2, 3, 5, 7, 10, 15, 20, 30, 40, 60, 90, 120, 180, 240, 360,
480, 600, 720, 1440 min to determine the arsenic concentration.
After that, the residual solution in the reactor was pumped out
through UF membrane, but the adsorbent was intercepted in the
reactor. For the second run, the same feeding solution was added
into the reactor, and the procedure was repeated. After the second
run, the residual solution was pumped out through UF membrane,
the third batch of feeding solution was added into reactor, and the
procedure was repeated.
To compare the effects of mechanic and aerated stirring styles
on arsenic removal efficiency, three different initial concentrations
of 0.1 (0.05 mg/L As(III) þ 0.05 mg/L As(V)), 0.5 (0.25 mg/L
As(III) þ 0.25 mg/L As(V)) and 1 (0.5 mg/L As(III) þ 0.5 mg/L As(V))
mg/L were prepared and the adsorbent dosage is 0.5 g/L. The me-
chanic stirring rate is 150 rpm, the gas flow rate of aeration is 0.2 L/
min. After reaction of 6 h, the samples were filtered through a
0.22 mm membrane, and residual arsenic concentration was
determined by using ICP-OES.
770 L. Hao et al. / Chemosphere 202 (2018) 768e776

2.4. Analytical methods

Response surface methodology (RSM) was extensively applied

in the optimization of process design parameters (Watson et al.,
2016; Wu et al., 2010). In this study, the five-level central com-
posite design (CCD) was used to run adsorption experiments.
Optimization studies were carried out by studying the effect of
three variables, i.e. pH, initial As concentration, and adsorbent
dosage. With these three variables, a total of 20 experiments are
required in order to find the optimum operating condition. The
parameters are shown in reverse with their coded levels (a, 1, 0,
1, a; a ¼ 1.68), respectively. The value of a, which depends on the
number of factors, is chosen to maintain rotatability, which refers to
the uniformity of the prediction error. The predicted adsorption
capacity of arsenic is explained by the following quadratic equation
(1):

Y ¼ b0 þ b1 A þ b2 B þ b3 C þ b12 AB þ b13 AC þ b23 BC þ b11 AA

þ b22 BB þ b33 CC
Fig. 1. FTIR spectra of the raw spent coffee powder, pretreated coffee and modified
(1) coffee cellulose adsorbents.

where Y is the predicted response, A, B and C are the coded values

of input variables, b0 is the intercept term, b1 ，b2 and b3 are the
coefficients of linear effect, b12 ; b13 ; b23 are the coefficients of
interaction effect, b11 ; b22 ; b33 are the coefficients of squared
effect.
Total As concentrations in solutions were determined using an
ICP-OES instrument (Dual-view Optima 5300 DV). The IR (Infrared)
spectra of the adsorbents were obtained using a Bruker Tensor 207
FT-IR spectrometer to analyze the surface functional groups and
recorded from 4000 to 600 cm1. A scanning electron microscope
(FEI Quanta-250) was employed to observe the morphology of the
adsorbents. The crystal phases of various materials were deter-
mined by a PANalytical X'pert PRO diffractometer equipped with Cu
Ka radiation (l ¼ 0.15418 nm), the 2q angles are collected between
10 and 70 with a step of 0.033 . TGA curves of the adsorbents were
obtained by using a Mettler Toledo TGA/DSC 1 star system from 35
to 800  C. Zeta potential measurements were done using a Malvern
Zetasizer Nano-ZS90 instrument.
3. Results and discussion
3.1. Characterization of the modified coffee cellulose adsorbents
The FT-IR spectra of spent coffee particles, pretreated coffee
cellulose, and modified coffee cellulose are shown in Fig. 1. The
strong band around 3500 cm1 could be assigned to the stretching
vibration of hydroxyl groups (eOH) (Mac et al., 2017). The sharp
peaks at 2920 cm1 and 2853 cm1 are assigned to C-H stretching
vibration of -CH2-/eCH3, and aliphatic C-H stretching vibration
from the cellulose backbone, respectively (Guo and Wu, 2017). A big
difference in the fingerprint region is observed after bleaching
treatment, the typical adsorption bands at 1720 and 1310 cm1
corresponding to C¼O and C-O stretching vibrations (Reddy et al.,
2017), respectively, are greatly weakened because some lipid sub-
stances are removed after bleaching treatment. For the modified
coffee cellulose, NeH stretching band (3500e3100 cm1) is
superimposed to the stretching vibration of OeH
(3200e3650 cm1), the wide peak at 1100e1300 cm1 is obvi-
ously enhanced after PEI modification, because the C-N stretching
vibration (around 1123 cm1) is overlapped with C-C vibration of
the cellulose (Yu et al., 2013).
The SEM images of coffee cellulose before and after modification
are shown in Fig. S2. For the raw spent coffee powder (Fig. S2 (A)), a
variety of flaky protuberances can be observed on the rough sur-
face. After bleaching treatment, the protuberances disappeared and
the cellulose rings are exposed as shown in Fig. S2 (B, C). After
cross-linking with PEI, the surface of the modified coffee cellulose
becomes smooth (Fig. S2 (D, E)). After arsenic adsorption, small
lumps can be observed on the surface of PEI modified coffee cel-
lulose (Fig. S2 (F)), but it is very different with the protuberances on
the raw coffee powder.
The XRD pattern (Fig. 2 (A)) showed that the bleaching coffee
cellulose has a low crystallinity, two diffuse reflections at 15.96
and 22.29 are characteristic peaks of cellulose, indicating the main
product of bleaching treatment is cellulose (Pereira et al., 2014).
Thermogravimetric (TGA) curves of raw spent coffee powder and
modified coffee cellulose are also investigated (Fig. 2 (B)). The first
step of weight loss about 15% in the range of 50e220  C is assigned
to the release of physisorbed water. The major charring for both
materials occurred above 220  C, weight loss of 35 and 56% at the
corresponding charring temperature (Tc) of 220  C are observed for
raw spent coffee and modified coffee cellulose, respectively. The
total weight loss of raw spent coffee powder is lower than modified
coffee cellulose, because the components of raw spent coffee
powder are more complicated.
Surface area is a very important factor to measure an adsorbent.
The BET (Brunauer-Emmett-Teller) specific surface area of raw
spent coffee powder is only 0.13 m2/g. Tiny cellulose fibers are
extracted after bleaching pretreatment, the surface area is greatly
increased from 0.13 to 23 m2/g. The significant rise in surface area
could surely enhance adsorption performance for arsenic. The N2
adsorptionedesorption isotherms for raw coffee powder and
modified coffee cellulose are shown in Fig. 2 (C, D).
3.2. The results of RSM model
The results of total 20 runs of experiments obtained from Design
Expert Software are presented in Table 1. The residuals between the
experimental and predicted removal efficiency (RE (%)) is also
calculated. The relationship between the responses and indepen-
dent variables (Solution pH, Initial conc., and adsorbent dosage) are
described in the following Eq. (2):
L. Hao et al. / Chemosphere 202 (2018) 768e776 771

Y ¼ 1  0:084A  0:061B þ 0:12C þ 0:046AB þ 0:05AC

þ 0:068BC  0:27AA  0:016BB  0:053CC (2)

Analysis of variance (ANOVA) is applied to assess the signifi-

cance of CCD model for predicting RE% (as shown in Table S2).
Table S2 shows the values obtained from the model are highly
significant with a confidence level of 99% and P-value smaller than
0.01. The obtained F-value of 16.28 is clearly larger than the tabu-
lated value (2.352 at 99% significance), which confirmed the
quadratic model is valid for describing the relationship between the
response and independent variables. All the three variables have
significant effect on RE (%), the adsorbent dosage (F-value ¼ 139.5)
produced the largest effect on RE (%). The second-order effect of pH
(A2) has the highest significant effect among the other second-
order effects, but the interactive effects of AB and AC are not sig-
nificant. The accuracy of the quadratic model is checked by the
experimental and predicted values, which are in good agreement
with a high correlation coefficient (R2 ¼ 0.946), indicating the
suitability of quadratic model for describing the adsorption of
arsenic on PEI-coffee. The good agreement between the experi-
mental and predicted RE (%) is illustrated in Fig. S3.
The combined effects of three parameters on the response are
shown in Fig. S4. Fig. S4 (A) shows the 3D response surface plot of
pH and initial concentration on RE%. RE% increases with increasing
initial concentration, because the higher initial concentration could
provide the stronger driving force to overcome the mass transfer
resistance, thus increasing both removal efficiency and adsorption
capacity. Fig. S4 (B) shows the 3D response surface plot of pH and
adsorbent dosage on RE%, the removal efficiency also increases
with increasing adsorbent dosage, because the excessive dosage
could ensure the greater availability of reactive sites on the adsor-
bent surface (Liu and Vecitis, 2012). Fig. S4 (C) shows the interactive
effects of initial concentration and adsorbent dosage on RE%. It is
evident that RE% increases with an increasing adsorbent dosage,
while it decreases with increasing initial concentration within its
respective experimental range.
pH is an important parameter in the CCD experiments. The
surface charge of adsorbent and arsenic species are always pH
dependent (He et al., 2017; Sarker et al., 2017). As(III) exists mostly
as neutral H3AsO3 when the solution pH is lower than 9.2 (the pKa1
of H3AsO3 is 9.2), while the dominant species of As(V) are H2AsO 4
and HAsO2 4 (The pKa1 of H3AsO4 is 2.3; the pKa2 of H3AsO4 is 6.8;
the pKa3 of H3AsO4 is 11.6) (Gettar et al., 2000). The total arsenic
removal efficiency was firstly increased when pH increased from
2.5 to 6.5, and then gradually reduced when solution pH changed
from the acidic to alkaline condition, indicating the weak acidic
condition is favorable for arsenic adsorption on PEI-coffee. When
pH < 2.5, almost all the As(III) and As(V) species exist as uncharged
molecule. When pH changed from the acidic to alkaline condition,
the protonation of amino groups on the adsorbent surface was
significantly reduced, the electrostatic repulsion resulted in the
decrease of RE%. In order to better understand the effect of pH on
arsenic adsorption on PEI-coffee, the point of zero charge of PEI-
coffee was detected to be around 6.8 by using Malvern Zetasizer
Nano-ZS90, which is shown in Fig. S5.
It is important to determine the optimal parameters by using
the CCD model to maximize the RE%. The optimal experimental
conditions within the defined experimental ranges were obtained
with an initial As concentration of 1 mg/L, an adsorbent dosage of
8.1 g/L, and pH of 5.1. At these conditions, the maximum arsenic

Fig. 2. (A) XRD patterns of coffee cellulose; (B) TGA curves of raw spent coffee and
modified coffee cellulose; (C) N2 adsorption/desorption isotherms of raw spent coffee
at 77 K; (D) N2 adsorption/desorption isotherms of modified coffee cellulose at 77 K.
772 L. Hao et al. / Chemosphere 202 (2018) 768e776

Table 1
Experimental ranges and levels of the independent variables.

Independent variable Symbols Range and level

a 1 0 1 a
Solution pH A 2.5 4.5 6.5 8.5 10.5
Initial arsenic conc., (mg/L) B 0.05 0.1 0.5 1 5
Adsorbent dosage, (g/L) C 0.2 2.1 5.1 8.1 10

Runs A B C Arsenic removal (%)

Experimental CCD Residuals

1 1 1 1 55 63 2.67
2 0 1.68 0 100 100 1.57
3 0 0 0 100 100 0.00
4 0 0 1.68 100 100 1.43
5 1.68 0 0 82 81 0.17
6 0 1.68 0 91 85 1.58
7 0 0 0 100 100 0.00
8 0 0 1.68 70 65 1.45
9 0 0 0 100 100 0.00
10 1 1 1 99 96 1.05
11 1 1 1 93 97 1.19
12 1 1 1 99 91 2.65
13 1 1 1 100 99 0.10
14 0 0 0 100 100 0.00
15 1 1 1 99 95 1.18
16 0 0 0 100 100 0.00
17 1.68 0 0 64 65 0.15
18 1 1 1 53 54 0.11
19 0 0 0 100 100 0.00
20 1 1 1 70 73 1.07

removal of 99.9% was reached according to the CCD model. The
optimized parameters were validated with the experimental result
of 99.9%, which demonstrated that the result of modeling is reliable
to predict arsenic removal under different operational conditions.
3.3. Thermodynamics of arsenic adsorption on PEI-coffee adsorbent
Batch experiments for As(III) and As(V) adsorption were carried
out at 293, 303 and 313 K to determine the thermodynamic pa-
rameters. As can be seen from Fig. 3, adsorption capacities
increased with an increase in temperature within 20e40  C.
Langmuir and Freundlich isotherms were used to determine the
parameters of adsorption affinity and the maximum adsorption
capacities at different temperatures. The calculated isotherm con-
stants were given in Table 2. The maximum adsorption capacity of
13.2 and 46.1 mg/g for As(III) and As(V), respectively, were obtained
at temperature of 313 K according to the Langmuir isotherm. The
parameters of adsorption affinity (kL) towards As(III) and As(V) also
increased with an increasing temperature, indicating the compar-
atively higher temperature could facilitate As(III)/As(V) adsorption
on PEI-coffee within 293e313 K. The maximum adsorption affinity
constants kL for As(III) and As(V) were 0.27 and 0.55 L/mg,
respectively. The higher kL value demonstrated the stronger
adsorption affinity to As(V) than As(III).
The thermodynamic parameters were obtained according to
Equations (3) and (4).
The DH value of 16.56 kJ/mol for As(III) is higher than that of
11.91 kJ/mol for As(V), which means As(V) adsorption is easier than
As(III). The negative values of DG (45.61 ~ 26.02 kJ/mol) in-
dicates the arsenic adsorption process is spontaneous with high
affinity towards PEI-coffee. The decrease of DG with a rise in tem-
perature suggests the stronger affinity at higher temperatures. The
values of DG for As(V) are obviously lower than that of As(III),
indicating As(V) adsorption process is much easier than As(III),
these results are consistent with the changes of DH values. The
positive value of DS implies an increase of randomness at the solid/
solution interface. For many adsorption in aqueous solutions, the
positive values of DS were frequently calculated (Liu et al., 2010; Hu
et al., 2014). In this study, the positive DS was explained as follows:
Before arsenic adsorption, some co-existing ions such as Cl, NO 3
may be pre-adsorbed on the adsorbent surface. When arsenic
species was added, the pre-adsorbed ions were dissociated from
the adsorbent, so as to increase the random of solid/solution
interface. The possible reactions were shown as follows:
S  NH3þ $Cl þ H2 AsO þ 
4 4S  NH3 $H2 AsO4 þ Cl

(5)
S  NH3þ $NO  þ  
3 þ H2 AsO4 4S  NH3 $H2 AsO4 þ NO3 (6)
3.4. Effect of aeration on removal efficiency

InðK0 Þ ¼ DS=R  DH=RT
DG ¼ RT$lnðKL Þ
where R is the universal gas constant 8.314 J/mol/K, T is tempera-
ture (K) and KL is the thermodynamic equilibrium constant (L/mol),
which is derived from Langmuir equation.
As shown in Table 2, the positive values of DH confirm the
endothermic nature of As(III) and As(V) adsorption on PEI-coffee.
(3) As(III) and As(V) are always co-existing in natural water sources
(Ben et al., 2011). The species of arsenic is greatly influenced by the
(4) redox potential in water (Guo et al., 2017), therefore it is necessary
to investigate the effect of dissolved oxygen (DO) on RE%. The
comparison between the mechanic and aerated stirring is shown in
Fig. 4 (A). It is revealed that RE% is significantly enhanced by using
aerated stirring at different initial As concentrations of 0.1, 0.5 and
1 mg/L. Compared with the mechanical stirring, the average RE% is
increased from 74% to 88% by using the aerated stirring method
 L. Hao et al. / Chemosphere 202 (2018) 768e776 773

Fig. 4. (A) Comparison of the mechanic and aerated stirring for total arsenic removal
efficiency; (B) Effect of UF membrane on the removal efficiency of arsenic.

Fig. 3. Adsorption isotherms for (A) As(III) and (B) As(V) adsorption on PEI-coffee at
20, 30, 40  C (initial As concentration of 1, 5, 10, 15, 20, 25, 35, 50 mg/L, respectively, the oxidation time (Wang et al., 2016; Yokohira et al., 2010), how-
adsorbent dosage 1 g/L, pH 5.1). ever, the excessive addition of these reagents is also posing a po-
tential threat to human health. Therefore the aerated stirring is
used as an environmental-friendly method to expect the oxidation
when the initial concentration is 1 mg/L and the adsorbent dosage
of As(III) to As(V). It needs to be mentioned that some co-existing
is 0.5 g/L (The mechanic stirring rate is 150 rpm, the gas flow rate of
ions, such as phosphate in Songhua river water, may have a nega-
aeration is 0.2 L/min). Because PEI-coffee exhibited much better
tive effect on arsenic removal. The competition between arsenate
adsorption performance for As(V) than As(III), the idea that As(III) is
and phosphate is well documented (Kanematsu et al., 2011). The
pre-oxidized to As(V) is considered. It was reported that many
dissolved Fe3þ can facilitate arsenic (III, V) adsorption by forming
oxidizing reagents, such as active chlorine, sodium hypochlorite,
FeAsO4 precipitate (Onanguema et al., 2010). High valance of
ozone and potassium permanganate, could significantly shorten

Table 2
Isothermal and thermodynamic parameters of linear fitting for arsenic adsorption on PEI-coffee.

Species T (K) Langmuir Freundlich DG (kJ/mol) DH (kJ/mol) DS (kJ/mol$K)

KL qm R2 KF n R2

As(III) 293 0.25 11.1 0.987 1.82 2.09 0.954 26.02 16.56 0.18
303 0.26 11.4 0.969 2.19 2.13 0.967 27.17
313 0.27 13.2 0.958 2.70 2.32 0.968 28.52
As(V) 293 0.49 44.5 0.996 7.68 1.42 0.914 45.56 11.91 0.13
303 0.46 44.9 0.986 9.32 1.52 0.905 45.69
313 0.55 46.1 0.972 11.4 1.72 0.892 46.61
774 L. Hao et al. / Chemosphere 202 (2018) 768e776

manganese compounds can oxidize As(III) to As(V) so as to enhance

the arsenic removal efficiency (Babaeivelni et al., 2014). Some
organic matters, such as humic acid, may also compete with arsenic
species for the surface active sites (Fakour et al., 2015).
The different gas flow rates of 0.2, 0.5 and 0.8 L/min are also
investigated as shown in Fig. S6. It is observed that RE% is very
slightly enhanced when the gas flow rate increased from 0.2 to
0.8 L/min, indicating the aerated intensity has a minor effect on RE
%. This can be explained by the change of DO content in water.
Compared with the conventional mechanic stirring, aeration could
significantly increase DO content from 4.5 to 8.7 mg/L in the
reactor. However, when the aerated intensity is further increased
from 0.2 to 0.8 L/min, the enhancement of RE% is not observed,
because DO content reaches the maximum of 8.9 mg/L.
The membrane flux changed with running time is monitored.
No obvious flux decline occurred during the filtration process and
no stacked layer was observed on the membrane surface. Plenty of
tiny bubbles are generated during the aeration process, the bubbles
could constantly flush the membrane surface, thus slowing down
the membrane fouling process (Meng et al., 2008).

3.5. Effect of UF membrane on removal efficiency

It was observed that using UF membrane alone could also reject

part of the dissolved arsenic. Therefore both the adsorbent and UF
membrane are contributed to arsenic removal. The use of UF
membrane alone for arsenic removal under the aerated and me-
chanic conditions is shown in Fig. 4 (B). When the initial As con-
centration is 1 mg/L, the RE% of UF membrane for As(III) is only 5%,
while that for As(V) is 20%, indicating that the UF membrane
rejection for As(V) is much higher than As(III). This result is
accorded well with that reported in literature [36]. For As(III) (1 mg/
L), after aeration of 4 h, the RE% is increased from 5% to 8%, but no
obvious increase is observed for As(V) (1 mg/L). It is suggested that
aeration could surely enhance the total arsenic removal efficiency
by oxidizing As(III) to As(V).
Fig. 5. (A) Kinetics of arsenic adsorption on PEI-coffee using the real Songhua water
3.6. The combined adsorption - UF process for arsenic removal from (Initial arsenic concentration is 1 mg/L (0.5 mg/L As(III)þ0.5 mg/L As(V), the adsorbent
dosage is 0.5 g/L); (B) Pseudo-second-order reaction kinetics plot for arsenic adsorp-
as-spiked Songhua river water
tion on PEI-coffee.

In order to investigate the combined adsorption - UF process for

arsenic removal under field condition, the As-spiked Songhua river
water is prepared to conduct the experiments. A flat UF membrane
module was used to separate the suspended solids after the arsenic
adsorption process and the treated water was pumped out through
the UF membrane (Fig. S7). The water quality of Songhua river
water is shown in Table S3. The kinetics of three successive runs is
shown in Fig. 5 (A). The feeding arsenic concentration is 1 mg/L
(0.5 mg/L As(III) þ 0.5 mg/L As(V)) and the adsorbent dosage is
0.5 g/L. For the first run, As concentration in the permeate is
gradually decreased with running time, and the adsorption equi-
librium can be reached within 200 min. After running of 200 min,
As concentration in the permeate is lower than 0.01 mg/L, which
could meet the requirement of drinking water standard in China;
For the second run, after reaction of 200 min, RE% reached 85%, and
As concentration in the permeate was detected to be 0.15 mg/L; For
the third run, As concentration in the permeate was over 0.7 mg/L,
which implies the adsorbent in the reactor is exhausted and needs
to be replaced.
The adsorption kinetics is simulated by the pseudo-second-
order model (as can be seen from Supporting Information) in or-
der to determine the adsorption rate constant. It was shown the
pseudo-second-order model fitted adsorption kinetics well
(>0.998) (Fig. 5 (B)), indicating the chemisorption in nature. The
adsorption rate constant k2 of 1.2 g/mg/min was obtained during
the first run, then the values of k2 decreased to 0.38 and 0.37 g/mg/
min for the second and third run, respectively. The decrease of k2
implies the decline of adsorption performance.
It needs to be mentioned that almost no flux decline was
observed during the three successive runs. After the continuous
running of more than 75 h, a slightly decline of the flux was
observed because of the accumulation of suspended solids (SS) in
Songhua river water. The water quality of As-spiked Songhua river
water after the combined treatment was shown in Table S3. The
combined technique has the advantage of removing arsenic as well
as other dissolved and particulate contaminants. After filtration, the
turbidity was reduced from 7.9 to 0.5 NTU, and 75% of total organic
carbon (TOC) was removed; SS was decreased from 1.2 to 0.003 mg/
L, the color was changed from yellow to colorless.
3.7. Regeneration of the adsorbent
Considering of the economic necessity, it is important to
investigate the stability and reuse of the modified sawdust (Gupta
and Babu, 2009; Hao et al., 2017). Different eluting agents such as
NaOH and NaCl solutions, are scrutinized in this study. Previous
study has demonstrated As adsorption on the modified sawdust is
highly pH dependent. Therefore, the desorption process
 L. Hao et al. / Chemosphere 202 (2018) 768e776
accomplished by immersing into NaOH solution is feasible. This
high-pH solution increases the competition of OH for surface
active sites and favors the desorption process. The regeneration
efficiency is defined as the ratio of adsorption capacity of regen-
erated adsorbent to that of the virgin adsorbent, which usually
varies from 0 to 100% (Narbaitz and Cen, 1994).
As can be seen from Fig. S8, 10 wt% NaOH solution recovers
90e93% of arsenic after 1 cycle, and finally recovers approximately
69e72% of arsenic after 6 cycles. The regeneration is also conducted
by using 15 wt% NaCl solution, more than 90% of adsorbed arsenic is
recovered after the first regeneration. After 6 cycles the regenerated
adsorbents still sustain very high removal efficiency for total
arsenic. The results indicate the reversible reaction is involved
between arsenic and adsorbent. Desorption process by using NaCl
solution is probably due to the anion exchange of Cl for arsenic
anions. It is also observed the regeneration efficiency by using
NaOH is higher than NaCl. Considering the cost of NaOH is higher
than NaCl, the mixture of 10 wt% NaCl and 10 wt% NaOH is selected
as an appropriate regenerant. The regeneration efficiency is 96%,
92%, 90%, 86%, 81% and 77% for the first, second, third, fourth, fifth
and sixth cycle, respectively. That is more effective than using
NaOH or NaCl solution alone. The regeneration study indicates that
the exhausted adsorbent could be mostly extracted by the eluting
agent, without significantly changing the adsorbent structure.
4. Conclusion
In this study, the combined adsorption - UF technique was
employed to remove arsenic from water and As-spiked Songhua
river water. The adsorption process was optimized by RSM based on
central composite design. The results demonstrated that the
maximum arsenic removal can be achieved at an initial As con-
centration of 1 mg/L, adsorbent dosage of 3.5 g/L, and initial pH of
5.5. The thermodynamic parameter of △H was calculated to be
16.56 and 11.91 kJ/mol for As(III) and As(V), respectively. When the
initial As concentration was 1 mg/L, the removal efficiency of 12%
was obtained by using UF membrane alone at aerated conditions.
The results of batch experiments by using As-spiked Songhua river
water showed the adsorption process was more accurately fitted by
a pseudo second-order model with a maximum adsorption rate (k2)
of 1.2 g/mg/min. The permeate water is purified from As-spiked
Songhua river water with As concentration lower than 0.01 mg/L.
It was observed that aerated stirring could significantly enhance
the total As removal efficiency through the oxidation of As(III) to
As(V). Moreover, membrane fouling was alleviated by the scouring
action of tiny bubbles. The saturated adsorbent can be effectively
regenerated by using the eluting agent of 10 wt% of NaOH together
with 10 wt% of NaCl solutions, the RE% of 77% was attained after 6
cycles of regeneration. Our study concluded that the combined
adsorption - UF process can be potentially applied for arsenic
removal from water or natural water sources.
Acknowledgment
This work is supported by Tianjin Natural Science Foundation
(Grant No. 17JCTPJC54300). The authors wish to thank the anony-
mous reviewers for their helpful suggestions to improve the paper
quality.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.chemosphere.2018.03.159.
775
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