Journal of Cleaner Production 208 (2019) 384e392

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Journal of Cleaner Production

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

Enhanced coagulation process by Fe-Mn bimetal nano-oxides in

combination with inorganic polymer coagulants for improving As(V)
removal from contaminated water
Hadi Eslami a, Mohammad Hassan Ehrampoush a, Abbas Esmaeili b, *,
Mohammad Hossein Salmani a, Ali Asghar Ebrahimi a, Mohammad Taghi Ghaneian a,
Hossein Falahzadeh c, Reza Fouladi Fard d
a
Environmental Science and Technology Research Center, Department of Environmental Health Engineering, School of Public Health, Shahid Sadoughi
University of Medical Sciences, Yazd, Iran
b
Occupational Environmental Research Center, Department of Environmental Health Engineering, School of Health, Rafsanjan University of Medical
Sceiences, Rafsanjan, Iran
c
Research center of Prevention and Epidemiology of non-communicable disease, Department of Biostatistics and Epidemiology, Shahid Sadoughi University
of Medical Sciences, Yazd, Iran
d
Research Center for Environmental Pollutants, Qom University of Medical Sciences, Qom, Iran

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

Article history: This study investigated the efficient removal of As(V) from contaminated water using enhanced coag-
Received 11 June 2018 ulation by Fe-Mn bimetal nano-oxides in combination with poly-ferric chloride (PFC) and poly-
Received in revised form aluminum chloride (PAC). The effects of coagulant dose, initial pH, initial As(V) concentration, Fe-Mn
30 September 2018
nano-oxide dose and flocs properties were investigated. The results showed that the combination of
Accepted 12 October 2018
Available online 13 October 2018
coagulants and nano-oxides significantly increased the As(V) removal efficiency in the optimal co-
agulants doses (25 mg/L). The As(V) removal efficiencies for PAC and PFC were 82.93% and 88.22% and for
PFC þ Fe-Mn and PAC þ Fe-Mn were increased to 96.83% and 98.26%, respectively. The residual As(V)
Keywords:
Enhanced coagulation
concentration was decreased to ˂10 mg/L in the presence of Fe-Mn nano-oxides. The best removal effi-
Bimetal nano-oxides ciencies for PAC þ Fe-Mn and PFC þ Fe-Mn were in pH 7 and 9, respectively. Based on FESEM - EDX
Arsenic removal analysis, the combined floc formation by coagulants - nano-oxides and the existence of Fe, Mn and As
Contaminated water elements in the precipitated flocs was confirmed, and the PFC þ Fe-Mn flocs were more uniform and
bigger than PAC þ Fe-Mn flocs. Total Fe and Al residual concentrations in optimum dose of PAC þ Fe-Mn
and PFC þ Fe-Mn were 0.15 and 0.25 mg/L and Cl residue concentrations were 6.87 and 4.72 mg/L,
respectively. Therefore, the combination of Fe-Mn bimetal nano-oxides with PFC and PAC coagulants can
be a suitable option to improve the removal of As(V) from the contaminated water resources.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction
The pollution of surface and groundwater resources by arsenic is
a major, serious problem for providing people with healthy fresh
water around the world (Wu et al., 2013). Arsenic is a poisonous
element that can exert direct or indirect adverse effects on humans
and other types of animals (Shan and Tong, 2013). Among these
devastating effects, various kinds of skin problems and bladder,
* Corresponding author.
E-mail addresses: hadieslami1986@yahoo.com (H. Eslami), esmailiabbas@yahoo.
com (A. Esmaeili).
kidney, or lung cancers have been reported (Rahman and Hassler,
2014; Wang et al., 2014). Arsenic compounds can enter water re-
sources either through natural processes such as stone weathering
or through human activities such as using fossil fuel and arsenic-
based pesticides (Hu et al., 2017; Mohan and Pittman, 2007;
Wang et al., 2016). Arsenic is usually found in water resources in the
form of trivalent arsenic or arsenite (As(III)) and pentavalent
arsenic or arsenate (As(V)) (Mo
lgora et al., 2013). Human beings are
mostly exposed to arsenic via polluted drinking water, food, cos-
metics and smoking cigarettes (Singh et al., 2015; Tsuji et al., 2015).
Among all the arsenic exposure resources, polluted water is the
most significant one because of the solvability of different arsenic

https://doi.org/10.1016/j.jclepro.2018.10.142
0959-6526/© 2018 Elsevier Ltd. All rights reserved.
 H. Eslami et al. / Journal of Cleaner Production 208 (2019) 384e392
compounds (Wang and Mulligan, 2006). It has been estimated that
more than 140 million people in at least 70 countries are exposed to
arsenic contaminations. Most of these people live in Asian coun-
tries and about 65 million of them consume arsenic-polluted water
on a daily basis (Singh et al., 2015; Singh and Vedwan, 2015). The
world health organization (WHO) and United States Environmental
Protection Agency (USEPA) have lowered their standard level of
arsenic from 50 down to 10 mg/L (Pio et al., 2015).
Different conventional and advanced methods have been
employed to remove arsenic from water resources. These techno-
logical methods include coagulation and flocculation (Qiao et al.,
2012), adsorption (Elwakeel and Guibal, 2015; Neumann et al.,
2013; Sandoval et al., 2011), lime softening, ion exchange resins,
active alumina (Awual et al., 2013; Donia et al., 2011), reverse
osmosis (Schmidt et al., 2016), enhanced coagulation with filtration
and adsorption, electrocoagulation (Jadhav et al., 2015; Mohora
et al., 2014), electrodialysis, and nanofilteration (Neumann et al.,
2013). The coagulation-flocculation and enhanced coagulation
have been the most frequent and optimal methods for arsenic
removal from polluted waters in real scales (Ghafari et al., 2009;
Wu et al., 2011; Xiao et al., 2013). The most common coagulants
consist of aluminum sulfate, ferric sulfate, and ferric chloride that
are used with polymers to act as coagulant aids or polymerized
compounds such as poly-aluminum chloride (PAC) or poly-ferric
chloride (PFC), which are more effective due to higher efficiency,
less sensitivity to lower temperatures and a reduction in the need
for pH adjustment (Gao et al., 2011; Moussas and Zouboulis, 2009;
Pio et al., 2015).
The enhanced coagulation process includes an increase in the
coagulant dose, pH adjustment or the utilization of new coagulants
in order to enhance the efficiency of coagulation and flocculation
process (Mao et al., 2013). This method has been regarded as an
effective technology for the removal of disinfection by-products
and enhance the removal efficiency of phosphorus, algae and
arsenic from water by USEPA (Song et al., 2006; Zhou et al., 2008).
Studies show that using nano particles to increase the efficiency of
coagulation process can be an effective, economical and safe factor
as compared with other advanced treatment processes such as
reverse osmosis, electrodialysis, electrocoagulation and nano
filtration (Amalia et al., 2015; Singh et al., 2015; Zhang et al., 2009).
Compounds based on iron, such as nano-oxides and metal hy-
droxides, are more popular than other types of compounds because
of their higher efficiency, lower cost and easy usage (Lo
pez-García
et al., 2017; Lou et al., 2017; Taleb et al., 2015). In recent years, Fe-
Mn bimetal nano-oxides have been used to adsorb arsenic from
aqueous environments (Lou et al., 2017; Rafati et al., 2012). These
particles comprise of iron and manganese metal oxides, so they can
be very effective in oxidation process and arsenic removal from
aqueous environments (Do et al., 2014; Zhao et al., 2012).
Therefore, this study used enhanced coagulation process by PAC
and PFC coagulants at the presence of Fe-Mn bimetal nano-oxides
to remove As(V) from polluted water resources. The study also
investigated the PFC coagulant synthesis and its relevant charac-
teristics, enhanced coagulation mechanism, determining the char-
acteristics of flocs, the effects of different coagulant doses, the
initial pH level, initial As(V) concentration and different Fe-Mn
nano-oxide doses.
2. Materials and methods
2.1. Preparation of coagulants
In order to prepare poly-ferric chloride by mole ratio of 0.5
(OH/Fe3þ) three types of matter were used: FeCl3.6H2O, Na2CO3
and Na2HPO4.12H2O (99 purity, Merk, Germany). Firstly, 24.133 g of
385
FeC13.6H2O and 2.3658 g of Na2CO3 were solved in deionized water.
Then, the Na2CO3 solution was added gradually, drop by drop, to the
FeC13.6H2O solution. Then, 2.55583 g of Na2HPO4.12H2O was added
to the compound as a stabilizer agent. Finally, the prepared solution
was increased up to 1 L and kept in complete mixture (CM) so that
the solution was pellucid. Given that the prepared poly-ferric
chloride coagulator by mole ratio of 0.5 (OH/Fe3þ) have proved
to be more effective in previous studies (Sun et al., 2016; Yang et al.,
2014), this ratio was used in this study. The PAC coagulant
(Al2(OH)nCl6-n. YH2O, Al2O3 ¼ 30 %wt, Basicity ¼ 55e85% and
pH ¼ 3e3.5) was also obtained from the international commercial
company (MBK chemical Co, Iran).
2.2. Coagulants and flocs characterization
In order to determine the characteristics of the synthesized PFC
coagulant, the FTIR (Fourier Transform Infrared spectroscopy)
(Thermo, AVATAR, USA) technique was used in the range of
400e4000 cm-1. Likewise, in order to determine the characteristics
of formed flocs by used coagulants after the process of coagulation
and flocculation, the precipitated flocs were kept in the oven in
60  C for 96 h until they dried out (Huang et al., 2014). Later, the
characteristics of precipitated flocs were compared by FESEM (Field
Emission Scanning Electron Microscopy) images and EDX (Energy
Dispersive X-ray) analysis (TESCAN-MIRA3, Czech Republic).
2.3. Synthesis and characterization of Fe-Mn bimetal nano-oxides
Synthesis and preparation method of the Fe-Mn bimetal nano-
oxides were explained in our previous study (Eslami et al., 2018).
For the synthesis of Fe-Mn nano-oxide was used from MnSO4.H2O
and FeCl3.6H2O in the co-precipitation method. The morphology
and size of these nano-oxides were characterized by FESEM image.
2.4. Jar test experiment
The 1-L jar test containers and programmable jar tester device
(7790-402 Phipps and Bird, USA) were used in lab temperature
(20  C) for coagulation and flocculation process. In order to opti-
mize the speed and mixing time of PAC and PFC coagulants, the
coagulants were analyzed in rapid mixing time (30 and 60 s), rapid
mixing speeds (100 and 200 rpm), slow mixing speed (30, 40 and
50 rpm), slow mixing time (15, 20 and 30 min) and sedimentation
time (20, 30 and 40 min). Then, the rapid mixing speed of 1 min by
100 rpm, slow mixing speed of 20 min by 40 rpm and sedimenta-
tion time of 20 min were selected as the optimal amounts. As co-
agulants were added to the solutions, the synthesized Fe-Mn
bimetal oxides in various doses (10, 20, 30, 40 and 50 mg/L) were
also added and analyzed. Moreover, pH parameters (5, 6, 7, 8, 9 and
10), coagulants dose (5, 10, 15, 20, 25 and 30 mg/L) and the initial
As(V) concentration (100, 200, 300, 400 and 500 mg/L) were also
investigated. The pH level was adjusted by HCl and NaOH solutions
(0.1 M).
The samples were taken from 2 cm of the surface of the water.
Next, the turbidity of the samples was measured by turbidity meter
(HACH, Germany). In order to analyze As(V) concentration, the
samples were passed through a 0.45 mm filter paper and then, was
used from the Hydride Generation Atomic Absorption Spectroscopy
(HGAAS, VARIAN, AA240FS, Australia). For the As(V) measurement,
Limit of Detection (LOD) and Limit of quantification (LOQ) were
found to be 0.1 and 0.5 mg/L, respectively. Determination of total Fe
and Al residual concentration performed by Graphite Furnace
Atomic Absorption (GFAAS), and the concentration of Cl was
determined by Mohr titration method (APHA, 2005).
386 H. Eslami et al. / Journal of Cleaner Production 208 (2019) 384e392

2.5. Statistical analysis

Water samples were analyzed three times. SPSS (Version 18.0)

software was employed to run one-way and univariate analysis of
variance (ANOVA), and Tukey post-hoc statistical tests.

3. Results and discussion

3.1. PFC characteristics

The FTIR spectrum for prepared PFC coagulant is shown in Fig. 1.

The analysis of the formed bonds and peak characteristics of the
synthesized coagulants showed that there were extensive adsorp-
tions peak in 3500e3400 cm1 and 1636-1635 cm1 spectra range,
which can be related to the stretching vibration of eOH and to the
bending vibration of absorbed, polymerized and crystalized water
in the synthesized PFC coagulant (Huang et al., 2014; Li et al., 2013;
Sun et al., 2011). With adding Na2CO3 to the metallic salt solutions
(FeC13) produced the supersaturated solution including amorphous
hydroxide colloids (Fe(OH)3). These hydroxide colloids finally
formed different species of Fe polymers (Sillanpa €€
a et al., 2018).
These results show that adding PO3 4 increases eOH and HeOeH
bonds in PFC, and such an increase of eOH, plays a crucial role in
the coagulation and flocculation process (Chen et al., 2016). The
adsorption peak in ranges of 1053e1211 cm1 spectra was attrib-
uted to FeeOHeFe bond (Chen et al., 2016; Sun et al., 2011) and
also, the peak of adsorption in ranges of 719e717 cm1 spectra was
related to FeeOH bond in synthesized PFC coagulant (Huang et al.,
2014; Li et al., 2013). Based on the results of FTIR spectra and PFC
species composition (FexOy(OH)zCln(H2O)m) (Yang et al., 2014), it
can be argued that the Fe-including PFC coagulant was perfectly
synthesized and polymerized.

3.2. Morphological properties of Fe-Mn bimetal nano-oxides

The main characteristic of Fe-Mn bimetal nano-oxides was

discussed in our previous study (Eslami et al., 2018). The EDX
analysis conforms to the presences of Fe and Mn elements in the
nanocomposite. XRD and XRF analysis showed these nano-
composites contain Fe2O3 (49.83 wt%) and Mn2O3 (29.36 wt%) ox-
ides. FESEM images of these nano-oxides are shown in Fig. 2. As
depicted, the bimetal Fe-Mn nano-oxides were agglomerated,
which could be considered as an advantage in coagulation and
flocculation process because it makes sedimentation process faster
(Bora et al., 2016; Ying et al., 2012). Also, based on FESEM images,
the range of Fe-Mn bimetal nano-oxides size was 7.51e19.95 nm.
Fig. 1. FTIR spectra of synthesized PFC coagulant.
Fig. 2. FESEM images (a and b) of Fe-Mn bimetal nano oxides.
3.3. Effects of initial pH
Fig. 3a shows the effects of different initial pH levels on the
As(V) removal efficiency by PAC and PFC coagulants in the presence
of Fe-Mn bimetal oxides (20 mg/L). As shown, the best efficiency for
PAC þ Fe-Mn coagulant-nono oxide was observed in pH 7 and for
PFC þ Fe-Mn in pH 9. In optimal pH range, the residual turbidity
was the lowest possible (1 and 5 NTU for PAC þ Fe-Mn and
PFC þ Fe-Mn, respectively) (Fig. 3b). The ANOVA analysis revealed
that there were significant differences between pH levels for each
of the coagulants (p  0.001). In PAC þ Fe-Mn, an increase in the pH
level from 5 to 7, raised the positive charge of Al hydrolyzed types
(Al (OH)þ 2þ
2 and Al (OH) ) in PAC coagulant and led to an increase in
As(V) anion adsorptions by charge neutralization mechanism;
therefore, the As(V) removal efficiency was increased. In higher pH
levels, the Al hydrolyzed types were formed by neutral or negative
charges forms (Al (OH)3, Al (OH)-4) which led to decrease the As(V)
removal efficiency and turbidity was increased (Pourrezaei et al.,
2011; Zhang et al., 2008). But, the PFC coagulant was formed in
the solution as positive hydroxides (Fe (OH)þ 2 ) in low pH and as
neutral or negative hydroxides in high pH (Fe (OH)3, Fe (OH)-2)
(Jadhav et al., 2015). Thus, the high As(V) removal efficiency in pH 9
 H. Eslami et al. / Journal of Cleaner Production 208 (2019) 384e392
Fig. 3. As(V) removal efficiency (a) and residual turbidity (b) in enhanced coagulation
by PAC þ Fe-Mn and PFC þ Fe-Mn in different pH.
and 10 by PFC þ Fe-Mn cannot be related to the As(V) charge
neutralization by Fe hydroxides. It is the presence of bimetal Fe-Mn
nano-oxides that makes the adsorption of As(V) anions because of
the positive charge of Fe3þ and Mn3þ and high specific surface area
(Ho€ll, 2010; Jadhav et al., 2015). Besides, the formed hydroxide flocs
that are combined with bimetal Fe-Mn nano-oxides act as the
central core of combined flocs formation and increase the adsorp-
tion, entrapment in the flocs and co-precipitation of As(V). This
finally can lead to higher removal efficiency in higher pH (Shi et al.,
2011). The Tukey test also showed that there were significant dif-
ferences in the efficiency levels between pH 9 and 10 with others
pH levels (p  0.045).
3.4. Effect of coagulants dose
The effects of PAC and PFC coagulants on As(V) removal effi-
ciency (with initial As(V) concentration of 300 mg/L and optimal pH
for each coagulant) in the presence and absence of Fe-Mn bimetal
oxides (20 mg/L) are shown in Fig. 4a. By increasing the coagulant
dose from 5 to 30 mg/L, the As(V) removal efficiency in both
presence and absence of Fe-Mn bimetal oxides were increased.
Based on ANOVA test, this difference was significant for both co-
agulants (p  0.001). Yet, the Tukey test revealed that for both PAC
and PFC coagulants, the different removal efficiency was significant
between coagulant doses of 25 and 30 mg/L with others coagulant
doses. Therefore, the optimal dose for both PAC and PFC coagulants
was 25 mg/L. Also, the amount of residual turbidity in optimal dose
was the lowest possible in a way that the residual turbidities for
PAC þ Fe-Mn and PFC þ Fe-Mn were 1 and 3 NTU, respectively
(Fig. 4b). These results are in agreement with Zhao et al. results,
focusing on the role of PAC in the removal of humic acids from
aqueous environments (Zhao et al., 2015). Similarly, these results
agree with the results of Gao et al. and Yang et al. studies about the
387
Fig. 4. As(V) removal efficiency (a) and residual turbidity(b) in enhanced coagulation
process by PAC and PFC in different dose and presence of Fe-Mn bimetal nano oxides.
role of PFC in the purification of dyes from wastewaters (Gao et al.,
2007; Yang et al., 2014).
Based on Fig. 4a, in the presence of Fe-Mn nano-oxides, the
As(V) removal efficiency in all the coagulant doses in the experi-
ment was higher than that the absence nano-oxides. The univariate
ANOVA results revealed that there were significant differences in
the As(V) removal efficiency of coagulants alone and coagulants in
combination with nano-oxides (p  0.001). In optimal coagulants
doses, the As(V) removal efficiency for PAC and PFC was 82.93% and
88.22%, respectively, and in the condition of coagulants-nano-
oxides combination, As(V) removal efficiency for PFC þ Fe-Mn
and PAC þ Fe-Mn was increased to 96.83% and 98.26%, respectively.
In addition, the remaining As(V) after enhanced coagulation by
PFC þ Fe-Mn and PAC þ Fe-Mn in the optimal conditions was
considerably lower than the standard threshold level for fresh
water as specified by WHO (˂ 10 mg/L) (WHO, 2011). Nevertheless, in
the condition of coagulation without Fe-Mn nano-oxides, the
remaining concentration of As(V) was higher than the standard
level. Also, the calculated cost of the Fe-Mn nano-oxides was 0.16
V/g (Eslami et al., 2018). Therefore, for use of 20 mg/L nano-oxides,
the cost was 0.0032 V for removing 300 mg As(V) from 1 L of the
contaminated water.
The reason behind the positive effects of PAC þ Fe-Mn nano-
oxides on the enhanced As(V) removal efficiency can be attrib-
uted to charge neutralization, adsorption, sweep flocculation, and
the entrapment of As(V) in the flocs in the enhanced coagulation -
flocculation process (Gao et al., 2005; Zhao et al., 2011). An increase
in coagulants dose, given the positive charge of Al species in the
solution (at pH 7) and the production of hydroxide colloids with
positive charge (Al (OH)þ 2 ), makes the adsorption of negatively

charged As(V) (HAsO2 4 and H2AsO4 ) (Matsui et al., 2017; Yang
et al., 2010) (Eq. (1)). Therefore, in the first stage, charge neutrali-
zation happens and As(V) ions are adsorbed on the surface of Al
hydroxide flocs. Also, the presence of positively charged (Mn3þ and
388 H. Eslami et al. / Journal of Cleaner Production 208 (2019) 384e392

Fe3þ) Fe-Mn bimetal nano-oxides is effective in the adsorption and

charge neutralization of negatively charged As(V) compounds
(Younker and Walsh, 2016). In a study conducted on the effects of
MnO2 nano particles on improving the efficiency of coagulation and
flocculation process for thallium removal from surface waters, the
results revealed that due to their high specific area of this nano
particles, thallium was adsorbed and sedimented with the formed
flocs in the process of coagulation and flocculation (Huangfu et al.,
2017). Additionally, these nano-sized Fe-Mn oxides due to high
specific surface area can adsorb As(V) from the solution (Ho € ll, 2010;
Jadhav et al., 2015). In the next stage, as the possibility of contact
between flocs and Fe-Mn nano-oxides in the suspension increases,
the sweep-flocculation mechanism happens and forms combined
flocs with Fe-Mn nano-oxides and make larger and heavier flocs.
Then, the co-precipitation of combined flocs increases the entrap-
ment of insoluble As(V) in these flocs. As a result, the As(V) removal
efficiency was increased in the presence of nano-oxides (Galloux
et al., 2015; Younker and Walsh, 2016).

Al(OH)þ 2
2 þ HAsO4 Al(OH)2ASO4 þ H
þ
(1)

In the enhanced coagulation and flocculation by PFC þ Fe-Mn

coagulant, the optimal pH was 9, the Fe hydroxide species are
neutral or negatively charged (Fe (OH)3, Fe (OH)-2) (Gao et al., 2011)
and As(V) had negative charge (HAsO2 4 ) in this pH (Song et al.,
2017); therefore, the charge neutralization mechanism by Fe hy-
droxide species was not successful. Nevertheless, the charge
neutralization and adsorption of As(V) happened by Fe-Mn bimetal
nano-oxides. Because of the existence of Fe3þ and Mn3þ cations in
the solution (Senn et al., 2018), the adsorption, sorption, and the
entrapment of the insoluble As(V) in combined flocs increased. The
combination of Fe hydroxide flocs with Fe-Mn nano-oxides as the
central core of the flocs in the floc sweeping stage and co-
precipitation is the main mechanisms for As(V) removal by
PFC þ Fe-Mn nano-oxides (Nidheesh and Singh, 2017; Shi et al.,
2011). Moreover, as shown in Fig. 4a, in the condition of co-
agulants without Fe-Mn bimetal nano-oxides, with increasing the
coagulants dose made the As(V) removal efficiency of PFC higher
than PAC coagulant. Hence, it can be argued that in higher doses of
PFC, the amount of produced Fe hydroxides flocs increases and can
lead to a more efficient sweep-flocculation and As(V) entrapment
in the flocs. Thus, the process of As(V) removal becomes more
efficient for PFC coagulant (Gao et al., 2007; Kabir and Chowdhury,
2017).
3.5. Effects of initial As(V) concentration
The effect of initial As(V) concentration on the enhanced coag-
ulation and flocculation process by PAC þ Fe-Mn and PFC þ Fe-Mn
coagulant-nano-oxides is shown in Fig. 5a. As observed, an increase
in the initial As(V) concentration from 100 to 300 mg/L slightly
decreased the As(V) removal efficiency by coagulants-nano-oxides.
The ANOVA statistical analysis shows that the As(V) removal effi-
ciency in different initial As(V) concentration for PFC þ Fe-Mn was
not significant (p ¼ 0.385). This difference, however, was significant
for the PAC þ Fe-Mn in concentration of lower than 300 mg/L with
higher than 300 mg/L (p ¼ 0.005). The reason may be related to the
positive charge of hydroxide flocs of the PAC coagulant and the Fe-
Mn bimetal nano-oxides in optimal concentration because there
was capacity to adsorb As(V) until to 300 mg/L in the solution (Sun
et al., 2013; Yang et al., 2010). Yet, increasing the As(V) concentra-
tion from 300 to 500 mg/L caused the efficiency of PAC þ Fe-Mn to
decrease with sharper slope that can be a result of a decrease in the
charge of PAC hydroxide flocs, Fe-Mn nano-oxides and the
completion of their adsorption sites for adsorbing As(V) in higher
Fig. 5. As(V) removal efficiency (a) and residual turbidity (b) in enhanced coagulation
by PFC þ Fe-Mn and PAC þ Fe-Mn in different initial As(V) concentration.
concentrations (Yang et al., 2010). In the PFC þ Fe-Mn coagulant,
compared with PAC þ Fe-Mn, the efficiency was not affected based
on initial concentration increase and there were not any significant
differences. The reason for this might be the existence mechanism
of an entrapment insoluble As(V) in the combined flocs and their
co-precipitation and therefore the insignificant effect of initial
As(V) concentration on the removal efficiency for this mechanism
(Shi et al., 2011). Nevertheless, the residual concentration of As(V)
after the enhanced coagulation and flocculation process for all the
experimented initial As(V) concentrations (100e500 mg/L) in
PFC þ Fe-Mn and for initial As(V) concentrations of 100e300 mg/L
in PAC þ Fe-Mn in optimal conditions of the pH and coagulant dose
was lower than the specified arsenic standard level (˂ 10 mg/L)
(WHO, 2011).
The results also demonstrated that the As(V) removal efficiency
in different initial As(V) concentrations was in PFC > PAC order, but
the residual turbidity (Fig. 5b) in different initial As(V) concentra-
tions after the enhanced coagulation and flocculation process for
PFC þ Fe-Mn was more than the PAC þ Fe-Mn coagulant. Other
studies also show that Fe-based coagulants are more efficient than
Al-based coagulants in removing pollutants but less efficient for
color and turbidity removal (Matilainen et al., 2010; Sillanpa€a
€ et al.,
2018).
3.6. Effect of Fe-Mn bimetal nano-oxides dose
The effects of different Fe-Mn bimetal oxide doses on the As(V)
removal efficiency in enhanced coagulation process are shown in
Fig. 6a. As depicted, with increasing the Fe-Mn bimetal nano-
oxides, the As(V) removal efficiency was increased in the
enhanced coagulation process. The ANOVA statistical analysis
shows that the difference of As(V) removal efficiency was signifi-
cant for PAC þ Fe-Mn (p ¼ 0.013) and PFC þ Fe-Mn (p ¼ 0.006) in
nono oxides dose lower than 20 mg/L with higher than 20 mg/L. It
can be due to increase the adsorption of As(V) by increasing the
 H. Eslami et al. / Journal of Cleaner Production 208 (2019) 384e392 389

Fe3þ and Mn3þ cations and also increasing the adsorption sites by
increasing the Fe-Mn bimetal nano-oxides dose (Huangfu et al.,
2017). This finding is in line with Huangfu et al. results where
they studied the application of MnO2 nanoparticles in coagulation
and flocculation process to remove thallium from surface water
(Huangfu et al., 2017).
The results also revealed that with increasing the Fe-Mn bimetal
oxides dose from 20 to 50 mg/L, the As(V) removal efficiency by
PAC þ FeMn increased with slightly slope. The reason for this may
be high agglomeration of nano-oxides and decrease the adsorption
sites for As(V) adsorption on the nano-oxides (Wang et al., 2018).
However, the higher slope of As(V) removal efficiency with the
increase in the Fe-Mn bimetal nano-oxide dose for the PFC þ Fe-Mn
as compared with PAC þ FeMn, can be related to the formation of
larger and bigger combined flocs (Based on FESEM images of flocs
in Fig. 7) to entrapment As(V) ions and removing them from the
aqueous environments (Cheng, 2002). In addition, the results
demonstrated that an increase in the dose of Fe-Mn bimetal nano-
oxides also increased the amount of residual turbidity that was
higher for the PFC þ FeMn (Fig. 6b). Given that the initial back-
ground color intensity for PFC was higher than PAC coagulants, the
remaining color in the solution was more for PFC after the
enhanced coagulation and flocculation process. This might be
attributed to the high optimal pH of PFC compared to PAC, in which
with increase of pH, the color intensity resulting from PFC
increased too (Sillanpa €€
a et al., 2018).

Fig. 6. As(V) removal efficiency (a) and residual turbidity (b) in enhanced coagulation 3.7. Flocs characteristics
by PFC and PAC in different Fe-Mn nano oxides.
The FESEM images of PAC þ Fe-Mn and PFC þ Fe-Mn

Fig. 7. FESEM images of precipitated flocs by PAC þ Fe-Mn oxides (a and b) and PFC þ Fe-Mn oxides (c and d).
390 H. Eslami et al. / Journal of Cleaner Production 208 (2019) 384e392

precipitated flocs after the enhanced coagulation process are

shown in Fig. 7. As depicted, the combined floc formation by
polymer coagulants e nano-oxides was confirmed. Also, the com-
parison of these flocs shows that the combined flocs made out by
PFC þ Fe-Mn nano-oxides were more uniform, bigger, denser and
stronger than those made out by PAC þ Fe-Mn nano-oxides. The
reason for this finding could be related to the better combination of
Fe hydroxides ions and Fe-Mn cations and also the heavier weight
of PFC flocs, and their faster sedimentation and higher condensa-
tion (Younker and Walsh, 2016). However, compared with the PAC
coagulant, one of the most noteworthy problems of the PFC coag-
ulant is the production of more combined flocs in the solution due
to high amount of Fe hydroxide in the higher pH (Xiao et al., 2010).
PAC þ Fe-Mn flocs had higher stickiness than PFC þ Fe-Mn flocs
because they were lighter and needed to adhere to Fe-Mn oxides
for sedimentation (Sillanpa€a
€ et al., 2018).
The results of EDX analysis for precipitated flocs of PAC þ Fe-Mn
and PFC þ Fe-Mn are shown in Fig. 8. Based on the EDX results, the
existence of Fe, Mn and arsenic elements in the precipitated com-
bined flocs were proved. The comparison of elemental analysis
shows that arsenic metal existed in two types of sediments and its
weight percent was higher in PFC þ Fe-Mn than in PAC þ Fe-Mn
that is in line with the results of As(V) removal efficiency for
PFC þ Fe-Mn (Fig. 4a). The existence of Al and Fe metals in the
sediments of PAC þ Fe-Mn and PFC þ Fe-Mn coagulants shows the
effects of hydroxide flocs formations by coagulants in the process of
As(V) removal (Wang et al., 2014). Yet, compared to Fe, Al metal has
lower weight percent of sediments that shows PAC flocs formation
were less in the solution and less able to combine with Fe-Mn
bimetal nano-oxides to form combined flocs and the weight
percent of Fe and Mn was higher than the weight percent of Al in
Fig. 9. Total Fe, Al (a) and Cl (b) residual after enhanced coagulation process by
the precipitated flocs (Thakur and Mondal, 2017). Similarly, the
PAC þ Fe-Mn and PFC-Fe-Mn at different dose.
FESEM images of PAC þ Fe-Mn (Fig. 6) show higher amounts of Fe-
Mn bimetal nano-oxides in the sediments as compared with
PFC þ Fe-Mn flocs. However, the higher weight percent of Fe metal
in the precipitated flocs of PFC þ Fe-Mn may be due to the existence
of Fe metal in the coagulant and in the bimetal nano-oxide.

3.8. Fe, Al and Cl residual in effluent

Fig. 9 present the total Fe, Al and Cl residuals after enhanced
coagulation process in different doses of PAC þ Fe-Mn and
PFC þ Fe-Mn. The total Fe and Al residual concentrations in opti-
mum coagulants-nano oxide dose for PAC þ Fe-Mn and PFC þ Fe-
Mn were 0.15 and 0.25 mg/L and Cl residue concentrations were
6.87 and 4.72 mg/L, respectively. Also, with increasing the co-
agulants dose, total Fe and Al residual concentration was decreased
(Fig. 9a) and total Fe residue concentration in optimum condition
was lower than WHO guideline (0.3 mg/L) for drinking water. In
contrast, for Al residue concentration, it was relatively higher than
WHO guideline (0.2 mg/L) (WHO, 2011).
With the increase of coagulants dose, Cl residue concentration
was increased (Fig. 9b) which can be related to chlorine released
from the chlorinated coagulants. In addition, total Cl residue
concentration in optimum condition was lower than WHO guide-
line (250 mg/L) for drinking water (WHO, 2011).

4. Conclusions

According to the results, using enhanced coagulation process by

PAC and PFC coagulants in combination with Fe-Mn bimetal nano-
oxides significantly increased the efficiency of As(V) removal from
Fig. 8. EDX analysis and Element Contents in Dried precipitated flocs by PFC þ Fe-Mn polluted water resources. In the optimal doses of coagulants
oxides (a) and PAC þ Fe-Mn oxides (b). (25 mg/L), the As(V) removal efficiency was 96.83% for PAC þ Fe-Mn
 H. Eslami et al. / Journal of Cleaner Production 208 (2019) 384e392
and 98.26% for PFC þ Fe-Mn and the residual As(V) concentration
was considerably lower than the permitted threshold level (˂ 10 mg/
L) for drinking water. The main mechanism of As(V) removal
PAC þ Fe-Mn and PFC þ Fe-Mn in the enhanced coagulation and
flocculation process was includes charge neutralization, adsorption,
sweep flocculation, entrapment of insoluble As(V) in the combined
hydroxide flocs with Fe-Mn nano-oxides and co-precipitation.
Finally, based on the results, Fe-Mn bimetal nano-oxides signifi-
cantly improved the removal of As(V) from polluted water re-
sources in the enhanced coagulation process.
Acknowledgments
This study is a PhD thesis in Environmental Health Engineering
(code: 4823) at Shahid Sadoughi University of Medicine Sciences in
Yazd, Iran. We hereby extend our gratitude to the university for
their financial supports. This study is also authorized in the Ethics
Committee of Shahid Sadoughi University of Medical Sciences by
the following authorization code: IR.SSU.SPH.REC.1396.12.
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