Journal of Environmental Chemical Engineering 4 (2016) 1008–1016

Contents lists available at ScienceDirect

Journal of Environmental Chemical Engineering

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

Effects of dissolved ions and natural organic matter on

electrocoagulation of As(III) in groundwater
Han Jo You1, Ihn Sup Han*
School of Environmental Engineering, University of Seoul, Siripdae-gil 163, Dongdaemun-gu, Seoul, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Article history: Electrocoagulation is an outstanding technique to remove pollutants. When current is applied to
Received 27 August 2015 electrodes, various amorphous iron hydroxides form complexes. Those complexes with high absorption
Received in revised form 2 December 2015 capacity such as arsenic and heavy metals are removed through the process. In this study, the effects of
Accepted 29 December 2015
various electrocoagulation conditions, such as the type of electrode, current, and pH, on the removal
Available online 4 January 2016
efficiency of arsenic were investigated. The removal efficiency varied significantly depending on the type
of electrode, as an iron electrode showed superior arsenic removal as compared to an aluminum
Keywords:
electrode. As the current increased, the removal rate of arsenic has increased. The validity of the method
Arsenic
Electrocoagulation
was examined by calculating the metal elution during electrocoagulation using Faraday’s law and
Iron hydroxide comparing it to the actual elution amount. Notably, amongst the various pH conditions pH 7 generated
Ion the fastest removal rate. The effects of dissolved ions on arsenic removal were also examined. When the
Humic acid magnesium concentration was less than 10 mg/L, the initial arsenic removal speed increased. No effects
were observed when the concentration of sulfate ions was low (1 mg/L, 10 mg/L). When the concentration
of sulfate ions was high (100 mg/L), the arsenic removal rate decreased. In addition, the presence of
phosphate ions and humic acid (HA) are reversely correlated with arsenic removal rate.
ã 2016 Elsevier Ltd. All rights reserved.

1. Introduction (reverse osmosis, electrodialysis), ion exchange, and adsorption

Arsenic is an artificial pollutant prevalent in leachates in mine
areas and agricultural chemicals (e.g., agricultural pesticides and
herbicides). Arsenic-containing minerals dissolve into water
source and cause natural pollution [1]. Most of the arsenic
pollution is natural pollution. Arsenic is abundant in earth’s crust,
and thus environmental arsenic pollution is observed worldwide.
Arsenic has adverse effects on humans and can cause various skin
diseases with long-term exposure; in severe cases, it can cause skin
cancer and death [2,3]. World Health Organization (WHO) have
established an allowable level of arsenic in drinking water to be
0.01 mg/L, many countries including South Korea abide the
standard [3,4].
Globally, numerous studies regarding the removal of arsenic
from water have been performed [1]. The main technologies used
for arsenic removal include precipitation technologies (coagula-
tion, Fe/Mn oxidation, lime softening), membrane technologies
* Corresponding author. Fax: +82 264902859.
E-mail addresses: yhjyzz@naver.com (H.J. You), ishan@uos.ac.kr (I.S. Han).
1
Fax: +82 264902859.
(activated alumina, granular ferric hydroxide, granular titanium
dioxide) [5,6]. In particular, electrocoagulation is effective for
removal of As(III) [7–9]. Many researchers have found that
electrocoagulation is effective for removal of pollutants in water
as well as removal of arsenic [10–21]. Eqs. (1)–(4) illustrate the
reaction that occurs when an iron electrode is used for electro-
coagulation [22]:
Anode:
4Fe(s) ! 4Fe2+(aq) + 8e (1)
4Fe2+(aq) + 10H2O(l) + O2(g) ! 4Fe(OH)3(s) + 8H+(aq) (2)
Cathode:
8H+(aq) + 8e ! 4H2(g) (3)
Overall:
4Fe2+(aq) + 10H2O(l) + O2(g) ! 4Fe(OH)3(s) + 4H2(g) (4)
In groundwater, arsenic primarily exists in the trivalent form;
many ions and organic matters also exist in groundwater [4]. Metal
ions and organic matter are expected to have a large effect on the

http://dx.doi.org/10.1016/j.jece.2015.12.034
2213-3437/ ã 2016 Elsevier Ltd. All rights reserved.
 H.J. You, I.S. Han / Journal of Environmental Chemical Engineering 4 (2016) 1008–1016
removal of arsenic from groundwater through electrocoagulation
[23]. In this study, effects of magnesium and sulfate as well as
phosphate and natural organic matter on the removal of arsenic
were investigated. Existing researches have focused only on the
efficiency of arsenic removal. Studies about residual iron concen-
tration as secondary pollution are insufficient. High iron ion
concentration is not as toxic as arsenic but it has chronic
significance on health and environment. The correlation between
ion profile of natural water bath and residual iron ion is a key to
future research on water resource and environment protection.
The study have investigated ion concentration levels within the
quality standard of drinking water.
2. Materials and methods
2.1. Materials
Samples were prepared using artificial raw water. Basic artificial
raw water was made with ultrapure water, As(III), NaCl, HCl, and
NaOH. Ultrapure water was the primary source for the artificial raw
water and all solutions. To prepare As(III), a stock solution was
made using NaAsO2, and the arsenic concentration of the artificial
raw water was set to 1 mg/L. NaCl (about 500 mS/cm) was injected
at a total concentration of 0.004 M to provide conductivity for the
electrocoagulation process. About 0.1 M NaOH and HCl solutions
were used to adjust the pH. The pH was determined using a pH
meter (238-180 model, Istek, Korea). Only As(III), NaCl, HCl, and
NaOH were injected into the raw water. When the effects of ions
were examined, each ion species was injected individually, in order
to minimize the effects of other ions. Magnesium, phosphate,
sulfate, and humic acid stock solutions were made from
MgCl26H2O, Na2HPO4, Na2O (17.0–19.0%) + SiO2 (35.0–38.0%),
Na2SO4, and humic acid, respectively.
2.2. Devices and experimental methods
Fig. 1 shows the electrocoagulation and filtering processes
used in this study. The size of the reactor was W190 mm 
L120 mm  H250 mm. The reactor had a volume of 4 L, and was
made of acrylic plates. The size of the electrode plate was
Fig. 1. Electrocoagulation and membrane process.
1009
W85 mm  L3 mm  H260 mm, and the plates were installed based
on a bipolar serial connection (BP-S), where they were fixed at
10 mm intervals so that the wide faces could face each other. Before
each experiment, the electrode plate was immersed in 1 M HCl for
10 min, and was then polished using sandpaper. Scale and rust on
the iron electrode were removed as mentioned above, and it was
then used for the experiment after cleaning with distilled water,
which increased the reproducibility of the experiments. A constant
current was supplied using a D.C. power supply. The interior of the
reactor was uniformly agitated at 60 rpm. During the electro-
coagulation process, samples were collected at specified times. The
samples were filtered through a 0.45 mm membrane filter
(Advantec, mixed cellulose ester) and were subsequently analyzed.
Initial arsenic concentration of raw water and accurate sampling
time are crucial factors for reducing errors.
2.3. Analytical methods
The samples were analyzed using the following machinery and
methods. Mg and Fe contents were measured using Inductively
Coupled Plasma (ICP, ICPE-9000, Shimadzu, Japan). It was difficult
to measure low concentrations of arsenic using ICP alone;
therefore, As was analyzed using Inductively Coupled Plasma–
Hydride Vapor Generator (ICP–HVG, Shimadzu, Japan). Ferrous
iron was analyzed using a UV/VIS spectrophotometer (Evolution
60S, Thermo, USA) based on the 3500-Fe Phenanthroline Method
of the Standard Methods [24].
The change in PO43 content was measured using ion
chromatography (IC, ICS-900, Dionex, USA). To examine the
removal efficiency of humic acid, the Dissolved Organic Carbon
(DOC) was measured using a Total Organic Carbon Analyzer (TOC
Analyzer, TOC-V, Shimadzu, Japan), and the adsorption at 254 nm
was measured using a UV/vis spectrophotometer.
A Zetasizer (Nano ZS, Malvern, UK) was used to measure the
zeta potential. The electrocoagulation by-product was precipitated
and dried, and was analyzed using X-ray diffraction (XRD,
D8 advance Sol-X, Bruker, Germany).
In order to reduce sample errors, maintaining standard
calibration curves of the equipment played a crucial role to keep
consistent and accurate results.
1010 H.J. You, I.S. Han / Journal of Environmental Chemical Engineering 4 (2016) 1008–1016

3. Results and discussion

3.1. Comparison of aluminum and iron electrodes

Iron or aluminum electrodes are used in most cases for

electrocoagulation. Iron electrodes generally are more corrosive
than aluminum electrodes; when an iron electrode is used, a red
residue is formed. Therefore, for materials that show similar
removal efficiencies, aluminum electrodes are preferred [25].
Iron and aluminum electrodes were evaluated in the removal
of arsenic. Four electrode plates with the same area were used
for both electrodes, and the removal efficiencies were deter-
mined at various currents. A distinct difference between the
electrodes was observed, as shown in Fig. 2. With the iron
electrode, the removal efficiency was 99% within 10 min at
0.2 A; at 0.1 A, a removal efficiency of 99% was achieved 15 min.
At 0.05 A, the removal efficiency was higher than 99% within Fig. 3. Comparison between theoretical and experimental iron concentrations
25 min. However, with the aluminum electrode, the arsenic using 2 iron plates at pH 7.

removal efficiency was less than 50% until 30 min at 0.2 A and
0.1 A. As the current increased, the elution of the metal
electrode increased, and thus the formation of metal hydroxides
increased. Presumably, the fast-forming metal hydroxide aids in
including a factor for the number of plates in Faraday’s law, as
the quick removal of arsenic. However, the aluminum electrode
shown in Eq. (5):
showed significantly lower arsenic removal than the iron
electrode. This indicated that iron hydroxide binds better to ITM
W¼  ðn  1Þ ð5Þ
arsenic than aluminum hydroxide [9]. zF
In subsequent experiments, 0.1 A current was used instead of
where W is the mass of the dissolved metal (g), I is the applied
0.2 A, because the fast removal of arsenic was not distinctly
current (A), t is the treatment time of the electrocoagulation
different in the presence of other ions.
process (s), M is the molar mass of the anode metal (g/mol), z is the
valence number of ions of the substance (zAl = 3, zFe = 2), F is
3.2. Elution of iron
Faraday’s constant (96,485 C/mol), and n is the number of plates.
The coefficients of determination (R2) between the theoretical
In electrocoagulation, the amount of metal ions dissolved in
and experimental values when the plate numbers were 3 and
water from an electrode plate is proportional to the reaction time
4 were 0.9931 and 0.9974, respectively, as summarized in Table 1.
and current. The current was fixed at 0.1 A at pH 7, and the
The absolute average errors were small (3.7432 and 4.6096,
electrical conductivity was adjusted using NaCl. First, the elution
respectively). As a result, when more than 2 plates were used, the
was compared by varying the number of plates (2, 3, and 4 plates).
metal elution was proportional to 1 less than the number of plates
As the number of plates increased, the concentration of iron also
(n). When the experiment was performed at pH values of 5, 7, and
increased. This was compared to the theoretical concentration
9 using 4 plates, the absolute average errors were within 5%.
using Faraday’s law [3,26].
Therefore, the use of Faraday's law was appropriate. However, at
When 2 iron plates were used, the coefficient of determination
pH 3, the absolute average error was 36.2848%. The experimental
(R2) between the theoretical and experimental values was very
value was significantly larger than the theoretical value because
high (0.9941), as shown in Fig. 3. The absolute average error was
the dissolution rate of the positive electrode was accelerated under
also very small (5.2395).
acidic conditions.
However, when 3 and 4 plates were used, the concentration of
At pH values less than 4, hydrogen evolution occurs, and it is
iron increased continuously. The results were compared by
called hydrogen evolution-type corrosion. At pH values between
4 and 10, the corrosion rate is nearly constant [27]. At
approximately pH 7, the protective oxide film on the electrode
surface is not stable, and thus the iron elution at the electrode is
high [28]. At pH 3, the rate at which the pH increases is slow, and
thus more elution of iron occurs until the pH increases above a
certain value. Therefore, Faraday's law could not be applied at pH 3.

Table 1
Comparison between theoretical and experimental iron concentrations as a
function of pH and plate number.

Plates number pH Coefficient of determination (R2) Mean absolute error

2 7 0.9941 5.2395
3 7 0.9931 3.7432
4 7 0.9974 4.6096
4 3 0.9981 36.2848
4 5 0.9988 2.1671
4 9 0.9991 2.4699
Fig. 2. Arsenic removal as a function of current on iron and aluminum plates.
 H.J. You, I.S. Han / Journal of Environmental Chemical Engineering 4 (2016) 1008–1016
Fig. 4. Arsenic removal as a function of initial pH after electrocoagulation and
membrane process at 0.1 A.
3.3. Effect of initial pH on removal efficiency
In the following experiment, 4 iron plates were used, and the
effect of pH on arsenic removal was examined by adjusting the pH
(3, 5, 7, and 9) using NaOH and HCl.
At pH 7, the arsenic content reached 0.01 mg/L (i.e., the standard
for drinking water) in the shortest amount of time, as shown in
Fig. 4. During the initial 8 min of the 30-min electrocoagulation
process, the highest removal efficiency was observed at pH 5. Due
to the fast oxidation of iron, arsenic was removed quickly. However,
after 10 min, the best arsenic removal efficiency was observed at
pH 7. At pH 7, after 10 min, fast-grown flocs were filtered by a
membrane filter, and a higher removal efficiency was observed. At
pH 9, the removal efficiency was lower than that at an initial pH of
5, but was similar to that at pH 7. After 5 min, the removal
efficiency significantly decreased compared to those at pH values
of 7 and 5. Although the removal rate decreased, the water quality
standard of arsenic (0.01 mg/L) could be satisfied within 30 min at
pH 9. However, at pH 3, the arsenic content could not reach
0.01 mg/L within 30 min.
Fig. 5 shows the concentration of iron that remained in water
after electrocoagulation and membrane filtering. At pH 7 and 9,
when the arsenic concentration decreased below 0.01 mg/L, the
iron concentration also decreased below 0.3 mg/L (i.e., the water
quality standard of drinking water). During the initial stages, iron
Fig. 5. Residual Fe concentration as a function of initial pH after electrocoagulation
and membrane process.
1011
mostly existed as ferric iron, and iron hydroxide remained as small
particles. The amount of remaining ferrous iron was much less than
that of ferric iron. However, at pH 3 and 5, a high concentration of
iron (more than 0.3 mg/L) was observed. Most of the remaining
iron at pH 3 and 5 was ferrous iron, and it could not be oxidized to
ferric iron and remained in the water. The concentration of
dissolved iron was likely high because iron hydroxide could not
form because the dissolution of iron hydroxide is high at low pH.
Moreover, the iron dissolution increased as the pH decreased.
Removal of arsenic absorbed by iron hydroxide through membrane
filtration decreased at pH 5. Fig. 4 shows arsenic concentration fall
in pH7 after 10 min compared to that of pH5.
3.4. Effects of metal ions and humic acid
Next, we examined the effects of dissolved ions on the removal
of arsenic from groundwater via electrocoagulation. First, to
investigate the effects of ion concentration, different concen-
trations of selected ions were injected at a current of 0.1 A, and the
pH was adjusted to 7.
3.4.1. Effects of magnesium
First, the effects of dissolved magnesium ions on the removal of
arsenic from groundwater via electrocoagulation were evaluated.
A concentration of 0.1 mg/L of magnesium had almost no effect on
the arsenic removal (data not shown). When the concentrations of
magnesium were 1 mg/L and 10 mg/L, the arsenic removal rate
increased; this trend was more distinct when the concentration of
magnesium was high (10 mg/L). However, the presence of 100 mg/L
of magnesium decreased the arsenic removal rate.
As shown in Fig. 7, more than 0.3 mg/L (i.e., water quality
standard of drinking water) of iron remained when 10 mg/L of
magnesium was injected, and the amount of iron continuously
increased as time passed. In particular, when 100 mg/L of
magnesium was added, the concentration of remaining iron was
compared to the total amount of iron dissolved in water that was
calculated using Faraday’s law. The concentration of iron remain-
ing in water after 3 min was about 44% of the total amount of iron,
and it was about 55% at 30 min, where it steadily increased as time
passed. The remaining iron was identified as ferrous iron, while
unoxidized iron was present in the filtered water.
Because magnesium combines with hydroxide ions to produce
Mg(OH)2 [29,30] (Eq. (7)), the production of iron hydroxide
decreased. Thus, ferrous iron in water could not be oxidized and
remain in the water. The decrease in iron hydroxide content
reduced the arsenic removal rate.
MgCl2 þ 2OH ! MgðOHÞ2 þ Cl2 ð7Þ
The change in magnesium content could were also examined
using ICP. The decrease in magnesium was about 10% at all
concentrations excluding 0.1 mg/L.
The solubility product of Mg(OH)2 @ Mg2+ + 2OH (Ksp at 25  C)
is 9  1012 [31]. It is a solid and it dissociates in water. Thus, more
OH was deficient, and this resulted in the decrease in iron
hydroxide.
Table 2 summarizes the zeta potential measurements. With
100 mg/L of magnesium, the zeta potential was positive at 3 min.
Negatively charged colloids or anions were quickly removed as
they approached 0 mV due to the dissolution of iron (i.e., cation).
However, the arsenic removal was not efficient because of the
reversed potential, due to the high concentration of magnesium.
Appropriate amounts of magnesium had a positive effect on
arsenic removal, but high concentrations of magnesium decreased
the arsenic removal rate due to the increase in the zeta potential
and the inhibition of coagulant formation. To prevent this, large
1012 H.J. You, I.S. Han / Journal of Environmental Chemical Engineering 4 (2016) 1008–1016

Table 2
Zeta potential as a function of time and additive concentration.

Time (min) No ion, HA Zeta (mV) Time (min) Mg (mg/L) Zeta (mV) Time (min) Mg (mg/L) Zeta (mV) Time (min) HA (mg/L) Zeta (mV)
3 0 21.2 3 10 11.9 3 100 22.6 3 10 32.6
5 0 20.3 5 10 9.46 5 100 22.2 5 10 24.9
10 0 2.79 10 10 10.6 10 100 23.7 10 10 29.4
20 0 5.83 20 10 22 20 100 22 20 10 13.5
30 0 2.53 30 10 27.4 30 100 22.1 30 10 6.31

amounts of magnesium should be removed first. Additionally, the
pH should be increased, and the time should be adjusted to reduce
the iron elution.
3.4.2. Effects of sulfate ions
The effects of sulfate ions on arsenic removal were evaluated.
Changes in the arsenic removal were examined by injecting 0.1, 1,
10, and 100 mg/L solutions of sulfate ions at pH 7. The results
obtained in the presence of 0.1 mg/L sulfate ions are not shown in
Fig. 8. With 1 and 10 mg/L sulfate ions, the results were similar to
that without sulfate. However, at 100 mg/L, the arsenic removal
rate decreased. In previous studies, it was reported that sulfate ions
had almost no effect on arsenic removal [8,23]. In the present
study, 10 mg/L of sulfate also had no effect on the arsenic removal
rate. However, at high concentrations of sulfate (100 mg/L), the
arsenic removal rate decreased. SO42 probably competed with
arsenic for the adsorption site of iron hydroxide [32]. Also,
considering that the concentration of iron initially increased and
then decreased when the sulfate concentration was 100 mg/L
(Fig. 8), the oxidation of iron was probably inhibited.
10 mg/L of phosphate ions were injected, the arsenic removal
efficiency was 70% within 30 min, and the drinking water quality
standard could not be satisfied. With 10 mg/L of phosphate ions,
the arsenic removal efficiency depending on the initial pH was
examined by increasing the electrocoagulation process time to
60 min.
The concentration of phosphate ions was measured using ion
chromatography; phosphate ions were not detected in the sample
collected at 5 min at 1 mg/L. The removal of phosphate ions was
faster than that of arsenic. Furthermore, when the concentration of
iron decreased below the standard value, it was nearly consistent
until the water quality standard for arsenic was reached. This
indicated that arsenic and phosphate ions have a competitive
relationship, but phosphate ions are quickly removed because they
react with iron faster than arsenic, and that the removal of arsenic
is relatively more difficult.
Fe3þ þ PO4 3 ! FePO4 ð8Þ

3.4.3. Effects of phosphate ions

Phosphate ions have been reported to inhibit removal of
arsenic. Arsenic and phosphorus are located in the same group of
the periodic table, and have the same tetrahedral structure. Thus,
they are removed by adsorption on the same adsorption site of iron
hydroxide [8,33,34]. Phosphate ions are less abundant in ground-
water than other ions. In this experiment, 0.1, 1, and 10 mg/L of
phosphate ions were added, and the removal efficiency of arsenic
as well as the concentration of dissolved iron were examined.
As shown in Fig. 9, the arsenic removal rate was affected by the
presence of 0.1 mg/L phosphate, unlike that with other ions. At
about 8 min, 0 and 0.1 mg/L showed a C/C0 difference of about 0.2.
The times required to reach the drinking water quality standard
were not significantly different. However, with 0.1 mg/L phos-
phate, it took more time for the concentration of iron to decrease
below the drinking water quality standard. As the concentration of Fig. 7. Residual Fe concentration as a function of magnesium ion concentration.
phosphate ions increased, the removal rate decreased. When

Fig. 6. Effects of magnesium concentration on arsenic removal. Fig. 8. Effect of sulfate concentration on arsenic removal.
 H.J. You, I.S. Han / Journal of Environmental Chemical Engineering 4 (2016) 1008–1016
Fig. 9. Effect of phosphate concentration on arsenic removal.
Phosphate is removed by the above mechanism (Eq. (8)), and it
could also be removed by adsorption on iron hydroxide [35,36].
Due to this removal mechanism, OH produced during the
electrocoagulation process remained in the water and did not
form iron hydroxide, which increased the pH. This increase was
compared to that observed in other experiments. With 10 mg/L of
magnesium (Fig. 6) and 0 mg/L of phosphate (Fig. 7), the pH values
after 15 min were 6.67 and 7.18, respectively, but for 10 mg/L of
phosphate, the pH increased to 9.52.
When 10 mg/L of phosphate ions were dissolved in water, the
arsenic removal efficiency was low. Therefore, the process time
was increased to 60 min. However, after 60 min, the removal
efficiency was only about 90%, and the drinking water quality
standard could not be satisfied (Fig. 10).
3.4.4. Effects of humic acid
The effects of humic acid on the removal of arsenic from
groundwater were also evaluated. Humic acid concentrations of
1 mg/L, 5 mg/L, 10 mg/L, and 20 mg/L were assessed.
Fig. 11 shows the removal efficiency of arsenic in the presence of
humic acid. There was almost no difference in the arsenic removal
rate or iron concentration upon addition of 1 mg/L humic acid as
compared to that without humic acid. When the concentrations of
humic acid were 5 mg/L, 10 mg/L, and 20 mg/L, the arsenic removal
rate decreased as the concentration increased, and a significant
amount of time was required to reach a concentration below the
drinking water quality standard. The target water quality was
obtained at 20 min for 10 mg/L, and at 25 min for 20 mg/L. Fig. 12
Fig. 10. Residual Fe concentration as a function of phosphate concentration.
1013
Fig. 11. Effect of humic acid concentration on arsenic removal.
shows the concentration of remaining iron. The iron concentration
increased as the humic acid concentration increased. This pattern
was similar to that of other ions, but there was a slight difference.
While the concentration of remaining iron ions increased during
the initial stage of the process, the decrease in arsenic content was
smaller than the case in which the inhibition of arsenic removal by
ions was observed. When the concentration of remaining iron
began to decrease, the arsenic and iron concentrations abruptly
decreased. In particular, the difference was large when the ion
concentration was high (Fig. 13).
These results were attributed to the sweep coagulation of
humic acid. Humic acid is comprised of hydrophobic and
hydrophilic materials. In particular, the hydrophobic compounds
constitute about 90% of the total material. In general, hydrophobic
compounds are more easily coagulated [37]. Thus, the coagulation
and formation of iron hydroxide flocs are improved; as a result,
sweep coagulation occurs due to the decrease in the zeta potential
of the floating colloidal material and the promotion of colloidal
particle removal by trapping [38].
The removal of humic acid was measured using the adsorption
at 254 nm and DOC. In previous study, it was mentioned that the
increase in the adsorption at 254 nm during electrocoagulation
using an iron electrode was due to production of colored iron
hydroxide particles [39]. In this study, the UV adsorption at 254 nm
also increased with the addition of 10 mg/L of humic acid. The
adsorption at 254 nm increased to 3.6 times the initial value, then
decreased to 0.05 after 15 min; DOC revealed a removal efficiency
of 83.5%. This value was continuously maintained until 30 min. In
Fig. 12. Residual Fe concentration as a function of humic acid concentration.
1014 H.J. You, I.S. Han / Journal of Environmental Chemical Engineering 4 (2016) 1008–1016

Table 3
Zeta potential.

Time (min) HA (mg/L) Zeta (mV) Time (min) HA (mg/L) Zeta (mV)
3 0 21.2 3 10 32.6
5 0 20.3 5 10 24.9
10 0 2.79 10 10 29.4
20 0 5.83 20 10 13.5
30 0 2.53 30 10 6.31

Fig. 13. DOC removal and UV254/UV2540.
addition, as mentioned previously, the concentrations of arsenic
and iron decreased abruptly at 15 min, indicating that humic acid
and arsenic were removed simultaneously.
Table 3 compares the cases in which there was humic acid in
water when there was no humic acid. Organic acids such as humic
acid have a negative charge in water, which usually inhibits
coagulation and adsorption. In this experiment, humic acid
exhibited a negative charge and lowered the coagulation and
adsorption of arsenic [39].
3.5. XRD
To confirm the formation of iron hydroxide, the particles
produced after the electrocoagulation process were collected and
dried, and were analyzed using X-ray diffraction (XRD).
Figs. 14 and 15 show the XRD of the products obtained after 60-
and 30-min electrocoagulation processes. Respectively, at pH
7 when the arsenic concentration was 1 mg/L. Iron existed as
lepidocrocite (g-FeO(OH)) and magnetite (Fe3O4) (Fig. 14). How-
ever, only lepidocrocite was observed after 30 min (Fig. 15),
indicating that the type of iron that formed varied as time passed.
Magnetite is an oxidized form of iron, and its formation over time is
consistent with the electrocoagulation mechanism mentioned
previously [8,40].
Fig. 16 shows the results of a 30-min electrocoagulation process
at pH 7 when 1 mg/L As(III) and 10 mg/L humic acid were present,
only lepidocrocite was observed in this process. Lepidocrocite
formation was observed under several sets of conditions (Figs. 14–
16), but the peaks intensity in the XRD spectra became sharper and
clearer as time passed. In addition, when arsenic or humic acid
were present, the peak intensity became weak.
Through XRD analysis, the electrocoagulation mechanism was
determined to proceed as shown in Eqs. (9)–(12).
Early stage:
Fe þ 3ðOHÞ ! FeðOHÞ3 ð9Þ
FeðOHÞ3ðsÞ ! FeOðOHÞðsÞ þ H2 OðlÞ ðlepidocrociteÞ ð10Þ

Fig. 14. XRD spectra of solids generated during electrocoagulation 60 min; conditions: pH 7, As(III) 1 mg/L.
 H.J. You, I.S. Han / Journal of Environmental Chemical Engineering 4 (2016) 1008–1016 1015

Fig. 15. XRD spectra of solids generated during electrocoagulation 30 min; conditions: pH 7, As(III) 1 mg/L.

Later stage: During electrocoagulation, arsenic is likely removed via

adsorption and co-precipitation by Fe(OH)3 and lepidocrocite
4Fe þ 12ðOHÞ ! 4FeðOHÞ3 ð11Þ
[26]; during the late stages of electrocoagulation, arsenic is
removed by the formation of magnetite [40].

4FeðOHÞ3ðsÞ ! FeðOHÞ2ðsÞ þ Fe3 O4ðsÞ þ H2 OðlÞ ðmagnetiteÞ ð12Þ

Fig. 16. XRD spectra of solids generated during electrocoagulation over 30 min; conditions: pH 7, As(III) 1 mg/L, HA 10 mg/L.
1016 H.J. You, I.S. Han / Journal of Environmental Chemical Engineering 4 (2016) 1008–1016
4. Conclusions
In this study, the effects of various ions and humic acid on the
removal of As(III) via electrocoagulation were investigated. The use
of an iron electrode resulted in a higher removal efficiency than an
aluminum electrode. The time required to reach the drinking water
quality standard varied depending on the pH. The fastest removal
efficiency was observed at pH 7, followed by pH 5, pH 9, and pH 3.
Magnesium increased the arsenic removal rate. However, high
magnesium concentrations inhibited arsenic removal, and abrupt-
ly increased the concentration of dissolved iron. A high concen-
tration of sulfate or phosphate ions decreased the arsenic removal
rate, and resulted in a substantial increase in the pH. In addition,
humic acid also decreased the arsenic removal rate. XRD analysis
indicated that iron was oxidized to lepidocrocite initially and
subsequently oxidized to magnetite during the later stages of the
process. These iron hydroxide and iron oxide species aided in the
effective removal of arsenic.
References
[1] P.L. Smedley, D.G. Kinniburgh, A review of the source, behaviour
and distribution of arsenic in natural waters, Appl. Geochem. 17 (2002)
517–568.
[2] M. Kobya, F. Ulu, U. Gebologlu, E. Demirbas, M.S. Oncel, Treatment of potable
water containing low concentration of arsenic with electrocoagulation:
different connection modes and Fe–Al electrodes, Sep. Purif. Technol. 77 (2011)
283–293.
[3] M. Col, C. Col, A. Soran, B.S. Sayli, S. Ozturk, Arsenic-related Bowen’s disease,
palmer-keratosis, and skin cancer, Environ. Health Perspect. 107 (1999) 687–
689.
[4] D. Mohan, C.U. Pittman Jr., Arsenic removal from water/wastewater using
adsorbents—a critical review, J. Hazard. Mater. 142 (2007) 1–53.
[5] S. Bang, E.Y. Choe, K.W. Kim, Treatment technologies for arsenic removal from
groundwater: review paper, Econ. Environ. Geol. 38 (5) (2005) 599–606.
[6] R. Singh, S. Singh, P. Parihar, V.P. Singh, S.M. Prasad, Arsenic contamination,
consequences and remediation techniques: a review, Ecotoxicol. Environ. Saf.
112 (2015) 247–270.
[7] E. Mohora, S. Roncevic, J. Agbaba, A. Tubic, M. Mitic, M. Klasnja, B. Dalmacija,
Removal of arsenic from groundwater rich in natural organic matter (NOM) by
continuous electrocoagulation/flocculation (ECF) val of arsenic from
groundwater rich in natural organic matter (NOM) by continuous
electrocoagulation/flocculation (ECF), Sep. Purif. Technol. 136 (2014) 150–156.
[8] W. Wan, T.J. Pepping, T. Banerji, S. Chaudhari, D.E. Giammar, Effects of water
chemistry on arsenic removal from drinking water by electrocoagulation,
Water Res. 45 (2011) 384–392.
[9] P.R. Kumar, S. Chaudhari, K.C. Khilar, S.P. Mahajan, Removal of arsenic from
water by electrocoagulation, Chemosphere 55 (2004) 1245–1252.
[10] N. Adhoum, L. Monser, N. Bellakhal, J. Belgaied, Treatment of electroplating
wastewater containing Cu2+, Zn2+ and Cr(VI) by electrocoagulation, J. Hazard.
Mater. B112 (3) (2004) 207–213.
[11] T.H. Kim, C. Park, E.B. Shin, S. Kim, Decolorization of disperse and reactive dyes
by continuous electrocoagulation process, Desalination 150 (2) (2002)
165–175.
[12] V. Khandegar, A.K. Saroha, Electrochemical treatment of distillery spent wash
using aluminum and iron electrodes, Chin. J. Chem. Eng. 20 (3) (2012)
439–443.
[13] E. Keshmirizadeh, S. Yousefi, M.K. Rofouei, An investigation on the new
operational parameter effective in Cr(VI) removal efficiency: a study on
electrocoagulation by alternating pulse current, J. Hazard. Mater. 190 (1–3)
(2011) 119–124.
[14] F. Janpoor, A. Torabian, V. Khatibikamal, Treatment of laundry waste-water by
electrocoagulation, J. Chem. Technol. Biotechnol. 86 (8) (2011) 1113–1120.
[15] C.Y. Hu, S.L. Lo, W.H. Kuan, Effects of co-existing anions on fluoride removal in
electrocoagulation (EC) process using aluminum electrodescts of co-existing
anions on fluoride removal in electrocoagulation (EC) process using aluminum
electrodes, Water Res. 37 (18) (2003) 4513–4523.
[16] I. Heidmann, W. Calmano, Removal of Cr(VI) from model wastewaters by
electrocoagulation with Fe electrodes, Sep. Purif. Technol. 61 (1) (2008) 15–21.
[17] D. Ghosh, H. Solanki, M.K. Purkait, Removal of Fe(II) from tap water by
electrocoagulation technique, J. Hazard. Mater. 155 (1–2) (2008) 135–143.
[18] E.S.Z. El-Ashtoukhy, N.K. Amin, Removal of Acid Green Dye 50 from wastewater
by anodic oxidation and electrocoagulation—a comparative study, J. Hazard.
Mater. 179 (1–3) (2010) 113–119.
[19] B. Merzouk, B. Gourich, A. Sekki, K. Madani, M. Chibane, Removal turbidity and
separation of heavy metals using electrocoagulation–electroflotation
technique, J. Hazard. Mater. 164 (1) (2009) 215–222.
[20] N. Daneshvar, A. Oladegaragoze, N. Djafarzadeh, Decolorization of basic dye
solutions by electrocoagulation: an investigation of the effect of operational
parameters, J. Hazard. Mater. B129 (1–3) (2006) 116–122.
[21] C.G. Alfafara, K. Nakano, N. Nomura, T. Igarashi, M. Matsumura, Operating and
scale-up factors for the electrolytic removal of algae from eutrophied lake
water, J. Chem. Technol. Biotechnol. 77 (2002) 871–876.
[22] M.Y.A. Mollah, R. Schennach, J.R. Parga, D. Cocke, Electrocoagulation (EC)—
science and applications, J. Hazard. Mater. 84 (1) (2001) 29–41.
[23] X.G. Meng, S. Bang, G.P. Korfiatis, Effects of silicate, sulfate, and carbonate on
arsenic removal by ferric chloride, Water Res. 34 (4) (2000) 1255–1261.
[24] American Public Health Association,, Standard Methods for the Examination of
Water and Wastewater, 21st ed., American Public Health Association,
Washington, D.C, 2005.
[25] J.S. Kim, T.E. Kim, I.S. Han, Phosphorus removal by a combined
electrocoagulation and membrane filtration process for sewage reuse,
Desalin. Water Treat. 54 (2015) 956–965.
[26] D. Lakshmanan, D.A. Clifford, G. Samanta, Ferrous and ferric ion generation
during iron electrocoagulation, Environ. Sci. Technol. 43 (10) (2009)
3853–3859.
[27] V.M. Balsaraf, Applied Chemistry—II, I. K. International, 2009.
[28] D.A. Jones, Principles and Prevention of Corrosion, second ed., Prentice Hall,
1995.
[29] E.T. Tolonen, J. Rämö, U. Lassi, The effect of magnesium on partial sulphate
removal from mine water as gypsum, J. Environ. Manag. 159 (2015) 143–146.
[30] J. Leentvaar, M. Rebhun, Effect of magnesium and calcium precipitation on
coagulation–flocculation with lime, Water Res. 16 (1982) 655–662.
[31] E.M. Qasim, Water Works Engineering: Planning, Design and Operation,
Prentice Hall of India, 2000.
[32] J.A. Wilkie, J.G. Hering, Adsorption of arsenic onto hydrous ferric oxide: effects
of adsorbate/adsorbent ratios and co-occurring solutes, Colloids Surf. A:
Physicochem. Eng. Asp. 107 (1996) 97–110.
[33] A. Voegelin, R. Kaegi, J. Frommer, D. Vantelon, S.J. Hug, Effect of phosphate,
silicate, and Ca on Fe(III)-precipitates formed in aerated Fe(II)- and
As(III)-containing water studied by X-ray absorption spectroscopy, Geochim.
Cosmochim. Acta 74 (1) (2010) 164–186.
[34] D. Lakshmanan, D.A. Clifford, G. Samanta, Comparative study of arsenic
removal by iron using electrocoagulation and chemical coagulation, Water
Res. 44 (2010) 5641–5652.
[35] _
Ş. Irdemez, N. Demirciog lu, Y.Ş. Yildiz, The effects of pH on phosphate removal
from wastewater by electrocoagulation with iron plate electrodes, J. Hazard.
Mater. 137 (2) (2006) 1231–1235.
[36] E. Lacasa, P. Cañizares, C. Sáez, F.J. Fernández, M.A. Rodrigo, Electrochemical
phosphates removal using iron and aluminium electrodes, Chem. Eng. J. 172
(2011) 137–143.
[37] E.L. Sharp, P. Jarvis, S.A. Parsons, B. Jefferson, Impact of fractional character on
the coagulation of NOM, Colloids Surf. A: Physicochem. Eng. Asp. 286 (2006)
104–111.
[38] V. Pallier, G. Feuillade-Cathalifaud, B. Serpaud, Influence of organic matter on
arsenic removal by continuous flow electrocoagulation treatment of weakly
mineralized waters, Chemosphere 83 (2011) 21–28.
[39] F. Ulu, S. Barışçı, M. Kobya, H. Särkkä, M. Sillanpää, Removal of humic
substances by electrocoagulation (EC) process and characterization of floc size
growth mechanism under optimum conditionsval of humic substances by
electrocoagulation (EC) process and characterization of floc size growth
mechanism under optimum conditions, Sep. Purif. Technol. 133 (2014)
246–253.
[40] H.A. Moreno C, D.L. Cocke, J.A.G. Gomes, P. Morkovsky, J.R. Parga, E. Peterson, C.
Garcia, Electrochemical reactions for electrocoagulation using iron electrodes,
Ind. Eng. Chem. Res. 48 (4) (2009) 2275–2282.