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Journal of Dispersion Science and Technology

ISSN: 0193-2691 (Print) 1532-2351 (Online) Journal homepage: https://www.tandfonline.com/loi/ldis20

Arsenic removal from tap water by


electrocoagulation: investigation of process
parameters, kinetic analysis, and operating cost

Daisy Das & Barun Kumar Nandi

To cite this article: Daisy Das & Barun Kumar Nandi (2019): Arsenic removal from tap water
by electrocoagulation: investigation of process parameters, kinetic analysis, and operating cost,
Journal of Dispersion Science and Technology, DOI: 10.1080/01932691.2019.1681280

To link to this article: https://doi.org/10.1080/01932691.2019.1681280

Published online: 25 Oct 2019.

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JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY
https://doi.org/10.1080/01932691.2019.1681280

Arsenic removal from tap water by electrocoagulation: investigation


of process parameters, kinetic analysis, and operating cost
Daisy Das and Barun Kumar Nandi
Department of Fuel and Mineral Engineering, Indian Institute of Technology (Indian School of Mines), Dhanbad, Jharkhand, India

ABSTRACT ARTICLE HISTORY


Presence of arsenic ion [As(V)] in ground water at different locations of India is a big health con- Received 26 July 2019
cern in present days. In this work, effort was made to remove As(V) ions from tap water by elec- Accepted 6 October 2019
trocoagulation (EC) using iron (Fe) electrodes having an effective surface area of 38.67 m2/m3.
KEYWORDS
Investigation was focused on studying the effects of various process parameters of EC like solution
Arsenic removal;
pH, current density (CD), inter-electrode distance (IED) initial arsenic concentration (Co), electrical electrocoagulation; iron
conductivity of water on removal of As(V) in efficient ways. Experimental results reveal that initial electrode; drinking
pH of 7, CD of 0.431 mA/cm2, IED of 0.5 cm, agitation speed of 200 rpm and NaCl dose of 0.33 g/L water; SEEC
are optimal conditions to reduce As(V) ion concentration from 100 mg/L to below 10 mg/L. Overall,
99.4% As(V) removal was achieved at 30 minutes of EC treatment. Different quality parameters for
drinking water such as TDS, turbidity, salinity, electrical conductivity were also assessed during the
EC, to verify drinking water quality in several aspects. Kinetic analysis infers that As(V) removal by
EC follow the first order reaction model. Present study affirms that, EC is an effective technique
for efficient As(V) removal from drinking water with an estimated energy consumption of
8.33  103 Kwh/m3, electrode utilization of 0.0486 kg/m3, and operational cost of 0.0488 US$/m3.

1. Introduction contaminated ground water is used as tap water and causes


health hazard to its users.
Arsenic contamination in various water bodies has become a
Numerous methods have been reported till date for
major health hazard at several locations of India in recent
removal of As(V) for safe drinking water like adsorption,[5]
years. Arsenic has been categorized as toxic, mutagenic, and
coagulation,[6] membrane separation,[7,8] oxidation,[9] ion-
carcinogenic pollutant. As per WHO, permissible limits of
exchange,[10] electrocoagulation (EC),[2,4,11] etc. Among all
arsenic for drinking water is 10 mg/L.[1] As major portion of
these technologies, EC has been identified as a promising
population relies on groundwater for drinking water, several
water purification method for potable water and wastewater
health hazards like gastrointestinal tract infection, hyper pig-
mentation, and keratosis of hands and feet, cancer in differ- by many investigators. Compared to other processes, EC
ent organs of human[2,3] may be possible due consumption shows several enticing advantages like minimal expenses,
of excess arsenic containing ground water. Generally, arsenic easy to install, no requirement of chemicals, and lower treat-
occurs in natural water in the form of arsenate [As(V)] and ment time.[12–14] In recent years, several works have been
arsenite [As(III)] based on redox potential and pH of reported on As(V) removal from water by EC.[14–17] Kobya
water.[3] Literature suggests that As(V) is more carcinogenic et al.[15] studied the effect of different operating conditions
than As(III).[3,4] Its occurrence in groundwater is primarily of As(V) removal by EC considering 560 mL of water with
due to weathering of arsenic containing rock, discharge of initial As(V) content in the range of 75–500 mg/L using iron
arsenic containing industrial wastewater and utilization of (Fe) and aluminum (Al) electrodes with 1.3 cm distance
herbicides and pesticides consisting of arsenic.[4] In various between the electrodes (IED) and attained lower operating
parts of India, ground water is considered as safe drinking time (12.5 minutes) of Fe electrode as compared to Al elec-
water. In rural sector, ground water is collected using hand trode (15 minutes) in attaining permissible limit of arsenic
pumps or using motorized pumps. In many municipal areas, (10 mg/L). Balasubramanian et al.[16] studied the efficacy of
motorized pump collects the ground water and sent to over- EC treatment considering 250 mL of As(V) solution using
head tanks of municipalities, housing complexes without mild steel, Al, and stainless steel electrodes with 1.5 cm IED
any treatment to reach domestic tap water network. In this and reported CD of 1.5 A/dm2, pH 7 and EC time of
process, domestic tap water contains all the contaminants/ 50 minutes as optimum condition to achieve desirable
minerals present in ground water. As a results As(V) removal from 100 mg/L of initial As(V) concentration.

CONTACT Barun Kumar Nandi bknandi2004@gmail.com Department of Fuel and Mineral Engineering, Indian Institute of Technology (Indian School of
Mines), Dhanbad, Jharkhand, 826004, India.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/ldis.
ß 2019 Taylor & Francis Group, LLC
2 D. DAS AND B. K. NANDI

Kumar et al.[17] investigated the efficiency of different elec-


trode material (Al/Fe/Ti) with 1000 mL of As(V) solution in
each run and confirms 99% of As(V) removal using Fe elec-
trode. Gilhotra et al.[18] reported 99.6% of As(V) removal
from 325 ml of working volume with 10–100 mg/L of As(V)
concentration and 1.5 cm IED. Notwithstanding, most of the
investigations reported in the literature were conducted con-
sidering very lesser volume of water and only arsenic
removal efficiency as water quality parameter. However, for
large scale municipal or industrial applications, water vol-
ume is extremely high and other parameters like turbidity,
salinity, pH, total dissolved solids (TDS), etc. are also
important which also undergo changes during EC process
and needs to assess before considering treated water as safe
for drinking purpose.
The current work aims to provide a deeper understand-
ing of the EC for As(V) removal by evaluating the impact of
various operating conditions like current density (CD), ini- Figure 1. Schematic design of the experimental set-up.
tial As(V) concentration (Co), IED, initial solution pH and
þ
initial NaCl dose (Cs), and determining the ideal condition ðaqÞ þ 10H2 OðlÞ þ O2 ! 4FeðOHÞ3ðsÞ þ 8H ðaqÞ
4Fe2þ (5)
for highest removal efficiency. Other important parameters
that determine the quality of drinkable water like TDS, elec- 
ðaqÞ þ 2OHðaqÞ ! FeðOHÞ2, s
Fe2þ (6)
trical conductivity, salinity were also taken into consider-
ation in this study and analyzed with respect to a different The iron hydroxide flocs formed entraps the arsenic pre-
operating parameter like CD, IED, Cs, and Co. Furthermore, sent in the solution by subsequent precipitation/adsorption
specific electric energy consumption (SEEC, KWh/m3), elec- mechanism:[2]
trode mass loss and operating cost was estimated with
respect to different parameters to classify the economic FeðOHÞ3ðsÞ þ AsO3
4 ðaqÞ ! ½FeðOHÞ3 AsO4 ðsÞ
3
(7)
feasibility of the process. Kinetic study has been carried out
During EC process, the pollutant removal kinetics may
for deeper understanding of the importance of operating
be interpreted by first-order chemical reaction models
parameters. Based on the kinetic study, a model design cal-
as[12,13,21]
culation has been shown to identify the necessary CD
required for treating arsenic contaminated water. Such dCA
 ¼ rA (8)
investigation will be helpful in designing EC based water dt
purification unit for safe drinking water. where (rA ) refers to the removal rate As (V) concentration
in mg/L/min and the EC treatment time is denoted by t in
2. Arsenic removal mechanism by EC min. After simplification of Equation (8) at initial concen-
tration C(0) ¼ Co prior to EC treatment (rA ¼ kCA ), gives:
During EC, in situ formation of FeðOHÞ3 flocs takes place
Co
due to the electrolytic dissolution of iron electrode. ln ¼ kt (9)
Generated FeðOHÞ3ðsÞ flocs entraps arsenic ions present in C
solution by subsequent adsorption of arsenic ions to form where C0 and C are the concentration of As (V) before and
½FeðOHÞ3 : AsO3
4  which can be separated effortlessly from after EC treatment and k is the EC rate constant.
the solution by filtration or similar methods.[4,16,18,19]
Various anodic and cathodic reaction using Fe electrode for
As(V) removal is summarized as follows:[19,20] 3. Experimental
Anodic reaction: EC experiments were performed at room temperature
(25 ± 2  C) using a 5 L beaker (height: 25 cm; diameter:
FeðsÞ ! Fe2þðaqÞ þ 2e (1) 14 cm) filled with 3 L of As(V) contaminated water in a
Cathodic reactions: batch mode with a pair of iron (Fe) electrodes (length:
10 cm; width: 5.8 cm; thickness: 0.1 cm) with effective surface
8HþðaqÞ þ 8e ! 4H2 (2) area of 116 cm2 (38.67 m2/m3). Electrode gap was main-
tained at 0.5 cm. Schematic design of the experimental setup
2H2 OðlÞ þ 2e ! H2ðgÞ þ 2OH ðaqÞ (3) is shown in Figure 1. Electrodes were connected in monopo-
lar mode with a DC regulated power source (L6410S, Aplab,
Bulk reaction:
0–10 A and 0–64 V). Stock solution of 1000 mg/L arsenate
[As(V)] was prepared by dissolving required amount of
2Fe2þðaqÞ þ 4H2 OðlÞ þ O2 ! 2FeðOHÞ3ðsÞ þ H2ðgÞ (4)
sodium arsenate heptahydrate [Na2HAsO4.7H2O] 98% purity
JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY 3

Table 1. Range of different process conditions examined for As(V) removal by EC.
Range of parameter varied Parameters kept constant
Sl. No. Effect of parameter studied during experiment during experiment Discussed in
1. Effect of initial pH pH: 5, 6, 7, 8, 9 CD: 0.431 mA/cm2, IED: 0.5 cm, Cs: Section 4.1 and Figure 2
0.33 g/L, Co: 100 mg/L, EC time:
30 min, stirring speed: 200 rpm.
2. Effect of CD (mA/cm2) CD: 0.172, 0.431, 0.689, 0.862 pH: 7, IED: 0.5 cm, Cs: 0.33 g/L, Co: 100 Section 4.2 and Figure 3a
(mA/cm2) mg/L, EC time: 30 min, stirring
speed: 200 rpm.
3. Effect of Co (mg/L) C0: 25, 50, 75, 100, 200, 300, CD: 0.431 mA/cm2, IED: 0.5 cm, Cs: Section 4.3 and Figure 4a
400 (mg/L) 0.33 g/L, pH: 7, EC time: 30 min,
stirring speed: 200 rpm.
4. Effect of IED (cm) IED: 0.5, 1, 1.5, 2 cm CD: 0.431 mA/cm2, pH; 7, Cs: 0.33 g/L, Section 4.4 and Figure 5a
Co: 100 mg/L, EC time: 30 min,
stirring speed: 200 rpm.
5. Effect of NaCl (g/L) NaCl: 0.33, 0.50, 0.66, 0.83 CD: 0.431 mA/cm2, pH; 7, IED: 0.5 cm, Section 4.5 and Figure 6
(g/L) Co: 100 mg/L, EC time: 30 min,
stirring speed: 200 rpm.

100 (GFAAS) of Thermo scientific (model: iCE 3000 Series) with


90
pH-5 standard arsenic solutions for AAS of Reagecon (1 g/L As in
pH-6
nitric acid of 0.5 M) after proper calibration. The analysis
80 pH-7
Residual As(v) concentration,µg/L

pH-8 was done using the furnace method with an electro graphite
70 pH-9 cuvette at ash temperature of 400  C, atomize temperature
60 of 2100  C. The removal percentage of As(V) was calculated
as:
50
C0 Ct
40 AsðVÞ ion removalð%Þ ¼  100 (10)
C0
30
where C0 and Ct is the As(V) concentration in initial and
20
EC treated water, respectively. The energy consumption in
10 WHO permissible limit the process corresponding to various operating parameters
0 like CD, IED, and Cs were calculated as SEEC (KWh/Kg Fe)
0 5 10 15 20 25 30 using standard equations described in literature as
Time (min) follows.[13,21]
Figure 2. Effect of initial pH on As (V) removal. Water: 3 L, CD: 0.431 mA/cm2,
M:I:tEC
Co: 100 mg/L, IED: 0.5 cm, Cs: 0.33 g/L. DMtheoritical ¼ (11)
n:F
(Loba Chemical, India) dissolved in tap water. Electrical
DM exp erimental
conductivity of water was modified using necessary amount /¼  100 (12)
of NaCl, (Loba Chemical, India). Salinity, TDS, pH, and DMtheoritical
electrical conductivity of water were measured by multi par-
nFU
ameter kit of EUTECH India (Model: PC2700) using differ- SEEC ¼ (13)
ent electrodes. Turbidity was measured by turbidity meter of 3600  M  /
Thermo Scientific (Model: TN-100). Digital magnetic stirrer where DMexperimental and DMtheoritical are the experimental
of TARSON India (Model: SPINIT Digital MC-02) was used weight loss and theoretical weight loss according to
for providing necessary agitation (constant stirring speed Faraday’s law, respectively, n denoted the number of elec-
200 rpm) in water during EC. After each experiment the tron moles in dissolution reaction, U denotes current effi-
electrodes was abraded using sand paper and successively ciency, U denotes cell voltage (volt), tEC denotes total time
rinsed with diluted hydrochloric acid, distilled water, and of electrocoagulation (minute), F denotes Faraday constant
finally acetone to remove impurities and cathode and anode (F ¼ 96487 C/mol), I denotes the applied current across elec-
was altered after each run for effective electrode utilization. trodes (A) and M denotes the molecular weight of Fe
To observe the experimental electrode material loss after (g/mol).
each experiment, the cleaned anode was dried and weighted
for material loss and considered for SEEC estimation.
Various operating parameters used during EC experiments 4. Results and discussions
are outlined in Table 1. During EC, treated water samples 4.1. Effect of pH on As(V) removal
was collected at 5 minutes interval and was filtered with
Whatman 42 filter paper and analyzed. All the experiments To investigate the influence of pH on the removal of As(V),
were repeated thrice and average data are reported as error experiments were conducted taking a wide range of initial
in all the figures. As(V) ion concentration was assessed pH (5–9) and the obtained results are presented in Figure 2.
using Graphite Furnace Atomic Absorption Spectrometer It is noticed from the Figure 2 that, as pH increase from 5
4 D. DAS AND B. K. NANDI

Table 2. Final TDS, turbidity, electrical conductivity, and salinity of water after 30 minutes of EC with different pH after 30 minutes
of EC.
Initial pH Turbidity (NTU) TDS (mg/L) Electrical conductivity (mS/cm) Salinity (mg/L) Final pH
5.0 0.08 ± 0.03 107.15 ± 0.5 318.21 ± 0.5 129.8 ± 0.4 6.21 ± 0.1
6.0 0.05 ± 0.02 104.51 ± 1.5 314.10 ± 0.3 127.60 ± 0.3 7.13 ± 0.3
7.0 0.03 ± 0.04 94.12 ± 1.0 302.20 ± 0.2 121.15 ± 0.5 7.87 ± 0.2
8.0 0.10 ± 0.02 109.75 ± 0.4 323.10 ± 0.4 132.76 ± 0.2 8.96 ± 0.1
9.0 0.17 ± 0.04 122.14 ± 0.5 329.30 ± 0.5 135.65 ± 0.4 9.80 ± 0.3
Initial values before EC: turbidity – 1.91 ± 0.5 NTU, TDS – 232 ± 1.0 mg/L, electrical conductivity – 912 ± 1.5 mS/cm, salinity –
195 ± 1.0 mg/L.

to 8, As(V) removal decrease from 100 mg/L to below Fe3þ ions accumulates at the top of the EC reactor due to
0.9778 mg/L. At pH 9, final As(V) concentration is bubble buoy effect and sometimes this Fe3þ ions enters the
9.2024 mg/L after 30 minutes of EC time. At lower pH, that solution and retains as secondary pollutant.[22] Therefore
is, 5, 6, and 7, the permissible limit of arsenic concentration determining the optimal CD is important in EC to avoid
is attained after 20, 15, and 12 minutes, respectively. Hence such circumstances. From Figure 3b the drastic change in
lower pH was found for suitable for removal of As(V). final pH can be seen after 30 minutes of EC at different CD.
Similar results have been observed by other It can be seen that at higher pH the final value almost above
authors.[3,4,15,17,19] This can be explained by the fact that at pH 8.5 which is the maximum permissible limit for drinking
highly alkaline pH, the solubility of the ferrihydrite water according to WHO.[1] Variations in SEEC with CD
[FeðOHÞ3ðsÞ ] increases which results in lower the adsorption are shown in Table 3. Table 3 infers that with increase in
rate of ½AsO34 ðaqÞ  formed.
[2]
In other words, at alkaline pH CD, the final TDS, turbidity, Salinity, and electrical conduct-
generation of more number of OH  ions occurs, which ivity decreases as well as the SEEC also increases from
results in complete oxidation of Fe2þ ions and forms iron 0.7457 KWh/kg Fe to 2.6822 KWh/kg Fe. This was due to
hydroxide complexes which slowdowns the process of increase in flocs generation at higher CD which enhances
coagulation and adsorption. Other parameters that affect the the pollutant entrapment rate and thus leads to faster
aspect of water like electrical conductivity, TDS, salinity, tur- removal.[13] As(V) removal for various CD follows first
bidity, and final pH at different initial pH are demonstrated order kinetics and the rate constants for various CD are pre-
in Table 2. It is observed from the table that final pH sented in Figure 3c. The rate constant (k) increase from
increases slightly after 30 minutes of EC and other parame- 0.1441 to 0.2549 min1 due to the increase in amount of
ters (TDS, turbidity, electrical conductivity and salinity) is Al3þ ions in the solution at higher CD and found to follow
removed up to a desirable limit. Since, natural pH of water the following equation:
is 7 and experimental results suggests that arsenic removal is
k ¼ 0:1684:CD þ 0:1102 (14)
high at pH 7, pH 7 was used as desirable pH in further
experiments. Considering all the above factors and to avoid the uses of
higher energy consumption CD of 0.431 mA/cm2 was con-
sidered for further experiments. Comparing the present
4.2. Effect of current density on As(V) removal work with the literature available it was found that
To evaluate the influence of current density (CD) on As(V) Balasubramanian et al.[3] used CD of 1 Ad/m2 for 250 ml
removal efficiency, experiments were performed for different with IED of 1.5 cm of As(V) contaminated water, Kumar
CD from 0.172 to 0.862 mA/cm2 (current of 0.02–0.1 A) and et al.[14] used 1.53 mA/cm2 with IED of 0.5 cm for 1 L of
the results are shown in Figure 3a. From the results, it is water. Wan et al.[4] used 0.386 mA/cm2 with IED of 2 cm
observed that with increase in CD, residual As(V) concen- for 1 L of water which is compared to the IED (0.5 cm) used
tration decreases. Concentration of As(V) decreases from in the current study and 3 L of contaminated feed consid-
100 mg/L to 5.9 mg/L (WHO limit: 10 mg/L) after 20 minutes ered. The CD used in the current study is also less in com-
for 0.172 mA/cm2 and almost 98.7% removal was achieved parison to other findings in the literature mentioned.[17,18]
after 30 minutes of treatment. As(V) concentration decreases Also, treatment time is very less in the present study with
to 7.5 mg/L after 15 minutes and 99.4% removal was achieved more removal efficiency compared to all the studies men-
at 30 minutes for 0.431 mA/cm2 of CD. Further, 99.90% and tioned above.
99.95% removal was achieved for higher CD of 0.689 and
0.862 mA/cm2, respectively. This phenomenon can be related 4.3. Effect of initial As(V) concentration
by the fact that the rate of anodic dissolution increases
when CD increases and as a consequences flocs of larger To evaluate the influence of initial As(V) concentration, a
size is generated. This larger flocs having larger surface area wide range of initial arsenic concentration varying from
increases the adsorption/coagulation rate and thus ensure 25 mg/L to 400 mg/L was considered and the obtained results
faster removal of As(V) ions.[13,21] It is also noticed from are presented in Figure 4a. It is observed from Figure 4a
the figure that increasing the CD after a certain limit does that with increase in initial As(V) concentration (Co), the
not affect the removal rate as most of the contaminant get residual As(V) concentration increases or removal efficiency
trapped in generated flocs after a certain electrolysis time. decreases. For the lower Co range, that is, 25–100 mg/L, the
But dissolution of the anode still undergoes and the excess permissible limit (10 mg/L) of arsenic was attained at a very
JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY 5

100 95.80, 95.64, and 96.80%, respectively. This can be explained


90 (a) CD- 0.172 mA/cm
2
by the fact that at constant CD, same amount of ferrihydrite
CD- 0.431 mA/cm
2
complex flocs are formed for all the initial concentration of
80 2
As(V) arsenic. For higher As(V) concentrations, available
Residual As(v) concentration,µg/L

CD- 0.689 mA/cm


2
70 CD- 0.862 mA/cm flocs are insufficient to capture all the As(V) ions present in
the water. As a result As(V) removal efficiency decreases
60
with increase in initial As(V) concentration. To increase the
50 removal efficiency in such case, increase in CD and effective
area of electrode may be helpful. Some other parameters
40
that influence the drinking water viz. turbidity, electrical
30 conductivity, TDS, salinity, and final pH are presented in
20 Table 4. From Table 4 it is observed that with increase in
WHO permissible limit
initial arsenic concentration, the final pH remains in the
10
range of 7.82 ± 0.1 to 7.89 ± 0.4, the final TDS remains in
0 the range of 90.10 ± 0.5 to 103.13 ± 0.5 mg/L after 30 minutes
0 5 10 15 20 25 30 of EC. Turbidity was removed to about 98% for all the cases.
Time (min) As(V) removal kinetics for different Co was found to follow
first order kinetics model (Equation (8)). The rate constant
8.6
WHO permissible limit (k1) for various Co are shown in Figure 4b. The value of
8.4 rate constant decrease from 0.2164 to 0.1224 min1 with
(b) increasing the Co from 25 to 400 mg/L. This is be due to
8.2 decrease in removal rate as a consequences of inadequate
enmeshment of pollutant ions at constant CD.[13] For fur-
8.0
ther experiments, 100 mg/L was considered as initial As(V)
Final pH

7.8
concentration.

7.6
2
4.4. Effect of the distance between an electrode on
CD- 0.172 mA/cm As(V) removal
7.4 2
CD- 0.431 mA/cm
7.2 CD- 0.689 mA/cm
2
To investigate the impact of IED on As(V) removal, experi-
CD- 0.862 mA/cm
2
ments were conducted with varied IED in the range of 0.5
7.0 to 2.0 cm and the results are presented in Figure 5a. Figure
0 5 10 15 20 25 30
5a infers that with the increasing the IED from 0.5 to
Time (min)
2.0 cm, the residual As(V) increases from 0.62 to 2.91 mg/L.
0.28 Corresponding removal efficiency decreased from 99.40 to
(c) 97.06%. Increase in residual As(V) on concentration with
0.26
increase in IED was due to decrease in Fe(OH)3 flocs in the
0.24 water.[3] With increase in IED from 0.5 to 2 cm at constant
2 CD, electrical resistance between electrodes increases. As a
.1 10
+0 result, movement of free electrons or interaction between
0.22
CD the electrodes becomes difficult which results in decreases
4.
-1

68
0.20
k, min

0.1 flocs generation rate. So in overall, EC process slows down


0.18 k= and rate of arsenic ion capture by flocs decreases. To main-
tain necessary flocs generation, necessary voltage required to
0.16
be increased from 1 to 2.3 V which increases the specific
0.14 energy consumption of the process. Corresponding varia-
tions on turbidity, electrical conductivity, salinity, TDS, final
0.12
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 pH, and energy consumption (SEEC) are shown in Table 5.
CD (mA/cm )
2 It is seen that variations of IED also affects the final concen-
tration of these parameters. SEEC was seen to increase dras-
Figure 3. (a) Effect of CD on As (V) removal. (b) Variation of pH for treated
water with EC time. (c) Variation in rate constant for different CD. Water: 3 L, tically from 1.4881 KWh/kg (Fe) to 3.4226 KWh/kg (Fe) with
pH: 7, Co: 100 mg/L, IED: 0.5 cm, Cs: 0.33 g/L. increase in the IED from 0.5 to 2.0 cm. As(V) removal kin-
etics at various IED was studied and rate constant are
less time of 10 minutes (arsenic concentration 0.04– shown in Figure 5b. The rate constant (k) is found to be
0.6169 mg/L). For higher concentration of above 200 mg/L, it decrease from 0.1726 to 0.1171 min1 as IED increase from
take more than 25 minutes to attain As(V) concentration 0.5 to 2.0 cm due to weakened interaction between the pol-
below 10 mg/L. Corresponding, removal efficiency for 25, 50, lutant ion and hydroxide flocs.[13] For further experiments
75, 100, 200, 300, and 400 mg/L are 99.51, 99.35, 99.33, 99.4, lower IED of 0.5 cm was used to make the EC process
6 D. DAS AND B. K. NANDI

Table 3. Final TDS, turbidity, electrical conductivity, and salinity of water after 30 minutes of EC with different CD after 30 minutes of EC.
CD (mA/cm2 Turbidity (NTU) TDS (mg/L) Electrical conductivity (mS/cm) Salinity (mg/L) SEEC (kWh/ kg(Fe)
0.172 0.07 ± 0.02 104.14 ± 0.5 232.10 ± 1.0 134.21 ± 0.4 0.7457
0.431 0.03 ± 0.04 94.12 ± 1.0 302.20 ± 0.2 121.15 ± 0.5 1.4894
0.689 0.02 ± 0.01 81.24 ± 0.4 292.12 ± 0.5 118.21 ± 1.1 2.0857
0.862 0.01 ± 0.02 78.37 ± 1.0 283.87 ± 0.4 109.34 ± 0.5 2.6822
Initial values before EC: turbidity – 1.91 ± 0.5 NTU, TDS – 232 ± 1.0 mg/L, electrical conductivity – 912 ± 1.5 mS/cm, salinity – 195 ± 1.0 mg/L.

efficiency.[12,13] Addition of NaCl in water significantly


400
Co- 25 µg/L
increases the electrical conductivity and salinity of solutions
(a)
350 Co- 50 µg/L
along with slight increase in TDS and turbidity. The vari-
ation in electrical conductivity, TDS, salinity, pH, and As(V)
Residual As(v) concentration, µg/L

Co- 75 µg/L
300 concentration after addition of lowest concentration of
Co- 100 µg/L
NaCl, that is, 0.33 g/L and after 30 min EC are listed in
Co- 200 µg/L
250 Table 6. Corresponding SEEC, TDS, turbidity, salinity, con-
Co- 300 µg/L ductivity, and final pH for NaCl concentration of 0.50, 0.66,
200 Co- 400 µg/L and 0.83 g/L are summarized in Table 7. Removal kinetics of
arsenic at different initial salt concentration was found to
150
follow first order kinetics and the results of the rate constant
100 are shown in Figure 6b. The SEEC estimated as per
WHO permissible limit
Equation (13) for salt dose of 0.33, 0.50, 0.66, and 0.83 g/L
50 are 1.4881, 1.0417, 0.744, and 0.5952 KWh/kg (Fe). From the
experimental results it is observed that, addition of NaCl
0 with higher concentration increases the removal efficiency of
0 5 10 15 20 25 30
the process. Since addition of higher quantities of NaCl are
Time (min)
not desirable as final purified water obtained after the treat-
0.24 ment may leave an undesired salty taste with Naþ ions
(b) which may deteriorate the drinking water quality. So, NaCl
0.22 of lower concentration, that is, 0.33 g/L may be considered
as desirable NaCl dose for all the EC experiments.
0.20
-1

0.18
4.6. Estimation of operating cost, electric energy
k, min

consumption, and electrode consumption at various


0.16
current density and NaCl dose
0.14
The operating cost of the EC process for removal of As(V)
after 30 minutes is calculated as:
0.12

Operating cost ðUS$=m3 Þ ¼ a:Cenergy þ b:Celectrode 
0.10
0 50 100 150 200 250 300 350 400 450 (15)
Initial As(V) concentration,µg/L
where a (0.083 US$/kWh) and b (0.65 US$/kg Fe) are the
Figure 4. (a) Effect of initial As(V) concentration on removal efficiency. (b) cost of electricity per unit and iron per kg, respectively, con-
Variation in rate constant for different initial As(V) concentration. Water: 3 L, CD:
0.431 mA/cm2, pH: 7, IED: 0.5 cm, Cs: 0.33 g/L. sidered as per Indian market price in 2018.[23]
Cell voltageðVÞ  currentðAÞ  timeðsÞ
economical and reduce energy consumption with a better Cenergy ¼ (16)
sample volumeðm3 Þ
As(V) removal efficiency.
i  t  mw
Celectrode ¼ (17)
4.5. Effect of initial NaCl dose on As(V) removal zFV
To understand the effect of solution electrical conductivity where i denotes current applies in amp, t electrolysis time
on As(V) removal, EC experiments were conducted consid- (s), mw molecular mass of Fe (55.845 g/mol), z is the chem-
ering the initial salt concentration of 0.33 g/L to 0.83 g/L ical equivalence (z ¼ 2), F is the Faraday’s constant
(electrical conductivity of 295.1 ms to 307.8 mS/cm). Figure (96487 C/mol), and v is the volume of the sample to be
6a shows the impact of initial NaCl dose on As(V) removal. treated in m3. Electric energy consumption per unit volume
It is observed from the figure that with an increase in initial (KWh/m3) for various process parameter was estimated by
salt dose from 0.33 to 0.83 g/L, As(V) removal slightly the following Equation (18):
increases from 99.4% to 99.7%. Such increase in As(V) ^  I  tr
U
removal was due to better transport of As(V) ions to the Energy consumption ðEECÞ ¼ (18)

flocs generated during EC to modify the pollutant removal
JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY 7

Table 4. Final TDS, turbidity, electrical conductivity, and salinity of water after 30 minutes of EC with different initial As(V) concentration
after 30 minutes EC.
Co (mg/L) Turbidity (NTU) TDS (mg/L) Electrical conductivity (mS/cm) Salinity (mg/L) Final pH
25 0.016 ± 0.03 90.10 ± 0.5 301.10 ± 0.5 121.20 ± 0.4 7.82 ± 0.1
50 0.02 ± 0.02 91.23 ± 1.0 304.30 ± 1.0 122.72 ± 0.2 7.85 ± 0.3
75 0.025 ± 0.01 93.12 ± 0.5 300.10 ± 1.5 121.90 ± 0.5 7.81 ± 0.2
100 0.03 ± 0.04 94.12 ± 1.0 302.20 ± 0.2 121.15 ± 0.5 7.87 ± 0.2
200 0.10 ± 0.03 97.70 ± 0.5 301.56 ± 0.5 120.98 ± 0.4 7.89 ± 0.4
300 0.17 ± 0.02 101.21 ± 1.0 302.30 ± 1.0 121.78 ± 0.3 7.87 ± 0.2
400 0.22 ± 0.01 103.13 ± 0.5 301.67 ± 0.5 120.99 ± 1.0 7.83 ± 0.1
Initial values before EC: turbidity – 1.95 ± 0.5; NTU, TDS – 242 ± 1.5 mg/L, electrical conductivity – 912 ± 1.5 mS/cm, salinity –
195 ± 1.0 mg/L

100 100
IED-0.5cm (a) Cs- 0.33 g/L
90 (a) 90
IED-1.0cm Cs- 0.50 g/L
IED-1.5cm

Residual As(v) concentration, µg/L


80
Residual As(v) concentration, µg/L

80 Cs- 0.66 g/L


IED-2.0cm
70 70 Cs- 0.83 g/L

60 60

50 50

40 40

30 30

20 20
WHO permissible limit WHO permissible limit
10 10

0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Time(min) Time(min)

0.18 0.28
(b) Co- 100 µg/L (b)
0.17
Co-200 µg/L 0.26

0.16 Co-300 µg/L


Co-400 µg/L 0.24
0.15
-1
k, min

0.22
-1

0.14
k, min

0.13 0.20

0.12 0.18

0.11
0.16
0.3 0.4 0.5 0.6 0.7 0.8 0.9
0.10
0.0 0.5 1.0 1.5 2.0 2.5 Initial NaCl concentration, g/L
IED (cm) Figure 6. (a) Effect of initial salt dose on As(V) removal. (b) Variation of first
order rate constant at different salt dose. Water: 3 L, CD: 0.431 mA/cm2, pH: 7,
Figure 5. Effect of inter IED on AS(V) removal efficiency. (b) Variation in rate con- Co: 100 mg/L, IED: 0.5 cm.
stant at different IED. Water: 3 L, CD: 0.431 mA/cm2, pH: 7, Co: 100 mg/L, Cs: 0.33 g/L.

where, U^ denotes the cell voltage (volt), I denotes the current Figure 7a shows the variation in operating cost, electric
applied (A), tr is the overall time of the EC process in an hour energy consumption and electrode consumption after
(tr ¼ 0.5 h), and  is the volume of the sample in m3 30 minutes of EC for 3 L of the sample treated at various
( ¼ 0.003 m3). The total amount of iron electrode dissolved current densities. It is observed from the figure that with
due to anodic dissolution in g/L (M) after 30 minutes of EC increase in current density from 0.172 to 0.862 mA/cm2, the
treatment was estimated from Faraday’s law as follows: EEC and operating cost increased from 0.00166 to
Applied Current ðampÞ  EC timeðsÞ  molecular mass of anode g  0.02999 kWh/m3 and 0.0196 to 0.3886 US$/m3, respectively.
M ¼  mol
These values are lower compare to the reported values in lit-
Chemical equivalenceðZÞ  Faradays constant 96485 mol
C

eratures[4,15,18,22] on removal of arsenic (V) from water


(19)
using EC. Consumption of electrode increased from
8 D. DAS AND B. K. NANDI

Table 5. Final TDS, turbidity, electrical conductivity, and salinity of water after 30 minutes of EC with different IED and NaCl concentration after 30 minutes
of EC.
IED (cm) Turbidity (NTU) TDS (mg/L) Electrical conductivity (mS/cm) Salinity (mg/L) Final pH SEEC (kWh/ kg(Fe)
0.5 0.03 ± 0.01 93.12 ± 0.5 300.20 ± 0.5 120.15 ± 0.5 7.87 ± 0.1 1.4881
1.0 0.03 ± 0.04 94.12 ± 1.0 302.20 ± 0.2 121.15 ± 0.5 7.87 ± 0.2 2.6786
1.5 0.12 ± 0.02 96.21 ± 0.4 310.30 ± 0.5 129.21 ± 1.0 7.71 ± 0.3 3.125
2.0 0.15 ± 0.01 99.35 ± 0.5 313.50 ± 1.0 133.23 ± 0.4 7.65 ± 0.1 3.4226
Initial values before EC: turbidity – 1.95 ± 0.5 NTU, TDS – 242 ± 1.5 mg/L, electrical conductivity – 912 ± 1.5 mS/cm, salinity – 195 ± 1.0 mg/L.

Table 6. Variation in TDS, turbidity, electrical conductivity, salinity, pH, and As (V) concentration of tap water, after addition of NaCl
and after 30 minutes of EC.
Parameter Tap water/ground water After NaCl addition(0.33 g/L) After 30 min EC
Electrical conductivity (mS/cm) 225 912 ± 1.5 302.20 ± 0.2
Salinity (mg/L) 181 195 ± 1.0 121.15 ± 0.5
TDS(mg/L) 201 242 ± 1.5 94.12 ± 1.0
Turbidity (NTU) 1.50 1.95 ± 0.5 0.03 ± 0.04
pH 7.02 7.0 7.87 ± 0.2
Arsenic concentration (mg/L) Not detectible 100 0.62
Co – 100 mg/L, IED – 0.5 cm, CD – 0.431 mA/cm2, pH – 7, and Cs –0.33 g/L.

Table 7. Initial and final value of TDS, turbidity, electrical conductivity, salinity, and pH before and after 30 minutes of EC.
Before EC After 30 min EC
Water quality parameter Cs: 0.50 g/L Cs: 0.50 g/L Cs: 0.83 g/L Cs: 0.50 g/L Cs: 0.50 g/L Cs: 0.83 g/L
Electrical conductivity (mS/cm) 962 ± 1.0 1020 ± 1.5 1102 ± 1.0 308.20 ± 0.3 319.21 ± 0.5 330.22 ± 0.2
Salinity (mg/L) 225 ± 1.5 255 ± 1.5 280 ± 1.5 129.2 ± 0.4 136.4 ± 0.3 141.2 ± 0.2
TDS(mg/L) 255 ± 1.5 265 ± 1.5 285 ± 1.5 92.10 ± 0.5 90.21 ± 0.4 88.32 ± 0.3
Turbidity (NTU) 1.97 ± 0.2 1.99 ± 0.3 2.01 ± 0.1 0.02 ± 0.01 0.01 ± 0.02 0.01 ± 0.03
pH 7.00 ± 0.05 7.00 ± 0.05 7.00 ± 0.05 8.23 ± 0.1 8.63 ± 0.3 8.79 ± 0.2
Co – 100 mg/L, IED – 0.5 cm, CD – 0.431 mA/cm2, and pH – 7

0.40 0.40
(a)
0.6 0.0299 kg/m3 to 0.594 kg/m3 with increase in the CD from
0.35
0.172 mA/m2 to 0.862 mA/cm2. This may be illustrated by
Electrode consumption, kg/m
3

0.35 0.30
0.5
0.25
the fact that with increasing the current density the dissol-
0.30 ution of anode becomes faster which results in higher con-
3

0.20
Operating cost , US$/m

0.4
0.15
sumption as well as may deteriorate the water quality as
3
EEC, kWh/m

0.25
excess Fe3þ ions accumulates at the top of the EC reactor
0.10

0.05 0.3
0.20
0.172 0.432 0.689 0.862 due to bubble buoy effect and sometimes this Fe3þ ions
enters the solution and retains as secondary pollutant[22] in
2
Current density, mA/cm
0.15 0.2
3
Operating cost (US$/m )
0.10
water as described in Section 4.2. From Figure 7b it is
EEC (kWh/m )
3 0.1
observed that with the expansion of NaCl concentration
0.05
0.0 from 0.33 to 0.83 g/L, electric energy consumption decreases
0.00 from 0.00833 kWh/m3 to 0.00332 kWh/m3. Similarly, the
0.172 0.432 0.689 0.862
2
operating cost also decreases slightly from 0.0488 US$/m3 to
Current density, mA/cm
0.0483 US$/m3.

0.0488 (b) 0.008


EEC,kWh/m
3
4.7. Design of electrocoagulation reactor based on the
3
Electric energy consumption, kWh/m

0.0487 Operating cost (US$/m )


3 0.007 results achieved from present investigation
3

0.006
Operating cost, US$/m

Based on the experimental data presented in previous sec-


0.0486 0.005 tions, it can be observed that CD is the most important
0.004 parameter and can be altered as per requirement com-
0.0485
0.003
pared to parameter like IED as it will affect the construc-
0.0484
tion of the EC reactor. Considering the kinetic results
0.002
presented in Section 4.2, calculation has been conducted
0.0483
0.001 to identify the desirable CD required for treatment of dif-
0.000 ferent concentrations of As(V) contaminated water. Figure
0.33 0.50 0.66 0.83 8a shows the schematic diagram of the continuous EC
NaCl concentration. g/L
reactor design based on the results obtained from the pre-
Figure 7. (a) Operating cost, electric energy consumption, and electrode con- sent work using batch reactor. Based on the equation
sumption at various current density. (b) Operating cost and electric energy con-
sumption various NaCl concentration. Water: 3 L, initial As(V) concentration: shown in Figure 3c for first order rate constant varied
100 mg/L, EC time: 30 min, IED – 0.5 cm. with CD and at constant IED of 0.5 cm, 30 minutes EC
JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY 9

parameters like CD, initial salt dose, initial pH of solution,


initial As(V) concentration, and IED on removal efficiency
of As(V) from tap water. Experimental results confirmed
that, EC process can be used to remove of 100 mg/L of
As(V) ions contaminated water to below 10 mg/L using CD
of 0.431 mA/cm2, IED of 0.5 cm, agitation of 200 rpm, and
initial salt (NaCl) concentration of 0.33 g/L. Overall, 99.4%
As(V) removal was achieved within 30 minutes of EC treat-
ment. During experiments it was observed that lower pH
(less than 7) favors higher As(V) removal. With increase in
CD from 0.172 to 0.862 mA/cm2, As(V) removal increased
from 98.72% to 99.95%, due to higher anodic dissolution
followed by formation of larger size flocs. However, with
increase in CD, SEEC was found to increase from
0.7457 KWh/kg Fe to 2.6822 KWh/kg Fe due to higher
energy consumption. Various quality parameters for drink-
ing water such as TDS, turbidity, salinity, electrical conduct-
60 ivity were also found to be within the WHO permissible
2
CD- 0.1 mA/cm (b) limits. Kinetic analysis infers that As (V) removal rate (k)
increases from 0.1441 to 0.2549 min1 with increase in CD
2
50 CD- 0.2 mA/cm
Cf, residual As(V) concentration (µg/L)

2
CD- 0.3 mA/cm from 1.5 to 12.93 mA/cm2. Based on the experimental results
2
CD- 0.5 mA/cm it may be concluded that EC process are more economical
40
and produce higher efficiency when higher volumes of water
are treated.
30

Acknowledgement
20
Any opinions, findings and conclusions expressed in this paper are
those of the authors and do not necessarily reflect the views of DBT
10 (New Delhi) - INNO INDIGO.

0
0 50 100 150 200 250 300 350 400 450 Funding
Ci, initial As(V) concentration (µg/L) The Investigation was sponsored by a grant from the Department of
Biotechnology (DBT), New Delhi, under DBT - INNO INDIGO
Figure 8. (a) Schematic design of continuous EC reactor based on the results of
present investigation. (b) Predicted residual As(V) concentration for different ini- joint call.
tial concentration of arsenic at different CD. IED: 0.5 cm, salt dose: 0.33 g/L, flow
rate: 100 mL/min, capacity of reactor: 3 L.

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