Water Research 187 (2020) 116433

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Water Research
journal homepage: www.elsevier.com/locate/watres

Review

Electrode passivation, faradaic efficiency, and performance

enhancement strategies in electrocoagulation—a review
Markus Ingelsson a, Nael Yasri a, Edward P.L. Roberts a,∗
a
Department of Chemical & Petroleum Engineering, University of Calgary, 2500 University Dr NW, Calgary, AB T2N 1N4, Canada

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

Article history: Treating water and wastewater is energy-intensive, and traditional methods that require large amounts of
Received 17 June 2020 chemicals are often still used. Electrocoagulation (EC), an electrochemical treatment technology, has been
Revised 30 August 2020
proposed as a more economically and environmentally sustainable alternative. In EC, sacrificial metal
Accepted 15 September 2020
electrodes are used to produce coagulant in-situ, which offers many benefits over conventional chem-
Available online 16 September 2020
ical coagulation. However, material precipitation on the electrodes during long term operation induces
Keywords: a passivating effect that decreases treatment performance and increases power requirements. Overcom-
Electrocoagulation ing this problem is considered to be the greatest challenge facing the development of EC. In this critical
Water treatment review, the studies that have examined the nature of electrode passivation, and its effect on treatment
Electrochemistry performance are considered. A fundamental approach is used to examine the association between passi-
Passivation vation and faradaic efficiency, a surrogate for EC performance. In addition, the strategies that have been
Faradaic efficiency
proposed to remove or avoid passivation are reviewed, including aggressive ion addition, AC current oper-
Polarity reversal
ation, polarity reversal, ultrasonication, and mechanical cleaning of the electrodes. It is concluded that the
success of implementing each method is dependent on critical operating parameters, and careful consid-
eration should be taken when designing an EC system based on the phenomena discussed in this article.
In conclusion, this review provides insight into passivation mechanisms, delivers guidelines for sustaining
high treatment performance, and offers an outlook for the future development of EC.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction
Electrocoagulation (EC) is a water and wastewater treatment
technology that produces metal coagulant in-situ by electro-
chemically dissolving sacrificial electrodes that are submerged
in contaminated water. This is achieved by applying a current
to the electrodes from an external power source (Vik et al.,
1984). The positively polarized anode, commonly made of steel
(Fe-EC) or aluminum (Al-EC), is electrochemically dissolved Eq.
(1) (Yasri and Gunaskearan, 2017). At the same time, H2 O is
electrolyzed at the negatively charged cathode to produce OH−
and H2(g) Eq. (2) (Mansoorian et al., 2014). Following anodic
dissolution, metal cations hydrolyze to form oxy(hydr)oxides and
H3 O+ ions (symbolized as H+ in this article) that cause the pH
to drop Eq. (3) (Lakshmanan et al., 2009). The acidic and alka-
line environments at the electrodes create distinctive layers that
have shown to be up to 0.5 mm thick using confocal imaging
(Fuladpanjeh-Hojaghan et al., 2019). Subsequently, H+ diffuses
to the electrolyte, where it is neutralized by OH− transported
∗
Corresponding author.
E-mail address: edward.roberts@ucalgary.ca (E.P.L. Roberts).
from the cathode (Yasri et al., 2020). The cationic character of
the metal-oxyhydr(oxides) neutralizes the negative surface charge
of colloidal contaminants, which causes them to destabilize and
form larger aggregates—together with the metal-oxy(hydroxides)—
that can be separated by filtration, flotation or sedimentation
(Garcia-Segura et al., 2017).
M(s ) → Mz+ (aq) + ze− (1)
2H2 O + 2e− → 2OH− (aq) + H2(g ) (2)
Mz+ (aq) + zH2 O → M(OH )z(s ) + zH+ (aq) (3)
where M represents the metal of which the electrode is made
of, and z is the charge transfer number. An illustration of the EC
process is shown in Fig. 1.
The amount of electrochemically produced coagulant in EC
can be predicted by Faraday’s Law of Electrolysis (Eq. (4)) and
is proportional to the amount of charge passed through the cell
(Yasri and Gunaskearan, 2017). The majority of EC experiments
reported in the literature are operated galvanostatically—i.e., at
constant current—to ensure effective addition of the coagulant.

https://doi.org/10.1016/j.watres.2020.116433
0043-1354/© 2020 Elsevier Ltd. All rights reserved.
M. Ingelsson, N. Yasri and E.P.L. Roberts
Nomenclature
EC electrocoagulation
CC chemical coagulation
Al-EC electrocoagulation with aluminum electrodes
Fe-EC electrocoagulation with iron electrodes
AC-EC alternating current electrocoagulation
DC-EC direct current electrocoagulation
PR-EC polarity reversal electrocoagulation
PRT polarity reversal time
Sono-EC ultrasonication electrocoagulation
The faradaic efficiency is often reported when evaluating EC per-
formance, which is the ratio of experimentally observed coagu-
lant mass over the theoretical mass predicted by Faraday’s Law
(Eq. (5)). The faradaic efficiency is determined by measuring the
amount of metal released over the duration of the experiment. This
is generally performed by dissolving all flocs in acid, followed by
analysis using inductively coupled plasma optical emission spec-
troscopy (ICP-OES) (Chow and Pham, 2019; Dubrawski et al., 2015).
A calculated faradaic efficiency of 100% is desirable since it is in-
dicative of effective current utilization.
ItM
Theoretical amount of coagulant metal dissolved =
zF
Observed Coagulant zF m
FE[%] = = × 100%
Theoretical Coagulant ItM
where F is Faraday’s constant (96,485 C mol−1 ), m is the exper-
imentally observed mass (g), I is the current intensity (A), t is
the electrolysis time (s), and M is the molar mass of the metal (g
mol−1 ).
EC is often compared to chemical coagulation (CC), where metal
ions are added to contaminated water as salts such as aluminum
sulfate or ferric chloride. However, it has been shown that EC is
more cost-effective than CC per unit water treated for many differ-
ent applications because of some significant advantages that EC ex-
hibits (Garcia-Segura et al., 2017; Price et al., 2018; Timmes et al.,
2010; Vik et al., 1984). For example, the cationic coagulant in
EC is produced in-situ without adding unnecessary counter-ions
that contribute to sludge production (Ölmez, 2009). Meanwhile,
counter-ions in CC remaining in the dissolved phase must be re-
moved in subsequent treatment steps depending on discharge lim-
its (Mamelkina et al., 2017). In addition, neutralizing chemicals
must be added in CC to mitigate the pH drop caused by the hydrol-
ysis of the metal salts (Eq. (3)). This is achieved by using a neutral-
Fig. 1. Schematic diagram of the electrocoagulation (EC) process.
Water Research 187 (2020) 116433
izing chemical such as lime, Ca2 (OH)2 (Garcia-Segura et al., 2017).
The cathodic reaction in EC produces H2(g) and OH− , providing an
in-situ pH neutralizing mechanism (Wang et al., 2009). Further-
more, the uniform metal dissolution of the electrodes (as opposed
to point-addition in CC) reduces the need for intense mechani-
cal mixing, which lowers energy demands while making the co-
agulation process more efficient. Uniform metal ion addition in EC
also permits lower coagulant dosing, which further curtails sludge
production. Additionally, the prospect of harnessing the H2(g) pro-
duced at the cathode makes EC a viable energy storage technology
(Phalakornkule et al., 2010). Lastly, using commonplace materials
such as iron and aluminum for local electrode manufacturing al-
lows remote communities to sustain treatment without relying on
resupplying chemicals, thus eliminating transportation costs that
are burdensome to areas such as Northern Canada (Ragush et al.,
2015; Tartakovsky et al., 2018).
However, problems with long-term EC operation persist. For ex-
ample, the precipitation of solids on the electrodes over time—and
its ensuing passivating effect—increases operating costs and low-
ers treatment efficiency (Bandaru et al., 2020; Garcia-Segura et al.,
2017; Müller et al., 2019). Furthermore, storing the electrodes
between treatment cycles and removing the initial passivating
surface layer during reactor startup has shown to be problem-
atic (van Genuchten et al., 2016). Additionally, non-uniform elec-
trode consumption can compromise the structural integrity of
(4) the electrodes, which requires them to be prematurely exchanged
(Bandaru et al., 2020; Wellner et al., 2018). It is widely recognized
that overcoming these challenges is imperative to the development
(5)
of EC (Bian et al., 2019; Kabdaşlı et al., 2012).
In this article, the existing body of scientific literature related
to the nature of electrode passivation in EC is reviewed. A funda-
mental approach is used to study the electrochemical and chemi-
cal mechanisms governing coagulant production and electrode pas-
sivation, while also examining different strategies that have been
proposed to mitigate the detrimental effects of passivation. Some
of these strategies include increasing the flowrate to enhance hy-
drodynamic scouring (Karamati-Niaragh et al., 2019; Timmes et al.,
2010), adding depassivating salts to the water (van Genuchten
et al., 2016), mechanically cleaning the electrodes (Sahu et al.,
2014), ultra-sonication (Maha Lakshmi and Sivashanmugam, 2013)
or changing the current waveform (Eyvaz et al., 2009; Karamati-
Niaragh et al., 2019; Pi et al., 2014; Sahu et al., 2014; Timmes et al.,
2010; van Genuchten et al., 2017, 2016; Yet, 2011). Each method is
evaluated, and suggestions for future research are provided.
To date, published reviews of EC have focused on general op-
eration or on the abatement of a specific pollutant (Chen, 2004;
Emamjomeh and Sivakumar, 2009; Garcia-Segura et al., 2017;
Kabdaşlı et al., 2012; Mollah et al., 2001, 2004a; Moussa et al.,
2017; Sahu et al., 2014; Yasri et al., 2020). While these reviews are
useful, pollutant removal is dependent on both coagulant dosing
in the EC reactor, and the subsequent separation process. Overall,
this involves many controllable variables, which makes it difficult
to distinguish between the sensitivity of different operating param-
eters. As concluded by Timmes et al., 2010, EC should be regarded
as a two-step process, i.e., coagulant dosing followed by floccula-
tion and separation. Therefore, the scope of this article is to fo-
cus on the coagulant dosing component, while disregarding floc-
separation.
2. Electrode surface layers, passivation, and EC performance
2.1. Principles of electrode surface layer formation and passivation
Passivation is a concept emanating from corrosion science,
which describes the formation of a protective film on a metal
surface, usually comprised of metal oxides. The passivation layer
2
M. Ingelsson, N. Yasri and E.P.L. Roberts
Fig. 2. The distribution of the cell potential in the EC reactor.
impedes the kinetics of otherwise thermodynamically favorable
metal oxidation, which increases the resistance at the electrode-
electrolyte interface (Schmuki, 2002). In the EC literature, this is
commonly referred to as a surface layer film (Müller et al., 2019;
van Genuchten et al., 2016). The terms “passive layer” and “sur-
face layer” are often used interchangeably. However, a surface layer
does not have to be passivating, i.e., it could also be conductive
(Bandaru et al., 2020; Schmuki, 2002). Furthermore, the surface
layer formation process has also been referred to as electrode foul-
ing (Schulz et al., 2009; Yasri et al., 2020).
To sustain effective electrochemical dissolution of the anode,
the applied cell potential (U) must overcome several resistances
within the cell (Eq. (6)). These energy barriers are expressed
as a series of overpotentials (η), which are encountered at the
electrode-electrolyte interfaces—namely, the activation, concentra-
tion, and passivation overpotentials (Chen et al., 2002). The acti-
vation overpotential is associated with the kinetic energy barrier
that the electron-exchange process exhibits, whereas the passiva-
tion overpotential pertains to the energy required for dissolved
metal to penetrate the passivating surface layer, which increases
the polarization resistance. Due to the availability of metal in the
anode, the concentration overpotential there is negligible.
d
U = E + ηan,a + ηan,c + ηan,p + |ηct,a |+|ηct,c | + |ηct,p | + i (6)
k porous layer due to its enhanced charge carrying properties. Sev-
where E is the thermodynamic equilibrium potential for the elec-
trochemical cell, and ηan,a , ηan,c , and ηan,p are the anodic acti-
vation, concentration, and passivation overpotentials, respectively.
Likewise, ηct,a , ηct,c , and ηct,p are the equivalent overpotentials at
the cathode. Furthermore, d is the distance between the electrodes,
k is the electrolyte conductivity, and i is the current density. Fig. 2
illustrates the distribution of the cell potential and breaks down
the components outlined in Eq. (6) within the EC reactor. The equi-
librium potential depicted at the anode is relative to the potential
of the cathode.
As an anodic surface layer is formed, metal dissolution is
impeded, which raises the passivation overpotential and in-
creases the energy consumption in EC Holt et al., 2005, 2002;
Mechelhoff et al., 2013a; van Genuchten et al., 2016; Xu et al.,
2015; Yang et al., 2015). Extreme passivation may lead to elec-
trochemical side reactions that decrease coagulant production dur-
ing galvanostatic operation or cause a complete termination of the
passage of current during potentiostatic (constant voltage) opera-
3
Water Research 187 (2020) 116433
tion (Huang et al., 2009). For example, anodic O2(g) or Cl2(g) evo-
lution (Eqs. (7) & (8)) have been proposed as unwanted side reac-
tions that occur when the total anodic overpotential is sufficiently
high during galvanostatic operation (Dubrawski et al., 2015).
2H2 O ↔ O2 + 4H+ + 4e− E o = 1.23 V vs SHE (7)
2Cl− ↔ Cl2 + 2e− E o = 1.36 V vs SHE (8)
The formation of the electrode surface layer is dependent on
specific EC operating conditions such as electrolyte conductiv-
ity/composition, electrode material, dissolved oxygen (DO), current
density, and polarization cycles (van Genuchten et al., 2017, 2016).
During EC operation, it is generally desirable to maintain a high
electrolyte conductivity and a low inter-electrode distance to re-
duce ohmic losses (potential drop) in the solution, which reduces
the cell potential (Eq. (6)) (Mollah et al., 2001). However, small
inter-electrode gaps and high electrolyte conductivities increase
the variations in the current density distribution over the electrode
geometry, which causes uneven wear of the anode and is problem-
atic to long-term operation (McBeath et al., 2020).
The electrode surface layer can be a mono-layer of absorbed
molecules, or consist of multiple layers (Schmuki, 2002). For ex-
ample, a porous surface layer will be less passivating than a non-
eral fouling mechanisms are possible and may include the pre-
cipitation of dissolved species, adsorption of colloidal/suspended
particles, or solid-phase transformations at the anode surface
(Pally et al., 2020). The formation of a metal oxide layer through
anodization to prevent further corrosion is an established phe-
nomenon for aluminum, zinc, magnesium, and several other met-
als (Roberge, 2008). For example, metal oxide coated anodes are
utilized for some electrochemical applications, e.g., anodic electro-
oxidation for wastewater disinfection (Wu et al., 2014).
At the anode interface, the low pH environment inhibits the
buildup of a surface layer, which works as a passivation prevention
mechanism. However, metal oxides can precipitate on the anode
over time if their solubility limits are exceeded (Chen et al., 2002).
Similarly, Ca2+ and Mg2+ in the electrolyte can precipitate as min-
erals and form a passivating surface layer in the high pH environ-
ment at the cathode (Doggaz et al., 2019; Sahu et al., 2014). Addi-
tionally, cations could be transported and sorbed to the negatively
polarized cathode by electrophoretic migration and electrostatic
M. Ingelsson, N. Yasri and E.P.L. Roberts Water Research 187 (2020) 116433

Fig. 3. Fouling processes at the anode and the cathode.

interactions (Sahu et al., 2014; Xu et al., 2017), otherwise referred

to as electro-condensation (Hu et al., 2003). Likewise, anions could
migrate towards—and bind to—the positively polarized anode. This
effect could explain why electrode surface layers have been ob-
served to be thicker at higher current densities (Dubrawski et al.,
2015; Mansouri et al., 2011; Müller et al., 2019), although the effect
of electrophoretic migration is diminished at high supporting elec-
trolyte concentrations (Mechelhoff, 2008). Alternatively, electro-
chemically produced metal cations could precipitate with oxyan-
ions and adsorb to the electrode surface. For example, a passivat-
ing AlPO4 surface layer has been observed on electrodes in phos-
phate electrolytes in Al-EC (Mansouri et al., 2011). Similarly, FeSO4
can form a passivating surface layer in the presence of SO4 2− in
Fe-EC (Gerónimo-López et al., 2014). The probability of exceed-
ing the solubility limits of metal salts at the anode interface is
greater while operating at higher current densities because of the
increased concentration of metal ions. The exact mechanisms for
how co-existing ions contribute to passivation in EC is not clear,
but an illustration of the possible mechanisms is provided in Fig. 3.
In batch experiments, it is often seen that the bulk solution Fig. 4. Tafel representation of potentiodynamic polarization data, a useful tool for
pH shifts towards higher values over time, especially at higher understanding the corrosion characteristics of metal in a specific electrolyte. Exper-
imental conditions: aluminum working electrode, platinum counter electrode, SCE
current densities due to OH− production outcompeting metal- reference electrode, pH 9, 0.1 M NaCl, 0.5 mV s−1 , T = 25 °C. Reprinted (adapted)
hydrolysis—i.e., H+ generation—which has more sluggish reaction with permission from Mansouri et al., 2011. Anodic dissolution of pure aluminum
kinetics (Garcia-Segura et al., 2017; Lakshmanan et al., 2009). during electrocoagulation process: Influence of supporting electrolyte, initial pH,
For example, the pH equilibrated around 8–9 in Al-EC after 60– and current density. Ind. Eng. Chem. Res. 50, 13,362–13,372. Copyright (2011) Amer-
ican Chemical Society.
80 min of galvanostatic operation, which was independent of the
initial pH (Mansouri et al., 2011). Additionally, when buffering
agents are present—i.e., salts of weak acids such as phosphates
(pKa1 = 2.1, pKa2 = 7.2, pKa1 = 12.4) and carbonates (pKa1 = 3.6, ther be beneficial or detrimental to avoiding passivation, depend-
pKa2 = 6.3, pKa3 = 10.3)—H+ protons produced through hydroly- ing on the solution composition.
sis at the anode are quenched. Consequently, the acidic pH bound-
ary layer is thinner in buffered solutions than in unbuffered sys- 2.2. Potentiodynamic polarization methods to study passivation
tems, which increases the likelihood of metal-oxyhydr(oxides) pre-
cipitating at the anode (Lumsden et al., 1981; Refaey, 2005). The nature of electrode passivation can be characterized by po-
However, it has been shown that adding salts containing NH4 + larization studies (Dura and Breslin, 2019; Schmuki, 2002). Poten-
(pKa = 9.3), which is amphoteric, enhances EC performance in tiodynamic polarization methods are often used in corrosion stud-
Al-EC by avoiding an excessive increase in bulk solution pH ies (Lee and Pyun, 20 0 0; Pyun et al., 1999). However, some studies
(Izquierdo et al., 2010; Trompette and Vergnes, 2009). It has also have adopted this methodology to investigate the characteristics of
been shown that the shift towards alkaline pH is less pronounced electrochemical dissolution in EC (Hu et al., 2003; Mansouri et al.,
in Al-EC than in Fe-EC due to the buffering effect of aluminum 2011; Panikulam et al., 2018). Data from these experiments are
monomeric species that form in the bulk solution ([Al(OH)]2+ , usually presented as Tafel plots (Fig. 4). The minimum in current
[Al(OH)2 ]+ , [Al2 (OH)2 ]4+ , [Al(OH)4 ]− ), and polymeric species such density determines the equilibrium potential (E), also referred to
as [Al6 (OH)15 ]3+ , [Al7 (OH)17 ]4+ , [Al8 (OH)20 ]4+ , [Al13 O4 (OH)24 ]7+ as the corrosion potential (Esmailzadeh et al., 2018). At this poten-
(Daneshvar et al., 2007; Fayad et al., 2017; Kobya et al., 2006). Ul- tial, the kinetic rates of reduction/oxidation are equal, and the net
timately, the presence of buffering agents in the electrolyte can ei- current approaches zero. The current density plateau in the anodic

4
M. Ingelsson, N. Yasri and E.P.L. Roberts Water Research 187 (2020) 116433

potential region—adjacent to the corrosion potential—is the passi-

vation range. Here, the presence of a passivating surface layer im-
pedes the dissolution of the electrode, even though electrochemi-
cal oxidation becomes more thermodynamically favorable with in-
creasing anodic potentials. However, the current dramatically in-
creases at a certain potential, indicating the start of the active dis-
solution range, also referred to as pitting corrosion (Zhang and
Ma, 2019). The width of this range corresponds to the passivation
overpotential, and an increase in the passivation range is indica-
tive of a higher polarization resistance at the electrode-electrolyte
interface.
Pitting is initiated by ions breaking down the electrode surface
layer, or by the dissolution of the surface film when the electrode
boundary layer becomes sufficiently acidic due to metal hydrolysis
(Lumsden et al., 1981). Aggressive ions such as Cl− enhance pitting
corrosion due to the ionic mobility that allows them to penetrate
the electrode surface oxide film. Consequently, Cl− reacts with the
metal oxides, which dissolves the surface layer and exposes the
underlying raw metal (Golder et al., 2007). It has also been pro-
posed that ClO− (formed at the anode following Cl− →Cl2 oxida- Fig. 5. Pourbaix diagram of iron in water at 25 °C; the dashed lines represent
the electrochemical stability range of water. Produced based on calculations by the
tion) destroys the passivating surface layer (Zhou et al., 2020). In MEDUSA-HYDRA software (Puigdomenech, 2019).
the presence of Cl− , the corrosion and pitting potentials shift to-
wards more negative potentials while decreasing the width of the
passivation range (Mansouri et al., 2011). 2.3. Passivation of different electrode materials
It is well established that the electrode corrosion character-
istics are dependent on the nature of the supporting electrolyte The mechanism and rate of electrode passivation and corro-
(Hu et al., 2003; Mansouri et al., 2011). By changing operating sion vary depending on the electrode materials that are used.
conditions such as the electrolyte composition, pH, or electrode EC is traditionally operated with either steel or aluminum elec-
material—the corrosion and pitting potentials shift. Higher corro- trodes. Other metals such as zinc (Liu et al., 2018; Vasudevan and
sion/pitting potentials are indicative of increased passivation, i.e., Lakshmi, 2012), magnesium (Kamaraj et al., 2013) and titanium
a greater voltage must be applied to initiate metal dissolution. (Ti) (El-Ghenymy et al., 2020) have also been shown to abate
Additionally, based on operating conditions, the current densities aqueous contaminants effectively using EC, but they are also sus-
within a potential window vary. For example, current densities ceptible to passivation (El-Ghenymy et al., 2020; Kamaraj et al.,
within the scanned potential window were higher in Fe-EC than 2013; Vasudevan and Lakshmi, 2012). Most research has focused
in Al-EC in a synthetic kaolin solution, indicating faster corrosion on studying the electrochemical behavior, speciation, and coag-
kinetics (Panikulam et al., 2018). Comparatively lower current den- ulation mechanisms for iron (usually steel) and aluminum elec-
sities in the active dissolution range are also indicative of greater trodes due to their abundant availability and low procurement
polarization resistance and electrode passivation. costs (Holt et al., 2002). The price of steel is more economi-
Hu et al., 2003 reported greater polarization resistance with cal than aluminum, but better removal performance with alu-
aluminum electrodes when scanning from low to high potentials minum electrodes for certain pollutants has made it an attractive
(−1.5 V to 3.0 V [vs. SCE]) in the presence of only F− , compared alternative.
to when Cl− , NO3 − , and SO4 − were present in the electrolyte. It
was hypothesized that enhanced electrophoretic migration and ad- 2.3.1. Passivation behavior of iron electrodes in EC
sorption of F− to the anode caused this effect. In contrast, no pas- Observed rates of metal dissolution indicate that Fe(II) ions
sive region was observed under similar experimental conditions, are initially dissolved from the Fe(0) anode (Eq. (9)), which is
but without F− in the electrolyte (Mansouri et al., 2011). thermodynamically favorable over Fe(0)→Fe(III) oxidation (Fig. 5).
Corrosion characteristics are also affected by the pH at the Fe(II) is subsequently oxidized to Fe(III) ions by dissolved
electrode-electrolyte interface. For example, by increasing the ini- oxygen in the bulk solution (Eq. (10)), which is favored at
tial pH from 2 to 11 in a NaCl electrolyte (0.1 M), it was ob- higher pH (Dubrawski and Mohseni, 2013; Holt et al., 2002;
served that the corrosion potential shifted towards more negative Lakshmanan et al., 2009; Sasson et al., 2009; van Genuchten et al.,
potentials when scanning from −1.5 V to 3.0 V (vs. SCE) in Al- 2017; Vepsäläinen, 2012). Additionally, given a sufficiently acidic
EC (Mansouri et al., 2011). In the same study, Mansouri et al. ob- environment, Fe(0) can be chemically dissolved from the anode
served that the pitting potential was independent of pH, which (Eq. (11)) (Golder et al., 2011).
corresponded to the increased width of the passivation range as
the pH was increased. A similar observation was also made by El- Fe(s ) ↔ Fe2+ (aq ) + 2e− E o = −0.44 V vs SHE (9)
Ghenymy et al., 2020 with titanium electrodes. Both studies at-
tributed the changes in the corrosion characteristics to a more fa- 4Fe2+ + O2 + 2H2 O → 4Fe3+ + 4OH− (10)
vorable dissolution of the electrode in alkaline pH. However, a shift
towards more negative corrosion potentials (when scanning from
Fe0 + 2H+ → Fe2+ + H2 (11)
cathodic to anodic currents) is also caused by the cathodic elec-
trolysis of H2 O being more thermodynamically favorable in lower Following the generation of these ions, they hydrolyze into
pH (Roberge, 2008). This effect explains why the corrosion poten- a wide variety of oxyhydr(oxides)—which can be comprised of
tials were relatively high at pH 2, even though aluminum dissolu- Fe(II), Fe(III), or a combination of both (Dubrawski et al., 2015;
tion was favorable under these conditions (see Section 2.3.2). The Lakshmanan et al., 2009). Some oxyhydr(oxides), such as magnetite
corrosion parameters reported from potentiodynamic polarization (Fe3 O4 ) and hematite (Fe2 O3 ), can form by the solid-phase oxida-
studies in EC are presented in Table 1. tion of Fe(0) in alkaline pH. Furthermore, Fe-oxyhydr(oxides) func-

5
M. Ingelsson, N. Yasri and E.P.L. Roberts Water Research 187 (2020) 116433

Table 1
Reported values for corrosion parameters from potentiodynamic polarization investigations for different electrode materials and electrolyte compositions in EC.

Electrode
Material Sample Type Corrosion Potential (V vs SCE) Pitting Potential (V vs SCE) Current Density (i) Author

Fe 5 mM K2 Cr2 O7 , 0–19 mM 5 mM K2 Cr2 O7, 5 mM K2 Cr2 O7 + Passivation (Xu et al.,

NaCl, K2 SO4 , pH 8 0–19 mM NaCl: incurred when Cl− 2015)
−
• 18 & 19 mM Cl : −0.41 V
−1.1V conc was lower
• 17 mM Cl− : −0.21 V
than 16 mM
• 0 & 16 mM Cl− : 0.84V

Al 0.47 M F− with: Highest i for F− & (Hu et al.,

Cl− . Lowest i for DI 2003)
• 5 mM Cl − • DI H2 O: −0.8 V • DI H2 O: No pitting
H2 O.
• 5 mM NO3 − • F− & Cl− : −1.3 V • F− & Cl− : −0.5 V
• 5 mM SO4 2− • F− & SO4 2− : −1.3 V • F− & SO4 2− : No pitting
• F− & NO3 − : −1.0V • F− & NO3 − : 1.8 V

Al Lower i for Na2 SO4

& NaH2 PO4 . High i (Mansouri et al.,
• 0.1 M NaCl • DI H2 O: −0.668 V • DI H2 O: No pitting
for NaCl and DI 2011)
• 0.1 M Na2 SO4 • NaCl: −1.213 V • NaCl: −0.646 V
H2 O.
• 0.1 M NaH2 PO4 • Na2 SO4 : −1.056 V • Na2 SO4 : ~0.4 V
• in DI Water (pH 9) • NaH2 PO4 : −0.519 • NaH2 PO: No pitting

Al 0.5 mM Na2 SO4 : Higher i in NaCl

−1.45 V soln. No i increase (Mechelhoff et al.,
• 0.5 mM Na2 SO4 , • 0.5 mM Na2 SO4 , 0.4 mM
in soln with only 2013a)
• 0.4 mM NaCl, NaCl: −0.52 V Na2 SO4 . Humic
• 5–10 g L−1 humic acid • 0.5 mM Na2 SO4 , 0.4 mM acid lowers i
• in pH 7 RO H2 O NaCl, 5 g L−1 humic acid:
• −0.52 V
• 0.5 mM Na2 SO4 , 0.4 mM
NaCl, 10 g L−1 humic acid:
• −0.52 V
• 0.5 mM Na2 SO4 : No pitting

Al – Mg Little/no passivation region, i.e., Little change in (Dura and

pitting initiated at corrosion corrosion current Breslin, 2019)
• 0.170 M NaCl • High NaCl: −0.664 V
potential between high/low
• 0.017 M NaCl • Low NaCl: −0.554 V
NaCl conc. KH2 PO4
• 0.017 M • NaCl + KH2 PO4 : −0.5V
decreased
NaCl + 8.12 × 10−4 corrosion current
KH2 PO4 by 35%

Ti Little change in (El-

corrosion current Ghenymy et al.,
• 0.5 M Na2 SO4 • Na2 SO4 : −0.325 V • Na2 SO4 : ~0.75 V
between high/low 2020)
• 0.5 M NaCl • NaCl: −0.398 V • NaCl: ~0.7 V
NaCl conc
• 0.5 M Na2 HPO4 • Na2 HPO4 : −0.040 V • Na2 HPO4 : —
• 0.5 M (NaCl + Na2 SO4 ) • NaCl + Na2 SO4 : 0.405 V • NaCl + Na2 SO4 : ~0.2 V
• 0.5 M • NaCl + Na2 SO4 + Na2 HPO4 : • NaCl + Na2 SO4 + Na2 HPO4 :
(NaCl + Na2 SO4 + Na2 HPO4 ) −0.386V ~0V

tion as the coagulant in the bulk solution, but also contribute to
the buildup of the electrode surface layer (van Genuchten et al.,
2017). Therefore, the nature of Fe(II/III) speciation is vital because
different oxyhydr(oxides) exhibit distinctive passivating character-
istics (Bandaru et al., 2020). The formation of different oxides is
best represented by Pourbaix diagrams (Fig. 5), which show the
stability range of metal oxides with respect to electrochemical and
pH conditions (Schmuki, 2002).
The speciation of Fe(II/III)-oxyhydr(oxides), depending on DO
and electrolyte chemistry, has been mapped and is shown in Fig. 6
(Dubrawski et al., 2015). It has been demonstrated that the pri-
mary Fe-oxyhydr(oxides) that form in EC are green rust, Fe3 O4 , and
lepidocrocite (γ -FeOOH) (Dubrawski et al., 2015; Dubrawski and
Mohseni, 2013). Of these products, Fe(III) species (γ -FeOOH) ex-
hibit the poorest conductivity, and their incorporation in the elec-
trode surface layer is conducive to a higher degree of passivation
(Bandaru et al., 2020; Gerónimo-López et al., 2014). Meanwhile,
Fe(II)-containing species (e.g., Fe3 O4 ) are more conductive and less
detrimental to passivation (Bandaru et al., 2020).
It has also been reported that the formation of the differ-
ent precipitates depends on the concentration of DO, pH, elec-
trolyte composition, and the [Fe(II)]:[Fe(III)] ratio within the re-
actor. The nature of these parameters varies based on the charge
loading rate (C L−1 min−1 ), which is a function of the current
density and reactor geometry. Because green rust and Fe3 O4 are
Fe(II/III) complexes, they form when the [Fe(II)]:[Fe(III)] ratio is
low, i.e., in acidic and low DO conditions when Fe(II)→Fe(III) ox-
idation is retarded (Dubrawski et al., 2015). Additionally, green
rust is an intermediate in Fe3 O4 and γ -FeOOH formation and
can be isolated in the presence of sulfates, phosphates, and car-
bonates (Dubrawski et al., 2015; Moreno et al., 2009). Further-
more, Fe(II/III)-oxyhydr(oxide) formation is favored when the rate
of Fe(II) generation is at least three times higher than the rate of
DO replenishment (van Genuchten et al., 2018). Therefore, if O2(g)
is produced in anodic side reactions, DO levels would increase and
prompt Fe(II)→Fe(III) oxidation, hence facilitating the formation of
Fe(III)-oxyhydr(oxides), i.e., γ -FeOOH (Fig. 6). By analyzing the an-
ode surface layer using X-ray powder diffraction (XRD), it was de-
termined that Fe3 O4 is its main constituent (Bandaru et al., 2020;
van Genuchten et al., 2016). Consequently, this makes the com-
position of the electrode surface layers in EC different than the
surface layers on naturally corroded steel, which usually contain

6
M. Ingelsson, N. Yasri and E.P.L. Roberts
Fig. 6. Diagram for the speciation of iron depending on operating conditions. Reprinted (adapted) with permission from Dubrawski et al., 2015. Production and transforma-
tion of mixed-valent nanoparticles generated by Fe(0) electrocoagulation. Environ. Sci. Technol. 49, 2171–2179. Copyright (2015) American Chemical Society.
Fig. 7. The effect of varying electrolyte composition on the anodic potential in Fe-
EC, 1 mA cm−2 , initial pH 7; concentrations: nitrate (10 mM), sulfate (5 mM), NaCl
(10 mM). Van Genuchten et al., 2017. Factors affecting the faradaic efficiency of
Fe(0) electrocoagulation. J. Environ. Chem. Eng. 5, 4958–4968.
Fe(III) species such as γ -FeOOH, akaganeit (b-FeOOH), or hematite
(a-Fe2 O3 ) (Cook, 2005; van Genuchten et al., 2016).
Furthermore, it is well-known that little passivation occurs
in solutions with high Cl− concentrations. In contrast, electrodes
are prone to passivate in the presence of dissolved oxyanions
such as nitrate, sulfate, carbonate, phosphate, silicate, formate,
citrate, molybdate, and chromate (Lakshmipathiraj et al., 2008;
Refaey, 2005; van Genuchten et al., 2017; Xu et al., 2015). As an
electrode surface passivates or depassivates, the anodic overpo-
tential increases or decreases, respectively. This response becomes
apparent in chronopotentiometric and chronogalvanometric stud-
ies (Fig. 7) (Mechelhoff et al., 2013a; van Genuchten et al., 2017).
Oxyanions exhibit strong affinities to Fe(0) and Fe-oxyhydr(oxides),
whereas Cl− and Br− ions replace oxyanions in the inner molecular
layer close to the electrode surface, effectively weakening the sur-
face layer—which ultimately leads to pitting corrosion because Cl−
and Br− form highly soluble complexes with iron. Maintaining suf-
ficient availability of aggressive ions can be used to prevent elec-
trode passivation, a strategy that is discussed in Section 3.1.
The effect of passivation in Fe-EC is particularly evident in
NO3 − solutions (Fig. 7). The passivating behavior of NO3 − is differ-
ent than other ions because it does not form a strong interaction
7
Water Research 187 (2020) 116433
with Fe(II/III) complexes (van Genuchten et al., 2017). However,
NO3 − accelerates Fe-oxyhydr(oxide) formation, which enhances the
buildup of the electrode surface layer. This effect may be caused
by the electrochemical reduction of NO3 − to NO2 − , NH3 , and N2 ,
which liberates hydroxide ions and raises the solution pH. Ad-
ditionally, in solutions with considerable sulfate concentrations,
Fe(II/III) ions have shown to form precipitates with SO4 2 − . For ex-
ample, FeSO4 and green rust sulfate may form on the electrode
surface, which contributes to passivation (Gerónimo-López et al.,
2014). The ordering of ionic species from least to most negative
impact on Fe(0) dissolution (and passivation) has been determined
as chloride < bromide < sulfate < formate < carbonate < phos-
phate < citrate < nitrate (van Genuchten et al., 2017).
The effect of increasing current density has also been shown
to affect passivation in Fe-EC. For example, high current densities
increase the total overpotential (η) at the electrode according to
the Butler-Volmer equation (Eq. (12)) (Dubrawski et al., 2015).
  a zF   a zF 
i = i0 exp
a
η − exp c η (12)
RT RT
where i is the current density, i0 is the exchange current density,
aa and ac are electron transfer coefficients, R is the universal gas
constant, T is the temperature, and η is the total electrode over-
potential (activation, concentration and passivation overpotentials).
When the anode overpotential corresponding to the applied cur-
rent density is sufficiently high, O2(g) evolution can be triggered.
This side reaction has been seen when operating at 125 mA cm−2
(Dubrawski et al., 2015), which is exceptionally high compared
to the typical current densities reported by other authors (see
Tables 2-4). Additionally, a higher current density leads to more
significant electrophoretic migration of charged suspended parti-
cles in the electrolyte, which could contribute to fouling and pas-
sivation (Alkhatib et al., 2020).
Sulfide species can exist in certain types of effluents, such as
produced water from oil production (Chow and Pham, 2019). The
presence of sulfides in Fe-EC is critical to acknowledge due to its
reactivity within the electrochemical stability range of water, and
its ability to affect EC performance (Vepsäläinen, 2012). Sulfide will
be present in different species depending on pH and DO concen-
tration. H2 S is a weak acid (pKa = 7) and exists in acidic environ-
ments, whereas HS− is present in alkaline conditions (Guan et al.,
2017). While the impact of sulfides on EC performance has not
M. Ingelsson, N. Yasri and E.P.L. Roberts Water Research 187 (2020) 116433

Table 2
Compilation of reported faradaic efficiencies, experimental conditions, and conclusions.

Electrode Faradaic
Material Sample Type Current Efficiency (FE) Conclusions Reference

Fe Cr3+ (0.03 M), NaCl 10.84 mA cm−2 64.5, 91.7% Higher FE in monopolar (Golder et al., 2007)
(0.05 M) in DI H2 O (Monopolar); configuration
32.52 (Bipolar)
mA cm−2
Fe Cr(VI), NO3 − in DI H2 O 0.16, 3.23 mA 1.7–111% ~100 FE at low current, no/low (Heidmann and
cm−2 FE at high current Calmano, 2008)
Fe Synthetic tap water; 0.86, 1.72, 3.45, 57–240% <pH 6: high FE (Sasson et al., 2009)
NaCl, organic buffers 6.9 mA cm−2 >pH 8: low FE
(MOPS, Glycine)
Fe Synthetic groundwater 2.8–44.4 mA 85–111% Multiple operating cycles: (Lakshmanan et al.,
(As) cm−2 high FE in first cycles; 2009)
progressively lower FE with
increasing cycles.
Fe Paper mill waste with 3.6–17.9 mA ~100% High FE in presence of sulfide (Vepsalainen et al.,
sulfide cm−2 2011)
Fe K2 Cr2 O7 , NaCl, NaNO3 , 4.36–30.74 mA 87.3–105.5%, Higher FE in presence of NaCl. (Golder et al., 2011)
Na2 SO4 , KH2 PO4 cm−2 110–210% (pH Higher FE at lower current
2–3) densities. Chemical dissolution
of Fe(0) in pH 2–3
Fe Na2 SO4 , NaCl in H2 O 5–125 mA cm−2 15–93% Lower FE at higher current (Dubrawski et al.,
density. Increased FE with 2015)
NaCl
Fe Synthetic groundwater 0.25–50 mA 0–100% FE ~0 in SO4 2− , CO3 2− , PO4 3− , (van Genuchten et al.,
cm−2 NO3 − , citrate, formate. ~100% 2017)
in soln with Cl− , Br−
Fe Synthetic smelting 4–10 mA cm−2 ~70–95% Lower FE at higher current (Xu et al., 2017)
wastewater with densities
cadmium, zinc,
manganese
Fe Synthetic mining 30 mA cm−2 77% Low FE caused by O2 evolution (Mamelkina et al.,
water (Cl− , NO3 − , 2017)
NH4 + , Cu2+ , Ni2+ ,
Zn2+ )
Fe Synthetic groundwater 0.8–10 mA cm−2 70–95% Efficiency high when CLR > (Müller et al., 2019)
4 min, and without oxyanions
Fe Groundwater 150A 12–35% Cell Potential: 7.8–11.8 V (Bandaru et al., 2020)
(before cleaning electrodes),
6.2–9.9 V (after cleaning)
Al Tap Water 2, 3, 5 mA cm−2 115–138% — (Jiang et al., 2002)
Al F− , Cl− , NO3 − , SO4 2− is 8.6 & 5.56 mA 24.3–128.2% Low FE with SO4 2− ; High FE (Hu et al., 2003)
Water cm−2 with Cl− & NO3 −
Al NaCl, Na2 SO4 in Water 0.5 mA cm−2 200–300% High Al3+ dissolution in >pH (Cañizares et al., 2005)
11
Al Na2 SO4 , NaCl, Ni2+ , 5–30 mA cm−2 120–224% High FE at lower i. Significant (Mouedhen et al.,
Cu2+ , Zn2+ chemical Al(0) dissolution at 2008)
cathode
Al Synthetic leachate 6V 0–131.1% No Al3+ dissolution in SO4 2− (Huang et al., 2009)
with NO3 − , SO4 2− , Cl− solutions
Al, Fe Commercial cutting oil 10 mA cm−2 Al: 150–300% Low FE in Fe-EC with NO3 − (Izquierdo et al., 2010)
in H2 O w/ NaCl, KCl, Fe: 0–100% salts & K2 SO4 2− (not Nas SO4 )
NH4 Cl, Na2 SO4 , K2 SO4
NaNO3 , KNO3
Al Algae in NaCl 2 mA cm−2 90–200% Increased FE with higher NaCl (Gao et al., 2010)
(0–0.47 g L−1 ) Water conc.
−2
Al NaCl, Na2 SO4 , 10 mA cm 100–133% — (Mansouri et al., 2011)
NaH2 PO4 in DI Water
Al (Pt CE) NaCl, 5 mA cm−2 100–180% FE generally ~100%; FE ~150% (Mechelhoff et al.,
Na2 SO4 , humic acid in in the presence of humic acid 2013b)
H2 O (>20 mg L−1 )
Al, Fe Acidogenic digestate, 9.3–27.8 mA 97–157% FE ~100% for iron, >100% for (Fayad et al., 2017)
(high organics conc.) cm−2 aluminum
pH 6.3
Al NaCl in DI H2 O (w/ 5 mA cm−2 145–320% Higher FE in NaCl (1 g L−1 ) (Ben Grich et al., 2019)
F− ), tap water (w/ F− ) than in tap water; Higher
Al(0) chemical corrosion at
cathode w/ increasing
temperature
Al Cl− , Fe2+ , Zn2+ , HCO3 − , 1.5 mA cm−2 130–270% Low FE in the presence of (Doggaz et al., 2019)
Ca2+ HCO3 −
Al 2,000 mg L−1 NaCl, pH 4–52 mA cm−2 80–116% Low FE at higher current (Chen et al., 2020)
8 densities
Ti 0.5 M NaCl in DI H2 O 7.5 mA cm−2 Slightly less Only electrochemical corrosion (El-Ghenymy et al.,
than 100% of Ti (no chemical) 2020)

8
M. Ingelsson, N. Yasri and E.P.L. Roberts Water Research 187 (2020) 116433

been extensively studied, it has been shown in potentiodynamic

polarization studies that their presence effectively mitigates passi-
vation and favors pitting corrosion (Hernández-Espejel et al., 2011).
The same study used thermodynamic modeling to show that Fe(0)
reacts with sulfide to form mackinawite (FeS), pyrite (FeS2 ), and
subsequently Fe2 O3 /Fe3 O4 in later oxidation stages. A sequence of
chemical and electrochemical reactions was proposed as mecha-
nisms for these transformations: Initially, Fe(II) is electrochemically
produced at the anode, which forms FeS upon reacting with H2 S in
the acidic boundary layer (Eq. (13)). Chemically generated FeS ei-
ther precipitates on the electrode surface or is transported to the
bulk solution. The formation of FeS by this mechanism has been
reported elsewhere (Guan et al., 2017; Rickard and Luther, 2007;
Vepsäläinen, 2012). Furthermore, XRD analysis has shown that a
mixture of iron sulfides and Fe-oxyhydr(oxides) form on steel elec-
trodes after anodic polarization. It was therefore proposed that
FeS is further oxidized to Fe-oxyhydr(oxides) at the anode surface
(Eqs. (14) & (15)) (Hernández-Espejel et al., 2011). It was also hy-
pothesized that sulfur-species could oxidize to SO4 2− at high over-
potentials.
Fig. 8. Anodic (electrochemical) and cathodic (chemical) dissolution of aluminum
electrodes (anode and cathode), 1 g L−1 NaCl, i = 40 mA cm−2 . Reprinted by per-
2+ +
Fe + H2 S → FeS + 2H (13) mission from Springer Nature Customer Service Centre GmbH: Springer Journal of
Solid State Electrochemistry, Electrochemical dissolution of aluminium in electroco-
agulation experiments, Fekete et al., Copyright 2016.
2FeS + 3H2 O → Fe2 O3 + 2H2 S + 2H+ + 2e− (14)

3FeS + 4H2 O → Fe3 O4 + 3H2 S + 2H+ + 2e− (15)
Post-experiment transmission electron microscopy (TEM) im-
ages of electrodes have also revealed signs of elemental sulfur
formation as a result of H2 S oxidation (Chow and Pham, 2019).
Lastly, in an attempt to electrodeposit FeS2 on steel electrodes,
researchers found that the surface layer was primarily comprised
of crystalline FeS, whereas no FeS2 was observed. This was ex-
plained by FeS2 formation exhibiting sluggish reaction kinetics,
even though it was thermodynamically favorable under the exper-
imental conditions (Guan et al., 2017).
2.3.2. Passivation behavior of aluminum electrodes in EC
Aluminum ions only have one oxidation state (z = 3), but
upon electrochemical dissolution, these ions can hydrolyze into
many types of polymeric hydroxide species (Mouedhen et al.,
2008). Following Al(0) dissolution, Al(OH)2+ and Al(OH)2 + tend
to form in acidic conditions, whereas Al(OH)4− forms in al-
kaline media (Phalakornkule et al., 2010). Meanwhile, solid
Al(OH)3 /Al2 O3 exist within the range of pH 4–9.5 (Moussa et al.,
2017; Roberge, 2008). Interestingly, observed concentrations
of aluminum in the electrolyte often exceed that of 100%
faradaic efficiency (Cañizares et al., 2007, 2005; Chen et al.,
20 0 0; Izquierdo et al., 2010; Mouedhen et al., 2008). It has
been shown that Al(III) is primarily produced electrochemi-
cally at the anode, but the “super-faradaic” behavior is a re-
sult of chemical corrosion at both the anode and the cath-
ode (Fig. 8) (Fekete et al., 2016), where the cathodic chemi-
cal corrosion of Al(0) is catalyzed by the alkaline environment
(Mouedhen et al., 2008).
Without applying an electrical current, Al(0) dissolution in-
creases dramatically above pH 11, compared to iron, which cor-
rodes spontaneously below pH 4 (Cañizares et al., 2007). It has
also been reported that the chemical corrosion of Al(0) at the
cathode accelerates with increasing temperature (Ben Grich et al.,
2019). Meanwhile, the authors claimed that the electrochemical
dissolution of the anode was unaffected by temperature changes.
Furthermore, it has also been shown (using gas chromatography)
that Al(0) is oxidized by H+ , hence generating H2(g) at the anode
(Fuladpanjeh-Hojaghan et al., 2019). The electrochemical and the
chemical dissolution of Al(0) are shown in Eqs. (16)–(18), respec-
tively.
Al(s ) ↔ Al3+ (aq ) + 3e− E o = −1.66 V vs SHE (16)
6H+ + 2Al(s ) → 3H2 + 2Al3+ (aq ) (17)
−
6H2 O + 2OH− + 2Al(s ) → 2[Al(OH )4 ] + 3H2 (18)
When aluminum metal is exposed to air, a film of alumina
(Al2 O3 ) forms on the surface, which is stable in water at circum-
neutral pH (Badawy et al., 1999; Schmuki, 2002; Trompette and
Vergnes, 2009). The oxide film thickness has been reported to
be between 1 and 5 nm using X-ray photoelectron spectroscopy
(XPS) and electrochemical impedance spectroscopy (EIS) analyses
(Martin et al., 2005; Mechelhoff et al., 2013a). Contrary to the
formation of oxyhydr(oxides) on iron electrodes, the Al2 O3 film
is insulating, hence functioning as a dielectric (Schmuki, 2002).
The insulating Al2 O3 surface layer must be broken down to facili-
tate effective EC performance and is replaced by a porous layer of
Al(OH)3 /Al2 O3 during EC operation (Badawy et al., 1999; Gao et al.,
2010; Mansouri et al., 2011). Furthermore, on the aluminum Pour-
baix diagram (Fig. 9), it is seen that Al(0)→Al(OH)3 oxidation oc-
curs in circumneutral pH, which is another example of a solid
phase transformation that contributes to electrode surface layer
growth.
Passivation has been studied for aluminum electrodes with dif-
ferent electrolyte compositions. Solutions containing Cl− , F− , and
NO3 − have shown to decrease electrochemical overpotentials and
produce higher faradaic efficiencies, compared to solutions with
high concentrations of SO4 2 − (Hu et al., 2003; Mansouri et al.,
2011). The passivating effect of SO4 2 − in Al-EC has also been
reported elsewhere (Huang et al., 2009; Izquierdo et al., 2010;
Mansouri et al., 2011), and it is well established in the cor-
rosion literature (Lee and Pyun, 20 0 0; Pyun et al., 1999). Po-
tentiodynamic polarization studies have shown that pitting po-
tentials are increased, and current densities are decreased in
SO4 2 − and H2 PO4 − solutions compared to in high concentration
NaCl electrolytes (Mansouri et al., 2011). In the presence of Cl− ,
the Al(OH)3 /Al2 O3 passivation layer breaks down according to

9
M. Ingelsson, N. Yasri and E.P.L. Roberts
Fig. 9. Pourbaix diagram of aluminum in water at 25 °C. The dashed lines represent
the electrochemical stability range of water. Produced based on calculations in the
MEDUSA-HYDRA software (Puigdomenech, 2019).
Eqs. (19)–(23) (Mansouri et al., 2011), which is conducive to pit-
ting corrosion.
Al2 O3 + 6Cl− + 6H+ → 2AlCl3 + 3H2 O
Al(OH )3 + Cl− → Al(OH )2 Cl + OH−
Al(OH )2 Cl + Cl− → Al(OH )Cl2 + OH−
Al(OH )Cl2 + Cl− → AlCl3 + OH−
−
AlCl3 + Cl− → AlCl4
At sufficiently high SO4 2 − concentrations, it was observed that
no Al(0) dissolved at all while operating at a constant voltage
(Huang et al., 2009). Additionally, the electrolyte pH remained the
same throughout the experiment, indicating that little or no cur-
rent passed through the reactor due to extreme passivation. Other
studies have reported evidence of current termination during po-
tentiostatic operation in SO4 2 − electrolytes, e.g., an aluminum an-
ode surface showed little sign of corrosion in post-experiment
scanning electron microscopy (SEM) images (Hu et al., 2003). There
was no sign of a thick or porous layer, indicating that the surface
layer was thin and not visible in SEM. In contrast, other researchers
showed that Al(0) dissolution was unaffected by changing the sup-
porting electrolyte from NaCl to Na2 SO4 (Cañizares et al., 2005). In
this case, the authors concluded that metal dissolution was more
sensitive to pH changes, i.e., higher alkalinity favoring Al(0)→Al(III)
dissolution. However, the salt concentrations used in these experi-
ments were 2.45 and 3.0 g L−1 , which are high. Side reactions such
as Cl2(g) evolution, triggered by high Cl− concentrations, could ex-
plain these trends. In contrast, some authors have recommended
using Na2 SO4 over NaCl as a supporting electrolyte in Al-EC due
to the enhanced conductivity of SO4 2− (Yildiz et al., 2008). The
choice between different supporting electrolytes in EC has been
a topic of controversy, and Ghernaout and Ghernaout, 2011 pub-
lished a review paper on the contradicting conclusions that have
been reported.
While NO3 − is detrimental to Fe-EC performance, it may pro-
mote metal dissolution in Al-EC (Hu et al., 2003). This effect may
be caused by NO3 − reduction to NO2 − , NH3 , and N2 at the cathode
(Eqs. (24)-(26), thus oxidizing Al(0)→Al(III) and generating OH−
(Hu et al., 2003). The increased concentration of OH− could trig-
ger a feedback loop that further promotes the chemical dissolu-
Water Research 187 (2020) 116433
tion of Al(0) (Eq. (18)). However, a thick Al(OH)3 surface layer was
observed on the anode in the presence of NO3 − , compared to no
observable oxide film in the Cl− electrolyte (Hu et al., 2003). Fur-
thermore, the reduction mechanisms for NO3 − is corroborated by
relatively higher pH values observed in NO3 − solutions than in Cl−
electrolytes (Huang et al., 2009). The authors hypothesized that the
lower pH in the presence of Cl− was caused by the anodic oxi-
dation of Cl− →Cl2(g) and further production of HOCl that had a
buffering effect, which enhanced the speciation of Al-hydroxides.
Consequently, higher contaminant removal efficiencies were re-
ported in the Cl− solutions compared to in the NO3 − electrolytes,
even though the faradaic efficiencies were similar in both cases.
The buffering effect of high Cl− concentrations has been reported
elsewhere (Ben Grich et al., 2019).
6NO−
3 + 18H2 O + 10Al → 10Al (aq ) + 3N2 + 36OH
0 3+ −
(24)
3NO− 0
3 + 18H2 O + 8Al → 8Al
3+
+ 3NH3 + 27OH− (25)
3NO−
3 + 3H2 O + 2Al (s ) → 2Al
3+
+ 3NO−
2 + 6OH
−
(26)
It has also been reported that the degree of passivation is de-
pendent on electrode roughness, i.e., depassivation is not as likely
to occur on smooth electrodes due to enhanced structural in-
(19) tegrity of the surface layers (Mechelhoff et al., 2013a). However,
it is not apparent if this phenomenon is unique to the nature of
Al(OH)3 /Al2 O3 surface layers, or if it applies to Fe-EC passivation
(20)
as well.
As mentioned in Section 2.1. formation of AlPO4 on electrode
(21) surfaces has been observed in phosphate electrolytes, which rein-
forces the passivating surface layer (Mansouri et al., 2011). Also,
(22) the presence of carbonates, phosphates, silicates, and arsenates has
shown to lower F− removal in Al-EC while operating galvanostati-
(23) cally (Vasudevan et al., 2011). However, it was unclear if this was
a result of electrode passivation. Instead, it was suggested that car-
bonates passivated the anode surface, whereas the other ions de-
creased F− removal by competitive adsorption on the aluminum
coagulant. However, as mentioned in Section 2.2., F− has been
shown to passivate aluminum electrodes in EC (Hu et al., 2003).
Furthermore, the passivating effects of carbonates and phosphates
have also been reported elsewhere (Doggaz et al., 2019; Dura and
Breslin, 2019). Lastly, the effect of organics such as humic acids
on the anodic dissolution and passivation of Al(0) is not appar-
ent (Mechelhoff et al., 2013a, 2013b), but it has been reported
that higher concentrations of humic acids form a gelatinous layer
on the anode surface, which effectively inhibits metal dissolution
(Yildiz et al., 2008).
2.3.3. Summary of passivation of different electrodes
The presence of most oxyanions in the electrolyte is detrimental
to both Al- and Fe-EC performance. The exception is that NO3 − is
passivating in Fe-EC (Izquierdo et al., 2010; Thiam et al., 2014), but
possibly conducive to chemical corrosion in Al-EC (Hu et al., 2003).
Few studies have investigated the effect of cations on EC perfor-
mance, but Trompette and Vergnes, 2009 found that the pres-
ence of Na+ had a negligible impact on Al-EC operation, whereas
Izquierdo et al., 2010 observed that K+ had a detrimental effect
on faradaic efficiencies in Fe-EC. Furthermore, bench-scale experi-
ments demonstrated that electrode fouling was not as pronounced
in Al-EC as in Fe-EC (Shamaei et al., 2018). However, severe mate-
rial precipitation on the electrodes in Al-EC has been reported on
the pilot-scale (Schulz et al., 2009). It is also unclear if there are
differences in passivation behavior for electrodes made of differ-
ent grades of steel and aluminum, which should be investigated in
future studies. Interestingly, Müller et al., 2019 found that overpo-
tentials were higher when using lower purity steel in Fe-EC field
10
M. Ingelsson, N. Yasri and E.P.L. Roberts
trials, compared to when using high purity steel in laboratory ex-
periments. However, it is unclear if the electrode purity was the
main contributor to this effect. Lastly, while SO4 2 − ions are pas-
sivating for both materials, sulfate electrolytes have shown to fa-
cilitate anodic dissolution in Ti-EC (El-Ghenymy et al., 2020). This
observation highlights the complex nature of electrode passiva-
tion/dissolution, which depends upon both the electrode material
and the electrolyte composition, which can vary widely.
2.4. Passivation and faradaic efficiency
It is generally presumed that higher faradaic efficiencies are
correlated with enhanced contaminant removal, and maintaining
high efficiency is imperative to sustaining efficient EC performance
(Müller et al., 2019). The faradaic efficiency of a given EC pro-
cess is related to the degree of electrode passivation, and as men-
tioned previously, severe surface layer growth can adversely af-
fect faradaic efficiency by triggering side reactions or terminating
the current. This is particularly evident in experiments with high
concentrations of oxyanions in the electrolyte (Hu et al., 2003;
Huang et al., 2009; Izquierdo et al., 2010; Müller et al., 2019).
Therefore, the relationship between the faradaic efficiency and pas-
sivation is important for understanding the electrochemical effi-
cacy of the EC process.
Generally, faradaic efficiencies are around 100% in Fe-EC,
independent of current density and the DO concentration
(Lakshmanan et al., 2009). Low faradaic efficiencies have been ob-
served at high current densities, which has been attributed to
unwanted anodic O2(g) evolution that was corroborated by bub-
bles forming on the anode (Dubrawski et al., 2015). Additionally,
the faradaic efficiency dropped from 116% to around 80% in Al-EC
when increasing the current density from 18 mA cm−2 to 52 mA
cm−2 (Chen et al., 2020). Low faradaic efficiencies have also been
reported for experiments carried out at pH 9, possibly caused
by O2(g) evolution, which is more favorable in alkaline conditions
(Sasson et al., 2009). As mentioned in Section 2.3.1, an increased
current density (Eq. (12)) strengthens the anodic polarization,
which attracts particles that could contribute to electrode passi-
vation. Additionally, once O2(g) evolution is initiated, γ -FeOOH for-
mation is favored, which further promotes passivation. The forma-
tion of O2(g) has either been observed or assumed to be the cause
of faradaic efficiencies lower than 100% (Cañizares et al., 2005;
Gao et al., 2010; Golder et al., 2007; Heidmann and Calmano, 2008;
Kobya et al., 2006; Mamelkina et al., 2017; Mollah et al., 2004b;
Müller et al., 2019; van Genuchten et al., 2017; Vepsäläinen, 2012).
The most convincing evidence substantiating O2(g) generation are
DO concentration measurements exceeding saturation values in Fe-
EC in a NO3 − electrolyte operating at 10 mA cm−2 (van Genuchten
et al., 2017). As mentioned in Section 2.3.2., it was also reported
and confirmed using confocal imaging and gas chromatography
that H2(g) forms on the anode—not O2(g) —in Al-EC when oper-
ating with current densities up to 16 mA cm−2 (Fuladpanjeh-
Hojaghan et al., 2019). Others have also hypothesized or observed
H2(g) formation in Fe-EC due to chemical corrosion (Eq. (11))
(Cañizares et al., 2007; Golder et al., 2011; Guan et al., 2017).
Furthermore, it has been suggested that O2(g) evolution does not
take place in Al-EC due to the thermodynamic favorability of
Al(0)→Al(III) dissolution (Mouedhen et al., 2008). Therefore, the
extent to which anodic O2(g) evolution in EC is responsible for
observed faradaic efficiencies below 100% is still uncertain. Other
mechanisms that can affect coagulant production must be ex-
plored.
During EC operation, measured metal dissolution quantities
could be artificially low due to inhomogeneous concentrations
within the reactor (Bandaru et al., 2020). As mentioned in the
introduction, the faradaic efficiency is commonly determined by
11
Water Research 187 (2020) 116433
sampling the bulk solution followed by acid digestion and ICP-OES
analysis (Müller et al., 2019). The potential issue is that the total
electrochemically dissolved iron is distributed between the bulk
solution, the electrode surface layer, and the precipitated sludge.
Ultimately, efficient coagulant mixing is essential, and high Fe-
oxyhydr(oxide) concentrations in the electrolyte are imperative to
sustaining high treatment performance.
Recent studies have provided more nuanced insights into the
cause of low faradaic efficiencies in Fe-EC (Bandaru et al., 2020;
Müller et al., 2019). For example, it has been demonstrated that
once a surface layer has formed, electrochemically produced Fe(II)
is trapped within the lattice of the surface layer (Bandaru et al.,
2020; Müller et al., 2019; van Genuchten et al., 2017, 2016). Con-
sequently, dissolved metal is hindered from diffusing or migrating
to the bulk solution, hence accelerating the surface layer buildup
(Fig. 10). Due to the porous and conductive nature of this type of
surface layer, it is non-passive, which has been shown in chronopo-
tentiometric studies (Müller et al., 2019). Therefore, assuming that
this effect is responsible for declines in electrochemically dissolved
metal, faradaic efficiencies of 100% would be expected if they were
determined from lost electrode mass after removing the surface
layer post-experiment. This method has been used by one study
(Cesar Lopes Geraldino et al., 2016), which still observed variations
in the faradaic efficiency of electrode consumption under different
experimental conditions. However, the connection between coagu-
lant accumulation in the surface layer, faradaic efficiency, and op-
erating conditions merits further investigation.
Alternatively, a shift from Fe(0)→Fe(II) to Fe(0)→Fe(III)
(Eq. (27)) at higher anodic overpotentials is thermodynami-
cally favorable over O2(g) evolution and could make it seem like
the observed faradaic efficiency is low (Moreno et al., 2009). As-
suming that this phenomenon takes place, there would be a shift
in the molar rate of electrochemically dissolved metal because the
charge transfer number would increase from 2 to 3. Therefore, less
iron coagulant would be produced per unit charge, which would
lower the calculated faradaic efficiency, assuming a two-electron
transfer reaction (Eq. (5)). However, it has been suggested that
direct Fe(0)→Fe(III) oxidation is negligible (Sasson et al., 2009),
and none of the reviewed studies reported evidence of this oc-
curring. In addition, using electrodes of different steel grades
could also affect faradaic efficiency. For example, impurities (Ni, V,
Cr) could be preferentially oxidized over Fe(0). Few studies have
compared using electrodes of different steel/aluminum purities,
but Müller et al., 2019 found that using a higher purity iron elec-
trode did not enhance the observed faradaic efficiency in Fe-EC.
Nevertheless, using low purity metal may be problematic due to
the release of toxic impurities into the water.
Fe(s ) ↔ Fe3+ (aq ) + 3e− E o = −0.037 V vs SHE (27)
Another suggested hypothesis is that Fe(II) and Fe(III) ions are
reduced to Fe(0) at the cathode, which would decrease the mea-
sured faradaic efficiency (van Genuchten et al., 2016; Yang et al.,
2015). However, this hypothesis has not been thoroughly inves-
tigated. Moreover, the evolution of Br2(g) and Cl2(g) is thermody-
namically possible at sufficiently high electrode potentials, and oc-
curs in electro-oxidation with boron doped diamond electrodes
(Ferro et al., 20 0 0). However, it has been suggested that these re-
actions are unlikely to occur in EC, even at overpotentials above
their standard reduction potentials (van Genuchten et al., 2017).
Direct-oxidation of organics at the anode surface could also cause a
drop in the measured faradaic efficiency, while positively affecting
treatment performance. However, direct electrochemical oxidation
of organics requires large overpotentials, and there is no evidence
that these processes occur in EC (Ghernaout, 2013).
The causes of low faradaic efficiencies observed in Fe-EC remain
unclear. However, many of the reviewed papers indicate that EC
M. Ingelsson, N. Yasri and E.P.L. Roberts
Fig. 10. Illustration of the surface layer buildup in Fe-EC, and consequent enmeshment of electrochemically dissolved metal, which impedes mass transfer to the bulk
solution. Reprinted from Chemosphere 153, van Genuchten et al., Formation of macroscopic surface layers on Fe(0) electrocoagulation electrodes during an extended field
trial of arsenic treatment, 270–279, 2016, with permission from Elsevier.
performance is heavily affected by the buildup of a passivating sur-
face layer on the anode. This phenomenon consequently increases
the anodic overpotential and may change the nature of the electro-
chemical activity at the anode. By inspecting the faradaic efficien-
cies reported by studies (Table 2), it is evident that low efficiencies
are more frequently observed in Fe-EC than in Al-EC. Therefore,
sustaining efficient coagulant dosing is seemingly more attainable
in Al-EC, which is likely caused by the thermodynamic favorabil-
ity of Al(0)→Al(III) oxidation (Eq. (16)). Izquierdo et al., 2010 also
reached this conclusion, i.e., Al-EC was more effective than Fe-EC
at avoiding passivation and maintaining effective electrode disso-
lution under identical operating conditions. Consequently, this in-
dication gives Al-EC a distinctive advantage over Fe-EC in long
term continuous EC operation. However, a systematic study of
long term Al-EC, similar to those for Fe-EC (Amrose et al., 2014;
Bandaru et al., 2020; Müller et al., 2019), has not been reported. As
mentioned in Section 2.3.3., severe material precipitation on alu-
minum electrodes has been reported to occur during pilot-scale EC
applications (Schulz et al., 2009).
3. Passivation mitigation strategies
Researchers have tested a variety of techniques to remove elec-
trode surface layers, or to avoid their formations. Implementing
effective strategies will enable continuous coagulant dosing while
keeping the cell potential low during long-term EC operation. The
depassivation and performance enhancement strategies that have
been reported are examined in the following sections.
3.1. Aggressive ion addition
One of the most frequently recommended depassivation tech-
niques in EC is to add an aggressive ion to the electrolyte, such as
Cl− or Br− (Arroyo et al., 2009; Chellam and Sari, 2016; Dura and
Breslin, 2019; van Genuchten et al., 2017; Xu et al., 2014, 2015).
12
Water Research 187 (2020) 116433
As described previously, the addition of an aggressive ion such as
Cl− triggers pitting corrosion, which breaks down the surface oxide
layer.
It has been shown empirically that the pitting potential is pro-
portional to the logarithmic ratio of the concentrations of the ag-
gressive and inhibiting ions in the electrolyte (Lumsden et al.,
1981; Refaey, 2005). The linearized expression for this relationship
is shown in Eq. (28). Experiments at different electrolyte concen-
trations have been fitted to this model (Dura and Breslin, 2019;
Mouedhen et al., 2008).
Cx
E p = A + Blog (28)
I
Where constants A and B are experimentally determined, and Cx
and I are the concentrations of the aggressive and the inhibitor
ions, respectively. In Fe-EC operation, it has been suggested that
1 mM of NaCl should be added for every 20 and 100 mM of NO3 −
and HCO3 − in the solution, respectively—to mitigate passivation
and ensure high faradaic efficiency (Fig. 11) (van Genuchten et al.,
2017). In the presence of SO4 2− , it has been reported that main-
taining a [Cl− ]/[SO4 2− ] ratio between 0.1–0.8 is sufficient to avoid
passivation and ensure high faradaic efficiency (Huang et al., 2009;
Mechelhoff et al., 2013a; Mouedhen et al., 2008; Trompette and
Vergnes, 2009).
However, there are several drawbacks to adding aggressive ions
to the electrolyte. Firstly, the added salts may need to be re-
moved in subsequent treatment steps before the treated water
could be re-used or discharged into the environment. Secondly,
a high Cl− concentration increases the risk of generating haz-
ardous byproducts, especially in the presence of organics, which
could form organochlorinated compounds (Donaldson et al., 2002;
Gotsi et al., 2005; Heidmann and Calmano, 2008; Kabdaşli et al.,
2009; Khandegar and Saroha, 2013). Furthermore, it has been
shown that adding too much Cl− can disrupt coagulation, e.g., dis-
solving Al(OH)3(s) to AlCl4 − (aq) (Wang et al., 2009). It was reported
M. Ingelsson, N. Yasri and E.P.L. Roberts
Fig. 11. Experimental data showing the abrupt decline in faradaic efficiency, coinciding with a spike in the anodic potential at specific electrolyte ratios. i = 1 mA cm−1 , pH
7.5. van Genuchten et al., 2017. Factors affecting the faradaic efficiency of Fe(0) electrocoagulation. J. Environ. Chem. Eng. 5, 4958–4968.
that adding > 1 g L−1 NaCl reduced the contaminant removal
rate by preferential sorption of Cl− on the Al-coagulant (Abdel-
Aziz et al., 2020). Additionally, it has been shown that Cl− in-
creases the aqueous stability of certain dissolved contaminants and
metal-oxyhydr(oxides), effectively inhibiting the coagulation pro-
cess (Abdel-Aziz et al., 2020; Golder et al., 2011, 2007). Another
concern is the increased sludge production associated with adding
salt to the water (Maha Lakshmi and Sivashanmugam, 2013).
Hence, aggressive ion addition should be optimized to avoid both
electrode passivation and the undesirable side effects associated
with excessive ion concentrations (Maha Lakshmi and Sivashan-
mugam, 2013).
Table 3 provides an overview of the studies that have explored
using aggressive ion addition as a depassivating strategy and shows
the suggested concentrations/ionic ratios that authors have recom-
mended.
3.2. Alternating current
Using current waveforms other than DC is an easily applicable
method that has been proposed to remove or inhibit the growth
of electrode surface layers in EC. Some studies have experimented
with using a sinusoidal alternating current (AC), which causes
the electrodes to oscillate between anodic and cathodic polarity
(Cerqueira et al., 2014; Ghanizadeh et al., 2016; Kamaraj et al.,
2013; Karamati-Niaragh et al., 2019; Mansoorian et al., 2014;
Vasudevan et al., 2011; Vasudevan and Lakshmi, 2012). It has
been shown that AC-EC is more cost-effective than DC-EC for
various applications (Cerqueira et al., 2014; Kamaraj et al.,
2013; Karamati-Niaragh et al., 2019; Mansoorian et al., 2014;
13
Water Research 187 (2020) 116433
Vasudevan et al., 2011; Vasudevan and Lakshmi, 2012). AC-EC has
also been tested with iron electrodes (Mansoorian et al., 2014),
aluminum (Cerqueira et al., 2014; Karamati-Niaragh et al., 2019;
Vasudevan et al., 2011), zinc (Vasudevan and Lakshmi, 2012) and
magnesium electrodes (Kamaraj et al., 2013).
Higher contaminant removal per unit mass of metal dissolved
has been observed in AC-EC, possibly due to enhanced coagu-
lant mass transfer caused by the corrosion of both electrodes
(Karamati-Niaragh et al., 2019). Ultimately, most studies have
found that AC-EC is comparatively more energy efficient than DC-
EC, which is often hypothesized to be a consequence of dimin-
ished electrode passivation (Alkhatib et al., 2020; Bian et al., 2019;
Kamaraj et al., 2013; Vasudevan et al., 2011; Vasudevan and Lak-
shmi, 2012). The mechanisms responsible for avoiding or remov-
ing passivation in AC-EC have not been discussed in the literature.
However, a proposed explanation for polarity reversal is provided
in Section 3.3.2., which can also be used to explain the mecha-
nisms for AC-EC.
Many authors have provided SEM images showing that
electrodes post-experiment display smoother surface morpholo-
gies after AC-EC operation compared to after DC-EC (Fig. 12)
(Kamaraj et al., 2013; Mansoorian et al., 2014; Vasudevan et al.,
2011; Vasudevan and Lakshmi, 2012). Electrodes in DC-EC ex-
hibit more crevices, localized corrosion, and material precipitation
on the electrodes. Therefore, pitting corrosion is likely less pro-
nounced in AC-EC, primarily due to the cyclic interruption and
restarting of anodic dissolution, which leads to the continuous for-
mation of new points of localized corrosion. Consequently, this
leads to more uniform consumption of the anode, which could
overcome the problem of non-uniform electrode dissolution asso-
M. Ingelsson, N. Yasri and E.P.L. Roberts Water Research 187 (2020) 116433

Table 3
Reported results from studies using aggressive ion addition in EC.

Electrode
Material Sample Type Current Suggested Aggressive Ion Conc. Author

Fe NaCl, NaNO3 , Na2 SO4 , K2 Cr2 O7 10 mA cm−2 0.5 g L−1 NaCl (Lakshmipathiraj et al., 2008)
Fe Cr(VI) in NaCl & H2 SO4 DI Water 45 mA cm−2 0.7 g L−1 NaCl (Arroyo et al., 2009)
Fe Dyes, NaCl in H2 O 0.27–5.46 mA cm−2 1.5 g L−1 NaCl (Secula et al., 2013)
Fe K2 Cr2 O7 , NaCl, K2 SO4 in DI H2 O 10 mA cm−2 0.36–1.47 g L−1 (Xu et al., 2015)
Fe Synthetic Groundwater 0.25–50 mA cm−2 1 mM NaCl for every 20 mM NO3 − , (van Genuchten et al., 2017)
100 mM HCO3 −
Fe/Al Cr2 O7 2− in DI H2 O 15.3 mA cm−2 0.57 g L−1 NaCl, 0.285 g L −1 KCl (Keshmirizadeh et al., 2011)
Fe, Al Diluted Tanning Waste 20 (optimal), 40 mA cm−2 1 g L−1 NaCl (90% COD removal) (Maha Lakshmi and
Sivashanmugam, 2013)
Al Synthetic leachate with NO3 − , SO4 2− , 45 mA cm−2 [Cl− ]/[SO4 2− ] = 0.4 (Huang et al., 2009)
Cl−
Al Na2 SO4 , NaCl Ni2+ , Cu2+ , Zn2+ 0.5–23 mA cm−2 [Cl− ]/[SO4 2− ] = 0.15 (Mouedhen et al., 2008)
Al Laundry waste 1–7 V 0.25 g L−1 NaCl (Wang et al., 2009)
Al Milk with NH4 Cl, NaCl, NH4 SO4 , 8 V (MSE) WE [Cl− ]/[SO4 2− ] > 0.1 (Trompette and Vergnes, 2009)
Na2 SO4
Al Algae in NaCl Water 2 mA cm−2 0.29 g L−1 NaCl (Gao et al., 2010)
Al Na2 SO4 , NaCl, humic acid in pH 7 RO 0–1.5 mA cm−2 [Cl− ]/[SO4 2− ] = 0.8 (Mechelhoff et al., 2013a)
H2 O
Al Synthetic NO3 − solution; pH 3 - 11, 2.94–10.3 mA cm−2 1 g L−1 (Abdel-Aziz et al., 2020)
NaCl 1–2.5 g L− 1

Xu et al., 2019). However, AC-EC has shown to offer benefits

such as reduced sludge formation, lower energy consumption, im-
proved mass transfer characteristics, and delayed electrode pas-
sivation (Alkhatib et al., 2020; Cerqueira et al., 2014; Karamati-
Niaragh et al., 2019; Mansoorian et al., 2014; Xu et al., 2019). In
contrast, one study reported that DC-EC was better than AC-EC
for the removal of F− with both iron and aluminum electrodes
(Ghanizadeh et al., 2016). Yet, in total, there have only been a
handful of authors that have examined the effects of AC opera-
tion, and more research is required to develop a comprehensive
understanding of the mechanisms, benefits, and drawbacks of this
technique. The operating conditions reported by authors of AC-EC
studies are included in Table 4 below.

3.3. Polarity reversal

3.3.1. Principles of polarity reversal electrocoagulation

Fig. 12. SEM images of the aluminum anode post-experiment after (a) AC-EC and
(b) DC-EC for operating with a F− electrolyte (5–20 mg L−1 ). Reprinted from Water
Sci. Technol. 65, Vasudevan and Lakshmi, Effect of alternating and direct current
in an electrocoagulation process on the removal of cadmium from water, 353–360,
Copyright 2011, with permission from Elsevier.
ciated with small electrode gaps and high solution conductivities
(McBeath et al., 2020).
It has consistently been reported that faradaic efficiencies
are lower in AC-EC than in DC-EC (Alkhatib et al., 2020;
In contrast to using a sinusoidal current to invert electrode po-
larity, operating with polarity reversal entails periodically switch-
ing the direction of a direct current, thus resulting in a square
wave (Fig. 13a). This technique is the most commonly used pas-
sivation control strategy in EC, and is often referred to as an al-
ternating pulsed current (Eyvaz et al., 2009; Keshmirizadeh et al.,
2011; Mao et al., 2008; Yang et al., 2015) or as polarity re-
versal electrocoagulation (PR-EC) (Bao et al., 2020; Liu et al.,
2018; van Genuchten et al., 2017; Vasudevan et al., 2011). Some
researchers have operated PR-EC with intermittently terminat-
ing/restarting (i.e., pulsing) the current in between polarity rever-
sals (Fig. 13b), which was proposed to enhance the mass trans-
fer of the coagulant to the bulk solution (Asaithambi et al., 2016;
Hasani et al., 2019; Ren et al., 2011; Xin et al., 2018; Zhou et al.,
2020). PR-EC is relatively easy to implement, and the only ad-
ditional infrastructure required is a DC time relay, or manually
switching the positive/negative terminals. The idea of reversing po-
larity as a method to consume both electrodes can be found in
patents from the 1970s (Miller, 1977, 1978). PR-EC later received
attention in the 1980s’ scientific literature as an electrode clean-
ing technique (Grøterud and Smoczynski, 1986; Jianqian, 1988). It
has since then been established as a strategy to depassivate, sus-
tain high treatment performance, and to extend electrode lifetime
(Mollah et al., 2001).
PR-EC has been evaluated for several applications (Table 4).
Most studies have operated PR-EC with current reversals tak-

14
M. Ingelsson, N. Yasri and E.P.L. Roberts Water Research 187 (2020) 116433

Table 4
Compilation of studies that have investigated the performance of PR-EC and AC-EC.

Electrode Current Energy

Material Type PRT Sample Type Current Consumption Conclusions Author

Fe PR 5–30 min Cr(VI) & NO3 − in DI 0.16, 3.23 mA 0.003–16.83 kWh Higher performance at low (Heidmann and
H2 O cm−2 m−3 current density. No Calmano, 2008)
reported effect of PRT
Fe PR 0.5–4.2 min Sea water 1.8–1.9 mA — Highest Farad. Eff. at (Timmes et al.,
cm−2 4 min 12 s PRT 2010)
−3
Fe PR 30 min K2 Cr2 O7 , KCL, NaOH, 10–40 46 kWh m No other PRT tested (Dermentzis et al.,
HCl mA cm−2 2011)
Fe PR 5 min Dyes, NaCl in H2 O 0.27–5.46 mA DC-EC: ~0.26 kWh PR-EC: lower energy (Secula et al.,
cm−2 m−3 ; consumption, same 2013)
PR-EC: ~0.23 kWh removal performance as
m−3 DC-EC
Fe PR Anode/cathode Arsenic in 45 A: 4.3–5 C 0.62–2.31 Mechanical cleaning (Amrose et al.,
reversed each groundwater L−1 min−1 kWh m−3 ; enhanced performance; 2014)
exp. cycle 0.83–1.04 effects of PR-EC not
US$ m−3 discussed.
Fe AC Not Reported Pb & Zn in battery 2–10 AC-EC: 0.69 kWh AC-EC higher performance (Mansoorian et al.,
water mA cm−2 m−3; than DC-EC 2014)
DC-EC: 1.97 kWh
m−3
Fe PR 0–15 min Electroplating effluent, 0.3–1.5 mA 10–20% lower 10–15 min PRT optimal for (Shao-qin et al.,
Cr(VI), pH 5–10 cm−2 energy Cr(VI) removal 2014)
consumption in
PR-EC than in
DC-EC
Fe PR 10 s - 30 min Cr(VI) & K2 SO4 in 10 — PRT >9 min 50 s required (Yang et al., 2015)
water mA cm−2 for high Farad. Eff.
Fe PR Anode/cathode Groundwater 45 A — PR and mech. cleaning of (van Genuchten
switched each electrodes can reduce et al., 2016)
exp. operating costs
Fe PR Dairy plant effluent, 1.5 A — Higher electrode (Cesar Lopes
Anodes/Cathodes pH 4.5 consumption in PR-EC Geraldino et al.,
switched each than DC-EC 2016)
exp. (60 min)
Fe PR 15 min Distillery effluent, pH 1.3 1.3–1.32 Improved performance in (Asaithambi et al.,
3–11 mA cm−2 kWh m−3 PR-EC compared to in 2016)
DC-EC
Fe PR 52.5 min & 21 Synthetic Groundwater 0.8 PR-EC: Increased electrode fouling (Müller et al.,
min mA cm−2 0.21–0.22 kWh in PR-EC caused by 2019)
m−3 ; trapping of Fe(II) in CaCO3
DC-EC:
0.2–1.48 kWh m−3
Fe PR 30, 120, 240 s Estrogen, Na2 SO4 , 4.16, 8.3, 16.7 — 30 s optimal PRT for (Maher et al.,
NaHCO3 in DI H2 O mA cm−2 estrogen removal. 2019)
Fe AC 50 Hz K2CrO4, NaCl, Ethanol, 0.27 AC-EC: Less electrode (Xu et al., 2019)
Diphenylcarbohy- mA cm−2 0.454 kWh m−3 ; consumption and better
drazide in DI DC-EC: removal for AC-EC than
H2 O 1.002 kWh m−3 DC-EC
(~96–97% Cr(VI)
removal)
PR 5 min Raw coke water 20 mA cm−2 1.93–3.30 PR-EC: removal efficiency (Ozyonar and
Fe + H2 O2 kWh m−3 than DC-EC Karagozoglu, 2015)
Fe, Al PR 4 s – 17 min 20 mg L−1 P 0.05 A 27 kWh m− 3 256 s optimal PRT for P (Grøterud and
removal Smoczynski, 1986)
Fe, Al PR 4 min Cr(VI), + ions in water 2–23 4–58 kWh m−3 PR-EC: decreased
mA cm−2 passivation, less energy (Keshmirizadeh et al.,
consumption than DC-EC 2011)
Fe, Al AC 50 Hz NaF (3–8 mg L− 1 ) 15–40 V — DC-EC: more effective F− (Ghanizadeh et al.,
removal than AC-EC 2016)
Fe, Al PR 2.5 min Brewery waste 3–30 Fe: 4.68 kWh m−3 PR-EC overall more (Eyvaz, 2016)
mA cm−2 (DC) efficient than DC-EC; Less
4.30 kWh m− 3 coagulant required per kg
(PR-EC) COD removed
Al: 4.85 kWh m− 3
(DC)
4.27 kWh m− 3
(PR-EC)
Fe, Al PR 0.01 s - 1 min Milk in tap water, pH 0.01–40 mA — PRT >1 min necessary for (Fekete et al.,
40 s 5.5. cm−2 high Farad. Eff. 2016)
NaCl, Na2 SO4 in DI
H2 O
Fe, Al PR 1, 3, 5 min Synthetic brine, pH 2.48–2.81 mA 0.63–2.89 No difference between PRT (Ashraf et al.,
9.44 cm−2 kWh m−3 & salt removal. Slight 2019)
increase in energy
consumption with 5 min
PRT
(continued on next page)
15
M. Ingelsson, N. Yasri and E.P.L. Roberts Water Research 187 (2020) 116433

Table 4 (continued)

Electrode Current PRT Sample Type Current Energy Conclusions Author

Material Type Consumption

Al PR Not Reported Greywater (cooking oil, 0.5–1.5 mA 30% lower energy Enhanced COD removal, (Mao et al., 2008)
scour, Na2 SO4 ) cm−2 consumption in and more uniform
PR-EC than DC-EC electrode dissolution in
PR-EC
Al PR 3–15 min Dyes in water 3.5–15 1.3–3.43 US$ (kg PR-EC: Decreased (Eyvaz et al., 2009)
(Disperse Yellow 241 mA cm−2 TOC)−1 passivation, enhanced TOC
and Reactive Yellow removal, lower cost than
135) DC-EC
Al AC 50 Hz NaF in DI H2 O 2.5–15 AC-EC: 1.883 kWh AC-EC prevents passivation (Vasudevan et al.,
mA cm−2 m− 3 ; 2011)
DC-EC: 2.541 kWh
m− 3
Al PR 1–30 s Methyl orange (MO), 150 PR-EC: 44 kWh (kg 15 s optimal PRT; PR-EC (Pi et al., 2014)
NaCl in H2 O mA cm−2 MO)−1 ; overall more effective than
DC-EC: 55 kWh DC-EC
(kg MO)−1
Al AC, PR 60 Hz (AC), Synthetic produced 20–100 mA 0.28 kWh m−3 Higher electrode (Cerqueira et al.,
5 min (PR) water (O/W emulsion) cm−2 consumption in PR-EC 2014)
than in AC-EC
Al PR 15, 30 min Groundwater (As) 7V 3.03 kWh m−3 No sign of passivation in (Mohora et al.,
(30 min PRT) PR-EC (6 h operation) 2014)
Al PR 5 min Produced water 1.2 V PR-EC + biochar PR-EC lower energy (Lobo et al., 2016)
filter: 0.15 kWh consumption than DC-EC
(kg SS)−1 for similar pollutant
removal
Al PR 4 min, 16 s Raw Sewage 10–15 A 0.53 kWh m−3 No other PRT tested (Smoczyński et al.,
2017)
Al PR 10 s Synthetic produced 89 mA cm−2 — No other PRT tested (Gobbi et al., 2018)
water
−3
Al PR 10 s PFOA in water 9V 0.04 kWh m No other PRT tested (Liu et al., 2018)
Al PR 0–3 min NaCl, NaHCO3 in DI 37.9 V 2.56 kWh m−3 3 min optimal PRT for (Wellner et al.,
H2 O (constant) depassivation and 2018)
coagulant production
Al AC 50 Hz NaNO3 & Na2 SO4 in 7–8 mA cm−2 DC-EC: US$54 (kg Electrode consumption (Karamati-
water NO3 − )−1 ; higher in AC-EC than in Niaragh et al.,
AC-EC: DC-EC 2019)
US$29 (kg NO3 − )−1
Al PR 0.5, 1 & 2 min Groundwater 3–10 0.92–1.95 1 min optimal PRT for F− (Betancor-
mA cm−2 kWh m−3 removal Abreu et al.,
2019)
Al PR, AC 0.1–4 s Synthetic bilge water 3.6–10.7 mA AC-EC: 0.977 kWh Less long-term passivation (Bian et al., 2019)
cm−2 m−3 ; & energy consumption in
DC-EC: 0.936 kWh AC-EC than in DC-EC
m− 3
Al PR 1–10 min Humic acids in DI H2 O 5–15 V DC-EC: 1.08 kWh Less electrode (Hasani et al.,
m−3 consumption and lower 2019)
PR-EC: 0.37 kWh passivation in PR-EC than
m− 3 in DC-EC for same removal
(~97–98% HA of humic acids
removal)
Al AC 50 Hz Secondary treated 0.8–4.3 mA — Better COD & TP removal (Alkhatib et al.,
effluent (WWTP), pH cm−2 performance in AC-EC than 2020)
6.9 DC-EC; Lower electrode
consumption in AC-EC
Zn AC 50 Hz Cd(NO3 )2 in DI H2 O 1–5 AC-EC: 0.655 kWh AC-EC prevents passivation (Vasudevan and
mA cm−2 m−3 ; Lakshmi, 2012)
DC-EC: 1.236 kWh
m−3
Mg AC 50 Hz CuNO3 in DI H2 O 0.1–10 AC-EC: 0.634 kWh AC-EC better performance (Kamaraj et al.,
mA cm−2 m−3 ; than DC-EC 2013)
DC-EC: 0.996 kWh
m− 3
Fe, Ti PR 12 s As(III/IV) groundwater 5–50 mA PR-EC: 0.101 kWh 6 s current break between (Xin et al., 2018)
(IrO2 /Ta2 O5 m−3 ; PR decreased fouling and
coating) DC-EC: 0.167 kWh passivation
m− 3
Mg, Al PR 2–8 min Dye (Indigo Carmine) 4.44, 7.30 mA — Short PRT favors dye (Donneys-
& NaCl in DI H2 O cm−2 removal, DC-EC favors Cl− Victoria et al.,
removal 2020)
Zn, Al PR 10 s PFSAs in synthetic & 6–12 V — No other PRT tested (Bao et al., 2020)
natural groundwater

16
M. Ingelsson, N. Yasri and E.P.L. Roberts
Fig. 13. Direct current with (a) polarity reversal, (b) pulsing polarity reversal (with current breaks).
ing place during operation (Eyvaz, 2016; Eyvaz et al., 2009;
Gobbi et al., 2018; Keshmirizadeh et al., 2011; Liu et al., 2018;
Mao et al., 2008; Müller et al., 2019; Ozyonar and Karago-
zoglu, 2015; Timmes et al., 2010; Yang et al., 2015). Others have
switched the electrodes in between operating cycles (Amrose et al.,
2014; Bandaru et al., 2020; Cesar Lopes Geraldino et al., 2016;
Maha Lakshmi and Sivashanmugam, 2013; van Genuchten et al.,
2016).
3.3.2. Benefits of polarity reversal electrocoagulation
Some authors have observed increased faradaic efficiencies in
PR-EC compared to in DC-EC for operating with both iron and alu-
minum electrodes (Cesar Lopes Geraldino et al., 2016; Ozyonar and
Karagozoglu, 2015; Wellner et al., 2018; Yang et al., 2015). This
effect was explained by the inevitable passivation in DC-EC, thus
triggering side reactions. The authors suggested that fouling is
avoided in PR-EC, hence sustaining effective metal dissolution. Ad-
ditionally, SEM imaging and XPS analysis have shown that a less
pronounced electrode surface layer forms in PR-EC with aluminum
electrodes (Hasani et al., 2019; Mao et al., 2008). It was also
demonstrated that PR-EC and DC-EC exhibit similar removal effi-
ciencies for current densities below 12 mA cm−2 for abating COD
in brewery wastewater using aluminum electrodes (Eyvaz, 2016).
However, the electrodes in DC-EC started passivating when operat-
ing at 12 mA cm−2 , whereas passivation was not detected in PR-EC
until current densities of 18 mA cm−2 .
It has been reported that PR-EC uses 30–60% less energy than
DC-EC for similar contaminant removal efficiencies with aluminum
electrodes (Hasani et al., 2019; Mao et al., 2008). Meanwhile, en-
ergy consumption data reported for PR-EC with iron electrodes
tend to be lower than for DC-EC, but the difference is not as dra-
matic as for aluminum (see Table 4). Apart from the alleged re-
duced passivation, the cell potential in PR-EC is lower than in
DC-EC because H2(g) evolution is thermodynamically favorable in
acidic pH. Therefore, cathodic H2(g) evolution will proceed at a
lower equilibrium potential following polarity reversal due to the
acidic environment at the cathode. However, this effect will dimin-
ish once the pH at the cathode interface equilibrates.
Due to the electrochemical dissolution of all electrodes in PR-
EC, metal ions are added more uniformly, which increases mix-
ing and induces a higher degree of contaminant-coagulant inter-
actions. Consequently, the coagulation process becomes more effi-
cient, which permits decreasing the charge loading rate—hence re-
ducing sludge production (Hasani et al., 2019; Keshmirizadeh et al.,
2011). It has also been suggested that PR-EC mitigates the effect of
concentration polarization in Al-EC, i.e., enhancing the mass trans-
fer of Al3+ and Al(OH)4 − that otherwise tend to concentrate at the
anode and cathode (respectively) during DC-EC operation (Pi et al.,
2011, 2008). Consequently, the speciation of Al-hydroxide polymers
was improved in PR-EC, which is conducive to more efficient con-
17
Water Research 187 (2020) 116433
taminant removal per unit coagulant produced. It was also ob-
served that the coagulant formed in PR-EC had a larger surface
area than the coagulant formed in DC-EC when operating with iron
electrodes (Zhou et al., 2020).
Similar to AC-EC, PR-EC could mitigate the problem of non-
uniform anodic dissolution, which causes pre-mature structural
failure of the electrodes (McBeath et al., 2020). Another benefit of
PR-EC is that two electrode materials could be used to produce two
types of coagulants (Keshmirizadeh et al., 2011). For example, this
permits using iron and aluminum electrodes together, which could
be beneficial for the treatment of certain types of wastes. For in-
stance, it has been shown that Fe-EC is more effective at removing
sulfides, while Al-EC is better at abating silica in produced water
from in-situ bitumen extraction (Chow and Pham, 2019).
The mechanism for how passivation is avoided or removed
when operating AC-EC or PR-EC is not clearly understood. A pos-
sible explanation could be scouring by the formation of H2(g) bub-
bles on the cathode (Bian et al., 2019; Timmes et al., 2010), which
mechanically remove the surface layer from the anode following
polarity reversal. Also, calcium and magnesium minerals formed
on the cathode can dissolve in the acidic boundary layer after the
cathode becomes the anode. By changing electrode polarity, elec-
trostatically adsorbed particles on the surface are repulsed, which
also contributes to depassivation. The surface layer could also be
weakened by the dissolution of the underlying metal, causing it to
fracture (Bian et al., 2019). Understanding these mechanisms re-
quires further investigation.
3.3.3. Effect of polarity reversal frequency
The polarity reversal time (PRT), i.e., the time in between
current reversals, has been reported to affect EC performance
(Eyvaz et al., 2009; Grøterud and Smoczynski, 1986; Timmes et al.,
2010; Yang et al., 2015). For example, short PRTs have shown to
reduce treatment performance (Yang et al., 2015). Meanwhile, the
nature of passivation becomes analogous to DC-EC when operat-
ing with longer PRTs. These observations indicate that this variable
can be optimized, but PRTs recommended in the literature differ
(Table 4), which suggests that the optimal PRT is dependent on op-
erating conditions such as electrolyte composition, current density,
and electrode material. For example, it was concluded that a 5 min
PRT was optimal for the treatment of organic dyes Disperse Yellow
241 and Reactive Yellow 135 in Al-EC (Eyvaz et al., 2009). Mean-
while, a 4 min PRT was recommended for removing phosphates
(Al/Fe-EC) (Keshmirizadeh et al., 2011; Smoczyński et al., 2017), a
15 s PRT for removing methyl orange dye (Al-EC) (Pi et al., 2014),
1 min for F− (Al-EC) (Betancor-Abreu et al., 2019), 15 min for Al-
EC operation (Chen, 2004), and 2.5 min for general EC operation
(Eyvaz, 2016). Additionally, a 10 s PRT has been used with alu-
minum electrodes to remove oil, perfluorooctanoic acids (PFOAs)
and perfluorosulfonic acids (PFSAs), although the results were not
M. Ingelsson, N. Yasri and E.P.L. Roberts
compared to DC-EC, or other reversal frequencies (Bao et al., 2020;
Gobbi et al., 2018; Liu et al., 2018).
It has been observed that faradaic efficiencies vary based on
PRT duration, particularly in Fe-EC. For example, it was reported
that the faradaic efficiency increased from 45% to 70% when in-
creasing the PRT from 10 to 590 s, which consequently enhanced
Cr(VI) removal in Fe-EC (Yang et al., 2015). Low faradaic efficien-
cies associated with short PRTs in Fe-EC have also been reported
by others (Ashraf et al., 2019; Fekete et al., 2016; Grøterud and
Smoczynski, 1986; Timmes et al., 2010). As mentioned previously,
the bulk solution pH typically increases gradually during DC-EC
operation. However, it was observed that the pH increase is not
as pronounced in PR-EC with short PRTs, compared to longer PRTs
or DC-EC (Grøterud and Smoczynski, 1986). This phenomenon has
been seen for other systems. For example, it took considerable
time for the pH to regain its equilibrium value after reversing
polarity with aluminum electrodes in a continuous flow system
(Wellner et al., 2018). Low faradaic efficiencies with short PRTs are
consistent with findings from studies of AC-EC, which are equiv-
alent to PR-EC with very short PRTs (i.e., high-frequency reversal)
(Cerqueira et al., 2014; Karamati-Niaragh et al., 2019). In contrast,
the removal of estrogen was reported to increase with shorter PRTs
when using iron electrodes (Maher et al., 2019). The authors con-
cluded that this was a consequence of avoiding electrode passiva-
tion. However, an alternative explanation is that an elevated rate of
direct anodic oxidation caused the improved removal rates, rather
than enhanced coagulation in the electrolyte. By using PR-EC, di-
rect oxidation takes place at both electrodes, and the rate of mass
transfer of pollutants could be improved. Enhanced mass transfer
and electrode utilization have been observed when applying po-
larity reversal in the electro-oxidation process (Thostenson et al.,
2018).
Longer PRTs have also been tested for the treatment of ground-
water by Fe-EC (Müller et al., 2019). In this study, the faradaic effi-
ciency was lower for a PRT of 21 min than observed for switching
polarity between every operating batch (105 min), which in turn
had a lower faradaic efficiency than DC-EC. It was also found that
the anodic interfacial potential was lower in PR-EC than in DC-
EC experiments, indicating that passivation was depressed. In con-
trast, Cesar Lopes Geraldino et al., 2016 demonstrated that elec-
trode consumption was higher over 24 cycles (relative to DC-EC)
when reversing polarity in between batches (60 min) in Fe-EC for
treating dairy plant effluent. The authors concluded that passiva-
tion led to reduced coagulant production in DC-EC, which is plau-
sible due to the high organic content of the wastewater. The dif-
ferences between the findings of these studies highlight the com-
plex nature of PR-EC and the effect of electrolyte composition on
faradaic efficiency and treatment performance. Due to the problem
of passivation in EC, and the widespread belief that PR-EC may ad-
dress this issue, it is essential to consider the connection between
performance, passivation, and PRT.
3.3.4. Mechanisms of passivation mitigation in polarity reversal
EC—discussion
Few studies have attempted to provide mechanistic explana-
tions for the association between PRT and PR-EC performance. As
discussed in Section 2.4., the buildup of the electrode surface layer
likely contributes to a decrease in faradaic efficiency by hinder-
ing coagulant mass transfer to the bulk solution (Bandaru et al.,
2020; Müller et al., 2019; van Genuchten et al., 2016). It has
been suggested that this effect is accelerated in PR-EC, which
is supported by thicker electrode surface layers observed on
iron electrodes in PR-EC relative to DC-EC (Ashraf et al., 2019;
Müller et al., 2019). An enhanced trapping capacity of iron species
by a CaCO3 surface layer that forms on the cathode before it
becomes the anode was proposed as the causation of this phe-
18
Water Research 187 (2020) 116433
nomenon (Müller et al., 2019). Another possible explanation for the
relatively thicker surface layers in PR-EC could be the occurrence of
changing pH boundary layers at the electrode interfaces. For exam-
ple, Fe(II/III) present in the acidic anodic boundary layer can form
Fe-oxyhydr(oxides) in the alkaline conditions that develop follow-
ing polarity reversal (Fig. 5). These species sorb to the electrode
surface and contribute to the surface layer buildup, which impedes
Fe(II/III) mass transport to the bulk solution. Furthermore, allowing
for the pH boundary layers to re-establish after polarity reversal
requires a particular duration, which depends on operating con-
ditions such as current density and electrolyte buffering capacity.
Also, the slow dissolution kinetics of calcium and magnesium min-
erals in the anodic acidic boundary layer adds additional time to
achieve effective depassivation. Consequently, applying longer PRTs
favor the completion of these mechanisms.
It has also been acknowledged that the “polarization time”,
i.e., the time it takes for the electrochemical reactions to
restart following polarity reversal, is detrimental to EC perfor-
mance (Grøterud and Smoczynski, 1986). Non-faradaic charg-
ing/discharging of the capacitive electrochemical double layer
(Hasani et al., 2019) and faradaic side reactions could occur dur-
ing this time. Therefore, the expected anodic and cathodic reac-
tions (Eqs. (1) & (2)) are presumably inactivated during this pe-
riod (Bian et al., 2019). This proposition is corroborated by rela-
tively lower pH and faradaic efficiencies observed in PR-EC com-
pared to in DC-EC (Fekete et al., 2016; Grøterud and Smoczyn-
ski, 1986). By approximating the duration of charging the capac-
itive double layer in EC—assuming 1 cm electrode separation and
C = 0.2 F m−2 (Conway, 2018)—periods within the range 2–100 ms
are obtained (based on electrolyte conductivities 1–20 mS cm−2 ,
where higher conductivity corresponds to faster charging). Most
PR-EC applications operate within these electrolyte characteristics
(Izquierdo et al., 2010; Shamaei et al., 2018; Yildiz et al., 2008),
and must therefore account for capacitive charging during po-
larity reversal cycling. This effect may explain why no net cur-
rent was observed when operating PR-EC at 60 Hz (17 ms PRT)
(Bian et al., 2019). Additionally, AC-EC is often operated at 50 Hz
(20 ms PRT). Therefore, this strategy may become ineffective when
treating low conductivity waste. This phenomenon may explain
why Ghanizadeh et al., 2016 concluded that AC-EC was ineffective
at removing F− (using iron and aluminum electrodes) from syn-
thetic solutions with low electrolyte concentrations.
It is also possible to prompt electrochemical side reactions fol-
lowing polarity reversal, especially in Fe-EC. Fe-oxyhydr(oxides) are
either comprised of Fe(II), Fe(III), or a combination of both (as de-
scribed in Section 2.3.1.). These species can be oxidized or reduced,
given the right environmental conditions. For example, it is possi-
ble that HFeO2 − (formed during a cathodic cycle in high pH) is
oxidized to FeO2 − during the subsequent anodic period according
to Eq. (29) Bard et al., 1985), which is thermodynamically favorable
over Fe(0)→Fe(II) oxidation (Eq. (9)). Fe(OH)2 formed at the cath-
ode can also oxidize to Fe3 O4 in the alkaline environment imme-
diately following polarity reversal (Fig. 5). Additionally, Fe(III) and
Fe(II/III)-oxyhydr(oxides) formed in the anode vicinity can reduce
to Fe(II) and FeO in a cathodic environment (Eqs. (30)-(34), which
is thermodynamically favorable over H2(g) evolution (E° = 0 V vs
SHE [at pH 0]) (Gorski et al., 2016; Xu et al., 2019).
HFeO− − − − o
2 + OH ↔ FeO2 + H2 O + e E = −0.685 V vs SHE (29)
Fe3+ + e− ↔ Fe2+ E o = 0.771 V vs SHE (30)
Fe(OH )3 + e− ↔ Fe2+ + 3OH− (31)
Fe3 O4 + 2H+ + 2e− ↔ 3FeO + H2 O (32)
M. Ingelsson, N. Yasri and E.P.L. Roberts
α -FeOOH + e− + 3H+ ↔ Fe2+ + 2H2 O E o = 0.768 V vs SHE (33)
α -Fe2 O3 + 2e− + 6H+ ↔ 2Fe2+ + 3H2 O E o = 0.769 V vs SHE (34)
As discussed in Section 2.4., it is also possible to reduce
Fe(II)→Fe(0) at moderate cathodic overpotentials (Fig. 5). For ex-
ample, this phenomenon has been utilized to make batteries
that electroplate Fe(II)→Fe(0) during charging at the cathode, fol-
lowed by oxidation back to Fe(II) during discharge (Hruska and
Savinell, 1981). This effect could also take place in EC, where an-
odically dissolved Fe(II/III) species could be reduced back to Fe(0)
following polarity reversal (Xu et al., 2019). Electroplated Fe(0)
could then be re-oxidized during the subsequent reversal cycle.
Therefore, over the entirety of the operating period, less metal is
transferred from the electrode to the bulk solution. For example,
it has been demonstrated using cyclic voltammetry that Fe(II/III)-
oxyhydr(oxides) are reduced/oxidized at the iron electrode follow-
ing anodic or cathodic current shifts (Yang et al., 2015). However,
the authors did not consider how this would affect faradaic effi-
ciencies in PR-EC. Additionally, H2(g) bubbles sorbed to the elec-
trode surface could be re-oxidized to H2 O upon polarity reversal,
which is also thermodynamically favorable over Fe(0)→Fe(II) oxi-
dation. However, it remains unclear if kinetics allow this reaction
to proceed to a significant extent. Interestingly, it has been shown
that terminating the current for 6 s in between each reversal with
iron electrodes decreases the buildup of the electrode surface layer
by allowing anodically dissolved metal to transfer to the bulk so-
lution (Xin et al., 2018). Consequently, less iron metal is available
to precipitate on the anode when it becomes the cathode.
In Al-EC, the electrochemical properties governing Al(0)→Al(III)
dissolution are different than those in Fe-EC. In particular, Al(III)
cannot be electroplated following polarity reversal due to its
very low reduction potential compared to the hydrolysis of wa-
ter (−1.66 V vs. −0.83 V vs. SHE [at pH 14]). The likelihood of
side reactions induced by polarity reversal is smaller or nonexis-
tent because aluminum does not exhibit the same reactivity as iron
within the electrochemical stability range of water (Roberge, 2008).
In contrast, due to the anodic activation of both electrodes, the
protective Al2 O3 surface layer can be removed and expose more
Al(0) to chemical corrosion that increases coagulant production.
For example, it has been observed that the consumption of alu-
minum electrodes in PR-EC is greater than in DC-EC (Pi et al., 2014;
Wellner et al., 2018). However, similar to iron, higher Al(0) dissolu-
tion rates have been observed with longer PRTs relative to shorter
PRTs (Fig. 14) (Fekete et al., 2016; Hasani et al., 2019). An expla-
nation for this could be that longer PRTs allow the pH boundary
layers at the electrodes to equilibrate, which accelerates chemical
corrosion after the electrode surface layers have been removed. In
contrast, there is not sufficient time to reach the required pH to
corrode aluminum when operating with shorter PRTs (Fig. 9). Ca-
pacitive charging may also affect Al-EC performance at PRTs < 1 s.
A group of Soviet researchers in the 1980s took an alterna-
tive approach, i.e., switching polarity for 5–10 s every 5–6 hrs
when operating with an aluminum anode and a titanium cathode
(Nikolaev et al., 1982). The purpose of this short period of polarity
inversion was to remove the calcium and magnesium precipitates
at the cathode, whereas it was claimed that polarity reversal was
not effective at removing the metal oxide layer at the anode. A
built-in automated scraper was used to remove the anodic surface
layer mechanically. By applying this technique, it was reported that
the current density increased by 6–10 times (when operating po-
tentiostatically) during long term treatment at a municipal water
supply plant.
PR-EC is seemingly effective at removing, delaying, or avoiding
the formation of electrode surface layers, which in turn enhances
19
Water Research 187 (2020) 116433
Fig. 14. Electrochemically dissolved metal with iron and aluminum electrodes at
varying PR frequencies, i.e., PRTs. i = 16 mA cm−2 , NaCl & NaSO4 electrolyte.
Reprinted by permission from Springer Nature Customer Service Centre GmbH:
Springer Journal of Solid State Electrochemistry, Electrochemical dissolution of alu-
minium in electrocoagulation experiments, Fekete et al., Copyright 2016.
treatment performance. This outcome has been particularly evi-
dent in Al-EC, whereas mixed results have been reported for Fe-EC.
Therefore, it is apparent that PRTs associated with long term treat-
ment must be optimized to avoid the adverse effects related high-
frequency polarity reversal, which has been acknowledged before
(van Genuchten et al., 2016). Furthermore, when PR-EC has been
used in field operations, polarity is reversed in between each batch
(Amrose et al., 2014). However, it is possible that this is still too
frequent to avoid the detrimental effects of re-polarizing the elec-
trodes.
If PR-EC is more effective at mitigating fouling and passivation
in Al-EC than in Fe-EC, it could change the cost-benefit analysis
of EC treatment for some applications. However, as mentioned in
Sections 2.3.3. and 2.4., it has been reported that material precip-
itation on the electrodes can be more significant and create oper-
ational problems for Al-EC compared to Fe-EC for operating DC-EC
on the pilot scale, which may have limited the industrial applica-
tion of Al-EC (Schulz et al., 2009). Of course, the electrode selection
will also depend on the solution composition. For example, for re-
moving some contaminants, such as Cr(VI), Fe-EC is more suitable
(Mouedhen et al., 2009).
3.4. Ultrasonication
It has been reported that coupling ultrasonication with EC,
referred to as sono-EC, can be an effective depassivation strat-
egy (He et al., 2016), while improving coagulant formation and
enhancing EC performance (Kovatcheva and Parlapanski, 1999;
Raschitor et al., 2014). Sonolysis can also produce radicals
(Eq. (35)), which mineralize organics while achieving disinfection
(Wang et al., 2009). In sonolysis, the ultrasound forms microscopic
bubbles, referred to as cavities, that collapse once a critical radius
is attained (De Lima Leite et al., 2003). This phenomenon generates
points of high temperatures and pressures, which is conducive to
the formation of radicals.
sonolysis
H2 O → H· + HO· (35)
Ultrasound also dislodges H2(g) bubbles sorbed to the elec-
trodes that reduce conductivity and increase the current density
(Kovatcheva and Parlapanski, 1999). As discussed in Section 3.3.4.,
the presence of hydrogen on the electrodes may also trigger side
reactions in PR-EC. Additionally, Sono-EC can enhance the forma-
M. Ingelsson, N. Yasri and E.P.L. Roberts
Table 5
Reported results from studies investigating sono-EC.
Electrode
Material Sample Type Current Sonication Settings
Fe, Al Tanning Waste 20, 40 mA 40 kHz, 350 W
cm−2
Al Laundry waste 1–7 V 43 kWz, 80 W
Al Dye in Wastewater 2–18 mA cm−2 0–150 W
Al PO4 3− in NaHCO3 60 V 0–450W
Water
Al Synthetic E. coli 0.5–2.5 mA 0.28 & 37 kHz;
solution, 5 g L−1 cm−2 Intermittent (5,
NaCl, pH 7 10 min)
tion of cracks and defects in the electrode (Kovatcheva and Parla-
panski, 1999), which can accelerate the rate of chemical corrosion
by exposing more electrode surface area. This effect could be par-
ticularly beneficial in Al-EC.
Continuous and intermittent sonication have both shown to be
effective at impeding the onset of electrode passivation, which was
confirmed using EIS (He et al., 2016). However, even though con-
tinuous sonication was more effective, coagulant formation was in-
hibited, which resulted in decreased contaminant removal efficien-
cies. Therefore, intermittent sonication proved to be favorable by
accomplishing effective depassivation while avoiding the destruc-
tion of flocs. Adverse effects on EC performance associated with
excessive sonication have been seen elsewhere (He et al., 2018). In
this study, the authors recommended operating at a lower soni-
cation power to mitigate floc destruction. Another study demon-
strated that removing COD from oil tanning waste using contin-
uous sono-EC was not economically sustainable, reporting a to-
tal energy consumption of 435 kWh m−3 (Maha Lakshmi and
Sivashanmugam, 2013). However, it was concluded that sono-EC
was an effective depassivating strategy. Therefore, it was suggested
that sonication could be used when re-starting a reactor with pas-
sivated electrodes. An overview of the studies that have investi-
gated sono-EC is provided in Table 5.
Even though sono-EC has proven to mitigate passivation suc-
cessfully while enhancing treatment performance, installing the
required infrastructure, and accounting for the ensuing operating
costs do not make sono-EC an attractive strategy.
3.5. Other passivation mitigation strategies
Other strategies that have been proposed for avoiding passiva-
tion, fouling, and enhancing EC performance include: mechanically
cleaning the electrodes (Bandaru et al., 2020; Lakshmanan et al.,
2009; van Genuchten et al., 2016); increasing the flow velocity to
enhance hydrodynamic scouring (Chen, 2004; Ghanizadeh et al.,
2016; Timmes et al., 2010); and chemically cleaning the electrodes
with organic acids (Müller et al., 2019). Additionally, temporally
varying the magnitude of a static voltage with 30 min intervals
has shown to decrease energy consumption by 48% in continuous
Al-EC and Fe-EC operations (Genc and Bakirci, 2015). Also, pulsing
a direct current, i.e., intermittently terminating/restarting the cur-
rent without reversing electrode polarity, has been demonstrated
to reduce energy consumption and sludge production by 89% and
30%, respectively (relative to DC-EC) (Zhou et al., 2020). This ef-
fect was attributed to the pulsed current inhibiting the formation
a passivating surface layer.
20
Water Research 187 (2020) 116433
Energy Consumption Conclusions Author
435 kWh m−3 (86% Cont. sono-EC not (Maha Lakshmi and
COD removal) recommended Sivashanmugam, 2013)
140 kWh m−3 (~60% Sono improved COD (Wang et al., 2009)
COD removal; removal
sonication power not
included)
6.38 kWh m−3 (82% Sono-EC reduces (He et al., 2016)
removal) passivation
0.31 kWh m−3 (83% 100 W: least (He et al., 2018)
removal) passivation, best
performance
0.212 $US m−3 Sono-EC reduced (Hashim et al., 2020)
(including treatment time by 56%
electricity + materials)
Using a steel brush to mechanically clean iron electrodes once
a week during long-term operation reduced energy consump-
tion by approximately 33% while enhancing the efficiency of ar-
senic removal (Amrose et al., 2014). Many have suggested that
this is the most effective depassivation strategy (Bandaru et al.,
2020; Lakshmanan et al., 2009; Müller et al., 2019). However, this
method requires terminating the treatment process and disassem-
bling the EC cell, which adds labor costs. In-situ mechanical clean-
ing may be a viable solution, i.e., installing scrapers that remove
the anodic surface layer, which has been shown to work with a
radial electrode configuration (Nikolaev et al., 1982).
It has also been shown that increasing the charge loading rate,
i.e., the current density, inhibits the buildup of the electrode sur-
face layer over long-term Fe-EC operation (Müller et al., 2019). It
was proposed that this effect was caused by the rapid depletion of
dissolved oxygen in the anodic boundary layer by an abundance of
electrochemically generated Fe(II). Consequently, Fe(II)→Fe(III) oxi-
dation was depressed, which decreased the precipitation of insu-
lating Fe(III)-oxyhydr(oxides) on the anode surface. Operating at
high current densities also increases the positive charge of the
anode (Eq. (12)), which intensifies the repulsive effect between
the cationic Fe(II/III) ions and the anode (Alkhatib et al., 2020).
However, an excessively high supporting electrolyte concentration
will diminish the magnitude of coagulant mass transfer by elec-
trophoretic migration. Care should also be taken when increasing
the current density due to the possibility of attracting oxyanions
to the anode surface, causing passivation and triggering side reac-
tions (Hu et al., 2003; Huang et al., 2009; Izquierdo et al., 2010;
Müller et al., 2019; van Genuchten et al., 2017).
Some researchers have tried operating with a horizontal elec-
trode configuration, where the cathode is placed at the bottom,
which allowed H2(g) to percolate through the solution (Abdel-
Aziz et al., 2020). It was claimed that this reactor design enhanced
mass transfer and decreased anodic passivation. Furthermore, us-
ing an oscillating anode has been shown to reduce the cell voltage
in Fe-EC and Al-EC (Panikulam et al., 2018), which was attributed
to improved mass transport of metal-oxyhydr(oxides) from the
anode. Consequently, this technique may inhibit material precip-
itation on the anode. A “self-assembled” electrode consisting of
magnetic iron particles on a non-magnetic substrate has been de-
scribed in a patent as an effective de-fouling method (Xia et al.,
2013). However, quantitative evidence for the performance of this
method has not been presented in the research literature.
Lastly, changing the storage conditions of the electrodes in be-
tween operating cycles has been investigated by some authors
(Müller et al., 2019; Wellner et al., 2018). It was found that stor-
ing iron electrodes in synthetic groundwater in between cycles
M. Ingelsson, N. Yasri and E.P.L. Roberts Water Research 187 (2020) 116433

Table 6
Overview of the advantages and disadvantages of the different depassivation and EC performance strategies.

Strategy Advantages Disadvantages

Aggressive ion addition

• Low cost • Increases sludge production

• Simple • Risk of byproduct formation
• Effective depassivation • May require additional treatment

AC-EC

• Automatable • Low faradaic efficiency

• Uniform electrode corrosion • Uncertain effectiveness
• Low sludge production • Reduces treatment performance
• Low energy consumption by possible side reactions and
• Does not requires chemicals capacitive charging

PR-EC

• Automatable • Optimal PRT dependent on

• Uniform electrode corrosion
• Effective depassivation
• Low sludge production
• Potentially more advantages for
Al-EC
• Does not require chemicals
operating conditions
• Reduces treatment performance
by possible side reactions and
capacitive charging
• Requires optimization
• Requires additional electrical
infrastructure

Sono-EC

• Effective depassivation • Costly

• Could enhance EC performance • Requires additional electrical
• Does not require chemicals infrastructure

Mech. cleaning

• Effective depassivation • Requires manual labor

• Does not require additional • Requires terminating treatment
infrastructure or chemicals

Chem. cleaning

• Possibly effective depassivation • Costly

• In-situ cleaning • Requires chemical addition
• Does not require additional
infrastructure

Increased flowrate

• Possibly effective depassivation • Requires continuous pump

• In-situ cleaning • Costly
• Does not require chemicals • Does not permit batch EC

had a detrimental effect on faradaic efficiency and EC performance All these strategies have been shown to be successful at
once the reactor was restarted due to the formation of a passivat- mitigating passivation under suitable conditions. However, each
ing and coagulant-trapping surface layer (Müller et al., 2019). Oth- method has drawbacks that need to be considered. For exam-
ers found that storing aluminum electrodes in a salt solution (1 g ple, excessive aggressive ion concentrations may generate haz-
L−1 NaCl) minimized the formation of a passivating surface layer, ardous byproducts and increase sludge production. While imple-
and increased treatment performance upon re-starting the reactor menting some form of alternating electrode polarity is the most
(Wellner et al., 2018). commonly used passivation control strategy, studies have shown
that there are also drawbacks to this technique. For example, AC-
4. Conclusions EC or high-frequency PR-EC with iron electrodes may accelerate
electrode fouling while triggering side reactions that divert the
The different strategies that have been proposed to de- current and depress faradaic efficiency. PR-EC with aluminum elec-
crease/avoid passivation, and to enhance long-term EC perfor- trodes may mitigate severe passivation that can occur in some sys-
mance include: tems, which could make Al-EC a more attractive option than Fe-EC
for continuous long-term operation, depending on operating con-
• aggressive ion addition ditions. It is also more suitable to operate PR-EC with aluminum
• alternating current operation electrodes because this system is not prone to reversible electro-
• polarity reversal operation chemical reactions, which likely reduce the faradaic efficiency in
• ultrasonication Fe-EC. However, care should be taken to avoid residual aluminum
• mechanical cleaning of electrodes due to its toxicity (Singh et al., 2017). Ultrasonication is effective
• chemical cleaning of electrodes but likely too costly for the conditions investigated to date. How-
• hydrodynamic scouring

21
M. Ingelsson, N. Yasri and E.P.L. Roberts
ever, this strategy could potentially be used as an in-situ electrode
cleaning technique in between treatment cycles. Mechanical clean-
ing is seemingly the most effective strategy at decreasing passiva-
tion and enhancing EC operation. However, this strategy increases
labor costs and requires shutting down treatment. Therefore, it
should be avoided as much as possible. In-situ cleaning using auto-
mated electrode scraping mechanisms merits further investigation.
A compilation of the advantages and disadvantages of each method
is provided in Table 6.
Based on the findings in this study, the most promising pas-
sivation control strategies are aggressive ion addition, PR-EC, and
mechanical cleaning of the electrodes. EC developers and opera-
tors should incorporate a combination of these strategies in their
process designs. However, parameters such as the concentration of
aggressive ions and PRT should be optimized based on specific op-
erating conditions. Failing to optimize a strategy could lead to de-
creased treatment performance or operational challenges. There-
fore, the processes, passivation mechanisms, and depassivation
strategies discussed in this article should be considered when as-
signing operating parameters in the design of EC systems. The se-
lection of electrode material should also be carefully considered
because passivation characteristics can vary significantly depend-
ing on the application.
It is also clear that the nature and mechanisms of depassivation
by aggressive ion addition and polarity reversal are sensitive to the
water composition, and are not well understood. Further studies of
the mechanisms of passivation and depassivation as a function of
water composition and operating conditions are needed to provide
deeper insight into these processes. Lastly, studies investigating the
effectiveness of implementing depassivation strategies during long-
term continuous EC operation are needed. More research is also
required to further understand the relationship between EC perfor-
mance, solution composition, and operating conditions.
Funding
This research was funded by the Natural Science and Engineer-
ing Research Council of Canada (STPGP 506,951–2017).
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Acknowledgments
The authors would like to thank Dr. Anh Pham and Héline Chow
at the University of Waterloo for sharing their expertise during the
writing process.
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