Desalination 250 (2010) 6–13

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

Electrocoagulation pretreatment of seawater prior to ultrafiltration: Pilot-scale

applications for military water purification systems
Thomas C. Timmes, Hyun-Chul Kim, Brian A. Dempsey ⁎
Department of Civil and Environmental Engineering, Pennsylvania State University, University Park, PA 16802, USA

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

Article history: The objectives were to investigate the performance of a pilot-scale electrocoagulation (EC) reactor and to
Received 17 February 2009 determine the feasibility of using in-line EC as a pretreatment to ultrafiltration (UF) of seawater. Work was
Accepted 6 March 2009 conducted at Port Hueneme, CA, using components of a U.S. military water purification system. Ferric chloride in-
Available online 14 October 2009
line coagulation was also tested. Both the EC and ferric chloride pretreatments improved UF membrane
performance compared to UF without in-line coagulation. EC resulted in slightly greater increases in
Keywords:
Electrocoagulation
transmembrane pressure (TMP) than observed following ferric chloride pretreatment during sub-critical flux
Pretreatment UF. Substantial accumulation of precipitates developed on the EC electrodes during the testing period. X-ray
Ultrafiltration diffraction identified magnetite, maghemite, lepidocrocite, and akaganeite phases. Accumulation of these
Corrosion precipitates was due in part to conservative hydraulic design of the EC unit. It is recommended that EC units
Seawater should be designed with short hydraulic retention times and higher electrode current density in order to increase
upflow (scour) velocity and thus inhibit accumulation on the electrodes. Progressively longer cycling times for
polarity reversal are also recommended. This research indicates that EC offers the potential for a feasible and
effective pretreatment strategy for mobile water production facilities.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction 2. Background

The objective of this research was to determine the feasibility of
using electrocoagulation (EC) as a pretreatment for seawater prior to
ultrafiltration (UF) at the pilot-scale. The experimental objectives
were (1) to investigate the performance of the pilot-scale EC reactor
and (2) to compare the effects of EC and ferric chloride pretreatment
based on increase in transmembrane pressure (TMP) during sub-
critical flux UF. Pilot-scale EC and chemical coagulant experiments
were conducted at the Naval Facilities Engineering Service Center
Seawater Desalination Test Facility in Port Hueneme, California, using
components of a U.S. military water purification system. Bench-scale
EC and ferric chloride experiments, using modified seawater from the
U.S. Army Coastal Seawater Purification Test Facility at Fort Story,
Virginia, were conducted prior to the pilot-scale tests (published
separately). This paper highlights the significant observations,
applications, and challenges from the pilot-scale testing of EC
pretreatment to provide insight and direction for further research.
⁎ Corresponding author. Department of Civil and Environmental Engineering,
Pennsylvania State University, 212 Sackett Building, University Park, PA 16802-1408,
USA. Tel.: +1 8148651226; fax: +1 8148637304.
E-mail addresses: Thomas.timmes@us.army.mil, timmes@psu.edu (T.C. Timmes),
bad5@psu.edu (B.A. Dempsey).
2.1. Military water purification
It is projected that 40% of the world's population in 2015 will live in
countries that are classified as “water-stressed” due to water quantity and
quality issues [1]. Thus it is likely that desalination will be an increasingly
important technology for the provision of clean and safe water. The U.S.
military requires generation of potable water throughout the world and
on short notice. Logistical constraints such as volume and weight of a
deployed system, on-site power requirements, and re-supply frequency,
are critical factors in the planning and execution of potable water
missions. In the early 1980s, the Army selected reverse osmosis (RO) as
the preferred technology to produce potable water from fresh, brackish,
or seawater sources. The pretreatment stage was initially polymer-based
coagulant followed by sand and anthracite mixed-media filtration, using
the 600 gal/h Reverse Osmosis Water Purification Unit (ROWPU).
Subsequently, microfiltration (MF) was used as pretreatment to RO
with the Tactical Water Purification System (TWPS), and then UF prior to
RO in the Lightweight Water Purifier (LWP) and the U.S. Navy's
Expeditionary Unit Water Purification (EUWP) system. Fig. 1 shows
each of these military water purification systems.
The LWP and EUWP use the same UF membranes, but the EUWP has a
larger form factor. The EUWP was deployed in 2005 to provide potable
water following Hurricane Katrina. The capability of its UF membranes to
provide pretreatment for seawater has been previously reported in this

0011-9164/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2009.03.021
 T.C. Timmes et al. / Desalination 250 (2010) 6–13
Fig. 1. Military Water Purification Equipment. Pictured are (a) the Reverse Osmosis Water Purification Unit (ROWPU), (b) the Tactical Water Purification System (TWPS), (c) the
Expeditionary Unit Water Purifier (EUWP) UF stage, (d) the EUWP RO Stage, and (e) the Lightweight Water Purifier (LWP). Stock photos courtesy of the U.S. Army.
journal [2]. The LWP was deployed in Iraq and Afghanistan to support
company sized units and is capable of producing 125 gal/h using fresh or
brackish water and 75 gal/h using seawater [3]. The LWP is a full scale
system, but the small size allows it to be used as a pilot-scale
representation of the Navy's Expeditionary Unit Water Purifier (EUWP),
and it is used in that mode for the current work.
EC has some potential tactical and logistic advantages over liquid
chemical coagulants. Electrodes are 100% iron by mass while liquid
coagulants range from 14 to 22% iron [4]. Liquid coagulants are
corrosive. Ferric chloride is particularly corrosive and requires special
handling. Thus, solid electrodes decrease volume, mass, and the hazards
associated with supplying liquid coagulants to remote locations.
This research focuses on the effects of in-line coagulation on UF.
Current Army doctrine dictates that all Army water purification
systems utilize reverse osmosis for production of potable water,
regardless of water source [5]. The option of using only UF when
treating certain freshwater sources (with doctrinal approval from the
Armed Forces Surgeons General) would dramatically increase the
quantity of water produced from the LWP and the EUWP and would
predictably lessen energy, operational, and maintenance costs.
Therefore the results from this research should be useful for stand-
alone production of UF water as well as for desalination.
2.2. Pretreatment of seawater
The goal of pretreatment for desalination systems is to provide a
consistent and high quality feedwater to mitigate the flux decline of RO
7
membranes. Seawater adversely impacts RO membranes primarily by
two mechanisms: scaling (inorganic precipitates) and fouling (due to
biofouling, organics adsorption, and pore-blocking by colloids) [6]. While
coagulation generally has little effect on scaling, coagulation pretreatment
can be effective for the removal of microorganisms, colloids, and organics
that are often responsible for membrane fouling. Pretreatment technol-
ogies for RO systems have advanced from conventional coagulation and
multimedia filtration, to MF, UF, and nanofiltration [7]. For a coastal Pacific
Ocean seawater with similar characteristics to the seawater used in this
present pilot-scale study, use of either MF or UF provided superior
pretreatment compared to conventional pretreatment for RO membranes
[8]. Lifecycle costs of the technologies verses the benefits realized by the
reduced fouling on the RO membranes typically dictate the appropriate
strategy given the scale of the operation. This research examines only the
EC pretreatment benefits and effects on the ultrafilters, although RO
membranes are clearly required for desalination of the seawater.
2.3. Electrocoagulation theory
The theoretical production of iron from the electrochemical
dissolution of iron anodes can be calculated by applying Faraday's 2nd
Law (Eq. (1)).
Þ = IM = Fn
−1 −1
Fe generated ðmg s e · ð1000 mg g Þ: ð1Þ
Where I is the applied current in Amps (coulombs/second), M is
the molecular weight of iron 55.85 g/mol), F is the Faraday constant
8 T.C. Timmes et al. / Desalination 250 (2010) 6–13

(96,485 C/mol), and nē is the number of electrons transferred in the

reaction (2e−/Fe ion). In a near neutral pH solution with adequate
dissolved oxygen, ferrous ion (Fe2+) produced at the anode will
undergo hydration, oxidation to ferric iron (Fe3+), and hydrolysis to
form ferric hydroxide precipitate (Eq. (2)). The hydrogen gas in
Eq. (2) is generated at the cathodes as an electrolysis product
(electrochemical water reduction) and could be recovered in order to
decrease the net energy required for the EC process.

5 1
Fe þ =2 H2 O þ =4 O2ðgÞ →FeðOHÞ3ðsÞ þ H2ðgÞ : ð2Þ

While this equation has been useful for predicting the total iron
concentration in the effluent from a bench-sale EC reactor, it does not
account for the galvanic (chemical) corrosion of iron immersed in
seawater (without an externally applied current). The contribution
from galvanic dissolution of the electrodes is a function of the
submerged iron surface area and water chemistry.
Iron accumulations on the electrodes and on the reactor walls can
affect the provision of coagulant, due to accumulation or due to
occasional sloughing of corrosion scale. This can result in a greater
variety of iron species produced by a pilot-scale reactor and may cause
transient spikes in the iron concentration. Settling of some iron
corrosion products in the reactor is also a possibility if the reactor
loading rate is insufficient to hydraulically promote movement of the
corrosion scale to the reactor outlet (settling rate > surface loading
rate). The iron species exiting an EC reactor can also vary based on the
seawater pH, dissolved ionic species, and the dissolved oxygen
concentration. With insufficient dissolved oxygen in the seawater to
ensure oxidation to the ferric state, a ferrous hydroxide intermediate
may develop [9]. “Green rust” (layered ferrous-ferric hydroxides) has
also been previously reported [10]. During the pilot-scale testing,
aerobic conditions were maintained in the continuous flow EC reactor
and a post-reactor detention (equalization) basin promoted oxidation
of ferrous intermediates to a ferric state prior to UF.
Fig. 2. The Pacific Ocean intake at the Naval Facilities Engineering Service Center Seawater
Desalination Test Facility in Port Hueneme, California, used for the pilot-scale studies.
3. Materials and methods
3.1. Seawater sample
The seawater used in this pilot-scale study was collected from the
Pacific Ocean via a surface water intake located in a shipping port at
the Naval Facilities Engineering Service Center Seawater Desalination
Test Facility in Port Hueneme, California (Fig. 2). The intake seawater
quality has been previously reported [2]; analytical results from this
study were similar and are reported in Table 1. No adjustments of pH,
TDS, or temperature were made to the Pacific Ocean seawater prior to
the pilot-scale testing. The seawater was briefly stored in a 1000
gallon storage tank (<3 h detention time) before being pumped to the
pilot-scale EC reactor.

3.2. Pilot-scale electrocoagulation reactor and ferric chloride dosing

2.4. Corrosion of iron in seawater
An upflow EC reactor was obtained from a commercial vendor (Powell
The “natural” corrosion of iron in seawater (without externally
Water Systems, Inc., Centennial, CO). At the time of this study, no
supplied current) can be modeled as a series of galvanic reactions. At the
commercial EC system had been specifically designed for seawater
iron-seawater interface, ferrous ions (Fe2+) generated from the zero-
pretreatment. The purchased unit was designed to match the 24.2 L/min
valent iron initially form a Fe(II) hydroxide intermediate, Fe(OH)2. In
(6.4 gal/min) capacity of the LWP, based on the vendor's experiences with
the presence of dissolved oxygen, this intermediate product oxidizes to
other EC applications. Table 2 compares the operating and design
an amorphous Fe(III) oxide scale, often described as hydrated (or
parameters of the pilot-scale EC reactor and the reactor used in a previous
hydrous) ferric oxide or ferric hydroxide, 2Fe2O3 · 3H2O or Fe(OH)3. The
bench-scale study. The total volume of the pilot-scale reactor was 56.85 L
accumulated corrosion scale restricts diffusion of dissolved oxygen,
(15 gal). Much of this volume was the freeboard above the electrodes and
allowing an inner layer of magnetite (Fe3O4) to form. This magnetite
the inlet zone below the electrodes. The total volume in contact with the
layer effectively can inhibit or prevent diffusion of dissolved oxygen
electrodes was also reduced by the volume of the electrodes themselves
from the bulk solution to the bare metal [11]. Within this anaerobic
(up to 17 iron electrodes each 19.05 cm×50.8 cm ×0.318 cm). The
environment, over time, sulfate-reducing bacteria (SRBs) may impact
electrodes fit into 0.635 cm (1/4 in.) slots, and the equivalent area was
the corrosion process. A ferric layer of lepidocrocite (γ-FeOOH) can form
excluded for surface area and current density calculations. Only 3 of the 17
and this may transition to a sulfated green rust [GR(SO2− 4 )] that is also
electrodes were directly powered. For the configuration shown in Fig. 3,
influenced both by SRBs and the interface with dissolved oxygen in the
the effective reactor volume was 16.1 L (4.25 gal) providing a detention
seawater [12]. Sulfated green rusts form as a hexagonal crystal structure
time during contact with the electrodes of approximately 40 s at a
(pyroaurite-type) with stacked Fe(II) and Fe(III) layers of alternating
flowrate of 24.2 L/min (6.4 gal/min). The loading rate was 18 m h− 1,
positive charge (hydroxide layer) and negative charge (hydrated
anion layer) commonly modeled as FeII4 FeIII 2 (OH)12SO4 · 8H2O [13] or
4Fe(OH)2 · 2FeOOH∙FeSO4 [14]. In seawater, despite the high ionic ratio
of [Cl−]/[SO2−
4 ], the sulfated green rusts form instead of the chloride
Table 1
Seawater quality for the pilot-scale study.
green rusts, GR(Cl−), due to sulfate affinity for divalent anions [12].
Other researchers using X-ray diffraction techniques have identified Parameter Port Hueneme, Ca. seawater (pilot-scale)
goethite (α-FeOOH), akaganeite (β-FeOOH), and maghemite (γ-Fe2O3) pH 8.0
on corroded iron and sludge generated from the EC process [15,16]. The Temp (oC) 17
bulk solution pH, dissolved oxygen concentration, applied current, and Total dissolved solids (mg/L) 33,000
the time-scale of the experiment can influence the nature of iron Turbidity (NTU) <1
Iron (mg/L) 0.06
corrosion products.
 T.C. Timmes et al. / Desalination 250 (2010) 6–13 9

Table 2
Operating and design parameters of the current pilot-scale EC reactor and previous bench-scale EC reactor.

Parameter Units Current pilot-scale Previous bench-scale study Comment

Flowrate L min− 1 (gpm) 24.2 (6.4) 0.5–1.5 (7.9–23.8) Constant for pilot-scale
Variable for bench-scale
Effective reactor volume Liters (gal) 16.1 (4.25) 0.18 (0.05) Defined by submerged electrodes
Upflow velocity m h− 1 18 230a a
for 1 L min− 1 flowrate
Detention time Seconds 43 10b b
for 1 L min− 1 flowrate
Voltage Volts 16–19 c 0.4–0.8 c
Cyclic, with polarity reversal (pilot-scale)
Amperage Amps 25–35d 0.1–0.5 d
Cyclic, with polarity reversal (pilot-scale)
Anodic surface area m2 1.55e 0.0166 e
calculated as 1/2 of all electrode surfaces since polarity was cycled
Anodic current density Amps m− 2 19 f 18 f f
using average amperage value

compared to 230 m h− 1 for the bench-scale EC reactor operating at 1 L/
min. The electrode polarization was alternated at variable intervals
(between 30 and 250 s) to reduce scale formation and maintain
consistent iron dosing. The reactor effluent flowed into a 265 L (70 gal)
detention basin before being pumped to the LWP UF unit. The pilot-scale
EC electrodes and reactor chamber were cleaned prior to testing using
10% sulfuric acid. The EC system was operated continuously for 222 h in
support of the pilot-scale UF testing.
The electronics of the pilot-scale EC reactor were operated by a
proprietary programmable logic controller (PLC) system. This system
controlled the power in a cyclic manner, by reversing polarity at user
programmed intervals. Neither current nor voltage remained constant, as
shown in Fig. 4a. The associated power demand is presented in Fig. 4b.
When the system was operated with a short fixed-time polarity cycle
(30 s), the effluent iron dose from the EC unit fell from the starting value of
about 0.75 mg/L to below 0.5 mg/L within 24 h, accompanied by an
accumulation of iron precipitates on the electrodes. It was discovered that
progressively lengthening the polarity reversal times resulted in more
constant iron dosing, apparently due to enhanced scouring by hydrogen
bubbles during cathodic operation. The initial polarity reversal time was
30 s, but gradually increased throughout the testing period, culminating at
250 s after 222 hours of operation (approximately 1 additional second for
every hour of operation). Progressive variation of the polarity cycle has not
been previously reported as an operational variable for EC systems. Iron
dosing by EC averaged 0.73 mg/L (including 0.06 mg/L in the feed water).
The ferric chloride pretreatment dose was 0.79 mg/L as Fe (including
0.06 mg/L in the feed water). This applied iron dose was maintained in the
range of 0.72–0.81 mg/L by metering in a ferric chloride slurry at a rate of
12.4 mL/min on the suction side of the UF feedwater pump. The slurry
consisted of 6.6 mL of commercial grade (42%) ferric chloride (Kemira
Water Solutions, Inc., Fontana, CA) mixed in 1 L of RO water.
3.3. Pilot-scale UF system
The UF module of the U.S. Army's LWP (MECO Inc., Sugarland, TX)
was used in this work. The UF component is rated at 19.6 L/min
(310 gal/h) from seawater or freshwater. The RO component system
can produce 7.9 L/min (125 gal/h) from freshwater and 4.7 L/min

Fig. 3. Pilot-scale electrocoagulation and ultrafiltration schematic. The inset (plan view) details the electrode configuration.
10 T.C. Timmes et al. / Desalination 250 (2010) 6–13

Fig. 5. Pilot-scale EC reactor iron dosing trend (a) and impact on pH following
electrocoagulation (b).

Fig. 4. Pilot-scale EC reactor current and voltage cyclic program (a) and power demand
(b). Electrode polarity reversal frequency at 145 s (2 cycles shown).
(75 gal/h) from seawater. The UF system uses 3 commercially
available 100 kDa polysulfone hollow-fiber bundled cartridges (Romi-
con® HF82-35-PMC, Koch Membrane Systems, Inc., Wilmington, MA)
providing a total filtration area of 22.8 m2. An automated backwash
with UF-finished water is run every 15 min followed by a forward
“fast-flush” with feed water. The UF membranes typically operate at
90% recovery in a “feed and bleed” configuration (reject water not
recycled to the feedwater).
Data were collected manually, including the following: feed, reject,
and permeate pressures; permeate and reject flows; and pressures
achieved during backwash and “fast-flush” hydraulic cleaning cycles.
TMP and specific flux were corrected for temperature. The LWP was
run continuously with minimal downtime during each testing cycle. A
baseline seawater run using new UF membranes and no coagulant
pretreatment was performed prior to the EC and ferric chloride
pretreatment studies. For the baseline seawater testing, a TMP of
29 psi was reached after 290 h of continuous operation, indicating the
need for chemical cleaning. The membranes were chemically cleaned
using a citric acid and high pH chlorination protocol. A pure water flux
test (using RO treated water) verified that an acceptable initial TMP
was achieved before starting the next test. The same hollow-fiber UF
membranes were used throughout the studies.
The pilot-scale EC reactor experienced substantial accumulation of
iron precipitates on the electrodes and inside the reactor chamber,
while such significant accumulations were not previously observed
with our bench-scale EC unit, nor has it been reported in the literature.
This may have been due to longer operation times at pilot-scale, but
also could have been due to much lower water scouring velocity
(surface loading rate) for the pilot-scale unit compared to our bench-
scale unit. Low scour velocity and surface loading rate resulted in mass
transfer limitations near the electrode surfaces and accumulation of
precipitates. Visually, a black and reddish-orange iron layer developed
on the electrodes within a few hours of operation and millimeter sized
“hairs” occasionally detached and overflowed from the EC unit.
Smaller and denser flakes and black specks were also observed. Some
precipitates overflowed to the detention basin and some settled to the
bottom of the EC reactor.
Fig. 6, a photograph of the reactor chamber (top view) at the end of
the 222 h test, shows the extent of the iron accumulation on the
electrodes and reactor walls and the variation in corrosion for powered

4. Results and discussion

4.1. Pilot-scale electrocoagulation reactor performance

A straightforward application of the Faraday law (Eq. (1)) is not

applicable given the cyclic amperage cycle. The iron dose from the EC
reactor ranged from 0.6 to 1.0 mg/L (Fig. 5a). The average iron
concentration applied to the UF membranes was 0.73 mg/L as Fe
(which included 0.06 mg/L Fe in the raw seawater). EC had a very Fig. 6. Pilot-scale reactor chamber (plan view) at the end of the 222 h testing period. Note
small effect on pH of the treated seawater (Fig. 5b), typically resulting the accumulation of iron on the powered electrodes, non-powered (bipolar) electrodes,
in a pH drop of about 0.04. and on the walls of the reactor chamber.
 T.C. Timmes et al. / Desalination 250 (2010) 6–13
Fig. 7. Non-powered electrode next to the center powered electrode. Locations for X-ray
diffraction samples noted.
and non-powered electrodes. The greatest amount of accumulation
(thickest corrosion scale) was observed on the powered electrodes. The
photograph in Fig. 7 shows fairly uniform corrosion of a non-powered
electrode that was located next to the center powered electrode.
X-ray diffraction (XRD) using a Scintag diffractometer (Thermo Fisher
Scientific Inc., Waltham, MA) revealed that iron precipitates on the
powered electrodes consisted predominantly of magnetite and maghe-
mite (Fig. 8). Examination of one of the non-powered electrodes (next to
the center powered electrode) showed magnetite, maghemite, lepido-
crocite and akaganeite at the bottom of the electrode (after 1 day of
operation), but no lepidocrocite and only a trace of akaganeite was
present at the top of the electrode (Fig. 9). Precipitates were quite small
and there was very little accumulation of solids in the unmixed 265 L
(70 gal) detention basin. This observation may be important in terms of
operation and required downtime when in-line EC is used. The purpose of
the detention basin (~10 min) in this work was to better ensure oxidation
of Fe(II) to Fe(III) to avoid possible adverse impacts due to precipitation
Fig. 8. XRD Analysis of electrode accumulations taken from the top of a non-powered electrode midway between two powered electrodes (a) and the top of the center powered
electrode (b). Approximate XRD peaks: lepidocrocite (6.31 A, 3.29 A, 2.46 A, and 1.93 A), akaganeite (7.53 A), magnetite and maghemite (2.53 A, 4.72 A, 2.96 A, 2.09A).
11
on/in the ultrafilters. Fe(II) average concentration in the feed water was
0.01 mg/L and was 0.08 mg/L exiting the detention basin.
4.2. Pilot-scale UF system performance
Fig. 10a shows the beneficial effect of EC and ferric chloride in-line
pretreatment on TMP during ultrafiltration. Since the backwash and
fast-flush were conducted automatically every 15 min, the effects of
hydraulic cleaning are reflected in this figure. Both EC and ferric
chloride addition substantially reduced TMP build-up compared to no
in-line coagulation. Ferric chloride pretreatment produced slightly
better UF performance results than achieved using EC.
Specific flux was consistently highest for ferric chloride and lowest
for no coagulant (Fig. 10b). Ferric chloride coagulant consists of Fe+ 3
and dilution in the feed water results in immediate production of
amorphous ferric hydroxide, Fe(OH)3. Thus the coagulant species for
ferric chloride were considerably less diverse than the precipitated plus
dissolved species that form during EC. We have demonstrated in bench-
scale tests that the coagulant species from EC are similar to those
produced by ferric chloride, although the size distribution of particles
appears to be smaller. While both pretreatment strategies yielded
improved UF membrane performance compared to the raw seawater,
the UF permeate must still undergo RO treatment before it is suitable for
drinking. Although the ferric chloride pretreatment outperformed the
EC pretreatment, both pretreatment strategies successfully reduced
fouling of the ultrafilters and yielded product water suitable for RO
feedwater. In both coagulation cases, the ultrafilters were restored to
initial flux conditions by chemical cleaning, although the terminal TMP
(30 psi) was not reached during the pretreatment studies.
4.3. Challenges for seawater electrocoagulation pretreatment
An initial challenge was to operate the EC system to produce a
consistent low dosage. Commercial EC systems have been designed to
treat high-strength industrial wastes and may be less practical for
dosing low concentration of coagulant. EC treatment of high-strength,
colored waste streams has typically involved high doses of coagulant
in order to oxidize and bleach by Fenton's reagent as well as to create
sweep floc to assist with subsequent settling or flotation. Examples
include ammonia removal in leachate [17], oil and grease separation
12 T.C. Timmes et al. / Desalination 250 (2010) 6–13
Fig. 9. XRD Analysis of pilot-scale EC reactor electrode accumulations taken from the center powered electrode (a), the top edge (b) and bottom edge (c) of a non-powered electrode
next to the center powered electrode.
in restaurant wastewater [18], and reactive dye decolorization from
cotton milling wastewater [19]. Production of voluminous floc may be
problematic for UF, since accumulation of solids can result in
excessive head loss and eventual clogging. Inclusion of a sedimenta-
tion stage would add to pretreatment costs, logistical footprint, and
system complexity. Also, some contaminants are more effectively
removed with production of green rust, but the presence of Fe(II) can
be detrimental for membrane filtration [20]. The ability of iron-based
coagulants to remove natural organic matter (NOM) was also not a
key consideration in these experiments, since NOM in seawater is
Fig. 10. Transmembrane pressure (a) and specific flux (b) trends during pilot-scale
ultrafiltration tests. Effects from EC and ferric chloride pretreatments plotted with raw
seawater (no coagulant) tests.
<0.5 mg/L and production of disinfection by-products is usually not a
critical consideration in treatment of seawater.
Accumulation of Fe(III)/Fe(II) precipitates on the EC electrodes
also presented an operational challenge in this study. Commercial EC
systems chemically clean the iron electrodes using a 10% sulfuric acid
solution, with additional mechanical scraping when necessary. The
transportation and use of strong acid is undesirable for the applica-
tions that were motivations for this study. Other strategies to address
problems associated with accumulation of precipitates on the
electrodes have included low-frequency sonication [21], electromag-
netic fields [22], and modifications of the electrode shape and the feed
water flow path [23]. These options all have drawbacks, including
higher energy demand, more intensive maintenance requirements,
and increased structural and operational complexity.
4.4. Design considerations
The EC pilot system that was used in this study exhibited low
overall efficiency in generation of coagulant, due largely to accumu-
lation of precipitates on the electrodes. A smaller reactor with fewer
electrodes might be preferable. Increased tangential flow would
improve scouring of precipitates from the electrodes and would
increase the mass transfer coefficient from the electrode to the bulk
solution. For seawater pretreatment prior to desalination operations,
future EC reactor design should be based on the concept of EC as a
dosing platform rather than a treatment process. A specific goal
should also be to minimize the accumulation of iron on the electrodes
and in the reactor.
It is instructive to compare the bench-scale and pilot-scale EC
reactors that were used in this research. The EC reactors are described in
Table 1. The EC pilot-scale unit had only 3 of 17 electrodes directly
powered, and the averaged current density was used for this
comparison. Current density was similar for the two reactors, but the
EC reactors had much different tangential velocities, i.e., 385 cm min− 1
for the bench-scale unit and 30 cm min− 1 for the pilot-scale EC device.
Tangential velocity divided by channel width is a predictor of the mass
transfer coefficient from the electrode surface to the bulk solution, and
this value was almost two orders of magnitude higher for the bench-
scale unit (960 min− 1) than for the pilot-unit unit (11 min− 1). Some
more sophisticated options for comparing the generation of coagulant
 T.C. Timmes et al. / Desalination 250 (2010) 6–13
transport away from the electrode may be possible [24,25]. This is a
subject for further investigation. At this point our evaluations indicate
that much higher flow velocities and narrower channels should be
considered for use in pilot-scale units for in-line coagulation prior to
ultrafiltration.
5. Conclusions
• Progressive iron accumulation in the pilot-scale EC reactor countered
efforts to achieve a steady-state electrocoagulated effluent iron dose.
• While Faradaic equations can predict the theoretical amount of anodic
electrochemical corrosion, iron accumulation in the pilot-scale EC
reactor made them less useful for estimating the actual effluent iron
concentration.
• Surface loading rate and tangential velocity at the electrode surface
are important design parameters that influence the mass transfer of
iron away from the electrodes. Values for these parameters appeared
to be too low in the pilot-scale reactor.
• Progressive lengthening of the electrode polarization time interval
effectively maintained the effluent total iron dosage in the desired
range and allowed the EC reactor to operate continuously, without
acidic cleaning, for 222 h.
• Corrosion of the powered and non-powered bipolar electrodes
contributed magnetite, maghemite, lepidocrocite, and akaganeite to
the total effluent iron dosage and to the developing cake layer on the
UF membrane surface.
• The EC generated cake layer was less efficiently removed after
hydraulic cleaning than the ferric chloride-based cake layer, which
resulted in higher transmembrane pressure over (ultrafiltration) time.
• Both pretreatment strategies successfully reduced fouling of the
ultrafilters and yielded product water suitable for RO feedwater.
• While experiments at the pilot-scale indicate EC is effective from a
pretreatment standpoint, additional EC reactor design and econom-
ic considerations are needed to optimize system practicality and
sustainability during field water purification operations.
Acknowledgements
This work was supported by the U.S. Army Research Office
(W911NF-07-1-0436). The mention or use of any commercial products
is not to be construed, and does not imply, in any manner, official U.S.
Army or U.S. Navy endorsement of said product, but is intended only for
identification of a specific product. Additional planning and support for
the pilot-scale electrocoagulation study was provided by Dr. Mike
Mickley, P.E., of Mickley & Associates and Scott Powell of Powell Water
Systems, Inc. On-site support in Port Hueneme, California, was provided
by William Varnava, P.E., of the Naval Facilities Engineering Service
Center Seawater Desalination Test Facility and Andrew Tiffenbach and
Yuliana Porras from the U.S. Bureau of Reclamation. On-site support and
assistance in all phases of the work was provided by Mark C. Miller, U.S.
Army Tank-Automotive Research, Development and Engineering
Center. This research is part of the Ph.D. dissertation of Thomas C.
Timmes.
13
References
[1] U.S. Army, Operations, Field Manual 3–0, Headquarters, Department of the Army,
Washington D.C., 2008.
[2] D. Halpern, J. McArdle, B. Antrim, UF pretreatment for SWRO: pilot studies,
Desalination 182 (2005) 323.
[3] Internet, UF membrane cartridges speed deployment of tactical water purification
systems, WaterWorld On-line, PennWell Corporation, Tulsa, OK, http://ww.
pennnet.com/display_article/334986/41/ARCHI/none/Caseo/1/UF-membrane-
cartridges-speed-deployment-of-tactical-water-purification-systems/ (2008).
[4] B. Dempsey, Coagulation characteristics and reactions, in: G. Newcombe, D. Dixon
(Eds.), Interface Science in Drinking Water Treatment: Theory and Applications,
2006, Chapter 24.
[5] U.S. Army, Sanitary Control and Surveillance of Field Water Supplies, Technical
Bulletin Medical 577, Headquarters, Department of the Army, Washington D.C, 2005.
[6] M. Kumar, S. Adham, W. Pearce, Investigation of seawater reverse osmosis fouling
and its relationship to pretreatment type, Environmental Science and Technology
40 (2006) 2037.
[7] P. Wolf, S. Siverns, S. Monti, UF membranes for RO desalination pretreatment,
Desalination 182 (2005) 293.
[8] M. Kumar, S. Adham, J. Decarolis, W. Pearce, Comparative seawater RO pretreatment
evaluation using bench- and pilot-scale testing, E-journal AWWA 99 (2007) 168.
[9] M. Mollah, S. Pathak, P. Patil, M. Vayuvegula, T. Agrawal, J. Gomes, M. Kesmez, D.
Cocke, Treatment of orange II azo-dye by electrocoagulation (EC) technique in a
continuous flow cell using sacrificial iron electrodes, Journal of Hazardous Materials
109 (2004) 165.
[10] H. Moreno-Casillas, D.L. Cocke, J.A.G. Gomes, P. Morkovsky, J. Parga, E. Peterson, C.
Garcia, Electrochemistry behind electrocoagulation using iron electrodes, Elec-
trochemistry Society Transactions 6 (2007) 1.
[11] P. Refait, J.B. Memet, C. Bon, R. Sabot, J.M.R. Génin, Formation of the Fe(II)-Fe(III)
hydroxysulphate green rust during marine corrosion of steel, Corrosion Science 45
(2003) 833.
[12] P. Refait, M. Abdelmoula, J.M.R. Genin, R. Sabot, Green rusts in electrochemical and
microbially influenced corrosion of steel, Comptes Rendus Geoscience 338 (2006) 476.
[13] S. Pineau, R. Sabot, L. Quillet, M. Jeannin, C. Caplat, I. Dupont-Morral, P. Refait,
Formation of the Fe(II-III) hydroxysulphate green rust during marine corrosion of
steel associated to molecular detection of dissimilatory sulphite-reductase,
Corrosion Science 50 (2008) 1099.
[14] P. Refait, J.M.R. Génin, The transformation of chloride-containing green rust one
into sulphated green rust two by oxidation in mixed Cl− and SO2- 4 aqueous media,
Corrosion Science 36 (1994) 55.
[15] A. Gismelseed, M. Elzain, A. Yousif, A. Al Rawas, I.A. Al-Omari, H. Widatallah, A.
Rais, Identification of corrosion products due to seawater and fresh water,
Hyperfine Interactions 156 (2004) 487.
[16] J. Génin, C. Ruby, A. Géhin, P. Refait, Synthesis of green rusts by oxidation of Fe
(OH)2, their products of oxidation and reduction of ferric oxyhydroxides; Eh-pH
Pourbaix diagrams, Comptes Rendus Geosciences 338 (2006) 433.
[17] F. Ilhan, U. Kurt, O. Apaydin, M.T. Gonullu, Treatment of leachate by electro-
coagulation using aluminum and iron electrodes, Journal of Hazardous Materials
154 (2008) 381.
[18] X. Chen, G. Chen, P.L. Yue, Separation of pollutants from restaurant wastewater by
electrocoagulation, Separation and Purification Technology 19 (2000) 65.
[19] I. Arslan-Alaton, I. Kabdasli, D. Hanbaba, E. Kuybu, Electrocoagulation of a real
reactive dyebath effluent using aluminum and stainless steel electrodes, Journal of
Hazardous Materials 150 (2008) 166.
[20] A. Bagga, S. Chellam, D. Clifford, Evaluation of iron chemical coagulation and
electrocoagulation pretreatment for surface water microfiltration, Journal of
Membrane Science 309 (2008) 82.
[21] V. Kovatcheva, M. Parlapanski, Sono-electrocoagulation of iron hydroxides, Colloids
and Surfaces A: Physicochemical and Engineering Aspects 149 (1999) 603.
[22] M. Ni'am, F. Othman, J. Sohaili, Z. Fauzia, Combined magnetic field and
electrocoagulation process for suspended solid removal from wastewater,
Proceedings of the 1st International Conference on Natural Resources Engineering
& Technology 2006, Putrajaya, Malaysia, 2006, p. 384.
[23] D. Mills, A new process for electrocoagulation, E-journal AWWA 92 (2000) 34.
[24] V. Shaposhnik, O. Grigorchuk, E. Korzhov, V. Vasil'eva, V. Klimov, The effect of ion-
conducting spacers on mass transfer - numerical analysis and concentration field
visualization by means of laser interferometry, Journal of Membrane Science 139
(1998) 85.
[25] W. Den, C. Huang, Electrocoagulation of silica nanoparticles in wafer polishing
wastewater by a multichannel flow reactor: a kinetic study, Journal of
Environmental Engineering-Asce 132 (2006) 1651.