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Removal of Humic Acids by Continuous Electromagnetic Treatment Followed

by Electrocoagulation in Batch using Aluminium Electrodes

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 Desalination 239 (2009) 295–308

Removal of humic acids by continuous electromagnetic

treatment followed by electrocoagulation in batch using
aluminium electrodes
D. Ghernaouta*, B. Ghernaoutb, A. Saibaa, A. Boucherita, A. Kellila
a
Chemical Engineering Department, Saad Dahlab University of Blida, Blida 09000, Algeria
Tel./Fax: +213 (25) 43 36 31; email: djamel_andalus@yahoo.fr
b
Algerian Waters, Medea Area, Medea 26000, Algeria

Received 10 June 2007; Accepted 17 April 2008

Abstract
This work studied the reduction of humic acids (HA) by continuous electromagnetic (EM) treatment followed
by electrocoagulation (EC) in batch of synthetic HA solution using two aluminium electrodes at neutral pH. After
continuous EM treatment until the filling of the electrocoagulator, the solution is electrocoagulated. The pH of the
HA solutions is adjusted to 12 prior to UV absorbance (300 nm) measurement to enhance HA absorbance since the
best dissolution of HA is obtained in neutral or acidic pH. The laboratory tests show that EC process in batch
(30 min) is highly efficient for HA removal at pH 7 (96%) and 3 (90%) and less efficient at pH 11 (51%). On the
other hand, EM treatment in batch (25 min) increases the induced effect by pH adjusting of HA solution [i.e. UV
absorbance decreases at pH 3 (13%) and increases at pH 7 (9%) and 11 (8%)]. However, when EM treatment is in
continuous mode and taken alone, it does not have a significant effect on HA removal. When EM treatment is
followed by EC in batch, it has an important contribution to increase UV absorbance removal by EC near 100% at
pH 7. EM treatment seems to increase the reactivity of HA macromolecules before their removal by charge
neutralisation–adsorption in the EC process.

Keywords: Humic acids; Electrocoagulation; Electromagnetic field; Aluminium

1. Introduction
Brown and black biopolymers associated with
soil, sediment and particulates in water consist of
*Corresponding author.
material derived from the degradation of animals
and plants and are called humic substances (HS).
Humic acids (HA) are one of the main com-
ponents of HS in water [1,2]; they are soluble in
dilute alkaline solution but precipitate from an

0011-9164/09/$– See front matter © 2008 Elsevier B.V. All rights reserved
doi:10.1016/j.desal.2008.04.001
296 D. Ghernaout et al. / Desalination 239 (2009) 295–308
acidified solution (pH <2) [3]. The acidic nature
of HA is usually attributed to the ionization
behaviour of –COOH and phenolic –OH groups
[4]. The presence of organic matter in surface
water potabilised by classical physicochemical
treatment has several problems such as disinfec-
tion by-products [5].
Electrocoagulation (EC) is not a new tech-
nology. Treatment of wastewater by EC has been
practiced for most of the 20th century with
limited success [6]. Using electricity to treat
water was first proposed in UK in 1889, and the
application of electrolysis in mineral beneficia-
tion was patented by Elmore in 1904 [6]. The
principle of EC was used to treat bilge water from
ships and was first patented in 1906 by Dietrich
[6]. EC has been used for the treatment of
wastewater by various authors, and several differ-
ences were found in comparison to the chemical
coagulation process [6].
A literature survey indicates that EC is an
efficient treatment process for different wastes.
EC is an effective process for the destabilisation
of finely dispersed particles by removing hydro-
carbons, grease, suspended solids and heavy
metals from different types of wastewater. Alu-
minium or iron is usually used as electrodes and
their cations are generated by dissolution of
sacrificial anodes upon the application of a direct
current [6]. The metal ions combine to the
hydroxyl ions produced by the water electrolysis
at the cathode to form the corresponding metal
hydroxides, which favour the formation of the
flocs by destabilisation of the contaminants or
particulate suspensions [6]. The formed flocs can
be recovered from the liquid surface by scraping
—when the bubbles of hydrogen produced at the
cathode allow flotation—or settle depending on
their density [7]. Normally, hydroxides, obtained
electrochemically, have a much higher sorption
ability than those obtained chemically because of
the finely dispersed structure and very well
developed specific surface [8].
The scientific explanation of magnetic water
treatment has been the subject of investigation by
several researchers [6]. These studies involved
the formation of scale and the methods for its
prevention. Magnetic treatment of water was first
patented by Vermeiren in Belgium in 1945, and
he is recognised as the discoverer of the fact that
magnetic fields affect water [6]. Magnetic treat-
ment of water is an attractively simple approach
by which the water to be treated flows through a
magnetic field, and consequently changes some
of its physicochemical properties [6]. Some
researchers developed a continuous electro-
magnetic (EM) sedimentation tank in wastewater
treatment to enhance the settling velocity of sus-
pended particles [6]. Another researcher has also
developed a very efficient magnet for wastewater
treatment. Some workers explained that magnetic
technology is a promising treatment process that
can enhance the separation of suspended particles
from the sewage. Among different physical and
chemical methods of water and wastewater treat-
ments, magnetic methods attract special attention
due to their ecological purity, safety, simplicity
and low operating costs [6]. Alteration of physi-
cal and chemical properties of water-dispersed
systems in the mode of magnetic treatment
implies a certain influence of magnetic field on
the structure of water and aqueous solutions [6].
Previous research by several scientific societies
has discovered that a magnetic field can improve
technological characteristics of the water, i.e.
better salt solubility, kinetic changes in salt
crystallization and accelerated colloidal coagu-
lation [6]. A magnetic field is known to create the
asymmetry of hydrated shells due to its effect on
water molecules situated around the charged
particles (colloid) [6]. Exposure to magnetic field
would lead to higher electro-kinetic movement
among the colloid. This will definitely increase
the probability of attracting particles to cloak
with one another [6].
This work is enclosed in an overall study
 D. Ghernaout et al. / Desalination 239 (2009) 295–308 297

concerning electromagnetically assisted EC

feasibility as a water treatment process. Thus, HA
in synthetic solution are electrocoagulated with
and without an EM field to define the conditions
of their removal and to understand implicated
mechanisms and electrochemical phenomena.
The aim of this work is to study the influencing
parameters on HA removal by EC and EM
treatments such as time, pH, and flow rate in EM
treatment device and pH in EC process beaker.

2. Experimental
2.1. Procedure
The HA used are a commercialised product
from Across Organics (USA). This product is like
a brown powder. A concentrated solution at
1 g L!1 is prepared by dissolving 1 g of HA in
62.5 mL of NaOH (2N) solution and then Fig. 1. Experimental set-up for the EC process.
completed to 1 L with distilled water (with
10 µS cm!1 at 25°C as conductivity) in a 1 L vial.
This solution is submitted to magnetic agitation
during 48 h and then conserved at 4°C in the
absence of light. From this solution, diluted
solutions are prepared for the EC and EM tests.
EC tests were conducted in batch (Fig. 1) and
EM tests in batch and in continuous modes
(Figs. 2 and 3, respectively). For EM tests in
continuous mode, there were two passages of the
HA solution: direct and helical (Fig. 4(a) and (b))
in the manual coil. Finally, the experimental set-
up used for the EM process (continuous mode) Fig. 2. Experimental set-up for the EM process (batch
followed by EC process is shown in Fig. 5. The mode). (a) Schematic view of the set-up. (b) Perspective
view of the beaker in the coil. 1 AC power source,
EC (Fig. 1) and EM tests (in batch, Fig. 2) were
2 ammeter, 3 voltmeter, 4 beaker (50 mL), 5 coil
made using equipment composed of two beakers (Leybold).
(the first with a 500 mL volume and 8 cm inner
diameter and the second with a 50 mL volume
and 4 cm inner diameter) and two commercialised distance between the electrodes is fixed at 4 cm.
plate aluminium electrodes. Both electrodes have The electrodes are connected to a direct current
the same dimensions (20 cm × 2 cm) with 2 mm power supply (Elektrolyser) with 15 V as the
as thickness. For each electrode, the immersed maximum voltage and 10 A as the maximum
(active) surface is 34 cm2 (17 cm × 2 cm) and the intensity. The applied voltage and current
298 D. Ghernaout et al. / Desalination 239 (2009) 295–308
Fig. 3. Experimental set-up for the EM process (con-
tinuous mode). 1 AC power source, 2 ammeter,
3 voltmeter, 4 coil (manual), 5 reservoir of HA solution,
6 regulator of flow rate, 7 reservoir of treated HA
solution.
intensity are measured by voltmeter and ammeter
which are connected in parallel and in series
respectively. The EM field is created by using
two coils. The first one is of Leybold 562 14 type
[for 18 V, the EM density B was 30 milliTesla
(MT)] and is used for batch tests. The second one
is made in the laboratory by rolling an electric
wire around a plastic tube (for 15 V, B was
39 mT) and is used for continuous tests (Fig. 4).
The coils were connected to an alternative current
power supply (Rft. Sparstell Trafolss 010) with
250 V as maximum voltage and 20 A as maxi-
mum intensity.
Before EC tests and in order to avoid any
interference, aluminium electrodes are prepared
as follows: (1) rinse with distilled water, (2) clean
in sodium hydroxide solution (10%), (3) rinse
with distilled water. They are then dried with
absorptive paper. After the introduction of HA
solution to treat in the beakers (Figs. 1 and 2), the
pH is adjusted at its selected initial value (3, 7 or
11) using H2SO4 or NaOH (2N) solutions. The
electrodes are plunged in the electrocoagulator
and fixed before their connection to the power
supply. When the current is applied in the EM
and EC beakers during 30 min, the HA solution
is in the quiescent state. Samples were taken for
analysis every 5 min. After 30 min of sedimen-
tation, a 50 mL sample is taken from the settled
solution by pipetting. Conductivity C and pH are
immediately measured. Before measuring UV
absorbance at 300 nm, pH is adjusted at 12. All
used chemicals are of analytical grade. An assem-
bling of the EM process (continuous mode)
followed by the EC process (Fig. 5) was done for
an optimised flow rate in the first process and
filling the EC beaker (500 mL) with electromag-
netically treated HA solution. After 30 min of the
EC treatment, the combined process is stopped.
All the tests were conducted at ambient tempera-
ture (20°C).
2.2. Analytical techniques
The performed analyses concerned turbidity T
in NTU [Turb 550 (wtw) turbidimeter], con-
ductivity C in µS cm!1 at 25°C (EC215 Hanna
Instruments conductimeter), and pH (Inolab pH
level 1 pH-meter). UV absorbance at 300 nm of
HA contained in the synthetic solutions is mea-
sured using a Spekol UV-Vis 3.02 spectro-
photometer with 1 cm cell quartz. The pH of the
solutions is adjusted to 12 prior to the absorbance
measurement to enhance HA absorbance (where
the best dissolution of humic macromolecules is
obtained than in neutral or acidic pH). The
removal of HA is calculated using the following
relation:
Abi  Ab f
R 00   100 (1)
Abi
where Abi and Abf are initial and final UV
absorbances, respectively. A calibration curve
expressing UV absorbance at pH 12 as a function
 D. Ghernaout et al. / Desalination 239 (2009) 295–308 299

Fig. 4. Photos of (a) direct and (b) helical passages used in the experimental set-up for EM process (continuous mode).

Fig. 6. Calibration curve expressing UV absorbance

Fig. 5. Experimental set-up for the EM process (con-
tinuous mode) followed by EC process. 1 DC power
source, 2 AC power source, 3 ammeter, 4 voltmeter,
5 reservoir of HA solution, 6 regulator of flow rate, 7 coil
(manual), 8 pipe to the electrocoagulator, 9 electro-
coagulator, 10 anode, 11 cathode.
of HA concentration is presented in Fig. 6. This
curve shows that UV absorbance is an accurate
method to measure HA concentration. The con-
centration of HA solution was fixed at 15 mg L!1
(Abi = 0.2518) for all the performed tests.
(300 nm) at pH 12 as a function of HA concentration.
3. Results and discussion
3.1. Preliminary observations
It is well known that the pH in the solution
changes during the EC process. Since its control
may be very interesting, in this study pH at initial
and final states is taken in consideration in order
to optimise the EM and EC processes of humic
macromolecules which are dependent of pH.
Consequently, three representative values of pH
300 D. Ghernaout et al. / Desalination 239 (2009) 295–308
range (3, 7 and 11) are chosen to understand the
effect of pH.
For the EM treatment, it was not easy to see
clearly the phenomena which are producing [due
to the darkness of the set-up which is constituted
of direct or helical pipe centred in the coil
(Fig. 4)]; but after the end of the EM treatment, it
was possible to see that there is a reduction of HA
solution colour proving some efficiency of this
process before UV absorbance measurement.
For the EC treatment, during the realised tests
some general observations were noted:
C Intense emission of hydrogen bubbles from
the cathode raising to the surface of the solu-
tion according to the following reactions:
2H2O(l) + 2e! 6 2OH!(aq) + H2(g) (2)
2H+(aq) + 2e! 6 H2(g) (3)
C Less intense emission of oxygen bubbles from
the anode according to the following reaction:
2H2O(l) 6 4H+(aq) + O2(g) + 4e! (4)
Simultaneously, there is the anode dissolution:
Al(s) 6 Al3+(aq) + 3e! (5)
In the solutions, there is Al(OH)3(s) formation
between Al3+(aq) and 3OH!(aq) [7,9]. Depending on
the Al3+ ion concentration, the solution pH range
and also aging, consecutive hydrolysis reactions
can generate the formation of various monomeric
hydroxides species such as AlOH2+, Al(OH)2+,
Al(OH)3, Al(OH)4!, and also some coagulating
polymers as Al6(OH)15 3+ 4+
, Al8(OH)20 5+
, Al13(OH)34
[10]. The small electrogenerated bubbles (less
than 1 mm in diameter) provide an advantageous
higher rate of bubble aggregate heterocoagulation
[10].
3.2. EM treatment in batch
The EM treatment in batch is done using the
set-up of Fig. 2. Table 1 presents the effect of
initial pH (3, 7 and 11) on the EM treatment of
HA solution in batch (IAC = 1.5 A, B = 8.33 mT).
For pH 3, the UV absorbance removal increases
until 13% for 10 min and decreases for 15 min
(8%) and 20 min (9%) and increases a second
time until 13% for 25 min. For pH 7, the UV
absorbance increases until 9% for 20 min. For pH
11, UV absorbance increases and decreases
sometimes.
As we can see, HA removal by the EM field
alone in batch is low (13% even when pH is acid)
and barely exists when pH is neutral or alkaline.
Indeed, HA macromolecules are a reticular poly-
mer which is connected by hydrogen bonds
between functional groups. The most active func-
tional groups are carboxyl and phenolic hydroxyl
groups, and dissociation of H+ relates to the pH of
the solution. When pH is acid, carboxyl and
hydroxyl radicals exist in -COOH and -OH forms
respectively. When pH is alkaline, they can exist
in –COO- and –O- forms. This fact means that
when pH is alkaline, HA macromolecules take
more negative charge and they consequently need
more positive charge to neutralise the negative
charge. So the treatment effect and efficiency are
all reduced when pH is alkaline [11]. On the other
hand, it has been suggested that the structure of
HA can undergo various changes from rather
linear to coiled or more spherical configurations
(or vice versa) due to the acidification of pH in
the solution [12].
Consequently, EM treatment alone in batch
does not provide any positive effect to the HA
system. Its direct efficiency is not important when
pH is acid. When pH is alkaline, the EM field
contributes to the “linearization” or solubilisation
of the HA macromolecules since their UV
absorbance is increased (Table 1).
3.3. EC treatment in batch
The effect of the initial pH on HA removal by
EC treatment in a batch mode (Fig. 1) for 30 min
is examined (Table 2). In addition, Fig. 7 shows
 D. Ghernaout et al. / Desalination 239 (2009) 295–308 301

Table 1
Effect of initial pH (3, 7 and 11) on the EM treatment of HA solution in batch (IAC = 1.5 A, B = 8.33 mT)

Initial pH Time, min pH C, µS cm!1 T, NTU Ab R, %

3 0 3 249 0.30 0.2123 0

5 2.93 324 0.26 0.1871 11.7
10 2.96 357 0.26 0.1829 13.85
15 2.92 341 0.25 0.1947 8.29
20 2.91 309 0.25 0.1921 9.51
25 2.91 304 0.24 0.1835 13.56
7 0 7 237 0.28 0.2071 0
5 7.44 225 0.28 0.2096 !1.21
10 7.34 220 0.28 02132 !2.94
15 7.27 226 0.28 0.2222 !7.29
20 7.25 227 0.28 0.2265 !9.37
25 7.22 146 0.28 0.2215 !6.95
11 0 11 196 0.67 0.2094 0
5 11.01 151 0.47 0.1891 9.69
10 11.04 154 0.35 0.2143 !2.34
15 11.18 164 0.25 0.2086 0.38
20 11.01 156 0.27 0.2262 !8.02
25 11.08 164 0.27 0.2061 1.58

Table 2
Effect of pH (3, 7 and 11) on the EC treatment (30 min) of HA solution in batch mode (iDC = 33.3 A m!2)

pH C, µS cm!1 T, NTU Ab R, %
Initial: 3 253 0.33 0.2299 0
Final: 7.23 205 0.12 0.0227 90.13
Initial: 7 235 0.22 0.2472 0
Final: 8.35 215 0.44 0.0095 96.15
Initial: 11 181 0.53 0.2793 0
Final: 9.36 99 0.16 0.1351 51.62

he activity–pH diagram for Al(III) species in
equilibrium with Al(OH)3(s) [13]. For pH 3,
AlOH2+, AlO+ and Al(OH)3(aq) coexist. For pH 7,
AlOH2+, AlO+, Al(OH)4!, Al(OH)3(aq) and
Al(OH)3(s) coexist. For pH 11, Al(OH)3(aq),
Al(OH)4! and Al(OH)3(s) coexist.
As we can see in Table 2, the best removal of
HA is achieved at pH 7. Removal of HA is
accomplished by charge neutralization and ad-
sorption in the presence of AlOH2+, AlO+,
Al(OH)4!, Al(OH)3(aq) and Al(OH)3(s). Charge neu-
tralisation is reduced here with Al(OH)4! and
adsorption is increased with Al(OH)3(s). For Zhou
et al. [14], the hydrolytic species such as Al(OH)3
with a large surface area and amorphous structure
is positively charged and is therefore strongly
adsorbed onto the organic anionic particles and
becomes insoluble; hydrolysed cationic species
such as AlOH2+ are more strongly adsorbed on
negative surfaces than the free, hydrated metal
ion [14].
For pH 3, charge neutralization predominates
by AlOH2+, AlO+ and Al(OH)3(aq) species. These
positively charged species attract the HA macro-
302 D. Ghernaout et al. / Desalination 239 (2009) 295–308
Fig. 7. Activity–pH diagram for Al(III) species in equi-
librium with Al(OH)3 (amorphous) [13].
molecules. This charge neutralisation promotes
flocs aggregation. For Zhou et al. [14], the pro-
tons and the metal hydrolysis products compete for
organic ligands and poor removal occurs because
some of the organic acids are not preci-pitated
[14].
For pH 11, on one hand the disprotonation of
HA macromolecules increases their negative
charge and consequently their dissolution (as seen
in Section 2.1. HA solution is moreover prepared
under alkaline conditions and pH is adjusted to 12
before UV absorbance measurement); on the other
hand, the presence of Al(OH)4!(aq) restricts the
adsorption that is accomplished by Al(OH)3(s). For
Zhou et al. [14], under more alkaline conditions
(pH = 7–8), the coagulation species become less
positively charged, diminishing their attraction to
anionic organic compounds [14]. For Koparal et
al. [15], zeta potential values of the Al(OH)3
crystals obtained from an experiment conducted
with distilled water indicate that as pH increases,
zeta potential values decrease (from 35 mV at
pH~8 to 25 mV at pH ~9). A decrease in zeta
potential values can be attributed to the increase in
OH! ion concentration and adsorption of these ions
onto surface of the Al(OH)3 crystals [15].
Koparal et al. [15] have measured zeta potential
of HS in different pH values. As pH increases
zeta potentials, of course the negative charge of
the HS increases (!25 mV at pH 4 to !40 mV at
pH 10). This phenomenon is attributed to the
disprotonation of some functional groups in HS.
Increasing negative charge at high pH values
requiring more aluminium to meet the HS binding
capacity is another factor responsible for decreas-
ing removal efficiency [15].
For pH 7, the formed amorphous Al(OH)3(s)
has “sweep flocs” with large surface areas. These
flocs are active in rapid adsorption of soluble
organic compounds (and trapping of colloidal
particles) and are easily separated from aqueous
medium by sedimentation or H2 flotation [9].
However, AlOH2+ and AlO+ contribute with the
electrical field to the destabilisation of HA
macromolecules by charge neutralisation produc-
ing HA–Al complexes which are then agglome-
rated as neutral colloidal entities. These hydro-
phobic solids are carried up to the surface by their
fixation on hydrogen bubbles (flotation process)
[9]. The Al(OH)3(s) flocs which are relatively
voluminous with low density do not adsorb
destabilised HA macromolecules and precipitate
as sediments in the bottom of the beaker. Other
investigators [13,16] have also reported that EC
is based on the fact that the stability of colloids,
suspensions and emulsions is influenced by the
produced electric charges. On the other hand, Wu
et al. [17] reported that the insoluble metal
hydroxides react with pollutants by surface com-
plexation, coagulation or electrostatic attraction
[17].
For Park and Yoon [18], adsorptive interac-
tions between HA macromolecules and the mine-
rals (Al(OH)3(s) in this study) can be explained by
Van der Waals’ forces, hydrogen bonding,
cations exchange with alkaline cations followed
by cation bridging. Basically, adsorption caused
by Van der Waals’ forces, which operate between
all molecules but are rather weak, can be of
considerable importance in the adsorption of
 D. Ghernaout et al. / Desalination 239 (2009) 295–308 303

neutral polar and non-polar molecules, particu-

larly those of high molecular weight [18] (humic
macromolecules at pH 7). Hydrogen bonding is a
linkage between polar groups of the organic
molecule and either adsorbed water molecules or
oxygen of the Al(OH)3(s) surface through bonding
with a single H+ ion [18]. C EBT-H1, with SO3! and one of the OH! groups
As a comparison with chemical coagulation ionized:
[19], coagulants are known to remove organic
macromolecules. Metallic salt coagulants, most
commonly alum and ferric chloride, are more
effective than cationic polymers in removing lower
molecular weight organic compounds with acidic
functional groups (such as carbonyl or carboxyl C EBT-H0, in which the SO3! and the two OH!
groups). For alum, two removal mechanisms are groups are ionized:
defined based on the acidity of the medium. In the
pH range of 6–8, conditions for rapid formation of
amorphous solids prevail, and removal most likely
occurs by adsorption of the HA on the precipitate
of Al(OH)3. In the pH range of 4–5.5, HA can be
assumed to precipitate by a charge neutralisation
mechanism through soluble or “incipiently solid-
phase aluminium hydrolysis species”, possibly According to the ionization constants of this
leading to an aluminium–humate precipitate molecule (pKa1: 6.6; pKa2: 11.6), for an EBT
through specific chemical interactions [19]. concentration of 100 mg L!1 (which is a typical
According to Cañizares et al. [20], the main concentration of pollutant) and taking into
coagulation mechanisms that can explain the account the experimental observations reported in
experimental observations for the EC of Erio- the literature [20] in which it was shown that EBT
chrome Black T (EBT) with aluminium are (1) the removal is only possible at pH values below 6
neutralization of the ionized groups of the EBT (with the EC process), only the species EBT-H2
molecules by binding of these groups to positively can be removed (efficiently) by the EC process
charged aluminium species and (2) the adsorption with aluminium electrodes [20].
or enmeshment of the organic mole-cules within a With the hypothesis that HA macromolecules
growing aluminium hydroxide precipitate [20]. are a combination of EBT-like molecules (given
The EBT molecules undergo ionization of several the substantial content of aromatic and aliphatic
functional groups in water, and the level of residues present in humics and the relatively
ionization depends on the pH. Thus, in aqueous small content of ionisable carboxylic groups
solution the EBT can be present as three different [15]), the behaviour of HA macromolecules in
forms (actual species) [20]: solution vs. pH would be similar to the behaviour
of EBT molecule as explained above [i.e., HA–H2
C EBT-H2, in which only the SO3! group is (pH 3), HA–H1 (pH 7), HA–H0 (pH 11)], even
ionized: though HA removal by EC (Table 2) is slightly
more efficient in pH 7 (96%) than pH 3 (90%).
304 D. Ghernaout et al. / Desalination 239 (2009) 295–308

The effect of initial pH on the removal of HS

from wastewater by electrocoagulation was
recently studied by Koparal et al. [15]. They
concluded that the effects of initial pH on an EC
system may be twofold. These are distribution of
aluminium hydrolysis product, transformation of
HS related to the initial pH and finally the effects
of the gel layer especially in high HS concen-
trations and high initial pH formed on the anode
surface. It has been observed that initial HS
concentration and initial pH are highly effective on
the removal rate and efficiency. For example, in
the range of 200–500 mg L!1, a decrease in the
removal efficiency was observed due to gel layer
formation on the surface of the anode surface. This
gel formation especially starts at an initial concen-
tration of 120 mg L!1; thickness and effect of the
layer increase as concentration increases. In order
to prevent this gel formation, initial pH of the
wastewater was adjusted to 5.0 and high removal
efficiencies were observed. Thus, the system
should be operated at low pH values (i.e. 5.0) at
high concentrations [15].

3.4. EM treatment in continuous mode

The EM treatment tests in continuous mode
were run using the set-up shown in Fig. 3. In
Fig. 4, the photos of direct (a) and helical passages
of the HA solutions used in the experimental set-
up for EM process (continuous mode) are pre-
sented. The direct passage has no effect on the HA Fig. 8. Schematic representation of EM in batch (a) and
solution (so its results are not presented here). continuous (b) mode, EC in batch (c), and EM in
continuous mode followed by EC in batch (d) of HA
However, the helical passage is relatively better.
solution (Abf : final absorbance).
The effect of initial pH (3, 7 and 11) on the EM
treatment of HA solution in continuous mode is
presented in Table 3. For pH 3, the UV absorbance alkaline) and approximately does not exist when
increases until 13% for 10 min as residence time. pH is neutral and acid.
For pH 7, the UV absorbance increases until 12% In comparison with the EM treatment of HA
for 10 min as residence time and decreases solution in batch (Table 1) and the EM treatment
thereafter. For pH 11, UV absorbance decreases of HA solution in continuous mode (Table 3), the
until 13%. As we can see, HA removal by EM UV absorbance is reduced in acidic pH for the
field in continuous mode is low (13% when pH is first and alkaline pH for the second in one hand.
 D. Ghernaout et al. / Desalination 239 (2009) 295–308 305

Table 3
Effect of pH (3, 7 and 11) on the EM treatment of HA solution in continuous mode (the volume of helical tube was
~100 mL, flow rate Q (mL min!1), residence time tR (min), IAC = 7.56 A, B = 36.4 mT)

Initial pH Q, mL min!1 tg, min pH C, µS cm!1 T, NTU Ab R, %

3 0 0 3 240 0.31 0.2355 0

10 10 3.04 379 0.37 0.2673 !13.50
15 7 3.02 325 0.40 0.2621 !11.29
20 5 3.07 302 0.38 0.2584 ! 9.72
25 4 3.10 298 0.37 0.2558 ! 8.62
7 0 0 7 252 0.22 0.2453 0
10 10 7.04 194 0.26 0.2767 !12.80
15 7 7.06 378 0.27 0.2353 4.08
20 5 7.14 276 0.30 0.2365 3.59
25 4 7.05 259 0.27 0.2405 1.96
11 0 0 11 195 0.76 0.2992 0
10 10 11.34 145 0.50 0.2577 13.87
15 7 11.22 184 0.52 0.2620 12.43
20 5 11.18 143 0.51 0.2730 8.76
25 4 11.05 154 0.55 0.2764 7.62

Table 4
Effect of pH (3, 7 and 11) on the EM treatment in continuous mode followed by EC in batch of HA solution (the volume
of helical tube ~100 mL, flow rate 10 mL min!1, residence time 10 min, IAC = 7.56 A, B = 36.4 mT, iDC = 33.3 A m!2)

pH C, µS cm!1 T, NTU Ab R, %
Initial: 3 225 1.06 0.2165 0
EM contin: 3.38 332 0.34 0.1884 12.98
EC in batch: 5.96 254 1.34 0.0426 77.39
Initial: 7 218 0.34 0.2433 0
EC contin.: 7.10 190 0.29 0.2769 !13.81
EC in batch: 8.28 210 0.83 0.0001 99.96
Initial: 11 171 0.84 0.2484 0
EC contin.: 10.36 215 0.12 0.2172 12.56
EC in batch: 9.00 116 1.06 0.1316 39.41

On the other hand, the UV absorbance is
increased when pH is not acid for the first and
when it is not alkaline for the second.
This inversion of the UV absorbance behav-
iour may be affected by the “torsional” motion
(helical passage) of HA macromolecules in the
EM helical passage so their solubilisation is
totally inversed. Consequently, in batch, EM
treatment enhances the phenomena which are
produced in the HA solution under the pH effect:
reduction of UV absorbance when pH is acid and
increase of UV absorbance when pH is alkaline.
However, in continuous mode, the EM field
inverses the phenomena, which are normally pro-
duced under the effect of pH (so there is a reduc-
tion of UV absorbance when pH is alkaline and
an increase of UV absorbance when pH is acid).
Fig. 8(a) and (b) schematically illustrate the
306 D. Ghernaout et al. / Desalination 239 (2009) 295–308
inversion of tendencies from the EM treatment in
batch (a) to EM treatment in continuous (b) mode
of the HA solution.
3.5. EM treatment in continuous mode followed
by EC in batch
In these experiments, as shown in Fig. 5, the
experimental set-up for the EM process (con-
tinuous mode) followed by EC process in batch
was used. The effect of initial pH (3, 7 and 11) on
the EM treatment in continuous mode followed
by EC in batch of HA solution (volume of the
helical tube ~100 mL, flow rate 10 mL min!1,
residence time 10 min, IAC = 7.56 A, B = 36.4 mT
and iDC = 33.3 A m!2) is presented in Table 4. For
pH 3, the EM (continuous mode) process–EC (in
batch) process achieved a result of 77% of UV
absorbance removal. When pH was 7, its effi-
ciency was nearly 100%. When pH was 11, its
efficiency was 39%.
As we can see, for pH 7 the EM process
coupled to the EC process is the most efficient.
When the EM process is considered alone, the
UV absorbance increases (13%) (Table 4) and
when the EC process is considered alone, the UV
absorbance is reduced to 96% (Table 2). These
results suggest that EM treatment enhances the
dissolution of humic macromolecules in the
solution so the UV absorbance increases (13%).
This enhanced dissolution of the humic macro-
molecules would increase their “receptivity” to
the charge neutralisation by positively charged
species (AlOH2+, AlO+, Al(OH)3(aq)) and adsorp-
tion on Al(OH)3(s) flocs.
In accordance to the modern theory of stability
[21], the coagulation of colloidal systems depends
not only on electro-kinetic potential but also on
colloidal particles hydration, which blocks up
mechanical agglomeration of colloidal particles.
The coagulation capability of electrolytes
depends on decreasing of the repulsive forces
between colloidal particles or zeta potential and
on the dehydration of the diffusive layer. The
magnetic water treatment reduces the magnitude
of the zeta potential of colloidal particles
approximately 23–29%. This shows that magnetic
exposure reduces thickness of diffusive layer
[21].
In addition, Fig. 8 schematically presents the
efficiencies of the EM process in batch (a) and
continuous (b) mode, EC in batch (c), and EM
process in continuous mode followed by EC in
batch of HA solution. The normal tendencies
mean that when pH is acid, humic macro-
molecules are less dissolved than for pH 7 and
12. For the EM process in batch (Fig. 8(a)), the
normal tendencies are emphasized. For the EM
process in continuous mode (Fig. 8 (b)), there is
an inversion of the normal tendencies. Finally,
there is a great performance of EC in the HA
removal (Fig. 8 (c)) which can be enhanced
electromagnetically especially when pH is 7
(Fig. 8 (d)).
4. Conclusions
The laboratory tests show that the EC process
using aluminium electrodes is highly efficient for
HA removal. The in situ formed cations (AlOH2+
and AlO+) neutralise humic macromolecules and
contribute to the formation of hydroxides
(Al(OH)3(s)) which adsorb organic matter at an
optimal pH 7. On the other hand, EM treatment in
batch increases the normal behaviour induced by
pH adjusting of a HA solution; however, when
this treatment is in continuous mode and taken
alone, it does not have a significant effect on HA
removal. When EM treatment is followed by EC
in batch, it has an important contribution to
increase UV absorbance removal by EC near
100% when pH is 7. Finally, EM treatment
coupled to the EC process is interesting not only
from a fundamental studies point of view but also
from a practical one but it needs more specific
study to understand how the “receptivity” of
humic macromolecules is enhanced under higher
EM densities.
 D. Ghernaout et al. / Desalination 239 (2009) 295–308
5. Symbols
Ab — UV Absorbance at 300 nm
B — Density of the electromagnetic field,
mT
C — Conductivity, µS cm!1 at 25°C
IAC — Alternative current intensity, A
iDC — Direct current density, A m!2
Q — Flow rate, mL min!1
T — Turbidity, NTU
tR — Residence time, min
Acknowledgements
The authors wish to acknowledge the financial
support made by the National Agency of Univer-
sity Research Development (ANDRU) (JO
901/01/06/04 project in 2004).
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