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Chemical Engineering and Processing 43 (2004) 12811287

Decolourization and removal of phenolic compounds from olive


mill wastewater by electrocoagulation
Nafaa Adhoum , Lotfi Monser
Dpartement de Chimie, Centre Urbain Nord B.P. No. 676, Institut National des Sciences Appliques et de Technologie, 1080 Tunis Cedex, Tunisia
Received 5 September 2003; received in revised form 8 December 2003; accepted 8 December 2003
Available online 25 January 2004

Abstract
The effective performance of electrocoagulation (EC) technique in the treatment of olive mill wastewater (OMW) has been investigated
using sacrificial aluminium electrodes. The optimum working pH was found to be in the range 46, allowing OMW to be treated directly
without pH adjustment. In addition, it is found that an increase in the current enhanced the speed of the treatment significantly. However,
simultaneous increase of electrode and energy consumption was observed. The optimum current density allowing the quickest treatment with
a low cost was found to be 75 mA cm2 . Therefore, a current density of 75 mA cm2 was selected as an optimum that allows fast and low cost
treatment.
Application of electrocoagulation procedure permitted high removal efficiencies of pollutants with both fresh and stored olive mill wastewater. The process produces a removal capacity of 76% of COD, 91% of polyphenols and 95% of dark colour, just after 25 min. The electrode
consumption was found to be 2.11 kg m3 of treated OMW. The results show that electrocoagulation could be considered as an effective
alternative solution for the treatment of OMW or may be combined with a classical biological process to achieve a high quality effluent water.
2004 Elsevier B.V. All rights reserved.
Keywords: Olive mill wastewater; Electrocoagulation; Aluminium electrode; Water treatment

1. Introduction
Olive mill wastewater (OMW) is a dark red to black effluent produced during olive oil extraction. It is estimated that
around 30 million cubic meter of OMW are generated annually in the Mediterranean area [1,2], during the seasonal
extraction of olive oil. This huge amount of wastewater
raised concerns about their possible negative effects on the
environment. In fact, OMW is characterised by high concentrations of several organic compounds including sugars,
tannins, pectins, lipids and phenolic substances [3,4] which
are responsible of their high COD and BOD. Their concentrations were generally in the range 80200 g l1 for
COD [5,6] and 1263 g l1 [7] for BOD. Specifically, it
has been reported that polyphenolic components of OMW
are responsible for its phytotoxicity [8,9] and antibacterial activity [2,10,11]. Therefore, the practice of spreading
OMW directly on agricultural soils must be accomplished
with great vigilance, since it may result in more damage
than beneficial effects on soil fertility. Moreover, OMW is

Corresponding author. Tel.: +216-1-703-627; fax: +216-1-704-329.


E-mail address: nafaa.adhoum@insat.rnu.tn (N. Adhoum).

0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2003.12.001

characterised by its dark colour ascribed to polymerisation


of tannins and low molecular weight phenolic compounds
[12,13]. Therefore, OMW must be treated to remove the
phenolic fraction, before being discharged in receiving
water bodies or used for irrigation purposes.
The simplest solution applied towards this direction consisted in constructing artificial big ponds into which OMW
is stored, awaiting for its natural evaporation. However, this
method, besides being very slow, causes subsequent unpleasant environmental pollution linked to generation of bad
odours due to anaerobic activity [12]. Many studies exist
on the biological treatment of OMW under aerobic [14,15]
or anaerobic conditions [3,13]. However, high organic load
specially phenolic compounds were found to inhibit the efficiency of anaerobic digestion and make OMW recalcitrant
to biological degradation [3,16]. Several other methods
were used for OMW treatment, such as that proposed by
Benitez et al. [17,18] who studied the chemical treatment
of wastewaters from olive industry by means of the ozone
or Fentons reagent in the presence and absence of UV
radiation. They showed that the combined action of UV
radiation with the chemical reagent enhanced the removal
efficiency to reach 76% of organic matter destruction,

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measured as COD. Other oxidising agents such as monosulphuric acid [19] and MnO2 [20] were also successfully used
for polyphenols removal from OMW. Another method was
recently applied to the treatment of OMW and consists of
the application of an integrated centrifugationultrafiltration
system [21] allowing an efficient reduction of pollution and
a selective separation of some useful products.
In a recent study, Galiatsatou et al. [22] investigated the
treatment of OMW using activated carbon produced from
olive pulp. Treatments of OMW by activated clay [23] or
lime [24] have also been reported to be effective for the
removal of phenolic compounds.
On the other hand, purification of industrial and urban
wastewaters by electrocoagulation (EC) is currently experiencing a renaissance. In this method, the coagulant is generated in situ by electrolytic oxidation of an appropriate anode
material that leads, at appropriate pH, to insoluble metal hydroxide able to remove pollutants by surface complexation
or electrostatic attraction. This technique characterised by
its simple equipment, easy operation and decreased amount
of sludge [25], was shown to be an effective and reliable
technology that provides an environmentally compatible
method for reducing a large variety of pollutants [2528].
In this study, electrocoagulation using aluminium electrodes was conducted to investigate the treatment of olive
mill wastewater. The removal efficiency of the treatment was
determined by monitoring the decrease of total phenol, COD
and dark colour intensity.
2. Experimental
2.1. Reagents and analytical procedures
Fresh olive mill wastewater was collected from a local
olive extraction plant which uses a classical process. OMW
was collected in a closed plastic container, diluted with tap
water (1:1) and stored at 0 C. Tap water was used for samples dilution because it is used in the extraction process.
OMW from the same sample was also stored for 3 months
at room temperature (>25 C) in an aerated vessel in order
to investigate the ageing effect. The main characteristics of
fresh and stored olive mill wastewater used in this work are
presented in Table 1.
Table 1
Physico-chemical characteristics of fresh and stored olive mill wastewaters
samples
Characteristics
pH
Total solid (g l1 )
COD (g l1 )
Polyphenol (g l1 )
OD (376 nm)
OD (280 nm)
Conductivity (ms cm1 )

Fresh OMW

Stored OMW

4.96
45.3
57.8
2.42
31.9
81.3
11.4

5.1
47
75.1
2.4
73
162
8.21

All used chemicals were of analytical grade. FolinCiocalteu reagent (FCR) (Flucka, England) was used at 1:10
dilution in distilled water. Determination of total polyphenols index was carried out with the official spectrophotometric procedure [29] in which FCR was used as a selective
reagent for polyphenols. Analysis of COD was determined
by the procedure described in the standard method [30]. The
total solid content was measured by drying a 100 ml aliquot
of OMW at 105 C until a constant mass was obtained.
The dark colour intensity was determined by measuring the
sample absorbance at 376 nm (UV-Vis spectrophotometer,
DR-5000). A digital calibrated pH-meter (Radiometer PHM
210) and a conductivity-meter (Radiometer CDM 230) were
used to measure the pH and the conductivity of the OMW
wastewater samples. The accuracies of COD, total polyphenols and colour intensity measurements were better than 4%.
2.2. Electrocoagulation procedure
The electrocoagulation experiments were conducted in
a home-made Plexiglas cell, with a special cover supporting a series of aluminium electrodes. Three electrodes
were connected as anodes and four as cathodes. A small
hole was drilled into the cover to serve as sampling port.
The electrodes having an immersed area of 60 cm2 each
(length 5 cm height 6 cm 2 faces) were fixed on the cover
and disposed vertically in the cell at a distance of 1 cm
from each other and there was a 2 cm distance between the
bottom of the electrodes and the bottom of the cell which
allowed easy stirring. The volume of the OMW treated each
time was 500 cm3 . A metrix (model AL 898 A) dc source
was used to supply the system with 0100 V and 20 A. In
preliminary tests, the effects of working parameters such
as electrode material, initial pH and current density were
studied in an attempt to achieve a more efficient treatment
of OMW. The optimised parameters were then applied for
the treatment of fresh and stored olive mill wastewater to
validate the treatment efficiency.
In a typical experiment, the specified volume of wastewater was poured into the cell, an initial sample was taken and
the current was then applied under regular magnetic stirring.
Different samples of 5 ml were taken at 10 min intervals for
up to 1 h and filtered before being analysed to determine the
residual polyphenol index, dark colour intensity and COD.
A gentle stirring rate of about 200 rpm was applied to
allow the chemical precipitate to grow large enough for
removal [25].

3. Results and discussion


Electrocoagulation is based on the in situ formation of the
coagulant as the sacrificial anode corrodes due to an applied
current, while the simultaneous evolution of hydrogen at
the cathode allows for pollutant removal by flotation. This
technique combines three main interdependent processes

N. Adhoum, L. Monser / Chemical Engineering and Processing 43 (2004) 12811287

operating synergitically to remove pollutants: electrochemistry, coagulation and hydrodynamics. An examination of


the chemical reactions occurring in the electrocoagulation
process shows that the main reactions occurring at the
electrodes are:
Al  Al3+ + 3e

(anode)

3H2 O + 3e  23 H2 + 3OH

(1)
(cathode)

(2)

If the anode potential is sufficiently high, secondary reactions may occur at the anode, such as direct oxidation of organic compounds and of H2 O or Cl present in wastewater.
2Cl  Cl2 + 2e

(3)

2H2 O  O2 + 4H+ + 4e

(4)

The produced chlorine undergoes a dismutation reaction at


pH higher than 34.
Cl2 + H2 O  HClO + H+ + Cl

(5)

HClO  ClO + H+

(6)

In addition Al3+ and OH ions generated at electrode


surfaces react in the bulk wastewater to form aluminium
hydroxide.
Al3+ + 3OH  Al(OH)3

(7)

This shows the complex nature of electrocoagulation. The


efficiency of the process depends on several operating parameters such as: the type of electrode material, initial pH
and current density. In order to enhance the process performance, the effects of those parameters have been explored.
3.1. Effect of electrode material
The most widely used materials, as sacrificial anode for
electrocoagulation, are aluminium and iron. For comparative

purpose, electrocoagulation has been carried out with both


materials under exactly the same conditions. The compared
results of COD, polyphenol and dark colour removal, obtained with the same current density (30 mA cm2 ) and
operating time of 30 min, are shown in Fig. 1. It appears
clearly that both materials are almost equally effective in
reducing COD and polyphenol index. However, aluminium
was found to be more effective in removing the dark colour
of OMW than iron. Indeed, the effluent treated with iron
as sacrificial anode appeared yellow first and then turned
brown. This behaviour was attributed to the excess of Fe(II)
and Fe(III) species generated during the electrolysis and
characterised by their yellow-brown colour. Another possible explanation is the occurrence of complexing reaction
between iron ions and polyphenol molecules leading to
brown soluble compounds. Thus, aluminium electrode was
selected as the most appropriate material for the present
application and was used for all subsequent experiments.
3.2. Effect of initial pH
It has been established in previous studies [2528] that
pH has a considerable effect on the efficiency of the electrocoagulation treatment. In this study, the pH was varied in
the range 210 in an attempt to investigate the influence of
this parameter on the treatment of OMW. Removal efficiencies of COD, polyphenol and dark colour as a function of
initial pH are presented in Fig. 2. All controlled parameters
showed the same trend and as expected, the treatment efficiency was very poor either at low (<2) or high pH (>10).
This behaviour is in accordance with the amphoteric character of aluminium hydroxide that does not precipitate at
pH less than 2. In addition it was demonstrated that too high
pH will increase Al(OH)3 solubility and lead to the formation of soluble AlO2 which is useless for water treatment
[28,31]. When initial pH was adjusted in the range 48, high

100
Iron
90

Aluminium

Removal efficiency, %

80
70
60
50
40
30
20
10
0

Polyphenol index

1283

COD

Dark colour

Fig. 1. Effect of electrode material on the treatment efficiency (initial pH 4.96, current density 30 mA cm2 , electrolysis time 30 min).

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N. Adhoum, L. Monser / Chemical Engineering and Processing 43 (2004) 12811287


100
Polyphenol

90

COD

Removal efficiency, %

80

Dark colour

70
60
50
40
30
20
10
0
0

12

10

Initial pH
Fig. 2. Effect of initial pH on the removal efficiencies of polyphenol, COD and dark colour (current density 30 mA cm2 , electrolysis time 30 min).

removals of COD (59%), polyphenol (78%) and colour


(92%) were achieved. The highest removal efficiencies
have been obtained in acidic medium, at pH values in the
range 46. This result is quite meaningful in the application
of electrocoagulation to OMW treatment, since the typical
pH of OMW is between 4.5 and 5.5, which allows it to be
directly treated by electrocoagulation without further pH
adjustment.
Furthermore, as shown in Fig. 3, the pH of OMW
changes during the process. As observed by other investigators [27,32], a pH increase occurs when the initial pH is
low (<7). Vik et al. [32] ascribed this increase to hydrogen
evolution at cathodes. However, this was contested by Chen
et al. [27] who explained this increase by the release of CO2
from wastewater owing to H2 bubble disturbance. Indeed, at
low pH, CO2 is over saturated in wastewater and can release
during H2 evolution, causing a pH increase. In addition, if

the initial pH is acidic, both reactions (6) and (7) would


shift towards the left hand side, which also causes a pH
increase. In alkaline medium (pH > 8), the final pH does
not vary very much and a slight drop was recorded. This
result is in accord with previously published works [27,33]
and suggests that electrocoagulation can act as pH buffer.
When the initial pH was 5 (typical of OMW), the final pH
reached 7.2 allowing the effluent to be directly discharged
into natural aquatic streams without pH adjustment. Thus,
in all subsequent experiments OMW was treated directly
without adjusting its initial pH.
3.3. Effect of current density
It is well-known that current not only determines the
coagulant dosage rate but also the bubble production rate
and size and the flocs growth [31,34], which can influence

11
10
9

Final pH

8
7
6
5
4
3
2
1
1

10

11

Initial pH
Fig. 3. The pH change of OMW after electrocoagulation as a function of initial pH (current density 30 mA cm2 , electrolysis time 30 min).

Residual polyphenol fraction, %

N. Adhoum, L. Monser / Chemical Engineering and Processing 43 (2004) 12811287

90

i = 15 mA cm-2

Table 2
Effect of current density on electrode consumptiona

80

i = 30 mA cm-2

Current density (mA cm2 )

Electrode consumption (kg m3 )

70

i = 45 mA cm-2

60

i = 75 mA cm-2

50

i = 120 mA cm-2

15
30
45
75
120

1.96
1.81
2.08
2.11
3.36

100

40
30
20

10
0

10

20

30

40

50

60

70

Time, min.

Residual fraction of COD, %

100
90

i = 15 mA cm-2

80

i = 30 mA cm-2

70

i = 45 mA cm-2

60

i = 75 mA cm-2

50

i = 120 mA cm-2

40
30
20
10
0
0

10

20

30

(b)

Residual dark colour fraction, %

Required to achieve more than 90% removal of dark colour.

(a)

40

50

70

60

Time, min.
100
90

i = 15 mA cm-2

80

i = 30 mA cm-2

70

i = 45 mA cm-2

60

i = 75 mA cm-2

50

i = 120 mA cm-2

40
30
20
10
0
0

(c)

1285

10

20

30

40

50

60

70

Time, min.

Fig. 4. Effect of current density on the pollutants removal rate: (a)


polyphenol; (b) COD; (c) dark colour (initial pH 4.96).

the treatment efficiency of the electrocoagulation. Therefore, the effect of current density on the pollutants removal
was investigated. Fig. 4 shows COD, polyphenol index and
dark colour removal upon electrolysis time, when current
density was varied from 15 to 120 mA cm2 . As expected,
it appears that for a given time, the removal efficiency
increased significantly with increase of current density.
The highest currents (75 and 120 mA cm2 ) produced the
quickest treatment with 80.6% COD, 91% polyphenol and
96% colour reduction occurring after only 30 min. This is
ascribed to the fact that at high current, the amount of aluminium oxidised increased, resulting in a greater amount of
precipitate for the removal of pollutants. In addition, it was
demonstrated that bubbles density increases and their size
decreases with increasing current density [35], resulting in a

greater upwards flux and a faster removal of pollutants and


sludge flotation. As the current decreased, the time needed
to achieve similar efficiencies increased. This expected behaviour is explained by the fact that the treatment efficiency
was mainly affected by charge loading (Q = It), as reported
by Chen et al. [27]. However, the cost of the process is
determined by the consumption of the sacrificial electrode
and the electrical energy which economically are the advantages of this method. Therefore, the amount of aluminium
oxidised to achieve high colour removals (>90%) was calculated at different current densities, using the Faradays Law:
m=

ItM
zF

(8)

where I is the current intensity, t is the time, M is the


molecular weight of aluminium (g mol1 ), z is the number
of electrons transferred in the reaction (=3) and F is the
Faradays constant (96,486 C mol1 ).
From the data presented in Table 2, it is seen that the
electrode consumption per cubic meter of treated OMW remained approximately constant with current density up to
75 mA cm2 . Any further increase beyond this value, induced a relatively high increase of electrode consumption.
A similar behaviour was previously observed by Holt et al.
[31] and was explained by the fact that, at higher currents,
the supply of aluminium ions is generated rapidly compared
to the coagulation process, resulting in a decrease of removal
efficiency calculated on an equivalent aluminium basis. In
addition, the faster removal of aluminium hydroxide from
solution by flotation leads to a reduction in the probability
of collision between the pollutant and coagulant.
These results suggest 75 mA cm2 as an optimal current
density for the treatment of OMW, since it ensures the quickest removal rate with the lowest cost.
3.4. Treatment of fresh and stored OMW
In a previous work, Hamdi and coworkers [13] showed
that during storage of OMW, autooxidation and subsequent
polymerisation of phenolic compounds and tannins, gives
rise to darkly coloured compounds which are recalcitrant to
biological treatment. To evaluate the efficacy of electrocoagulation, fresh and stored olive mill wastewater samples
were treated with the electrochemical method. The current
density was fixed at the optimum value of 75 mA cm2 and
OMW samples were used directly without adjusting their

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N. Adhoum, L. Monser / Chemical Engineering and Processing 43 (2004) 12811287

100
90

Removal efficiency, %

80
70
60
50
40

Fresh OMW

30
Polyphenol

20

COD

10

Dark colour

0
0

10

20

(a)

30

40

50

60

Time, min.
100

colour) present in fresh and stored olive mill wastewater.


The optimum value of current density, allowing fast removal
(25 min) of pollutants with low electrode consumption, was
found to be 75 mA cm2 . In addition, it was demonstrated
that the naturally occurring pH of OMW is appropriate to
achieve an effective treatment. Moreover, the final pH of
treated OMW was nearly neutral which allows it to be directly discharged in natural aquatic streams. Consequently,
electrocoagulation can be considered as a suitable alternative to existing methods or applied as pre-treatment step
of biological process used for the treatment of OMW. Indeed, the reported results show that electrocoagulation is
faster and more effective process as compared to biological
methods alone. Nevertheless, further studies should be carried out to confirm the practical feasibility of downstream
biological treatment.

90

Removal efficiency, %

80

References

70
60
50
40

Stored OMW

30
Polyphenol
20

COD

10

Dark colour

0
0

(b)

10

20

30

40

50

60

Time, min.

Fig. 5. Polyphenol, COD and colour removal rates from (a) fresh OMW;
(b) stored OMW (current density 75 mA cm2 ).

pH, since they were found to be in the optimum range: 4.96


and 5.1 for fresh and stored wastewater, respectively.
Removal efficiencies of polyphenol, dark colour and COD
as a function of time are presented in Fig. 5. As can be
seen, the treatment was successful for both samples and
was not affected by polymerised compounds present in the
stored OMW. Indeed, COD and polyphenol removals of
fresh OMW reached 75.8 and 91.4%, respectively, while
they reached 71 and 90.3% for stored OMW, just after
25 min. At this time, more than 95% colour reduction was
achieved for both OMW samples and the effluent became
visually very clear.
These results demonstrate clearly that electrocoagulation
is effective in reducing the amount of pollutants in fresh and
stored OMW.

4. Conclusion
In this work it was shown that electrocoagulation treatment achieves a fast and effective reduction of pollutants
(76% of COD, 91% of polyphenol and 95% of dark

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