Process Biochemistry 40 (2005) 2409–2416

www.elsevier.com/locate/procbio

Feasibility of physico-chemical treatment and Advanced Oxidation

Processes (AOPs) as a means of pretreatment
of olive mill effluent (OME)
Kadir Kestioğlua, Taner Yonara, Nuri Azbarb,*
a
Uludag University, Environmental Engineering Department, Gorukle, Bursa 16059, Turkey
b
Ege University, Bioengineering Department, Bornova, Izmir 35100, Turkey
Received 30 September 2003; received in revised form 10 July 2004; accepted 25 September 2004

Abstract

The efficiency of alternative pretreatment methods for an olive mill effluent (OME) in producing a final effluent conforming to Turkish
Water Pollution Standards for discharge into the public sewage was studied. For this purpose, various treatment alternatives such as acid
cracking, chemical coagulation, adsorption and Advanced Oxidation Processes (AOPs) were studied. A significant amount of Chemical
Oxygen Demand (COD), total phenol and oil and grease removal were obtained by acid cracking followed by chemical coagulation either
using alum or iron chloride salts. Among the alternative chemicals, both Al2SO4 and FeCl3 resulted in the same COD and total phenol removal
efficiency in this study (94–95% COD removal and 90–91% total phenol removals). Both H2O2/UV and O3/UV combinations studied in this
paper were found to give practically same COD and total phenol removal efficiencies (over a 99% removal for both COD and total phenol).
# 2004 Elsevier Ltd. All rights reserved.

Keywords: Olive oil mill effluent; Coagulation; Phenol; Pretreatment; Advanced oxidation

1. Introduction organic loads (Chemical Oxygen Demand, COD: 100–

Demand for olive oil is rapidly expanding worldwide due
to its healthy image. Olive oil has gained an increasing
popularity due to its oleic acid content, which may affect
plasma lipid/lipoprotein profiles and richness in antiox-
idants, which may prevent some human diseases [1,2].
Ironically, while the olive oil itself provides health during its
consumption, its resulting byproducts (olive mill wastes,
OMW) during olive processing pose a serious environmental
pollution especially in the Mediterranean, Aegan and
Marmara regions that account for approximately 95% of
worldwide olive oil production. Olive oil production results
in the generation of significant amounts of both solid and
liquid wastes composed of many complex coloured and
recalcitrant compounds (aromatics: 1–10 g m
3) with high
* Corresponding author. Tel.: +90 232 3434400x38;
fax: +90 232 388 4955.
E-mail address: nuriazbar@yahoo.com (N. Azbar).
300 g m
3) [3–6]. Conventional press extraction process
results in 0.5–0.8 m3 per ton of olives, whereas the waste
stream volume is 1.18–1.68 m3 per ton of olives from 3-
phase continuous centrifugal process. Production facilities
and wastes are usually associated with strongly odorous
volatile compound emissions. Olive mill wastes are a
significant source of environmental pollution especially in
some important olive oil producing countries such as Spain,
Italy, Greece, Tunisia, Turkey, Lebanon, Syria and Portugal
[7,8]. When disposed into the environment, OMW create
serious deteriorations such as colouring of natural waters, a
serious threat to the aquatic life, pollution in surface and
ground waters, alterations in soil quality, phytoxicity and
odor nuisance.
OMW can be regarded as either a resource to be recycled
or as a waste that needs to undergo expensive treatment
processes before its release into the environment. In order to
avoid the economic and social problems leading to potential
crisis in olive oil enterprizes due to the very high capital and

0032-9592/$ – see front matter # 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.procbio.2004.09.015
2410 K. Kestioğlu et al. / Process Biochemistry 40 (2005) 2409–2416
operating expenses of the treatment plants, several provisory
legislative and ministerial decrees were promulgated as well
as strategic plans were applied in some countries such as
Spain and Italy. Italy permits controlled use of OMW for the
purpose of irrigation, which is not acceptable in Turkey.
Spain promotes the construction of storage and evaporation
ponds and accepted a national policy of converting
conventional olive mills to a mill using the 2-phase
ecological extraction method, which eliminates the genera-
tion of liquid wastes as a separate phase.
OMW is tough to deal with and biological treatment of
OMW is a challenge because of biologically resistant
compounds such as tannins, polyphenols, polyalcohols,
pectins and lipids in OMW [9,10]. Many central municipal
wastewater treatment plants in Turkey had to be shut down
during the olive campaign period due to discharges of
untreated OMW with disastrously high organic and
recalcitrant content into the sewage [7]. Several methods
were tested for the treatment of OMW such as mechanical,
physical, chemical, biological and thermal methods. An
advisable single treatment method that is economically
viable has not been suggested yet. Evaporation in storage
lagoons is currently the common disposal method applied in
most countries as long as sufficiently large land areas are
available.
Commonly applied treatment solutions for COD and
colour removal from industrial effluents consist of integrated
processes involving various combinations of biological,
physical and chemical decolourization methods with limited
success [11–15]. Traditional physical-chemical techniques
such as ultrafiltration, reverse osmosis, ion exchange and
adsorption on various kinds of adsorbents (activated carbon,
peat, fly ash and coal, wood chips, silica gel, corncob, barley,
etc.) have efficiently been used for the purpose of colour and
COD removal from effluents. Nevertheless, these techniques
are non-destructive, since they just transfer the pollutant
from water to solid matrix. Advanced oxidation processes
(AOPs) based on the generation of very reactive and
oxidizing free radicals, especially hydroxyl radicals, have
been used with an increasing interest due to the their high
oxidant power.
Water Pollution Control Regulation in Turkey permits the
discharge of wastewater with COD up to 4000 mg L
1 into
the common sewage channels ending with a municipal
wastewater treatment plant. This study was conducted since
limited data have been reported with regard to the
consecutive application of physico-chemical methods and
AOPs for the pretreatment of olive mill effluent prior to the
discharge into common public sewage channels.
1.1. Principles of AOPs used in this study
AOPs have common principles in terms of the participation
of hydroxyl radicals that are assumed to be operative during
the reaction. Although it is claimed by some authors [15] that
there are other species involved, the active species responsible
for the destruction of contaminants in most cases seems to be
the hydroxyl radical (OH) which is unstable and quite
reactive. Due to the instability of OH radical, it must be
generated continuously in situ through chemical or photo-
chemical reactions described below:
(a) O3: there are two possible ways of oxidizing action in
the form of either direct reaction of dissolved
compounds with ozone or the reaction with generated
radicals. The dosage applied to the dye-containing
effluent is dependent on the total colour and residual
COD to be removed with no residue or sludge formation
[16] and no toxic metabolites [12]. One of the
drawbacks with ozonation is cost, continuous ozonation
is required due to its short half-life typically being
20 min. Stability is also affected by the presence of salts,
pH, and temperature. Alkaline solutions, for example,
accelerate ozone decomposition [17].
(b) O3/UV: The energy supplied by UV radiation interacts
with O3 to generate hydroxyl radicals as follows [18,19]:
hv
O3 þ H2 O
!2OH þ O2
(c) UV/H2O2: This process uses ultraviolet radiation to
cleave the O–O bond in hydrogen peroxide and generate
the hydroxyl radical [20,21]. The hydroxyl radical can
then be scavenged by an organic compound to initiate a
radical chain degradation of hydrogen peroxide in the
series of reactions [20,21]:
hv
Radical formation : H2 O2
!2OH
Hydroxyl radicals produced in either way described a-
bove may attack organic molecules by abstracting a hydr-
ogen atom from the molecule [20]. Carey [22] described a
common pathway for the degradation of organics by the
hydroxyl radicals as follows:
OH þ RH ! H2 O þ R
R þ H2 O2 ! ROH þ OH
R þ O2 ! ROO
ROO þ RH ! ROOH þ R
2. Materials and methods
2.1. Experimental setup
Wastewater samples used in this study was obtained from
the homogenization tank of an olive mill plant with a daily
olive processing capacity of 100 tones in Bursa City, Turkey.
This wastewater sample was characterized as shown in Table
1 [23–25]. Experiments were carried out in two ways as
chemical treatment and advanced oxidation trials. Acid
cracking was first applied to all samples by adjusting pH
 K. Kestioğlu et al. / Process Biochemistry 40 (2005) 2409–2416 2411

Table 1
Comparative characteristics of the OMW used throughout the study
Parameters Hamdi Steegmans Andreozzi This
(g L
1 except [23] [24] et al. [25] study
for pH)
pH 3–5.9 5.3 5.09 4.65–5.5
Suspended solids (SS) 1–20 19.2 102.5 65  8.0
Oil and grease 1–23 2.33 9.8 35  3.4
Total nitrogen 0.3–1.2 0.6 0.95 0.67  0.13
Total phosphorus – – – 0.175  0.08
Total COD 40–220 108.6 121.8 185.6  23.8
Filtered COD – – – 35  4.0
Total phenol 5–80 0.002 6.2 9.68  1.18

manually to less than 2 using sulphuric acid. Samples used in

all other experiments such as chemical coagulation,
adsorption and AOPs tests were carried out using these
acid cracked samples. In the physico-chemical treatment
experiments using jar test equipment, Al2(SO4)318H2O, and
FeCl3 (supplied from Merck) reagents were tested to
investigate the effects of different coagulants at various
dosages between 1000 and 6000 mg L
1 on the treatment
efficiency in removing the phenolic and COD content of
OMW. The jar tests were carried out using acid cracked
samples, in the following order: At first, the initial
concentrations of total phenol and COD were measured
for each sample in accordance with Standard Methods [26].
Optimum pH was first determined and then the optimum
reagent doses that provide best COD removal were first
determined for each chemical at room temperature (20 8C).
1 L of a wastewater sample given in Table 1 was dosed with
each chemical at varying dosages separately. One-hour
sedimentation was applied following coagulation time of
30 min (20 rpm) after flash mixing for a minute (120 rpm).
The final pH was recorded in the sample taken from the
supernatant phase above the precipitate; then, the final or
effluent concentrations of total phenol and COD in that
sample were measured as described in analytical methods
section.
Adsorption experiments using granular activated carbon
(GAC) on the effluent of acid cracking and chemical
coagulation pretreatment samples were also carried out. For
this purpose samples having varying dilution ratios were
contacted with 10 g GAC per liter for 24 h and COD in each
vessel after filtration was measured at the end of 24 h
reaction time.
A photoreactor as shown in Fig. 1 was set up for the
experiments with UV in batch mode operation. A TUV-15
model Phillips 15 W lamp (wavelength of l = 254 nm)
enclosed in a quartz sleeve with an inner diameter of 39 mm
and a length of 39 cm was positioned within the center of a
3 L cylindrical stainless steel reactor as the light source. The
body of the reactor was made of 316-Ti stainless steel with
an inner diameter of 98 mm and a length of 41 cm. The light
intensity along axial length was measured and thereby the
diameter of the photoreactor was determined. A water jacket
Fig. 1. Schematic representation of photoreactor used during oxidation
experiments.
was installed around the reactor to keep the reactor at a
desired temperature (20  0.5 8C) by means of a continuous
water recirculation controlled by a thermostat. The
recirculating cooling solution and the wastewater sample,
which is the effluent of acid cracking and chemical
coagulation pretreatment, and never contacted each other.
The content of the reactor (2.8 L) was continuously mixed
by the help of a magnetic stirrer.
An ozone generator (Opal 200 model) with an ozone
production rate of 0.3 g h
1 was integrated into this reactor
in order to produce the ozone needed in the reaction during
O3/UV experiments. The ozone produced by using oxygen
with a purity of 99.5% was bubbled into the reactor by
means of a diffuser. H2O2/UV and O3/UV experiments were
carried out under various pH values between 2 and 9. In both
O3/UV and H2O2/UV (CH2 O2 ¼ 500 mg L
1 ) experiments,
the effect of various pH values on COD removal was
assessed by keeping pH values at 2, 7 and 9, respectively.
The pH was manually adjusted manually to the desired range
using sulphuric acid and/or sodium hydroxide from Merck,
then the predetermined amount of H2O2 (supplied from
Riedel de Haen, 35%) added and the lamp and ozone
generator turned on. Following the determination of
optimum pH as above, the experiments were carried out
at the optimum pH with varying H2O2 dosages of 250–
1000 mg L
1 for H2O2/UV. H2O2/UV experiment was run
for 24 h at a pH of 2 at an optimum dose of H2O2
concentration and total phenol concentration by time were
monitored. O3/UV experiment was also run for another 24 h
at a pH of 7 and both COD and total phenol concentration by
time were monitored. Samples were taken at regular time
intervals for the determination of COD and total phenol. All
experiments were done in batch reactors.
In order to decompose residual H2O2, which interferes
with the COD and absorbance measurements, the samples
containing H2O2 were treated with MnO2 powder. Before
each analysis, samples were centrifuged and filtered on
0.45 mm Millipore membranes to remove MnO2. COD
2412 K. Kestioğlu et al. / Process Biochemistry 40 (2005) 2409–2416

(closed reflux method), oil and grease, suspended solids Table 2

(SS), total nitrogen and phosphorus were measured in Characteristics of the OMW after acid cracking
accordance with Standard Methods [26]. Total phenol (TP) Parameters Unit Value
content was determined according to a modification of pH – <2
Folin-Ciocalteau method [27]. Total phenol content was SS mg L
1 3250  275
Oil and grease mg L
1 350  48
determined by the addition of 500 ml Folin-Ciocalteau (four-
Total nitrogen mg L
1 670  38
fold diluted) phenol reagent to 100 ml 20-fold diluted Total phosphorus mg L
1 175  23
samples. After 5 min, 500 ml sodium carbonate (200 gl
1) Total COD mg L
1 115000  8700
was added and the absorbance was measured at 725 nm Total phenol (as caffeic acid) mg L
1 7500  387
against a blank after 30 min at room temperature.

of 6000 mg L
1. Chemical treatment generated a tremen-

3. Results and discussion dous amount of chemical sludge. Volumetrically, chemical
sludge generation was about 500–700 ml per liter of influent.
3.1. Acid cracking, coagulation and adsorption tests An adsorption study with granular activated carbon
(GAC; Jacobi; 0.5–1.0 mm) was carried out for samples
As mentioned in materials and methods, COD and total after acid cracking and chemical coagulation at room
phenol removal experiments consisted of two stages being temperature. For this purpose jar test equipment of 1 L
chemical coagulation and oxidation processes after acid capacity was used. A fixed amount of adsorbent (10 g L
1)
cracking in order to compare the results. Characteristics of was mixed with diluted solutions (five dilution ratios of 1/1,
OMW after acid cracking are given in Table 2. Acid cracking 1/2, 1/4, 1/5 and 1/10) having initial COD concentrations of
resulted in 38% COD, 23% total phenol removal and 8160, 4120, 1850, 1552 and 724 mg COD L
1, respectively.
significant amount of oil and grease removal (Table 3). At the end of the mixing period, residual COD concentra-
Al2(SO4)318H2O and FeCl36H2O coagulants were used tions in each container were measured according to the
during the chemical treatment experiments with varying Standart Methods. Effluent COD measurements were
dosages under predetermined optimum pH conditions measured as 2672, 1820, 542, 486 and 275 mg COD L
1,
(Fig. 2a and b). For comparison, the COD and total phenol respectively. Adsorption isotherm was found to fit with
removal results of under best pH conditions are given in Langmuir [28] isotherm and adsorption capacity of the GAC
Table 3. Optimum pH for each chemical was found to be as used in this study was found to be 217 mg COD per gram of
follow; pH 8 for Al2(SO4)318H2O and pH 8 for GAC and 186 mg total phenol per gram of GAC. These
FeCl36H2O. Between the two chemicals used in this study, results indicates that about 50 kg of GAC per cubic meter of
FeCl36H2O resulted in a 95% COD, 90% total phenol and pretreated effluent (effluent from acid cracking and chemical
99% suspended solids (SS) removals at a dosage of coagulation) is required.
3000 mg L
1. Resulting effluent concentrations of COD,
total phenol and SS were found to be 9600, 972 and 3.2. Advanced oxidation tests
560 mg L
1, respectively. On the other hand, 94% COD
(COD in the effluent = 11,200 mg L
1), 91% total phenol Several substances like phenolic compounds in olive oil
removal (total phenol in the effluent = 915 mg L
1) and mil effluents have been shown to present some kind of
99% SS removal (SS in the effluent = 400 mg L
1) were inhibitory effect when undergoing biological oxidation. In
observed in experiments using Al2(SO4)318H2O with a dose order to eliminate the toxicity to microorganisms arising
Table 3
COD and phenol removal efficiencies of various pretreatment methods for the OMW
Pretreatment method COD Phenol pH CH2 O2 cchemical CO3 Effluent Effluent
removal (%) removal (%) (mg L
1) (mg L
1) (g h
1) COD (mg L
1) phenol (mg L
1)
Acid cracking 38 23 2a – 5 ml concentrated 115000 7500
H2SO4 per liter
Acid cracking + alum coagulation 94 91 8b – 6000 – 11200 915
Acid cracking + FeCl3 coagulation 95 90 8c – 3000 – 9600 972
Acid cracking + ferric coagulation + O3/UV 98 99 7d 750 – – 4560e 21e
Acid cracking + ferric coagulation H2O2/UV 99 99 2f – – 0.3 3800g 22g
a
pH of acid cracking.
b
pH of alum coagulation.
c
pH of ferric coagulation.
d
pH of O3/UV process.
e
pH 7; T = 20 8C; t = 440 min.
f
pH of H2O2/UV.
g
pH 7; T = 20 8C; CH2 O2 ¼ 750 mg L
1 ; t = 720 min.
 K. Kestioğlu et al. / Process Biochemistry 40 (2005) 2409–2416
Fig. 2. (a) COD and (b) total phenol removals by chemical coagulation.
from phenolic content, integration of a pre-treatment step
including chemical oxidation has been proposed previously.
In this study, oxidation of olive mill effluents after physico-
chemical pretreatment was undertaken using the combina-
tions of O3/UV and H2O2/UV processes in order to assess
COD and total phenol removal efficiency of these processes.
The experiments were carried out at pH values of 2, 7 and 9
for O3/UV and H2O2/UV experiments, respectively, to
observe the effect of pH on the COD removal. Optimum pH
that results in highest COD and total phenol removal was
determined by initially running the photo reactor under
varying pH but constant H2O2 for H2O2/UV experiments
(Fig. 3a). H2O2/UV experiments were then run at pH of 2 for
varying H2O2 dosages between 250 and 1000 mg L
1 (Fig.
3b). COD dropped down to 3060 and 3650 mg L
1 for H2O2
dosages of 750 and 1000 mg L
1, respectively, at the end
1440 min reaction time (initial COD was 10,240 mg L
1).
Four hundred minutes of reaction time seems reasonably
long enough since there is no significant change between the
results of 400 and 1440 min in effluent CODs. The same
experiment was carried out a H2O2 dose of 750 mg L
1 to
observe the total phenol removal together with COD
removal. The initial total phenol, which was 975 mg L
1,
2413
was dropped down to 22 and 10 mg L
1 at the end of 400
and 1440 min reaction times, respectively.
In the second part of oxidation experiments, O3/UV
process was applied to the OMW samples after pretreatment
by acid cracking and coagulation. An Opal 200 model ozone
generator with an ozone production rate of 0.3 g h
1
produced the ozone needed in the reaction. pH values of 2, 7,
and 9 were tested in order to find the best pH for optimum
COD removal. Fig. 4 depicts the effects of various pH on the
COD removal by O3/UV process. Alkaline conditions
showed better removal efficiency, pH of 7 and 9 however
showed similar results in terms of COD removal. Therefore,
O3/UV experiment was run at pH of 7 for 1440 min of
reaction times to observe the phenol removal. Total phenol
concentration after 300 min of reaction time was found to be
21 mg L
1. There was no significant change in both COD
and total phenol concentration after 300 min of reaction
time.
Choosing among the candidate processes will be
determined by the capital and operating costs including
costs of pH adjustment, disposal costs of chemical sludge,
electricity, etc. As it was summarized in Table 3, AOPs
resulted in 99% total phenol removal.
2414 K. Kestioğlu et al. / Process Biochemistry 40 (2005) 2409–2416

Fig. 3. (a) Effect of pH (CH2 O2 ¼ 500 mg L
1 , T = 20 8C) and (b) H2O2 concentration (pH = 2; T = 20 8C) on the removal of COD during H2O2/UV
experiments.

Fig. 4. Effect of pH on the removal of COD by O3/UV process (T = 20 8C).

 K. Kestioğlu et al. / Process Biochemistry 40 (2005) 2409–2416 2415

Table 4 followed by chemical coagulation methods. A clear

Costs of the reagents and operating cost of the treatment methods used (cost separate phase of residual olive oil was observed after
of labor, sludge disposal and UV lamps are excluded) acid cracking, which volumetrically equals to 10–15%
Reagents used Basis Cost ($) Process Treatment of the effluent. A tremendous amount of chemical
cost ($/m3) sludge was generated during coagulation processes,
H2O2 (35%) kg 0.54 Acid cracking 2.0 which may dictate the use of dewatering equipment
O3 kg 2.64 Alum coagulationa 3.18 (press filter or centrifuge, etc.) in the main treatment
Electricity kW h 0.0765 Ferric coagulationa 2.67
H2SO4 kg 0.224 O3/UVb 12.62
flow scheme.
NaOH kg 0.224 H2O2/UVb 13.17 (ii) AOPs resulted in over a 99% removal for both COD and
Al2SO4 kg 0.197 Activated carbonb 141 total phenol colour with no sludge generation. The
FeCl3 kg 0.223 AOPs techniques (O3/UV, H2O2/UV) studied resulted
GAC kg 2.76 in the same removal efficiencies for both COD and
a
Includes acid cracking + neutralization costs. phenol. Although the combination of O3/UV resulted in
b
Includes acid cracking + neutralization + ferric coagulation costs. slightly higher COD in the effluent than what is stated
in the Turkish Water Pollution Regulation, it appeared
to be the economically most viable option since there is
3.3. Cost evaluation
no need for pH adjustment before and after reaction.
(iii) Adsorption by GAC is an efficient but economically not
The overall costs are represented by the sum of the capital
a practical solution for the pretreatment purpose before
costs, the operating costs and maintenance. For a full-scale
discharge into common public sewage.
system, these costs strongly depend on the flow rate of the
effluent and the configuration of the reactor as well as the
nature of the effluent. In this study, only operating costs such References
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