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Low Cost Biosorbent “Banana Peel” for the Removal of Phenolic Compounds
from Olive Mill Wastewater: Kinetic and Equilibrium Studies

Article in Journal of Hazardous Materials · November 2008

DOI: 10.1016/j.jhazmat.2008.11.036

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 Journal of Hazardous Materials 166 (2009) 117–125

Contents lists available at ScienceDirect

Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Low cost biosorbent “banana peel” for the removal of phenolic compounds
from olive mill wastewater: Kinetic and equilibrium studies
M. Achak a , A. Hafidi b , N. Ouazzani a , S. Sayadi c , L. Mandi a,∗
a
Laboratoire d’Hydrobiologie, d’Ecotoxicologie et d’Assainissment, Université Cadi Ayyad, Faculté des Sciences Semlalia, Boulevard Prince Moulay-Abdelah,
BP 2390 Marrakech, Morocco
b
Laboratoire Sciences des Aliments, Université Cadi Ayyad, Faculté des Sciences Semlalia, Boulevard Prince Moulay-Abdelah, BP 2390 Marrakech, Morocco
c
Laboratoire des Bioprocédés, Centre de Biotechnologie de Sfax, Route Sidi Mansour, BP: “K” 3038 Sfax, Tunisia

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

Article history: The aim of this work is to determine the potential of application of banana peel as a biosorbent for remov-
Received 16 April 2008 ing phenolic compounds from olive mill wastewaters. The effect of adsorbent dosage, pH and contact time
Received in revised form 4 November 2008 were investigated. The results showed that the increase in the banana peel dosage from 10 to 30 g/L sig-
Accepted 5 November 2008
nificantly increased the phenolic compounds adsorption rates from 60 to 88%. Increase in the pH to above
Available online 21 November 2008
neutrality resulted in the increase in the phenolic compounds adsorption capacity. The adsorption process
was fast, and it reached equilibrium in 3-h contact time. The Freundlich and Langmuir adsorption models
Keywords:
were used for mathematical description of the adsorption equilibrium and it was found that experimen-
Banana peel
Adsorption
tal data fitted very well to both Freundlich and Langmuir models. Batch adsorption models, based on
Phenolic compounds the assumption of the pseudo-first-order, pseudo-second-order and intraparticle diffusion mechanism,
Olive mill wastewaters showed that kinetic data follow closely the pseudo-second-order than the pseudo-first-order and intra-
Desorption particle diffusion. Desorption studies showed that low pH value was efficient for desorption of phenolic
compounds. These results indicate clearly the efficiency of banana peel as a low-cost solution for olive mill
wastewaters treatment and give some preliminary elements for the comprehension of the interactions
between banana peel as a bioadsorbent and the very polluting compounds from the olive oil industry.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction [2–4], chemical [5–7] and physical treatment [1,8,9]. Among them,
physical adsorption method is generally considered to be the best,
Olive mill wastewaters (OMW) are a significant source of envi- effective, low cost and most frequently used method for the removal
ronmental pollution related to olive oil production industries. Olive of phenolic compounds. Adsorption is a well-known equilibrium
oil extraction processes generate three phases: olive oil, solid separation process and an effective method for water decontam-
residue and aqueous liquor (OMW) which averagely represents 20, ination applications. Adsorption has been found to be superior to
30 and 50%, respectively, of the total weight of the processed olives. other techniques for water reuse in terms of initial cost, flexibility
OMW cause serious environmental deteriorations such as coloring and simplicity of design, ease of operation and insensitivity to toxic
of natural waters, alteration of soil quality, phytotoxicity and odor pollutants [10]. Adsorption also does not result in the formation of
nuisance. harmful substances and the organic sorbents can be used as fuel for
Since olive oil is mainly produced in the Mediterranean region power generation or as ferment substrate.
(95% of the world production), countries from this area are partic- The most popular and widely used adsorbent material for treat-
ularly concerned by this environmental problem. About 11 million ment of OMW is activated carbon [11,12]. However, the relatively
tons of olives are produced each year in this region from which high initial cost and the need for a costly regeneration system make
about 1.7 million tons of olive oil is extracted. The seasonal pollut- the activated carbon less economically viable as excellent adsorbent
ing load of olive oil production is reported to be equivalent to that [13,14].
of 22 million people per year [1]. Many sorbents based on low cost agricultural by-products had
Conventional methods for the removal of phenolic compounds been used for dye sorption from wastewater, which included
from OMW can be divided into three main categories: biological banana pith [15], orange peel [16], wheat straw [17], sawdust [18],
powdered waste sludge [19], wheat shells [20], wheat bran [21]
and hen feathers [22]. However, at the best of our knowledge, the
∗ Corresponding author. Tel.: +212 24 43 46 49; fax: +212 24 43 74 12. adsorption and removal of specific organics from OMW by banana
E-mail address: [email protected] (L. Mandi). peel has not been reported.

0304-3894/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2008.11.036
118 M. Achak et al. / Journal of Hazardous Materials 166 (2009) 117–125

The purpose of this work is to investigate the efficiency of Table 1

Chemical and physical properties of banana peel used in the experiments.
banana peel as a biosorbent for removal of phenolic compounds
from OMW. Banana peel is an abundant and low cost agricultural Parameters Data
waste residue and is easily available in large quantities. The effects Moisture content (%) 13.55
of various operating parameters on biosorption such as initial pH, Volatile matter (%) 86.44
sorbent dosage and contact time were monitored and optimal Ash (%) 3.85
experimental conditions were determined. Different adsorption C content (%) 31.79
O content (%) 42.87
isotherms (Langmuir and Freundlich isotherms) and kinetic models
K content (%) 14.86
(pseudo-first, pseudo-second-order kinetics and intraparticle dif- Na content (%) 1.33
fusion) were used to find out most suitable models describing our Si content (%) 1.48
experimental findings. Al content (%) 1.05
Cl content (%) 3.22
pH 6.60
2. Experimental Particle size (mm) <1

2.1. OMW origin

Density was determined by weighing an exactly measured vol-
OMW were obtained from a three-phase continuous extraction ume of sample.
unit from Marrakech, southern Morocco. The OMW were first stored Phenolic compounds were quantified by means of the
in a plastic can (120 L-capacity) at ambient (20–30 ◦ C) temperature. Folin–Ciocalteu colorimetric method [27] using caffeic acid as
a standard. The absorbance was determined at 765 nm. Chro-
2.2. Preparation of the adsorbent matographic separations of phenolic substances were carried
out on C-18 column (5 mm, 4.6 mm × 250 mm) using H3 PO4
Banana peel was from a local market. The collected biomaterial (0.1%)–water–acetonitrile/water (7/3) mobile phase system. The
was extensively washed under tap water to remove any partic- HPLC system consisted of an injector with a 20-␮L sampling loop
ulate, sprayed with distilled water. This biosorbent was cut into and a UV–visible spectrophotometric detector. Detection was per-
small pieces, dried in sunlight, crushed and sieved through a 1 mm formed at 280 nm and an isocratic elution rate was 0.8 mL/min.
size before its use in adsorption experiments without any further K+ , Na+ and Ca2+ were analysed with a flame photometry
treatment. method.

2.3. Physical–chemical analysis of OMW

2.4. Physical–chemical analysis of adsorbent
pH was determined with a pH meter (716 DMS Titrino). Electrical
Surface images of the adsorbent before and after adsorption
conductivity (EC) was measured with a conductivimeter (Tacussel)
were captured by scanning electron microscopy (SEM), with a JEOL
[23]. Total solids (TSs) were obtained by weighing sample before
JSM-5500 apparatus. Rates of volatile matter, ash and moisture
and after drying overnight at 105 ◦ C. Total suspended solid (TSS) was
were determined by Rodier method [23]. Results summarized in
determined after filtering a sample through a GF/C filter (0.45 ␮m)
Table 1 show the measured characteristics. Chemical analysis of the
and drying the retained residue at 105 ◦ C for 60 min. Mineral matter
banana peel showed that major constituents are carbon, potassium
was determined after calcination at 450 ◦ C for 4 h. The difference
and oxygen, Na, Si, Al and Cl has been found in traces.
between TS and mineral matter was defined as volatile solids (VSs)
[23].
Total and dissolved chemical oxygen demand (COD) was deter- 2.5. Adsorption experiments
mined by a colorimetric method [24]. An appropriate amount of
sample was introduced into a commercially available digestion Batch adsorption experiments were carried out using a rotary
solution and the mixture was then incubated for 120 min at 150 ◦ C shaker (rotatest 74581) at 200 rpm min−1 at 30 ± 2 ◦ C in a 250-mL
in a COD reactor. COD concentration was measured colorimetrically shaking flasks containing 100 mL of OMW with a known concen-
using UV/VIS spectrophotometer (500 serie DU). The absorbance tration of phenol (13.45 g/L). Different doses (1–5 g) were tested
was determined at 620 nm. at various pHs (2–11). pH studies were conducted to determine
The biochemical oxygen demand (BOD5 ) was assessed by mea- the optimum pH at which maximum phenolic compounds removal
suring the oxygen uptake in a sample over a period of 5 days at 20 ◦ C, could be achieved. The pH of the suspension was adjusted by
in the dark, using the BOD Track apparatus. The sample was diluted, 0.1N HCl or NaOH. The flasks were sealed to prevent change in
mixed with domestic wastewater and its pH was adjusted. As dis- volume of the solution during the experiments. The changes of
solved oxygen was consumed, air pressure in the bottle dropped adsorption rates of phenols were monitored at different time inter-
and pressure changes were continuously recorded [25]. vals (1; 1.5; 2; 2.5; 3; 4; 18; 24 h). Samples were taken out from
Kjeldahl N (Kj-N) was determined by the Kjeldahl digestion flasks and the solutions were separated from the adsorbent by fil-
and distillation method. Ammoniacal nitrogen (NH4 ) was deter- tration with a 0.6-mesh stainless steel sieve and centrifuged for
mined colorimetrically according to AFNOR method [25]. Nitrite 20 min at 5100 rpm min−1 . Phenolic compounds concentration in
(NO2 ) was determined by coupling diazotation followed by a col- the supernatant solutions was determined. The experiments con-
orimetric method according to AFNOR method [25]. Nitrate (NO3 ) ducted in duplicate and the negative controls (without adsorbent)
was determined like nitrite after its reduction by passage in a were simultaneously carried out.
cadmium–copper column [23]. The amount of adsorption at equilibrium, qe (mg/g) and the
The phosphorus content (expressed as phosphate equivalents) percent adsorption (%) was computed as follows:
was determined colorimetrically using the AFNOR method [25]. (C0 − Ceq )V
Chloride (Cl− ) was determined by a titrimetry method according qe = (1)
X
to AFNOR method [25].
Reducing sugars were determined by a colorimetric method C0 − C
percent adsorption (%) = × 100 (2)
according to Dubois et al. [26]. C0
 M. Achak et al. / Journal of Hazardous Materials 166 (2009) 117–125 119

where C0 and Ceq are the initial and equilibrium concentration of

phenolic compounds (g/L), V volume of solution (L), X the weight
of banana peel (g) and C the phenolic concentration at the end of
adsorption.

2.6. Desorption experiments

The adsorbent (3 g) used for the adsorption experiments of

OMW at pH 7 was separated from the solution by centrifugation
and washed gently with water to remove any unabsorbed pheno-
lic compounds. Desorption experiments were conducted on 1 g of
used adsorbent which was agitated at 200 rpm min−1 for 12 h with
100 mL of: neutral pH water, water at pH 12 and water–acetic acid
Fig. 1. HPLC chromatograms of the phenolic compounds from raw olive mill effluent.
(pH 1.20).

3. Results and discussion Total COD were higher than those reported by some Moroc-
can researchers [31,32]. Total phenolic compounds concentrations
3.1. OMW characterization were also higher than those obtained by other authors [32–34].
These differences in the levels of phenolic compounds may be due
Table 2 shows the main properties of OMW after 1-week to the variety and the degree of maturity of the processed olives
decantation to remove the total suspended solids. As depicted in [35] and also to the extraction techniques used. Caponio and Cata-
Table 2, the sample shows an acidic pH value (5.06). Due to this lano have shown that even the temperature of the olives before and
relatively low pH value, biological treatment of OMW may be lim- during crushing influences strongly the solubilization of phenolic
ited by the ability of micro-organisms to grow at such acidic pH. compounds and consequently their amounts in OMW [36].
In general, bacteria show maximum growth at pH between 6.5 and HPLC chromatograms depicted in Fig. 1 show Hydroxytyrosol
7.5 [28]. If the pH of OMW is not modified prior to discharge, they (0.275 g/L) and tyrosol (0.062 g/L) as the two main monomer phe-
may alter the pH of natural waters [29]. The electrical conductivity nolic compounds encountered in our samples. Such composition is
was very low (6.9 mS/cm) compared to that reported by Zenjari et almost similar to that reported by other researchers [37]. As deter-
al. which varies between 25.3 and 36.6 mS/cm [30]. This parame- mined by the HPLC analysis the phenolic compounds content is
ter may be directly related to salting practices of the olives before found to be less than that obtained by the Folin-Ciocalteu determi-
trituration according to some Moroccan traditional practices. nation. The Folin-Ciocalteu method is known to be not specific to
OMW show high concentrations of total solids (20.4 g/L) and phenolic compounds, other molecules can react with this reagent
total suspend solids (2.07 g/L). The high TS of the raw OMW make leading to an over estimation of the phenolic content.
it unsuitable for irrigation use. Number of farms in rural areas in The OMW contain some valuable nutrients such as nitrogen and
Morocco, occasionally, uses raw OMW for irrigation aiming benefits potassium, which would be useful in agriculture after effluent treat-
of its high fertilizing value. ment. The high concentrations of sodium (0.46 g/L) and chloride
OMW contain also a high level of organic matter (70.2 g O2 /L of (1.4 g/L) were probably due to salting of the olives.
total COD, 48.7 g O2 /L of dissolved COD) and high amounts of total
phenolic compounds (13.4 g/L) which are known highly phytotoxic. 3.2. Preliminary adsorption tests
The content of phenolic compounds in OMW is usually higher than
the standard limits (mostly less than 0.5 mg/L) established for their Preliminary tests were carried out at two concentrations of
release into aquatic environment. adsorbents (1% and 5%) at ambient temperature, under agitation
and 1-day contact time. The results (Table 3) showed that with
Table 2 1% of banana peel, we obtained an elimination of 34%, 11.5% and
Physical–chemical determination of the raw OMW (mean values of three separate 16% of phenolic compounds, COD and color intensity, respectively.
analysis ± standard deviation). The increase of this amount of adsorbent to 5% improved the elim-
Parameters Data ination of the phenolic compounds (66%), COD (54%) and color
intensity (67%) (Table 3).
pH (25 ◦ C) 5.06
Electrical conductivity (mS/cm) at 20 ◦ C 6.85
The HPLC analysis of the residual phenolic compounds of the
Total suspend solid (TSS) (g/L) 2.07 ± 0.02 OMW after adsorption on the banana peel at a concentration of 1%
Total solid (TS) (g/L) 20.41 ± 0.4 (Fig. 2a) shows an elimination of 41% of the hydroxytyrosol and
Mineral matter (MM) (g/L) 5.29 ± 0.05 34% of the tyrosol. With 5% of the bioadsorbent, the treatment
Volatile solid (VS) (g/L) 1.51 ± 0.03
allowed an important elimination of monomeric compounds, 90%
TKN (g/L) 1.96 ± 0.01
NH4 + (mg/L) 0.64 ± 0.04 of hydroxytyrosol and 56% of tyrosol (Fig. 2b).
NO3 − (mg/L) 0.4 0 ± 0.07
NO2 − (mg/L) 4.00 ± 0.03 3.3. SEM analysis
Total phenols (g/L) 13.45 ± 0.01
Total COD (g O2 /L) 70.22 ± 1.22
Dissolved COD (g O2 /L) 48.69 ± 3.18 SEM has been a primary tool for characterizing the surface mor-
BOD5 (g O2 /L) 16.74 ± 0.19 phology and fundamental physical properties of the adsorbent. It is
PO4 − (g/L) 0.36 ± 1.43
Total P (g/L) 0.42 ± 0.003
Cl− (g/L) 1.42 ± 0.001 Table 3
K+ (g/L) 2.11 ± 0.00 Efficiency of reducing pollutant charges in OMW using banana peels as bioadsorbent.
Ca2+ (g/L) 0.06 ± 0.00
Banana peel (%) % polyphenols % COD % coloration
Na+ (g/L) 0.46 ± 0.00
Reducing sugar (g/L) 0.12 ± 0.008 1 34 11.5 16
Density (g/L) 1.10 ± 0.02 5 66 54 67
120 M. Achak et al. / Journal of Hazardous Materials 166 (2009) 117–125

Fig. 2. (a) HPLC analysis of the phenols from OMW after treatment with 1% of banana
peel and (b) HPLC analysis of the phenols from OMW after treatment with 5% of
banana peel.
Fig. 3. (a) SEM images for original banana peel and (b) SEM images for banana peel
after adsorption.
useful for determining the particle shape, porosity and appropriate
size distribution of the adsorbent.
The chemical characterization of the powder before and after the increase in the adsorbent dosage and it, therefore, results in
adsorption showed a change of the characteristics of the surface of the increase in the amount of adsorbed phenolic compound. The
the powder (Table 4). The difference in percentage of each element increase in adsorbent rate over 30 g/L has not allowed any addi-
before and after adsorption demonstrates the change of the char- tional improvement in adsorption. This seems to be due to the
acteristics of the surface of the banana peel powder, and confirms binding of almost molecules of phenolic compounds to the sor-
the adsorption phenomenon. bent and the establishment of equilibrium between the molecules
Scanning electron micrographs of original banana peel (Fig. 3a) bounded to the sorbent and unadsorbed molecules in the solu-
show that the peel particles pores are highly heterogeneous. After tion. Thus, all our subsequent experiments were performed at an
adsorption, a significant change in the structure of the peel is adsorbent dosage of 30 g/L.
observed (Fig. 3b). The peel appears to have a rough surface with The adsorption capacity was found to be high at low dosages.
crater-like pores because they are partially covered by organic Many factors can contribute to this adsorbent concentration effect.
molecules. The most important factor is that adsorption sites remain unsatu-
rated during the adsorption reaction. This decrease in adsorption
3.4. Effect of adsorbent rates capacity with the increase in the adsorbent dosage is mainly
attributed to the non-saturation of the adsorption sites during the
Adsorbent dosage is an important parameter because it deter- adsorption process [38,39].
mines the capacity of an adsorbent for a given initial concentration
of the adsorbate. The equilibrium uptake for the adsorption of phe-
nolic compounds on banana peel was determined with 100 mL
of OMW containing 13.45 g/L total phenolic compounds. The sys-
tem was agitated for 24 h (200 rpm) at a constant temperature
(30 ± 2 ◦ C) at the initial pH 5. Fig. 4 shows that the increase in adsor-
bent dosage from 10 to 50 g/L resulted in a decrease from 13.45 to
0.34 g/L in of phenolic compounds of the OMW. It is readily under-
stood that the number of available adsorption sites increases with

Table 4
Chemical characterization of the powder before and after adsorption.

Elements

C O K Na Si Al Cl
Fig. 4. Influence of adsorbent concentration on adsorption rates of phenolic com-
% before adsorption 31.8 42.8 14.8 1.33 1.48 1.05 3.22
pounds and the equilibrium uptake (conditions: 100 mL of OMW, temperature: 30 ◦ C,
% after adsorption 40.11 47.7 2.37 5.02 0.74 0.70 1.03
contact time: 24 h and initial pH 5).
 M. Achak et al. / Journal of Hazardous Materials 166 (2009) 117–125 121

Fig. 5. Effect of pH on adsorption of phenolic compounds by banana peel (condi-

tions: 100 mL of OMW, temperature: 30 ◦ C, contact time: 24 h and sorbent dose: Fig. 6. Effect of contact time on adsorption of phenolic compounds by banana peel
30 g/L). (conditions: 100 mL of OMW, temperature: 30 ◦ C, sorbent dose: 30 g/L and pH 7).

3.5. Effect of pH on phenolic compounds biosorption ment of textile industry effluents [18]. In this latter study almost
100% dye removal was obtained at pH values above 7.
The most important parameter influencing the adsorption The mechanisms of action of pH cannot be reduced to a surface
capacity is the pH of adsorption medium [40]. The final pH of charge modification and the adsorption of phenolic compounds
an adsorption medium affects the adsorption mechanisms on and other compounds must not be seen only as the result of elec-
the adsorbent surface and influences the nature of the physico- tric interactions. Many other interactions can lead to adsorption of
chemical interactions of the species in solution and the adsorptive molecules on adsorbent surfaces especially in the case of bioadsor-
sites of adsorbents [41]. The experiments of the pH effect were bents. Adsorption can result from weak forces interactions, ionic
conducted on 100 mL OMW. Agitation was maintained for 24 h strength and chemical reactions leading to irreversible bindings.
(200 rpm) at (30 ± 2 ◦ C) at the predetermined optimal adsorbent However, the mechanisms involved governing the effect of pH on
dosage (30 g/L). phenolic compounds adsorption mechanism need to be further
The effect of pH on the adsorption of phenolic compounds by investigated.
banana peel at pH ranging between 2 and 11 is shown in Fig. 5. The
adsorption efficiency increased from 12% (10.45 g/L) to 90% (0.3 g/L) 3.6. Effect of contact time
when the solution pH varied from 2 to 7. Little improvement was
obtained above neutrality. As it is well established, pH affects the Effect of contact time on adsorption of phenolic compounds
degree of ionization of the phenolic compounds. Banana peel mate- by banana peel is presented in Fig. 6. The adsorption equilibrium
rial is composed of various functional groups, such as amino and of phenolic compounds was obtained after 3 h with an adsorp-
carboxyl, which could also be affected by the pH. tion of approximately 96% of the phenolic compounds. Almost, no
When pH = pKa, the anion and neutral forms will be 50% respec- remarkable improvement was observed after longer contact time.
tively. With the increase of the pH, the anion form increases while Adsorption rate of phenolic compounds on banana peel was found
neutral form decreases. The neutral form can be neglected when to be relatively much faster than those reported for some other
pH > pKa more than 2 units. At higher pH values the concentration of normal adsorbents. Xiaolo and Youcai investigated the adsorption
the negatively charged phenoxide ion increases. At lower pH values, of phenolic pollutants in the aqueous solution by aged-refuse [48]
phenolic compounds are present as the acidic compounds [42]. and reported that the remaining concentration of the phenolic pol-
As shown in Fig. 5, at low pH values, the rate of the sorbed pheno- lutants in the liquid phase becomes asymptotic to the time axis
lic compounds was very low. At higher pH, the adsorption increased after 4 h of shaking. Thawornchaisit and Pakulanon determined
and stabilized from pH 7 to 11. Thus high elimination (96%) of nat- that the sorption equilibrium of phenol on dried sewage sludge
ural phenolic compounds in OMW is achieved in a large pH zone was reached within 20 h [49]. Adsorption of bromophenols onto
above neutrality. From a practical point of view, this will be of great carbonaceous adsorbents derived from fertilizer solid waste was
interest, since it will not necessitate very accurate adjustment of performed by Bhatnagar [50] and reported an equilibrium time of
the medium pH. about 8 h.
Controversially, Thawornchaisit and Pakulanon [43], Aksu and Initially, large number of vacant surface sites is available for
Yener [10] studying adsorption of phenols on dried sludge, adsorption; the adsorption rate is very fast thus increases rapidly
reported an increase of adsorption at lower pH values, and a the amount of adsorbates accumulated on the banana peel surface
decrease at higher pH values. Many other authors who have mainly within the first hour of adsorption. As a result, the remain-
obtained similar behavior stated an adsorbent surface charge ing vacant surface sites are difficult to be occupied due to formation
modification. As the pH of the system increases, the number of of repulsive forces between the phenolic compounds on the solid
negatively charged sites increases which must be less favorable surface and the bulk phase [51]. The phenolic compounds have to
to the adsorption of phenolate ions due to electrostatic repulsion penetrate deeper into the pores encountering much higher resis-
[44,45]. tance [52]. This can explain the decrease of adsorption rates which
However, in other studies we can find appreciable adsorp- is well illustrated by the plateau line after 3 h adsorption.
tion rates at alkaline pH. Works of Lin et al. demonstrated that The HPLC analysis of the residual phenolic compounds of the
an increase of the pH to high-alkalinity (pH 8–11) resulted in OMW after adsorption on the banana peel at a concentration of
an increase in the phenol adsorption capacity on hydroxyapatite 30 g/L, pH 7 and at 3 h shows an elimination of 94% of the hydrox-
nanopowders [46]. Namasivayam et al. reported significant removal ytyrosol and 100% of the tyrosol.
of anionic dyes using banana pith as bioadsorbent at alkaline pH Nevertheless, it must be notice that the residual concentration
[47]. Similar behavior was obtained with sawdust used for treat- of the phenolic substances remain above of the limit authorized by
122 M. Achak et al. / Journal of Hazardous Materials 166 (2009) 117–125

legislation (0.5 mg/L). As the OMW contains in addition to the phe- Also, data were studied with the Freundlich isotherm, which can
nolic substances many other types of compounds such as sugars, be expressed by logarithmic form as
aminoacids, and proteins a competition may occur for adsorption
1
on specific sites. This may contribute to lower removal efficiency ln qe = ln KF + (5)
n ln Ce
of the phenolic substances. Further elimination of these latter sub-
stances is needed before discharging these wastewaters in nature. where KF is a Freundlich constant that shows adsorption capacity
Such a complete removal may be achieved by a system with series of adsorbent, n is a constant which shows greatness of relation-
of adsorption units. ship between adsorbate and adsorbent. Freundlich isotherm was
Subsequent sorption steps may probably lead to a complete based on the assumption that the adsorption occurs on hetero-
elimination of these pollutants. geneous sites with non-uniform distribution of energy level. The
Freundlich describes reversible adsorption and is not restricted to
the formation of monolayer. It has been found that the adsorption
3.7. Adsorption isotherms
for phenolic compounds on the banana peel is favorable and has an
n value between 1 and 10 (Table 5).
Adsorption is the accumulation of a mass transfer process that
The equilibrium isotherm for the adsorption of phenolic com-
can generally be defined as material at the interface between
pounds on banana peel was determined with 100 mL of OMW with
solid and liquid phases. Equilibrium relationships between sorbent
a known concentration of phenolic compounds (13.45 g/L). The sys-
and sorbate are described by sorption isotherms, usually the ratio
tem was agitated for 24 h (200 rpm) in a constant temperature
between the quantity sorbed and that remaining in the solution at
(30 ◦ C) at initial pH 5. Fig. 4 shows the adsorption isotherms of
a fixed temperature at equilibrium.
phenolic compounds (qe versus Ce ) using banana peel. The Qm , b,
In order to optimize the design of a sorption system to remove
RL , R12 (correlation coefficient for Langmuir isotherm), KF , n, and R22
phenolic compounds from OMW, it is important to establish the
(correlation coefficient for Freundlich isotherm) are given in Table 5.
most appropriate correlation for the equilibrium curve. Many
The R12 and R22 values shown in Table 5 are evidence that the
theories which describe adsorption equilibrium were applied.
phenolic compounds adsorption in this study is well fitted to both
Several isotherm equations are available, and two important
Langmuir and Freundlich models; a possibility of mono and hetero-
isotherms are selected for this study: the Langmuir and Fre-
layer phenolic compounds formation on the adsorbent surface. This
undlich [53,54]. The linearised Langmuir equation is represented as
observation is not rare as similar findings have been reported before
follows:
[56–58]. This phenomenon can be further explained by understand-
Ce 1 Ce ing the surface chemistry of banana peel. The presence of active
= + (3)
qe bQm Qm functional groups with different intensity and non-uniform distri-
bution may cause differences in the energy level of the active sites
where qe (mg/g) and Ce (g/L) are the amount of adsorbed pheno-
available on the banana peel surface thus affecting its adsorption
lic compounds per unit weight of adsorbent and the unadsorbed
power. Active sites with higher energy level tend to form het-
phenolic compounds concentration in solution at equilibrium. b
erolayer phenolic compounds coverage with robust support from
is the equilibrium constant or Langmuir constant related to the
strong chemical bonding while active sites with lower energy level
affinity of binding sites (L/g) and Qm represents a particle lim-
will induce monolayer coverage due to electrostatic forces.
iting adsorption capacity when the surface is fully covered with
From the comparison of the adsorption capacity of different type
phenolic compounds and assists in the comparison of adsorption
of low-cost adsorbent used for removal of phenols and phenolic
performance.
compounds (Table 6), the banana peel showed a high adsorption
This equation has been successfully applied to many adsorp-
capacity of phenolic compounds (688.9 mg/g).
tion processes [7–14]. The Langmuir isotherm was developed on
the assumption that the adsorption process will only take place at
3.8. Kinetics of the adsorption process
specific homogenous sites within the adsorbent surface with uni-
form distribution of energy level. Once the adsorbate is attached
3.8.1. Kinetic model of phenolic compounds adsorption
on the site, no further adsorption can take place at that site; which
Adsorption kinetics has been proposed to elucidate the adsorp-
concluded that the adsorption process is monolayer in nature. The
tion mechanism. The mechanism of adsorption depends on the
essential characteristic of the Langmuir isotherm can be expressed
physical and chemical characteristics of the adsorbent as well as
by the dimensionless constant called the equilibrium parameter, RL ,
on the mass transport process. In order to investigate the mecha-
defined as:
nism of phenolic compounds adsorption on the banana peel and
1 examine the potential rate-controlling step, i.e., mass transfer or
RL = (4)
1 + bC0 chemical reaction. The capability of pseudo-first-order and pseudo-
second-order kinetic models was examined in this study.
where b is the Langmuir constant, C0 is the initial phenolic com-
The pseudo-first-order equation [62,63] is
pounds concentration (g/L) and RL values indicate the type of
isotherm to be irreversible (RL = 0), favorable (0 < RL < 1), linear ln(qe − qt ) = ln(qe ) − k1 t (6)
(RL = 1), or unfavorable (RL > 1) [55]. Our results show that the
where qe and qt refer to the amount of phenolic compounds
adsorption for phenolic compounds on the banana peel is favorable
adsorbed (mg/g) at equilibrium and at any time, t (h), respectively,
and has an RL value between 0 and 1 (Table 5).
k1 (h−1 ) is the equilibrium rate constant of pseudo-first-order sorp-
tion.
Table 5 On the other hand, a pseudo-second-order equation [62,63]
Isotherm constants and the correlation coefficients of Langmuir and Freundlich based on the adsorption capacity is expressed in the form:
isotherms.
t 1 t
Effluent Langmuir isotherm Freundlich isotherm = + (7)
qt k2 q2e qe
Qm (mg/g) b (L/g) R12 RL KF n R22
where k2 is the rate constant for pseudo-second-order kinetics
OMW 688.9 0.24 0.94 0.57 0.13 1.13 0.99
(g/g h).
 M. Achak et al. / Journal of Hazardous Materials 166 (2009) 117–125 123

Table 6
Langmuir and Freundlich constants for phenol and phenolic compounds adsorption by various adsorbents reported in literature.

Adsorbent Adsorbate Qm (mg/g) b (L/g) KF n References

Activated coal Phenol 1.84 0.065 0.79 0.79 [57]

Resin AP-246 0.071 0.584 0.112 0.35
Resin OC-1074 0.043 0.445 0.0053 0.16 [59]

Carbonised beet pulp Phenol ♦ ♦ 29.35 5.13 [46]

Hydroxyapatite Phenol ♦ ♦ 0.37 1.66 [56]
Coconut shell Phenol 205.84 3.91 37.11 3.66 [48]

Aged-refuse Phenol ♦ ♦ 0.019 1.19

2-Chlorophenol ♦ ♦ 0.042 1.22
4-Chlorophenol ♦ ♦ 0.195 1.59
2,4-Dichlorophenol ♦ ♦ 0.180 1.50

Palm pith carbon 2,4-Dichlorophenol 19.16 0.70 * * [60]

Paper mill sludge 2,4-Dichlorophenol 4.49 0.003 * * [61]
Banana peel Phenolic compounds 688.9 0.24 0.13 1.13 This study

♦ Does not follow Langmuir isotherm/not reported. * Does not follow Freundlich isotherm/not reported.

Table 7
Kinetics constants and the correlation coefficients for different kinetic models.

Effluent Pseudo-first-order Pseudo-second-order

q(e,exp) (mg/g) q(e,cal) (mg/g) k1 (h−1 ) R12 q(e,cal) (mg/g) k2 (g/g h) R22

OMW 688.9 200.03 0.88 0.82 370.3 12.82 0.99

The pseudo-first-order and pseudo-second-order equation, k1 , mechanism is predominant and the overall rate of the adsorption
k2 , correlation coefficients, theoretical and experimental qe values process appears to be controlled by the chemical reaction.
were compared in Table 7.
As shown in Table 7, the correlation coefficient of pseudo- 3.9. Desorption studies
second-order equation is higher than that of pseudo-first-order and
the theoretical qe value calculated from pseudo-second-order was Desorption studies can further aid in elucidating the mechanism
more close to the experimental qe value than from pseudo-first- of adsorption. The studies of Namasivayam and Yamuna showed
order. It can be concluded that the pseudo-second-order kinetic that if the adsorbed dye on the solid surface can be desorbed by
model fits for the adsorption of phenolic compounds on the banana water, demonstrating that the attachment of the dye on the adsor-
peel. It indicates chemical sorption in the adsorption process, which bent is by weak bonds. If alkaline water (pH 12) is needed, then the
may be partly due to the hydrogen-binding between the hydroxyl adsorption is by ion exchange. If organic acids, like acetic acid, are
groups of phenolic compounds and the active functional groups in the most efficient for desorption, then the adsorption is held by the
the banana peel, and it may be the rate-limiting step. adsorbent through chemisorption [65,66].
Neutral pH water (pH 7.3), acetic acid (pH 1.2) and alkaline
3.8.2. Diffusion model water (pH 12) have shown 0.17, 0.30 and 0.12 g/g of desorbed
Since neither the pseudo-first-order and pseudo-second-order amounts of phenolic compounds, respectively. This indicates that
kinetic model can identify the diffusion mechanism, the intraparti- various mechanisms contribute to the adsorption of phenolic com-
cle diffusion model [64] was also used to analyze and elucidate the pounds on banana peel but chemisorption might be the main
diffusion mechanism. The intraparticle model is expressed as mechanism.
The adsorption of phenolic compounds increased in an alkaline
qt = kp t 1/2 + C (8)
medium and decrease in an acidic medium. As the pH of the system
where qt is the amount of phenolic compounds adsorbed at equi- decreases, the number of positive charged sites increased. A posi-
librium (mg/g) at time t, C is the intercept and kp is the intraparticle tively charged surface site on the adsorbent favours the desorption
diffusion rate constant (g/g h1/2 ). of phenolic compounds due to electrostatic repulsion. At pH 1.2, a
In order to quantify the applicability of the model, the correla- significantly high electrostatic repulsion exists between the posi-
tion coefficient was calculated from the plot as in Table 8. It is clear tively charged surface of the adsorbent and phenolic compounds.
to see that the R22 value for pseudo-second-order kinetic model is
much higher than these for the intraparticle diffusion kinetic model 4. Conclusion
and the coefficient is lower than that of the pseudo-second-order
model. Therefore, this section suggested that the pseudo-second- Banana peel has proven to be a promising material for the
order model is the best choice among the three kinetic models removal of contaminants from olive mill wastewaters. Not only
to describe the adsorption behavior of phenolic compounds onto banana peel is an abundant cheap adsorbent, but also it is highly
banana peel, suggesting that the pseudo-second-order adsorption efficient for removing phenolic compounds from OMW. All those
add more credits to banana peel for removing pollutants from
Table 8 wastewaters. The main characteristics of the adsorption process of
The parameter of the intraparticle diffusion model. the natural phenolics from OMW on banana peel can be summa-
Effluent OMW rized as follows:
kp (g/g h1/2 ) 0.021
C (g/g) 0.28 • The banana peel showed a high adsorption capacity of pheno-
R32 0.42
lic compounds (689 mg/g), revealing that banana peel could be
124 M. Achak et al. / Journal of Hazardous Materials 166 (2009) 117–125

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