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a,*
, Nil
ufer Cihangir b, Nalan T
uzmen c, G
uleren Alsancak
Received 12 June 2003; received in revised form 15 September 2003; accepted 10 November 2003
Available online 12 April 2004
Abstract
In this study, the potential use of the fungus Pleurotus sajor caju to remove phenols (i.e., phenol, o-chlorophenol, p-chlorophenol
and 2,4,6-trichlorophenol) from aqueous solutions was evaluated. Biosorption of phenol or chlorophenols reached equilibrium in 4
h. The maximum adsorptions of phenol and chlorophenols onto the Pleurotus sajor caju were 0.95 mmol/g for phenol, 1.24 mmol/g
for o-chlorophenol, 1.47 mmol/g for p-chlorophenol and 1.89 mmol/g for 2,4,6-trichlorophenol. The anity order was as follows:
2,4,6-trichlorophenol > p-chlorophenol > o-chlorophenol > phenol. Phenol and chlorophenols bindings onto Pleurotus sajor caju
were clearly pH dependent. The adsorption of phenol and chlorophenols increased with increasing pH. Desorption was achieved
using methanol solution (30%, v/v). Pleurotus sajor caju biomass is suitable for reuse for more than ve cycles without noticeable loss
of adsorption capacity.
2004 Elsevier Ltd. All rights reserved.
Keywords: Chlorophenols; Fungal biomass; Biosorption; Organic pollutants; Pleurotus sajor caju
1. Introduction
Phenolic compounds are very toxic, and many are
known or suspected human carcinogens (EPA, 1988;
Slein and Sansone, 1980; IWRS, 1990). Loss of appetite,
headache, rapid fatigue and severe chronic insomnia are
given as symptoms of chronic phenol intoxication in
humans after long-term intake of excessive phenol concentrations. Phenolic compounds are present in the
wastewater generated from paint, solvent, petroleum and
petrochemical, coal-conversion, pharmaceutical, wood
preserving chemicals, plastic, rubber-proong, pesticide,
iron-steel, phenol-production, paper and pulp industries.
Large-scale coal gasication and carbonization plants
generate huge quantities of high-strength phenolic
wastewater (Dutta et al., 1998). United States Environmental Protection Agency (EPA) regulations call for
lowering phenol content in the wastewater to less than
1 mg/l from the several thousand mg/l often present.
0960-8524/$ - see front matter 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2003.11.029
Traditionally, activated carbon adsorption and solvent extraction are the most widely used methods for the
removal of phenolic compounds. But recently, microorganisms have been considered as one of the most
promising adsorbents (Kennedy et al., 1992; B
ulb
ul and
Aksu, 1997; Brandt et al., 1997; Aksu and Yener, 1998).
In the concept of biosorption, several chemical processes
may be involved, such as adsorption, ion exchange, and
covalent bonding with the biosorptive sites of the
microorganisms including carboxyl, hydroxyl, sulphydryl, amino and phosphate groups (Fourest and Volesky, 1997). Fungal cell walls and their components have
major role in the biosorption (Tsezos et al., 1997; Hafez
et al., 1997; Kapoor and Viraraghavan, 1997). Fungal
biomass can also take up considerable quantities of
pollutants from aqueous solution by adsorption or a
related process, even in the absence of physiological
activity (Gadd and White, 1989).
The purpose of this investigation was to examine the
extent of removal of model phenol or chlorophenol
pollutants.In this study, Pleurotus sajor caju was used as
biosorbent and adsorption/desorption of phenol, ochlorophenol, p-chlorophenol and 2,4,6-trichlorophenol
60
2. Methods
2.1. Cell line and medium
The strain used was Pleurotus sajor caju which was
kindly supplied by Dr. I.F. Zadrazil (Insitut f
ur
Bodenbiologie, Braunschweig, Germany). Cultures were
maintained on potato-dextrose-agar slaints and subcultured every month, then transferred to storage at 4 C.
Pleurotus sajor caju was grown in a liquid medium
containing (g/l) glucose, 10.0; KH2 PO4 , 2.0;
MgSO4 7H2 O, 0.5; CaCl2 , 0.1; NH4 Cl, 0.12 and thiamine, 0.001 (Blais et al., 1993). The initial pH of the
medium was adjusted to 5.5 before sterilization. Media
were inoculated with Pleurotus sajor caju and incubation
was carried out at 28 C on an orbital shaker incubator
at 150 rpm for 7 days. The biomass in growth media was
detected according to dry weight. The biomass was
separated from the broth by ltration. The growth
media were ltered and preweighed lter paper (Whatmann no. 1) and biomass was washed with deionized
and distilled water then dried in an incubator at 30 C
for 24 h (Presscott et al., 1993). The dried sample was
then ground using a blender and sieved to pass through
a 100-mesh sieve to obtain uniform particle size.
2.2. Adsorption/desorption of phenol or chlorophenols
Adsorption of phenol or chlorophenols was investigated in a batch system. Phenol and chlorinated phenols
were obtained from Sigma (St. Louis, USA). Eects of
the initial concentration of phenol or chlorophenols and
pH of the medium on the adsorption rate and capacity
were studied. 250 ml of aqueous phenol or chlorophenol
solutions with dierent concentrations (in the range of
251000 mg/l) were treated with the biomass (50 mg per
batch) at dierent pH (in the range of 2.08.0, adjusted
with HClNaOH) at room temperature, in the asks
agitated magnetically at 600 rpm. All water used in the
experiments was puried using a Barnstead (Dubuque,
IA) ROpure LP reverse osmosis unit with a high ow
cellulose acetate membrane (Barnstead D2731) followed
by a Barnstead D3804 NANOpure organic/colloid
removal and ion exchange packed-bed system. The
resulting puried water had a specic resistance of 18
M X. The concentration of the phenol or chlorophenols
in the aqueous phase was measured by high performance liquid chromatography. The LC equipment
consisted of a Cecile CE1100 liquid chromatograph
pump and Hewlett Packard HP 3395 integrator. Cecile
CE1220 LC UV variable wavelength monitor was used
61
62
Table 1
Adsorptiondesorption cycles for phenol or chlorophenols
Cycle no.
1
2
3
4
5
Phenol
o-Chlorophenol
2,4,6-Trichlorophenol
p-Chlorophenol
Adsorption
(mmol/g)
Desorption
(%)
Adsorption
(mmol/g)
Desorption
(%)
Adsorption
(mmol/g)
Desorption
(%)
Adsorption
(mmol/g)
Desorption
(%)
0.95
0.93
0.92
0.89
0.91
92.1
92.6
90.6
92.7
94.5
1.24
1.22
1.20
1.23
1.21
89.5
93.3
91.6
94.0
92.5
1.47
1.46
1.43
1.44
1.42
91.1
90.8
92.0
93.2
91.0
1.89
1.87
1.88
1.85
1.83
89.5
87.3
92.0
90.9
92.7
4. Conclusions
Wastewaters containing phenolic compounds present
a serious problem. Phenol containing wastewater may
not be conducted into open water without treatment
because of the toxicity of phenol. Recently, polymer
based adsorbents were widely employed for the removal
of phenols. But the high cost of polymers has stimulated
interest in examining the feasibility of using cheaper
adsorbents. Cheaper raw material Pleurotus sajor caju
was used for adsorption/desorption of phenol or chlorophenols (i.e., phenol, o-chlorophenol, p-chlorophenol
and 2,4,6-trichlorophenol) from aqueous solutions. The
present studies led to the following conclusions: The
maximum adsorption capacities of the Pleurotus sajor
caju biomass from their single solutions were 0.95 mmol/
g for phenol, 1.24 mmol/g for o-chlorophenol, 1.47
mmol/g for p-chlorophenol and 1.89 mmol/g for
2,4,6-trichlorophenol. The adsorption order was as follows: 2,4,6-trichlorophenol > p-chlorophenol > o-chlorophenol > phenol. The adsorption of phenol or
chlorophenols increased with increasing pH. Consecutive adsorption and desorption cycles showed the feasibility of the Pleurotus sajor caju biomass for phenol or
chlorophenol removal from aqueous solutions.
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