Iran. J. Environ. Health. Sci. Eng., 2005, Vol. 2, No. 3, pp.

201-206

ULTRASONIC DEGRADATION OF PHENOL AND DETERMINATION OF

THE OXIDATION BY-PRODUCTS TOXICITY
*A. Maleki, A. H. Mahvi, F. Vaezi and R. Nabizadeh
1
Center for Environmental Research and Department of Environmental Health Engineering, School of Public
Health, Tehran University of Medical Sciences, Tehran, Iran

Received: 30 January 2005; revised: 7 March 2005; accepted: 20 May 2005

ABSTRACT
Phenol is a potential hazard to human health and the environment. The sonochemical degradation of
phenol in aqueous solution was investigated by use of a 35 kHz bath sonicator. Experiments were
performed at initial phenol concentrations varying from 1 to 100 mg/L. The effects of parameters such
as pH and initial phenol concentration on the sonochemical degradation and bioassay test have been
studied. The results of the study showed that the ultrasonic phenol degradation increased with
decreasing the pH values and phenol concentration. But the rates of phenol degradation under
different conditions had always been quite low. It was found that the rate of ultrasonic phenol
degradation was first high but it was later substantially reduced and the experimental data fitted well
with first order reaction rate equation. Bioassay tests showed that phenol was toxic to Daphnia magna
and so resulted in quite low LC50 values. Comparison of toxicity units (TU) of phenol and the effluent
flow showed that TU value for effluent was 1.65 times lower than that obtained for phenol. Thus,
sonication was able to eliminate the toxicity of by-products which were formed during the degradation
of phenol.

Key words: Ultrasound, sonochemistry, phenol, bioassay, daphnia magna

INTRODUCTION
Phenol is a potential hazard to human health and resins and plastics, petroleum refining, steel
the environment. This compound has attracted production, coal gasification and conversion,
public attention due to its presence in groundwater, surface runoff from coal mines, byproducts of
rivers and drinking waters (Entezari et al., 2003). agricultural chemicals, dyestuff, textiles, tanning,
Acute exposure to phenol and its quinone fiberboard production and paint stripping
analogues is known to cause skin irritation, kidney operations, pulp and paper, pesticides, medications,
damage, gastrointestinal discomfort, and pharmaceuticals and even from food processing
headaches. Aesthetically, this compound also poses industries (Lesko, 2004; Entezari and Petrier, 2004;
a nuisance with detectable taste and odors in water Entezari and Petrier, 2005; Mahamuni and Pandit,
at concentrations as low as 1-8 mg/L (Lesko, 2005; Lathasreea et al., 2004; Beltran et al.,
2004). It has been listed as the priority pollutant in 2005). Due to its toxicity, hazardous character and
the list of USEPA (Mahamuni and Pandit, 2005). an increasing social concern on environment, the
Most of the countries specify the maximum discharge of such compounds in the environment
allowable concentration of phenol in the effluent has become more restrict. Therefore, there is more
streams to be less than 1 mg/L (Mahamuni and demand for improved methods of treatment
Pandit, 2005). (Entezari and Petrier, 2004; Beltran et al., 2005).
Phenol can be found in aqueous effluents from Traditional methods of removal such as
various industries such as the manufacturing of conventional chemical, physical and biological
treatments for dephenolization of wastewater have
*Corresponding author: Tel: +982188954914, their own limitations (Entezari and Petrier, 2004;
Fax: +9821 88950188 Email: [email protected] Entezari et al., 2003). Lately, there has been a lot

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A. Maleki, Sci.ULTRASONIC
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of interest in application of the advanced oxidation ultrasonic reactions were carried out for 5 hr.
processes (AOPs) for the removal of phenol from The initial pH value of the sample was adjusted
the effluent streams (Mahamuni and Pandit, 2005). to a constant value of 3. Sonication was
Ultrasound irradiation is a novel advanced accomplished at the frequency of 35 kHz (500
oxidation process that has emerged as an answer W) with an ultrasonic generator (Elma TI-H-5,
to the growing need for lower levels of Germany) equipped with two piezoelectric
contaminants in wastewater (Wu et al., 2001; transducers (5cm diameter) fixed at the bottom
Nikolopoulos et al., 2005). Since 1990, several of the vessel. The apparatus was open to air.
studies have focused on the use of ultrasound to Dimensions of ultrasonic bath were: L=25 cm,
remove organic xenobiotics from water (Pétrier W=13 cm, H=15 cm. Ultrasonic energy dissipated
et al., 1994; Kruus et al 1997; Pétrier et al., in the reactor was set at 2.5 W/cm2 through the
2001; Entezari et al., 2003). Ultrasonic irradiation calorimetric method. The solution was irradiated
introduces cavitation bubbles into an aqueous for 15 min and then sonication was stopped for
solution. T hese bubbles for m, gr ow and the next 10 min. This process was continued till
subsequently collapse through compression- the solution was irradiated for a predetermined
rarefaction cycles. The temperature in the time (15-300 min). Phenol analysis was then done
collapsing bubbles can reach to 3000-5000 °K according to a direct colorimetric method using
and the pressure to 500-10,000 atm. Under such 4 aminoantipyrine reagent (Anonymous, 1995).
extreme conditions, water molecules undergo Color was measured spectrophotometrically at
homolysis to yield hydroxyl radicals and hydrogen 500 nm by the use of a UV/VIS apparatus
atoms. Since oxidation by hydroxyl radical is an (Lambada 25 Perkin Elmer,Sheltom), after the
important degradation pathway, the amount of the filtration of samples through Whatman filter paper
hydroxyl radicals present in the sonolysis system had been performed. Acute toxicity of phenol and
is directly related to the degradation efficiency the toxic effects of its degradation products after
(Zheng et al., 2005). ultrasonic irradiation were studied with Daphnia
The main objective of this work was to focus on magna test according to the procedure described
the degradation of phenol by the ultrasonic in Standard Methods (Anonymous, 1995).
equipment operating at 35 kHz. The influences Daphnia was found to be the most sensitive
of various factors, such as initial pH and phenol organism to phenol (Guerra, 2001), so bioassay
concentrations on phenol ultrasonic degradation tests were done using this organism. Primary
have also been studied. Also, the LC 50 (the daphnia was caught from their living site; then,
statistically determined concentration that causes one of them was cultured alone, and infants of
50% mortality in a given exposure period) of the primary daphnia were used for culture in large
aqueous phenol solution befor e and after amounts. Dilution water which was used for tests
sonication (reaction by-products) using Daphnia was groundwater with the general characteristics
magna as the test organisms, was studied. Such of as follows: pH =8.1, total hardness 130=mg/L
data can be considered as an indication of acute as CaCO3, total alkalinity =306 mg/L as CaCO3,
toxicity reduction resulting from treatment. electrical conductivity = 1197 µS/cm, calcium =36
mg/L, magnesium=10 mg/L, chloride = 75 mg/L,
sulfate =147 mg/L and nitrate = 44 mg/L.
MATERIALS AND METHODS Daphnia magna was maintained in a 10 L glass
Analytical grade phenol (from Merck) was used vessel containing culture medium in temperature-
for the experiments. All other chemicals were of controlled condition of 22±2 ºC and a 12/12 light-
at least 99% purity and were used without further dark cycle. Culture medium was made of sheep
purification. Deionized water was used for manure. Daphnia magna was fed with yeast at a
preparing all aqueous solutions. concentration of 100 mg/L every two day.
For each of the experiments, the reaction volume For running the experiment, 10 infants (with the
was 2000 mL and the initial concentration of age of < 24 h) were exposed to the test volume
phenol was in the range of 1–100 mg/L. The of 100 mL in a 250 mL glass beaker. The initial
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concentration of phenol was 100 mg/L and the min sonication of 100 mg/L phenol solution. The
concentration of phenol in mixture was 89 mg/L experimental data from this study fitted well
after 120 min sonication (according to phenol with first order reaction rate equation (Fig. 2).
conversion percent from Fig. 1). Experimental We observed that the initial rate of ultrasonic
samples concentrations were, 100, 75, 50, 40, 30, degradation was high but later it reduced
20, 10 and 5 % of phenol sonicated effluent diluted substantially. Fig. 3 demonstrates the removal
with dilution water. After the setting periods of efficiency of phenol by the sonochemical
24, 48, 72 and 96 hrs, LC50 values were calculated process at different pH valuse. It clearly shows
for toxicity tests by use of the special computer that lower pH values had favored the phenol
program [PROBIT] (Goi et al., 2004). Finally, for degradation. The maximum and minimum
a certain comparison, the toxicity values were efficiencies of phenol degr adation wer e
converted to toxic units (TU). The TU of an determined to be 37 % and 19 % at pH valuse
effluent or mixture is equal to100 divided by the of 3 and 11, respectively.
LC50 of that effluent or mixture (Guerra, 2001; The LC50 values of phenol and the mixture of
Jin et al., 1999). All experiments were run in its sonodegradation by-products are presented
triplicate to ensure reproducibility. in Table 2. Results showed that, as it was
expected, phenol was toxic to Daphnia magna
RESULTS and resulted in quite low LC50 values (LC50 96
Study on phenol degradation was carried out for h of 15.7 % v/v). As it can be seen from Table
5 h irradiation time. Fig. 1 shows the variations 2, 24 and 48 h LC50 (% v/v) values have ranged
of phenol concentration with time. Only 13% from 33.1 and 19.5 for phenol to 51.3 and 32.2
degradation of phenol has been observed for 300 for the effluent mixture, respectively.

1
0.9
0.8 Conc= 1 mg/L
0.7 Conc=20 mg/L
0.6
Conc=40 mg/L
C/Co

0.5
Conc=60 mg/L
0.4
0.3 Conc=80 mg/L
0.2 Conc=100 mg/L
0.1
0
0 50 100 150 200 250 300
T ime (min)

Fig. 1: Effect of 35 kHz sonication on phenol decomposition at different initial phenol concentrations

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Maleki,Health.
et al., Sci. Eng., 2005,
ULTRASONIC Vol. 2, No. 3, OF
DEGRADATION pp. ...
201-206

Conc= 1 mg/L
1
Conc=20 mg/L
0.9
0.8 Conc=40 mg/L

- Ln (C/Co) 0.7 Conc=60 mg/L

0.6 Conc=80 mg/L
0.5
Conc=100 mg/L
0.4
0.3
0.2
0.1
0
0 20 40 60 80 100 120
T ime (min)

Fig. 2: Neperian logarithm of different concentrations of phenol vs. time for sonication of phenol

40
Degradation efficiency (%)

35
30
25
20
15
10
5
0
3 5 7 9 11
pH

Fig. 3: Effect of pH on phenol degradation under 35 kHz ultrasound irradiation

(phenol concentration = 1 mg/L, time= 60 min)

Table 1: First order kinetic values for degradation of phenol at different initial
phenol concentrations by ultrasound irradiation
Phenol concentration
1 20 40 60 80 100
(mg/L)
Rate constant
0.0076 0.0028 0.002 0.0016 0.0013 0.0011
(min-1)
Correlation
0.995 0.99 0.97 0.97 0.97 0.97
coefficient

Table 2: Toxicity data for phenol and sonicated phenol solution at 35 kHz
Test sample Phenol Sonicated effluent
Time (day) 24 48 72 96 24 48 72 96
LC50 (% v/v) 33.1 19.5 18.1 15.7 51.3 32.2 24.6 19.8
Toxicity Unit (TU) 3.02 5.13 5.52 6.36 1.95 3.1 4.06 5.04

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DISCUSSION The initial rate of ultrasonic degradation was

As Fig. 1 shows, only 13% degradation of phenol observed to be high but later it was reduced
has been observed after 300 min sonication of substantially. This can be explained by the fact
phenol solution with initial concentration of 100 that whatever dissolved air is present in the solution
mg/L. Mahamuni et al. reported 17 % removal is degassed after the initial period of sonication
for phenol (Co=85 mg/L) by a bath of ultrasonic and resulted in a decrease in the amount of
equipment working at 20 kHz (120 W) during 60 hydroxyl radicals generated. Also, there could be
min (Mahamuni and Pandit, 2005). Also, 20 % a competition between the oxidation of phenol and
degradation has been reported by Entezari et al. the intermediates formed resulting into a net
by means of ultrasound at 35 kHz (50 W) for initial reduction in the degradation rate. This phenomenon
phenol concentration of about 60 mg/L during 150 has proved by other researcher (Mahamuni and
min (Entezari et al., 2003). This may be related to Pandit, 2005).
the hydrophilic nature of phenol. Phenol is a moderately As shown in Fig. 3, pH values influenced the
soluble compound in water (Cwsat =0.63 M) with a phenol degradation. It is observed that phenol
relatively low vapor pressure -4(4.6 × 10-4 -1atm) and degradation can be favored by lowering the pH of
Henry’s constant (4.0 × 10 L atm M ). These solution and the sonochemical degradation rate of
physiochemical properties preclude significant phenol increases with decreasing solution pH,
concentrations of phenol molecule diffusing into the because the ionic species of phenol is predominant
vapor phase of the acoustic cavitation bubbles, so it when the pH exceeds 10.0 (equal to pKa value of
remains in the bulk of the solution during cavitation. phenol at 25 ºC), but the molecular species
Most of the hydroxyl radicals that are formed predominates when pH is less than the pKa. The
within the cavity during the sonication might get fraction in the molecular state of phenol was larger
recombined before they attack the phenol when the pH was smaller. The phenolate ions are
molecules in the bulk liquid. The attack of hydroxyl uncomfortably concentrated in the gas water
radicals on phenol was confirmed through the interfaces of bubbles, where the hydrophobicity is
formation of small quantities of catechol, strong, and cannot vaporize into the cavitation
hydroquinone and resorcinol. The lack of pyrolysis bubbles; they can react only outside of the bubble
products (e.g., acetylene and methane) during the film with the OH radicals cleaved from water.
sonolysis of aqueous phenol indicates that the However, in the molecular state, phenol more
sonochemical reactions primarily occur within the easily enters the gas–water interfaces of bubbles
bulk solution rather than within the superheated and even vaporizes into cavitation bubbles; thus
regions of the interfacial zone surrounding the can react both inside by thermal cleavage and
cavitation bubble. There are many reports which outside with OH radicals. Therefore, it has been
have proved the formation of hydroxyl radicals concluded that sonolysis of phenol is pH dependent
during sonication (Lesko, 2004). Petrier reported and increases when more acidic conditions are
that this low efficiency is mainly due to the low carried out. This might be the reason why lower
concentrations of phenol and of hydroxyl radicals pH favored the ultrasonic degradation of phenol.
that escape from the cavitation bubble at 35 kHz The results from previous studies (Okouchi et al.,
frequency (Petrier and Francony, 1997). Similar 1992; Wu et al., 2001) showed that lower pH
to the previous work (Petrier and Francony, 1997; values favored for degradation of phenol by
Naffrechoux et al., 2000; Nikolopoulos et al., ultrasound.
2005), the experimental data in this study fitted Results showed that phenol was toxic to Daphnia
well with first-order reaction rate equation. The magna and resulted in quite low LC50 values (LC50
initial first order rate constants of phenol 96 h of 15.7 % v/v). Comparison of TUs of phenol
degradation were estimated to be 0.0076 min-1 to and effluent toxicity showed that TU value of
0.0011 min-1 for initial concentrations of 1 mg/L to effluent was 1.65 times less than that obtained for
100 mg/L, respectively. Table 1 shows the major phenol (according to 48 h-LC50). Thus, sonication
calculated reaction rate coefficients. was able to eliminate the toxicity of by-products

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A. Maleki, Sci. ULTRASONIC
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DEGRADATION OF ...

which were formed during the degradation of of classical equipment with a new cylindrical reactor.
phenol. This reduction was achieved by phenol Ultrason. Sonochem., 10, 103-108.
Goi, A., Trapido, M. and Tuhkanen, T., (2004). A study of
degradation and transformation of aromatics by toxicity, biodegradability, and some by-products of
products to aliphatic products by ring opening ozonised nitrophenols. Adv. Environ. Res., 8, 303-311
reactions. However, the end-product solutions Guerra, R., (2001). Ecotoxicological and chemical evaluation
were somewhat more toxic than would be predicted of phenolic compounds in industrial effluents.
Chemosphere, 44 (8),1737-47.
from the known concentration of initial phenol. This
Jin, H., Yang, X., Yin, D. and Yu, H., (1999). A Case Study
situation was reported by Guerra for phenolic on Identifying the Toxicant in E.uent Discharged from a
compound decomposition due to production of Chemical Plant. Mar. Pollut. Bull, 39, 122-125.
hydroquinone, benzoquinone and catechol (Guerra, Kruus, P., Burk, R. C., Entezari, M. H. and Otson, R.,
2001). (1997). Sonication of aqueous solutions of chlorobenzene,
Ultrason. Sonochem., 4, 229-233.
Data of this study showed that bioassay can be Lathasreea, S., Nageswara, R. A., SivaSankarb, B.,
used as a suitable method for evaluation of the Sadasivamb, V. and Rengarajb, K., (2004). Heterogeneous
efficiency of treatment procedures by ultrasound. photocatalytic mineralisation of phenols in aqueous
solutions. Mol. Catal. A- Chem., 223, 101-105.
Lesko, T. M., (2004). Chemical Effects of Acoustic
ACKNOWLEDGEMENTS Cavitation, Ph.D. thesis reported in California Institute
The authors would like to thank Tehran University of Technology, Pasadena, California, USA.
of Medical Sciences, Research Deputy and the Mahamuni, N. N. and Pandit, A. B., (2005). Effect of
additives on ultrasonic degradation of phenol. Ultrason.
Center for Environmental Research for their Sonochem, 13 (2), 165-174.
financial and administrative supports. Naffrechoux, E., Chanoux, S., Pe´trier, C. and Suptil, J.,
(2000). Sonochemical and photochemical oxidation of
organic matter. Ultrason. Sonochem, 7, 255-260.
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