Literature Review Chapter 2

2.1 Numerous studies on degradation of textile dyes and polycyclic aromatic

hydrocarbons with the use of ultrasound have been reported in the literature. However,
only the important ones, which had direct relevance to the present study, are being
reported here briefly;

Gayathri et al (2010) investigated [73] sonochemical degradation of two basic dyes

(Rhodamine B, Methylene Blue) and two acid dyes (Acid Orange II, Acid Scarlet Red
3R) in aqueous solution using sulphate radicals activated by immobilised cobalt ions. The
decolorisation efficiency for all four dyes solutions were in the order: persulphate
(PS) < cobalt activated persulphate (PS + Co) < persulphate + ultrasonication (PS + US)
< cobalt activated persulphate + ultrasonication (PS + US + Co).

Okitsu et al (2005) studied [74] sonochemical degradation of two azo dyes

(C.I. Reactive Red 22, Methyl Orange). Ultrasound favoured the decolorization of azo
dyes while addition of t-butyl alcohol radical scavenger suppressed the sonochemical
decolorization. Attack of high concentration of OH radicals at the interface region of
cavitation bubbles facilitated the decomposition of azo dyes.

Petrier et al (2010) reported [75] sonochemical degradation of bisphenol–A through

bicarbonate ion in water which increased by a factor of 3.2 at low concentration of
bisphenol A (0.022 µ mol l-1). This increase was due to the OH radicals which reacted
with bicarbonate ions to produce carbonate radical, which then migrated towards the bulk
of solution and helped in the degradation of bisphenol-A.

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Rehorek et al (2004) used [76] ultrasound of 850 kHz at 60, 90 and 120 W for the
degradation of different industrial azo dyes (Acid Orange 5 and 52, Direct Blue 71,
Reactive Black 5 and Reactive Orange 16 and 107) to mineralize to non–toxic end
products. All investigated dyes had been decolorized and degraded within 3–15 hours at
90 W and within 1–4 hours at 120 W, respectively. They reported simultaneous azo bond
scission, oxidation of nitrogen atoms and hydroxylation of aromatic ring structures
through hydroxyl radicals attack on azo dyes. Degradation measured in terms of absolute
quantities (µmol/h) implied a linear correlation between the radical formation and the
amount of pollutants.

Wang et al (2008) investigated [77] sonochemical degradation rate of Acid Red B and
Rhodamine B and found that the degradation was much higher in the presence of
nanosized ZnO powders than with ultrasonic irradiation alone. They found that the rate
of degradation of Acid Red B was about two times higher than that of Rhodamine B at
the initial concentration of 10.0 mg/L, 1.0 g/L nano-sized ZnO powder, pH 7.0 and 60
min of irradiation and reported the difference of chemical forms of both dyes and surface
properties of ZnO powders. The kinetics of sonocatalytic reactions of Acid Red B and
Rhodamine B had pseudo first-order kinetics. The optimal conditions for high
degradation ratios of Acid Red B and Rhodamine B were found when 1.5 and 2.0 g/L
nanosized ZnO powders were added at pH 7.0 and 11.0, respectively, for the initial
concentration of 10 mg/L.

Priya et al (2006) studied [78] ultrasonic degradation of two dyes Rhodamine B and
Rhodamine Blue in the absence and presence of anatase TiO2 and Degussa P-25 TiO2.
The degradation rate was more in the presence of both catalysts but a higher rate of
degradation was found with anatase than Degussa P-25. The degradation rate increased
with decreasing pH, increasing temperature and higher intensity.

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Wang et al (2008) reported [79] sonocatalytic degradation of Orange II, Ethyl Orange and
Acid Red G in the presence and absence of Au/TiO2. Discoloration and total organic
carbon removal of these dyes increased in the presence of catalyst compared to its
absence. Au/TiO2 led to the formation of active OH and H radicals which enhanced both
oxidation and reduction mechanisms.

Vinu et al (2009) examined [80] sonophotocatalytic degradation and reduction of total

organic carbon of anionic dyes (Orange G, Methyl Blue, Indigo, Carmine) using
combustion synthesized TiO2 (CS TiO2) and Degussa P-25 TiO2. The degradation rate
and the reduction of total organic carbon with combined sonophotocatalytic method were
found higher compared to photocatalyst and ultrasound alone.

Stock et al (2000) evaluated [81] degradation of Napthol Blue Black azo dye and
observed an additive effect of sonolysis and photocatalysis process. Sonolysis enhanced
the degradation rate while photolysis promoted mineralisation of dyes.

Madhavan et al (2010) investigated [82] the degradation and mineralisation of Orange G

by ultrasound and in combination with TiO2. Low pH favoured sonolytic degradation of
Orange G while alkaline pH favoured photocatalytic degradation. Total organic carbon
(TOC) measurement suggested that the mineralisation efficiency was higher with
sonophotocatalyst compared to ultrasound and photocatalyst alone.

Perez et al (2008) compared [83] the degradation process of Malachite Green in the
presence of ultrasound with or without photocatalyst in CCl4. Ultrasound alone improved
the degradation rate in CCl4 and not with sonophotocatalyst.

Wang et al (2007) investigated [84] sonocatalytic degradation of Acid red B in the

presence of anatase- and rutile- TiO2 and found that the degradation rate of dye was faster
in the presence of anatase TiO2 powder compared to rutile TiO2.

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Wang et al (2008) investigated [85] sonophotocatalytic degradation of Methyl Orange
using Degussa P-25, Yili TiO2 and Ag/TiO2. Ag/TiO2 was found to be the most effective
photocatalyst for dye degradation. In this investigation, mannitol and dimethyl sulfoxide
behaved as scavengers, and decreased the degradation rate.

Abdullah et al (2010) reported [86] sonocatalytic degradation of Congo Red,

Methyl Orange and Methylene Blue by TiO2 catalyst and H2O2. Ultrasound increased the
degradation rate. Small amount of rutile phase of photocatalyst showed better
sonocatalytic activity while excessive rutile phase showed poor activity. The highest
degradation rate of Congo red was due to multiple labile azo bonds which caused highest
reactivity with free radicals.

Abbasi et al (2008) performed [87] sonochemical degradation of Basic Blue 41 dye with
TiO2 as a catalyst in aqueous solution. Increase in H2O2 concentration and lowering the
initial dye concentration increased, but lower pH decreased the dye removal rate.
Ultrasound was found to be efficient for the degradation of azo dyes to non-toxic end
products.

Wang et al (2009) studied [88] sonocatalytic degradation of azo fuchsine in the presence
of cobalt and chromium-doped mixed crystal of TiO2. The sonocatalytic activity of
Cr-doped TiO2 powder was higher than that of Co-doped TiO2 and undoped TiO2.

Zhang et al (2009) studied [89] degradation of C.I. Acid orange 7 by ultrasound in

combination with Fenton process. Experimental results showed that increase of H2O2,
ultrasonic power and dissolved O2 increased the decolorization rate of dye. Increase in
initial pH decreased the decolorization rate. Decolorization rate varied a little at different
power or iron powder additions at the fixed H2O2 concentration. High COD removal
could be achieved by more H2O2 dosage and increased duration of sonic radiation.

14
Song et al (2009) investigated [90] the combination of ultrasound with fly ash/H 2O2
(Fenton like reagent) for the degradation of C.I. Direct Black 168. Fly ash was the most
efficient heterogeneous catalyst. Concentration of the dye, H2O2, dosage of fly ash and
pH of solution affect the removal of dye considerably.

Ai et al (2010) studied [91] the degradation of several azo dyes such as

Rhodamine B, Methylene Blue, Reactive Brilliant Red X-3B and Methyl Orange by
ultrasound assisted electrocatalytic oxidation (US-EO) process and found effective in the
degradation. Ultrasound and electrocatalytic oxidation showed synergistic effect.

Wang et al (2010) studied [92] the degradation of Reactive dye and Brilliant Red X 3B by
coupling of electrolysis with ultrasound. The experiment was carried out in aqueous
solution with Ti-IrO2 as anode and graphite as cathode. The azo bond of the dye molecule
and the naphthalene ring were broken, facilitating the degradation of dyes, compared to
ultrasound or electrolysis alone. Degradation rate increased with increase in dye
concentration and addition of Cl- ion into the solution. Decolorization of reactive dye was
favoured by acidic condition.

Meshram et al (2010) investigated [93] the degradation of Congo red by ultrasound at

various parameters. It was found that the degradation of Congo red followed pseudo-first
order reaction kinetics and the degradation rate constant was found to be
1.13 x 10-3 min-1 for 20 mg/L dye at temperature 25º C and pH 5.9. The effects of
different parameters on the degradation were studied. It was found that with increasing
initial dye concentration and temperature, the rate of degradation was decreased. Effect of
pH indicated that both high acidic and high basic conditions were favourable to ultrasonic
degradation of dye. The effects of Fe2+ and Fenton reagent addition on the sonochemical
degradation were also investigated and the results indicated that the degradation rate of
Congo red was accelerated by Fe2+, NaCl or Fenton reagent addition.

15
Tauber et al (2008) investigated [94] degradation of azo dyes by oxidative processes,
such as; Laccase and ultrasound treatments. Laccase treatment degraded Acid Orange and
Direct Blue dyes but none of the Reactive dyes. Ultrasound and Laccase showed
synergistic effect.

Laughrey et al (2001) studied [95] sonochemical degradation of aqueous polycyclic

aromatic hydrocarbon (PAH). Oxygen was an important precursor in degradation. It was
proved by increase in degradation rate constant when oxygen was bubbled into PAH
solution. Addition of organic compound decreased degradation rate due to scavenging of
oxygen.

Psillakis et al (2004) studied [96] the degradation of naphthalene, acenaphthylene and

phenanthrene. Degradation decreased with increasing initial concentration and
temperature, decreasing applied power, ultrasound frequency and in the presence of
excess dissolved salts. Addition of 1-butanol decreased the degradation due to scavenging
of hydroxyl radical while addition of Fe2+ ions increased degradation by Fenton like
reaction.

Kim et al (2003) studied [97] sonochemical decomposition of benzothiophene following

pseudo first order kinetics. The rate constant increased with increasing ultrasound energy
intensity and showed 77% decomposition of benzothiophene in presence of OH radicals.

Psillakis et al (2003) found [98] that the sonochemical treatment was capable of
destroying the lower molecular weight polycyclic aromatic hydrocarbons
(naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene,
fluoranthene and pyrene) completely but the higher molecular weight polycyclic aromatic
hydrocarbons, such as, benzo[a]anthracene, benzo[a]pyrene, benzo[b]fluoranthene,
chrysene, benzo[k]fluoranthene, indeno[1,2,3-cd]pyrene, dibenzo[ah]anthracene,
benzo[ghi]perylene were recalcitrant to ultrasound treatment.

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2.2 Some important studies on degradation of textile dyes and polycyclic aromatic
hydrocarbons without the use of ultrasound have also been reported, as under;

Meric et al (2005) evaluated [99] the effectiveness of three processes, Fenton’s oxidation,
ozone and coagulation–flocculation to remove toxicity, colour and COD from textile
industry waste water. Daphnia magna was used to test acute toxicity. A colour range of
150-250 platin-cobalt (Pt-Co) units was assessed for toxicity. All three processes had
same rate for colour removal but COD removal rate was same only with Fenton and
coagulation-flocculation method.

Rauf et al (2009) discussed [100] decolorisation and degradation of dyes with high energy
radiation such as gamma radiation and pulsed electron beam. The transient species e-aq
found to be effective in decolorization but less effective in degradation. Degradation of
dye was initiated by attack of OH on electron rich site of dye molecule. The effect of
radiation dose, oxygen, pH, H2O2, added ions and types of dyes induced dye degradation.

Liu et al (2007) investigated [101] the decolorization of anthraquinone dyes by ozone.

The dyes were decolorized to 96% in 40 minutes converting complicated dye molecule
with the transformation of their –SO3H, Cl, nitrogen groups into SO4-2, Cl-, NO3-
respectively.

Barragan et al (2007) examined [102] the biodegradation of an azo dye (Acid orange 7)
by Enterobacter, Pseudomonas and Morganella species of bacteria inoculated on solid
media such as Kaolin, bentonite and powdered activated carbon (PAC). Solid media
selected must have certain special characteristics such as adequate particle size,
adsorption capacity, and surface texture. PAC with 0.490 nm particle size showed
favourable condition for bacterial degradation of dyes.

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Swati et al (2012) proposed [103] the photocatalytic degradation of azo dye, Acid Red 73
in presence of Methylene Blue Immobilized Resin (MBIR) Dowex11 with solar light in
aqueous solution. The operational parameters such as dye concentration, catalyst loading,
pH and light intensity were investigated during the process. The results showed that the
optimum degradation larger than 92% of Acid Red 73 was observed in around 160 min at
room temperature at 7.5 pH and catalyst loading in around 2.0 gm.

Chatterjee et al (2010) reported [104] the reductive degradation of Reactive Black 5

(RB5) dye by zero-valent iron (ZVI) particles which were synthesized by the aqueous
phase borohydride reduction method. Three different surfactants, triton X-100 (TX100,
non-ionic surfactant), cetyl trimethyl ammonium bromide (CTAB, cationic surfactant),
and sodium dodecyl sulfate (SDS, anionic surfactant) were selected for the treatment of
ZVI in the decolourisation of RB5. The normalized residual concentration after
decolorization of 500 mg/L RB5 by ZVI for 3 h was 0.236, while ZVI particles treated
with TX100 (0.5 g/L), CTAB (1.0 g/L), and SDS (2.5 g/L) exhibited normalized residual
concentration of 0.172, 0.154, and 0.393, respectively, after 3 h. ZVI exhibited good
color removal efficiency at acidic pH. Decolorization kinetics by pseudo-first-order rate
equation showed that removal rate was increased after treatment with TX100 as well as
CTAB, while that was reduced after SDS treatment.

Rahmani et al (2010) reported [105] the removal of two azo dyes, Acid Orange 7 (AO7)
and Reactive Black 5 (RB5) by Fenton-like reaction. Removal of dye was increased by
increasing the iron mass and contact time. It was observed that high removal of dyes for
UV system was obtained at pH =11, while at pH=3 in the Feº and Feº/UV system.
Removal of AO7 in Feº/UV and Feº was increased by increasing the initial dye
concentration, while in the UV system it was decreased. Removal of RB 5 in Feº/UV and
Feº system was decreased by increasing the initial dye concentration while increased in
the UV system.

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Abadulla et al (2000) reported [106] the degradation of triarylmethane, indigoid, azo, and
anthraquinonic dyes by Trametes hirsuta and a purified laccase. It was found that the
decolourisation velocities of dyes were dependent on the substituents present on the
phenolic rings of dyes. The laccase lost 50% of its activity at 50 mM NaCl while the 50%
inhibitory concentration (IC50) of the immobilized enzyme was 85 mM. Treatment of
dyes with the immobilized laccase reduced their toxicities (based on the oxygen
consumption rate of Pseudomonas putida) by up to 80% (anthraquinonic dyes).

Taheri et al (2008) employed [107] photocatalytic degradation of Acid Red 114 by

titanium dioxide nanoparticles. UV-Vis, Ion Chromatography (IC) and Chemical Oxygen
Demand (COD) analysis were employed to obtain the details of the photocatalytic
degradation of the AR 114. The effects of different experimental parameters such as dye
concentration, anions (NO3-, Cl-, SO42-, HCO3-) and pH were investigated.

Nikazar et al (2008) investigated [108] the photocatalytic degradation of azo dye Acid
Red 114 in water with TiO2 supported on clinoptilolite (CP) using solid-state dispersion
(SSD) method. The effects of experimental parameters such as pH, amount of
photocatalyst, and initial dye concentration were examined. The maximum effect of
photodegradation was observed at 10 wt % TiO2, 90 wt % clinoptilolite. A first order
reaction with k = 0.0127 min−1 was observed for the photocatalytic degradation reaction.

Chen (2009) carried [109] out the photocatalytic degradation of azo dye Reactive Orange
16 by TiO2. The effects of various parameters, such as photocatalyst amount, dye
concentration, light intensity, and temperature on photocatalytic degradation were
investigated. It was found that the decolourization efficiency was 87 % after 20 min
reaction and 100 % after 80 min reaction. The total mineralisation was 70 % after 20 min
and 100 % after 120 min, respectively. The results indicated that color degradation was
faster than the decrease of total organic carbon. The photocatalytic degradation process
was well described by first-order kinetics.

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Plata et al (2008) studied [110] photochemical degradation of polycyclic aromatic
hydrocarbons. Disappearance rate of one set of polycyclic aromatic hydrocarbon isomer
benzo[a]pyrene and benzo[e]pyrene (kBAP/kBEP = 2.2 approximately) is different from
other set of isomer benzo[a]anthracene and chrysene (kBAA/kCHR = 2 approximately).
Inspite of their close structural similarity the difference in rate was presumed to be due to
differing capacity for direct photoreaction in oil film. However, the PAH
photodegradation was later discovered to be due to other compounds in the oil mixture.

Tran et al (2009) carried [111] out electrochemical degradation of polycyclic aromatic

hydrocarbons in a parallelepipedic electrolytic cell containing five anodes (Ti / RuO2)
and five cathodes (stainless steel). Current density of 9.23 mA cm-2 was beneficial for
polycyclic aromatic hydrocarbon (PAH) oxidation. (500-4000 mg) electrolyte Na2SO4
and initial PAH concentration had no effect on oxidation efficiency of hydrocarbon.
Alkaline media was not favourable for PAH oxidation.

Zhang et al (2008) investigated [112] photocatalytic degradation of phenanthrene, pyrene

and benzopyrene in presence of TiO2 using U.V. light source in a photochamber
maintaining the temperature of 30ºC. Degradation rate of these hydrocarbons increased
by TiO2 which reduced the half life of phenanthrene, pyrene, benzopyrene from 533.15 to
130.72 h, 630.09 to 192.53 h and 363.22 to 103.26 h respectively. Acidic or alkaline
condition favoured photocatalytic degradation than neutral condition. The degradation

was increased by combination of U.V. irradiation and TiO2 catalysis.

Bertrand et al (1990) investigated [113] biodegradation of hydrocarbon by an extremely

halophilic archaebacterium (strain EH4). Maximum growth of it on eicosane was
observed for 3.5 mol/L NaCl concentration while no growth was observed for less than
1.8 mol/L NaCl concentrations.

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Lal et al (1996) tested [114] biodegradability crude oil from the different sources viz:
Bombay High and Gujarat crude oil using two bacteria strains, Acinetobacter
calcoaceticus (S30) and Alcaligenes odorans (P20). Oil samples from Bombay and
Gujarat were degraded to the extent of 50% and 29% respectively with S30 while 45%
and 32% respectively with P20 and in combination with both bacteria by 58% and 40%
respectively. S30 degraded more of alkanes fraction than aromatic fraction and could not
grow on pure polycyclic aromatic hydrocarbon compound except naphthalene. P20
degraded alkane and aromatic fraction equally and could grow on anthracene,

phenanthrene, dibenzothiophene, fluorene, fluoranthene, pyrene and chrysene.

Jonsson et al (2006) investigated [115] the capacity of Fenton’s reagent and ozone to
degrade polycyclic aromatic hydrocarbons (PAH) in soil. The degradation efficiency for
both methods was dependent on initial PAH concentration in soil. It was observed that
low molecular weight PAHs were more susceptible for degradation whereas high
molecular weight PAHs appeared to be strongly sorbed to soils and therefore less
chemically available for oxidation.

Tran et al (2009) investigated [116] the electro-oxidation of polynuclear aromatic

hydrocarbons (PAH) from creosote solution using Ti/IrO2 and Ti/SnO2 circular mesh
electrodes. Circular Ti/SnO2 electrode was found more effective in removing PAHs.
Degradation efficiency was greatly influenced by current density and retention time while
circulation flow rate and oxygen injection have very little influence.

Chung et al (2008) evaluated [117] the degradation efficiency of polycyclic aromatic

hydrocarbon in sewage sludge by electron beam irradiation and found to be effective in
removing PAHs. The degradation of PAHs was of first order with respect to adsorbed
dose.

21
Oleszczuk et al (2003) analysed [118] the degradation of polycyclic aromatic
hydrocarbons (PAH) such as phenanthrene, anthracene, fluoranthene, pyrene,
benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[e]pyrene,
benzo[k]fluoranthene and benzo[a]pyrene in the surface layer (5 cm) of soil polluted with
aircraft fuel in an amount of 10 mL/kg was analysed. Group of microorganism occurring
naturally in the soil were able to degrade pollutants. Favourable conditions for the
development of microorganisms and the high content of nutrients played an important
role in the case of degradation of 3- rings PAHs, and the degradation of PAHs with a high
number of rings (> 4) was determined by their bioavailability.

Gonzalez et al (2010) reported [119] the biological degradation of anthracene. Earthworm

has been used to remediate anthracene-contaminated soil. About 41% removal of
anthracene was found for treatments without earthworms and 93% for those with
earthworms. Four degradation products were detected in soil of which
9,10-anthraquinone was most abundant. Thus the removal of anthracene and
9,10-anthraquinone was accelerated by E. Fetida.

Hammel et al (1995) reported [120] the degradation of polycyclic aromatic hydrocarbons

(PAHs) by ligninolytic fungi. Extracellular peroxidises by these fungi were responsible
for the initial oxidation of PAHs. Fungal lignin peroxidises oxidized certain PAHs
directly, whereas fungal manganese peroxidases cooxidise them indirectly during
enzyme-mediated lipid peroxidation.

Eibes et al (2006) reported [121] the enzymatic degradation of anthracene,

dibenzothiophene and pyrene by manganese peroxidase in media containing acetone.
These compounds were degraded to a large extent after a short period of time (7, 24 and
24 h, respectively). The order of degradability, in terms of degradation rates was as
follows: anthracene > dibenzothiophene > pyrene. Anthracene was degraded to phthalic
acid. A ring cleavage product of the oxidation of dibenzothiophene, 4-methoxy benzoic
acid, was also observed. Thus it was concluded that the addition of acetone increased the
solubility of PAHs and it did not hamper significantly the MnP activity.

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Bisht et al (2010) reported [122] biodegradation of naphthalene and anthracene by
chemo-tactically active Rhizobacteria of populous deltoides. Kurthia sp and B.Circulans
showed positive chemotactic response for naphthalene and anthracene. B.Circulans SBA
12 and Kurthia SBA4 degraded 87.5% and 86.6% of anthracene while Kurtia sp. SBA 4,
B.Circulans SBA 12 and M.Varians SBA 8 degraded 85.3%, 95.8% and 86.8% of
naphthalene respectively after 6 days of incubation.

Kim et al (2001) studied [123] the effect of non-ionic surfactants on biodegradation of

polycyclic aromatic hydrocarbons (PAHs) in the aqueous phase and in the soil slurry.
Brij 30 surfactant was utilised for exsitu remediation, while Tween 80 and Triton X-100
for in-situ remediation because they have a higher dispersion in the aqueous phase. The
desorption experiments suggested that the surfactant concentration of 0.5, 1 or 2 g/L, with
a soil to water ratio of 1:10 (g/mL), would transfer substantial amount of the
phenanthrene from the soil to liquid phase. Brij 30 was the most biodegradable surfactant
tested, showed no substrate inhibition upto a concentration of 1.5 g/L. Naphthalene and
Phenanthrene were completely degraded by Phenanthrene- acclimatized cultures within
60 h.

Han et al (2004) investigated [124] the degradation of phenanthrene by white rot fungus
Trametes versicolor 951022 and its laccase. About 46% and 65% of 100 mg/L of
phenanthrene were removed, respectively after 36 h of incubation. Phenanthrene
degradation was maximum at pH 6 and temperature 30º C. The removal percentage of
phenanthrene was highest (76.7%) at 10 mg/L of phenanthrene concentration while the
transformation rate was maximal (0.82 mg/h) at 100 mg/L of phenanthrene concentration.
In the presence of mediator 2,2 azino-bis- (3-ethyl benzthiazoline-6-sulphonic acid)
(ABTS) or 1-hydroxy benzotriazole (HIBT) in the oxidation of phenanthrene was
increased to 40% and 30%, respectively by laccase.

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Eibes et al (2005) reported [125] the degradation of anthracene by ligninolytic enzyme
manganese peroxidase in organic solvent mixtures (acetone, methylethylketone, methanol
and ethanol). Due to the maximal solubilisation of anthracene and minimum loss of MnP
activity, acetone (36%) was found to be important (it enhanced 143- fold the anthracene
solubility). Complete degradation of anthracene was attained after 6 h of operation under
optimal conditions.

Simarro et al (2011) determined [126] the optimum values for the biodegradation process
of PAH (naphthalene, phenanthrene and anthracene) by a bacterial consortium C2PLO5.
The most effective values of each optimised factors were: a C/N/P molar ratio of
100: 21:16, NaNO3 as nitrogen source, Fe2(SO4)3 as iron source using a concentration of
0.1 m mol L-1, a pH of 7 and a mixture of glucose and PAHs as carbon source. It was
concluded that the high concentration of nutrients, soluble form of nitrogen and iron and
addition of glucose to PAHs as carbon source enhanced PAH biodegradation due to the
augmentation of PAH degrader microorganisms.

Thongkred et al (2011) reported [127] the oxidation of polycyclic aromatic hydrocarbons

by a tropical isolate of Pycnoporus Coccineus and its Laccase. The highest laccase yield
(5.97± 0.40 U/mL) was obtained when grown at 28ºC for 8 days in basal medium
containing 2% (w/v) glucose and 0.25% (w/v) peptone at an initial pH of 5. The
oxidation of anthracene, pyrene and fluoranthene were 59.7, 50.7 and 49.8%, when added
to liquid culture by P. Coccineus at 100 ppm within 24 h, whereas benzo[a]pyrene and
phenanthrene were oxidised to only 25.3% and 32.4 %, respectively. When P. Coccineus
crude laccase (1U/mL) was used, pyrene and anthracene were oxidised to 76.4% and
74.3% respectively within 2 h and fluoranthene to 84.2% within 24 hr. Benzo[a]pyrene
and phenanthrene oxidation by the enzyme were enhanced when 1 mM 2,2’- azino bis
(3-ethyl benzothiazoline- 6-sulphonic acid) was added, resulting in 66.3% and 50.5%
oxidation after 24 h at initial 100 ppm.

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Jinquan et al (2006) investigated [128] the effects of chlorine dioxide (ClO2) on the
degradation of anthracene (ANTH), pyrene (PYR) and benzo[a]anthracene (BaA). The
maximum degradation ratio of ANTH, PYR and BaA was found to be 99.0%, 67.5% and
89.8% respectively, when reaction time was 30, 60 and 120 min, the concentration of
ClO2 was 0.1, 0.4 and 0.5 m mol L-1, and pH was 7.2. The oxidation product formed in
the reaction between ANTH and ClO2 was 9,10 anthraquinone and the mechanism of
single electron transfer (SET) was proposed as the possible pathway for ANTH-ClO2
reaction.

Zaidi et al (1999) studied [129] the microbial degradation of polycyclic aromatic

hydrocarbon phenanthrene in the Caribbean coastal water. Addition of KNO3 as a source
of inorganic nitrogen (N) resulted in a 10-fold increase in the rate of phenanthrene
degradation within 125 h period, whereas, addition of K2HPO4 as a source of inorganic
nutrient phosphorus (P) had no effect. It was observed that phenanthrene in seawater
samples degraded rapidly when first pretreated with hydrogen peroxide (H2O2) and then
inoculated with a known indigenous phenanthrene degrading bacterium, Alteromonas sp.

2.3 Various studies on adsorption of textile dyes and polycyclic aromatic hydrocarbons
with the use of ultrasound have been reported briefly, as under;

Li et al (2009) reported [130] the removal of C.I. Direct Blue 78 dye by the combination
of ultrasound and exfoliated graphite. It was found that Direct Blue 78 was decolourised
nearly 100% by the combined ultrasound/exfoliated graphite at pH 1, dosage of
exfoliated graphite 1 g/L, contact time 20 min and 45οC. The maximum adsorption
capacity of exfoliated graphite towards the dye was found to be 152.9 mg/g. Equilibrium
data were fitted to Langmuir and Freundlich isotherm and were best described by
Freundlich isotherm model. The adsorption followed first order kinetics.

25
Entezari et al (2007) carried [131] out the removal of Reactive Black 5 (RB5) from
aqueous solutions by the sorption process in the presence and absence of ultrasound.
Sorption of the dye was investigated to determine the influence of different parameters
such as contact time, amount of sorbent and concentration of pollutant on the removal
efficiency of RB5 with and without ultrasound. The experimental data were fitted
properly to the Freundlich model and the isotherm constants were 28.2 and 7.4 for kf and
0.13 and 0.38 for 1/n in the presence and in the absence of ultrasound (20 kHz)
respectively. The data were analyzed with different sorption kinetic models and were
better fitted with a pseudo-second-order kinetic model. Two ultrasonic generators at 20
and 500 kHz were used for sonication and it was found that the rate of removal was
higher at the high frequency than at the lower one.

Sayan et al (2008) investigated [132] the decolorization of reactive dye C.I. Reactive
Blue 19 from aqueous solution using ultrasound, activated carbon and combined
ultrasound/activated carbon. The decolorization of RB 19 by using ultrasound, activated
carbon and combined ultrasound/activated carbon was found to be 36%, 91% and 99.9%,
respectively. The decolourisation was modelled statistically and optimised by means of
the Matlab computer software.

Entezari et al (2006) examined [133] the sorption of methylene blue as a basic dye onto
cellulosic materials such as waste newspaper in the presence of ultrasound
(sono-sorption) and in its absence (conventional method). The results showed that in case
of conventional method, dye removal was increased accordingly by increasing the
amount of adsorbent while it was stopped at specific amount of adsorbent in case of
sono-sorption. More than 98% removal of the dye could be achieved in a very short
period of time of sonication with respect to the conventional method.

26
2.4 Few interesting studies on adsorption of textile dyes and polycyclic aromatic
hydrocarbons without the use of ultrasound have been reported, as under;

Abdelwahab et al (2005) investigated [134] the use of rice husk, an agricultural waste for
adsorption of synthetic Direct F. Scarlet (Direct Red 23). The results indicated that the
ability of the rice husk in removing the Direct Red 23 (DR-23) were dependent on the
dye and rice husk concentrations. Maximum dye colour removal was observed after 72
hours for all the system conditions. The adsorption isotherm of DR-23 was described by
the Langmuir isotherm model. Kinetics of adsorption followed Lagergren first order
kinetic model with film diffusion being the rate- controlling step. Activated rice husk was
observed to have higher adsorption capacity than the untreated rice husk in the removal
of DR-23. The maximum adsorption capacity was ~13 mg of dye per one gram of dry
rice husk. This study showed that the rice husk could be employed as low-cost and
effective sorbent for the removal of Direct F. Scarlet from aqueous solution.

Namasivayam et al (2002) reported [135] the adsorption of Congo Red by coir pith
carbon by varying the parameters such as agitation time, dye concentration, adsorbent
dose, pH and temperature. Equilibrium adsorption data followed both Langmuir and
Freundlich isotherms. Adsorption followed second-order rate kinetics. The adsorption
capacity was found to be 6.7 mg dye per g of the adsorbent. Acidic pH was favourable
for the adsorption of Congo Red. Very low desorption of dye suggested that
chemisorption might be the major mode of dye removal by the adsorbent.

Bozlur et al (2010) investigated [136] the use of acid activated saw dust in removing
Lurazol Brown pH (LBP) dye as a function of agitation time, adsorbent dosage and initial
dye concentration. The adsorption obeyed both Langmuir and Freundlich isotherm and
the values of their constants indicated favourable and beneficial adsorption. It was found
that only 2.5 gm of acid activated sawdust was capable of removing 94% of dye from an
initial concentration of 300 mg/L of 40 mL of solution. A two-stage filtration system has
been designed, constructed and demonstrated.

27
Shabudeen et al (2006) reported [137] the use of activated carbon which was prepared
from waste kapok hull in removing Rhodamine dye-B. The factors affecting the rate of
adsorption such as initial dye concentration, agitation time, carbon dose, particle size and
pH variation have been studied at various temperature ranges at 300, 318 and 330K. The
experimental data was analyzed for possible agreement with the Lagergren, Langmuir
and Freundlich adsorption isotherm equations. The intraparticle diffusion rate constant,
adsorption rate constants, diffusion rate constants and diffusion coefficients were
determined. The adsorption rate was mainly controlled by intraparticle diffusion. The
structural and morphological of activated carbon were characterized by XRD and SEM
studies respectively.

Singh et al (2011) investigated [138] application of saw dust (raw and modified) for the
removal of Orange G from its aqueous solutions. The raw saw dust was modified by
sulphuric acid and sodium bicarbonate. Equilibrium data were fitted to Langmuir and
Freundlich isotherm and were best described by Freundlich isotherm model. The
maximum adsorption capacity was found to be 0.40 mg g-1 for an initial concentration of
2.5 mg L-1 of Orange G at a dose of 1.0 g L-1 of the adsorbent. A maximum removal
(44%) of Orange G was found at 298 K. The negative values of ΔG were indicative of the
spontaneous nature of the process of dye removal, whereas the negative values of ΔH and
ΔS indicated the exothermic nature of adsorption and decrease in degree of freedom of
the adsorbed species, respectively.

Zawani et al (2009) investigated [139] the removal of Remazol Black 5 from the
synthetic wastewater using palm kernel shell activated carbon in terms of initial pH,
initial concentration, contact time and temperature. The optimum pH was found at acidic
range, pH 2. Equilibrium data were fitted to Langmuir and Freundlich isotherm and were
best described by Freundlich isotherm model. The maximum adsorption capacity at 30ºC,
40ºC and 50ºC were found to be 58.8. 96.7 and 98.6 mg/g, respectively. The pseudo
first-order kinetic model fitted very well with the adsorption behaviour of RB5 dye. The
negative value of ΔGº and ΔHº indicated that the adsorption was a spontaneous and
exothermic process.

28
Sharma et al (2009) investigated [140] the application of activated carbon developed
from rice husk, an agricultural waste product for the removal of Malachite Green from
aqueous solutions and wastewaters. The removal increased from 93.75 to 94.91% by
decreasing the initial concentration from 100 to 60 mg/L. Time of equilibrium was found
to be 40 min. Equilibrium data were fitted to Freundlich and Langmuir isotherm
equations and the isotherm constants were determined. Kinetics of adsorption followed
first order kinetic model. The monolayer adsorption capacity of rice husk activated
carbon for adsorption of the dye was found to be 63.85 mg/g at room temperature.

Nourouzi et al (2009) studied [141] the adsorption of two reactive dyes, Reactive Black 5
and Reactive Red E onto palm kernel shell-based activated carbon. The experiment was
carried out to investigate three models: film diffusion model, film surface and film-pore
diffusion models. The results showed that the external coefficients of mass transfer
decreased with increasing of initial adsorbate concentration. Film surface diffusion model
was able to fit experimental better than film pore diffusion model.

Jayarajan et al (2011) discovered [142] the effect of agricultural waste product

nano-porous adsorbent of Jack fruit peel waste for removing Rhodamine dye (RD) from
aqueous solution. The effects of adsorption isotherm were studied at different adsorbent
dosages, temperature and pH. Adsorption behaviour of the dye could be described well
by Langmuir and Freundlich models. The monolayer adsorption capacity determined was
determined to be 4.361 to 1.98 mg/g.

Ofomaja et al (2008) investigated [143] the biosorption of Methyl Violet dye from
aqueous solution using Mansonia wood sawdust. The equilibrium biosorption data were
analyzed using three isotherm models; Langmuir, Freundlich and Redlich-Peterson
isotherm. Best fits were yielded with Langmuir and Redlich-Peterson isotherms. The
removal percentage of dye became significant above pH 7, which was slightly higher
than the pHPZC of the sawdust material. The thermodynamic parameters, such as
∆G°, ∆H°, and ∆S° suggested that the biosorption was a spontaneous and endothermic
process.

29
Annadurai et al (2002) investigated [144] the adsorption of Methyl Orange (MO),
Methylene Blue (MB), Rhodamine B (RB), Congo Red (CR), Methyl Violet (MV) and
Amido Black 10B (AB) by low-cost banana and orange peels as adsorbents. The
adsorption capacities for both peels decreased in the order: MO > MB > RB > CR > MV
> AB. The Freundlich equation showed a better fit than does the Langmuir equation for
adsorption of dyes using banana peel, but exactly reversed using orange peels. An
alkaline pH was favorable for the adsorption of dyes. Based on the adsorption capacity, it
was shown that banana peel was more effective than orange peel. Kinetic parameters of
adsorption such as the Lagergren rate constant and the intraparticle diffusion rate constant
were determined. For the present adsorption process intraparticle diffusion of dyes within
the particle was identified to be rate limiting.

Bhattacharyya et al (2003) reported [145] the adsorption of Brilliant Green dye on

powdered dry leaves of the Neem tree. The adsorption process was carried out in a batch
process with different concentrations of the dye solution (2.07 x 10-2 to 10.36 x 10-2
m mol dm-3), different adsorbent doses (0.13-0.63 g dm-3), and temperature (300, 303,
313, and 323K). The removal of dye was nearly 25% with 0.13 g dm-3 of adsorbent after
1 hr of contact time which increases to 71.8% after 5 hr and further increment upto 98%
was achieved by an increase in adsorbent dose to 0.63 g dm-3. The suitability of the
adsorbent was tested by fitting the adsorption data with Langmuir and Freundlich
isotherms and by computing equilibrium thermodynamic and kinetic parameters.

Suteu et al (2005) reported [146] the sorption of reactive dye Brilliant Red HE-3B from
aqueous solutions on commercially powdered activated charcoal as a function of solution
pH, initial dye concentration, temperature and contact time. The equilibrium sorption data
fitted well to Langmuir model. The apparent thermodynamic parameters of sorption
suggested an entropy-driven, endothermic sorption process. The kinetic of the sorption
fitted well to the pseudo-second order kinetic model, indicated an intraparticle diffusion
mechanism.

30
Sarioglu et al (2006) reported [147] the mechanism of Methylene Blue adsorption on
biosolid (waste sludge) through batch experiments. The effects of various experimental
parameters, such as pH (3 - 11), bio solid dosage (1-10 g L-1), contact time (5-1440 min)
and initial dye concentration were investigated. The results showed that the dye removal
increased with increase in the initial concentration of the dye and also increased with
amount of bio solid used and initial pH. Adsorption data was modelled using the
Freundlich adsorption isotherm. The results show that bio solid could be employed as an
effective and low cost material for removal of dyes and colour from aqueous solution.

Filipkowska et al (2002) investigated [148] the adsorption of reactive dyes onto chitin
from aqueous solutions at pH 3. Ten reactive dyes were examined, including 5 dyes from
the helactine group, 3 dyes from the polactine group and 2 dyes from the remazol group.
The K and b constants were calculated from the Langmuir equation that assumes the
presence of two sites of different nature. It was found that the dye adsorption on chitin in
type I and II sites differed in both the adsorption affinity and maximum adsorption
capacity. Based on the dimensionless separation factor RL it was found that the dye
adsorption mechanism in type I sites was an ion exchange in the following decreasing
order: helactine dyes > polactine dyes > remazol dyes, whereas in the case of type II sites
it was a physical adsorption in the following increasing order: helactine dyes < polactine
dyes < remazol dyes. The experiments indicated a correlation between dye adsorption on
chitin and a number of sulphonic groups in a dye molecule while correlation with the
number of aromatic rings, benzene or naphthalene was not found.

Maximova et al (2008) investigated [149] the adsorption of two basic dyes, Basic Red 18
and Basic Blue 5, onto two fractions, Perfil M-100 and Perfil M-150. The equilibrium
sorption isotherms were correlated well by the Langmuir and Redlich-Peterson isotherms
for Basic Blue 5 and by the Freundlich model for Basic Red 18. The adsorption capacity
of two sorbents for Basic Red 18 followed the order: perfil M-100 > perfil M-150 and for
Basic Blue 5 it was perfil M-150 > Perfil M-100. The kinetics models of sorption were
analysed using pseudo- first order and pseudo- second order kinetic models and were
successfully fitted by pseudo-second order model.

31
Chiou et al (2006) reported [150] the adsorption behaviour of acid dye
(MY, metanil yellow) and reactive dye (RB15, reactive blue 15) in aqueous solutions by
the cross-linked chitosan beads. The adsorption capacities was 3.56 m mol g-1
(1334 mg g-1) for dye MY and 0.56 m mol g-1 (722 mg g-1) for dye RB15 at pH 4, 30 °C.
The Langmuir model agreed very well with the experimental data (R2 > 0.996). The first-
order kinetic model fitted well for lower initial dye concentrations, while the second-
order kinetic model fits well for higher initial dye concentrations. It was found that high
adsorption capacity of anionic dyes onto chemically cross-linked chitosan beads was due
to strong electrostatic interaction between the -NH3+ of chitosan and the dye anions. The
competitive adsorption favoured the dye RB15 in the mixture solution
(initial conc. (mM): MY = 1.34; RB15 = 1.36); while it favoured the dye MY in the
mixture solution (initial conc. (mM): MY = 3.00; RB15 = 1.34) and the adsorption
kinetics for dye RB15 has the tendency to shift to a slower first order model.

Nasuha et al (2011) reported [151] the adsorption of cationic, Methylene blue (MB) and
anionic, Congo Red (CR) dye from aqueous solution by using chemically modified
papaya seed (PS). The results showed that the chemical modification esterification of
carboxyl group could increase the adsorption capacity of papaya seed in removal of
cationic dye compared to anionic dye. The effect of different experimental parameters
such as initial dye concentration (50-500 mg/L) and various adsorbents (NPS and EPS)
were investigated. The Langmuir isotherm showed a better fit than does the Freundlich
for adsorption of MB, but for CR the best fit isotherm model was Freundlich. Maximum
monolayer adsorption capacity was found to be 250.00 mg/g and 200.00 mg/g at 30°C for
EPS and for NPS respectively. The adsorption kinetics obeyed pseudo-second order with
higher coefficient of correlation R2 0.99.

Vacha et al (2006) investigated [152] the adsorption of benzene, naphthalene, anthracene,

and phenanthrene by means of molecular dynamics simulations. Potentials of mean
force, i.e., free energy profiles were evaluated when moving the studied molecules across
an aqueous slab. In all cases, deep surface free energy minima, corresponding to orders of
magnitude of surface enhancement of the aromatic molecule, were located. It was found

32
that the hydration free energies computed from MD calculations and the experimentally
determined values were in good agreement. Data pertaining to the importance of the
air–water interface in the adsorption and transport of PAHs on micron sized water
droplets were described. The relevant data on adsorption and reaction (ozonation and
photochemical) at the air–water interface of planar surfaces and droplets were also
summarized.

Saba et al (2011) examined [153] the adsorption kinetics of two polycyclic aromatic
hydrocarbons anthracene and phenanthrene on soil from different areas of Attock
Refinery Limited (ARL), Rawalpindi, Pakistan. It was found that the high concentration,
acidic pH and high organic matter contributed to higher adsorption capacities. The
maximum adsorption exhibited for anthracene and phenanthrene were 95.2% and 95.4%,
respectively under optimum condition of pH and initial concentration. The experimental
results were analysed by Freundlich and Langmuir isotherms.

Gok et al (2008) investigated [154] the adsorption kinetics of naphthalene onto

organo-sepiolite from aqueous solutions. Natural sepiolite was modified by a surfactant,
which was dodecyltrimethyl ammonium (DTMA) bromide. The optimum pH values and
the equilibrium contact time for the adsorption of naphthalene onto DTMA-sepiolite were
found as 6 and 75 min, respectively. The adsorption capacity of DTMA sepiolite
increases with increasing temperature indicated that the adsorption process was
endothermic in nature. The maximum adsorption capacity of DTMA-sepiolite for
naphthalene was found to be 2.867 mg/g.

Huang et al (2010) investigated [155] the potential of Gomphidius viscidus, a kind of

ectomycorrhizal fungi, for phytoremediation of anthracene in soil. Adsorption capacity of
1886.79 mg/g and 1515.15 mg/g at 25º C, pH 6.0 for active and inactive mycelia
respectively, was obtained. It was found that the process of equilibrium could be reached
within 40-60 min and described well by the Langmuir isotherm model and pseudo-second
order sorption kinetics. The adsorption capacity increased with an increase in initial
anthracene concentration while decreased with rise in temperature at 25ºC and 35ºC.

33
Eiceman et al (1983) examined [156] the adsorption of six polycyclic aromatic
hydrocarbons on fly ash. Direct measurement of adsorption using elution analysis with
gas-solid chromatography has been made on fly ash from a municipal incinerator and a
coal fired power plant. Results showed that the irreversible adsorption occurred at
concentration below 30 µg PAH per gram of flyash, while at concentration above 30 µg/g
adsorption of PAH were governed by vapour pressure.

Duc et al (2010) examined [157] the adsorption of polycyclic aromatic hydrocarbon on

graphite surfaces. Coronene (C24H12) was chosen as a model compound to study the
interaction between a typical PAH and a graphite surface. They investigated the problem
by adopting an applied mathematical modelling approach and therefore exploit the
continuous atomistic approximation together with the Lennard Jones potential instead of
using conventional computational methods, such as full ab initio, which was not feasible
owing to the large molecules involved. They described the mechanism of adsorption of a
Coronene molecule on a graphite surface using an analytical expression for the
interaction energy.

Yuan et al (2010) studied [158] the adsorption of polycyclic aromatic hydrocarbons:

naphthalene, fluorene, phenanthrene, pyrene and fluoranthene from aqueous solution
using petroleum coke-derived porous carbon. The specific surface area (SSA) of the
carbons ranges from 562 to 1904 m2/g, while their point of zero charges pHpzc varies
from 2.6 to 8.8. The adsorption capacity parameter Kf for any given PAH, increase with
the SSA and pHpzc of the carbons, confirming the roles of dispersive interactions. The
value of Kf followed the order: naphthalene > fluorene > phenanthrene > pyrene. Results
indicated that the uptake process was likely to be controlled by diffusive transport
processes.

34
Walters et al (1984) examined [159] the adsorption of polycyclic aromatic hydrocarbons
onto activated carbon. An evaluation of Henry’s law, Langmuir, BET, Freundlich and
Redlich-Peterson equations indicated that the Langmuir equation was most useful for
representing the data. The Henry’s Law adsorption constants ranged from
2390 (mg/g)/(mg/L) for naphthalene to 326000 (mg/g)/(mg/L) for chrysene. The
adsorption capacity obtained from Langmuir equation ranged from 580 mg/g for
naphthalene to 14.7 mg/g for benzo[a]anthracene. Results indicated that the adsorption of
PAH onto activated carbon was much stronger than was adsorption of PAH onto soils,
sediments and suspended organic matter.

Hall et al (2009) investigated [160] the adsorption of polycyclic aromatic hydrocarbons

onto silica gel. Acenaphthene was selected as target compound. Kinetic results were
analysed using pseudo-first and pseudo-second order equations, and equilibrium data
were described by the Langmuir and Freundlich isotherms. It was concluded that the
lower molecular mass PAHs, such as acenaphthene, were well represented by the pseudo-
first order equation. Adsorption mechanisms were analysed using boundary layer mass
transfer and intra particle diffusion models, indicating intraparticle diffusion as the main
adsorption controlling step.

Low et al (1988) examined [161] the adsorption of anthracene, pyrene and

dibenzo[a,c]anthracene on nine fly ash samples from the combustion of Australian
bituminous and brown coals by a high-performance liquid chromatographic procedure.
Results indicated that the adsorption data was well represented by the Freundlich
equation. From the correlation analysis between the adsorption capacity of PAHs and
physical and chemical characteristics of fly ashes, it was indicated that the residual
carbon content was the main regulating parameter.

35
Crisafully et al (2008) investigated [162] the removal of polycyclic aromatic
hydrocarbons (PAHs) from petrochemical wastewater using various low-cost adsorbents
of natural origin including sugar cane bagasse, green coconut shells, chitin, and chitosan.
Adsorption experiments of mixtures of PAHs (5.0-15.0 mg/L) have been carried out at
ambient temperature (28+/-2 degrees C) and pH 7.5. The adsorption isotherms of PAHs
were in agreement with a Freundlich model, while the uptake capacity of PAHs followed
the order: green coconut shells > sugar cane bagasse > chitin > chitosan. The adsorption
properties of green coconut shells were comparable to those of some conventional
adsorbents such as Amberlite T.

Chen et al (2011) investigated [163] the removal of polycyclic aromatic hydrocarbons

onto wood chips (WC), ryegrass (RR), orange peels (OP), bamboo leaves (BL) and pine
needles (PN). Biosorption isotherms fitted well with Freundlich equation and the
mechanism was dominated by partition process. The magnitude of phenanthrene partition
coefficients (Kd) followed the order of PN > BL > OP > RR > WC, ranged from
2484 ± 24.24 to 5306 ± 92.49 L/kg. Except the WC sample, the Kd values were
negatively correlated with sugar content, polar index [(N + O)/C] of the biosorbents,
while the aromatic component exhibited positive effects.

Ma et al (2011) determined [164] the cell wall-cosolvent partition coefficients (Km) of

polycyclic aromatic hydrocarbons for Rhizopus oryzae cell walls by controlling the
volume fraction of methanol (f) ranging from 0.1 to 0.5. Five cosolvent models were
employed for extrapolating the cell wall-water partition coefficients (Kw) in pure water.
The extrapolated Kw values of PAHs on R. oryzae cell walls were ranged from 2.9 to 5.1.
Comparison of various Kw values of pyrene generated from extrapolation and the QSPR
model, together with predicted different (PD), mean percentage deviations (MPD), and
root mean square errors (RSE), revealed that the performance of the LL and Bayesian
models were the best among all five tested cosolvent models. This study suggested that R.
oryzae cell walls played an important role in the partitioning of PAHs during
bioremediation because of the high Kw of fungal cell walls.

36
Long et al (2008) investigated [165] the adsorption of naphthalene on a spherical
microporous carbon adsorbent (CR-1), which had been obtained by carbonization and
activation of the waste polysulfonated cation exchange resin. . The adsorption data fitted
best with Polanyi-Dubinin-Manes model, although tested simultaneously with
Freundlich, Langmuir, Brunauer-Emmett-Teller models as well. Through both isotherm
modeling and constructing "characteristic curve", Polanyi theory was useful to describe
the adsorption process of naphthalene by CR-1, providing evidence that a micropore
filling phenomenon was involved. Adsorption process was found to follow pseudo-first-
order kinetic equation.

Chang et al (2004) examined [166] the adsorption of naphthalene on zeolite from

water-butanol solution, which was a surfactant-enriched scrubbing liquid. The adsorption
data was successfully evaluated by Langmuir, Freundlich, and linear isotherms. The
adsorption kinetics fitted best with the pseudo-second order equation, although tested
simultaneously with pseudo-first order and Elovich rate equation.

Sener et al (2010) investigated [167] the adsorption behaviour of naphthalene onto

sonicate talc from aqueous solution. The naphthalene uptake of talc was found as
276 mg/g and increased to 359 mg/g after the sonication. Adsorption studies also showed
that the adsorption of naphthalene onto the sonicated talc was not affected by changes in
pH suggesting that the main driving forces for naphthalene adsorption onto talc was
hydrophobic bonding rather than electrostatic force. The Freundlich isotherm best fitted
for the adsorption of naphthalene onto talc and the adsorption process followed the
pseudo-second-order rate expression for different initial naphthalene concentrations.

37
Long et al (2009) investigated [168] the adsorption of naphthalene onto two adsorbents, a
hypercrosslinked polymeric adsorbent (NDA-150) and a macroporous polymeric
adsorbent (XAD-4), which have the same matrix of poly (styrene-divinylbenzene) and
similar surface area. The equilibrium data were correlated with Polanyi–Manes–Dubinin
equation, and the adsorption enthalpy changes (ΔHmeas) were determined. The good fits
of Polanyi–Manes–Dubinin equation and high-exothermic adsorption enthalpies
indicated that micropore filling was involved during the adsorption of naphthalene onto
two adsorbents. The higher adsorption capacity of hypercrosslinked adsorbent compared
to macroporous adsorbent was due to its larger micropore volume. The adsorption of
naphthalene was found to follow a pseudo-second-order process which was controlled by
intra-particle diffusion. The adsorption rate of macroporous adsorbent (XAD-4) was
faster than that of hypercrosslinked adsorbent (NDA-150) as it has more suitable porous
structure for transporting the adsorbate into the adsorption sites.

Demirkan et al (2011) investigated [169] the adsorption of two nonpolar petroleum

contaminants, naphthalene, and o-xylene, onto seven fly ashes with varying carbon
contents, with powdered activated carbon (PAC). Six equilibrium isotherm models were
used to evaluate the batch data. The naphthalene and o-xylene adsorption capacity of the
fly ashes was correlated with the unburnt carbon content, specific surface area of the
sorbent, and the percentage of the anisotropic and isotropic carbon content of the ash. A
pore-filling mechanism was the dominant mechanism for the adsorption of nonpolar
organic chemicals onto PAC as evaluated on the basis of the Polanyi-Dubinin-Manes
model, whereas the adsorption onto fly ash was likely to be governed by the unburned
carbon content and the specific surface area of the ash.

Manop et al (2009) investigated [170] the adsorption of anthracene (C14H10) and pyrene
(C16H10) on two types of soot, rubber-wood furnaces soot (RB) and diesel engine soot
(DE). Characteristics of the soot, such as carbon contents, specific surface area and pore
volume were investigated. Adsorption isotherms models, i.e., Freundlich (Fre) and
Polanyi-Dubinin-Manes (PDM) were fitted well. KF in Fre and VO in PDM illustrated
adsorption degree of the soot in which KF of anthracene on RB and on DE were 0.97 and

38
0.74 and VO of anthracene was 200.30 and187.78 cm3 mol-1, respectively. On the other
hand, KF of pyrene on RB and on DE were 0.97 and 0.74 and VO of pyrene was 50.07
and 44.66 cm3 mol-1, respectively. Results indicated the amount of adsorption of
anthracene was higher than that of pyrene and the adsorption capacities of RB was larger
than DE. The energy of adsorption E as calculated from PDM model for anthracene on
RB and DE was found to be -8.84 and -8.62 kJ mol-1 and those of pyrene on RB and DE
were -7.39 and -7.45 kJ mol-1, respectively.

Owabor et al (2010) investigated [171] the adsorption and desorption kinetics of

naphthalene, anthracene and pyrene in a soil slurry reactor to ascertain the mechanism
controlling the retention and release rates of these compounds. A stirred flow method was
employed to perform the experiments. The extent of partitioning for the polycyclic
aromatic hydrocarbons (PAHs) tested was found to be dependent on their solubility and
diffusivity in the aqueous phase. Apparent adsorption and desorption rate coefficients
were determined using the Langmuir and Freundlich isotherm models. Equilibrium
adsorption and desorption at the external surface and in the internal pore of the soil
particle obeyed the Freundlich isotherm equation. The pseudo-equilibrium condition
established at the minimum contact time suggests that equilibrium adsorption attained for
the contaminant PAHs was not instantaneous but rather time dependent.

Dyachuk et al (2009) examined [172] the adsorption of PAHs by solid phase

luminescence from micro heterogeneous media containing an anionic surfactant
(sodium dodecyl sulphate, SDS) and a nonionogenic polymer (polyethylene glycol, PEG
1000), on cellulose and polyurethane foams (PUF). Thus, the adsorption of PAHs by the
modified cellulose considerably decreased the detection limit of PAHs in aqueous media.
The highest sensitivity of the determination was attained in the phosphorescence method.
The best results were obtained in the determination of PAHs using the preconcentration
in the microvolume of SDS micelles modified with polyethylene glycols followed by the
solid-phase extraction of PAHs and the analysis in the adsorbent phase.

39