Beruflich Dokumente
Kultur Dokumente
11
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.
12
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.
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.
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.
13
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.
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.
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.
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.
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.
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.
16
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.
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.
17
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.
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.
18
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).
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.
19
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.
20
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,
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.
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.
22
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.
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.
23
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.
24
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
39