B.TECH.

FINAL YEAR
PROJECT
WORK

Dipanwita Mondal

Chemical Engineering
Department

University College of
Science and Technology

University of Calcutta
 PROJECT REPORT

DEGRADATION OF DYE POLLUTANT IN WASTE

WATER BY SONO-FENTON OXIDATION

A Project Report Submitted for Partial Fulfillment of B.Tech. Degree

of Calcutta University

BY

DIPANWITA MONDAL

Roll No: 91/CME/121010

B.Tech in Chemical Engineering
3rd year
University Collage of Science and Technology
University of Calcutta

UNDER THE GUIDANCE OF

Dr. Sampa Chakrabarti

Associate Professor
University Collage of Science and Technology
University of Calcutta
 ACKNOWLEDGEMENT

I would like to acknowledge Dr. Sampa Chakrabarti, Associate Professor for

providing me the opportunity to do my B.Tech project under her supervision.

I would like to thank Ms. Amrita Dutta, Mr. Anirban Roy, Research Scholars
working in the laboratory, for providing me with their guidance and useful
suggestions as well as explaining the minute - details during carrying out the
project work.

Date:

Dipanwita Mondal

Roll No: 91/CME/121010

Chemical Engineering Department
3rd year, 5th semester

ABSTRACT
Industrial wastewater containing non-biodegradable organic pollutants can be treated by

advanced oxidation processes (AOP) such as Fenton’s reaction involving hydroxyl free

radical to oxidize recalcitrant organic compounds. In presence of additional sources of energy

like light or ultrasound, the efficacy of Fenton’s reaction in enhanced by orders of magnitude.

The advantage of ultrasound over light is that, the reactor configuration is comparatively

simple and sono-Fenton reaction can be accomplished with turbid or dark-coloured effluent

which is difficult for photo-Fenton process due to poor penetration of light.

The present project aims at the study of efficacy of the combined process of acoustic

cavitation and Fenton’s reaction for the treatment of wastewater containing organic dye

pollutant. In this project work Trypan Blue, an azo dye will be degraded by sono-Fenton

oxidation in a batch reactor placed in a bath type sonicator. Effect of changing various

process parameters such as concentrations of FeSO4 and H2O2, pH of the medium and initial

concentration of dye, will be studied. Efficiency of ultrasound will be examined by

comparing with ordinary Fenton’s reaction. A kinetic model will be proposed and the

performance will be compared with reactions under sunlight and probe-type sonicator.
Contents

1. Introduction......................................................................................................................................4

2. Literature Review............................................................................................................................5

2.1 Advance Oxidation Process (AOP)...........................................................................................5

2.2 Review of various literature on treatment of wastewater by AOP’s…..............……...............10

2.3 Review of literature on sono-Fenton degradation of organic pollutants

3. Objective and scope of work...........................................................................................................5

4.Materials and methods....................................................................................................................16

4.1 Materials used..........................................................................................................................16

4.2 Analytical methods

4.3 Experimental set up.................................................................................................................17

4.4 Experimental procedure...........................................................................................................17

5. Results

6. Present Status of the Project and Plan of Further Work

1. Introduction

Modern technology has enormously improved our way of life. While we

enjoy the benefits of modern equipments of science and technology, we also

expose ourselves and the environment to numerous possible dangers from the

unknown types of pollutants, which are not only toxic but also non-

biodegradable. One of the major threats to environment vis-à-vis modern human

life is raised from waste water effluent, discharged unscrupulously from large

and small scale industries, contaminating limited amount of available fresh

water. Fresh water resources all over the world are threatened by over

exploitation, poor management and low natural ecological degradation

processes. Many industrial, agricultural, domestic and commercial activities

use water are discharged into the aquatic environment without any

treatment. Thus, the waste water generated from different activities contains

various contaminants. Organic environmental contaminants in water are a

major problem particularly those with known carcinogenic [1] and mutagenic

[2] properties. Waste water from the textile industry contained large amount

of dyes which possess a great danger to o u r ecosystem [3]. Thus the innovative

procedures are needed to deal with the wide range of organic contaminants.

Several physical [4-7], chemical [8-11] and biological [12-15] methods are

available for the treatment of textile waste water; however, drawback of most

of these methods is that they require considerable amount of time, energy,

and also they lack from a broad scope of treatment efficiency needed to reduce
and/or mineralise dyes in waste water. The traditional waste water treatment

processes, such as coagulation/flocculation, membrane separation or activated carbon

adsorption are based on phase transfer mechanism. Biological treatment is not also suitable

due to the biological resistivity of some dyes. So, it is necessary to develop some effective

processes e.g. Advanced Oxidation Process (AOP) for complete degradation of the dyes.

Advanced oxidation processes, which involve the in situ generation of highly potent

chemical oxidants such as the hydroxyl radical (OH•), have recently emerged as an

important class of technologies for accelerating the oxidation and destruction of a wide

range of organic contaminants in polluted water and air [16, 17]. AOP when applied on a

right place, give a good opportunity to reduce the contaminant concentration from several

hundreds ppm to less than 5 ppb. That is why they are called “the treatment processes of the

21st century”. Amongst numerous treatment technologies, used recently,

ultrasonic irradiation is an attractive and promising technology. In terms of

convenience and simplicity of operation, ultrasound could be more

competitive and far superior to many alternative approaches. Many simple

[18] and complex [19] molecules from low to high toxicity levels, polluting

the aquatic life and the environment have been successfully degraded by the

ultrasound to relatively non-toxic or lesser harmful species. The appropriate

choice of ultrasonic frequency, power and the duration of introduction

contribute not only to the oxidation of organic pollutants by free radicals, but

also provide a basis of the thermal decomposition of the given substance in the

gaseous phase [20]. In the past several years, ultrasound has been utilized extensively for

the removal/degradation of organic pollutants from waste water [21-28]. Several sonolysis

studies conducted with chemicals addition such as Fenton's reagent with three states of iron

(i.e., Fe0, Fe2+ and Fe3+) have proven the improvement of pollutant degradation [29-33].
Although the efficiencies of these hybrid techniques are significantly greater, their

fundamental concepts and reaction mechanisms still need to be researched. Furthermore,

coupling of hydrodynamic cavitation in conjunction with the Fenton process is an effective

method for the continuous remediation of aqueous organic compounds and non-

biodegradable pollutants. Therefore, a proper understanding of sono-Fenton process, i.e.,

theory, optimal operating conditions, and future research challenges, will definitely improve

its real-time application for the treatment of wastewaters or effluent containing organic

pollutants.

2. Objective and scope of work

The present project aims at the study of efficacy of the combined process of acoustic

cavitation and Fenton’s reaction for the treatment of wastewater containing organic dye

pollutant.

Objectives and scope of work are as follows:

 In this project work Trypan Blue, an azo dye will be degraded by sono-Fenton

oxidation in a batch reactor placed in a bath type sonicator.

 Process parameters to be studied are pH, dosing of Fenton’s reagent and initial

concentration of dye pollutant. Optimum process parameters will be determined.

 Analysis of the residual pollutants will be done with UV-vis spectrophotometer

 Decrease in the Chemical Oxygen Demand (COD) will be monitored by standard

methods in APHA.

 Efficiency of ultrasound will be examined by comparing with ordinary Fenton’s

reaction.
  A kinetic model will be proposed and the performance will be compared with

reactions under sunlight and probe-type sonicator.

3. Literature review

3.1. Advance Oxidation Process (AOP)

Advanced oxidation processes, abbreviated as AOPs, refer to a set of chemical

treatment designed to remove organic and inorganic materials in water and waste

water by oxidation through reactions with hydroxyl radicals (OH•). It involves two stage of

reaction,

(i) The generation of strong oxidants (e.g. hydroxyl radicals) and

(ii) The reaction of these oxidants with organic contaminants in water.

Oxidation is defined as the transfer of one or more electrons from an electron donor

(reductant) to an electron acceptor (oxidant), which has a higher affinity for electrons. These

electron transfers result in the chemical transformation of both the oxidant and the reductant,

in some cases producing chemical species with an odd number of valence electrons. These

species, known as radicals, tend to be highly unstable and, therefore, highly reactive because

one of their electrons is unpaired. Oxidation reactions that produce radicals tend to be

followed by additional oxidation reactions between the radical oxidants and other reactants

(both organic and inorganic) until thermodynamically stable oxidation products The most

powerful oxidants are fluorine, hydroxyl radicals (OH•), ozone and chlorine with oxidation

potentials of 2.85, 2.70, 2.07 and 1.49 electron volts, respectively [34]. The ability of an

oxidant to initiate chemical reactions is measured in terms of its oxidation potential. The end

products of complete oxidation (i.e. mineralization) of organic compounds benzene are

carbon dioxide (CO2) and water (H2O). AOPs involve the two stages of oxidation as

mentioned above: Firstly, the formation of strong oxidants (e.g., hydroxyl radicals) and then
the reaction of these oxidants with organic contaminants in water. However, the term

advanced oxidation process refers specifically to the process in which oxidation of organic

contaminants occurs primarily through reactions with hydroxyl radicals [16-17]. In water

treatment applications, AOPs usually refer to a specific subset of processes that involve O3,

H2O2, and/or UV light. However, in this analysis, AOPs will be used to refer to a more

general group of processes that also include ZnO catalysis, cavitations, E-beam irradiation,

and Fenton’s reaction. All of these processes can produce hydroxyl radicals, which can react

with and destroy a wide range of organic contaminants, including MTBE. Although a number

of the processes noted above may have other mechanisms for destroying organic

contaminants, in general, the effectiveness of an AOP is proportional to its ability to generate

hydroxyl radicals.

With additional sources of energy like UV or visible light or ultrasound, AOPs

generate OH radical at a higher rate and hence become more effective compared to the non-

energized ones.

A brief review below will summarize the trends of recent research on energy assisted,

especially ultrasound enhanced Fenton process for degradation of organic pollutants.

 Figure 1: Advance oxidation process due to UV light, H2O2 and O3

3.2. Fenton and photo-Fenton processes for oxidative degradation of

pollutants in wastewater

3.2.1. Fenton Reagent

Fenton’s reagent a mixture of ferrous iron (catalyst) and hydrogen peroxide (oxidizing agent),

has been known to be a powerful oxidant for organic contaminants. The mechanism of the

Fenton process is reported below ,

Fe2+ + H2O2→ Fe3+ + OH- + HO• ……... (1)

Fe2+ + HO• → Fe3+ + OH- …….... (2)

HO• + RH → H2O + R• …….... (3)

R• + Fe3+→ R+ + Fe2+ …….... (4)

The free radicals generated by this process then engage in secondary reactions. Oxidation of

an organic compound by Fenton's reagent is rapid and exothermic and results in the oxidation

of contaminants to primarily carbon dioxide and water. In this process, the organic compound

i.e. RH is oxidized by OH• during radical chain reaction as proposed by Perkowski et al. [35]

HO• + RH → H2O + R• ……….. (5)

R• + H2O2 → ROH + HO• ……….. (6)

The kinetic chain in the reactions between the radicals [36] is terminated according to

following reaction

HO• + HO• → H2O2 ………… (7)

HO• + HO2• → H2O + O2 ....……… (8)

HO2•+ HO2• → H2O2 + O2 ....……… (9)

Radicals R• and RO2• also recombine and then gets terminated by following chain reaction:

R• + RO2• →ROOR ………….. (10)

RO2• + RO2• → ROOR + O2 ………….. (11)

3.2.2 A few papers on Fenton and Photo-Fenton processes are reviewed below:

3.2.a. Discoloration of Azo Dye Acid Red 18 by Fenton Reagent in the Presence of Iron

Powder; Barbusiński,K., Majewski, J., (2003) [37]

Barbusiński and Majewski studied the Fenton process by using alternative iron source.

They used iron powder and Acid red 18 dye as sample solution. In a glass reactor with

magnetic stirrer the solution is vigorously mixed with iron powder of different doses at acidic

pH maintained by H2SO4 added externally. They also varied the hydrogen peroxide

concentration and used NaOH to maintain the pH at 9 and further generation of OH•. Then

the sample solution is centrifuged at 3000 rpm and finally studied under maximum

wavelength 510 nm at UV-VIS spectrophotometer. They found that commercial azo dye

solution of concentration 100 mg/dm3 can be completely decolorized by 60 mg/dm 3 H2O2 and

50 mg/dm3 Fe powder at optimum pH 3. The smaller amount of iron powder requires longer
reaction time. This reaction is very sensitive at pH in between 2.5-3.5. Beyond the pH range a

rapid decrease on discoloration efficiency was observed.

In between 10-600mg/dm3 loading of final pH is constant. But on increasing the loading

further the final pH increases hence requirement of smaller doses of base for final

neutralization of waste water. Moreover, the same iron powder can be used repeatedly in the

process. It was also found that the time of dissolution of iron powder at acidic conditions

(before H2O2 was added) is an important parameter that influences the rate of discoloration

time. A longer time of iron powder dissolution caused a higher amount of Fe2+ ions in

solution and in consequence, a larger amount of hydroxyl radicals is generated in the system.

Thus, the oxidation kinetic of Acid Red 18 in the H2O2/Fe0 process is more effective.

3.2.b. Decolourization and mineralization of commercial reactive dyes by using

homogeneous and heterogeneous Fenton and UV/Fenton processes; Papi´c, S., Vujevic,

D., Koprivanac, N., Sinko, D., (2009) [38]

Papi´c et al studied Organic dyes: Cibacron Yellow R (C.I. Reactive Yellow 3, RY3),

Cibacron Blue 3G (C.I. Reactive Blue 2, RB2) and Cibacron Violet 2R (C.I. reactive violet

2). Fe powder and FeSO4, 7H2O and 30% H2O2 were used as Fenton reagent. 100 mg/l dye

solutions are examined under λmax= 390 nm for RY3, λmax = 620 nm for RB2 and λmax =

550nm for RV2. Dye solutions were also characterized on the basis of TOC (total organic

carbon) and pH parameters. The reactive dyes are mineralized and decolorized by using

homogeneous (Fe2+/H2O2) and heterogeneous (Fe0/H2O2) Fenton and UV/Fenton processes.

Experiments are performed with different dose of homogeneous and heterogeneous Fenton

reagent under UV radiation at pH 3.0 using H2SO4 or NaOH solutions. In the 90 min process

the reaction temperature was kept at T=23±1oC.

In both homogeneous (Fe2+/H2O2) and heterogeneous (Fe0/H2O2) Fenton processes, initial iron

and hydrogen peroxide concentrations and initial molar ratios of iron to hydrogen peroxide is
equally important with the characteristic of each azo dye. The employment of the UV lamp

(125W) in Fenton processes increases mineralization much more than decolourization.

Among the four process (Fe2+/H2O2, Fe0/H2O2, UV/Fe2+/H2O2 and UV/Fe0/H2O2)

UV/Fe2+/H2O2lead to the highest mineralization (78–84%) and decolourization (95–100%) of

all three studied dyes.

3.2.c. Treatment of textile dyeing waste water by photo oxidation using UV/H 2O2/Fe+2

reagents; Sahunin, C., Kaewboran, J., Hunsom, M., (2006) [39]

Sahunin et al. have shown that waste water treatment from textile industry was carried

out at room temperature in a batch reactor by photo Fenton Oxidation process. By employing

ferrous ion concentration (0-100 mg/lit), UV power (0-220 W), initial pH of the solution (1-

7) the effects on chemical oxygen demand (C.O.D) and colour removal was observed. The

optimum condition was found to be at Ph 3, [Fe +2] = 80 mg/lit, [H2O2] = 200 mg/lit, 60 W

UV-power, 5 to 10 minutes operating time. At this optimum condition 52% and 90% of

C.O.D and colour were removed respectively. When the treatment process was finished a

small amount of sludge of textile dye was generated (5.8 x 10-5 kg.kg C.O.D-1) compared with

the conventional anaerobic process (0.611±0.33 kg.kg COD -1) [69]. In presence of

heterogeneous photo catalyst, (e.g. TiO2) the percentage removal of C.O.D and colour is

accelerated and it can be reused by using a simple filtration.

3.2.D. Advanced oxidation processes for de-colorization of aqueous solution Containing

Acid Red G azo dye; Surpateanu, M., Zaharia, C., (2004) [40]

Surpatean et al. have investigated the de-colorization of Acid Red G azo dye by photo

oxidation with hydrogen peroxide. The influence of pH, oxidant conc., presence of ferrous

ion or other metal ions as potential catalysts are investigated.

As the concentration of hydrogen peroxide is increased the rate of de-colorization is

increased rapidly due to higher production of OH•. And the mechanism is suggested as

follows

H2O2 + hυ→2HO• ..………… (12)

HO• + H2O2 →HO•2 + H2O ….……….. (13)

HO•2 + H2O2 →HO• + H2O + O2 . ...………….(14)

2HO•2 →H2O2 + O2 …………… (15)

HO2 + HO•→H2O + O2 …………... (16)

They also studied that after 10 minutes of irradiation, the decolonization was 89.16% in the

acid medium, 81.03% in the neutral medium and 82.48% in the alkaline medium. They also

studied that the addition of ferrous ion in UV/H 2O2system increases the generation of highly

reactive hydroxyl ion and hence the rate of dye de-colorization is increased. This catalytic

effect can be described by the generation of supplementary hydroxyl radical in addition to the

photo cleavage of hydrogen peroxide by UV radiation. It is experimentally found that after 15

minutes of photo oxidation the degree of de-colorization was greater than 99 % in the

presence of ferrous ions. The following reactions are given as support.

Fe2++ H2O2→Fe3++ OH− + OH• ………………..(17)

Fe3++ H2O2→Fe2++ H++ HO2• ...…………… (18)

3.2.e. Oxidation of acidic dye Eosin Y by the solar Photo-Fenton processes; Zheng, H.,

Pan, Y., Xiang, X., (2007) [41]

Zheng et al. have studied oxidation of acidic dye Eosin Y with Fenton process and photo

Fenton process (solar light or artificial light source). The percent of degradation was

approximately double in photo-Fenton than in Fenton process in artificial light source and

reduce the operation cost. The degradation of dye depends on the concentration of dye, pH,
conc. of ferrous sulfate and H2O2 etc. Higher the concentration of Eosin Y, lower is the

degradation efficiency. It was also studied that oxalic could improve the photo catalytic

efficiency in the solar Fenton process by absorbing greater energy as well as adjusting pH at

optimum (3.5) which reduces the operation cost . They also proposed the following reaction

in support of oxidation of dye.

H2O2 + hυ = 2OH• ………….. (19)

OH• + dye = dye intermediate ………….. (20)

OH• + dye intermediate = CO2 + H2O + mineralization products .………… (21)

3.2.f. Treatment of Textile Dyeing Wastewater by Hydrogen Peroxide and Ferrous Ions;

Perkowski, J., Kos, L., (2002) [42]

Perkowski et al. studied the waste water collected from dyeing of cotton,

polyacrylonitrile and polyester. It was characterized by strong or very strong colour, COD,

BOD and content of anionic detergents. Waste water was treated by means of coagulation

with the use of Fenton reagent containing ferrous salts (FeSO4 × 7H2O, FeCl2 × 4H2O).

They found that the COD and CT reduction is much higher with ferrous sulphate than

chloride salt in all types of waste water studied. Addition of H 2O2 in an optimum

concentration increases the efficiency of the reagent except the waste of polyester dye. As far

as the other parameters, i.e. dry residue and soluble substances, are concerned, no significant

changes are found and the final pH of the solution is decreased. the increase of the treated

wastewater susceptibility to biodegradation is found. Along with all other experiment they

also conclude that the process efficiency can increase several times by addition of hydrogen

peroxide.

3.2.g. Chemical oxidation of C. I. Reactive Red 2 using Fenton like reactions; Dutta, K.,

Bhattacharjee, S., Chaudhuri, B., Mukhopadhyay, S., (2002) [43]

 Dutta et al. have investigated the kinetics of the oxidative degradation of C. I. Reactive

Red 2 dye by hydroxyl radicals generated by hydrogen peroxide and ferrous ion in aqueous

media. The effects of initial conc. of the dye, hydrogen peroxide, ferrous ion, pH of the

solution, reaction temperature, added electrolytes on the degradation has been studied.

Fe+2 + H2O2 = Fe+3 + HO - + HO + ………….. (22)

Fe+3 + H2O2 = Fe+2 + HO2· + H+ …………... (23)

Fe+3 + HO2· = Fe+2 + O2 + H+ ....………... (24)

Fe+2 + HO· = Fe+3 + HO – ………….... (25)

H2O2 + HO· =HO2· + H2O ...………… (26)

3.2.h. Discoloration and Mineralization of Orange II Using Different Heterogeneous

Catalysts Containing Fe: A Comparative Study; Feng, J., Hu, X.,Yue, P.L., (2004) [44]

Feng et al. studied the photo Fenton discoloration and mineralization of 0.2 mM Orange

II dye solution using four heterogeneous catalysts containing Fe including a bentonite-clay-

based Fe nanocomposite (Fe-B), hematite (R-Fe2O3), amorphous FeOOH, and calcined

FeOOH (denoted as FeOOH-M). They observed the discoloration and mineralization at two

different pH, 3.0 and 6.6.The results showed that the photocatalytic activity of the different

heterogeneous catalysts in the discoloration of Orange II in the presence of 10 nM H2O2 and

8 W of UVC at an initial solution pH of 3.0 followed the order Fe-B > FeOOH, FeOOH-M >

R-Fe2O3. For mineralization activity the catalysts were followed the same order at same

condition. In the absence of any catalyst there were no mineralization was observed where as

complete discoloration was done. This phenomenon can be expressed as long live colorless

intermediate formation. At higher pH for discoloration and mineralization the catalysts were

followed the same order but the rate was slower. The heterogeneous photo Fenton reaction

was mainly responsible for the discoloration and mineralization of Orange II and no
significant homogeneous photo-Fenton was observed due to the negligible Fe concentration

in solution. Here FeOOH, FeOOH-M were used as heterogeneous catalysts.

3.3. Ultrasound assisted Fenton process for wastewater treatment

3.3.1. Fundamentals of ultrasound

Ultrasound are waves at frequencies above those within the hearing range

of average person, i.e., at frequencies above 16 kHz (16,000 cycles per second).

Ultrasonic energy (high frequency sound waves) [45-46] produces an alternating

adiabatic compression and rarefaction of the liquid media that being irradiated. In

the rarefaction part of the ultrasonic wave (when the liquid is unduly stretched or

“torn apart”), micro-bubbles are formed because of reduced pressure (i.e.

sufficiently large negative pressures). These micro-bubbles contain vaporized

liquid or gas that was previously dissolved in the liquid. The micro-bubbles can be

either stable about their average size for many cycles or transient when they

grow to certain size and violently collapse or implode during the compression part

of the wave. The energy put into the liquid to create the micro-voids is released in

this part of the wave, creating high local pressures up to 1000 atm and high

transitory temperatures up to 5000 K [47-50]. This energy releasing phenomena of

the bubble formation and collapse is simply called cavitation or (“cold boiling”) or

acoustic cavitation [51-53].

 Figure2: Ultrasound at different wavelength producing compression and rarefaction

3.3.2. Fenton reagent in sono chemical process

Fenton reaction can be accelerated by application of sound, which is called sono Fenton

reaction. Use of ultrasonic sound gives faster rates and higher degrees of mineralization

comparing to conventional Fenton process, which can significantly reduce the operational

cost of the treatment. Sono-Fenton oxidation generates two mechanisms to degrade organic

compounds: (1) reaction with ·OH and (2) thermal cleavage. During sonication, extremely

high temperature and pressure are generated with the collapse of the cavitation bubbles,

which causes the rupture of O-H bond and results in the formation of ·OH (Equation (27)),

where [ ))) ] denotes the ultrasound.

H2O + ))) → OH· + H· …………(27)

X (organic compounds) (g) → products ………….(28)

OH· + X → CO2 + H2O ………….(29)

Fe2+ + H2O2 → Fe3+ + OH· + OH- …………..(30)

Fe3+ + H2O2 → Fe-OOH2+ + H+ …………..(31)

Fe-OOH2+ → Fe2+ + OOH· …………..(32)

Fe-OOH2+ + ))) → Fe2+ + ·OOH (fast) …………..(33)

Fe2+ + H2O2 + ))) → Fe3+ + ·OH + OH- …………..(34)

Fe3+ + H2O + ))) → Fe2+ + ·OH + H+ …………..(35)

Fe0 + 2H2O + ))) → Fe2+ + H2 + 2·OH …………..(36)

2Fe0 + O2 + 2H2O + ))) → 2Fe2+ + 2H2 + 4·OH …………..(37)

The effects of sonolysis arise mainly from acoustic cavitation, namely the formation, growth,

and implosive collapse of bubbles in a liquid, which produces unusual chemical and physical

environments. The collapse of bubbles generates localized “hot spots” with transient

temperature of about 5,000 K and the pressure about 64 x 10 4 kPa. During collapse, gas

molecules are thermally fragmented to generate a variety of reactive species, including OH·.

Alternatively, organic compounds in the vicinity of a collapsing bubble may undergo

pyrolysis degradation. The generated OH· can react with organic compounds and mineralize

them to carbon dioxide and water (Equation (29)) [54]. As the Fenton's reagent is added, OH·

can be easily produced (Equation (30)) and the Fe2+ is oxidized to Fe3+. Then the Fe3+ will

react with H2O2 to produce a complex intermediate (Fe-OOH2+) as shown in equation (31).

Although the Fe-OOH2+ can be decomposed to Fe2+ and ·OOH (Equation (32)), the reaction

rate is much lower [55-57]. When the sono-Fenton process is applied to organic pollutant

degradation, a synergetic effect between Fenton's reagent and ultrasound takes place, which

spontaneously decomposes Fe-OOH2+ to Fe2+ and ·OOH (Equation (33)). This isolated Fe2+

can react subsequently with H2O2, produce OH· again and thus, establish a cyclic mechanism.

The combination of ultrasound and Fenton's reagent not only enhances the reaction rate of

Fe2+ isolation from Fe-OOH2+ but also accelerates the formation of OH by the reaction

between Fe0/H2O, Fe2+/H2O2 or Fe3+/H2O2 [54-56] as shown in equations (34-37). Therefore,

as the sono-Fenton process is carried out for the degradation of organic pollutants, two

mechanisms such as (1) more OH• are produced than sole ultrasound or Fenton process to

react and oxidize the organic pollutant, and (2) thermal cleavage oxidation in ultrasonic

cavitational bubbles takes place so that the degradation efficiency of organic pollutants can
be improved. The major parameters affecting Fenton process are solution pH, amount of

ferrous ions, and concentration of H2O2, initial concentration of the pollutant and presence of

other ions. As the optimum pH value is in between 2 and 4, the waste water pH is adjusted

accordingly before treatment. Increase of ferrous ions and H2O2 concentration results to an

increase of degradation rate. As the H2O2 is toxic to several microorganisms, the use of

excess amounts of H2O2 could possibly deteriorate overall degradation efficiency of Fenton

process. Fenton oxidation of organic compounds is inhibited by phosphate, sulfate, fluoride,

bromide and chloride ions may be due to precipitation of iron, scavenging of HO• or

coordination to dissolved Fe(III) to form a less reactive complex. Though Fenton processes

requires acidic conditions, interference by substances that complex iron ions, produce iron

oxide sludge, the Fenton and sono Fenton processes have been used for the treatment of

several types of waste water including those produced in dye manufacture, pulp bleaching,

agricultural processing and chemical manufacture. Moreover, biological waste water

treatment may be improved with the addition of a Fenton pretreatment step.

3.3.3. Factors affecting aqueous sono-chemical process

Sono chemistry is complicated by the fact that the nature or the

physicochemical properties of the solvent, solute or gas in the bubble can have

dramatic effect on the cavitational collapse. Cavities are more readily formed

when using solvents with high vapor pressure (VP), low viscosity (µ), and low

surface tension (σ); however, the intensity of cavitation is benefited by using

solvents of opposite characteristics (i.e., low VP; high µ, σ, and density ρ). The

intermolecular forces in the liquid must be overcome in order to form the bubbles.

Thus, solvents with high densities, surface tensions, and viscosities generally

have higher threshold for cavitation but more harsh conditions once cavitation

begins. There are several properties of gases that can affect sono chemical
activities. The heat capacity ratio (Cp/Cv) or polytropic ratio (γ) of the gas in the

bubble affects the amount of heat released and hence, the final temperature

produced in an adiabatic compression and the cause of reaction.

3.3.4. A few papers on sono-Fenton degradation of organic pollutants in

wastewater are reviewed below:

3.3.4.a. Sono-Fenton process to remove COD in palm oil mill effluent; M.R. Taha, A.H.

Ibrahim et al. (2014) [58]

Taha et al investigated that in the conventional Fenton process, FeSO4 is used as the major

source of Fe2+. In the process, the degradation of organic pollutants occurs through silent

mode. Enhancement of the Fenton process can be made through utilization of the Nano zero-

valent iron (nZVI) particle and ultrasound. In this work, we studied the characteristics of the

nZVI particle and the effect of ultrasound on the efficiency of the Fenton process. The nZVI

particle has an average size of 49 nm and consists of two layers, the outer of which is

comprised mostly of iron oxides (i.e. FeO), while the inner part is the elemental iron (Fe).

Production of Fe2+ by the nZVI particle is very much dependent on the pH of the solution.

Due to the presence of an iron oxide shell, the nZVI particle is only capable of producing Fe 2+

at pH 3 and below. At a higher intensity and longer sonication time, the nZVI particles were

well dispersed in the solution and thus able to produce more Fe2+ compared with FeSO4. In

addition, self production of H2O2 by nZVI and higher Fe2+ concentration in the solution

directly accelerates the removal process of COD from POME through the Fenton process. He

show that the maximum COD removal was 80% and it was achieved within 2 h instead of 24

h of silent degradation.
3.3.4.b. Degradation of reactive, acid and basic textile dyes in the presence of

ultrasound and rare earths [Lanthanum and Praseodymium]; Pankaj

Srivastava, Shikha Goyal, Prem Kishore Patnala et al. (2014) [59]

Srivastava et al showed that amongst numerous treatment technologies,

used recently, ultrasonic irradiation is an attractive and promising technology.

In terms of convenience and simplicity of operation, ultrasound could be more

competitive and far superior to many alternative approaches. Many simple and

complex molecules from low to high toxicity levels, polluting the aquatic life

and the environment have been successfully degraded by the ultrasound to

relatively non-toxic or lesser harmful species, if not mineralized. The appropriate

choice of ultrasonic frequency, power and the duration of introduction

contribute not only to the oxidation of organic pollutants by free radicals, but also

provide a basis of the thermal decomposition of the given substance in the

gaseous phase. The effects of ultrasound, in fact, results from acoustic

cavitations, which includes the formation, growth and impulsive collapse of

bubbles in liquids. Degradation of five textile dyes, namely Reactive Red 141

(RR 141), Reactive Blue 21 (RB 21), Acid Red 114 (AR 114), Acid Blue

113 (AB 113) and Basic Violet 16 (BV 16) in aqueous solution had been

carried out with ultrasound (US) and in combination with rare earth ions (La 3+

and Pr3+). Kinetic analysis of the data showed a pseudo-first order degradation

reaction for all the dyes. The rate constant (k), half life (t 1/2) and the process

efficiency (u) for various processes in degradation of dyes under different

experimental conditions have been calculated. The influence of concentrations

of dyes (16–40 mg/L), pH (5,7 and 9) and rare earth ion concentration (4,12

and 20 mg/L) on the degradation of dyes have also been studied. The
degradation percentage increased with increasing rare earth amount and

decreased with increasing concentration of dyes. Both horn and bath type

sonicators were used at 20 kHz and 250 W for degradation. The sonochemical

degradation rate of dyes in the presence of rare earths was related to the type of

chromophoric groups in the dye molecule. Degradation sequence of dyes was

further examined through LCMS and Raman spectroscopic techniques, which

confirmed the sonochemical degradation of dyes to non-toxic end products.

3.3.4.c. Sonochemical decolourisation of textile azo dye; Meral Dükkancı, Mircea

Vinatoru, Timothy J. Mason et al (2014) [60]

Dükkancı et al showed that removal of textile azo dye Orange II (O-II) from aqueous

solution using sonication at 850 kHz had been studied. The effects of the combined use of

Fenton type reagents and UV light with sonication were also investigated. The degree of

decolourisation of O-II increased 1.6 and 2.6-fold with the addition of ferrous sulphate alone

(i.e., in the absence of H2O2) and with the addition of Fenton reagent (Fe 2+ and H2O2),

respectively. A Fenton reagent ratio of 1:50 M of Fe 2+:H2O2 gave the best degree of

decolourisation (76.4%) and highest first order rate constant of 2.9×10 -2 min-1 under the

experimental conditions used in this study. The degree of decolourisation obtained (47.1%)

using a heterogeneous Fenton system was lower than that using the homogeneous Fenton

system (76.4%). This was probably due to the presence of suspended zeolite which reacted

with OH radicals and so prevented their recombination to form hydrogen peroxide. The

highest decolourisation degree of 81% was obtained in sonophoto-Fenton system which

showed an overall synergetic effect of each of the processes.

3.3.4.d. Enhancing decomposition rate of perfluorooctanoic acid by carbonate radical

assisted sonochemical treatment ; Lan-Anh Phan Thi, Huu-Tuan Do, Shang-Lien Lo et

al. (2014) [61]

Lan-Anh Phan Thi et al studied………. Perfluorooctanoic acid (PFOA) is a recalcitrant

organic pollutant in wastewater because of its wide range of applications. Technologies for

PFOA treatment have recently been developed. He shows that PFOA decomposition by

ultrasound treatment (150 W, 40 kHz), with or without saturated N 2, was <25% after 4 h

reaction. The extent and rate of PFOA decomposition and defluorination efficiencies of

PFOA, however, greatly increased with the addition of carbonate radical reagents. PFOA was

decomposed completely after 4 h of sonochemical treatment with a carbonate radical oxidant

and saturated N2. Without saturated N2, PFOA was also decomposed to a high (98.81%)

degree. The highest PFOA decomposition and defluorination efficiencies was observed in N2

saturated solution containing 30 mM of NaHCO3. Sonodecomposition of PFOA with •CO3-

radical was most favorable in a slightly alkaline environment (pH = 8.65) because the •CO 3-

radical concentration was low under acidic conditions, and the •CO3- radical concentration

could decay quickly by second-order reactions in highly alkaline conditions. We did not

detect any shorter-chain perfluorinated carboxylic acids in the final reaction solution and CO,

CO2 and HF are the final products.

3.3.4.e. The effects of hydrogen peroxide on the sonochemical degradation of phenol and

bisphenol A; Myunghee Lim, Younggyu Son, Jeehyeong Khim et al. (2014) [62]

Lim et al showed that the degradation of phenol and bisphenol A (BPA) was enhanced

by the addition of H2O2 during sonochemical processes. For the sonochemical degradation of

phenol and BPA, the degradation ratio increased from 10% to 50% and 30% to 50% upon the

addition of H2O2 respectively. The effects of H2O2 on the sonochemical degradation of phenol

were more effective than on BPA because of the hydrophobicity of BPA. There was no
significant effect on the sonochemical degradation of phenol using 0.1, 1, or 10 mM H 2O2.

The degradation of TOC (total organic carbon) was enhanced by the addition of H 2O2 and the

effects of H2O2 were quite significant in the BPA solution compared to phenol because some

intermediates of BPA have high Kow values and a greater probability to react with the

hydroxyl radicals. The degradation ratios of TOC were lower than the degradation ratios of

phenol and BPA because some intermediates cannot readily degrade during the sonochemical

reaction. High concentrations of H2O2 can act as a radical scavenger (especially hydroxyl

radicals). Therefore, the determination of an optimum H2O2 concentration is crucial.

3.3.4.f. Influence of sonochemical reactor diameter and liquid height on methyl orange

degradation under 200 kHz indirect sonication; Kandasamy Thangavadivel, Kenji

Okitsu, Gary Owens, Peter J. Lesniewski, Rokuro Nishimura et al. (2013) [63]

Kandasamy Thangavadivel et al investigated while, industrial ultrasound is emerging as a

viable alternative to traditional environmental remediation technologies, either as a

standalone technology or in combination with other technologies, attenuation of ultrasound

currently limits the volumes that can be treated and hence practical applications. In order to

clearly understand the relationship between the sonochemical activity and acoustic energy

attenuation, calorimetric and degradation studies using methyl orange (MO) as a contaminant

surrogate were investigated with indirect sonication at 200 kHz (transducer diameter: 65 mm)

with various cylindrical glass reactors of different diameter (20, 48, 65, 95 and 117 mm) and

liquid height (21, 58, 81 and 118 mm). He had clearly that both reactor diameter and liquid

height significantly influenced degradation efficiency. In addition to the inherent acoustic

pressure distribution within the reactor due to the transducer acoustic pressure profile, the

diameter of the reactor affected mainly attenuation of ultrasound in the radial direction, while

attenuation in the axial direction was principally influenced by reactor height. With a liquid

level of 21 mm, the overall performance of reactor D117 was better in terms of calorimetric
power, but at higher liquid levels the D95 reactor exhibited the best overall performance

other than H81 where D20 performed well. However, overall, reactor D95 with a ratio

(reactor diameter/transducer diameter) of 1.45 performed most competitively over a wider

range of liquid levels and would therefore be ideal for a wider range of applications.

3.3.4.g. Advanced oxidation processes (AOPs) involving ultrasound for waste water

treatment: A review with emphasis on cost estimation; Naresh N. Mahamuni, Yusuf G.

Adewuyi et al. (2009) [64]

Naresh N. Mahamuni et al was made an attempt to estimate the cost for the waste water

treatment using ultrasound. The costs have been calculated for 1000 L/min capacity treatment

plant. The costs were calculated based upon the rate constants for pollutant degradation. The

pollutants considered were phenol, trichloroethylene (TCE) and reactive azo dyes. He found

that Combination of ultrasound with different AOPs was economically more attractive than

the use of ultrasound alone for waste water treatment and US + UV + O 3 process was found

to be the most economical ultrasonic process for phenol ($89.78/1000 gallon) and US + UV +

H2O2 was found to be the most economical ultrasonic process for waste water treatment

containing reactive azo dye ($65.17/1000 gallon) and US + UV was found to be the most

economical ultrasonic process for TCE degradation ($25.82/1000 gallon).

3.3.4.h. Integrated heterogeneous sono–photo Fenton processes for the degradation of

phenolic aqueous solutions; Y. Segura, R. Molina, F. Martínez, J.A. Melero et al. (2009)

[65]

Y. Segura et al showed that the sequentially integrated sono–photo-Fenton process is an

interesting alternative for the degradation of phenolic aqueous solutions with a total

degradation of phenol and ca. 90% of TOC reduction, approaching nearly towards complete

mineralization. The solid Fe2O3–SBA-15 catalyst used for this study evidenced a high

stability under the operation conditions of ultrasound and UV–light irradiations during both
oxidation processes; the amount of iron leached out into the resultant aqueous solution after

reaction never exceeded 4 mg/L, which is within the limits stated in the EU water legislation.

The effective degradation of sequential Sono-photo-Fenton process seem to be related to the

benefits of ultrasound for the partial degradation of amenable aromatic compounds towards

further oxidized by-products along with the fragmentation of catalyst to finer particles that

produces more activity in photo-Fenton systems. Besides, a simplified energy cost

assessment of all processes indicated that the sequential US→UV process also shows the best

cost-effective ratio for mineralization of phenol.

3.3.4.i. Sonochemical degradation of PAH in aqueous solution; Bernard David et al.

(2008) [66]

Bernard David et al. investigated that in aqueous mixture, highly hydrophobic

compounds such as PAHs undergo ultrasonic degradation at low frequency (20 kHz) and

high frequency (506 kHz). Pseudo-first-order rate constants of PAH degradation are linked

to the physico-chemical properties of PAHs, since higher the Henry’s constant, higher the

vapour pressure and higher the water solubility, higher the rate constants of

sonodegradation. At both frequencies, PAHs are mainly pyrolyzed within the bubble in

accordance with the experimental evidence of gaseous by-products formed with a

saturated PAH aqueous solution. The oxidation of PAHs with •OH appear as a minor way,

because of the low inhibition of the degradation by means of terbutanol and since the

expected steady-state hydroxyl radical concentration in the interfacial region of the

cavitation bubble, where PAHs accumulate, is lower or equal to 10 -13 M, which is not

sufficient for a complete degradation of PAHs. Because of their properties, PAHs are then

expected to be mainly localized in the heart and/or in the surrounding shell of the bubble,

inhibiting the production of hydroxyl radicals and hence the oxidation pathway.
4. Experimental details

4.1. Materials used

1. Trypan Blue: A dye manufactured by Loba Chemie. C.I. No. 23850. The formula

weight is 960.80 and wavelength of maximum absorbance is 590 nm. The appearance is dark

blue and is water soluble.

2. Ferrous Sulfate: Crystalline ferrous sulfate was from SISCO RESEARCH

LABORATORIES PVT. LTD., Mumbai-400099, INDIA. Batch No. T/830449. Molecular

weight 278.02. Molecular formula: FeSO4. 7H2O. 0.5% of FeSO4 solution has been used.

3. Hydrogen peroxide: Liquid hydrogen peroxide (50%) was from Merck Specialities Private

Limited., Worli, Mumbai. A colourless liquid, Molecular weight 34.0, Molecular formula:

H2O2.

4. Sodium bi-sulphite: Manufactured by Loba Chemie. The molecular formula is NaHSO 3

and the Molecular Weight: 104.06, 5 (N) solution has been used.

5. Freashly prepared double-distilled water was used for preparation of solutions. GR grade

H2SO4 and NaOH, from Loba Chemie were used for adjusting pH.

4.2. Experimental set up

Figure 3: The figure represents the schematic of the ultrasonic water bath used in the

experiment

4.3. Experimental procedure

4.3.1. For calibration curve

For construction of calibration curve 500 ml, 0.052 × 10 -4 mole.L-1 stock solution was

prepared by dissolving Trypan Blue in distilled water. Then ten numbers of solutions with

desired concentration of Trypan Blue were prepared from the stock solution by dilution with

distilled water. These are standard solutions. Now corresponding absorbance were measured

with a UV-vis spectrophotometer at λmax =590 nm. From the absorbencies & the

concentration data the calibration curve was made. Now if we have the absorbances of some

unknown solution then the corresponding concentration can be determined from the

calibration curve.

4.3.2. For base line experiment

For a typical baseline experiment, 0.052 × 10-4 mole.L-1 initial concentration of dye was taken

in a beaker. Then 2.8 × 10-4 mole.L-1 ferrous sulphate; H2O2, 0.03 mole.L -1 were added into
it. Temperature of the solution was 28℃ and pH was 7. There after the beaker was placed on

bath type sonicator (Oscar Ultrasonic cleaner, model Microclean 101 with 20 kHz frequency)

for sonochemical degradation of the dye. Samples were collected at specific time intervals,

few drops of 5(N) solution of sodium bi sulphite was added for arresting oxidation reaction

and were analyzed with a Shimadzu UV-160A UV-vis spectrophotometer at λmax =590 nm.

Blank experiments were carried out by eliminating each of the components, that is,

ultrasound, FeSO4 and H2O2.

4.4. Results

4.4.1. Calibration curve

6
f(x) = 0.06 x
5 R² = 1

0
0 20 40 60 80 100 120

Figure 4: The figure shows the calibration curve

4.4.2. Sonofenton degradation of Trypan Blue dye

Table 1: Time-concentration data for degradation of dye

Time (min) C/Co(for blank test) C/Co(for sono fenton effect)

0 0.9988 1

3 0.9888 0.670753065

10 0.9876 0.464098073

20 0.9876 0.35201401

30 0.98753 0.259194396

40 0.9875 0.255691769

50 0.9798 0.209982487

60 0.9787 0.183537653

70 0.9786 0.175656742

80 0.9779 0.138003503

90 0.9778 0.105954466

100 0.9776 0.087215412

110 0.9776 0.085989492

120 0.9775 0.065849387

1.0

0.8 Blank test

Sono fenton effect

0.6
c/c 0

0.4

0.2

0.0
0 20 40 60 80 100 120

Time (Min)
 Figure 5: Change in concentration or degradation of Trypan blue dye with time.

5. Discussion
The colour of Trypan Blue azo dye could be effectively removed using sono-Fenton

oxidation with FeSO4 and H2O2 in presence of ultrasound. In a typical experiment

degradation of 0.052 × 10-4 mole.L-1 Trypan blue dye was 93.4% when dosing of FeSo4, 2.8

× 10-4 mole.L-1 and H2O2, 0.03 mole.L-1 at pH 7 and 28℃ temperature and the initial colour

was removed.

But for the blank test where 0.052 × 10-4 mole.L-1 Trypan blue dye was taken by eliminating

each of the components, that is, ultrasound, FeSO4 and H2O2, no degradation of the dye was

found.

6. Scope of future work

The following parameters will be studied in future

1. Effect of pH of the solution on the oxidation process.

2. Effect of varying initial substrate (dye) concentrations on the oxidation

3. Effect of varying hydrogen peroxide concentration on the oxidation

4. Measurement the COD of the final dye solution.

5. References

[1] J. Aubert, Water pollution and carcinogenic risks, IARC Sci. Publ. 13 (1976) 95–103.

[2] K.T. Chung, C.E. Cerniglia, Mutagenicity of azo dyes: structure–activity relationships,
Mutat. Res. 277 (1992) 201–220.

[3] J.T. Li, B. Bai, Y.L. Song, Degradation of acid orange 3 in aqueous solution by
combination of Fly ash/H2O2 and ultrasound irradiation, Indian J. Chem. Technol. 17 (2010)
198–203.

[4] J.S. Ledakowicz, T. Koprowski, W. Machnowski, H.H. Knudsen, Membrane filtration of

textile dyehouse wastewater for technological water reuse, Desalination, 119 (1998) 1–9.

[5] P.W. Wong, T.T. Teng, N.A.R.N. Norulaini, Efficiency of the coagulationflocculation
method for the treatment of dye mixtures containing disperse and reactive dye, Water Qual.
Res. J. Canada 42 (2007) 54–62.

[6] J.A. Laszlo, Regeneration of azo dyes-saturated cellulosic anion exchange resin by
Burkholderia cepacia anaerobic dye reduction, Environ. Sci. Technol. 34 (2000) 164–172.

[7] R. Kant, V.K. Rattan, Adsorption of dye Green B from a textile industry effluent using
two different samples of activated carbon by static batch method and continuous process,
Indian J. Chem. Technol. 16 (2009) 240–244.

[8] I. Bridgeman, A.T. Peters, Photochemical degradation of aminoazobenzene disperse dyes

in ethanolic solution. Part I: effect of concentration, water and temperature, Text. Res. J. 44
(1974) 639–645.

[9] P.A. Soloman, C.A. Basha, M. Velan, V. Ramamurthi, K. Koteeswaran, N.

Balasubramanian, Electrochemical degradation of remazol black B dye effluent, Clean 37
(2009) 889–900.

[10] A. Kunz, H. Mansilla, N. Duran, A degradation and toxicity study of three textile
reactive dyes by ozone, Environ. Technol. 23 (2002) 911–918.

[11] M.S. Lucas, J.A. Peres, Decolorization of the azo dye Reactive Black 5 by fenton
and Photo-fenton oxidation, Dyes Pigm. 71 (2006) 236–244.

[12] N. Capalash, P. Sharma, Biodegradation of textile azo dyes by phanerochaete

chrysoporium, World J. Microbiol. Biotechnol.

[13] D.K. Sharma, H.S. Saini, M. Singh, S.S. Chimni, B.S. Chadha, Biological treatment of
textile dye acid violet-17 by bacterial consortium in an up-flow immobilized cell bioreactor,
Lett. Appl. Microbiol. 38 (2004) 345–350.
[14] S. Palamthodi, D. Patil, Y. Patil, Microbial degradation of textile industrial effluents,
Afr. J. Biotechnol. 10 (2011) 12657–12661.

[15] S.D. Barr, Mechanisms white rot fungi use to degrade pollutants, Environ. Sci. Technol.
28 (1994) 78–87.

[16] W.H. Glaze, J.W. Kang, Advanced oxidation processes for treating groundwater
contaminated with TCE and PCE: laboratory studies. Journal AWWA, 80(5), (1998) 57-63.

[17] W.H. Glaze, J.W. Kang, D.H. Chapin, The chemistry of water treatment involving
ozone, hydrogen peroxide and ultraviolet radiation. - Ozone Science & Engineering, 9(4),
(1987) 335-342.

[18] P. Calza, E. Pelizzetti, Photocatalytic transformation of organic compounds in the

presence of inorganic ions, Pure Appl. Chem. 73 (2001) 1839–1848.

[19] T.K. Kim, M.K. Kim, Y.J. Lim, Y.A. Son, Degradation of the disazo acid dye by
sulphur-containing amino acids of wool fibres, Dyes Pigm. 67 (2005) 127–132.

[20] V.V. Goncharuk, V.V. Malyarenko, V.A. Yaremenko, Use of ultrasound in water
treatment, J. Water Chem. Technol. 30 (2008) 137–150.

[21] C. Minero, M. Lucchiari, D. Vione and V. Maurino, Fe(III)-Enhanced sonochemical

degradation of methylene blue in aqueous solution. Environ. Sci. Technol., 39(22), (2005)
8936-8942.

[22] Y. Dai, F. Li, F. Ge, F. Zhu, L. Wu and X. Yang, Mechanism of the enhanced
degradation of pentachlorophenol by ultrasound in the presence of elemental iron. J. Hazard.
Mater., 137(3), (2006) 1424-1429.

[23] R.A. Torres, F. Abdelmalek, E. Combet, C. Petrier and C. Pulgarin, A comparative study
of ultrasonic cavitation and Fenton's reagent for bisphenol A degradation in deionised and
natural waters. J. Hazard. Mater., 146(3), (2007) 546-551.

[24] J.H. Sun, S.P. Sun, J.Y. Sun, R.X. Sun, L.P. Qiao, H.Q. Guo and M.H. Fan, Degradation
of azo dye Acid Black using low concentration iron of Fenton process facilitated by
ultrasonic irradiation. Ultrason. Sonochem., 14(6), (2007) 761-766.

[25] G. Qiu, M. Nie and Q. Wang, Ultrasonically initiated emulsion polymerization of

styrene in the presence of Fe2+. Ultrason. Sonochem., 15(4), (2008) 269-273.

[26] H. Ghodbane and O. Hamdaoui, Degradation of Acid Blue 25 in aqueous media using
1700 kHz ultrasonic irradiation: Ultrasound/Fe(II) and ultrasound/H O combinations.
Ultrason. Sonochem., 16(5), (2009) 593-598.

[27] Y. Ku, Y.H. Tu and C.M. Ma, Decomposition of monochlorophenols by sonolysis in

aqueous solution. J. Environ. Eng. Manage., 16(4), (2006) 259-265.

[28] I.K. Kim and C.P. Huang, Sonochemical process for the removal of DBPs and precursor
in water. J. Environ. Eng. Manage., 17(1), (2007) 39-48.
[29] W.S. Chen and G.C. Huang, Sonochemical decomposition of dinitrotoluenes and
trinitrotoluene in wastewater. J. Hazard. Mater., 169(1-3), (2009) 868-874.

[30] J.J Pignatello, E. Oliveros and A. MacKay, Advanced oxidation processes for organic
contaminant destruction based on the Fenton reaction and related chemistry. Crit. Rev. Env.
Sci. Tec., 36(1), (2006)1-84.

[31] J. Liang, S. Komarov, N. Hayashi and E. Kasai, Improvement in sonochemical

degradation of 4-chlorophenol by combined use of Fenton-like reagents. Ultrason.
Sonochem., 14(2), (2007) 201-207.

[32] Y.S. Ma, C.F. Sung and J.G. Lin, Degradation of carbofuran in aqueous solution by
ultrasonic and Fenton processes: Effect of system parameters and kinetic study. J. Hazard.
Mater., 178(1-3), (2010) 320-325.

[33] Y.S. Ma and C.F. Sung, Investigation of carbofuran degradation by ultrasonic process.
Sustain. Environ. Res., 20(4), (2010) 213-219.

[34] L.M. Dorfman and Adams, G.E. Reactivity of hydroxyl radical in aqueous solution,
NSRDS-NBS No. 46, US Department of Commerce, National Bureau of Standards, Bethesda
(1973).87.

[35] J. Perkowski, L. Kos, Treatment of Textile Dyeing Wastewater by Hydrogen Peroxide

and Ferrous Ions.Institute of Knitting Technology and Techniques “Tricotextil, 270, (2002)
90-361.

[36] J.E.F. Moraes, F.H. Quina, C.A.O. Nascimento, D.N. Silva, O. Chiavone-Filho,
Treatment of Saline wastewater contaminated with hydrocarbons by the photo-Fenton
process, Environ. Sci. Technol., 38, (2004) 1183-1187.

[37] Barbusiński,K., Majewski, J., Discoloration of Azo Dye Acid Red 18 by Fenton Reagent
in the Presence of Iron Powder, Pol. J. Environ. Stud.,(2003) 12, 151-155.

[38] Papi´c, S., Vujevic, D., Koprivanac, N., Sinko, D., 2009. Decolourization and
mineralization of commercial reactive dyes by using homogeneous and heterogeneous Fenton
and UV/Fenton processes, J. Hazard.Mater.164, (2009) 1137–1145.

[39] Sahunin, C., Kaewboran, J., Hunsom, M., Treatment of textile dyeing waste water by
photo oxidation using UV/H2O2/Fe+2 reagents. (2006) 240-560.

[40] Surpateanu, M., Zaharia, C., Advanced oxidation processes fordecolorization of aqueous
solution containing Acid Red G azo dye, Cent. Eur. Sci. J. 2(4), (2004) 573-588.

[41] Zheng, H., Pan, Y., Xiang, X., Oxidation of acidic dye Eosin Y by the solar photo-
Fenton processes.J.Hazard.Mater., (2007) 141, 457-464.

[42] Perkowski, J., Kos, L., Treatment of Textile Dyeing Wastewater by Hydrogen Peroxide
and Ferrous Ions.Institute of Knitting Technology and Techniques “Tricotextil., (2002) 270,
90-361.
[43] Dutta, K., Bhattacharjee, S., Chaudhuri, B., Mukhopadhyay, S., Chemical oxidation of
C.I Reactive Red 2 using Fenton-like reactions. J Environ. Monit., 4., (2002) 754-760.

[44] Feng, J., Hu, X.,Yue, P.L., Discoloration and Mineralization of Orange II Using
Different Heterogeneous Catalysts Containing Fe: A Comparative Study. Environ. Sci.
Technol. 38, (2004) 5773-5778.

[45] D. Ensminger, Ultrasonic: The Low and High-Intensity- Applications; Marcel Dekker:
New York, 1973.

[46] H. F. Mark, D. F. Othmer, C. G. Overberger, G. T. Seaborg, Eds.; Wiley: New York, 23,
(1983) 462.

[47] Suslick, Sonochemistry. Science, 247, (1990) 1439.

[48] K. S. Suslick, The Chemical Effects of Ultrasound. Sci. Am., 260, (1989) 80.

[49] K. Makino, M. M. Mossoba, P. Riesz, Chemical Effects of Ultrasound on Aqueous

Solutions. Formation of Hydroxyl Radicals and Hydrogen Atoms. J. Phys. Chem., 87, (1983)
1369.

[50] N. Serpone, P. Colarusso, Sonochemistry I. Effects of Ultrasounds on Heterogeneous

Chemical Reactions A Useful Tool to Generate Radicals and to Examine Reaction
Mechanisms. Res. Chem. Intermed., 20, (1994) 635.

[51] F. R. Young, Cavitation; McGraw-Hill: New York, 1989.20-24.

[52] C. Von Sonntag, G. Mark, A. Tauber, Schuchmann. Adv. Sonochem. (1999) 5.

[53] J. Lorimer, T. Mason, Sonochemistry Part 1-The Physical Aspects. Chem. Soc. Rev., 16,
(1987) 239.

[54] C.G. Joseph, G.L. Puma, A. Bono and D. Krishnaiah, Sonophotocatalysis in advanced
oxidation process: A short review. Ultrason. Sonochem., 16(5), (2009) 583-589.

[55] J.J. Pignatello, E. Oliveros, A. Mackay, Advanced oxidation processes for organic
contaminant destruction based on the Fenton reaction and related chemistry, Crit. Rev.
Environ. Sci. Technol., 36, (2006) 1-84.

[56] Z. Guo, Z. Zheng, S. Zheng, W. Hu and R. Feng, Effect of various sono-oxidation

parameters on the removal of aqueous 2,4-dinitrophenol. Ultrason. Sonochem., 12(6), (2005)
461-465.

[57] H. Zhang, H. Fu and D. Zhang, Degradation of C.I. Acid Orange 7 by ultrasound

enhanced heterogeneous Fenton-like process. J. Hazard. Mater., 172(2-3), (2009) 654-660.

[58] M.R. Taha, A.H. Ibrahim et al. , Characterization of nano zero-valent iron (nZVI) and
its application in sono-Fenton process to remove COD in palm oil mill effluent., (2014) 1-8.
[59] Pankaj Srivastava, Shikha Goyal, Prem Kishore Patnala et al., Degradation of
reactive, acid and basic textile dyes in the presence of ultrasound and rare earths
[Lanthanum and Praseodymium]., (2014) 1994–2009.

[60] Meral Dükkancı, Mircea Vinatoru, Timothy J. Mason et al., The sonochemical
decolourisation of textile azo dye Orange II: Effects of Fenton type reagents and UV light.,
(2014) 846-853.

[61] Lan-Anh Phan Thi, Huu-Tuan Do, Shang-Lien Lo et al., Enhancing decomposition rate
of perfluorooctanoic acid by carbonate radical assisted sonochemical treatment., (2014) 1875-
1880.

[62] Myunghee Lim, Younggyu Son, Jeehyeong Khim et al., The effects of hydrogen
peroxide on the sonochemical degradation of phenol and bisphenol A., (2014)1976-1981.

[63] Kandasamy Thangavadivel, Kenji Okitsu, Gary Owens, Peter J. Lesniewski, Rokuro
Nishimura et al., Influence of sonochemical reactor diameter and liquid height on methyl
orange degradation under 200 kHz indirect sonication. (2013) 275-280.

[64] Naresh N. Mahamuni, Yusuf G. Adewuyi et al., Advanced oxidation processes (AOPs)
involving ultrasound for waste water treatment: A review with emphasis on cost estimation.,
(2009) 990.

[65] Y. Segura, R. Molina, F. Martínez, J.A. Melero et al., Integrated heterogeneous sono–
photo Fenton processes for the degradation of phenolic aqueous solutions., (2009) 417-424.

[66] Bernard David et al., Sonochemical degradation of PAH in aqueous solution. Part I:
Monocomponent PAH solution (2008) 260-265.