A PROJECT REPORT ON

PHOTOCATALYTIC DEGRADATION OF
PESTICIDES BY TiO2

Submitted to the

Department of Chemical Engineering

BHARATI VIDYAPEETH UNIVERSITY
COLLEGE OF ENGINEERING

under the guidance of

Mrs. S.J.RAUT
Submitted By:-
Vinit rungta (436372)
Pratik kumar (436368)
Khushbu kumari (436360)

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 DEPARTMENT OF CHEMICAL ENGINEERING

BHARATI VIDYAPEETH UNIVERSITY

COLLEGE OF ENGINEERING

CERTIFICATE

This is to certify that the project entitled

“PHOTOCATALYTIC DEGRADATION OF PESTICIDES BY
TiO2 PARTICLES” carried out by Vinit Rungta, Pratik
kumar and Khushbu Kumari of 3rd year Chemical
Engineering, during academic year 2008-09, is a bonafide
work submitted to the Department of Chemical
Engineering of B.V.U.C.O.E.

Mrs. S.J.Raut Mr. S.J.Attar

Project Guide Head of the department

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Department of Chemical Engg.
Department of Chemical Engg.

INDEX

Topic PageNumber

INTRODUCTION
04

CHAPTER 1 - USES OF PESTICIDES

05-06

CHAPTER 2 - PHOTOCATALYTIC DEGRADATION

OF VARIOUS PESTICIDES
07-11

CHAPTER 3 - SOLAR PHOTOCATALYSIS

12-14

CHAPTER4 - DEGRADATION BY TIO2

NANO-PARTICLES
15-24

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CHAPTER5 - HEALTH IMPACTS
25-27

CONCLUSION
28

REFERENCES
29

INTRODUCTION:-

A pesticide is a substance or mixture of substances used to

kill a pest. A pesticide may be a chemical substance,
biological agent (such as a virus or bacteria), antimicrobial,
disinfectant or device used against any pest. Pests include
insects, plant pathogens, weeds, molluscs, birds, mammals,
fish, nematodes (roundworms) and microbes that compete
with humans for food, destroy property, spread or are a
vector for disease or cause a nuisance. Although there are
benefits to the use of pesticides, there are also drawbacks,
such as potential toxicity to humans and other animals. FAO
has defined the term of pesticide as:
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any substance or mixture of substances intended for
preventing, destroying or controlling any pest, including
vectors of human or animal disease, unwanted species of
plants or animals causing harm during or otherwise
interfering with the production, processing, storage,
transport or marketing of food, agricultural commodities,
wood and wood products or animal feedstuffs, or substances
which may be administered to animals for the control of
insects, arachnids or other pests in or on their bodies.

DIFFERENT TYPES OF PESTICIDES:-

A. OP insecticides

B. Organochlorine insecticides

C. Carbamate insecticides

D. Herbicides

E. Fungicides

CHAPTER 1
1.1 USES OF PESTICIDES:-

Pesticides are used to control organisms which are

considered harmful.For example, they are used to kill
mosquitoes that can transmit potentially deadly diseases like
west nile virus, yellow fever, and malaria. They can also kill
bees, wasps or ants that can cause allergic reactions.
Insecticides can protect animals from illnesses that can be
caused by parasites such as fleas.Pesticides can prevent
sickness in humans that could be caused by mouldy food or
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diseased produce. Herbicides can be used to clear roadside
weeds, trees and brush. They can also kill invasive weeds in
parks and wilderness areas which may cause environmental
damage. Herbicides are commonly applied in ponds and
lakes to control algae and plants such as water grasses that
can interfere with activities like swimming and fishing and
cause the water to look or smell unpleasant.Uncontrolled
pests such as termites and mould can damage structures
such as houses. Pesticides are used in grocery stores and
food storage facilities to manage rodents and insects that
infest food such as grain. Each use of a pesticide carries
some associated risk.

1.2 PESTICIDES BANNED FOR

MANUFACTURE, IMPORT AND USE (IN
INDIA)
1. Aldrin

2. Benzene Hexachloride

3. Calcium Cyanide

4. Chlordane

5. Copper Acetoarsenit

6. CIbromochloropropane

7. Endrin

8. Ethyl Mercury Chloride

9. Ethyl Parathion

10. Heptachlor

11. Menazone

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 12. Nitrofen

13. Paraquat Dimethyl Sulphate

14. Pentachloro Nitrobenzene

15. Pentachlorophenol

16. Phenyl Mercury Acetate

17. Sodium Methane Arsonate

18. Tetradifon

19. Toxafen

20. Aldicarb

21. Chlorobenzilate

CHAPTER-2

2.1 PHOTOCATALYTIC DEGRADATION OF

VARIOUS PESTICIDES:-
Photocatalysis has been proved to be an effective and
inexpensive tool for the removal of organic and inorganic
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pollutants from water. Of particular interest in this context,
in recent years, has been the complete photocatalytic
mineralisation of a variety of pesticides into harmless
products. The technique is now reaching the pre-industrial
level, with several pilot plants and prototypes being
operational in various countries. This paper reviews the
major developments in the area, with special reference to
the mechanism of the process involved, nature of the
reactive intermediates and final products.
Photocatalytic degradation has
been proved to be a promising method for the treatment of
wastewater contaminated with organic and inorganic
pollutants. The process, as a means of removal of persistent
water contaminants such as pesticides, which exhibit
chemical stability and resistance to biodegradation, has
attracted the attention of many researchers in recent years
[1-19]. Many of these investigation have utilised aqueous
suspension of semiconductors illuminated by UV light to
photodegrade the pollutants. The method offers many
advantages over traditional wastewater treatment
techniques such as activated carbon adsorption, chemical
oxidation, biological treatment, etc. For example, activated
carbon adsorption involves phase transfer of pollutants
without decomposition and thus induces another pollution
problem. Chemical oxidation is unable to mineralise all
organic substances and is only economically suitable for the
removal of pollutants at high concentrations. For biological
treatment, the main drawbacks are: slow reaction rates,
disposal of sludge and the need for strict control ofproper pH
and temperature. In this context, photocatalytic processes
offer many advantages for the removal ofpollutants of low
concentration from water. These include:

1. Complete oxidation of organic pollutants within few

hours.

2. No formation of polycyclised products.

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3. Availability of highly active and cheap catalysts capable of
adapting to specially designed reactor systems.

4. Oxidation of pollutants in the ppb range, etc.

2.2 DIFFERENT PHOTOCATALYSTS

AVAILABLE:-
Several catalysts have been studied as potential
photocatalysts for this purpose. These include: CdS, ZnS, a-
Fe2O3, y-Fe2O3, TiO2, ZrO2, SnO2 and WO3, CN~,
Cr2O7,AgCl/Al2O3, niobium oxides, lanthanide tantallates,
ZnO/TiO2, TiO2/SiO2 and TiO2/Al2O3. Among the
semiconductors used, TiO2 is one of the most popular and
promising materials, because of its stability under harsh
conditions, commercial availability, different allotropic forms
with high photoactivity, possibility of coating as a thin film
on solid support, ease of preparation in the laboratory, etc.
Its absorption spectrum overlaps with the solar spectrum
and hence opens up the possibility of using solar energy as
the source of irradiation. Another advantage is that the
photocatalytic activity of TiO2 can be studied in the fixed bed
form as well as in the form of a suspension. Further, TiO 2-
based mixed oxide catalysts such as TiO2/In2O3, TiO2/SiO2 and
TiO2/ZrO2 supported catalysts such as Pt/TiO2, Rh/TiO2 and
Ru/TiO2 and titania-based thin films have also been proved
to be very good photocatalysts.

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2.3 PRIMARY EVENTS AND REACTIVE
SPECIES IN PHOTOCATALYTIC PROCESSES

Pelizzetti et al has summarised the primary events taking

place in a photocatalysed reaction as follows:
TiO2 + hv —>• e~ + h+, (1)

(O2)ads + e~ —>• (O^ )ads, (2)

Ti(IV)—OH~+h+<->-Ti(IV)— *OH, (3)

Ti(IV)—OH2+h+ <->Ti(IV)— * OH + H+. (4)

2.4 PHOTOCATALYTIC DEGRADATION OF

CONTAMINENTS IN WATER

The presence of pesticide contaminants in surface and

ground water has increased many fold in recent years due to
their large-scale use in intensive agriculture. The sources
ofthis contamination may be summarised as follows:

(i) pesticide treatment as routine agricultural practice;

(ii) rinse water polluted with pesticides from containers and

spray equipment

(iii) wastewater from agricultural industry (cleaning or post-

harvest treatment of fruits and vegetables) and

(iv) plant residues contaminated with pesticides.

All these end up ultimately in polluting water bodies with

pesticides. The inherent disadvantages of conventional
decontamination techniques (as discussed earlier in this
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paper) have prompted scientists to examine the possibility
of using the advance oxidation process (AOP) based on
photocatalysis. Both heterogeneous photocatalysis by
semiconductors such as TiO2 and homogeneous catalysis by
photofenton have been tested in this context. Most of the
photocatalytic studies, reported so far in this field, are briefly
reviewed here. For convenience of reference, the pesticides
are classified according to their chemistry (OP,
organochlorine, etc.) as well as the chief mode of action
(insecticides, herbicides, etc.).

2.5 ROLE OF ADDITIVES

The effect of H2O2 on the photocatalytic degradation

oforganic pollutants has been a subject of many
investigations, with the view of exploiting the same for
enhanced degradation rates. The formation of H2O2 in the
photocatalytic degradation of organic compounds has been
reported earlier by many workers. H2O2, formed as an
intermediate in many photocatalysed reactions was found to
undergo simultaneous decomposition resulting in the
generation of d OH radicals, which enhance the
photodecomposition of many pollutants in water, The
autocatalysis observed in the ZnO-catalysed photooxidation
ofbenzyl alcohol was attributed to the formation of H2O2 and
its subsequent participation in the process.

The presence ofions such as CO3H~, CO3 , Cl-, etc., normally

present in surface and ground water has been reported to
retard the oxidation of organic carbon over illuminated TiO2.
In the case of EPTC and lindane, this retarding effect was
very small. The effect of Cl-, PO4- and NO^ on the
photocatalytic degradation ofphosphamidon on TiO2 also was
found to be negligible at lower concentration of the ions.

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Sulphate and hydrogen phosphate anions also inhibit the
photocatalytic degradation rate oforganic pollutants.
Presumably, these anions penetrate the inner co-ordination
sphere ofTiO2, thereby inhibiting its catalytic efficiency.

2.6 CHARACTERISTICS OF TIO2

PARTICLES:-
By far, the most investigated photocatalyst for the removal
of organic pollutants from water is TiO2 in various
physicochemical forms. These studies suggest that the
photocatalytic activity of suspended TiO2 in the solution
depends on physical properties of the catalyst (e.g. crystal
structure, surface area, surface hydroxyls, particle size) and
operating conditions (e.g. light intensity, oxygen, initial
concentration of chemicals, amount ofTiO2 and pH value).
Ohtani et al. investigated the effects of crystal structures of
TiO2 on its photocatalytic activity and reported that the
activity of amorphous TiO2 is negligible, whereas anatase
having the same particle size has appreciable photoactivity.
Tanaka et al. studied the effect of crystallinity of TiO2 on its
photocatalytic action for the degradation of trichlorethylene,
dichloracetic acid and phenol, and reported that pure
anatase has the best catalytic efficiency while pure rutile has
the least. However, Lee et al. report that the rutile–anatase
ratio of TiO2 is not very important in determining its
photocatalytic efficiency to degrade organic pollutants. They
observed that irradiation ofTiO2 with laser light resulted in
the development of a more rutile form of the oxide. The
treatment results in the formation of more spherical-shaped
particles, though the average particle size remains mostly
unchanged. The band gap or surface area also does not
undergo much change by this irradiation. While studying the
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effect of particle size on the photocatalytic hydrogenation of
propyne (CH3CCH), using TiO2 suspensions, Anpo et al. noted
that the activity increases with decrease in particle size,
especially with particles ofsize less than 10 nm. According to
them, reduction in particle size might result in some
electronic modification ofTiO2 and produce an enhancement
ofthe activities ofelectrons and holes and/or suppression
often radiationless transfer ofabsorbed photon energies.
Similar results were reported by Xu et al. from the study on
the photocatalytic degradation ofmethylene blue in aqueous
suspensions.

CHAPTER-3

3.1 SOLAR PHOTOCATALYSIS IN THE

DEGRADATION OF PESTICIDES
Heterogeneous photocatalysis is now approaching the pre-
industrial level. Several pilots and prototypes have been built
in various countries. Different types of photoreactors have
been built, with the catalysts used in various forms/shapes:
fixed bed, magnetically or mechanically agitated slurries,
catalyst particles anchored on the walls ofthe photoreactor
or on membranes or on glass beads or on glass wool sleeves,
small spherical pellets etc.. The main criterion is to have
easy separation ofthe catalyst from the fluid medium and
this is achieved using supported TiO2.

Various devices have been developed and tested. These

include TiO2-coated tubular reactors, annular and spiral
photoreactors, falling-film photoreactors, etc. Of these, two
systems are in commercial use at present for the treatment

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of wastewater. One uses TiO2 powder while the other uses
TiO2 supported on fibreglass mesh cloth. Comparison ofthe
heterogeneous photocatalysis using TiO2/UV with other UV
oxidation systems such as O3/UV, H2O2+additive/UV for the
removal of 2,4,6-trinitrotoluene from groundwater showed
that the former can compete economically with the other UV
oxidation processes for water treatment.

The solar photocatalytic treatment for the decontamination

of pesticide pollutants in water, reported from PSA
(Plataforma Solar de Almeria, Spain) is an excellent example
of solar water detoxification using photocatalysis. The
treatment system employs the compound parabolic collector
(CPC) technology in which the static collectors capture
diffuse as well as direct sunlight. The CPC system is
intrinsically simple, cost-effective, easy to use and requires
low capital investment. Design and configuration details on
the CPCs have been illustrated by Malato et al.. The
technique has been successfully applied to a number of
pollutants such as benzofuran and oxamyl.

14 | P a g e
 Fig 3.1.1 Isometric drawing of solar
detoxification demonstration plant

The use of additional oxidants is recommended when the

organic content of the water is relatively high and/or the
mineralization rate is low. These additives should be capable
of dissociating into harmless by-products and leading to the
formation of d OH or other oxidizing agents.
Peroxydisulphate is one such additive which has been
successfully used to enhance the photocatalytic degradation
of oxamyl in water. The effect is being explained both in
terms of the scavenging action of S2O8~ and often
participation of SO4 ~ in the oxidation reactions, directly or
through the formation of d OH radicals .

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3.2 REMARKS
A large volume of literature has been published in the last
10–15 years on the photocatalytic degradation of pesticide
pollutants. In most cases, the degradation products have
been identified. However, mechanistic studies leading to the
formation of such products are relatively few. This may be,
in part, due to the very short lifetime of most intermediates
and the absence of ultrafast kinetic techniques such as laser
flash photolysis or pulse radiolysis in the nano- or picosecond
regime in many laboratories. The effect of many parameters
such as the presence of salts and other natural organic
matter in the water also is not clearly understood. Studies on
the use of sunlight as the source of energy for the
degradation process have yielded encouraging results and
the solar photocatalytic treatment pesticides is already at
the pilot.

16 | P a g e
CHAPTER-4

DEGRADATION OF DIFFERENT
TYPES OF PESTICIDES BY TiO2
NANO-PARTICLES.

4.1 Photocatalytic Degradation of a Water

Soluble Herbicide by Pure and Noble
Metal Deposited TiO2 Nanocrystalline Films.
We present the photocatalytic degradation of a water soluble
sulfonylurea herbicide: azimsulfuron in the presence of
titania nanocrystalline films. Efficient photodegradation of
herbicide was achieved by using low-intensity black light
tubes emitting in the Near-UV. The degradation of the
herbicide follows first-order kinetics according to the
Langmuir-Hinshelwood model. Intermediate products were
identified by the LC-MS-MS technique during photocatalytic
degradation. In order to increase photodegradation rate of
the herbicide, we examined the effect of titania modification
by depositing noble metals at various quantities and valence
states. The presence of platinum at neutral valence state
and optimum concentration induced higher
photodegradation rates while silver-modified titania
exhibited similar photocatalytic rates with those obtained
with pure nanocrystalline TiO2 films. Finally, the effect of
initial pH value was also examined. Acidic or alkaline media
were unfavorable for azimsulfuron photodegradation.

Photodegradation of
various organic pollutants by pho-tocatalysis, using wide

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bandgap semiconductors, has been extensively studied [1–
3]. Among them, TiO2 a relatively inexpensive
semiconductor exhibits high photocatalytic activity, stability
in aqueous solution, nontoxicity and so forth. However, TiO2
usage has a few drawbacks; for example, it absorbs only in
the UVA part of the light spectrum where solar radiation is
only 2-3% of the total reaching the surface of the Earth.
Moreover, the application of TiO2 for photocatalytic
oxidation of organic molecules is limited by high charge
carrier recombination rates that results in low quantum
efficiency. In recent years, surface metallization of TiO2 has
received considerable attention as an option to overcome
the high degree of charge carrier recombination. Platinum,
and some other noble metals, may be used for this purpose
thus providing an electron sink. In addition, they may extent
TiO2 absorbance in the Visible. The presence of a metal at
the surface of TiO2 results in the formation of a Schottky
barrier at the metal-semiconductor interface, which
facilitates the interfacial electron transfer and subsequently
encourages the charge carrier separation.

Among the various organic substances, which are known as

water pollutants, herbicides are a major pollution source for
both underground and surface waters. Advanced oxidation
processes are used, among others, also for the degradation
of herbicides. Azimsulfuron (AZS, see Scheme 1 for chemical
structure) belongs to the class of sulfonylurea herbicides,
which have a broad spectrum of weed control, low
application rate, and low animal toxicity. Sulfonylurea
herbicides, in addition to playing an important role in
modern agriculture, are also degradable by heterogeneous
photocatalysis, as it has been proven in the past. In the
present work, sol-gel prepared TiO2 films, which were further
modified with noble metal ions, were examined for the
photodegradation of AZS in water. The effect of various

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parameters, such as the amount of metal deposits and pH
value of herbicide aqueous solution, were studied in order to
evaluate the optimum conditions for the photocatalytic
oxidation of AZS.

4.1.1 DESCRIPTION OF THE PHOTOCATALYTIC REACTOR

The cylindrical reactor schematically shown in Figure 1 was

used in all experiments [19]. Air was pumped through the
gas inlet using a small pump to ensure continuous oxygen
supply to the reaction solution while simultaneously agitating
it. In cases where experiments were carried out in the
absence of oxygen, the solution was deoxygenated by
nitrogen flow and the openings were sealed. Four black light
fluorescent tubes of 4 W nominal power were placed around
the reactor. The whole construction was covered with a
cylindrical aluminum reflector. Cooling was achieved by air
flow from below the reactor using a ventilator. The catalyst
was in the form of four-glass rings, covered on both sides
with nanocrystalline TiO2 film. Film deposition is described
below. The glass rings were of 38 mm of diameter and 15 mm
height, stacked and coaxially placed inside the reactor. Thus,
the total surface of the photocatalyst film was approximately
2x71.6= 143 cm2. The intensity of radiation reaching the
surface of the film on the side facing lamps was measured
with an Oriel radiant power meter and found equal to
0.79mW/cm2.

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 Fig no.4.1.1 Nanocrystalline Titania films and metal deposition

Titania films were deposited by following the previously

reported procedure [20, 21]. Briefly, for 25 mL solution, 3.6 g
of the nonionic surfactant Triton X-100 (polyoxyethylene-10-
isooctylphenyl ether) was mixed with 20 mL of ethanol,
followed by addition of 1.6 mL of glacial acetic acid and 1.8
mL of titanium isopropoxide under vigorous stirring. Self
organization of the surfactant in this original sol creates
organized assemblies that act as templates defining
nanoparticle size. The surfactant is burned out during
calcination. After a few minutes stirring, the glass rings
described above, which were previously thoroughly washed,
sonicated in ethanol and dried in a N2 stream, were dipped
in the above sol and withdrawn slowly by hand. After the film
was dried in air for a few minutes, it was calcined in an oven.
The temperature was increased in a ramp rate of 20°C/ min
up to 550°C and left at that temperature for about 10
minutes. When the titania-covered rings were taken out of
the oven, they were transparent and optically uniform. The
above procedure was repeated several times in order to
reach the quantity of catalyst necessary for the purposes of
the present work. The final mass of titania on the four glass

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rings was 80 mg (20 mg on each glass ring). Noble metal
ions were deposited on titania films by adsorption from
aqueous solutions containing one of the following metal
salts: Na2PtCl4-xH2O or AgNO3 at various concentrations
(from 10-4 to 10-3 M for the platinum salt and from 5 X 10-4 to
10-2M for the silver salt). After the last layer of TiO2 was
deposited and immediately after the film was taken out from
the oven, the rings were submerged in the salt aqueous
solution and were left for half an hour in the dark. Then, the
rings were washed, dried, and subjected to UV radiation for
30 minutes; or they were additionally heated at 500° C for 15
minutes. UV and heat treatment were performed to reduce
cationic species to neutral metallic particles.

4.1.2 REMARKS

The herbicide azimsulfuron can be effectively photode-

graded by employing pure or noble metal-modified titania
nanocrystalline films as photocatalysts with black light tubes
as low-intensity UV illumination source. The catalyst was
deposited by the sol-gel method on glass rings; it could be
thus easily recuperated and repeatedly used in subsequent
photodegradation procedures. The best photocatalytic rates
were achieved in the case of platinum modified nanocrys-
talline TiO2 films. The pH of AZS aqueous solution affected
photodegradation rates. The fastest rate was obtained in the
case of natural pH of the solution.

4.2 Photocatalytic degradation of 3,4-

xylyl N-methylcarbamate and other

21 | P a g e
carbamate pesticides in aqueous
TiO2suspensions
Five carbamate pesticides were degraded photocatalytically
on TiO2. The comparison of their disappearance rates
showed that the degradation rate is governed predominantly
by their adsorbability to TiO2, and followed Hammett’s law in
a different manner from ordinary electrophilic reaction. As a
degradation pathway of 3,4-xylyl N-methylcarbamate
ŽMPMC. successive hydroxylation of aromatic ring was
suggested, and polyhydroxylation is considered to lead to
the opening of the aromatic ring to form oxygenated
aliphatic intermediates. It was indicated in this process that
the formation of acetic acid, one of the major aliphatic
intermediates, mainly originates from methyl substituents on
the aromatic ring.

Photocatalysis provides a
new method for water decontamination. Recent intensive
study showed that it can be applied to the degradation of
many pollutants w1x. Among them, pesticides have been
considered to be one of the major pollutants to which it is
promising to apply photocatalysis w2,3x. Many pesticides
cannot be degraded by conventional biological methods
w4,5x, whereas complete mineralization can be achieved by
photocatalysis w6,7x. In this work the photocatalytic
degradation of several carba-mate pesticides were studied in
regard to degradation rate, degradation process and
intermediate compounds, and the degradation rate was
correlated to the chemical structure of the pesticides to
investigate the factors influencing the photocatalytic
reaction.

Carbamates are an important group of insecticides which are

widely used throughout the world. Contamination of surface
and underground waters by these pesticides have been
22 | P a g e
reported in different parts of the world w8–11x. Because of
their toxicity and that of their degradation intermediates
w12x, their complete degradation is of great environmental
concern.

Carbamate pesticides used in this study are of analytical

grade and their chemical structures are shown in Fig. 4.2

Fig.4.2 Chemical structures of five carbamate pesticides.

4.2. 1 EXPERIMENTAL
The TiO2 used throughout the experiment is TP-2 Žanatase.
supplied by Fujititan. Its specific surface area is 17.3 m2rg
w13x.

Carbamate pesticides used in this study are of analytical

grade and their chemical structures are shown in Fig. 1.

For degradation experiment 75 mg of TiO2 powder was

suspended in 25 ml of 10y4 mol ly1 solution of pesticide in a
Pyrex glass bottle by stirring magnetically. The bottle was
illuminated by a 500 W super-high-pressure mercury lamp
through a water filter. After illumination for a given time, the
sample was filtered through a Millipore membrane filter of
0.2-mm pore size and the filtrate was subjected to analyses.

23 | P a g e
Degradation was monitored by a JASCO 880-PU with a
multiwavelength UV–VIS detector JASCO MD-90. The
aromatic intermediate was identified by the same
instrument. Organic acid intermediate was analyzed by an
ionchro-matograph Yokogawa IC 7000.

NOy3 , NOy2 and NHq4 were detected by an ionchromatograph

consisting of a JASCO 880-PU pump and Shodex CD-4
conductometer. Total organic carbon ŽTOC. was measured
by a Shimadzu TOC-500. Aldehyde and ketone were
determined following the method described in the literature
w14,15x. Solubilities of pesticides were measured as follows
w16x. An adequate amount of pesticide was dissolved in
water at room temperature by stirring for 1 week, and then
left standing for 1 day at 258C. After filtration the filtrate
was analyzed.

4.2.2 REMARKS
Disappearance of the five carbamate pesticides were quick
and the rates increased with pH. Their photocatalytic
degradations are governed by their adsorbability to TiO2
more than electron density on the aromatic ring and fol-
lowed Hammett’s law, but in a different manner from
ordinary electrophilic reaction. The formation of acetic acid
as major intermediate was attributed partly to methyl
substituents on the aromatic ring. In the mineralization
process nitrogen was converted predominantly to NHq4.

24 | P a g e
4.2 Photocatalytic degradation of
agricultural N-heterocyclic organic
pollutants using immobilized
nanoparticles of titania.

Degradation and mineralization of two agricultural organic

pollutants (Diazinon and Imidacloprid as N-heterocyclic
aromatics) in aqueous solution by nanophotocatalysis using
immobilized titania nanoparticles were investigated.
Insecticides, Diazinon and Imidacloprid, are persistent
pollutants in agricultural soil and watercourses. A simple and
effective method was developed to immobilization of titania
nanoparticles. UV–vis, ion chromatography (IC) and chemical
oxygen demand (COD) analyses were employed. The effects
of operational parameters such as H2O2 and inorganic anions
(NO3-, Cl- and SO42-) were investigated. The mineralization of
Diazinon and Imidacloprid was evaluated by monitoring of
the formed inorganic anions. The selected pollutants are
effectively degraded following first order kinetics model.
Results show that the nanophotocatalysis using immobilized
titania nanoparticle is an effective method for treatment
Diazinon and Imidacloprid from contaminated water.

The presence of highly

biorecalcitrant organic contaminants such as pesticides in
25 | P a g e
the hydrosphere due to industrial and intensive agricultural
activities is of particular concern for the freshwater (surface
and groundwater), coastal and marine environments . In
general, pesticides applied directly to soils, turf, or plants can
be washed into waterways during storm events or through
irrigation. As a result, pesticide presence in storm water runoff
can directly impact the health of aquatic organisms and
present a threat to humans through contamination of
drinking water supplies. Pesticides such as Diazinon and
Imidaclo-prid have been associated with toxicity in ambient
waters, point source discharges, and agricultural discharges.

4.3.1 DEGRADATION METHOD OF INSECTICIDES

Photocatalytic degradation processes were performed

using a 5 L solution containing specified concentration of
pollutants (0.13 mM Diazinon, 0.22 mM Imidacloprid, pH:
neutral (5.5) and room temperature). The solutions were
first agitated under gentle air in the dark for 30 min to
reach equilibrated condition. Samples were withdrawn
from sample point at certain time intervals and analyzed
for degradation.

4.3.2 IMMOBILIZATION OF TITANIUM DIOXIDE

NANOPARTICLES AND PHOTOCATALYTIC REACTOR

A simple and effective method was used to immobilization of

TiO2 nanoparticles as follows: inner surfaces of reactor walls
were cleaned with acetone and distilled water to remove any
organic or inorganic material attached to or adsorbed on the
surface and was dried in the air. A pre-measured mass of
TiO2 nanoparticle (16g) were attached on the inner surfaces
of reactor walls using a thin layer of a UV resistant polymer
(silicon polymer). Immediately after preparation, the inner
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surface reactor wall–polymer–TiO2 system was placed in the
laboratory for at least 60 h for complete drying of the
polymer .

Experiments were carried out in a batch mode immersion

rectangular immobilized photocatalytic reactor made of
Pyrex glass, which is shown in Fig.4.3.2. The radiation source
was two UV-C lamps (15W, Philips). A water pump and air
pump were utilized for the transferring and aeration of
polluted solution, respectively.

Fig.4.3.2. Scheme of immobilized titania nanopartcles

photocatalytic reactor.

Two insecticides, Diazinon and Imidacloprid, could be suc-

cessfully degraded and mineralized by nanophotocatalysis in
an immobilized titania nanoparticles photocatalytic reactor.
The degradation rate for insecticides goes through a
maximum when the concentration of the hydrogen peroxide
increases from 0 to optimal concentration (3.53 mM) and
then it does not appreciable change. Chloride exhibited the
strongest inhibition effect on the selected insecticide followed
by nitrate. The photocatalytic degradation kinetics follows a
first order model. The formation of carboxylic acids
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intermediates (acetic, formic and oxalic) initially increased
with the illumination time, and then dropped due to directly
reaction with holes and generation of CO2 according to the
photo-Kolbe reaction. MineralizationofDiazinon and Imi-
dacloprid is identified by production of inorganic anions
(nitrate, sulfate, phosphate and chloride). Thin-film coating of
photocat-alyst may resolve the problem of suspension system
of selected insecticides degradation. Nanophotocatalysis by
immobilized titanium dioxide nanoparticle in the presence of
hydrogen peroxide is able to treatment of selected
insecticides from polluted waters without using high pressure
of oxygen or heating. Hence, this technique may be a viable
one for treatment of large volume of water polluted by
insecticides.

CHAPTER 5
HEALTH IMPACTS
Application and health effects of pesticides
commonly used in India

S.No. Pesticide What it is used for Health impacts

Name
1. ddt effective against chronic liver
wide variety of damage cirrhosis
insects, including and chronic
domestic insects hepatitis,
and mosquitoes endocrine and
reproductive
disorders, immuno
suppression,
cytogenic effects,
breast cancer, non
hodkins
lymphoma,
polyneuritis.
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2. endosulfan it is used as a effects kidneys,
broad spectrum developing foetus,
non systemic, and liver immuno-
contact and suppression,
stomach decrease in the
insecticide, and quality of semen,
acaricide against increase in
insect pests on testicular and
various crops prostate cancer,
increase in defects
in male sex
organs, and
increased
incidence of
breast cancer. it is
also mutatagenic
3. aldrin effective against lung cancer, liver
wireworms and to diseases
control termites
4. dieldrin used against liver diseases,
ectoparasites such parkinson's &
as blowflies, ticks, alzheimer's
lice and widely diseases
employed in cattle
and sheep dips.
also used to
protect fabrics
from moths,
beetles and
against carrot and
cabbage root flies/
also used as seed
dressing against
wheat and bulbfly
5. heptachlor it controls soil reproductive
inhibiting pests. disorders, blood
dyscariasis

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6. chlordane it is a contact, reproductive
stomach and disorders, blood
respiratory poison dyscariasis, brain
suitable for the cancer, non
control of soil hodkins lymphoma
pests, white grubs
and termites.
7. lindane it is used against chronic liver
sucking and biting damage-cirrhosis
pest and as smoke and chronic
for control of pests hepatitis,
in grain sores. it is endocrine and
used as dust to reproductive
control various soil disorders, allergic
pests.such as flea dermatitis, breast
beetles and cancer, non
mushroom flies. it hodkins
is effective as soil lymphoma,
dressing against polyneuritis.
the attack of soil
insects
8. fenitrothion it is a broad human
spectrum contact epidemiological
insecticide evidence indicates
effective for the fenitrothion
control of chewing causes eye effects
and sucking pests- such as retinal
locusts aphids, degeneration and
caterpillars and myopia. chronic
leaf hoppers. it is exposure to
also used against fenitrothion can
domestic insects cause frontal lobe
and mosquitoes impairment.
organo-
phosphates are
suspected of
causing neurologic
deficits.
9. fenthion it is a persistent fenthion may be
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 contact insecticide mutagenic:
valuable against causing genetic
fruitflies, leaf aberrations. it may
hoppers, cereal be a carcinogen
bugs, and
weaverbirds in the
tropics
10. parathion a contact parathion is a
insecticide and possible
acaricide with carcinogen
some fumigant
action. very
effective against
soil insects with
high mammalian
toxicity

CONCLUSION:-

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Pesticides can save farmers' money by preventing crop
losses to insects and other pests but the illeffects can’t be
ignored. many side effects,as we mentioned above are very
dangerous.study has linked breast cancer from exposure to
DDT prior to puberty.Poisoning may also occur due to use of
chlorinated hydrocarbons by entering the human food chain
when animal tissues are affected. Symptoms include
nervous excitement, tremors, convulsions or death.
Scientists estimate that DDT and other chemicals in the
organophosphate class of pesticides are cause of many
human deaths in 1977. One study found that use of
pesticides may be behind the finding that the rate of birth
defects such as missing or very small eyes is twice as high in
rural areas as in urban areas.Another study found no
connection between eye abnormalities and pesticides.In the
USA, increase in birth defects is associated with conceiving
in the same period of the year when agrichemicals are in
elevated concentrations in surface water

So its essential to degrade the pesticides,by the methods

mentioned above.tio2 particles are accepted world
wide,nowdays.

SO, USE IT AND MAKE THE WORLD FREE FROM

PESTICIDE POLLUTION.

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