NIGER DELTA UNIVERSITY

SCHOOL OF POSTGRADUATE STUDIES

FACULTY OF SCIENCE

A SEMINAR PAPER

ON
PESTICIDE POLLUTANTS: A GLOBAL ISSUE, A GLOBAL RESPONSE

PRESENTED

BY

OGBALAJE O. LUCKY

DEPARTMENT OF CHEMICAL SCIENCES

Introduction

In contrast to simple biodegradable substances which decompose quickly, there are

some com pounds which have a remarkable degree of resistance to the natural
agencies of decay and decomposition. These are often harmful substances which
persist in the environment for long duration of time during which they are taken up
in the biosphere, accumulated and bio-magnified to concentration potentially toxic
to organisms at higher trophic levels in the food chain. Many of these chemicals
are carcinogenic, teratogenic and mutagenic in nature.

Pollutants grouped together under the category of wastes resistant to degradation,

are organic substances produced naturally or are synthesized by man. Many of
these are such chemicals which have caused much concern due to their wide-
spread use and dissemination. Broadly speaking these chemicals can be grouped
into the following three categories:

(A) Pesticides and allied chemicals.

(B) Crude petroleum and its derivatives.

(C) Polymers, plastics, plasticizers and other wastes.

Though most of these chemicals are referred to as being persistent, the versatile
and efficient machinery which Nature employs for decay and decomposition of
pollutants is capable of decomposing even these recalcitrant and refractory
chemicals. But to do so, suitable conditions and abiotic as well as biotic processes
have to be put together for which Nature requires time on its own scales and not on
scales dictated by human needs. These chemicals, if left to Nature's devices alone
are degraded father slowly, slower than the rate of their entry into the environment.
They tend to accumulate within the system causing toxicity to those living
organisms which happen to get exposures. Grave ecological problems appear
where the magnitude of pollution is considerably large.

PESTICIDES AND ALLIED CHEMICALS

Under the name pesticides are grouped a large number of chemicals which are used
to suppress Or eliminate undesirable organisms. Most of these chemicals are
poisonous substances capable of damaging one type of organism drastically while
causing none or only nominal damage to the desired one even if the two are in a
close association. It is due to this property of exerting a selective action on
different species or group of species that these chemicals have acquired a very
important role in a modem society.

In his endeavor to feed a rapidly growing population man had to develop

sophisticated technology for raising vegetables, fruits, cereals and live-stock of
which the control of various pathogens, insects, pests, nematodes, rodents etc.
forms an integral part. In good old days the problem was not so severe. Sprawling
human establishments and practices of intensive agriculture have created additional
resources for subsistence of various pathogens, insects and pests etc., while the
disturbed prey predator relationship in a drastically altered ecosystem has
weakened or eliminated the natural means of population regulation. The number of
disease causing organisms and pestilent insects has been estimated to be well over
86000 apart from a large number of species of fungi, ticks, mites and nematodes.
On global scale these could cause a loss of over 50% of total world food stuff
production. (Annonymous 1979).

(I) A BRIEF HISTORY OF USE OF SYNTHETIC PESTICIDES

The history of application of various substances to suppress or eliminate unwanted
organisms is a long one. Most of the chemicals used earlier were simple inorganic
preparations such as salts of mercury copper and arsenic or products of biological
origin. However, it was only after the discovery of the remarkable insecticidal
properties of DDT by Mueller in 1933 that a chemical war has been waged against
various insects, pests and other undesirable organisms. The discovery of DDT was
followed by many other synthetic pesticides and the decade following the Second
World War witnessed extensive use of DDT, Aldrin, Dieldrin, Hexachlorobenzene,
etc. in North America, Europe and Japan after which its application spread to other
parts of the world. In India also these insecticides were extensively applied to
eliminate mosquitoes during the Anti-Malaria drive undertaken soon after the
independence. No doubt this has curtailed losses caused by diseases, insects and
pests but the damage caused to the environment has probably been heavier than
gains from the reduced pest menace.

Though there were many episodes of poisoning caused by synthetic organics

earlier (Murty 1986), it was only in 1962 that publication of Rachel Carson's book
entitled "The Silent Spring" which brought the problem of pesticide contamination
to public attention. The book presented alarming picture of dangers of pesticide
contamination in the environment and raised many controversies. However, many
of her predictions have already become realities. For instance about 70% of the
robin population of Hanover, New Hempshire, died in 1963, as a consequence of
DDT sprays on elm trees to check the Dutch elm disease. There has been a decline
in the number of osprays and bald eagles along the eastern coast of the United
States due to pesticide contamination. DDT reaches these birds through food in a
much higher concentration as a result of bio-magnification. It makes eggs non-
viable as the disturbed calcium-metabolism in these birds causes the formation of
eggs with fragile shells (Peakali 1970).

The Science Advisory committee to U.S. President reported in 1967 that about 20
tons of DDT or its residue was contained in the bodies of peoples of United States
alone. The total amount of DDT in the entire biosphere on this globe was estimated
to be about 1,000,000,000 lbs (McCaull 1971). Agricultural and industrial workers
who are regularly exposed to DDT and other pesticides were found to possess 600-
1000 ppm of these chemicals in different tissues of their body. A post mortem
examination of the bodies of unfortunate victims of pesticide toxicity in Hawaii
revealed a variety of carcinoma and extensive focal or general pathology of liver
(Casarett et al 1968). In long run many pesticides may also cause genetic effects by
damaging DNA molecules (Niering 1968). In the face of rising public demands
DDT application was banned in the United States in the year 1972. However, its
use still continues in many developing countries and till the year 1981 A.D. about
4,000,000,000 lbs of DDT had been used to control insects and insect borne
diseases on global scale (Gold et al 1981).

(II) PROBLEMS ASSOCIATED WITH THE USE OF PESTICIDES

Pesticides are unique in position among toxic substances as they are deliberately
added tosuppress or eliminate some form of life. Under ideal conditions the
injuring action should be highly specific and affect only the target organisms. The
toxicity should disappear after the purpose for which it was applied has been
achieved. However, none of these features are met with in most of the pesticides
which are in common use these days. This has made the use of these synthetic
organics extremely hazardous pollutants of the environment and the biosphere.
Some of the characteristic features of pesticide application may be summarized as
follows:
1. The use of synthetic pesticides has become a necessity in various branches
of our economy. Fast expanding human establishments, intensive agriculture
and higher input rate of waste material into the environment have created
additional resources for various insects, pest and other harmful pathogens to
multiply. Natural means of population regulation through prey-predator
interactions have become ineffective due to disturbed functioning of natural
systems. We are faced with a large number and variety of unwanted
organisms. The application of the synthetic pesticides seems to be the only
effective solution.
2. Most of the pesticides are violent poisons and their handling is hazardous.
The selective action of pesticides is never perfect and many non-target
organisms are affected by their toxicity - some of which may be useful
organisms. For example elimination of some insects and bees which vitally
aid in pollination of many plants could cause considerable damage to
agricultural productivity (Pimental et al 1980). These non-target organisms
may also include domestic animals, live-stock, poultry etc. Accidental
exposures may lead to human casualties as well.
3. It is difficult to prevent the circulation of these chemicals in the
environment. They are usually applied with the help of some aerial or
surface spraying device or simply dusted manually. Air, water and living
organisms carry them to far off places. Pesticides applied in tropics may
appear in arctic or subarctic regions. Some of these pesticides have already
attained a global distribution (for example DDT).
4. Most of these synthetic organics or their decomposition products persists in
toxic state in the environment for long durations. Thus, once applied they
continue to harm the non-target organisms for long periods of time. They are
bio-accumulated and bio-magnified, features which cause problems at higher
 trophic levels in an ecosystem. Persistence of DDT has been recorded for
periods as long as twenty five years.
5. It is impossible to reduce the rate of application of pesticides. Their
application should be in adequate doses so as to eliminate the entire
population of unwanted organisms without providing them any chance to
develop resistance to the chemical employed. However, in actual practice,
uneven distribution of insecticides over the area under operation usually
exposes many of the undesired organisms also to lower concentrations (sub-
toxic or sub-lethal concentrations). Thus resistant populations are developed
and subsequent applications have to be in a higher and higher doses.
Decreasing the rate of their application could defeat the very purpose for
which they are applied.

(Ill) ECOLOGICAL EFFECTS OF PESTICIDE POLLUTION

Differential toxic action of pesticides on different species results in an unbalanced

biotic community. Species susceptible to the toxic action of the pesticide are
eliminated while the resistant ones multiply without competition. Organisms on
which the eliminated species depended for its food requirement are also affected.
Absence of predation causes these forms to multiply in numbers. Thus a chain of
events is initiated which alters the species composition of the ecosystem beyond
recognition. Insignificant pest may become so numerous as to cause another
pestilence.

Pesticides often kill a series of organisms owing to their non-specific action.

System diversity and complexity is, therefore, drastically reduced which make it
highly vulnerable. The population which emerges to replace the older one is often
characterized by a faster rate of growth at the level of primary consumers while the
predator population takes longer time to built up enough strength to keep the
primary consumers in check. This may result in development of population of
another organisms as serious threat to productivity.

Pesticides exert a remarkable influence on microbial community in an ecosystem.

Moderate concentration of most of the pesticides, to begin with, depress the
activity of microbes. Following this initial depression resistant strains appear, as a
consequence of which an enhanced activity is observed. The differential action of
pesticides on different groups of microbes causes repression of some while others
are stimulated. Since microbes function as coordinated entity with each of its
components performing certain specific tasks, selective action of pesticides on
different components of microbial population causes changes in over-all activity of
the community which is no longer capable of carrying out its normal functions.

(IV) PERSISTENCE OF PESTICIDES IN THE ENVIRONMENT

The persistence of pesticides in the environment depends upon their chemical and
physical properties, dose and formulations (e.g., liquid, powder or granules etc.),
type of the soil, its moisture content, temperature, physical properties of the soil,
composition of the soil microflora and the plant species present. As far as the
duration of existence in the environment is concerned various pesticides may be
divided into the following categories:

1. Organochlorine insecticides with persistence in the environment of more

than 18 months. Some of these compounds may persist for periods over 10
years.
2. Derivatives of thiazine, urea, pictogram etc. with a persistence in the
environment of about 18 months or so.
3. Derivatives of benzoic acid, amides and various other acids with a
persistence in the environment of about 12 months.
 4. Phenoxyalkylcarboxylic acids, nitriles and derivatives of toluidines with a
persistence in the environment of about six months.
5. Organophosphate pesticides and derivatives of carbamic acid with a
persistence in the environment of about three months or below three months.

It should be noted here that the persistence of these chemicals in the environment
depends on a number of factors. Under favorable conditions of decomposition, the
degradation may be brought about rather quickly while adverse conditions may
delay it for considerable period of time. For example DDT may be eliminated
within two years only, under favorable conditions while its persistence for periods
ranging between 20-25 years has also been recorded.

(V) BIO-ACCUMULATION AND BIO-MAGNIFICATION OF

PESTICIDES

Pesticides, even though present in exceedingly low concentration in the soil or the
surrounding water are taken up by various microbes, plants and animals which may
accumulate and concentrate them several thousand times. The concentration of
0.00001 ppm of DDT, for example, may get magnified to almost 70,000 times in
oysters within a period of 40 days. One kg of soil may contain only 0.0001 mg of
an organo-chlorine pesticide whereas carrots grown on this soil may contain as
much 2-6 mg per kg and the rabbits feeding on these carrots may contain as much
as 22-35 mg per kg of the toxicant. Toxaphene may occur in lake waters only in
the concentration range of 0.0002- 0.0006 mg per ltr but the water plants growing
in the lake may contain as much as 0.2-0.4 mg per kg, invertebrates 0.5 - 1.5 mg
per kg and trout and salmon may contain as much as 3.0 - 6.0 mg per kg.
Toxaphene is decomposed very slowly and even after a period of six or seven
years there is little significant change in its concentration. Similar bio-
accumulation and bio-magnification have been recorded for a number of other
pesticides as well (Gruzdyev et al 1980).

The process of bio-accumulation and bio-magnification makes exceedingly low

quantities of pesticides or their toxic residues available to the living organism in a
highly concentrated state. The symptoms of toxicity either appear in the animal
accumulating the poisonous material or it makes the animal poisonous to other
organisms which feed on it. The worst suffers are animals at the top of the trophic
structure. For example, a very low concentration of DDD, an organochlorine
insecticide was bio-magnified 5000 times in fishes in Lake Clear of California
soon after it was sprayed in 1957. Each fish possessed about 100 ppm of the
pesticide and grebes which represented the toplevel of the trophic structure
succumbed to its toxicity after eating 20 such fishes (Hunt and Bischoff 1960,
Rudd and Herman 1972).

Another undesirable consequence of the phenomenon of entry, accumulation and

bio magnification of highly persistent pesticides is the transport and dissemination
of these poisons to far off places in a highly concentrated state, within the bodies
of living organisms. If a bird carries 100 mg per kg of DDT within its body, with
thousands of birds migrating from one place to another a large quantity of the
pesticide, about 1 kg per 10,000 kg of bird-biomass, shall get transported to new
regions where it is released after the birds die and their bodies decay. Thus the
pesticide applied in Florida may appear in Polar Regions and cause toxicity there
(George and Lahmann 1966).

(VI) CLASSIFICATION OF PESTICIDES

As any chemical which possesses the capacity of suppressing or eliminating

unwanted organisms while causing none or nominal damage to the desired
organisms, can be used as pesticide, it is difficult to classify these chemicals on the
basis of their chemical nature and structure. In general, these substances are
classed

into several groups which are named after the type of organisms against which they
are used. For example, insecticides are the poisons which are used against insects,
lerbicides are used to control unwanted weeds, iungicides for suppressing fungal
infections, rodenticides, molluscicide and piscicides etc. are so called because they
are used to eliminate unwanted rodents, molluscs and fishes'. As far as the
chemical nature and structure of these substances are concerned, there occurs a
bewildering variety. Various organo-chlorine, organo-phosphate derivatives,
carbamates, thio-carbamtes, triazines, bipyridyls, urea, nitriles, nitroanilines,
amides, phenols, derivatives of aresenic, copper and mercury, even diesel and
kerosene may be employed as pesticides. Major groups of these chemicals which
are employed on such large scale as to cause problems of poisoning,
carcinogenesis, mutagenesis and environmental degradation are:

 Insecticides.
 Herbicides.
 Fungicides.

INSECTICIDES

Insecticides are chemicals which are used to suppress unwanted insects while
inflicting none or little harm to the organisms or objects which are damaged by the
insect concerned. The selective action of most of the insecticides in common use
these days, stems from the fact that it implicates such vital systems in the body of
the organism to be eliminated which are altogether absent in organisms to be
protected. In most cases the target is the nervous system. It is the damaged nervous
system which is responsible for the death of the insect. As this system does not
occur in plants no harm is done to its productivity. Insecticides in common use
these days can be grouped into three main categories. These are:

 Organochlorine insecticides
 Organophosphate insecticide.
 Carbamates and miscelleneous chemicals

(1) ORGANOCHLORINE INSECTICIDE:

These insecticides include chlorinated derivatives of ethane such as DDT, DDD,

cvclodienes which include Aldrin, Dieldrin, Heptachlor, Toxaphene etc, and hexa-
chloro- cyclohexanes such as Lindane. In general these are very stable chemicals
which can withstand the action of various environmental factors, like temperature,
solar radiations and moisture for long duration of time. In a biological system also
they are degraded with considerable difficulty. It is stability and persistence of
these synthetic organics which is responsible fortheir prolonged toxicity to insects
and pests. Most of these chemicals dissolve well in organic solvents and fats while
their solubility in water is very poor. They have a broad spectrum of action which
implicates the nervous system of the insect causing disruption of transmission of
nerve impulses. The animal dies of malfunctioning of the nervous system. Table
12.1 lists some of the common organochlorine insecticides.
(1) ORGANOPHOSPHATE INSECTICIDES

Organophosphate insecticides are one of the most important group of pesticides in

common use these days which are preferred over organo-chlorine derivatives. They
are effective over a wide range of pestilent insects and are quickly degraded into
harmless metabolites within a living system as well as in the environment. Within
a period of three months after the application they are almost completely
eliminated from the system. Though fat soluble and capable of rapid penetration
into living organisms, they are never deposited to an appreciable extent within a
living system. They are required in much lower amounts than most of the
organochlorine derivatives.

However, an extremely toxic nature and relatively rapid development of resistant

populations following repeated use, are the main negative features of these
insectides. Most of the cases of accidental or intentional insecticide poisoning
involve organophosphate insecticides such as parathion or malathion. Moreover
due to the rapid decomposition, the insecticidal action of these substances is not as
long lasting as those of organochlorine insecticides. This necessitates their repeated
use and makes them costlier.

Like organochlorine derivatives most of the organophosphate insecticides

implicate the nervous system of the target organisms. They are capable of
inhibiting the activity of the enzyme acetyl- choline-esterase which catalyzes the
removal of acetyl-choline from the synaptic cleft after an impulse has passed
through the junction. The inactivation of this enzyme causes acetyl choline to
accumulate in the synaptic cleft which as a consequence remains in a charged state
blocking further transmission of nerve impulses through the cleft. Some of the
important organophosphate insecticides are given in Table no. 12.1.
(2) CARBAMATE INSECTICIDES

These insecticides are analogues of carbamic acid which are very effective against
many insects and pests. As compared to organophosphate derivatives most of these
compounds have a lower toxicity to mammalian systems.

Carbamate insecticides are readily degraded in the environment and in a living

system also they are easily detoxified and excreted. Apparently the insecticidal
activity of most of these compounds is due to competitive inhibition of enzyme
acetyl-choline-esterase which catalyses break-down of acetylcholine in the
synaptic cleft between two nerve endings and at the neuro-mascular junctions. Like
organophosphate insecticides these also block the conduction of nerve impulses
through the synaptic cleft. Important insecticide of this group are given in table no.
12.1 The episode of toxic gas leakage in Bhopal, M.P., on December 3, 1984
involved methyl isocyanate which is used in the manufacture of Carbaryl or Sevin.
Though the cause of the tragedy is still shrouded in mystery, scientific explanation
suggests that the accidental addition of water in MIC storage tanks could be the
cause of the tragedy. The manufacture of Carbaryl involves the following
reactions:

CH-N

MIC is stored with phosgene which prevents its polymerization. Addition of water
causes phosgene to react with water molecules to produce HCI. HC1 catalyses
polymerization of MIC, a reaction which is strongly exothermic. Accidental
addition of water triggered the reaction. An enormous amount of heat was
produced due to which things went out of control. About 40 tons of MIC was
consequently released MIC is an extremely reactive, poisonous and volatile
chemical with a capacity to penetrate living systems. The damage caused in the
living organisms, particularly, in biological membrane systems are irreversible.
The tragic incidence left about 2890 people and 3000cattles, goats and other
animals dead while 2,00,000 were affected with its chronic poisoning.

A. HERBICIDES

Herbicides are chemicals which are used to suppress unwanted plants. The use of
these chemicals has increased markedly during the last twenty years. The
production of herbicides now rivals or even exceeds those of insecticides in
quantity, the volume of application and the total area under treatment. Therefore,
these poisonous substances possess almost similar potential to cause environmental
problems, contamination of our food and water supplies, as do various insecticides.
Fortunately in India, herbicides are not used on such a large scale as they are in
developed countries.

There are only forty or fifty species of plants which provide 90% of the world’s
food supply, whereas about 7000 species are considered undesirable since most of
them compete with plants cultivated on large scale for nutrition, water and space.
The unwanted plants or weeds can cause considerable damage if allowed to grow
uninhibited under the highly favorable conditions which we provide to plants we
grow. In smaller establishments such as are frequent in India, it is possible to weed
out mechanically most of the useless plants but in larger ones it is not possible to
do so. Herbicides have, therefore, become a necessity.

Herbicides prepared with intentions to eliminate unwanted herbs should present

little problems of chemical toxicity to vertebrates because of the obvious
morphological and physiological dissimilarities between the two. Indeed many
 herbicides have very low toxicity to mammals. However, there are some herbicides
which are extremely toxic to higher animals including man. Some common
herbicides are listed in table no. 1.2.

Table12.2.Somecommonherbicides.

(II)DINITROPHENOLS

30 mg/kg

2.DINOSEB
Toxicity as mg/kg of LD50 in male rats.

A great deal of public attention has been drawn to the application of about 44
million lbs of Agent Orange by the Americans on about 1.4 million hectares of rich
fertile land and forests in Vietnam war during the years 1961-71. It consisted of a
mixture of 2-4-D and 2-4-5-T with varying degrees of contamination by tetra-
chloro-dibenzo-p-dioxan (TCDD) which develops during the manufacturing of the
herbicide concerned. TCDD is an extremely toxic compound (oral LDS0 inguinea
pigs being 0.0006 mg per kg only) and has been shown to be carcinogenic as well
as teratogenic(Von Miller et al 1977, Kociba 1978).

2-3-7-8-tetrachlorodibenzo-p-dioxan

The entire stretch of land subjected to the application of Agent Orange was
rendered barren and famine like conditions ensued with hundreds of claims of
carcinogenesis and teratogenesis among people exposed to the herbicide mixture
(Young et al 1987) There is no conclusive evidence about 2-4-D or 2-4-5-T but the
contaminant, TCDD, has been shown to be definitely carcinogenic, and
teratogenic. This was an incidence of havoc caused by biological warfare which
was more disastrous for the people than a conventional war.

B. FUNGICIDES

Fungicides are chemicals used to kill fungi. These chemicals may be used before
the onset of fungal infection in which case they are termed as protective
fungicides. The fungal infection is unable to enter and develop in the host plant in
presence of these fungicides. Eradication or curative fungicides are applied to cure
the fungal infection which has already set in.

Detailed toxicological investigations have only been performed in cases of few

fungicides. A detailed review of the action of fungicides on target organisms has
been published by Lukens (1971). Although many of these compounds have little
toxicity to vertebrates, there are few notable exceptions. Compounds containing
mercury have caused great concern many times. Consumption of grains treated
with organo-mercurial has resulted in many deaths and permanent neurologic
disability in humans in Pakistan and Iraq and other countries (Haq 1963). Some of
the important fungicides which are in general use these days are listed in table no.
12.3

Table no. 12.3 important fungicides in common use.

(VII) SPECIAL FEATURES ASSOCIATED WITH USE OF PESTICIDES

Some of the special features associated with the use of pesticides and the problems
which arise as a result of their unrestricted use include:

Synergistic Action: Synergism is the cumulative action of two or more than two
foreign chemicals introduced simultaneously or consecutively into a biological
system. Even small doses which have a nominal effect, or none at all, may cause
acute toxicity if another foreign chemical is present in the system - the toxic
response being often stronger than the cumulative action of the toxicants.
Malathion which is usually considered to be safest of all organophosphate
insecticide (oral LD50 in male rats being 1375 mg per kg) in presence of small
amounts of EPN, (ethyl-p- nitrophenyl phenylphosphonothionate) produces strong
toxic reaction in vertebrates. It has been shown that malathion is detoxified by
carboxyl-esterases and amidases which are inhibited by EPN (Frawley el al 1957).
Similar reaction is obtained if malathion samples are contaminated with phenthoate
another organophosphate insecticide (Baker et al 1978).

Antagonistic Action Antagonistic action of two or more than two chemicals

introduced simultaneously or one after the other results in production of a milder
toxic response than would normally be expected. The toxicant nullify the effect of
each other. Several organochlorine insecticides are known to exercise a protective
action against the acute toxicity of organophosphate insecticides (Du Bois 1959,
Murphy 1969). Malathion administered with DDT results in quick disposal of the
insecticide mixture. Accumulation of DDT in adipose tissues is considerably
reduced when it is fed with Dieldrin (Street et al 1969). It is suggested that
presence of some other foreign chemical induces the activity of bio-transformation
enzymes which cause quick metabolism and excretion of other toxicants and hence
the reduced toxicity.

Inter-Action With Clinically Administered Drugs : The capacity of some

pesticides, for example organochlorine derivatives, to induce the activity of liver
microsomal cytochrome P-450 enzyme system may cause rapid inactivation or
elimination of many drugs administered for benefit of the organism. Persons who
are frequently exposed to DDT. drugs like hydroxycortison and phenylbutazone
have little effect. Similarly acute toxicities may be caused by many clinically
administered drugs if some bio-accumulated pesticide is already present in the
system which causes the inactivation of the mechanism of bio-degradation
(Hodgson et al 1980).

Effect of Pesticide Exposures on Fertility: There has been an increased concern

about the effect of pesticides on fertility. Post-natal exposures to low doses of
many pesticides have been shown to depress fertility in mouse, rats, dogs, bull and
even human beings (Me Lachlan et al 1981). If the reproductive system is
susceptible to such small doses at which no obvious toxic response occurs it may
have a subtle effect on reproductive capacity of organisms. This in turn cauld
adversely affect population densities and thereby the biotic spectrum present in the
habitat concerned.

Immunotoxicity of Pesticide and Allied Chemicals: The effect of various pesticides

on immune system has become on area of great concern. A number of pesticides
which include atrazine, captan, dinitro-ortho-cresol, hexachlorobenzene, 2-4-5-T
have been shown to have marked effect on immune system of laboratory rats (Vas
et al 1983). About forty different pesticides have been cited to influence the host
defence mechanism by Street (1981). With an impaired immune system, the
organism becomes susceptible to any type of infection howsoever mild arid
symptoms like AIDS syndrome could follow. The mechanism of this depression is
not clear nor is the degree or extent of damage done well documented. The fact
that many pesticides affect the defence mechanism of such animals which show a
remarkable degree of resemblance to human system should be enoughto caution us
and trigger further studies.

Mutagenic, Carcinogenic and Teratogenic Action: A number of pesticides like

DDT, Aldrin, heptachlor, Hexachlorobenzene, Toxaphene, Captan, Mirex etc. all
of which are in common use these days have been shown to induce cancerous
growth and tumors in mammalian systems (IARC 1983). Likewise Carbaryl,
Captan, Folpet, Difolatan, Organo-mercury compounds, 2-4-5-T,
Pentachloronitrobenzene and Paraquat has been demonstrated to cause teratogenic
effects in experimental animals (Durham and Wilburns 1972). Similarly many
pesticides have been shown to cause mutations in a series of tests by Epstein and
coworkers (1972).

Mutagenic, carcinogenic and teratogenic action of foreign chemicals in biological

systems stem from the interference which they cause in function, synthesis and
structure of DNA and RNA molecules. Most of these observations conducted on
test animals in laboratory do suggest that exposure to these chemicals may bring
about irreversible carcinogenic, embryo-toxic and even mutagenic affects in higher
animals including man.

(VIII)CHEMICAL BASIS OF TOXICITY OF PESTICIDES

Toxicity of pesticides and allied chemicals depends mainly on chemical structure

of the substance. However, a precise co-relation between toxic properties and the
chemical structure of substances is not well understood. Since long it has been
observed that there are certain chemical groups or atoms which when introduced
into the molecule induce or enhance its toxicity. These groups or atoms which may
be called toxophoric groups include halogen atoms (F, Cl, Br, I), the nitro group,
atoms of heavy metals (Hg, Sn, Cu etc.) and the rhodanic group (-SCN). It is due
to the presence of bromine atoms that Methyl bromide, an effective fumigant, is
much more toxic than Methane. Presence of nitro group in phenols increases its
insecticidal activity sharply. LD50 of pehnol for leguminous aphids is only 0.3%,
while of 4-nitrophenol is 0.0075% and that of 2-4-dinitrophenol is 0.001 %. The
substitution of chlorine atoms in second position of triazine ring in chlorine-
derivatives of 1-3-5- triazines with hydroxyl ions results in complete loss of
herbicidal activity.

In many cases toxicity of a substance may increase by addition of chemically inert

groups. Addition of methyl group in 2-4-dinitrophenol results into the formation of
2-4-dinitro-5-methyl phenol the insecticidal activity of which is almost twice as
strong as that of the parent compound (LD for leguminous aphids being 0.0005%).
Substitution of hydroxyl group in DDT causes a sharp changes in the spectrum of
its activity. The toxicity of a chemical may also depends on the precise spatial
arrangement of various atoms or groups. Isomers of hexachlorocyclohexane differ
from each other in spatial arrangement of chlorine and hydrogen atoms. It is the
gamma-isomer which is the strongest in its insecticidal activity (Lindane).Toxicity
as LD5<) in male rats. LDS0 is the dose of a toxicant which if given to all
members of a population shall kill 50% of individuals.

(IX) DETOXIFICATION OF PESTICIDES AND ALLIED CHEMICALS

The process of detoxification involves abiotic or biotic trasformation of pesticides

into relatively harmless substances, it has often been observed that toxicity of
substances depends on its chemical structure and a slight change in which may
result in radical changes in its properties. Loss of toxicity naturally follows if
active groups are detached and in many cases a little change in structure of the
compound detoxifies it completely. Substances possessing highly branched
structure, increased substitution, aromiatic compounds, cycloparaffins etc. are
degraded with difficulty and hence their persistence. Degradation of pesticides in
environment involves :

Abiotic transformation: Abiotic transformation includes mainly photolysis,

hydrolysis, cleavage of various types of bonds, adsorption by humid material and
other colloids and formation of stable complexes within the medium. Solar
radiations, presence of moisture, temperature, the chemical nature of the humid
material and other substances present in the medium etc. play an important role in
abiotic transformation of poisonous substances in the environment.

Biotic transformation: Biotic transformation involves biochemical reactions

brought about by enzymatic machinery of living organisms. Most of the pesticides
are lipophilic compounds whichthough readily absorbed by living system cannot
be excreted in an unchanged form. They have to be acted upon by the enzyme
systems in such a way as to convert them into hydrophilic ones so that they could
be excreted out. The process of bio-transformation,however, does not always result
in detoxification. In certain cases products much more toxic than parent
compounds are also formed.

Important biochemical reactions which occur in a living system bring about a

variety of transformations. These include the following:

Degradation reactions: These reaction involve oxidation,reduction,hydrolysis,

cleavage of important bonds etc . Which result in displacement of important
functional groups of the pesticide molecules by groups like -OH, -COOH, NH2
etc. Many pesticides loss their toxicity in the process.

Conjugation reactions: Conjugation reactions which usually follow degradation

reactions involve synthetic reactions in which the pesticide molecules, now
carrying groups acquired during the earlier reaction, are conjugated to other
molecules within the living system to form highly ionized water soluble
substances. These are quickly excreted from the living system.

Although all living organisms are capable of bio-degradation, tiny microbes such
as bacteria, algae, fungi etc. play a very important role in decomposition of
pesticides in the environment. They are able to perform diverse bio-chemical
reactions at a much faster rate per unit body weight as compared to higher plants
and animals while the diversity in their species composition ensures that a wide
variety of pollutants shall be subjected to the degradation activity. Usually a
number of species have to act, each performing its own specific task to bring about
the complete decomposition of pesticide molecules. Therefore, rapid
decomposition of pesticides in the environment depends upon:

(1) The presence of suitable microbes capable of performing the biochemical

reactions involved.
(2) Establishment of contact between the substrate and microbial species
involved and induction in some cases of the the enzymatic machinary
required for the purpose.
(3) Availability of favourable conditions of environment such as pH,
temperature, moisture, nutrients etc. under which microbes may grow and
perform their activity.
In most of the living organisms a battery of enzymes is located on endoplasmic
reticulum which is a network of lipoprotein membranes within a cell. Microbial
decomposition is brought about mainly by these enzymes. In higher animals
including man the cells of the liver carry most of the function of degradation,
though other cells are also capable of performing a certain degree of bio-
degradation activity.

(X) TOWARDS SAFER PESTICIDES

It has become essential for mankind to curb the ever-growing losses caused by
insects, pests and unwanted herbs to feed an ever-growing human population. The
chemical methods of insect pest and weed control appear to be a convenient
solution to the problem. However most of the pesticides and related chemicals are
violent poisons which in addition to suppress the pestilent organisms also harm
non-target organisms. Apart from toxicity and threat to the environment the
unequivocal demonstration of carcinogenic, teratogenic and mutagenic action of
many pesticides adds a frightful dimension to their continued use.

Needless to say, all of the pesticide formulations in use these days are not so
dangerous. A large number of pesticides are rapidly degraded in the environment
or in the living organisms to yield simple non-toxic constituents. When used
judiciously much of the harmful consequences of application can be avoided.
However, due to ignorance or economic considerations, a large number and
quantity of such pesticides are freely used which produce an array of immediate
and delayed tragic consequences . For example, compounds like DDT, Gamexene,
Toxaphene etc. and the whole assortment of organochlorine derivatives are highly
persistent chemicals which stay in toxic state forlong duration of time and are
shown to cause carcinogenic, teratogenic or mutagenic effects. But their long
lasting action and low cost are the chief reasons for their continued use.
Organophosphate derivatives and carbamates are costly as they decomposed rather
faster than organochlorine pesticides and due to their nominal residual action have
to be applied more frequently.

The chemical methods of insect, pest and weed control have other drawbacks also.
Repeated application of these chemicals results in the development of resistance
and cross-resistance among the target organisms. Population resistant to one
pesticide or one type of pesticide may also develop a certain degree of resistance to
other pesticides as well. The development of resistant population’snecessitates
increasingly larger subsequent doses and ultimately a point may be reached when
the effective control becomes costly, potentially injurious to non-target organisms
and is no longer of any practical utility. A satisfactory solution to the problem,
therefore, can no longer be found in chemical methods.

A number of methods are available with which an efficient insect, pest and weed
control can be achieved. Often a single method is not enough and an integrated
approach which involves simultaneous application of more than one method, is
required. These methods can be grouped into the following major categories:

MECHANICAL CONTROL:

Hand picking, capturing and killing insects and pest by hand nets, shaking the
plants to dislodge the organisms, sieving to remove the insect in case of grains or
excluding the pest from plants by screens etc*, are some of the common means of
mechanical control. These methods, are however, labour intensive devices and
hence are often too expensive for large establishments.
PHYSICAL CONTROL:

Physical control involves manipulation of physical factors like temperature,

moisture, light, radiations etc. to curb the population of pestilent insects. 1 hese
methods are feasible in case of food grains only.

CULTURAL CONTROL:

Cultural control involves manipulations in regular agricultural practices to

minimize the level of economic injury. These methods require such adjustments as
ploughing, sowing, irrigation and harvesting time, crop rotation using resistant
varieties, pruning, stimulating vigorous growth, mixed cropping etc. Though
cheapest of all methods, cultural control is often insufficient against a number of
pestilent insects.

BIOLOGICAL CONTROL:

Insects and pest may also be controlled by introduction, encouragement and

strengthening of biological agencies which normally restrict a population within
reasonable limits. Just as the nuisance caused by rats in a house-hold can be
checked by introducing a few cats, pestilent insects can be kept under control by
introducing or encouraging their natural enemies.

Bacillus thuringiensis has successfully been used to suppress the population of

many coleopterons and lepidopterans larvae in Russia, USA and many European
countries. The spores ofB. thuringiensis are dusted or their suspension in water is
sprayed over the plants. This bacteria parasitizes a number of insects. It produces
inclusions which are crystalline proteins, termed delta endotoxins when forming
spores inside the body of host organisms. These crystals are toxic to a variety of
insects and pests. Similarly, many viruses such as cytoplasmic polyhedrosis virus,
nuclear polyhedrosis virus, entomopox virus etc. have also been tested as
insecticide. A nuclear polyhedrosis virus which parasitizes Heliothis species has
been extensively studied and is now the world's first viral insecticide being
successfully used against two serious pests of cotton. Nuclear polyhedrosis virus is
also very effective in checking the out-break of douglas fir tossock moth.

Likewise a number of predatory insects, birds, frogs and reptiles play a significant
role in curbing the population of pestilent insects. Introduction ofVedalia lady
beetle, Rudolia cardtnalis in

California as far back as 1890, effectively controlled the population of fluted scales
which were almost completely eradicated within five years from the area. The
block-headed caterpiller, Nepentis serinopa a serious pest of coconut palm has
been successfully controlled by Perisierola nephantidis which eliminates its grown
up caterpillers. Another organism which can be used to control the population of
coconut insects is Trichospilus pupivora which feeds on pupae of Nepentis
serinopa. In India sugar cane borer, Chilo sacchariphagus is effectively controlled
by Trichograma australicum which destroys eggs of C. sacchariphagus. Similarly
insectivorous birds and other such animals which feed on pestilent insects could be
reared, protected and introduced into the fields to prey on insects. In South India
ducks are allowed in paddy fields to feed on the stripped bug. Tetroda histeroides.
Giant Mexican toads were introduced in Hawaiian Island to reduce the population
of the white grubs of sugar cane.

Biological control, therefore, offers a promising means of combating the problem

of insect and pests. We do not have to apply any poisonous or toxic substances on
the insects and as such there is no danger of environmental contamination or
causing harms to non-target organisms. However, this method requires a lot of skill
and understanding of the behaviour and prey-predator relationship of the
organisms concerned which is often not available to a common farmer.

HORMONAL CONTROL:

The complicated changes which occur during the development of an insect are
controlled by hormones secreted from neuro-endocrine system of the insects. An
important enzyme present in the younger stages of many insects is Juvenile
hormone which prevents metamorphosis of the organism to adult reproductive
stage'. Juvenile hormone interferes with embryogenesis hence its application
disrupts reproductive process of the insects concerned and reduce their population.
There are a number of synthetic chemicals which have the same action, as Juvenile
hormone, on a number insects. These are called juvenile-hormone-analogues which
can be conveniently prepared in laboratory or commercially manufactured. One
such analogue is Altocid or Methoprene which is very effective against
mosquitoes, homflies, stable flies etc. and has been approved by the Environmental
Protection Agency on an experimental basis. The half-life of altocid is only two
hours and within 24 hours its chemical residue disappears from the waters treated
while its activity persists for many days.

The prothoracic gland of insects secretes moulting hormones or ecdysone which is

responsible for moulting, pupation and maturation of insects. This hormone can be
used to bring the insect in developing conditions during the wrong seasons thus
forcing them to commit ecological suicide. One such compound has recently been
isolated from Eichornia crassipes (Jalakumbhi) by scientists of Regional Research
Laboratory, Hyderbad, which is very effective against the rice moth Corcyra
cephalonica.

PHEROMONAL CONTROL:
The group of chemicals secreted by insects to attract their mate during
reproduction are termed as pheromones. A large number of pheromones have been
identified and their usefulness as bait or an attractant to collect a large number of
insects to be killed or herded away from the opposite sex has been proved. Some of
these compounds are simple chemicals like phenols which attract the grass grubs
while others have a very complicated structure. Synthetic methyl eugenol has
practically been used for controlling fruit flies.

CONTROL BY STERILIZATION:

Control of insects populations by sterilization was first introduced by Knipling in

USA in 1930. It involves collection, sterilization and release of sterilized male
insects. These sterilized individuals mate with fertile females and result in sterile
eggs. In Alabama, Florida and Gerorgia screw worm population has been
successfully reduced in this way.

RESOURCES

The following resources or references provide more information on pesticide and

the global role in its reduction and elimination
 REFERENCES

Anonymous, 1975, Petroleum in the marine environment. National Academy of

Science, Washington D.C.

Anonymous, 1979, the plant protection arsenal. Environ. Sci. Technol., 13: 1335.

Atlas R.M., Bartha R., 1973, Fate and effect of polluting petroleum in marine
water. Residue Rev. 49:40.

Baker E.L., et al., 1978, Epidemic Malathion poisoning in Pakistan Malaria

workers. Lancet,1:31.

Carson Rachel, 1960, The Silent Spring. Houghton, Mifflin, Boston.

Casarett L.J., et al., 1968, Organochlorine pesticide residue in human tissues -

Hawaii, Arch.Environ. Health, 17 (3) : 306.

Cynthia Pollock, 1987, Realizing recycling’s potential. In State of the World-1987.

Eds Brown L.R. et al., Prentice Hall of India, New Delhi.

Du Bois K.P., et al., 1957, Studies on the toxicology and pharmacologic action of
dimethoxy ester of benzotriazine dithiophosphoric acid to an
anticholinesterase agent. J. Pharmacol. Exp. Ther., 119: 572.

Dunlap T.R., 1981, DDT, Scientists, citizens and public policy. Princeton Univ.
Press, Princeton.
Durham W.F., Williums C.H., 1972, Mutagenic, teratogenic and carcinogenic
properties of pesticides. Ann. Rev. Entomol. 17 : 123.

Epstein S.S., et al., 1972, Detection of chemical mutagen by dominant lethal assay
in the mouse.Toxicol. Appl. Pharmacol., 23 : 288.

Frawley J.P., et al., 1957, Marked potentiation in mammalian toxicity from

simultaneous administration of two anticholine esterase compounds. J.
Pharmacol Exp. Ther., 121 : 96.

George J.L., Lahmann E., 1966, Pesticides in the Antarctic. J. Appl. Ecol., 3 : 155
(Suppl.).

Gold B., et al, 1981, Metabolism of a DDT metabolite via chloroepoxide. Chem.
Biol. Interact.,35: 159.

Gruzdyev G.S., et al, 1988, Chemical protection of plants. Mir Publ. Moscow
(English translation).

Haq I.U., 1963, Agrosan poisoning in man. British Medical Journ., 1 : 1579.

Headly J.C., Kneese A.V., 1969, Economic implications of pesticide use. Annals
N.Y. Acad.Sci., 160 : 30.

Hodgson E., et al, 1980, Induction of hepatic drug metabolizing enzymes in

mammals by pesticides - a review. J. Environ. Sci. Health, 15 (B) : 723.

Hunt E.G., Bischoff A.I., 1960, Inimical effects on wildlife of periodic DDD
application to Clear Lake. Calif. Fish. Game, 46 : 4.

IARC, 1983, Monographs on evaluation of carcinogenic risks of chemicals to man.

Vol. 30 :Miscelleneous pesticides. International Agency for Research on
Cancer-Lyon, France.
Kanahan C.B., 1972, Solid wastes. Environ. Sci. Technol., 5 : 594.

Kociba R.L., et al, 1978, Results of a two year study on chronic toxicity and
oncogenicity of 2-3-7-8 tetrachlorodibenzo-p-dioxin in rats. Toxic. Apl.
Pharmacol., 46 : 279.

Lukens R.J., 1971, Chemistry of fungicidal action. Springer-Verlag N.Y.

Matsumura F., Bousch G.M., Misato T. (Eds), 1972, Environmental toxicology of

pesticides.Academic Press N.Y.

Me Caull J., 1971, Question for an old friend. Environment, 13 : 2.

Me Lachlan J.A., et al, 1981, Transplacental toxicity : prenatal factors influencing

postnatal fertility. In Development. Toxicity. Kimmel C.A., Buelke-Sam J.,
(Eds), Raven Press N.Y.

Mayer F.L., et al, 1972, Phthalate esters as environmental contaminants. Nature

(London), 238 :411.

Murphy S.D., 1969, The mechanism of pesticide interaction in vertebrates. Residue

Rev. 25 : 201.

Murphy S.D., 1986, Toxic effects of pesticides. In Casarett and Doull's Toxicology
: The basic science of poisoning, III Eds. Klassen C.D., Amdur M.O., Doul
J. (Eds). Mac Millan Publ. N.Y.

Murty A.S., 1986, Toxicity of pesticides to fish. Vol. I. CRC Press Inc. Florida.

National Academy of Sciences, 1976. Pest control: an assessment of present and

alternative technology, Vol. V. Pest control and Public Health National
Academy of Sciences, Washington D.C.
Niering W.A., 1968, Environmental problems : pesticides, thermal pollution and
environmental synergims. In Effects of Pesticides, Ed. Wilson Billy R.,
Philadephia.

Peakal F.L.M., 1970, Pesticides and reproduction of birds. Sci. American., 222 :
72.

Primental D., et al, 1980, Environmental and social cost of pesticides - a

preliminary assessment.Oikos, 34: 126.

Rudd R.L., Herman S.G., 1972, Ecosystem transferal of pesticide residue in

aquatic environment. In Environmental Toxicology of pesticides Part VII.
Eds. Matsumura et al. Academic Press, New York.

Southwick C.H., 1972, Ecology and quality of our environment. Von Nostrand
Company, N.Y., London.

Street J.C., et al, 1969, Insecticide interaction affecting residue storage in animal
tissues. J. Agri.Food Chem. 14 : 545.

Street J.C., 1981, Pesticide and immune system. In Immunologic considerations in

Toxicology.Vol. I. Ed. Sharma R.P., CRC Press, Florida.

Von Miller, et al, 1977, increased incidence of neoplasm in rats exposed to low
levels of 2-3-7-8 tetrachlorodibenzo-p-dioxin. Chemosphere, 6 : 537.

Vas J.G., et al, 1983, Methods for testing immune effects of toxic chemicals:
evaluation of immunotoxicity of various pesticides in rats. In Mayamoto J.,
Keaney P.C., (Eds) : Pesticide chemistry, human welfare and the
environment. Vol. 3 : Mode of Action : Metabolism and Toxicology.
Pergamon Press, Oxford.