Embed Size (px)
Citation preview
CliAPTER - I
INTRODUCTION
•Kan is horrified by the thought of a nuclear war, but
careless of the fact that he is at war with nature•.
- E.J. Ferguson-Wood.
We inhabit a natural world of amazing beauty, o~
extraordinary complexity, much of it too easily disrupted
by our onslaughts and interferences. Many of ua are
undoubtedly concerned at the awful spectre of nuclear war.
Yet it is the terrible attrition we are causing to our
natural systems that poses the moat certain threat to
survival.
Our planet is poised on the brink of an unprece
dented ecological catastrophe. Deserts are advancing
where ever deserts are. .Foresta are being destroyed at
an alarming rate where ever forests are. Lakes, rivera
and even seas are being degraded and polluted far beyond
their natural •self-purifying" capacities. Mark Twain
once said in his inimitable style •water taken in
moderation will not hurt•. He would have hesitated a
thousand times before recommending even moderate quanti
ties if he had only seen some of our river waters of
today which are so grossly polluted that no self
respecting fish even would care to be found in tliem.
1
Soil ia contaminated by cheaicala, radiation and rubbiah,
and perhapa moat ainiater ot all, the very air we have to
breathe ia becoming dramatically altered, tor the worae
and air, like diaeaae, knowa no :trontiera. The catalogue
of diaastera which man is intlicti.ng on the Earth 1a a
grim one which growa almost daily.
The maximum extent ot our environment corresponds
more or lesa to the space available to us in the thin
layer o£ biological activity which covers the planet
Earth like a frail akin and which we generally call the
biosphere. Various demands are made ot this environment.
It is a sobering thought that the levelling processes at
present taking place in the biosphere are chiefly the
consequence of human activity, the more so because the
size ot the global population and hence the influence
which the human species has on the environment iS increasing
in a disquieting, not to say frightening manner. Some
human activities upset symbiotic relationships with
nature so that exploitation of natural resource& begins
increasingly to look like over exploitation. At the same
time there are tears, or there is evidence, that develop
ments in the use ot chemicals in agriculture, in industry
and in other sectors ot our society have a similar form
of inflation built into them, so that they too will
eventually contribute to the exhaustion of natural
resources.
2
The over-exploitation of the en vironaent due to
man's present search tor recreation, for example, brings
with it a gradual impoverishment llhich ia only aekDowleciged,
when much has already been lost for good.
ENVIRONMmTAL POLLUTION AND POLLUTANTS
•Environmental pollution• or •the spoiling of
natural assets• can be defined as •touling the environment•
or • unfavourable alteration o! our surroundings, wholly
or largely aa a by-product of man• a action through direct
or indirect effect of changes in energy pattern, radiation
level, chemical and physical constitution and abundance
of organism. These changes may affect man directly or
through his supplies of water and of agricultural and other
biological products, his physical objects or possessions
or his opportunities tor recreation and appreciation of II
nature (1).
The slide towards Environmental collapse is already
well advanced: that is hardly any longer in dispute (2-7) •
Many research institutions and organi~ations abroad and
in India like Agricultural Chemical Approval Scheme (ACAS),
Environmental Protection Agency (EPA), EnvironmEntal
Research Committee (ERC), Food and Agriculture Organiza
tion (FAO), Food and Drug Administration of USA (FDA),
International Agency for Research into Cancer (IARC),
Indian National Man and Biosphere Committee (MAB), Int...
grated Pest Management (IPM), National Institute of
Occupational Safety and Health in USA (NIOSH), National
3
Environmffltal Engineering Research Inst1 tute (NEERI),
United Nations Environment Progr..-e (UNEP), World
Health Organization (WHO), etc, are contributing a lot
for the control and measurement of the level o! pollution
in the environment,
Pollution has many forma ranging from chemical
pollution to that arising from dumping of waste or refuse
about the countryside, It can be broadly categorised
into Air, Water, Noise, Thermal, Radiation, Agricultural,
Marine and Pesticide pollution (8-14), The major sources
of pollution and types of pollutants emitted !rom them
are illustrated in Fig, 1 and Table - I, respectively,
TABLE - I
SOURCES OF POLLUTION AND POLLUTANTS ( 15-17)
------------------------------------------------Sources Pollutants ---------------------------- ------------------·----Industrial
Domestic
Transportation
Agriculture
Smoke, dust, so2, N02 , F-, phosphate, heavy metals, explosives, pesticides, and fertilizers.
Smoke, dust, so2, co2 , organic wastes, detergents, oils, etc.
No2, so2 , aldehydes, hydrocarbons, o11, lead, etc.
Fertilizers, pesticides and organic matter.
Cigarette smoke N02, CO, Cd, Ni, n1 trobenzene, benzo(a)pyrene, etc.
-------------------------------------------------------
THE ENVIRONMENT UNDER ATTACK ThL· ~lnhal~.·nvirunmc:nt c:.m ht• hrokl·n ~.town lllhl
thrL'l' m.tm t·knu:nt"- land, w:au:r :uulair I hrou~h mar tbily ou·uviciL'!., we.· m:uugt' 10 pollutL' .111d (Uiltallllll.tll' all thH'l' datfl'fl'lll d .. ·nH.'nt'. If 11
c.:nntinuc-s. tlu: dama~~.· r.nN.·d hy tim 1113)' hl'fUilll' irrl'Vt'r)lihh.•.
POLLUTION FROM ENERGY PRODUCTION.~-~~ The need tor large supplies of energy generatn pollution on a huge scale. Energy derived from to&sil fuels contaminates the atinosphere, white nuclear power threatens a1r, water and land.
INDUSTRIAL AIR POLLUTION ____ / The manufacture of many of the products we use in our homes·· especially plasticsproduces serious pollution, as mdustrial chemicals are released into the atmosphere.
WATER POLLUTION --~~~i~i~~~~~ Water is polluted boU~-by Industrial and by domestic users. like &It. water disperses contammants ao that they affect a wide area. and reach places far tram their point ot origin.
POLLUTING THE SOIIL~-k~ The burial of household an<l mdustrial waste pollutes lhe ground. and also produces chemical run--on which may reach the groundwaler reservo1rs that are used for publiC water supplies.
Th•s rclat•vely new lorm Of poiiUIIOO IS 8 by-product of atmoa-phenc contam•nat•on The gases that are released mto the &If from cars. fadones &nd power slaltOM read wtth atmosphenc mOisture to lorm ra.,.. whtch rs potentially lethal to trees
TRANSPORT POLLUTION Foss• I fuels prov1de ttle chief sources of enefrgy lor transport. They a .. e a mar or source ol air pollution. one whiCh over the last two decades has grown enormously
~~;;f--~ AGRICULTURAL CHEMICALS The food we eat is prepared from crops grown with the aid ol a w•de range of agricultural chenucals. These chemicals may end up 1n our lood and m the water supply.
GROUNDWATER CONTAMINATION Much ollhe world's fresh water hes m natural reservoirS deep underground. These are slowly becoming contaminated by dissolved chemtcal:s whtch are washed through the ground.
Fig. 1. TYPES OF mVIRONMENTAL POLLUTION.
5
>
Toxic Subatanceo:
Toxic aubstancea are defined as •materials which
kill or damage biota•. The effect of a toxic substance
depends on the concentration and duration of exposure.
For many poisons, over a wide range of concentrations,
these two factors act reciprocally: a low concentration
over a long period has the same effect as a high concen
tration for a short period (18). It is, therefore,
necessary to establish allowable concentration limits and
reliable methods for analysis. The "Threshold Limit
Value" (TLV) by American Conference of Governmental
Industrial Hygienists (ACGIH), and "Maximum Arbei tapletz
Konzentration Values (MAK) by V D I Committee of German
Research Association are the values being published on the
basis of known data on the toxic effects of a contaminant.
This is a limit value for a given substance or material
to which a worker can be exposed for 8 hours a day, without
showing any adverse effect on health. Values are given
6
for pure substances and not for the mixture of toxicants( 19).
In the presence of mixture of toxicants their total
effects are either enhanced or decreased which are termed
as "synergism" and 11 antagonism" respectively (20,21). For
pesticides the commonest measure of toxicity is the LD50 test. The Ln50 is defined as the weight of active
ingredient needed to kill 50 percent of the test animals
exposed to the pesticide. Similarly the toxicity of
pesticide on aquatic organism is often expressed as the
median lethal concentration (Lc50) tor a given period
of exposure, for example, 24, 48 or 96 hours (22-24),
Certain groups of compounds tend to qualify aa
toxicants and are classified es EEC 'Black' and 'Grey'
list substances (Table- 11){18). The moat dangerous o~
these forms are the substances of 'Black list' while
those \olhich are considered to be less dangerous are
'Grey list' substances.
Similarly, Environmental Protection Agency, (EPA,
USA) has declared a list of one hundred and twenty nine
priority pollutants generally encountered in the indus
trial waste waters (25). These pollutants are divided
into eight groups:
1. Metals 2. Asbestos (Fibrous) 3. Total cyanides 4. Pesticides 5. Compounds extracted under acidic conditions 6. Compounds extracted under alkaline/
neutral condi tiona 7. Total phenols 8. Purgeable compounds.
To meet the need of ever-growing population, the
developing countries seem to have no alternatives but to
enhance their activities pertaining to agriculture,
forestry and horticulture net work expansion, This has
resulted in search of better and mre powerful pesticiC.es
and fertilizers. Among the various groups of toxicants
7
TAI!Ll - II
CLAS,•l>'~CAl'lON OF 'IQXlCb!jTS ( 1@)
(U:C 'BLACK LlST' IJI'lJ 'VHJ:.Y l.l§T' Sli8!)T/.NCl.S)
-----------------------------------------------------------------------------------------Liot No, 1 (Black Liat)
The aubatancee on thia list were selected ~inly !or their toxicity, peraistenc• or bioaccuaUlation.
1. Orcanohaloaen oompounde und substancee which may 1'or111 auch coapounda in the aquatic C).Vironrnnt.
2. Organophosphorus compounds
3. Orgenotin co11pound.a
4. Substances, the carcinogenic activity o! which ia exhibited tn or by the aquatic environaent (substances in list 2 which are carcinogenic are included here)
5. Mercury and 1 ta co mpounda
6. Cadmium and 1 ta compounds
7. Persistent mineral!\~ oils and hydrocarbons o! petroleum
8. Persistent synthetic subs~ances
Liat N0 • 2 (Grey List)
These substance• are regarded as leas dangerous than those of list 1 and the im.-act aay be local.
1. The following metalloids/metals and their compounds:
1. Zinc 2. Copper 3. Nickel 4, ChroaJ:u• 5. Lead 6. Selenium 7. Ar6en~c B. AnU.Ony
9. Molybdenum 10. Titanium 11. Tin 12. Bariua
13. lleryllium 14. Boron 15. Uranium 16. Vanad1ua
17. Cobalt 18·. Thelium 19. Tellurium 20. Silver
2. Biocidea and their derivatives not appearing in List 1.
3. S\lbatancea which have a deleterious effect on the taste and/or smell of produeta for bU.IIan consumption derived from the aquatic environment and co•powda lle.ble tc
give rise to such substances in water.
4. Toxic or persis~ent organic compounds of silicon and substences ~icb. may give riae to such compounds in water, excluding those which are biologically harml.~a or are rapidly converted in water to harmless substances.
5. Inorganic compounds of phosphorus and elemental phosphorus.
6. Non-persistent mineral oils and hydrocarbons of petroleum origin.
7. Cyanides, fluorides.
8. Certain substances \Jihich may have an adverse effect on the oxygen balance.
particularly ammonia and nitrites.
9
listed above, the commonly used pesticides are considered
to be the most toxic - compounds and are blamed for
pollution of water, air and soil.
"PESTICIDES AROUND THE WRLD"
Lord, what fools these mortals be.
- Wm, Shakespeare, A Mid Summer Night's Dream.
Man's knowledge bas made him foolish and he is
playing with his environment thoughtlessly. Synthetic
pesticides have been so thoroughly distributed throughout
the animate and inanimate world that they occur virtually
everywhere. The reckless and irresponsible use of these
pesticides in the lllOdern world has led to much greater
emphasis on the possibility of serious environmental
pollution arising from their use. Rachael Carson has
dramatically highlighted the environmental contamination
caused by indiscriminate use of pesticides in her book
"Silent Spring" (26). There had been numerous signs of
warning in advance which can easi1y be traced to a variety
of reasons: increasing production and use of, and
exposure to pesticides; occasional but numerically
increasing and accumulating accidents through misuse and
careless overdosing; observations of untoward effects on
wild life and other sectors of man's environment, etc,
Indian pesticide industry has made rapid strides
for the past three decades matching with ever-increasing
9
10
demands. The total installed capacity has increased
leaps and bounda from 8,620 tonnea in 1960-61 to the
present installed capacity of 86,670 tonnes (27) ss shown
in Fig. 2. The Government o~ India has included the
pe~ticide industry in the core sector because of its role
in the extensive application for plant protection measures
and public health. Keeping in view of the environmental
impact ca~sed by the pesticide industry, some pesticides
are being phased out whilepew ones are being added to the
list of registered pesticides. Though the total production
of pesticides in India is not significant when compared
to the world production (Fig. 3)(2), pollution control
agencies are greatly worried over the problems created by
the indiscriminate discharge of pesticide waste water on
land and rivera. Due to this the sweet fruits of
the green revclution have been accompanied by a bitter
one in the form of water pollution, which cause delete
rious effects on aquatic organisms.
Pesticides and their effects:
"Pesticide" (pest control agent) or "Biocide• is
a polite word that has come to replace the old English
word "Poison", which doesn't sound so nice. The whole
purpose of pesticide is to control various pests. Most
of them are very slowly biodegradable, persistent and
remain in the environment for a long period causing
harmful effects on human beings, animals and plants.
8,6 20
19 60
TOTAL P EST.lC!D E S
2 4,32 5 ton nes
tonnes
58,980 tonnes
tonnes
19 70
86,6 70 ton nes
DDT & BHC
1980
FIG.2..RISING USAGE OF PESTICIDES IN INDIA.
SOURCE: INDIA TODAY JUNE 15,1989 .•
11
1989
THE BIOCIDE EXPLOSION ' J \ ' 1 I II' I I ~t I \\ l Ill \ \ l II~. tit, I'' ' ,, h h \II Ill L " I) h II hI, ' \\ 11.11 I hnr l 'tllll.ltl'd J'l P<\111 II• Ill ~~·\ l h .Ill II\ 1 f I h' .11 1\
l\\11 dl'Lhln Ahhough illl di!ll 1\l'l'' ul hHI\Id•
,j,,lnhnl hcH 111.1~~ up ilh' hulL 11! the!\~· .tpphnltu 1 rop ... l'\'l'll Ill\ Hl' l lll'IIIH .1\\ lll.l \' ill' ll\l'll (II l 0111h,1t
, rop' 'utkr111~ t'rtllll In' uHiliiHlll pt''" ~~h h ·'' lll'III.II011l· \\ llrlll' .uhllllltl''
' L',IJ,Ul!tJr.d pt>hLIII\ h.l\ !hill Pill 1d !Ill ~~~~~t'•,[
.,,,, th .HLI' ntthc t lunnt .d uJdu,tr\ .. 1nd tl,d." k"
'Hrtl\ lit \\ JthcHII lht·tr \{Oft• ul jl<l)\011\ \\ 111111~~ \0 ht• :··.lltllllhl'[UJd 'Jht\Lihk\hU\\\\\h,lfdh IJI.IIIlt\pt''
:i'h'thh .HV.JJJdwh.,tdktt,th,, h.tvv II tl"''h'''''
FUNGICIDES
What they kill Fung•cides are used to kill the often mtcroscopic fungi that 1nfect growtng crops, frutt and stored seed These fungt tnclude the mildews, rusts, pin· moulds and yeasts
What they contain Most fung1C1des are based on :ompounds contatntng metals such as copper and somettmes :nercury. or on hydrocarbons conta1ntng sulphur
Health hazards Fungic1des are often sprayed directly onto the part of a crop that IS destined to be eaten 7races of fung1cides are •requently found on fruit and vegetables and these can build up w1thm the body with as yet unknown consequences
WORLDWIDE USE -:-tle use of fung1c1des w111 have grown by r>early 20 t1mes 1n the same number of }'ears
t-niiiJOnS of tonnes)
0.66
1972 1980 1990
What they kill Insecticides kill aphids, weevils and other 1nsect pests, and are used on grow1ng crops, and to a lesser extent on stored grain. As well as k1ll1ng pests, they often also kill the 1nsect predators wh1cn feed on them
What they contain The most commonly-used msect .. 1c1des are the organophosphates (compounds conta1n1ng phosphorus) and chlonnated hydrocarbons (compounds conta1n1ng chlorine)
Health hazards Many 1nsechc1des have proved very perSIStent They do not degrade rapidly and can be passed on in food to cause cond1t1ons such as liver failure.
WORLDWIDE USE The use of insect1c1des Will have 1ncreased by nearly 17 t1mes 10 two decades
4.8
1972 1980
18.0
1990
HERBICIDES
What they kill Herbicides kill plants. They may be non-specific (killing all plants when land is cleared) or they may be specific, for example killing broad-leaved weeds growing in cereal crops
What they contain Herbicides are a group of highly varied chemtcals Many are po1sonous mim1cs of natural substances w1th1n plants Once they are absorbed. they kill plants by block1ng the1r metabolism.
Health hazards Some herbicides are deadly 1f accidentally consumed Others may cause non-fatal illnesses when eaten 1n food 16.0
WORLDWIDE USE The use of herb1c1des w11\ have grown by about 15ttmes 1n two decades.
4.08
1972 1980 1990
Fig. 3. WORLDWIDE USE OF PESTICIDE.
12
Pesticide is defined sa any chellical substance or llixture
of aubstencesintended for preventing, repelling or migra
ting insects, rodents, fungi, weeds end any other forma
ot plant or animal life selectively (23,31). Pesticides
can be classified in a number of different ways:
(1) by their target:
(i) Insecticides: pesticide used against insects.
13
(ii) Fangicides: Pesticide used against fungi end moulds.
(111)
(iv)
Rodenticides: Pesticide used against mice and rats.
Algaecide&: Pesticide used against algae.
(v) Molluscicides: Pesticide used against slugs
and snails.
(vi) Acaricides: Pesticide used against spiders and
mites.
(vii) Herbicides: Pesticide used against weed and
grasses.
(viii) Nematocides: Pesticides used against nematodes
or eel worms.
(2) by their chemical nature:(natural organic compounds,
inorganic compounds, organophosphates, chlorinated
hydrocarbons, carbamates, organometallic, etc.).
(3) by their physical state:(dusts, dissolved solutions,
· suspendedsolutions, volatile solids, etc.) or
(4) by their mode of action:(stomach poisons, contact
poisons, fumigants, etc.),
A wide range ot compounds are used sa pesticides.
They can be broadly classi!ied according to their general
chemical nature into several principal types as shown in
Table - III.
Pesticide contamination has !ound ita way to
every corner of our environment - soils (32,33) where
they are sorbed on minerals and other substances (34);
sediments (35) where pesticides can be further concentrated
by solvent extraction by petrochemical pollution (36),
water including drinking water, lakes, ponds, rivers,
streams and ground waters as well as the oceans (37,38);
Antarctic snow (39); even the air (40) is dirtied with
them. Many of the paths that these dangerous chemicals
follow in our environment lead back to us - our food and
to our own bodies (Fig. 4) (41,42).
Fig. 4. SOME PESTICIDE PATHS IN OUR .. EI'I VI flO N f'llENT - - .
T.ABLI:. lll 15
CHD'IlCAL CI..ASSlr'lCATlON OF 9?1'\J'ON I'LSTlCl ut.!i
---------------------------~----------------------------------------------------------Example Typical actio.'!
--------------------------------------------------------------------------------------
Organophosphorus
0 rgano ehlorin e
Carb81118te
Chlorophenoxy acid
Heterocyclic
Dithiocarbamate
Organometallic
Inorganic
Parathion
BHC
DDT
Carbaryl
2,4-D
Simazine
Thiram
Phenyl mercury
acetate (PMA)
Paris green
Jo'luorine
compound
~@ (:::zHs0 >z - r-o - Q - Nv2 Insecticide and 1-caricide
Cl
Cl Insecticide and
"¢ 1-caricide
Cl Cl
(;l
Cl -@-~-@- Cl Insecticide and Acaricide
CC1 3
0-QC.NH.CH3
lnsecticJ.de
I
00 C1
Cl - @-o - .CH2-co2H Herbicide
N N .
c2H5NH@ NH.C2H
5 Herbicide
N
(CH3) 2N .cs.s.sc.SN-(CH3) 2
Fungicide
@- Hg.OOC-Oi3
. Fungicide
Insecticide
Inse-ctic:1d.e
------------------------------------------------------------
HAZARDS OF PESTICIDES:
Pesticides in tbe form of sprays, dusts and
aerosols are now applied almost universally to farms,
gardens, forests and homes - nonselective chemicals that
have the power to kill every insect, the 'good' and the
'bad' to still the song of birds, the leaping of fishes
in the streams, to coat the leaves with deadly film, and
to linger on in soil - all this though the target may be
only a few insects or weeds.
In 1972, the WHO's ExPert Committee on Insecticides
estimated that there were approximately 500,000 cases of
pesticide poisoning every year. About one percent of
these were thought to result in the victim's death, even
in countries 'where medical treatments and antidotes are
readily available'. In developing countries where the
pesticide use is still increasing at an average rate of
12.5 percent a year, the annual accidents levels are
running at well over a million people, and deaths approach
ing 20,000 a year (22).
When these pesticides are discharged into natural
waters, they cause massive fish kills (24,43) and poison
the aquatic flora and fauna. When they reach the ocean,
they contaminate fish, prawns and other marine life (44).
People who consume the contaminated fish and prawns
accumulate the pesticides in their body tissues. Far
more serious is the possibility that pesticides can also
have long term effects on our own health, and on the
health of future generations as Albert Schweitzer has
said "man can hardly even recognize the devils of his
own creation" • Three • chronic effects• are usually
included in this category: carcinogens, teratogens and
mutagens. Some pesticides which are considered to show
these effects are shown in Table- IV (22,45,46).
Pesticides and kids:
A new study charges that pesticide residues pose
an 'intolerable' risk to children. The Natural Resources
Defence Council alleges in a new report that children are
exposed to dangerous levels of pesticide residues 1n
fruits and vegetables may lead to cancer or subtle neuro
logical effects. The worst offenders are some of the
foods that kids like best, including fruity dessert:
banana or orange, fruit juices and other sweetslike
colourful jalebis, barfis, toffees, etc. (22,27,47).
Pesticides in our food:
It is surely one of the great ironies of our time
that our farmers scarcely eat their O'Nn produce. In 1983,
the British Association of Public Analysts dropped a quiet
bombshell with their report "surveys of Pesticide Residues
in Food~. They found that more than a third of the fruits
and vegetables they sampled contained detectable amounts
of pesticide residues as shown in Table- V (22). A
current survey on the pesticide residues in Indian food
has also showed contamination, including •reportable'
TABLt. 1Y
Oit~"l< LioT OF PESTlCliJ"- HAZA!!pS (22 .~),46)
---------------------------------------------------------------------------------------·---------
Peatioide
c 0
;l • u -< ... ... • • • .... u
li • -< 0 u.
• li .. 0 c -< u
" • u
• i .. :1 il ..._ 0 ., • " • ••
.. ~ • ., -.:: " ....
• ~ • .... 0.
~ • .. !
• 0
i .. • ... • ~ • ..
• g ;: 0 ... !I • :.
-------------------------------------------------------------------------------------------------Acrylonitrile
Al41carb
Aldrin
Alii traz
A ramie
Atrazine
Benoaryl
Cap tan
Carbaryl
Carbo!'uran
Chlordane
2,4 D
DDT
Dichlorovoa
Dieldrin
Diquat
Endosul.fan
Endrin
Galllla BHC
Hydrogen cyanide
Malathion
Paraquat
Parathion
Phenyl aercury acetate
Propoxur
Quinolphoa
2,4,5,-T
Zineb
I
A
H
H
F
I
l
I
H
I
I
I
H
I
I
I
H
F
I
I
H
F
• • • • • • • • • • •
• • • •
* • • • • • * • * •
• • • • •
• •
• • • • • •
• • • • • • • • • • • • • • •
• • • • • • •
• •
• • • • •
• • * • • •
• •
• •·
• • •
•
• • • • • •
• • • •
• • •
• • • • • •
• • •
• • • • • • • • • •
• •
• • •
• • • •
•
• • • • • • •
• • • • • • •
• • • • • • • •
• • •
• • • •
• •
•
Key: H • herbicide, F • Fungicide, F 1 • Fumigant, I • Ineecticicle, A - Acaricide,
+ Carcinogen, Mutagen/Teratogen include both known and suspected.
• • • • •
• •
• •
• • •
•
• •
•
TABLE V
PESTICIDE CONTAMINATION IN FRUIT AND
VEGETABLES (22)
---------------- ·--------------------------------------Fruit/ Number Number Number o! vegetable sampled contaminated different
pesticides present
-------------------------------------------------------Apples 42 9 5
Black currants 11 4 2
Grape fruit 13 2 2
Grapes 23 6 6
Lemons 12 3 3
Oranges 20 8 5
Tomatoes 33 11 6
Beans 4 1 1
Beet root 1 1 1
Cabbage 17 2 2
Carrot 4 2 2
Cucumber 16 6 2
Onions 3 2 1
Peppers 5 1 2
Potatoes 5 5 2
-------------------------------------------------------
levels o! lindane and other organopbospherus pesticides,
which reach one of the highest levels in the world(22,27).
Maximum acceptable daily intake, tolerances on some food
items and common methods of the determination of some
commonly used pesticides are summarized in Table - VI
(48-109).
Growing Pesticide Hazards:
Incidents of environmental. hazards due to pesti
cides are widely reported (22,110-116). Malpractices in
spraying have been a major cause of the high residue levels
and ineffective controls as well as a lack of strict guide
lines have worsened matters. Poisoning effects may be
worse in people suffering from malnutrition. Dr. Y.R.
Reddy of Niloufa Children's Hospital in Hyderabad, has
pinpointed one of the main reasons for the vast toll of ((
pesticide poisoning in the Third World; safe-guards are I)
usually appallingly inadequate. In this context our
former Prime Minister late Mrs. Indira Gandhi has once
said that 11 Environmental sat eguards are irrelevant:
Poverty is our greatest environmental hazard"(22,113).
In India, the well-documented incidents are those
of (i) "Handigodu Syndrome" at Handigodu in Karnataka
where people, who ate crabs and fish; contaminated with
folidol and endrin were permanently crippled (117).
(ii) An outbreak of epilepsy amongst 150 people in
Sitapur, Lakshmipur and Khetri District of U.P. in
1977-78, due to consumption of wheat contaminated with
1'ABU. - V1
MAXIMUM ACCEPTABLE_DAILY INTAKE, TOLERANCES AND COMMON METHODS OF Ju\ALYSIS Or' SO~·!:. IMPORTANT I'ESflCl!..!o~
Pesticide l"~aximum acceptable intake
(mg/kg body weight)
TLv*** (ppm or mg/m3)
* ** Tolerances and Guideline levels (ppm)
Acute oral LD50 ( mg/kg)
Animal COIDIDOn methods Ret rrenc ••
---------------------------------------------------------------------------------------------------------------------------------1 2
Acrylonitrile
Aldrin 0.0001
Arsenic (as calcium or lead arsenate)
'Y oHC (Lindane)
Cap tan
Carbaryl
Carbon disulphide
0.0125
0.125
0.01
3
2 ppm
0.25 mg/m3
0.1 mg/m3
0.5 mg/m3
5 mgjm3
10 ppm
4
Vegetables 3 Grapes, cherries, plums 3 Fat of meat (cattle, 2
pig, sheep) Beans (dried) 1 Raw cereals 0.5
Apples, cherries 40 Pears 30 Citrus fruit, tomatoes 15 cucumber, green beans,
pepper t<aisins
Black berries, okra, leafy vegetablea,nuts. Citrus fruit Apples, beans, peas Poultry Rice Meat of cattle Potatoes
ltaw cereala
'0 5
10
7 5
0.5 3.0 1.0 0.2
Milled cereal products aread and other cooked
50 10
0.05 products.
- - - - - - - - - - - - - - - - - --- - - - - - -
5
40-60 93
67
35-100 (calcium arsenate) 10-50(Lead arsenate)
88
9,000
500-700 2,000
16 mgflit
6
Mouse Rat
Rat
Macr.mals
..
list
;{at
Rat ltabbit
Rabbit
7
GC Colorimetry
8
50 51
IR, GLC, Colori~etry 52-54
AAS, f\AA
Colorimetry
GC, Titrimetry, Colorimetry
Titrimetry Colorimetry
GC HPLC Co~orimetry
Colorimetry
55,56
57
56,59 60
61 62
63 64 65
66
------------------ -·- -·----1\) -
Tabl~ - VI (contd)
------------------------------------------------------------------------------------------------1 2 3 4 5 6 7 8
---------------------------------------------------------------------------------------------------------------------------------Chlordane
Chloropicrin
2,4-D
DDT
Demeton
Dichlorvos (DDVP)
Dieldrin
0.001
0.01
0.3
0.005
0.0025
o.oo4
0.0001
uithiocarbaffiates, 0.025 dimethyl (Ferbam) thiran, and ziram) Endoaul!an 0.0075
0.5 mg/•3
0.1 ppm 3 0.7 mg/m
10 mg/m3
1 mg/m3
0.1 mg/m3
1 mg/m3
0.2 mg/m3
15 mg/m3
(Ferbam~ 5 mg/m ( thiram)
- ..... ...,-.,.. ........... - .....
Potatoes, turnips, radishes 0.3 Spinach, cabbage, cauliflower 0.2 Cucumber, pumpkins 0.1 4~7-590 Rat Mangoes, guavas, papaya 0.1 Wheat, rice, maize 0.05 Beans, peas, tomatoes 0.02
Barley, Oats, wheat
Apples, vegetables, meat of poultry
Nuts, root vegetables Citrus, tropical fruits
0.2
7
1 3.5
Cocoa beans 5 Raw grain (wheat,rice,maize, 2
etc). Milled products from raw 0.?
Soyabeans, coffee Fresh vegetables Fresh fruits Meat of cattle Milk Eggs
grain
Asparagus, cabbage, cauliflower, onions, peppers Fruits (other than citrus) Citrus fruit Rice (rough) Potatoes
Tea Fruit, vegetable• Cotton ued Cotton a .. d oil nto•
2.0 0.5 0.1
0.05 0.02 0.05
0.1
0.1 0.05 0.02 0.2
JO 2
0.5 0,2 0.1
1,5 mg/lit Rabbit
375
250
9
:>6-80
87
4000 (Ferbam) 375-865 ( thiram)
40-50
Ra.t
Rat
Rat
Rat
Rat
Rat
MalliDBlB
Ret
Coloriaetry
Colorimetry
GC, Colorimetry
"!'itrimetry GLC Colo:ia:~try
IR, Colori<tetry
~LC, GC
Colorime.,ry
T1tr1metry Colorimetry
T1 trimetry uv Colorimetry (F•rbaa:, thirem)
GC, IR Golorlattry
-------- ............... -- - -- - - - - - - - - - - - -
67
68
69,70
71 72 73
74,7:>
76,77
71::,79
eo 81
82 83 84,8~
86 07
r\,) t'-)
rable - VI ( contd)
---------------------------------------------------------------------------------------------------------------------------------1 2 3 4 5 6 7 8
---------------------------------------------------------------------------------------------------------------------------------Endrin 0.0002 0.25 mg/m3 Cotton seed 0.1 IR, Ti trimetry 66
Maize oil 0.02 10-12 Rat Coloriooetry 88,89
~eptachlor 0,0005
~ydrogen cyanide 0,05 (HCN)
Malathion 0.02
Paraquat (cation) 0.0007
Parathiop
Parathionmethyl
0.005
0.001
0.5 mg/m3
10 ppm 3 11 mg/m·
15 mg/m3
Apples, Wheat, rice 0.02 Apples, peaches, fat of meat,
cherries Cabbage, cauliflower Grapes, oranges, peas Wheat, rice, milk products
(fat baris) Hilk (whole)
Pineapple(edible portion)
Raw cereals Flour
2 1
0.5
0 .1 0.05
0.01
75 6
Raw cereals, nuts, dried fruits 8 Wheat flour 2 Citrus fruit 4 Cabbage, Spinach 8 Tomatoes, turnips 3 Beans (green)·, apples 2
0.5 mg/m 3 Cotton seed 0.2 0.1
0.05 0.05
0.1 mg/m3
3 0.1 mg/m
• Potatoes Cotton seed oil Sugarcane juice
Vegetables Citrus fruit Other fresh fruit
Fruit, cucurbits Other vegetables Cotton seed oil
0.7 1
0.5
0,2 1
0.05
- - - - - - - - - - - - - - - - - - - - - - -------
215 Rat
60 Male rat
uv ColoriZLetry
GLC 142 Female rat Colorimetry
4
1,400 5,800
nab bit
net
15~-203 Rat (Paraquat dichloride) 320 Rat
(Paraquat dimethylsulphate)
6-15 Rat
GCi Ti tria;e:ry, .:o orimetry
~~ ~y
Colorimetry
Bioassay Colorimetry
Polarography Colorimetry
Polarography Colorimetry
90 66
91 t·.'
92, 9~ "". 95 96 97
98 99
100 101 f 10£
100 101.102
- - - - - - - - - - - - - - - - - - - - - - - - - - -
N c...>
Table - VI (contd)
---------------------------------------------------------------------------------------------------------------------------------1 2 3 4 5 6 7 8
-----------------------------------------------------------------------------------------~--------------------------------------
Phenyl mercury ecetate (PMA)
- 0.01 mg/m3 - - - c;c, Coloria.etry 1C3,104
2,4,5-T 0.05 5 mg/m3 - )00 Rat uv, Colorin.etry 105,106 100 Dog
Toxaphene- - - - 60-80 Rat Colorimetry 107. 108
Zineb - - - 5000 Rat Ti triml'try 66. 109
---------------------------------------------------------------------------------------------------------------------------------* Unless otherwise indicated, the tolerance residue limits should apply as soon as practicable after harvest to the rev
agricultural products II:.OVing to commerce and prior pro.cessing.
** Guideline levels included to assist administering authorities.
*** The ppffi and mg/m3 can be calculated from the following relation:
ppm 1 mg/m3 x 22.4/mol. wt. at N. T. P.
Note1 BlAnk apAce• innicate no recommendation• made.
Gamaaexane ( 117). (iii) Contallination of wheat with
parathion, a highly toxic organophosphorus peaticide,
led to 100 or more known deatha in Kerala in 1958 (22).
(iv) A massive leak of methyl isocyanate, an intermediate
product of well known pesticide carbaryl from tbe Union
Carbide Plant, Bhopal, M.P., killing 2- 5000 people in
1984 (22,113).
Apart from the incidents of pesticide poisoning
in India, many other accidents have also been reported in
other countries, including developed countries such as
330 deaths in Turkey from eating seed grains treated with
hexachlorobenzene, 80 deaths in Colombia from eating
flour contaminated with parathion, 17 deaths in Mexico
from eating sugar contanining parathion (11), mercury
poisoning in New Mexico, Japan and Iraq (3,11,22), damage
caused by the defoliant 'Agent Orange' (a mixture of
2,4-D and 2,4,5-T) in Vietnam (127), and the accident at
Union Carbide Plant, Virginia, USA (22}, etc.
There are about 23 technical grade pesticide
manufacturing units in India and about 200 units in the
small-scale sector making formulations. Despite the
massive quantities of pesticide production and undoubted
advantages in their usage, concern has been expressed at
the potentially harmful effects of using pesticides which
are stable and can accumulate in man and his environment.
It is therefore very important to have sufficient infor
mations on the characterisation, pollution effects, treat
ment disposal practices and methods for their identification
and determination.
25
26
IMPORTANCE OF ANALYTICIJ, CHEMISTRY
IN THE ANALYSIS Oio' PESTICIJ:;ES
The increasing awareness about the significances
of the presence of small amounts of chemical species in
our surroundings, the contamination of the human environ
ment with residues of persistent pesticides has received
attention all over the world and stimulated research to
develop and refine analytical techniques for the esti
mation of such residues (118-120). Soils form an
environmental reservoir which is continuously contaminated
by usage of pesticides for agricultural purposes. Pesti
cide residues in soil can move into the atmosphere, water
or living beings and give rise to several adverse effects,
hence the analysis of pesticides on a variety of commo
dities would be of great value. The analysis is often
complicated by chemical changes undergone by pesticides
when absorbed into living tissue, adsorb on to the soil,
or exposed to u1 traviolet light or sunlight.
There are five basic methods of pesticide
analysis (24):
(a) Functional group analysis: Methods involve colori
metric assay of a particular group.
(b) Biological test methods.
(c) Chromatographic methods: These include gas, gas
liquid and thin-layer chromatography.
(d) Spectrophotometric methods: These provide
evidence of identity and can also in ideal condi
tions be used in quantitative analysis.
(e) Radiochemical methods: Included under this head
ing are neutron activation analysis, direct
isotope dilution method and the more sophisticated
double isotope derivative analysis technique.
Most of the pesticidal residue estimation proce-
dures currently employed ere quite elaborate and require
expensive instruments (24,121,122). Coupled with the
requirements of high purity reagents, adequately trained
manpower and expert instrument maintenance, it is diffi
cult to use such methods in remote areas or developing
countries (119). Moreover, high sensitivity provided by
sophisticated methods of residue analysis is not required
in all situations and the need for simple and inexpensive
screening procedures has been emphasized by several
workers ( 119, 123). The use of affordable and rapid
determining methods can help not only in analysing
relatively large number of samples at laboratories with
limited facilities and manpower to indicate dimensions
of the problem of environmental pollution in a region,
27
but also aid in recognizing samples containing residues
that are high enough to require further, more accurate
quantitation (12§-126). Hence, in the present work,
because of its speed, simplicity and relatively low cost,
the spectrophotometric methods have been chosen as an
attractive alternative over other methods of determination
SCOPE AND SUP't!ARY OF THE PRESENT 'tlORK
Analytical chemistry playa a significant role in
obtaining the data upon which pollution control regulations
are being based, therefore analysis of commonly used
hazardous pesticides is o! great importance. In the
present investigation new and simple spectrophotometric
methods have been developed !or the detection and determi
nation of some commonly used pesticides. In the foregoing
discussion, the pollution problem due to pesticides, their
sources and effects have been discussed briefly.
In Chapter II, a new extractive spectrophotometric
method is described for the determination of organo
phosphorus pesticides. Method is based on the reaction
of phosphorus present in organophosphorus pesticides with
molybdate in acidic medium to form molybdophosphoric acid
which is reduced with malonyldihydrazide to give molybdenum
blue. Molybdenum biue is extracted in n-butanol. The
proposed method is simple, sensitive and colour is stable
for 2 days. Proposed method has been successfully applied
for the determination of organophosphorus pesticides in
various vegetable samples.
In Chapter III, parathion is determined spectro
photometrically as an azo dye using 1-naphthol as a new
coupling reagent. The reaction is based on the reduction
of parathion with zinc/HCl to amino parathion, which is
subsequently diazotized and then coupled with 1-naphthol
to form an orange coloured dye. The method has been easily
applied for the determination of parathion in various
vegetable and soil samples,
In Chapter IV, a new aimpl e spectrophotometric
determination of "f BHC, a chlorinated pesticide, ia
described, Method is baaed on the dechlorination of "1 BHC
with zinc/ acetic acid into benzene, The benzene thua
formed ian nitrated to m-dinitrobenzene, The m-dinitro-
benzene is then reduced to m-phenylene diamine, diazotized
and eoupled w1 th N ( 1-naphthyl) ethylene diamine hydro
chloride to form a purple coloured dye, Method has been
successfully applied for the determination of Y BHC in
polluted water and cereals.
In Chapter V, a new chromogenic reagent, p-amino
acetophenon~as been used for the spectrophotometric
determination of carbaryl, a pesticide of carbamate group,
The reaction is based on the coupling of carbaryl with
diazotized p-aminoacetophenone in a fairly alkaline
medium to produce a purple coloured dye. The method is
rapid, sensitive and has been successfully applied for
the determination of carbaryl in grains and insecticide
formula tiona.
In Chapter VI, a simple spectrophotometric deter
mination of acrylonitrile, an important fumigant, is
described. The acrylonitrile from air is absorbed in
dilute potassium permanganate and subsequently Oxidized
to cyanid~. The cyanide thus .!orm~ 1a convt:rted to
cyanogen bromide with bromine and reacted with pyridine
to form glutaconic aldehyde ~ich ia subsequently coupled
with sulphanilic acid to give a yellow-orange polymethine
dye. Method has been applied for the determination of
acrylonitrile in biological samples such as urine, blood,
cystein and saliva.
I~ Chapter VII, a spectrophotometric method for
the determinatiox#>f hydrogen cyanide, a well known fumi
gant, and its application in biological samples is
described. The reaction is based on the absorption of
hydrogen cyanide from air into a dilute sodium hydroxide
solution. The absorbed cyanide is converted to cyanogen
bromide and reacted with pyridine to form glutaconic
aldehyde, The glutaconic aldehyde so formed is condensed
with sulphanilic acid to give a yellow-orange coloured
dye.
In Chapter VIII, Part A, a new spectrophotometric
method for the determination of endosulfan is described.
Method is based on the liberation of sulphur dioxide
from endosulfan which is subsequently absorbed into an
absorbing reagent, malonyl dihydrazide and estimated by
using p-aminoazobenzene and formaldehyde in an acidic
medium to give a pink coloured dye. The proposed absorb
ing reagent has an absorption efficiency of ---' 100 %.
Method has been successfully applied for the determination
of endosulfan in river water and soil samples.
In Chapter VIII, Part B, a simple method !or the
detection of endosul!an ia described. The reaction is
based on the liberation of sulphur dioxide !rom endosul~an
and its subsequent estimation using zinc acetate, sodium
nitroprusside and malonyldihydrazide (MDH) to !orm e
brick red coloured sulphite nitroprusside ion
[Fe (CN) 5 NO so3 J 4-. This reaction has been success
fully applied to detect and semiquantitatively determine
the endosulfan in soil and water.
In Chapter IX, a simple field test for the dete-ct
ion of phenyl mercury acetate (PMA) is described. The
method is based on the ligand-exchange reaction, e.g.,
hexacyanoferrate (III) [K3 Fe (CN) 6 ] exchanges cyanide
ions with chromogenic organic ligand, succinyl dihydro
xamic acid ( SDHA) in presence of mercury. In the
reaction the colourless SDHA reacts with yellow
K3 Fe (CN) 6 to give a greenish blue coloured complex
( ).. max - 670 nm) in a slightly acidic solution contain
ing PMA. The reaction has been used to detect PMA and
other mercury containing compounds in air, soil and
foliages.
Ra'E~CES
1, C.H. Southwick, "Ecology and the Quality of Our Environment", D. Van Nostrand Co,, New York, (1976).
2, J. Seymour and H. Girardet, •s1ue Print !or a Green Planet", Dorling Kindersley, London, (1987).
3. P. Bunyard and F. Morgan-Grenville, •The Green Alternative", Methuen, London, (1987).
4, B. Ward and R. Dubas, "Only One Earth 11, W.W. Norton,
and Co. Inc., (1971),
5. E.J. Calabrese, "Pollutants and High-Risk Groups", John Wiley and Sons, New York, (1978),
6. F. Graham Jr., "Since Silent Spring", Houghton Mifflin Co., (1970).
7. P ,G, Meerman, Toxicol. and Environ. Chem., 6, (1982), 29.
8, R.H. Horne, "The Chemistry of Our Environment", Wiley Interscience, (1978).
9. I .H. Suffet, "Fate of Pollutants in the Air and Water Environments", John Wiley and Sons, New York, Part 1, (1977).
10. D.E. Painter, "Air Pollution Technology", Reston Publ, Co. Inc,, rteston, (1974).
11. L. Hodges, 11 Environmental Pollution", Holt Rinel:art and Winston, Inc., New Y 0 rk, ( 1973) •
12. A. Turk, J. Turk and J .T. Witts, "Ecology Pollution Environment", Saunders, Philadelphia, ( 1972).
13. G.S. McClellan, "Protecting Our Environment", E.W. Wilson Co,, New Y0 rk, 42 (1), (1970),
14, K. Mellan, Chemistry in Britain,.§ (5), (1970), 198.
32
15. J .A. Black, • Water Pollution Technology" , Reston Publ. Co. Inc., Reston, (1977), p. 99.
16. H. Gysin, z. Anal. Chem., 282, ( 1976), 282,
17. A,'l', ltossano, Jr., "Air Pollution Control", .McGraw Hill Book Co., !'lew York, ( 1959), p. 12.
18. J,i'•• Hellawell, Environ. Pollut., 50, (1988), 61,
19. D.L. Klayman and W.H. Gunther, "Organic Selenium Compounds, Their Chemistry and Biology", Wiley Interscience, (1971), p, 646.
20.
21.
22,
23.
24.
25.
26.
27.
28.
u.s. Dept. of Health, Education and Welfare, "Air Quality Criteria for Sulphur Dioxide", N,A,P.C,A. Publ. No, AP-50 (1969),
C.G. Wilbur, "The Biological Aspects of Water Pollution", c.c. Thomas Publ,, Springfield, (1969).
N. Dudley, "This Poisoned Earth", Piatkus Publishers Ltd., London, (1987).
F,A, Gunther and L.R. Jeppson, "Modern Insecticides and World Food P:t'oduction"", Chapman and Hall, London, ( 1960).
C,A. Edwards, "Environmental Pollution by Pesticides", Plenum Press, London, (1973).
L.H. Keith and W.A. Telliard, Environ. Sci. Technol.., j2, ( 1979)' 416.
R. Carson, "Silent Spring" , Hamish Hamil ton, London, ( 1963).
Rajchengappa and C. Rajghatta, India Today, June 15, (1989), 74.
H. Cremlyn, "Pesticides, Preparation and Mode of Action", John Wiley and Sons, (1978), p. 210.
29. J.H. Koeman, "IUPAC '1/orld Food Production Environment Pesticides", L.urich, Pergamon Press, Oxford, (1978), p. 25.
30. F. Matsumura, "Toxicology of Insecticides", Plenum Press, New York, (1985).
33
31. J,J::. l'lcKee and H.W. Wolt, •water Quality Criteria", Calif. State Water ~uality Control Board Publ., (1963), p. 3.
32. G,t., Bailey and J,L, White,T.Agric. Food Chem., _g, ( 1964). 324.
33. A.I. Nasi111, Environ. Pollut., _!, (1971), 1.
34. R.H. Haque and W.H. Coshow, Environ. Sci. Tech., ~. {1971). 139.
35. H.V. Leland, Environ. Sci. Tech.,l, (1973), 833.
36. R. Hartung and G.W. Klinger, ~viron, Sci. Tech., 4, (1970), 407.
37. C.A. Edwards, "Persistent Pesticides in the Environment", The Butterworth Group, London, { 1970) , p. 19.
38. E.P. Lichtenstein, T.W. Fuhremann and K.R. Schultz, J. Econ. t.ntomol., 60, {1967), 1714,
39. T,J. Peterle, Nature, 244, {1969), 620.
40. C. W. Stanley, l:.nviron. Sci. Tech,, ,2, ( 1971), 430.
41. F .A. Gunther and J.D. Gunther, "rlesidue Review", Springer Verlag, New York, 35, {1971).
42. H.J. Hayes, Life Sci., 4, (1965), 1611.
43. P.K. Saxena and K. Mani, Ecotoxicol, Environ, Saf., 14, {1987), 56.
44. N. Motoyama, w.c. Dauterman and G.C. Rock, J. Econ. Entomol., 70 {4), (1977), 475.
45. N .I. Sax, "Cancer Causing Chemicals" , Van Nostrand Reinhold Co., New York, {1981).
46. L. Fishbein, W.G, Flamm and H.L. Falk, 11 Chemical Mutagens", Academic Press, New York, ( 1970), p, 235.
47. L. Roberts, Science, 243, ( 1989), 1280.
48, r·.A. Patty, "Industrial Hygiene and Toxicology•, Inter.science Publishers, ~. ( 1963).
49. W. Lei the, "The Analysis of Air Pollutants", Ann Arbor Science Publishers, Ann ~rbor, (1971).
50. D.J. Freed and A.M. Mujace, Anal. Chem., 49, (1977), 139.
51. N.W. Hanson, D.A. Reilly and H.E. Stagg, "The Determination of Toxic Substances in Air",
52.
53.
w. Heffer and Sons, Ltd., (1965), p. 41 •
. M.D. Gerhart, F'.J. Wittmer and Y.A. Tajima, J. Agric. F'ood Chem., £!!, ( 1952), 851.
D.M. Coulson and D.M. Cavanagh, Anal. Chem., ~. (1960)' 1245.
35
54. A.E. O'Donnell, M.h. Neal, F.T. Weiss and T.M. Deci.ne, J. Agric. Food '-hem.,~. (1954), 573.
55.
56.
57.
58.
59.
60.
61.
62.
n.J. Wilson, T.S. Oostdyk and P.N. Keliher, J. Assoc. Off. Anal. Chem., 11 (6), ( 1988), 1090.
W .M. Mok and C.M. Wai, Talanta, 35 ( 3), ( 1988), 183.
H.J. Magnuson and E.B. Watson, Ind. 1ng. Chem. Anal. Ed., 16, (1944), 339.
M.J. De Faubert Maunder, H. Egan and J. Roburn, Analyst, .§2, ( 1964), 157.
M.G. Ashley and A.N. Bates, Analyst, §1, (1962), 220.
W. Hancock and E.A. Laws, Analyst, 80, (1955), 665.
G. Zweig, "Analytical JV,ethods for Pesticides, Plant Growth RegJJlators, and Food .Additives", Academic Press, New York,], (1964), p. 9.
H.P. Burchfield and P.H. Schuldt, J. Agric. Food Chem., ..§., (19~8), 111.
C. w. Stanley and J .s. l),orton, J. Agric. Food Chem., ~0, ( 1972), 1265.
64. I'\. C. Pietrogrande, G. Blo and c • .8igh1, J. Chromatogr., ~ (1), (1985), 63.
65. R. f>'!iscus, H.T. Gordon and D.A. George, J. Agric. Food Chem., 1. ( 1959), 613.
66. H. lr.artin, "Pesticide Manual", British Crop Protection ~ouncil, (1968), p. 68-442.
67. E.P. Ordas, v.c. Smith and C.F. Meyer, J. Agric. Food Chem., f:!, ( 1956), 444.
68. L. Feinsilver and F.w. Oberst, Anl\1• Chern., 25, (1953). 820.
69. A. Bevenue, G. Zweig and N,L. Nash, J. Assoc. xgr. Chem., f:!2, (1962}, 990.
70. R.P. Marquardt and E.N. Luce, J. Agric. Food Chem., 9, (1961), 266.
71. F.A. Gunther, Ind. Eng. Chern. ~nal. Ed., .11· (1945), 149.
72. D.M. Coulson, L.A. Cavanagh and J.E. De Vries, J. Agric. Food Chem., ~. (1960), 399.
73. G.A. Sergeant and R. Wood, Analyst, 84, (1959), 423.
74. P.A. Giang and M.s. Schechter, J. Agric. Food Chem •• 14, (1966)' 380.
75. E.Q. Laws and D.J. Webley, Analyst, 84, (1959), 28.
76. P.A. Giang, F.F. Smith and S.A. Hall, J. Agric. Food Chern., 4, (1956), 621.
77. G .J. Sharp, S. ililli and J .N. Desmarchelier, Analyst, m. ( 1988)' 1493.
78. J.T. Hughes, Analyst, 88, (1963), 318.
79. W. Buchler and 'II.Z. Heizler, z. Anal. Chem,, 194, (1964), 422.
80. A.E. O'Donnell, H.W. Johnson and F .T. Weiss, J. Agric. Food Chem., _2, ( 1955), 757.
81.
82.
84.
85.
86.
87.
88,
89.
90.
91.
92.
93.
94.
95.
96.
97.
C.J. Cueto, J. Agric. F'ood Chem., _!2, (1960),
H.L. Pease, J. Assoc. Off. Agric. Cheu:., 40, (1957)' 1113.
K • !:., Kress, Anal. Chem., ~. ( 1951)' 1313.
w.K. Lowen, Anal. Chem., n. (1951), 1846.
G,E, Keppel, J. Assoc. Off. Agric. Chern,, 39' ( 1956) ' 709.
273.
G. Zweig and T.E. Archer, J. Agric. Food Chem., 8, ( 1960)' 190, 403.
G. Zweig, "Analytical Methods for Pesticides, Plant Growth Regulators and Food Additives'', Academic Press, New York, 2, (1964), p. 508.
E.J. Skerrett and E.A. Baker, Analyst, 85, (1960), 448, 606.
J.E. Fahey and M.s. Schechter, J. Agric. Food Chem., 9, ( 1961)' 193.
F .B. Ibrahim and J .c. Cavagnol, J. ~•gric. Food Chern., 14, ( 1966), 369.
E.S. Goodwin, R. Goulden and J.G. Reynolds, Analyst, 86, (1961), 1028,
C.R. Schneider and H. Freund, Anal. Chern., 34, ( 1962). 69.
37
I.M. Kolthoff' and V.A. Strenger, 11 Volumetric Analysis", Interscience Publishers Inc., New York, 2, (1947),227.
W .N. Aldridge, Analyst, 69, ( 1944). 262.
L.S. Bark and H.G. Higson, Tal&nta, jj, (1964), 621.
A.!',, Kadoum, J. Agric. Food Chern., .Jl, ( 1969). 1178.
H.w. Conroy, J. Assoc. Off. Agric. Chern., 40, (1957), 230.
98. H .H. Funderburk and J .M. Lawrence, Nature, m. (1963), 1011.
99. A. Calderbank, S.H. Yuen, Analyst, .2Q, ( 1965), 99.
100. C. V. Bowen and F. I. Edwards, Anal. Ch em. , 2 2' ( 1951) ' 706.
101. P.R. Averell and ~;. V. Norris, Anal. Chern., 20, ( 1948)' 753.
102. R. Buckley and J.P. Colthurst, Analyst, ~. (1954), 285.
103. R.E. Adams, rl.H. James and L.D. Johnson, Environ. Sci. Technol., 20, (1986), 711.
104. D.C. Abbott and E.I. Johnson, Analyst, 82, (1957), 206.
105. N. Gordon and M. 3eroza, Anal. Chern., 24, (1952), 1968.
106. V .H. Freed, Science, 107 ( 1948), 98.
107. D.P. Johnson, J. Assoc. Off. Anal. Chem., 38, (1955)' 153.
108. A.J. Graupner and C.L. Dunn, J. Agric. Food Chem., §, (1960)' 286.
109. W.K. Lowen, J. Assoc. Off. Agric. Chem., 36, (1953), 484.
110. R. Fullner and H. Weissner, Proceedings of Conference on Hazardous Materials Spills, Am. Institute of Chem. Eng. ' ( 1976) ' 345.
111. J. Cook and C. Kaufman, "Portrait of a Poison", Pluto Press, London, (1982).
112. A. Hay, "The Chemical Scythe", Plenum Press, London ( 1983).
113. D. Weir, "The Bhopal Syndrome", Earthscan FublicationLtd., London, (1987), p. 61.
114. D. Weir, and M. Schapiro, •circle of Poison", Institute of r'ood P0 11cy, London (1981).
115. s. George, "How the other Half Dies", Penguin, London, ( 1976).
116, F.M. Leppe and J. Collins, 11 iood First", Ballantine Sooks, London, (1978).
117. Indo-u.s. Workshop on Bio-degradable Pesticides, April 16-19, Lucknow, Report, (1979), 44.
118. H. Geissbuhler, "Advances in Pesticide Science", Pergamon Press, Oxford, Part 3, (1979), p. 619.
119. J. Miyamoto and P.C. Kearney, "Pesticide Chemistry: Human Welfare and the Environment", Pergamon Press, Oxford, ~. ( 1983), p. 3-238.
120. G.H. Morrison, Anal. Chern., 59, (1987), 1341 A.
121. P .H. Watts, Analysis of Pesticide Residues in Humaz:: and Environmental Samples", EPA, North Carolina, ( 1980).
122. G. Zweig, 11 Analytical Methods for Pesticides, Plan~ Growth Regulators, and Food Additives", Academic Pi'ess, New York, ..!• ( 1963).
123. W.P. McKinley, J. Assoc. Off. Anal. Chern., 63, ( 1980), 158.
124, J. Sherma, "Analytical f11ethods for Pesticides and Plant Growth Regulators", Academic Press, New York, ..!..!· (1980), p. 79-122.
125. A.B. Wood and L. Kanagasabapathy, Pesti. Sci., 14, (1983), 108.
126, J.D. Mac Neil and R.W. Frei, "Analysis of Pesticide Residues", John Wiley and Sons, (1981), p. 137-156.
127. P.M. Boffey, Science, 171, (1971), 43.
