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This is to certify that the
thesis entitled
RESIDUE ANALYSIS OF SELECTED ORGANOCHLORINE, ORGANOPHOSPH?’

ATE AND CARBAMATE PESTICIDES IN A SOIL—FILLED WASTE

GAMAL ELSAYED KHEDR

has been accepted towards fulfillment
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Wdegree in may

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MSU Is An Affirmative Action/Equal Opportunity Institution

 

 

RESIDUE ANALYSIS OF SELECTED ORGANOCHLORINE, ORGANOPHOSPHATE
AND CARBAMATE PESTICIDES IN A SOIL-FILLED
WASTE DISPOSAL FACILITY

BY

Gamal Elsayed Khedr

A THESIS

Submitted to
Michigan State University
in partial fulfilment of the requirements
for the degree of

MASTER OF SCIENCE

Department of Entomology and Pesticide Research Center

1989

(gb4o'z\4-

ABSTRACT

RESIDUE ANALYSIS OF SELECTED ORGANOCHLORINE, ORGANOPHOSPHATE

AND CARBAMATE PESTICIDES IN A SOIL-FILLED
WASTE DISPOSAL FACILITY

BY
Gamal Elsayed Khedr

Dilute pesticide wastes resulting from rinsates of
used containers, spray tanks and application equipment are
deposited in a soil—filled waste disposal facility at
Michigan State University. residues of more than 20
different pesticides are deposited in this disposal
facility each year. Dicofol, endosulfan I, endosulfan II,
diazinon, chlorpyrifos, phosmet, azinphos-methyl and
carbaryl were selected as pesticide residues to monitored
over a two-year period for possible dissipation and/or
accumulation.

Two methods were used for analyses of the pesticides,
one for organochlorine and the other for organophosphate
and carbamate pesticides. The pesticides were quantitated
by gas liquid and high performance liquid chromatography.
Gas chromatograph-mass spectrometry was used for the
structural confirmation of each pesticide.

The concentration of all pesticides monitored
decreased 25% to 87% from the highest concentration of the
year to the end of that year. Therefore this waste disposal
facility appears to be a good system for disposal and

dissipation of dilute pesticide wastes.

 

DEDICATION

To the memory of my father

iii

ACKNOWLEDGEMENT

I would like to express my sincere appreciation to my
major professor, Dr. Matthew Zabik for his encouragement,
guidance, support, friendship, patience and all he has done
for me throughout the course of this investigation. He
really has earned my highest level of respect and
admiration.

I would also like to extend my appreciation to Drs.
Donald Penner and Roger Hoopingarner for serving on my
graduate committee. Special thanks to Drs. Richard Leavitt
and Robert Kon for their many helpful discussions and
suggestions.

Special thanks to my parents and every one of my
family for their encouragement and support, I will always be
greatful to you all.

Finally I would like to extend my appreciation to all
my special friends, Gadelhak Gadelhak, Emad Zidan, Ahmed
Raafat, Ahmed Madkour, Mohammed Shereif, Dr. Gregory Orr and
Nailah Orr for all that we have shared together. Also
special thanks to every one in our laboratory Dr. Hai-Dong
Kim, former student Dr. Susan Erhardt-Zabik, Mary ann
Heindorf, Glenn Dickmann, Eboua Wandon, Mohamed Elhadidi,

Bob Schultz and lester Geissel for their help.

iv

TABLE OF CONTENTS

LIST OFTABLES 0.0.0.0.... ....... ..OOOOOOOOOOOOOOOOOOOOX
LIST OF FIGURES............................. ..... ......Xiii
CHAPTER 1: INTRODUCTION ...............................1

I

II

III

IV

VI

VII

VIII

IX

XI

XII

XIII

XIV

XVII

Soil As an Influence on pesticides Degradation...7

Evironmental dynamics of pesticides....... ....... 8
Behavior of Pesticides in the Environment ........ 9
Fate of Pesticides in Soil........... ............ 10
Volatilization of Pesticides............... ...... 11

Effect of Soil Microorganisms on Pesticides......12

‘Chemical Degradation of Pesticides...............13

Photodecomposition of pesticides. ....... . ....... .13
Dilute pesticide wastes........... .......... .....14
Pesticides characteristic and toxicity...........17

Characteristic of the pesticides in this study...18

Dicofol (Kelthane)...............................18
Endosulfan (Thiodan)........ ............ .... ..... 19
Diazinon (Spectracide)....... ..... . .............. 20
Chlorpyrifos (Dursban) ........ . ..... . ............ 20
Phosmat (Imidan)......................... ...... ..21
Azinphos-methyl (Guthion)............. ...... .. ..21

XVIII carbarY]. (SeVin)000000.00.......00.000000 ..... .0022

XIX Objectives..0...........0..00.0.. .......... 0.0.0.28

CHAPTER 2: MATERIALS AND METHODS.......................3O

I MATERIALS...... ....... .. ........... . ............... 31
A- Sampling.............. ....... ................31

1- Soil samples...................... ..... ...31

2- Water Samples............... ........ ......33

B- Glassware Preparation.............. .......... 33

C- Reagent80000000.0.000000000.0.....00....0000033

1- Solvents............. ..................... 33

2- Chemicals........ ....................... ..34

3- Miscellaneous Items ..................... ..34

0- Equipment ................................ ....35

II METHODS.0.0000000...... ..... 0.0.0....00....00.0000035
1- Chlorinated Hydrocarbon Pesticides ........... 36

a. Extraction....... ........... . ............. 36

b. Clean up....... ..... .0. 0000000000000 . 00000 37

c. Recovery Study... ............ . ........... .37

d. Quantitation.......... ........ . ........... 38

2- Organophosphate pesticides... ................ 39

a. Extraction... ...... . ................ ......39

b. Clean up.......0..00....0..0....00.00000.039

c. Recovery Study... ...... ... ...... .... ..... .40

d. Quantitation. 0 0 . . . . . ...... 0 0 . . . ...... 0 0 0 . . 4o

3- Carbamate Pesticides......... ...... . ......... 41

a. Extraction, Clean up and recovery ......... 41

b. Quantitation. 0 0 . 0 0 0 . 0 0 . 0 0 0 0 ..... 0 0 . 0000000 42

III CALCULATION OF THE PESTICIDES CONCENTRATIONS ....... 42
IV WATER ANALYSES.. ................................... 43
V pH DETERMINATION........... ......... . ........... ...44

vi

VI ORGANICmTTER........O..O0.0......O.’ ...... 0.....044

VII CATION EXCHANGE CAPACITY (CBC)......0......0...00.045

VIII CONFIRMATION OF THE PESTICIDES IDENTIFICATIONS.....47

CHAPTER 3:

I

II

CHAPTER 4:

CHAPTER 5:

LITERATURE

RESULTS AND DISCUSSION......................57

The Dissipation Rate of the Pesticide
residues in the Waste Disposal Facility.....61

Distribution of the Pesticide residues in

the Waste Disposal Facility...........- ..... 80
SUMMARY AND CONCLUSIONS................ ..... 91
FUTURE WORK............ ................ .....96
CITED............:............... ..... ......99

vii

 

Table

Table

Table

Table

Table

Table

Table

Table

Table

Table

3:

4:

5:

6:

7:

10:

LIST OF TABLES

Pesticides Characteristics and Toxicity.......

Chromatographic Conditions Used for Analysis

of the Pesticides..... ........ ... ...... .......
Percent Recovery and Standard Deviation
(st. dev.) of Chlorinated Hydrocarbon
Pesticides. ....... .. ................... . ......
Percent Recovery and Standard Deviation
(st. dev.) of Organophosphate and Carbamate
PestiCides 000000000 0.....00....0..00......0.00

Characteristics of the Soil Used in the Waste
Disposal Facility............... ......... .....

The Monthly Mean and the Standard Deviation
(S.D.) of the Concentrations (ppm) of the
Selected Organochlorine pesticides in a Waste
Disposal Facility at Michigan State University
in 1987........... ........ . ...................

The Monthly Mean and the Standard Deviation
(S.D.) of the Concentrations (ppm) of the
Selected Organochlorine Pesticides in a Waste
Disposal Facility at Michigan State University
in 1988............ ..... ......................

The Monthly Mean and the Standard Deviation
(S.D.) of the Concentrations (ppm) of the
Selected Organophosphate Pesticides in a Waste
Disposal Facility at Michigan State University
in 1987... ....................................

The Monthly Mean and the Standard Deviation
(S.D.) 0f the Concentrations (ppm) of the
Selected Organophosphate Pesticides in a Waste
Disposal Facility at Michigan State University
in 1988 ....... ...... ...... ..... ...... .... .....

The Monthly Mean and the Standard Deviation
(S.D.) of the Concentrations (ppm) of the

Selected Carbamat Pesticide in a Waste
Disposal Facility at Michigan State University
in 1987 ...... . ............. . .......... ........

23

54

55

56

6O

66

68

69

70

71

 

Table

Table

Table

Table

Table

Table

Table

Table

Table

Table

Table

Table

Table

11:

12:

13:

14:

15:

16:

17:

18:

19:

20:

21:

22:

23:

The Monthly Mean and The Standard Deviation
(S.D.) of the Concentrations (ppm) of the
Selected Carbamat Pesticide in a Waste
Disposal Facility at Michigan State University
in 1988..... ..... .............................

Distribution of Dicofol (Kelthane) in a Waste
Disposal Facility at Michigan State University
11119870000000.0000. ...... ......00...0....00.

Distribution of Dicofol (Kelthane) in a Waste
Disposal Facility at Michigan State University
1111988 000000 ...... ....... .00.... ....... 00....

Distribution of Endosulfan I (Thiodan) in a

Waste Disposal Facility at Michigan State
UniverSj-ty in 1987 ......... . . . . . 0 0 0 . 0 . . . . . . . . O
Distribution of Endosulfan I (Thiodan) in a
Waste Disposal Facility at Michigan State

univerSity in 1988. 0 0 0 0 0 . . 0 . 0 . 0 ........ 0 0 0 0 O 0
Distribution of Endosulfan II (Thiodan) in a
Waste Disposal Facility at Michigan State
University in 1987 ...... ...... ........ .. ......

Distribution of Endosulfan II (Thiodan) in a
Waste Disposal Facility at Michigan State
University in 1988 ......... ......

Distribution of Diazinon in a Waste Disposal
Facility at Michigan State University in 1987.

Distribution of Diazinon in a Waste Disposal
Facility at Michigan State University in 1988.

(Dursban) in a
State

00000..

Distribution of Chlorpyrifos
Waste Disposal Facility at Michigan
University in 1987.....................
Distribution of Chlorpyrifos (Dursban) in a
Waste Disposal Facility at Michigan State
University in 1988...... ...... ... .............

Distribution of Phosmet (Imidan) in a Waste
Disposal Facility at Michigan State University
111198? 0000000000 00.00....00.00....00..0.00000

Distribution of Phosmat (Imidan) in a Waste
Disposal Facility at Michigan State University

ix

83

83

84

84

85

85

86

86

87

87

88

 

Table 24:

Table 25:

Table 26:

Table 27:

in 1988......00...............0......0000.000.

Distribution of Azinphos-methyl (Guthion) in
a Waste Disposal Facility at Michigan State
University in 1987..................... ...... .

Distribution of Azinphos-methyl (Guthion) in
a Waste Disposal Facility at Michigan State
University in 1988............................

Distribution of carbaryl (Sevin) in a Waste
Disposal Facility at Michigan State University

in 19870000....0000000..00............0......0

Distribution of Carbaryl (Sevin) in a Waste
Disposal Facility at Michigan State University
in1988...000....000..000.0000.....0.00......O

88

89

89

90

9O

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

10:

LIST OF FIGURES

The pesticides used in this study...........

Soil-Filled Concrete-Lined Waste Disposal
Facility at Michigan State University.......

GC chromatogram of a standard mixture of
Chlorinated Hydrocarbon pesticides..........

GC chromatogram of a soil sample for
Chlorinated Hydrocarbon pesticide residues..

GC chromatogram of a standard mixture of

Organophosphate pesticides............. .....

GC chromatogram of a soil sample for
Organophosphate pesticide residues..........

HPLC chromatogram of a standard of a
Carbamat pesticide...... ............. .. .....

HPLC chromatogram of a soil sample for a
Carbamat pesticide residue..................

The dissipation of dicofol in a waste
disposal facility at Michigan State
UniverSity in 1987 . 0 . . 0 0 . 0 0 0 0 0 O . . 0 0 0 0 0 0 . . . . .

The dissipation of dicofol in a waste
disposal facility at Michigan) State
University in 1988 ...... ...................
The dissipation of endosulfan I and

endosulfan II in a waste disposal facility
at Michigan State University in 1987.......

The dissipation of endosulfan I and
endosulfan II in a waste disposal facility
at Michigan State University in 1988.......

The dissipation of diazinon, Chlorpyrifos,
phosmet and azinphos-methyl in a waste
disposal facility at Michigan State
University in 1987.. .......................

The dissipation of diazinon, Chlorpyrifos,

xi

25

32

48

49

50

51

52

53

72

73

74

75

76

 

phosmet and azinphos-methyl in a waste
disposal facility at Michigan State

univerSityin19880.00.00.0000...00....00.. 77

Figure 15: The dissipation of carbaryl in a waste
disposal facility at Michigan State

univerSitYin19870000000...00000000000000. 78

Figure 16: The dissipation of carbaryl in a waste
disposal facility at Michigan State

University in 1988.................... ..... 79

xii

CHAPTER 1

INTRODUCTION

CHAPTER 1

INTRODUCTION

Pesticides play a major role in our society. The use
of pesticides, (insecticides, herbicides, nematicides,
fungicides, and rodenticides), in the United States has
grown ten-fold in the past three decades. Approximately
70 percent of the insecticides are applied by the farmer
(Pike & Colwell 1984). About 2.3 billion pounds of
pesticides, worth $4.1 billion are purchased by U.S.
farmers each year (Wassertrom & Wiles 1985). The
widespread use of pesticides has greatly benefited
agriculture, but has also led to many problems.
The most important of these is the effect of
pesticides on the environment including environmental
contamination by improperly disposed dilute pesticide

wastes.

Disposal of pesticide and pesticide-related wastes
represents a serious problem in the United States and in
other parts of the world. Many pesticide producers and
applicators simply dump pesticide wastes on the ground or
into nearby water bodies, because they have no other
disposal methods that can handle pesticide wastes

economically (Little 1977). As a result, some pesticides

2

may leach through the soil profile and contaminate
groundwater and surface waters and eventually reach

human food chains.

It is extremely difficult to clean up groundwater
that has become contaminated with pesticides. Therefore
measures that prevent pesticides from reaching
groundwater are the best control methods "An ounce of
prevention is worth a pound of cure". Overall contained
disposal of dilute pesticide wastes is one of the best

ways to keep pesticides out of groundwater.

Many methods have been proposed or used for the
disposal and detoxification of pesticide wastes, such
as, incineration, open burning, deep-well injection and

land disposal. In general, some characteristics of an

ideal waste disposal system are:- 1)- inexpensive and
available for everyone 2)- adaptable to any
climatological or geographical region, and 3)- able to

handle a wide range of different pesticide types, or
formulations and concentrations. In addition, a system
should not require highly skilled labor to operate the

system.

Land disposal is the most widely used, least
expensive, and most often available disposal system, at
the present time. Land disposal includes sanitary
landfills, surface impoundments, evaporation ponds and
land farming. Disposal in a toxic substance landfill is
the current method of choice for disposal and
detoxication of pesticide wastes for environmental and

economic reasons.

Landfills represent the cheapest method for
disposal of pesticides wastes, with costs ranging from $2
to $13 metric/ton (Ghassemi and Quinlivan 1975, Gruber
1975). This method has been used by both pesticide
producers and consumers for disposal and detoxication
of pesticides and pesticide-related wastes. In an
examination of hazardous waste management facilities in
the United States, Straus (1977) indicated that landfills
were an important method for waste disposal, and Gruber
(1975) estimated that 40% of the industrial pesticide

wastes are directly or indirectly deposited in landfills.

Disposal of pesticides in landfills can produce
both environmental and public health problems if

sufficient precautions are not followed. At one

industrial chemical landfill, endrin, heptachlor, and
heptachlor epoxide caused surface water contamination and
runoff problems and moved into groundwater 30 meter below
the landfill (Kiein 1974, Rima 1967). The construction of
secured landfills in desert regions is generally without
problems; however, in wet regions, control of leachate
and leachate recycling must be considered when yearly
rainfall is high or when the groundwater table is near
the surface. In attempts to dispose of pesticide wastes
in a safe manner, newly constructed landfills have been
designed using natural bottom sealing layers such as clay
or granite (Ghassemi and Quinlivan 1975). In areas where
this is not possible, synthetic barriers of polyethylene,

cement, or asphalt have been employed (Geswein 1975).

Pesticide wastes can be released from a landfill
either as volatilized gases or as leachate. Therefore
design of a landfill should be to reduce the release of
wastes. The rate of release should not impair air or
water resources. In other words, a landfill may
contaminate the surrounding air by volatilized gases.
Therefore the chemical nature of pesticide wastes must be
considered, because some volatile wastes form toxic gases

(Dillon 1981). Wastes (liquids) are able to leak through

compacted clay or synthetic lining materials in spite of
factors designed to prevent waste leaching. Some of these
factors are: soil adsorption, physical barriers, and
chemical and biological degradation. Soil adsorption is
dependant on the physical structure of soil. A soil
containing high percentages of clay and/or organic matter
has a high adsorption capacity(Dillon 1981). In addition,
reducing the migration potential of toxic constituents
from a soil in a landfill requires minimizing the

production of liquid input of pesticide wastes.

Landfills can be designed to reduce migration, of
pesticide to groundwater but there is no standard design.
Advanced designs would have at least the following
features: a bottom liner, a leachate collection and
recovery system, and a top cover. Bottom liners are
constructed of compacted clay, a clay and soil mixture or
synthetic material. Leachate is collected through a
series of pipes to a drainage bed placed above the bottom
liner. A mechanical pump raises the leachate through
stand pipes to the surface. The top cover reduces the
amount of rainfall entering the landfill (Technologies
and Management Strategies for Hazardous Waste Control

1983).

SOIL AS AN INFLUENCE ON PESTICIDES DEGRADATION

Pesticides are affected by soil. Soil is a complex
and highly variable mixture of components containing many
types of living organisms i.e., bacteria, fungi, algae,
and invertebrate and vertebrate animals. Soil may
metabolize or attenuate pesticide wastes by these
organisms. Under proper environment condition and
sufficient time microbial degradation can play a role in
reducing pesticide concentrations in soil and most of
organic compounds can be broken down biologically
(Bingham 1973). Aromatic compounds are more resistant to
biodegradation than aliphatic and alicyclic compounds. A
compound which has a carbon in the skeletal chain or ring
make the structure more susceptible to breakdown (Atkins
1972). Halogens on an aromatic ring increase resistance
to biodegradation, however, amino and hydroxy
substitutions tend to increase biodegradability (Bingham

1973).

Pesticides are also affected by chemical and

physical nature of soil. Oxidation and hydrolysis act on

the chemical structure of the pesticide, breaking the
molecule down into smaller components, or by removing
various functional groups. Hydrolysis seems to be faster
when the pesticides are adsorbed onto clay or silt
particles (Baker 1972). pH can significantly influence
degradation. The hydrolysis half-lives of malathion in
neutral water and at pH 9 has been demonstrated to be of
one month and ten hours, respectively (Paris 1975).
Alkaline hydrolysis is not effective with every pesticide
but has been shown to work with organophosphates,

carbamates, imides and hydrazides (Ferguson 1975).

ENVIRONMENTAL DYNAMICS OF PESTICIDES

Environmental dynamics of pesticides includes all
processes that occur to pesticides from the time of
pesticides application into the environment until their
degradation products or parent compound reach some steady
state. The environmental dynamics includes_irreversible
binding to soil particles, mineraliztion or incorporation
into biological material. This phenomena can be divide
into three groups: distribution, movement, and

attenuation. Distribution determines how pesticides or

their degradation products can move from their original
location to new locations by wind, erosion,
volatilization from soil, plant, aqueous surfaces, and
diffusion and/or mass flow in the soil air. Pesticides
may move with or in the soil water, leaching down and
through the soil or back to the soil surface with
evaporation. Runoff and soil erosion can carry pesticides
over land, either in solution, adsorbed on sediment, or
in the crystalline state. Pesticide attenuation means
that all processes tend to reduce the amount of free
pesticide residue. These processes include: chemical,
photochemical, biological degradation, irreversible soil
adsorption, and plant and organism uptake. Volatilization
may be considered an attenuation mechanism when a
pesticide is dissipated by this route and can no longer

be measured at some point down wind.

BEHAVIOR OF PESTICIDES IN THE ENVIRONMENT

Behavior of pesticides in the environment is
influenced by many factors: 1)- physical and chemical
properties of pesticides, which include chemical
structural and configuration, molecular size, water

solubility, lipophicity, polarity, acidity or basicity,

10

and vapor pressure. 2)— soil characteristics, which
effect pesticides behavior include: soil type (percent
silt, clay, organic matter, oxides, hydroxides) clay
type, pH, soil structure (pore size, bulk density),
cation exchange capacity and microbial population. 3)-

environmental factors that influence pesticide behavior

include: temperature, air movement (speed, direction,
turbulance) rainfall (amount, intensity, duration,
chronology of events), humidity, solar radiation,
topography.

FATE OF PESTICIDES IN SOIL

The fate of pesticides in soil is ultimately connected
with such expression as "disappearance" or dissipation
and "persistence" or accumulation in the environment. The
term disappearance of a pesticide from a certain
substrate has been widely used in the past and was, in
most cases, synonymous with the impossibility to detect
the originally applied compound where it previously had
been applied. Disappearance or loss through
volatilization means, the parent compound or its
metabolites really have not disappeared, except that they

have been transported some where else (Lichtenstein

11

1970).

On the other hand, persistence has to be regarded
in relation to the area to which the pesticide has been
applied. This persistence depends on different factors:
the physical and chemical properties of the pesticide
itself, the formulation in which it has been applied and
the mode of its application to the soil or other target

areas .

Overall environmental factors are the most
important such as the soil type, soil microorganisms, the
presence of other chemicals, temperature, moisture, air
movement, cover crops, soil cultivation, plant surface,
etc. (Lichtenstein et a1. 1962, 1964). Because these
factors differ from place to place, it is impossible to
attribute an absolute half life to any pesticide.
Dependent on the environmental conditions, pesticides may
have a relatively short persistence or may be detectable

for a relatively long time.

VOLATILIZATION OF PESTICIDES

Volatility of several pesticides is found to be a

12

function of the vapor pressures and water solubilities of
each pesticide. This loss was also dependent on the
substrate into which the pesticide had been incorporated.
Pesticides are volatile when bound to soil particles but
considerably more volatile when dissolved in water
(Lichtenstein, 1961). Several researchers have reported
higher rates of volatilization of insecticides and
herbicides from wet than from dry soils. (Bowman et al.,
1965, Gray et al., 1965 and Parochetti et al., 1966).
Increase volatility in wet soils is due to displacement
or desorption of the pesticide from the soil surface,
resulting in an increased vapor density or partial
pressure of the pesticide (Spencer et al., 1969c; 1970b).
Soil-water content affects volatilization losses of
organochlorine pesticide simply by competition for

adsorption sites (Igue et al., 1970).

EFFECT OF SOIL MICROORGANISMS ON PESTICIDES

Soil microorganisms have a considerable effect on
the metabolism or stability of pesticide in the soil
(Lichtenstein et al. 1960). The effect of moisture and
soil microorganisms on parathion was reported by

Lichtenstein et al., 1964. Parathion was most persistent

13

in dry soil and least persistent in soils with a high
moisture content. The role which soil microorganisms
play can be seen by measuring the rate of decomposition
in sterilized versus non-sterilized soils (Kanfman et al.
1968). A general review on the subject of microbial
effect on pesticide degradation in the soil can be found
by Wainwright (1978). In general, factors which effect
microbial degradation are soil moisture, temperature,

percent organic matter, pH and pesticide concentration.

CHEMICAL DEGRADATION OF PESTICIDE IN SOIL

Hydrolysis, oxidation and isomerization are the
three most prevalent reactions in soil. Hydrolysis is
faster in moist soils than dry soils. Oxidation reaction
of parathion to paraoxon was reported by Helling et a1,
(1971). Isomerization of parathion in soil can be
demonstrated by conversion of the sulfur thion (=3) to

thiol (—S—) as in S-methyl parathion.

PHOTODECOMPOSITION OF PESTICIDES

Photochemical reactions can occur when a pesticide

absorbs light energy (Zabik 1983). On the other hand

14

pesticide molecules can absorb particular wavelengths of
light. In some cases, the energy involved is dissipated
by the breaking of chemical bonds in the molecule. PCP
(pentachlorophenol), was found to decompose readily in
sunlight whether in ionized form (Munakata et al., 1969)
or not (Hamadmad, 1967). Methoxychlor in aqueous alcohol
was converted to dimethoxybenzophenon, p-methoxyphenol

and anisic acid (Fernandez, 1966).
DILUTE PESTICIDE WASTES

Dilute pesticide wastes, result from the rinsate of
used pesticide containers, spray tanks, and equipment
used for application of pesticides. Such wastes represent
special disposal problems. Over 400,000 meter3 (100
million gallons) of dilute pesticide solutions are
generated in the United States each year (Dillon 1981).
In the past, many pesticide applicators simply dumped the
pesticide wastes on the ground because they had no other
disposal methods that could handle dilute pesticide

wastes economically (Little, 1977).

A three-year study on the disposal of dilute

pesticide wastes was conducted by Hall et al. (1984) and

 

15

six departments at Iowa State University. They
demonstrated that wastes from over 45 pesticides were
safely disposed (6000 gallons of liquid each year) in a
concrete pit which allowed the evaporation of liquids,
biodegradation and other forms of pesticide decay. The
soil layer within the pit contained relatively normal
aerobic bacterial. The primary bacterial group was
Bacillus pseudomonas No contamination of the
surrounding soil, water, or air was detected. Junk and
Richared (1984) analyzed samples taken from two disposal
pits located at Iowa State University. Water, soil, and
air samples were collected and analyzed to evaluate the
possible contamination of the surrounding environment.
Summarized conclusions from these investigations are:

1- a well-designed pit disposal system is effective in

containing many pesticides.

2- the release of pesticides to surrounding air and

water is insignificant.

Ten lined evaporation beds located at the
University of California, for disposing of pesticide
wastes from used pesticide containers and application
equipment, were monitored over a two-year period for

possible buildup or decay of deposited pesticides

 

 

16

(Winterlin, Schoen, and Mourer, 1984). Conclusions from

these investigations are:

1-

the beds do not generally buildup high levels of
pesticides and are effective in containing many
pesticide wastes as well as degrading the pesticide
without excessive exposure via air vapor.

pesticides generally rise to the surface of the bed
where they can be degraded by photochemical, chemical
and biological forces as well as be distributed via
air vapor.

the amendment of the beds with lime may be an
important factor in the degradation of some

pesticides.

17

PESTICIDE CHARACTERISTICS AND TOXICITY

Chlorinated hydrocarbons are more persistent in the
environment than other classes of pesticides. The
organophosphates are often more toxic to humans than
chlorinated hydrocarbons; however they are deactivated in
the environment much more rapidly. Carbamates are similar
to organophosphates in their persistance and they are
rapidly degraded in the environment. Their toxicities
vary widely some are less toxic than DDT while others
have four or five times higher toxicity. The toxic action
of organophosphates and carbamates pesticides is to
deactivate the acetylcholinesterase enzyme (Kaufman
1974). While the organochlorine pesticides can also be
classed as neuropoisons. However, their mechanism of
action is not the same as that of phosphates and
carbamates. Indeed the precise mechanism is unknown for

most of them.

Microbial metabolism, chemical reactions, and
photodecomposition are the processes of greatest

significance in degrading chlorinated hydrocarbon

18

pesticides in soil. Strong adsorption to soil consituents
limits the availability of these chemicals and their
degradation products for more rapid degradation in soil.
Although both anaerobic and aerobic degradation of
chlorinated hydrocarbons have been observed, it is
generally believed that anaerobic degradation is more

rapid (Hill & McCarty, 1967).

Organophosphate pesticides degrade fairly rapidly
in soil. The rate of degradation increases with increased
soil moister content, temperature, and acidity (Harris &
Lichtenstein, 1961; Lichtenstein & Schulz, 1964; Corey,
1965; Menn et al., 1965 Whitney, 1967). These factors
enhance pesticidal loss by chemical degradation,
volatilization, or microbial activity. Carbamate
pesticides have a relatively short residual life in soil,

and they are readily degraded by non target organisms.

CHARACTERISTICS OF THE PESTICIDES IN THIS STUDY

DICOFOL (KELTHANE)

Dicofol is a non-systemic acaricide with little

insecticidal activity, and is recommended for the control

19

of mites on a wide range of crops. Although residues in
soil decrease rapidly, traces may remain for a year or
more. The acute oral LD50 for male rats is 776 to 842
mg/kg, for female 668 to 700 mg/kg. The acute dermal LD50
for rabbits is 1870 mg/kg. Dogs were fed one year on a
diet containing 300 ppm with no evidence of toxicity

(Smith 1959).

ENDOSULFAN (THIODAN)

Endosulfan is a mixture of two stereoisomers,
alpha-endosulfan, or endosulfan I, with a melting point
of 108 to 110°C, and accounts for 70% of technical
endosulfan. Beta-endosulfan, or endosulfan II, with a
melting point of 208 to 210°C, accounts for 30% of
technical endosulfan. Endosulfan is a non-systemic
contact and stomach insecticide. It is used for controls
of aphids, thrips, beetles, foliar feeding larvae, mites,
borers, cutworms and bugs. The acute oral L050 of the
technical product in oil solution for rats is 80 to 110
mg/kg. The acute dermal L050 in oil solution for rabbits
is 359 mg/kg. Rats which were fed for two years on a diet

containing 30 ppm suffered no ill effects.

20

DIAZINON (Spectracide)

The solubility of diazinon in water at room
temperature is 40 mg/l. It is a non-systemic insecticide
with some acaricidal action. Main applications are in
rice, fruit trees, vineyards, sugar can, corn, tobacco,
potatoes, horticultural crops for a wide range of sucking
and leaf-eating insects. The acute oral L050 for rats
ranges from 300 to 850 mg/kg. The acute dermal L050 for
rats is 2150 mg/kg. Rats fed for ten months on diets

containing up to 65 ppm showed no gross toxic symptoms.

CHLORPYRIFOS (DURSBAN)

The solubility of Chlorpyrifos in water at 35°C is
2 mg/kg. It has a broad rang of insecticidal activity and
is effective by contact, ingestion and vapour action. It
is non-systemically active. It is used for the control of
mosquitoes (larvae and adults), flies, various soil and
many foliar crop pests and household pests. It is used
for ectoparasite control on cattle and sheep. The acute
oral L050 for male rats is 163 mg/kg, for female 135
mg/kg. The acute dermal L050 in solution for rabbits is

about 2000 mg/kg and it is rapidly detoxified in the

21

animals body.

PHOSMET (IMIDAN)

The solubility of phosmet in water is 25 mg/kg at
25°C. It is a non-systemic acaricide and insecticide. It
is used on a variety of crops including alfalfa, almond,
apples, apricots, cherries, citrus, corn, cotton, graps,
peaches, and ornamental trees. The acute oral L050 for
male rats is 230 mg/kg, for female 299 mg/kg. The acute
dermal L050 for albino rabbits is more than 3160 mg/kg.
Rats and dogs which were fed for two years on diets

containing 40 ppm showed no effect.

AZINPHOS-METHYL (GUTHION)

The solubility of azinphos-methyl in water is 33
mg/kg at room temperature. It is a non-systemic
insecticide and acaricide. It is used on a wide variety
of fruit, vegetable, nut, melon and field crops. The
acute oral L050 for female rats is 16.4 mg/kg. No
symptoms of poisoning occurred in rats fed 2.5 ppm/day

for two years.

22

CARBARYL (SEVIN)

The solubility of carbaryl in water is 40 mg/kg at
30°C. It is a contact insecticide with slight systemic
properties recommended for use against many insects pests
of fruit, vegetables, cotton and other crops. The acute
oral L050 for male rats is 850 mg/kg. The acute dermal
L050 for rabbits more than 2000 mg/kg. Rats fed for two
years on a diet containing 200 ppm suffered no ill

effects.

A summary of the above pesticides characteristics
and their toxicities is given in Table (1). Their

structures are given in Figure (1)

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.umums ca mandaomcH omen Hmuo mofiowumom vascumhmucoc acuoowo
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23

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24

25

Figure (1) The pesticides used in this study

 

common name chemical name

(In:
c1 ci' c1
cc13

2,2,2-trichloro-1,1-di-(4-chlorophenyl)ethanol

 

dicofol
(Kelthane)

 

endosulfan
. l
(Thiodan) Cl C
C1
C1
C1 0
>520
Cl 0
endosulfan I
Cl\\\ c1
C1
Cl
0
:;s::o
C1 0
Cl

endosulfan II

6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-
6,9-methano-2,4,3-benzo[e]dioxathiepin 3-oxide

 

26

Figure (1) continued

 

 

common name chemical name
diazinon 0%
(Spectracide)

u/ S
l ‘ "/0...“
(€33)’- \\\h o-__-P‘\‘ocnzcu,
0,0-diethyl-O-Z-isopropy1-6-

methylpyrimidin-4-yl phosphorothioate

Chlorpyrifos c1 c1
(Dursban) \\\
’/,, /’0C2H5
c1 a 0-—P\\ y
I] oczn,
s
0,0-diethyl 0-3,5,6-trichloro-2-byridyl
phosphorothioate
phosmet o
(Imidan) 5
mm
m——a5———s——U<: 3
cog
o

0,0-dimetheyl S-phthalimidomethyl

phosphorodithioate
azinphos-methyl o
(Guthion) a: n
3°\\\\\
p——:-—-cn——-n
mgo’///’ l
N
\

S-(3,4-dihydro-4-oxobenzo[d]-[1,2,3]-
triazin-3-ylmethyl)

 

 

 

 

27

Figere (1) continued

 

 

common name chemical name
carbaryl

(Sevin) fi *1

0—C—N—CH3

1-naphthyl methylcarbamate

 

 

 

28

OBJECTIVES

The pesticide waste disposal facility at Michigan
State University, Trevor Nichols Research Station,
Fennville, Michigan, is being utilized as a demonstration
model of a single compartment facility for multi-residue
dilute pesticide wastes input. The soil-filled, concrete-
lined facility was constructed in 1985. Dilute pesticide
wastes resulting from the rinsing of used pesticide
containers, spray tanks, and equipment used in pesticide
applications are disposed of each year into this
facility. We have no control over the input, as the
applications were made in response to insect control. No
storage tank was present thus rinsate inputs could not be
guantitated. The wastes consist of more than 20 different
pesticides (including pyrethriods, organochlorine,
organophosphate, carbamate pesticides etc.). Eight
pesticides were selected from the disposed pesticides
wastes for this study. These pesticide residues were
monitored from April to October over a two-year period,
1987-1988 for possible accumulation and/or dissipation.
No ammendments (e.g Lime, Microbes) were added to the

soil. The eight pesticides (Figure 1) were:-

29

- dicofol (Kelthane), endosulfan I (Thiodan), and
endosulfan II (Thiodan) as chlorinated hydrocarbon
pesticides.

- diazinon (Spectracide), chlorpyrifose (Dursban),
phosmet (Imidan), and azinphos-metheyl (Guthion) as
organophosphate pesticides.

- carbaryl (Sevin) as a carbamate pesticide.

The objectives of this investigation were:-

1- To determine the rate of dissipation and/or
accumulation of the pesticide residues in the soil at
monthly intervals.

2- To compare the dissipation of chlorinated hydrocarbon,
organophosphate and carbamate pesticides.

3- To evaluate this method or system for disposal and

dissipation of dilute pesticide wastes in Michigan.

CHAPTER 2

MATERIALS AND METHODS

CHAPTER 2

MATERIALS AND METHODS

MATERIALS

A. Sampling

1. Soil samples

The pesticide waste disposal facility
located at the Michigan State University, Trevor
Nichols Research Station, Fennville, Michigan, was
divided into 12 equal compartments, (Figure 2): Two

soil sample cores of about 100 grams each were taken
from each compartment through the soil profile (30-40 cm
deep). Twenty four soil samples were taken every month
from April 1987 to October 1988 . Twelve samples from
positions (A) were taken for analysis of chlorinated
hydrocarbon pesticides and another 12 samples from
positions (B) were taken for organphosphate and
carbamate pesticides. All soil samples were stored at

-20°C until analysis.

31

 

 

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32

33

2. Water samples

Water samples were taken from a drainage
tile surrounding and under the concrete-liner of
the waste disposal facility. The sample volume was

4 liters. Water samples were stored at 1°C until

analysis.

B. Glassware preparation

Glassware (round—bottomed flasks, separatory
funnels, beakers, funnels and chromatographic columns)
was thoroughly washed with detergent and hot water, and
then rinsed with distilled water followed by acetone.
The glassware was placed in a furnace and heated

overnight at 450°C before use.

C. Reagents

I. Solvents

Acetone, acetonitrile, petroleum ether, ethyl

acetate and methylene chloride were pesticide grade

solvents and used as received.

 

34

II. Chemicals

- Sodium sulfate (granular, anhydrous) was reagent
grade, and shown to be free of interference
to an electron capture detector. A

- Florisil- PR grade, 60-100 mesh was activated
at 135°C for 48 hours before use.

- Concentrated sulphuric acid (AR grade) was
used as received.

- Liquid Nitrogen.

- Dicofol (Kelthane) (97.4%), endosulfan I
(Thiodan) (99.8%), endosulfan II (Thiodan)
(97.9), diazinon (99.4%), Chlorpyrifos

(Dursban) (99.7), phosmet (Imidan) (99.8%),

azinphos- methyl (Guthion) (99.7) and carbaryl

(Sevin) (99.8%). All reference chemical
standards were obtained from (U.S.
Environmental Protection Agency (EPA),

Pesticides and Industrial Chemicals Repository,

Research Triangle Park, N.C.

III. Miscellaneous items.

- Glass wool (pyrex)-free of interference to an

electron capture detector.

 

 

35

- Whatman extraction thimbles were single

thickness, 33mmx94mm.

0. Equipment

- PERKIN-ELMER gas chromatograph (GC) model 8500
with Ni63 electron capture detector (ECD).

- Beckman Gas Chromatograph (GC) model GC-65
with flame photometric detector (FPD) in
phosphorus mode.

- SpectroMonitor 3100, MILTON ROY High
Performance Liquid Chromatography (HPLC)
equipped with a variable wavelength detector
(190-700 nm). BISCHOFF HPLC pump model 85.0
was used (anspec company).

- Gas Chromatograph Mass Spectrometry (GC/MS)

NERMAG RIO-10C.

- ROTAVAPOR-R BUCHI rotary evaporator.

METHODS.

Two different methods were used for analyses of
the pesticides one for chlorinated hydrocarbon and the
other for the organophosphate and carbamate

pesticides. Each soil sample was mixed thoroughly and

 

36

a 20 gram subsample was taken for each analysis.

1. CHLORINATED HYDROCARBON PESTICIDES

a. Extraction

An air-dried soil sample of 20 grams was placed in
a 250 ml round-bottomed flask and mixed with a 50 ml
mixture of acetonitrile-acetic acid-water (30:10:10). The
soil sample in the extraction solvent mixture was placed
in the dark for 16 hours at room temperature. The mixture
was then boiled under reflux for 15 min, cooled and the
extract was then decanted through glass wool into a 500
ml separatory funnel. The soil sample in the flask was
mixed again with 50 ml of the extraction solvent mixture
and again boiled under reflux for 15 min. This extract
was allowed to cool, decanted through glass wool and then
combined with the previously obtained extract. Three
hundred ml of distilled water was added to the combined
extract in the separatory funnel and mixed well. The
chlorinated hydrocarbon pesticides were partioned from
the aqueous layer into 50 ml of petroleum ether which was
separated and saved. This step for partitioning was

repeated two more times. After that the aqueous layer

 

 

37

was discarded. The combined petrolum ether extract was
washed with two 50 ml portions of water to remove
residues of acetic acid and acetonitrile. The extract was
dried by passage through a layer of anhydrous sodium
sulphate and concentrated to a small volume in a rotary
evaporator. The concentrated extract was transferred into

a 15 ml tube and the volume was adjusted to 10 m1.

b. Clean up

The concentrated extract was cleaned up by
intensive shaking of the extract with 1 ml of
concentrated sulphuric acid for 1 min. The tube was left
for 1 min until good phase separation occurred The upper
layer was removed with a pipette and dried by passing it
through a layer of anhydrous sodium sulphate and
concentrated to a final volume of 2.0 ml by a rotary

evaporator.
This followed the procedures of Waliszewski and
Szymczynski (1985) for extraction and clean-up with

some minor modifications.

c. Recovery study

 

38

The recovery study was carried out by adding a 1
ppm pesticide mixture (Kelthane, Endosulfan I, and
Endosulfan II) to three portions of 20 gram soil (muck
soil). These fortified soils were left for 24 hrs. so
that the binding reaction of pesticides with soil
particles could take place. The above procedure for
extraction and clean up was used. The recovery of
kelthane was 90%, Endosulfan I was 88% and Endosulfan II

was 85% Table (3).

d. Quantitation
A Gas Chromatograph with Ni63 electron
capture detector was used for the analyses. The following
conditions were employed for the analysis.
Column : DB-5 fused silica capillary column (30 m x
0.25 mm i.d.) with 0.25 micron phase
thickness.

Oven The temperature was programed from an

initial temperature of 200°C to a final
temperature of 260°C at a rate of
2°C/min.

Injector : Temperature 220°C.

Detector : Temperature 350°C.

Carrier gas : Helium at a flow rate of 20 psi.

 

39

Integrator : Perkin Elmar computer integrator was used

for quantitation.

2. ORGANOPHOSPHATE PESTICIDES

a. Extraction

A dry soil sample of 20 grams was transferred into
an extraction thimble, and subjected to soxhlet
extraction overnight with 140 ml mixture of acetone-
acetonitrile (1:1). The solvent extract was reduced to
25 ml with a rotary evaporator and transferred into a 500
ml separatory funnel. Distilled water (150 ml) was added
to the solvent extract. The organophosphate pesticides
were partition from the aqueous layer into 50 ml of
methylene chloride by shakeing for 2 minutes, separated
and saved. This step for partitioning was repeated two
more times. The combined methylene chloride extracts were
evaporated almost to dryness on a rotary evaporator. The
resulting extract was diluted to 25 ml with methylene

chloride.

b. Clean up

Florisil 60-100 mesh was activated at 135°C for

 

4O

48 hours before use. Pyrex column (10 cm internal
diameter (i.d.) x 51 cm length) with a Teflon stopcock
was packed with 10 gram of activated Florisil topped with
a 2 cm layer of anhydrous NaZSO4. The chromatographic
column was gently taped. This column was washed with 50
ml of ethyl acetate - methylene chloride (3:2). The
column was not allowed to dry at any time during the
procedure. The methylene chloride extract was
transferred to this column and then eluted with a 150
ml mixture of ethyl acetate - methylene chloride (3:2).

The total elution was collected, evaporated to dryness

and dissolved in 8 ml of acetone.
c. Recovery study

The recovery study was carried out by adding 1
ppm, 5 ppm and 10 ppm of a pesticide mixture (diazinon,
chlorpyrifos, phosmet azinphos-methel and carbaryl) to
three portions of 20 gram soil (muck soil) and then left
for 24 hours at room temperature. The above method of
extraction and clean up was followed. The average

recoveries ranged between 91% to 99.1% (Table 4).

d. Quantitation

 

41

Organophosphate compounds were detected by a

Beckman GC-65 gas liquid chromatograph equipped with a

flame photometric detector operated in the phosphorus

mode. Analyses were performed using the following
conditions:
Column : DB-S MegaBore capillary cloumn (30 m x

Oven

Injector :
Detector :
Carrier gas:

Gas flows :

Integrator :

0.53 mm i.d.) and a film thickness

of 1.5 micron.

The temperature was programed from an
initial temperature of 180°C to a final
temperature of 230°C at a rate of
10°C/min.

Temperature 200°C.

Temperature 300°C.

Helium at a flow rate 10 of ml/min.

Air at 200 cc/min and hydrogen at 150
cc/min.

An SP4270 Spectra Physics Integrator was

used for quantitation.

3. CARBAMATE PESTICIDE:

a. Extraction and Clean up

 

 

42

The methods for extraction and clean up of
organophosphate pesticides was followed except for the
final step where the pesticide residue was dissolved in
acetonitrile instead of acetone. The recovery for this

method was 96.2% for sevin (Table 4).
b. Quantitation

High Performance Liquid Chromatography (HPLC)
(reverse phase) with UV detector was used for these
analyses. Analyses were performed at the following
condition:-

Column : C18 column was used (4.6x220 mm), at 35°C.
Mobile phase: Acetonitrile-water (50:50 v/v).
Flow rate : 1 ml/min.

Detector : UV absorbance detector at 280 nm.
CALCULATION OF THE PESTICIDES CONCENTRATIONS

Quantitations of pesticides were based on peak
heights. A standard curve was constructed for each
pesticide from different concentrations of standard
solutions. The amount of each pesticide in the soil
sample was determined from its standard curve and the

following equation was used to caculate the concentration

 

 

43

of a pesticide in soil ug/gm (ppm).

ug/qm (ppm) = -----------

Where:-
X = amount of pesticide from a standard curve*.
Vf = the final extract sample volume (ml).
Ws = weight of soil sample (9).

* Linear regression was used for quantitation of

pesticides.

A standard mixtures were injected at the beginning
of each run and after every four samples. Figures 3, 4,
5, 6, 7 and 8 illustrate chromatograms of a standard

mixture and a sample.

WATER ANALYSES

Water samples were taken from a drainge tile under
the waste disposal facility. Water samples were analyzed
to check whether or not pesticide residues had leaked

from the concrete-lined disposal facility.

 

 

44

Method of analyses

A volume of water sample (900 ml) was placed into
a one-liter separatory funnel. The pesticides were
partitioned from the water into 50 ml of methylene
chloride which was separated and saved. This step for
partitioning was repeated three more times. The
combined methylene chloride was dryed with anhydrous
sodium sulfate (5 min.). The combined methylene chloride
extract was evaporated to dryness. The pesticide
residues were dissolved with petroleum ether for
chlorinated hydrocarbon, acetone for organophosphate and

acetonitrile for carbamate pesticides.

pH DETERMINATION

pH was determined by using the procedure of Smith
and Atkinson (1975). Distilled water (50 ml) was added to
20 grams of dry soil and thoroughly mixed. pH
determinations were recorded by using pH/meter model PHH-

80 (AE company).

ORGANIC MATTER

Organic matter was determined by following the

 

45

method of Miller and Keeney (1982). Ten grams of soil was
taken, dried in an oven (95°C) for 2 to 3 hrs and the
weight was recorded (W1). The soil sample was placed in
an oven for 24 hrs at 430°C, cooled in a disicator and
weight was recorded again (W2). The percentage organic

matter was calculated according to the formula.

W2
% organic matter = —--- x 100
W1
CATION EXCHANGE CAPACITY (CEC)
The procedure of Warncke (1988) was used for

analysis of the CEC. Two grams of soil was weighed and
transferred to a 50 ml centrifuge tube. Twenty ml of 1 N
neutral ammonium acetate was added and mixed for 15
seconds with a Vortex mixer. The sample was allowed to
stand for two hours. The sample was mixed and centrifuged
for 5 minutes at 2500 rpm. The supernant liquid was
decanted. These steps were repeated two more times. 15
ml ethyl alcohol (95%) was then addedd, and mixed for 15
seconds . This mixture was centrifuged and the supernant
liquid was then decanted. These last two steps were

repeated two more times. 5 m1 of an acidified sodium

46

chloride solution (10% NaCl + 0.3 ml conc. HCL per liter)
was added and was mixed. The sample was transferred
quantitatively to a steam distillation flask using
deionized distilled water. Six drops of 10 N NaOH was
added just prior to distillation. The steam was distilled
into boric acid collecting 30 ml (Blank for distillation=

5 ml NaCL solution + 10 ml distilled water).

ml(s) - ml(b) N
CEC = --------------------
S
where:
ml(s) = ml acid to titrate sample
ml(b) = ml acid to titrate blank
N = normalcy of acid

8 = sample weight

 

47

CONFIRMATION OF THE PESTICIDE IDENTIFICATIONS

Capillary Gas Chromatograph-Mass Spectrometry
(GC/MS) (Nermag R10-10C) was used for confirmation of
pesticide identifications. Capillary column 08-1 30 meter
by 0.25 mm ID (J&W Scientific) with 0.25 micron phase
thickness was used. Helium was used as a carrier gas with
a column pressure of 20 psi. The oven was temperature
programmed from 200°C to 260°C at 5°C per minute. The
filament current varied from 150 to 195 mA depending upon
source cleanliness. Methane was used as the moderating
gas with a source pressure of 0.035 Torr as measured by a
thermocouple gauge adjacent to the source. The heated
interface between the mass spectrometer source and GC was
maintained at a constant temperature of 250°C. The
electron multiplier voltage was 2.6kV with a dynode
voltage of 4.8kV. The quadrupoles were scanned from 70 to

500 u at a rate of 2 scans per second.

A summary of the chromatographic conditions used
for the analysis of the pesticides is given in Table

(2)-

 

48

 

 

 

 

 

 

 

 

 

 

 

 

16
dicofol
W
7.53
endosulfan I
*fififiF—v
endosulfan II
Aif?55==1tIti========================B
END
RUN 14 0831 88/12/12
METHOD 9 .GAHRL '""”"”"'CGLCULRTXOH: %
RT HEIGHT IO HEIGHTX
6.16 1263.71 7 6.9197
6.91 6463.62 1 6.1745
7.33 417.94 :8 0.3041
9.26 54316.46 1 99.5279
16.16 .536.96 '75 . 6.2452
16.52 143.97 76 6.1647
11.46 356.92 75 6.2597
11.66 72663.96 0 52.4636

Figure (3) CC chromatogram of a standard mixture of
chlorinated hydrocarbon pesticides.

 

16

 

49

 

 

 

 

 

 

 

 

 

 

 

 

 

 

15

RUN 52 18:23 88x12/13

METHOD 9 GGHGL CALCULATION: 2
RT HEIGHT EC HEIGHTX
6.66 1666.67 75 5.2717
6.76 1661.19 T5 2.7972
6.66 12216.16 T 34.1366
7.73 219.45 T5 6.6131
6.51 434.67 TS 1.2127
6.63 665.73 T6 1.9156
9.22 11666.16 T 36.9732
9.52 167.46 T5 6.3663
16.11 366.66 TS 1.6656
16.45 1616.42 T 4.5166
11.62 4626.65 T 11.2561
11.96 771.96 T 2.1566
12.16 1663.65 0 3.6275
12.39 263.94 6.7374

Figure (4) CC chromatogram of a soil sample for
Chlorinated hydrocarbon pesticide residues.

50

.« «mm

: C: "IN-

> wwStmozdcflum

Lev

nunmwwwuw

 

uoEmona

 

ma xmnzH

ohm mm.m mnm.a
04m mm.m mm..a
mom mn.m mmm.a
kmm¢ m~.m m5k.oa
new. mm.v mom.“
mamm mm.4 mo.~a
wage. mm.a mmm.mm
omm mm.w mm.o
mmv km.a 66.5
aav ~m.« mmm.o
mamma 60.5 kvw.m¢
e: 21 cm 3»:
ma 22m .o eczema

.mmunvumm mmumeumo

 

 

MD .M mowfiuzcuoflso

 

cocHume

 

 

aco>Hom

#mmnmmma
fiNM fifl

axmwm
.H mgnm
szcm

 

 

 

Figure (5) CC chromatogram of a standard mixture of OrganOphesphate

pesticides.

 

 

mo ...? mm .6 m3 S 3
ma mmom am.m mmo.m 45
mm new 4m.v m.m ma
mm .mmv. «6.4 m.m.m ma
mm 4mm mm.¢ amm.o «a
ma nvm mm.v 4m..o ma
mo med m4.m mmm.o m
we amen 2.. .N ...mm .N m
we 6mm ma.m mm..o A
ma Snead 4m.“ mmo.«~ m
we mmmma . m¢.a .mon.«m n
ma Sum am.a amm-a 4
ma «mama km.o mmm.«m m
do own m.s wmv.s m
«a was km.o mmm.o 5
cm A: xm pm we: excma
mm xquH mm 23m .9 noxemz .a m3_u
m .5 uma .m. 1:0 «muwmnao mauvoumo . sczce
e um

 

 

 

 

 

 

 

 

 

 

Figure (6) CC chromatogram of a soil sample for OrganOphOSphate pesticides

residues.

52

da mnamw mw.n

 

 

 

www.mm M

Ma nmv mm.M amw.a N

do «dam mM.N aan.aa a
om w: x1 hm xhz :xcma
mm xquH mm 23m .9 noth: .d wJHm
.d uma :c: uzu mmumduNd mmumaufid chmm

M. .mflu. in

qumnumo

 

Figure(7) HPLC chromatogram of a standard of a Carbamat

pesticide.

 

53

U266”-

8

 

‘ 9

E I
i tile-l
; '3'

w?

 

 

 

 

 

NJ

"'3 P111

Figure (8) HPLC chromatogram of a soil sample for
a Carbamat pesticide residue.

 

54

 

 

 

com

0.

:fls\o.m
omm oomnoom

mm

c«s\o.oa
cow onmnowa

:fis\0.~
0mm oomloom
nsH so>o

ousunuonaoa

ofiuflucwfiom awn
wmwcxofinu
omega sm~.o
Ass m~.ox56nc
sumo

mama mwaszoum

Ass o-x6.vv
canaoo wHO

ofluflucmflom zen
mmmcxofinu
mmmnm 5m.a
Assomm.ox2mav
wuon on“: mums

ofluflucmflom zen
mmwcxowsu
mmmnm 5mm.o
Ass m~.oxEonv
humaaflmmo mumo

EC 0mm
>D

0mm

Hz
nmom

uouoouoa

nonwouuuom on»
no mfiahadnu you can: unanuwcnoo oasmcuuouaaouno A". canes

Am=\oov
ooanoam mmsumz

Aoqmmv ooam
Houflcozouuommm

sou coca“:

Aoov meuoo
cmfixomm

Aoov comm
Mozamucwxumm

Oahu .aougo

55

 

mm.H hm.mm vw mm mm HH CMHHDMOUGO

mm.H om.mm hm mw om H CGMHSMCOCO
mw.N oo.om mm mm mm HOMOUflU
.>MQ .Bm 24m: m N H . DZDOQZOU
mZOHB<UmAme
>mm>00mm w

 

mmOMOMmeQ :onumoouphn pmumsfiuoano mo A.>mp .uwv
cofiu6M>wU cumucmum can >um>oomu unmoumm Amy dance

56

 

 

mN.oo mn.oo m¢.oo mm.oo Nh.oo .>OU .um
N.Nm H.mm m.wm m.~m o.Hm came
Hm My mm mm mum ----mm---
m.mm m.mm m.mm H.nm m.Hm m
v.mm H.mm m.wm v.~m N.o¢ H
“mum“... wwmwwwummmmmwmm “Emma mmmwmwmmmwfl mmmmmmwm
.......................... ------....-..-----..:-..--..-..--.. ..--.mmu-
Am>mfl ZOHB
>mw>oomm » I<UHhHBmom

 

mopflofiumwm wumSmnHmo can mumnmmonmoscwuo A.>mv .umv
mo cowum«>mo oumccmum.p:m >uw>oomu unmoumm Avv wanna

CHAPTER 3

RESULTS AND DISCUSSION

 

CHAPTER 3

RESULTS AND DISCUSSION

The concentration of pesticide residues were
monitored every month from April to October for 1987 and
1988 in a soil-filled, concrete-lined waste disposal
facility. This facility is located at Michigan State
University, Trevor Nichols Research Station, Fennville,
Michigan. This study was determine the rate of
dissipation and/or accumulation of pesticide residues for
three chlorinated hydrocarbons, four organophosphates and
one carbamate. Also this research was conducted to
evaluate this method for disposal of dilute pesticide
wastes. These wastes are produced from the rinsing of
used containers, spray tanks and equipment which had been

used in the application of the pesticides.

Twelve soil samples were taken from the waste
disposal facility for analyses of the chlorinated
hydrocarbon pesticide residues and another 12 samples for
analyses of the organophosphate and carbamate pesticide
residues each month. Each soil sample was mixed
thoroughly and 20 g was taken for analyses.

58

 

59

The soil type used at this pesticide waste disposal
facility was muck. The pH, organic matter and the cation
exchange capacity were determined. The pH varied from 5.1
to 5.8; the organic matter varied from 50% to 60% and
the cation exchange capacity was 83.7 meq/100 g soil

Table (5 ) .

Pesticide residue concentrations in the soil
samples from the waste disposal facility was shown not to
accumulate in the soil of the facility. All chlorinated
hydrocarbon, organophosphate and carbamate pesticide

residues concentration decreased with time.

 

60

Table (5) Characteristics of the soil

used in the waste disposal facility

Soil type Muck
pH 5.1 to 5.8
Organic matter 50% to 60%

Cation exchange capacity 83.7 meq/loo g soil

61

I - THE DISSIPATION OF THE PESTICIDES RESIDUES IN THE

WASTE DISPOSAL FACILITY.

All the pesticide residue concentrations
decreased with time. The dissipation of dicofol
(Kelthane), endosulfan I (Thiodan) and endosulfan II
varied from 53% to 80% from the highest concentration to
the end of the seasons of both year 1987 and 1988. Tables
6 and 7 show the mean and the standard deviation for
dicofol, endosulfan I and endosulfan II each month. Each
mean represents 12 soil samples. While dissipation of
diazinon, Chlorpyrifos (Dursban), phosmet (Imidan) and
azinphos-methyl (Guthion) varied from 25% to 87% from the
highest concentrations to the end of the seasons of both
year 1987 and 1988. Tables 8 and 9 show the mean and the
standard deviation of these pesticides conentrations.
Again each mean represents 12 soil samples. Carbaryl
(Sevin) was rapidly dissipated as seen in 1987 where
within two months the concentration decreased from the
high of 6.71 ug/g (ppm) to 0.93 ug/g (ppm), a 87%
decrease. Also in 1988 the concentration decreased from

3.79 ug/g (ppm) to 0.78 ug/g (ppm), a 80% decrease.

62

Tables 10 and 11 show the mean and the standard deviation

of carbaryl each month.

From our study the chlorinated hydrocarbon
pesticide residues concentrations decrease by the end of
the season for both years 1987 and 1988 even though this
class of pesticides are more persistent in the
environment than the other classes of pesticides (Kaufman

1974).

None of the eight pesticides were detected in the
water samples which had come from the drainage tile.
Which means that, the concrete-line was intact and no
leakage had occurred from the facility after three years

of use.

 

63

There are many process or path ways that may be
used to explain the dissipation of these' pesticide
residues from the soil of this facility. Decrease of the
pesticide concentrations or dissipation could happened by
volatilization of these pesticides which is a major route
for dissipation of many pesticides (Caro and Taylor,
1971). July and August in both 1987 and 1988 were warm at
the site of study and the temperature varied from 30°C to
35°C which could increase the rate of volatilization.
There are two environmental factors affecting
volatilization, temperature and soil moisture (Spencer
and Cliath, 1970). On the other hand volatilization rate
is also dependent upon other environmental factors that
modify the effective vapor pressure of the pesticides

(Nash,1983).

Dissipation of the pesticides could be by
microbial activity because microbial degradation is an
important phenomenon affecting the degradation of
pesticides in soil (Tollefson, 1986). Microorganisms are
capable of degrading some pesticides to many metabolites.
Their activity is influenced greatly by environmental

factors, temperature and soil moisture are considered

64

the most important factors (Hill and McCarty 1967).

Chemical degradation was also possible for
dissipation of many pesticides. Oxidation, reduction,
hydrolysis, and polymerization of pesticide compounds
have all been proven or postulated in soil incorporation
studies (Leaonard et al., 1976). Soil pH plays an
important role in degradation of many pesticides. The
chemical degradation in an alkaline soil is more rapid
than acid or neutral soils (Paschal 1976). In general,
warmer temperature-and higher soil moisture facilitate

chemical reactions.

Photochemical degradation plays a role in the
degradation of pesticides in the soil. Radiant energy is
strongly sorbed by soil but it available to pesticides

only on the soil surface (Goring, 1975).

Most likely most of the above factors were
responsible for the dissipation of these pesticide during

this period.

The pesticide waste disposal facility at Fennille,

Michigan, Michigan State University has prove to be a

 

65

good method for the dissipation of dilute pesticide
wastes. Thus, for a disposal pit suitable for individual
farmers' and small applicators (Hall 1984). Pit disposal
systems are effective for degradation of pesticides as
well as other organic chemicals and not contaminate the

surrounding air or water (Junk and Richard 1984).

Figures 9, 1o, 11, 12, 13, 14, 15 and 16 illustrate

the monthly concentrations of the pesticide residues

in a waste disposal facility at Michigan State University.

66

.noamauu Haou «a muconoumou coca noun.

» 20H

wow wow «Nb lfidewwHD
--qum--mmum-------mwum--mmum------mwnwm--mwumm ....... mmmmmmm
mm.o nn.o om.o bn.o vw.HH wN.mo mmmzmfimmw
mn.o 4N.o wN.o om.o Nv.Ho HH.No BmDUD<
mv.o vn.o mm.o mm.o wn.mN 5H.ma wflbb
mw.o vv.o no.0 mw.o No.no hn.no mZDb
no.0 No.0 ¢o.o Ho.o nh.oo on.oo AHmm<
”mum 1mm” ”mum mama ”mum mums ........
mm-mmwwmmmmmw “-mwmmwwmmmm ---Mmmmmmm- ....z

 

.hoaa aw huaauo>wao oudsm savanna:
an mundaouu Henchman enact 6 ad nocqoaunon
oawuoanoonuuuo veuoonoa on» no unoaueuuaoooo on» «0
1.6.6. coauaapoo canons». on» on. .auoa Saguaoa one .6. canny

67

.noamaam Hwon «a musomouaou duos noun.

 

 

 

w 20H

wnh #bh wmm IB<mHmmH0
--mum:mum::-:mum--mm...m-------mmqmm--mu ....... mmmmmmm
m0.0 mv.0 00.H 00.0 mH.00 mv.m mmmzmfimmm
0N.0 vH.0 v0.0 0N.0 0m.ho mm.m 800054
hH.0 0H.0 v¢.0 0n.0 mm.0H mm.m wQDU
00.0 0H.0 0n.0 mN.0 HN.m0 h0.¢ @290
0H.0 00.0 hH.0 VH.0 «b.0H mm.0 AHdfid
.....mm mama“ ”mm mm. 4mm... mummy .....

HH ccuasmovcm H cmuasmopcm Houoowc mazoz

 

.cooa a“ hudauo>wao ouuum savanna:
an hadnuoau Haaomaao Quad: a nu nonwowuaom
onuuo~noonduuo concedes on» no enouuuuunoonou on» uo
..o.u. no«uua>oo uneven». on» can .auoa Sanunoa one .5. canes

 

.noamado Hwon «H muaomoumou coca noun:

 

68

x 20H

000 000 00m 000 IBdflHmmHD
---...mm-...m..---mam--mmm---...mm--...mm---mmm--mfl---mmmmm
00.00H 00.50 00.55 H5.00 H0.n5 00.00 50.H v0.H 000209000
00.0H vv.00 00.00 m0.v0 H5.5H 00.0H 00.0 05.H 800004
H0.00 00.00 00.50 00.00 50.00 00.0H nv.0 00.H MADb
00.00 00.50 00.50 05.00 00.00 H0.0H 0H.0 mn.H QZDb
00.00 00.50 00.00 v0.00 00.0H 00.50 00.0 00.0 AHmmd
mm mm. 4mm mm. Am -...M. ”mm... mm. ........
magmas...“ --mmmm “mama 9mm“

.uaau aw huuauo>wab ouaum nemanoax
an hauawo¢u Haaonaav 00066 a a« novaoaunom
cunnnnonaonauuo concedes on» uo .Iaav acoaucuuaooaoo on» «0
1.6.6. nouuna>ov canon.»- onu can .naoa hanaqoa one .6. canes

69

 

.u0003uu 000» «0 nanomoumou

duos noun.

 

w 200
050 «00 «00 050 I84000000
mmm--...mqmm---mmm-..wmum---w......m:00:00.0-..«Mm- --mmmmso
00.00 00.00 00.00 00.00 00.00 00.00 00.0 v0.0 000208000
05.50 00.00 00.00 00.00 00.50 50.00 00.0 00.0 800004
00.50 00.00 00.00 00.00 00.00 00.00 50.0 00.0 0000
00.v0 00.00 00.00 00.00 05.00 00.00 00.0 0v.0 0200
00.00 50.00 05.00 00.00 05.00 00.00 00.0 00.0 00000
”mm 001 ”mum 000. Maw 00. ”mm. mm... ........
000003000- 0me.01.10 mmmmmmmmm .0000 :98:
.0000 a0 hu0uuo>0ao ouuum nu00n00z IIIIII
an 00000ouu 0uuonu0u onus: a a0 uou000uaom
ouunmuonnoauouo usuOO0OQ on» no .aau. an00uuuunooaoo onu uo

..n.e. acquau>ou unsung». on» uuu .aaoa hanuuoa one

.3 033.

7O

.mo00aua 000m «0 munoaou0ou nuoa noum.

 

«00
0v.0 00.0
05.0 00.0
00.5 05.0
00.0 00.0
0v.0 00.0
00.0 00.0
”mum 01mm
---mmmmmmw:

* ZOHB¢0000HQ

000209000

909090

0030

 

.5000 :0 huuuuo>0no ouu»
an muaaaouu auaoauau
00000006 on» 00 «S00

do0uu0>ou uuuuaunn on» uau a

Quad: 1 :0 no

0 nuo0n00z

000uuo0 unaunuuo

0 aa00uauusounoo on» 00 ..a.00
duos h0nuaoa any “on. 00nua

71

.aoamadu Hwou «« manonoumou anoa noon:

wmh w ZOHB<mHmmHQ
Sis.------..wum::m~.....m ........................ mmmmmmm
hH.H Hm.H mmmzmfimmm

Mb.n mb.n Bmawbd

mv.m mm.m wdDb

0H.H vn.H NZDU

bn.o Hw.o AHmmd

ahumnumu

.ooau a“ madauo>aap ounam manage“:

an h3aaq0du aduomnwc can.) 0 ad ovaowuuon unadnudo
couooaon can we .lmn. anoduduunoooo on» no A.o.m.
noauua>oo uuaonuua on» can .auoa maaunoa ona .«a. canoe

72

WEAR l987

 

I dicofol

 

 

 

CONCENTRATION (PPM)

 

APR JUN JUL AUG SEP OCT
MONTHS

Figure (9) The monthly concentration of dicofol in a waste

disposal facility at Michigan State University in 1987.

73

 

    

 

E WEAR 119" .

o. 20W I dicofol
E:

Z

2

’—

31: 10- ‘-{-

'2 2

E

u o-

 

APR JUN JUL AUG SEP OCT
MONTHS

Figure (10) The monthly concentration of dicofol in a

waste disposal facility at michigan state university in 1988.

74

WEAR l©87

_/ ‘
0.8 I endosulfan l
lendosulfan II
0.6 -

 

 

 

CONCENTRATION (PPM)

 

MONTHS

Figure (11) The monthly concentrations of endosulfan I
and endosulfan II in a waste disposal facility at Michigan

State University in 1987.

75

—————— VEAR IQII
0.8 W I endosulfan I
A Iendosulfan ll

 

 

 

CONCENTRATION (PPM)

 

APR JUN JUL AUG SEP OCT
MONTHS

Figure (12) The monthly concentrations of endosulfan l and
endosulfan II in a waste disposal facility at Michigan

State University in 1988.

76

 

 

 

 

 

.W.
.n
a
s
o m
f _
n .n t S
o v. e o
n m. m .m.
.I S
u m o .m
onl- h h
d C p Mu.
I a I Z
7///////////////////N////M///
A: % rs
.x///////////./,A/...///_/,.
7/////////////////////JJJJJJ/V/////////,
x///////////////////AA//flflnflg//z
W 7/JJ1.
9 7/////A/.
a“
a.“ ///////////JJJ/,
% 7////////.AAA
V.
////////////////J/..
,/////////A
7.7/1.
/////
I d I - I - I - I d I d
O O o 0 o o o
6 S 4 3 2 l

9.7:: ZO_._.<~_._.ZmUZOU

JUN JUL AUG SEP OCT
MONTHS

APR

Figure (13) The monthly concentrations of diazinon,

chlorpyrifos phosmet and azinphos-methyl in a waste disposal

facility at Michigan State University in 1987.

77

 

WEAR IQII

 

60
50 "
4O .
3O "

20-

 

CONCENTRATION (PPM)

I diazinon
Ichlorpyrifos
phosmet
.azinphos-methyl

  

 

>\\\\\\V

  

APR JUN JUL AUG SEP OCT
MONTHS

Figure (14) The monthly concentrations of diazinon,

chlorpyrifos phosmet and azinphos-methyl in a waste disposal

facility at Michigan State University in 1988.

78

 

/— WEAR IQI'?
a 7 I carbaryl

 

 

 

CONCENTRATION (PPM)

 

APR JUN JUL AUG SEP OCT
MONTHS

Figure (15) The monthly concentrations of carbaryl in a
waste disposal facility at Michigan State University

in 1987.

79

VEARIQBE

 

 

CONCENTRATION (PPM)

APR JUN JUL AUG SEP OCT
MONTHS

 

 

I carbaryl

Figure (16) The monthly concentrations of carbaryl in a

waste disposal facility at Michigan State University

in 1988.

80

II. DISTRIBUTION OF THE PESTICIDE RESIDUES IN THE WASTE

DISPOSAL FACILITY.

The concentrations of the pesticide residues were
found to be extremely variable in the soil of the waste
disposal facility. The pesticide residues were heavily
concentrated in the middle and less concentrated near the
sides of the waste disposal facility. The highest
concentrations were found in the compartments numbered 4,
5, 7, and 8. This was due to the location of the two
distribution sprayers which were) located above these
compartments. The first sprayer was located above
compartments number 4 and 5 and the second sprayer was
located above compartments number 7 and 8 Figure (2).
Tables 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24
25, 26 and 27 show the distribution of dicofol
(Kelthane), endosulfan I (Thiodan), endosulfan II,
diazinon, chlorpyrifos (Dursban), phosmet (Imidan),
azinphos-methyl (Guthion) and carbaryl (Sevin) in the
facility for the 1987 and 1988 seasons. An example of the
distribution of one of the pesticides in the waste
disposal facility is chlorpyrifos. The highest

concentration of chlorpyrifos was 209.20 ug/g (ppm) in

81

compartment number 8 and the lowest concentration was
1.05 ug/g (ppm) in compartment number 11 in September of
1987. These tables also show fluctuations of the
pesticide residue concentrations during the both years
1987 and 1988 was due to dispose of pesticide wastes in
any time. We had no control over any pesticide waste

input as no storage tank was available

The the pesticide formulation wastes was minimized
in 1988 by calculating the exact amount needed for
applications. Therefore the concentrations of the
pesticide residues in the waste disposal facility in the

second year was lower than that in the first year.

The lack of statistics for this study was due to a
variety of reasons. The first reason was one could not
calculate the pesticide waste input as no storage tank
existed for sampling . The second reason concerned the
uneven distribution of pesticide wastes in the soil. As
a result, of the gross variations of pesticide
concentrations in the twelve sampling areas in 1987 and
1988 it was difficult to get a representative sample.
This is illustrated in the following example for

azinphos-methyl (Guthion). It was observed in September

82

1987 That where varied from 1.53 ug/g in one area (ppm)
to 367.67 ug/g (ppm) in another. Thus, the next study

should correct the distribution problem and replicate

plots must also be incorporated.

Table (12) Distribution of dicofol (Kelthane) in a waste
disposal facility at Michigan State University
in 1987.

COMPARTMENT I CONCENTRATION (PPM)

 

10 0.10 0.76 8.49 0.32 0.40 0.10
11 0.08 3.06 9.88 1.19 0.72 1.24
12 0.15 1.16 8.78 1.78 25.95 0.98

Table (13) Distribution of dicofol (Kelthane) in a waste
disposal facility at Michigan State University

 

COMPARTMENT # CONCENTRATION (PPM)

10 0.17 0.60 0.73 0.12 0.28 0.18
11 2.07 3.53 3.67 2.09 2.16 8.16
12 1.64 6.76 9.98 0.34 1.92 5.18

83

Table (14) Distribution of endosulfan I (Thiodan) in a
waste disposal facility at Michigan State University

 

 

in 1987.
s! n W
COMPARTMBNT # CONCENTRATION (PPM)

10 0.00 0.02 0.00 0.00 0.01 0.00
11 0.00 1.28 0.00 0.00 0.01 0.02
12 0.00 0.06 0.00 0.00 0.03 0.04

 

 

Table (15) Distribution of endosulfan I (Thiodan) in a
waste disposal facility at Michigan State University
in 1988.

 

COMPARTMENT # CONCENTRATION (ppm

10 0.32 0.03 0.22 0.03 0.03 0.03
11 1.19 0.04 0.09 0.03 0.04 0.03
12 1.78 0.32 0.34 0.04 0.04 0.17

 

.84

Table (16)

Distribution of endosulfan II (Thiodan) in a
waste disposal facility at Michigan State University

in 1987.

 

COMPARTMENT I

Table (17)

E.—

CONCENTRATION (PPM)

Distribution of endosulfan II (Thiodan) in a

waste disposal facility at Michigan State University

in 1988.

 

COMPARTMENT #

CONCENTRATION (PPM)

85

 

Table (18) Distribution of diazinon in a waste
disposal facility at Michigan State University
in 1987.

 

 

COMPARTMENT # CONCENTRATION (pm)

1 . . .

2 0 00 1.37 1.75 1.66 0 92 0 45
3 0 00 1.28 1.61 1.62 0 92 0.45
4 0 00 1.28 1.61 1.62 0 92 0 03
5 0 00 1.37 2.76 1 62 4 63 10 57
6 0 00 1.28 2.76 2 50 0 92 0 30
7 0 00 1.80 1.73 1 62 0 92 0 32
8 0 00 1.36 1.88 2 42 0 92 0 30
9 0 00 1.40 1.76 1 62 1 04 0 21
10 0 00 1.28 1.62 1 62 0 92 0 30
11 0 00 1 28 1.62 1 62 0 92 0 30
12 0 00 1 27 1.62 1 62 0 92 0 30

 

Table (19) Distribution of diazinon in a waste
disposal facility at Michigan State University
1n 1988.

 

COMPARTMENT # CONCENTRATION (PPM)

1 . .

2 0 38 1.38 1.32 1.10 0 96 0 91
3 0 38 1.38 1.19 1.10 0 96 0 91
4 0 30 1.38 1.19 1.10 0 96 0 91
5 0 83 2.40 1.19 1.10 0 96 0 91
6 0 38 1.38 1.19 1.10 0 96 0 91
7 0 38 1.38 1.19 1.10 0 96 0 91
8 0 38 1.38 1.19 1.10 0 96 0 91
9 0 38 1.38 1.19 1.10 0 96 1 14
10 0 38 1.38 1.19 1 33 0 96 0 91
11 0 38 1 38 1.19 1 10 0 96 0 91
12 0 38 1.41 1.19 1 10 0 96 0 91

 

86

Table (20)

Distribution of chlorpyrifos (Dursban) in a

'waste disposal facility at Michigan State University
in 1987.

CONCENTRATION (PPM)

COMPARTMENT 8

 

 

 

 

APR JUN JUL AUG SEP OCT
1 0.2 1.25 1.62 1.51 1.97 1.17
2 0.51 3.75 4.02 2.16 8.96 2.16
3 0.34 1.72 1.63 4.30 3.90 2.13
4 0.32 75.35 6.86 5.78 12.31 4.55
5 36.69 7.29 33.90 2.49 204.47 41.59
6 7.9 12.38 4.56 29.17 8.58 1.99
7 12.43 25.82 63.68 7.54 11.19 2.81
8 16.45 50.51 87.18 54.30 187.14 209.20
9 3.45 2.53 8.68 6.99 2.93 15.35
10 2.42 1.32 5.24 1.53 1.35 1.68
11 2.01 2.72 2.99 38.70 73.70 1.05
12 3.49 1.36 3.09 1.32 7.05 58.65
Table (21) Distribution of chlorpyrifos (Dursban) in a

waste disposal facility at Michigan State University
in 1988.

 

COMPARTMENT #

1.27
1.42
2.43
0.22
73.87
8.62
12.24

101.53

5.12
10.12
15.81

2.68

CONCENTRATION (PPM)

 

87

Table (22)

disposal facility at Michigan State University
in 1987.

Distribution of phosmet (Imidan) in a waste

 

 

 

1.36

 

1 0.43 0.98 1.01 1.21
2 0.43 1.49 1.85 1.76 3.76 0.94
3 0.43 0.93 0.82 2.09 1.56 0.93
4 0.43 4.42 3.13 4.99 3.15 1.85
5 0.43 4.42 22.75 1.89 273.82 106.18
6 0.73 12.38 2.41 21.62 10.07 0.68
7 0.90 25.82 4.19 1.68 1.27 0.68
8 0.78 11.70 22.79 9.23 16.12 29.40
9 0.70 3.85 7.30 5.77 2.50 9.35
10 0.77 2.23 3.87 1.53 1.39 1.66
11 0.85 2.10 1.42 2.65 3.13 0.37
12 0.85 1.90 1.53 1.38 2.38 3.56
Table (23) Distribution of phosmet (Imidan) in a waste

disposal facility at Michigan State university
in 1988.

 

COMPARTMENT #

CONCENTRATION (PPM)

 

 

88

Table (24)

waste disposal facili

Distribution of azinphos-methyl (Guthion) in a
ty at Michigan State University
in 1987.

 

 

CONCENTRATION (PPM)

 

APR JUN JUL AUG SEP OCT
1 0.29 0.75 0.80 1.34 1.53 0.09
2 0.33 2.85 1.71 1.59 1.53 0.10
3 0.69 2.85 0.80 2.30 1.68 1.13
4 0.33 53.42 2.90 3.95 3.86 1.59
5 0.94 2.31 21.13 1.88 367.67 122.86
6 5.18 2.95 2.15 25.29 8.51 0.75
7 7.15 10.15 20.26 2.13 5.22 0.50
8 1.21 244.30 218.75 51.39 281.13 371.13
9 1.46 3.55 3.21 5.74 2.12 6.14
10 0.69 1.93 2.14 1.44 1.44 3.20
11 0.61 1.89 2.64 2.94 7.93 0.30
12 73.01 1.39 1.85 1.27 2.07 6.14

Table (25) Distribution of azinphos-methyl (Guthion) in a

waste disposal facility at Michigan State University
in 1988.

 

COMPARTMENT #

1.21
1.69
1.34
0.54
103.17
10.31
6.98
208.82
7.98
11.20
1.54
1.23

CONCENTRATION (PPM)

1.16
2.23
5.74
6.39
145.36
3.10
10.28
86.24
1.86
1.11
3.58
1.29

89

 

 

Tab1e(26) Distribution of carbaryl (Sevin) in a waste
disposal facility at Michigan State University

 

in 1987.
COMPARTMENT # CONCENTRATION (PPM)

APR JUN JUL AUG SEP OCT
1 0.26 1.81 2.31 3.09 1.40 0.62
2 0.55 2.07 1.75 3.19 1.54 1.01
3 0.44 1.18 1.86 2.32 0.86 0.61
4 1.46 1.80 2.97 18.59 2.89 1.60
5 2.43 3.71 5.16 20.95 4.30 1.86
6 0.36 1.57 2.99 4.48 1.15 0.62
7 0.72 1.15 1.28 1.92 0.60 1.19
8 0.90 5.73 0.86 15.66 2.88 0.63
9 1.32 1.77 2.31 2.79 0.86 0.55
10 0.28 0.35 0.55 0.94 5.98 0.54
11 3.35 1.77 2.89 4.53 2.89 1.18
12 0.90 1.00 1.43 2.16 1.00 0.69

Table (27) Distribution of carbaryl (Sevin) in a waste
disposal facility at Michigan State University

 

in 1988.
COMPARTMENT # CONCENTRATION (PPM)
""""""" £13?""36.7""362""’§65"'"§£E""-683"
333 I39 II. I? {:37 3:25

10 0.46 0.72 1.07 0.34 0.68 0.21
11 0.61 0.99 0.34 3.36 2.13 3.03
12 0.29 0.58 1.18 1.44 1.01 0.75

90

CHAPTER 4

SUMMARY AND CONCLUSIONS

CHAPTER 4

SUMMARY AND CONCLUSIONS

Dilute pesticide wastes resulting from the
rinsing of used containers , spray tanks, equipment
used for pesticide applications and leftover spray
solution of pesticides are disposed each year in a
waste disposal facility. This facility is a concrete-
lined, soil-filled (muck soil) single compartment.
This waste disposal facility located at Michigan State
University, Trevor Nicols Research Station, Fennville,
Michigan. More than 20 different pesticides are
disposed each year in this facility. Eight pesticides
were selected from the disposed pesticides wastes for
this study. These pesticides were three chlorinated
hydrocarbon pesticides, four organophosphate pesticides
and one carbamate pesticide. These pesticide residues
were monitored over a two-year period for possible
accumulation and/or dissipation without manipulation of

soil microorganisms or soil types.

92

93

The waste disposal facility appeared to be an
adequate method for the dissipation of dilute pesticide
wastes. The pesticide residues did not accumulate after
three years of use. Also the concentration of the
pesticide residues decreased with time from the highest
concentration of the pesticides (highest input) to the
end of the seasons of 1987 and 1988. Even the
chlorinated hydrocarbon pesticide residues decreased
with time which was unexpected for this class of
pesticide. In addition, no pesticide residues were
found in the drainage tile under the facility, which

means no leakage had occurred during the study.

Organic matter and water in a soil are essential
for an effective dissipation in a waste disposal
system. Organic matter in a soil bind pesticides and,
therefore, affects the adsorption capacity of
pesticides. High adsorption capacity of pesticides on
soil particles is required for increase retardation of
movement of pesticides in soil. Water is important for
volatilization and hydrolysis of some pesticides. Also,
it is important for soil microorganisms. 0n the other

hand the temperature is very important for dissipation.

94

A warm temperature increases the volatilization of

pesticides and facilitate chemical reactions.
Microorganisms are also more active at warm
temperature.

A high concentration of pesticides can kill soil
microorganisms and therefore the input of pesticide
wastes should be minimized. To maintain the native
microorganisms in a soil, addition of nutrients to a
waste disposal facility may be necessary. Also the
distribution of pesticide wastes over a soil surface of
a waste disposal facility should be uniform in order to

maximize the dissipation potential which is required.

In order to maintain a reasonable level of safety,
any waste disposal facility should be monitored at
least twice a year. Checks of surrounding air and

grondwater should be conducted.

Moreover, minimizing the pesticide wastes input
should be consider by calculating the exact amount of
pesticides needed. Also the contamination of
groundwater from landfills can be avoided by improved

design, construction, operation, and maintenance.

95

Design considerations should always include the
hydrogeology of the location, area to be served, and
types of wastes. The use of liners and covers, as well
as collection and treatment of leachate further reduce
the potential for groundwater contamination
(Conservation Foundation 1987). Therefore disposal of
pesticide wastes must be in accordance with the Federal
Resource Conservation and Recovery act, state and local

regulations.

CHAPTER 5

FUTURE WORK

97

CHAPTER 5

FUTURE WORK

There are some projects which I can see for the
continuation of the research I have completed on the
dissipation of some pesticides in a concrete-lined,

soil-filled waste disposal facility.

1- MASS BALANCE

One of these projects would be an investigation
of the mass balance of the pesticides in a waste
disposal facility. This study would concentrates on
where are the parent pesticides going? There are many
pathways for dissipation of any pesticides such as:

a- Volatilization.
b- Chemical degradation.
c- Biological degradation.

d- Photochemical degradation.

98

2- CHEMICAL OR PHOTOCHEMICAL PRE-TREATMENT

Another project would be pre-treatment of the
pesticide wastes by chemical or photochemical
processes. This kind of pre-treatment would be very
useful for initiating the breakdown of the pesticide
wastes specially to the more stable pesticides
(chlorinated hydrocarbon pesticides) prior to input to
a waste disposal facility. This could enhance the rate

of degradation of these pesticides.

99

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