PB 202 202
ORGANIC PESTICIDES AND PESTICIDE CONTAINERS -
A STUDY OF THEIR DECONTAMINATION AND
COMBUSTION
Robert C. Putnam, et al
1971
NATIONAL TECHNICAL INFORMATION SERVICE
Distributed ,.. 'to foster, serve
and promote the nation's
economic development
and technological
advancement.'
U.S. DEPARTMENT OF COMMERCE
This document has been approved for public release and sale.
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ORGANIC PESTICIDES AND PESTICIDE CONTAINERS
A Study of Their Decontamination and Combustion
This report (SW-21c) was prepared for the
Federal solid waste management program by
ROBERT C. PUTNAM,
FRANK ELLISON,
ROBERT PROTZMANN, and
' JOHN HILOVSKY
Foster D. Snell, Inc.
under Contract No. CPE 69-140
U.S.. ENVIRONMENTAL PROTECTION AGENCY
1971
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DATA? [1. Report
SHEET
EPA-SW-21C-71
3' Recipient's Accession No.
4. Title and Suit itle .
Organic Pesticides and Pesticide Containers; A Study of Their
Decontamination and Combustion
5. Report Date
1971
6.
7. Authors) Robert C. Putnam, Frank Ellison,
Robert Protzmann, and John Hilovsky
8> Performing Organization Kept.
No.
9. Performing Organization Name and Address
Foster D. Snell, Inc.
Florham Park, New Jersey 07932
10. Project/Task/Work Unit No.
11.
CPE 69-140
12. Sponsoring Organization Name and Address
U.S. Environmental Protection Agency
Office of Solid Waste Management Programs
Rockville, Maryland 20852
13. Type of Report & Period
Covered
14.
15. Supplementary Notes
\
16. Abstracts I ne problem of the disposal of waste pesticides is constantly increasing in
acuteness with the diversification of their use and th/3 growth of population. Their
escape into the environment as a resul'. of disposal p.';..ctices must be controlled or pre-
vented. Some waste pesticides are bein^ stored until safe disposal methods are avail-
able; however, they cannot be accumulated indefinitely. The purpose of this project was
to investigate methods of combustion applicable to disposal of pesticide residues and
their containers and to devise a means for their destruction that would keep environ-
mental pollution to a minimum. Oxidizing agents and binders generally aided the
destruction of pesticides; the combination of oxidants and petroleum oil binders was no
more effective than the oil binders alone. By using polyethylene, which under heating
or combustion conditions softens or degrades to products of lower molecular weight, the
advantages of a liner and a binder were obtained with one material. A practical system
was devised that consisted of burning the pesticide in a flattened polyethylene bag on
or surrounded by other combustible material. Suggestions were made concerning an
improved design of polyethylene container or liner to aid in carrying out the purpose
of this investigation.^- . . ___,
17. Key Words and Document Analysis. 17o. Descriptors
Refuse disposal,*Pesticides,*Containers--Waste disposal,*Combustion efficiency,
Pyrolysis,Thermal degradation,*0xidants,*0xidizing agents,*Binders, Polyethylene,
Liners
17b. Identifiers/Open-Ended Terms
Environmental pollution, Petroleum oil, Malathion, DDT, Gas liquid chromatography,
Perkin Elmer Pyrolysis Unit, Scanning calorimeter, Potassium Chlorate, Mineral oil,
Nitrates, Chlorates
'7e. COSATI Field/Group 13B
18. Availability. Statement
Release to public
19.. Security Class (This
Report)
UNCLASSIFIED
20. Security Class (This
Page
UNCLASSIFIED
21. "Mo. of Pages
182
[22. Price
$3 'or $0.95
FORMNTIปaBttO-70> USCOMM-OC 4032ป-P7l'
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Details of illustrations in
.this document may be better
studied on microfichq
THIS REPORT HAS BEEN REPRODUCED AS RECEIVED
FROM THE CONTRACTOR. NO EDITORIAL OR OTHER
CHANGES HAVEiBEEN MADE, ALTHOUGH A NEW TITLE
PAGE 'AND FOREWORD HAVE BEEN ADDED. MENTION OF
COMMERCIAL PRODUCTS-DOES NOT IMPLY ENDORSEMENT
BY THE U.S. GOVERNMENT.
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FOREWORD
A major emphasis of the 1965 Solid Waste Disposal Act and its
amending 1970 legislation is directed toward rectifying inefficient and
improper methods of disposal that create serious hazards to public
health, including the pollution of air and water resources. In this
respect, pesticide wastes are a growing concern. These difficult-to-
dispose-of wastes are expected to receive more attention in the future,
as has been evident in recent legislation.
The Office of Solid Waste Management Programs decided to
investigate specific combustion temperatures and general burning
characteristics of representative pesticides in order that a complete
and safe method of decontamination and disposal could be recommended.
This report represents the results of that investigation under contract to
the Foster D. Snell, Inc. , Florham Park, New Jersey. The Office of
Solid Waste Management Programs was represented by Henry Johnson
during the implementation of the contract and the preparation of the
report.
--RICHARD D. VAUGHAN
Deputy Assistant Administrator
for Solid Waste Management
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Details of i!!?.!^.r lions'in
this document may be better
studied on microfiche
CONTENTS
Paqe
SUMMARY 1
INTRODUCTION 2
OBJECTIVES OF THE PROJECT 4
WORK PLAN 5
THERMAL DEGRADATION OF PESTICIDES ." 7
Pyrolysis Unit 8
Pyrolysis of Pesticides 8
Screening of DDT and Malathion via
Gas Liquid Chromatography 8
Temperature Profile of DDT 8
Temperature Profile of ''Malathion 14
The Effect of Oxidants on the
Decomposition of Malathion 14
Modification of the Perkin Elmer Pyrolysis Unit 16
Differential Scanning Calorimeter 17
Theory of Operation 17
Closed-System Operation 20
Materials 20
Instrumental Conditions 22
Experimental Results 22
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CONTENTS
(Continued)
..^..-'. . \ .-... :. ; Paqe
The DSC Screening of Pesticides in an Open
System With and Without Potassium Chlorate 25
Open-System Operation 25
Instrumental Conditions 25
Experimental Results 26
The DSC Screening of Binders for Use in an Open System 28
Selection of Binders 28
Experimental Results 28
The DSC Screening of Pesticides With and Without
Potassium Chlorate and Containing Mineral Oil as
a Binder 29
The DSC Screening of Oxidants Other Than Nitrates
and Chlorates in an Open System With DDT 31
Reagents 31
Instrumental Conditions 31
Experimental Results 32
The Pyrolysis of Pesticides in the Presence of
Mineral Oil and Potassium Chlorate 32
Apparatus 32
Instrumental Conditions 34
Experimental Data 35
Reproducibility of Results 35
Pyrolytic Degradation Products 35
Conclusions " 38
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CONTENTS
(Continued)
Page
THERMAL INVESTIGATION OF CONTAINER MATERIALS 39
Container Materials Study 39
Apparatus 39
Materials Investigated 39
Experimental Data 40
Burning Characteristics ;; 40
<
Maximum Combustion Temperature i 42
I
Pesticide Combustion Apparatus 42
THERMAL DESTRUCTION OF PESTICIDES IN CONTAINERS ' 44
A Practical System for Pesticide Combustion 44
Pesticide Combustion Gases 47
Experimental Data 48
'' ]
Analysis for 261D, F, G, and H 49
End Product Gases 51.
Gaseous Products 52
CONCLUSIONS AND RECOMMENDATIONS 53
REFERENCES 56
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SUMMARY
The purpose of this project was to investigate methods of
combu'stion applicable to residues of pesticides and their
containers and to devise a means for their destruction that
would keep environmental pollution to a minimum.
It was found that the destruction of pesticides was
generally aided by oxidizing agents. Binders were also found
to be effective in their destruction, and it was discovered
that the combination of oxidants and petroleum oil binders
was no more effective than the oil binders alone.
By using polyethylene, which under heating or combustion
conditions softens or degrades to products of lower molecular
weight, the advantages of a liner and a binder were obtained
with one material. A practical system was devised that consisted
of burning the pesticide in a flattened polyethylene bag on or
surrounded by other combustible material. Suggestions were made
concerning an improved design of polyethylene container or liner
to aid in carrying out the purpose of this investigation.
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INTRODUCTION
The problem of"the disposal of waste pesticides is constantly
increasing in acuteness with the diversification/of? their use and
the growth of population. Their escape into the environment as a
result of disposal, practices must be controlled or prevented.
Some waste pesticides are being, stored until safe disposal methods
are available, however, they- cannot be accumulated* indefinitely.
Various investigations leading, to their proper disposal are
presently being conducted.
A program conducted, by the Environmental Health Sciences
Center at Oregon State University, Corvallis, is in operation
under the direction of R. L. Goulding. This project has as its
objectives to develop a management system for the reduction of
pesticide waste problems and to-develop technical information
concerning the treatment and... disposal of these wastes. It is
intended to utilize soil for biological and physical degradation
of these wastes.. Because this approach may offer, an'-improved
method of waste pesticide.management, the U.S. Department of
Health, Education., and Welfare:1 s Bureau of Solid Waste Management
(now the Office of' Solid Waste Management Programs in the U.S.
Environmental Protection. Agency) is providing two-thirds of the
cost for demonstrating and^evaluating the concept, through a grant
to the university,.
Another program, in this field on the disposal of pesticides
and containers is,funded by a, grant from the U.S. Department of
I
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Agriculture and is administered through the Crops Research
Division of the Agricultural Research Service. This is being
conducted at Mississippi State University, College of
Agriculture and Agricultural Experiment Station., State College,
Mississippi, under the direction of B. J. Stojanovic, I. L.
Shuman, and M. V. Kennedy, principal investigators. Some of the
7
data obtained in the latter study are available in Residue Reviews.
The present study was not concerned with the use of soil
microflora as an aid in decomposition of pesticides in soils or
with the development of an incinerator for disposal of pesticides
and containers. Rather, it was oriented toward the use of oxidizers
and binding agents as aids in the proper combustion of pesticides
and containers. It was hoped that a practical, simple solution to
the disposal of pesticide residues could be developed for use in
the field.
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OBJECTIVES OF THE PROJECT
The objectives of this investigation were the following;
1. To investigate the use of oxidizers and binding
agents to assist in the combustion of pesticides
2. To investigate the combustion characteristics
of c.ontainer materials. .
3. To develop requirements for container compositions
and possible use of special liners possibly impregnated with
oxidizers to aid in the combustion ofcthe pesticide and
container
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WORK PLAN
A. Research ProgramThermal Properties
1. Obtain DSC instrument
2. Operate with it as follows:
a. Obtain decomposition temperature of pesticide
b. Obtain thermal history of oxidants
c. Obtain thermal history of binders
d. Observe combinations of a, b, and c in closed
systems
e. Observe same operations in open systems
f. Endeavor to get open system to imitate closed
system by using binders, oxidants/ or other
additives
B. Research ProgramPyrolytic Studies
1. Run crude pyrolysis experiments
2. Investigate pyrolysis products by GLC
3. Obtain Perkin Elmer pyrolyzer for use with PE 900 GLC
4. Operate pyrolyzer as follows:
a. Investigate the pyrolysis products of the pesticides
b. Investigate the pyrolysis products of the oxidants
c. Investigate the pyrolysis products of the binders
-------
d. Investigate the*, pyro lysis products of a, b, and
c in combination
e. Study cpmbinatipns. of pesticides, additives, and
container materials
f. Screen data for most promising combination
C. Research ProgramSimulated Field Trials
1. Investigate packaging; presently in use
2. Investigate; cpmb.ustipni,.under simulated field conditions.
a. Construct combustion, test apparatus
b. Study,effect, of open flame on combustion
c. Apply - procedures to, the promising combinations
derived from pure and, applied,, research programs
3. Determine^ comple.tenes.s of,, combustion by using, the
appropriate additives.,, packaging, and operational
system
4. Prepare recpiranendatipiig fpr- combustible containers and
operatipnal prppedujre;
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THERMAL DEGRADATION OP PESTICIDES
It is known that chlorine-containing pesticides are the most
difficult pesticides to decompose by combustion with air. DDT,
1 2
for example, is used in burning fumigant mixture. * Some
investigators have decomposed pesticides containing organic
chloride by the following methods: .
1. Treatment with steam and air at 900 to 1,400 C^
2. The addition of ferric chloride to accelerate thermal
4 ฃ5 .
decomposition of;DDT and DDD^ .
3. Pyrolysjs of pesticide with metal salt catalysts in a
closed system j
1 ''."... '
Pesticides have been burned in o'xygen in a dry combustion
7 " ' '..''''
furnace, but this does not serve the purpose of this
investigation, which is to/find a practical procedure for disposal
of pesticide residues and the containers. The same authors also
7
ashed pesticides in a muffle furnace. This procedure imitates
results that may be obtained by furnace destruction of residues
and containers but may not be representative of open-field
destruction, which is the principal means used to destroy
/- . ' .
combustible containers and their contents.
Thermal analysis by differential scanning calorimetry was
able to provide theoretical data that it was hoped could then be
used in practical pyrolytic procedures.
-------
A useful p.yrblysis unit had tte meet the following
requirements.
1. The sample should be reproducibly heated-to a
defined temperature.
1 . ' i '
2. The atmosphere in which pyrolysis occurs should be
controlled.
3. The reaction chamber should be designed to permit
convenient and. complete sampling of the reaction products.
.':...' , ' 1. '
.Pyrolysis Unit .
The Perkin E*lmer pyrolysis unit met these requirements
(Figure 1) . The .weighed sample of pesticide was placed in a
porcelain boat. The reaction atmosphere was air flowing at
30 ml/min. The decomposition products -were formed -when the
boat was placed under the heated quartz tube area, cand the
temperature of degradation was measure'd with a thermocouple.
The flowing air then ^swept ail the reaction products Jinto a
Perkin Elmer gas ehromatograph for analysis.
Pyrolysis of, P.es,ticides
screening of DDT and Malathion via gas -liquid .;ehromatography
Temperature profi-le. of .DDT. A temperature profile of
DDT from 250 to 900 ^G (Figure -2) -iridicate's/ -in a gross
manner, that the higher-b'oilihg isomers :of-the ,DDT (tech)
-------
-MCH m
OUTLET TUM
MADEO SEAL
WM.VCOVC*.
CRAOCO SEAL
tm.tr eปp
OUARTZ / UHL040IMO
SECTKJK HUT
ruae
Figure 1. Schematic diagram of pyrolysis accessory (rear view).
Arrows at valve indicate carrier gas flow with valve in OPERATE
NOT REPRODUCIBLE
9.
-------
figure 2
GAS CHROMATOGRAPHIC
PATTERNS OF DDT AFTER
PYROLYSIS
AT: 250ฐC, 500ฐC, 900ฐC
-------
mixture degrade rapidly to lower boiling compound as temperature
increases. For example, the major component E, at 250 C,
decreases as temperature increases while peaks A and B increase.
A measure of this decomposition is expressed by the ratio of
peaks A to E. The ratio at 250 C is 0.1/1; at 500 C it is 0.2/1;
at 900 C it is 1.1/1.
The reproducibility of these gas liquid chromatography
measurements was compared with samples of varying size having
been pyrolyzed at 500 C (Table 1). The percent deviation from the
mean for the three measurements was ฑ20. These data also
indicate that sample size has an effect on reproducibility. The
normalized peak heights of samples I and II, which are of equal
size, were extremely reproducible. Their peak-height measurements
differed markedly from sample III, which was seven and one-half
times larger.
These data indicate that the system was reproducible
enough to distinguish differences in gas liquid chromatography
patterns greater than 20 percent when the pyrolysis temperature
was 500 C. The data also indicate that increase in decomposition
of DDT was a direct function of temperature, other things being
constant.
Peak figures represent the ratio of a component relative
to peak E set at 1.00 (Table 2). Peaks A and B, which represent
decomposition products, have lower values when the oxidant is
present than when it is absent. This indicates that under
the conditions of the experiment the oxidants retarded rather
than assisted decomposition.
11
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TABLE 1
GAS CHROMATOGRAPHIC DATAREPRODUCIBILITY OF DDT
PYROLYZED AT 500 C.
Retention
time (min)
Sample I
(0.20 mg)
Sample II
(0.20 mg)
Sample III
(1.5 mg)
Mean
Deviation
from mean (%)
A
. , ' i
30,8
0.23
0.24
.0.34
0.27
17
. .. Peak
B
31.8
1.00
1.4
.1.9
1.4
21
heights* . Mai or peak
C D
32.6 33.6
.
0.44 1.00 B
'
0.41 1.00 B
0.63 1.00 B
0.49
18
*Normalized to 1 mg DDT and relative to the height of
peak E.
12
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TABLE 2
GAS CHROMATOGRAPHIC DATADDT PYROLYZED AT 500 C WITH OXIDIZING AGENTS
Sample of
DDT
Retention
time (min)
I
(1.0 mg)
None
II
(0.9 mg)
None
III
(1.0 mg)
None
Mean DDT sample
calculated
from Table 1
agent A B C D E
30.8 31.8 32.1 32.6 33.6
Sodium nitrate 0.16 0.57 0.50 1 MO
Sodium nitrate None detected
Potassium nitrate 0.15 0.81 0.44 1.00
Potassium nitrate None detected
Potassium chlorate 0.15 0.64 0.44 1.00
Potassium chlorate None detected
Nona 0.27 1.4 0.49 1.00
Major
peak
E
E
E
B
*Normalized to 1 mg DDT and relative to the height of peak E.
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Temperature profile of malathion. A temperature profile
I
of malathion from 200 to 900 C is presented (Figure 3). As the
temperature increased, peak C, which represents malathion,
degraded to yield lower boiling peaks A and B. .The .ratio of
peak A to C is an expression of the quantity of degradation.
This ratio at 200 C is 0/1; at 500 C it is 1/1; at 900 C it is
15/1. These data indicate that rapid decomposition occurred at
temperatures of 500 C or greater. No residue was detected at
200 C; a slight brown residue was detected at 500 C; and a large
black residue was detected at 900 C, which indicates much
carbonization.
The effect of oxidants on the decomposition of malathion.
When milligram quantities of malathion were mixed
and pyrolyzed at 500 C the following results were
a minimum of two experiments per oxidant:
Oxidizing
agent
Potassium
chlorate
Peaks
detected
None
Sample
residue
.Yellow
Potassium
nitrate
Major peak
disappeared
with
formation of
lower boiling
components
Potassium
nitrate
with oxidants
observed for
Explanation
of results
Complete
^decomposition
of malathion
to oxides of
carbon and
water
Complete
decomposition
of'malathion
to lower
boiling
components
14
-------
.:.!: -I-. :!: .1 , .11
i GAS CHROMATOGRAPMIC PATTERNS
OF MALATHION AFTER PYROLYSIS
I . : . (A) !
"oj
t ccui ---
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Modification of the Perkin Elmer Pyrolysis Unit
The Perkin Elmer pyrolysis unit had two flaws in its
construction as follows:
1. The valve oven and heated connector could not be heated
t
above the melting point of the Teflon tubing used to conduct the
pyrolyzate to the gas chromatograph. Condensates collected in
the valve and heated inlet tubing.
2. The heated connector to the gas chromatograph was
subject to breakage. This section was .replaced twice in a short
period.
In order to"*overcome these design flaws/ the,end of the
pyrolysis tube was disconnected from the valve and connected
directly to the gas chromatograph via 1/8-in. stainless steel
tubing. The tubing was wrapped with heating'tape., arid a
thermocouple was imbedded next to the tubing. The-entire
assembly was then coated wi'th asbestos for insulation. The
temperature of this connecting line was maintained,at 200 C.
When samples of pesticides alone .were heated at relatively
low temperatures (150 C) , very small amounts of the pesticides
were detected. It was assumed that the hot steel surface's being
in the presence of airwas responsible for .the poor recovery.
Modification was, 'therefore, made, as discussed later.
16
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Differential Scanning Calorimeter
i) ' '"...'
The Perkin Elmer differential scanning calorimeter (DSC)
used in the work to be described consisted of the following:
Item
Calorimeter including
temperature-programming
unit
Sample-handling unit
Filter dryer for gas purge
filtration
Inlet line assembly
Sample pan crimper press
120 VA constant-voltage
transformer
Plug-in sample holder
Recorder with 15, 60, and
240 in./hr speeds
Range card for 10-mv recorder
Volatile-sample sealer accessory
with sample pans and covers
Manual
Theory of Operation. The sample holder of the DSC unit
consists of two miniature pans, a reference and a sample
pan (Figure 5). The pesticide was encapsulated in aluminum
17
-------
and placed in the sample pan. Aluminum-ballast was placed in
the reference pan. Heat was supplied to both pahs at a
constant rate to raise their temperatures 20 C/min.
When a physical or chemical change took place in the
..'-.-' '
sample pan, the heat generated or absorbed to complete this
reaction was sensed by a platinum resistance thermometer embedded
under that pan. Heat "was then supplied to the sample pan if the
reaction was endothermic (fusion/ vaporization, etc), or heat was
withheld if the sample reaction was exothermic (chemical reaction,
decomposition, oxidation, etc). This change in power required to
maintain the sample holder at the same temperature as the
reference holder during the transition was the. differential power
and was recorded as a peak (Figure 4). The temperature of the
transition was recorded on the curve abscissa as a pen stroke for
each degree Centigrade. The recorded peak area indicated the
total energy transferred to or removed from the sample. The
reference pan should generate no signal, since the aluminum
ballast had no transition below 660 C, its melting point. All
signals generated in these experiments were attributed to
reactions of the sample.
Peaks registered below the base line are endotherms and
those above the base line are exotherms. The gradual change of
base line slope was attributed to the change of the sample's
specific heat as a function of temperature.
18
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CAPACITY
INCREASING
TYPICAL EXOTHERMIC BEHAVIOR
GRADUAL
SLOPE
-*
CHEMICAL REACTION
CURING, OXIDATION, CHEMICAL
REACTION
TEMPERATURE INCREASING
TYPICAL ENDOTHERMIC BEHAVIOR
a. NORMAL
b.WITH
ENDOTHERM
^_ -ซ"'
AT
MELT TRANSITION
*dซcrซaiing htat capacity
dut to tampl* Ion
GLASS TRANSITIONS
T2 / " T"
<
CRYSTALLIZATION
GRADUAL
SLOPE
INCREASING HEAT
CAPACITY WITH TIME
Figure 4. Typical chart indications'of endothermic and exothermic
transitions. (Asterisk indicates decreasing heat capacity due to
sample loss.)
Figure 5. Sample holders in sample holder assembly.
NOT REPRODUCIBLE
19
-------
Closed-System Operation. T.he sample was encapsulated in
a volatile sample pan (Figure .,6), and this permitted the major-"
portion of the sample to decompose.
Many organic compounds, such as pesticides, will sublime or
vaporize before the energy input is sufficient to decompose them.
The effect of heating a sample of camphor in an open and closed
system is illustrated (Figure 7). In the open system the major
portion of the sample has sublimed before fusion. In the closed
system the heat of fusion was accurately determined.
As the camphor sample was heated in the closed system,
!. ,
increased vapor pressure caused the sample pan to rupture. A
microscopic pinprick was, therefore, made in the cover of each
sealed pesticide sample pan to prevent rupture. Only a small
portion of the pesticide volatilized when this procedure was
employed. Some oxidation of the sample may be attributed to
the diffusion of air through this pinhole.
Materials
DDTtechnical grade, 77 percent pure, American Association
of Economic Entomologists, Madison, Wisconsin. WQ20551
Aldrin99+percent recrystallized analytical grade, Jules
Hyman and Co., Denver, Colorado. Lot 8001
Diazinon50 percent wettable powder, Geigy Chemical
Corporation, Ardsley, New York. FL 6423 :
Dalapon99 percent analytical standard, Dow Chemical
Company, Midland, Michigan. AGR20073
20
-------
Figure 6. Sealer operation.
SEALER HANDLE
MSI INDEX
MN RETAINER
SAMPLE PAN
HOLDER
ASSEMBLY
SEALER BASE
CAMPHOR
I *y ia
STANDARD PAN
CAMPHOR
I ซ in
VOLATILE SAMPLE SEALER
FUSION
FUSION
RUPTURE OF
SEALED SAMPLE |
PAN N.
DEFORMATION
OF SAMPLE PAN
r i r. r .
IซO WO
I I
Figure 7. Heats of fusion of open and sealed samples of camphor.
21.
-------
Amino triazole99.4 percent 3-amino-l,2/5 triazole, American
Cyanamid Co., New York, New York. 3671B-32-2
Sevin99.86 percent analytical grade/ Union Carbide Co.,
New York, New York. Lot 14-ORD-18
Maleic hydrazide-58 percent diethanolamine salt of maleic
hydrazide, MH-30, Uniroyal Chemical, Naugatuck, Connecticut.
Lot 2281
Malathion95 percent: analytical reagent, American Cyanamid
Co., New York, New York. Lot W-10628-2
Potassium nitrate99 percent analytical reagent,
Mallinckrodt Chemical Works, New York, New York. Lot 7028
Potassium chlorateMallinckrodt Chemical Works, New York,
New York. Lot 6834
Pentachlorqnitrobenzene (PCNB)Aldrich Chemicals, Cedar
Knolls, New Jersey. P22C-5
Instrumental Conditions ;
InstrumentPerkin Elmer DSC
Scanning rate20 C/min
Range (sensitivity)16 to 64
Slope426
Chart speed1 in./min
Temperature *range67 to 500 C
Gas flow over sampleair at 20 ;ml/min
Sample:
Size0.5 to 3.0 mg pesticide or;
oxidant, or both
Experimentai Results. Pesticides without arid with the
Addition of potassium nitrate and .potassium chlorate,
respectively, were scanned by closed-rsystem*DSC. "The oxidants
were also examined by DSC (Curves I-XXIX).
22
-------
Decomposition or oxidation of the sample was defined as
the production of an exothermic peak on the DSC curve. These
decompositions were confirmed by examination of the sample for
V.
charring or ashing after the exotherm. The temperatures ranged
from a maximum decomposition (Table 3). The initial temperature
of decomposition was defined as the first departure from the
base line. The final temperature of this range was defined as
resumption of the base line.
The curves also contain first-order endotherms. Many of
these peaks have been identified as either intercrystalline
transitions or fusions based on the literature values for these
transitions.
The data (Table 3) indicate the following for pesticides
in a closed system:
1. The temperatures at which maximum decomposition
of pesticides occurs can be measured.
2. The decomposition or oxidation of pesticides is
accelerated when oxidants are present.
3. The presence of oxidants tends to decrease the
temperature of maximum decomposition or oxidation.
4. Potassium chlorate is a better oxidizing agent
for pesticides than potassium nitrate is.
23
-------
.TABLE 3
THE TEMPERATURE RANGE OF PESTICIDE DECOMPOSITION WITH
AND WITHOUT OXIDANTS IN A CLOSED SYSTEM
-------
The DSC'Screening- of Pesticides" in'ah
Open System With and Without Potassium Chlorate
Open-System Operation. In the field, the burning of
pesticides will take place in an open system where air will
diffuse into the system and gaseous and vaporized products will
leave the system. The following DSC conditions were used to
approximate an open system:
1. The sample was weighed into a small aluminum
pan. A thin aluminum disc was placed on top of the
sample in the pan to ensure even heat distribution within
the sample. The pan was not sealedgases could diffuse
into and out of the sample.
2. An atmosphere of air flowing at a rate of 20 ml/min
was allowed to pass over the sample. Potassium chlorate
was selected as the oxidant since it was most effective in
i
the closed system.
Instrumental Conditions
InstrumentPerkin Elmer DSC
Scanning rate--20 C/min
Range (sensitivity)16 to 64
Slope400
Chart speed1 in./min
Temperature range67 to 500 C
25
-------
Gas flow over samplei-^air at 20 mi/min
Sample:
Size0.6 to 2.7 mg pesticide or
oxidarit, or both
Experimental Results * The DSC curves "obtained' from an open
- ' :i ''-.
system are interpreted in the same way as DSC curves obtained
from a closed system. In the open system* however* condensation,
charring, and rapid movement of the pah contents could be visually
observed when the "pan was heated. The temperatures at"which such
events were seen are indicated in Curves XXX-XXXXVi-I i
The results of heating pesticides with and without an oxidant
in an open system are summarized (Table 4).
In most cases Where.pesticides alone were examined> in
the open system, condensation was rioted-oh the interior of the
apparatus. This condensation was coincident with>ah eridothefm
V '.
on the DSC curve, "and this indicated that vapbfiiatidri of
sublimation of the pesticide had occurfedi
The data from this 'experiment indicate the following:
1. Pesticides heated in ah open system do hot
decompose but appear to vaporize "of-sublime.
2. The addition of potassium chlorate appeared to
oxidize the fallowing pesticides: maleic hydfazd.de,
diazinon, malathion, and 3-ami-no-l',-2-4-triazolei
26
-------
TABLE 4
OPEN SYSTEM. EXOTHERM EVIDENT OR NOT EVIDENT.
RANGE OF MAXIMUM DECOMPOSITION (C)
Compound
Alone
Potassium chlorate
added
DDT
Maleic hydrazide
Aldrin
Dalapon
Diazinon
Malathion
3-amino-l,2,4-triazole
Sevin
PCNB
Not evident
No charring
Not evident
Charring occurred
Not evident
No charring
Not evident
No charring
Not evident
No charring
Not, evident
No charring
Not evident
No charring
Not evident
No charring
Not evident
No charring
Not evident
No charring
200-250 (minor)
344-357 (major)
Charring occurred
Not evident
No charring
Not evident
No charring
371-397
191-215
319-352
Not evident
No charring
Not evident
No charring
27
-------
The DSC Screening of Binders For Use in an- Open System
-' j-- j
. * .-' ',"
.-.. '' .. .
Selection of Binders.; Binders weife sought' to retard the
vaporization and promote decomposition of the pesticide. The
,f . '. '' '
. $ . " ' - ' '
binder was not to react with the oxidant and was to possess
-'' f '' . '
reasonable thermal stability. The following materials were
examined: /',
Mineral oilf "Xaydol" (Sonneborn Chemical and Refining
Cpmpany, White Oil/Division, New York, New York)
Paraffin wax--(City Chemical Corporation, New/ York.,> New-
York) ;: :
bow Corning 200 fluida methyl silicone--(Applied Science
Laboratories, Inc., State, College, Pennsylvania)
Carbowax. 20 Mr-a. polyethylene glycol. (Applied, Science
Laboratories, Inc., State College, Pennsylvania)
SE-30-a methyl sili.cone rubber (Applied Science
Laboratories, Inc.,, State College, Pennsylvania)
Apiezon Mhydrocarbon grease.-. (James G. Biddle Company,
1316 Arch Street, Philadelphia, Pennsylvania) ';
PolyethyleneEastman; Epplehe; N^ld, Eastmen Epoleneu C-10 .
Experimental 'Results.. The instrumental conditions were the
same as those used in*, the. screening, of pesticides in an open
system. All the materials, showed some evidence of volatility or.
decomposition. The followi-ng materials were selected; for further
testing because of their s^tab.ility:
28
-------
Dow Corning 200 fluid
Carbowax 20 M
Apiez&n M .
. Mineral oil
These materials were analyzed by DSC with only potassium
chlorate added, with only DDT added, and with only potassium
chlorate and DDT added. The following results were obtained
(Curves XXXXVIII-LII):
Dow Corning 200 fluidThe addition of this substance
did not aid oxidation or decrease volatilization of the
pesticide. No exotherm or charring was observed.
Carbowax 20 M-The potassium chlorate reacted with
Carbowax 20 M. This type of.reaction is undesirable since it
competes with the oxidation of the pesticide. '
Apiezon M.the Apiezon M reacted with potassium
chlorate, and this made it undesirable as a binder.
Mineral oilPotassium chlorate did not react with
mineral oil. When both potassium chlorate and DDT were added
to mineral oil, there was a large exothermic response that was
interpreted as probable decomposition of the DDT.
The DSC Screening of Pesticides With and Without
Potassium Chlorate and Containing Mineral Oil as a Binder
The addition of mineral oil to DDT and potassium chlorate
appeared to aid oxidation in the open system. The remaining
eight pesticides were screened in the same fashion tp determine
the effect of this binder (Curves LIII-LXVIII). The results of
this screening are summarized (Table 5).
In every case the admixture of both potassium chlorate and
mineral oil resulted in an exothermic reaction indicative of
29
-------
..OPEN-SYS.TEM;, E?.05PHEHMSu?sn;-DENT,"OR NOT::EVIDENT.
I^j^j.OP/l^ij^^-pEQOiiffidsiTlDN: (C) WITH AND"'WITHOUT
POTASSIUM GHIiQRAT& BUTf' WITHi; MINERAL, OIL, ASy- A;BINDER IN ALL CASES
Compound:
Diazinom
Malathion- '
"'.:.
3-artdno-l, 2;r
...... .-''
Sevin
PCNB- .;v- -:
Alone;
Potassium, chlorate
.-. added
DDT
Maleic hy.dri
Aldrin
Dalapon
* . : N6,tj evident:,,
azdjde* " . ">- "' Note evidenfc
'..'.. v {' ' .2':9]3|r:29,;7/' (^e'XVj
' ; /'{ /'' ' "-Nigt' evident, '
27X);r-325
337-390
231r258
336-378
,f small);: J-33^T3;69
336:- 364
(minor).
(major)
(minor)
(major)
evident:
::2;8,8-31'8'
350
'
267r-3ll?5
312- 34-5 '
-324-354'
30
-------
degradation. These data did not allow us to determine the
exact reaction occurring or its extent. This information would
be obtained when this system was tested by pyrolysis and gas
chromatographic analysis.
The DSC Screening of Oxidants Other Than
Nitrates and Chlorates in an Open System With DDT
Five oxidizers were tested with DDT only, mineral oil only,
and with both DDT and mineral oil. DDT was selected as a test
pesticide because it is relatively stable to oxidation.
Reagents
Potassium persulfateMallinckrodt analytical reagent
Ammonium bichromateFisher Scientific Company
Potassium permanganateJ. T. Baker Chemical Company
Sodium peroxideJ. T. Baker Chemical Company
Potassium dichromateJ. T. Baker Chemical Company
Instrumental Conditions
InstrumentPerkin Elmer DSC
Scanning rate20 C/min
Range (sensitivity)32
Slope400
Chart speed1 in./min
.Temperature range67 to 500 C
Gas flow over sampleair at 20 ml/min
Sample:
0.6 to 2.7 mg of DDT was weighed
into an aluminum pan that was not
sealed
31
-------
Experimental Results. The following summarizes the results
obtained in the experiments leading to the results shown by
t
Curves LXIX-LXXXIV, ?
Potassium persulfateThere was no evidence that
the potassium persulfate reacted with the DDT alone
or in admixture with mineral oil. ,
Ammonium-bichromateThere was no evidence that
the ammonium bichromate reacted with the DDT alone
or in admixture with mineral oil.
. ' '
P.otassivmV permanganateThe potassium permanganate
reacted with the mineral oil, which was used as a
binder. Thus/ it is an undesirable oxidant.
Sodium peroxideThe sodium peroxide reacted with
the aluminum^pan.This made it impossible to
obtain a DSC trace.
Potassium dichromateThere was no evidence that
the potassium dichromate reacted with the; DDT
alone or in admixture with mineral oil.
..*''
The results of these tests, indicate that potassium chlorate
is still the most suitable oxidizer investigated.
The Pyre-lysis of Pesticides in the
Presence of Mineral Oil and Potassium Chlorate
'..',-'
Apparatus. As reported/ the Perkin Elmer pyrolysis unit was
modified to measure the pyrolytic; decomposition of pesticides.
The unit was modified in the following manner:
1. Ttie section of the pyrolysis tube between the
furnace and the exit was kept.at 200 C.by means of heating
tape.
32,
-------
2. A 10-cm length of Teflon tubing (1/8 inch OD) was
attached to the end of the pyrolysis tube by means of a
swagelok fitting.
3. The other end of the Teflon tubing was inserted
into a U-shaped collector bottle (Varian Aerograph, Model
66-023, 1-ml size) , which was clamped vertically in a dry
ice/ethanol bath.
Air was passed through the apparatus at a known flow rate
and for a definite length of time. At the end of the experiment,
the collector bottle removed, and 0.5 ml of an appropriate
solvent was added to the cold bottle. Portions of this solution
were examined by means of gas chromatography to determine the
amount of pesticide in the cold trap.
This method measured the effectiveness of the pyrolysis,
since the amount of pesticide placed in the pyrolysis furnace
was known. At the same time, any indication of the kind of
degradation products on the gas chromatograms was noted.
Gaseous products that would not respond to the hydrogen flame
detector (such as carbon dioxide, water/ or hydrogen chloride)
could not be detected. Low-boiling organic compounds not
separated from the solvent (diethyl ether or ethanol) were also
undetected.
33
-------
Instrumental Conditions
Perkin Elmer pyrolysis Unit;
Furnace temperature:
Gas ' :
Collection period :
Gas chromatography;
300 C *
Air at 100 ml/min
10 min
Aerograph 705': Column: 4 ft x 1/8 in. OD
stainless steel
packed with 15%>SE-30
on Gas Chrom P
Temperatures:
.^' Column:
Detector:
Injector: 240 C
Carrier gas: Nitrogen at 25 ml/min
as indicated
220 C
Aerograph 1520: Column: 3-1/2 ft x 1/8 in. OD
stainless steel
packed with 3% SE-30
on Gas Chrom P
Temperatures:
Column: as indicated
Detector: 220 C
Injector: 240 C
Carrier gas: Nitrogen at 25 ml/min
Sample size: Equal amounts (2-4 mg) of each
ingredient
All the pesticides studied were examined under these conditions.
Dalapon, maleic hydrazide, and'2-amino-l,2,4-triazole, which
are not gas chromatographabile, were omitted. Atrazine was
substituted for 3-amino-l,2,4-triazole. A furnace temperature
of 300 C was selected. Previous DSC studies showed that in the
34
-------
presence of both mineral oil and potassium chlorate, the
pesticides would decompose at this temperature. Other flow
rates of air arid collection times were tried, but that selected,
t
100 ml/min for 10 min, gave the most consistent results.
Experimental Data. The chromatograms are shown in Curves
LXXXV-CXIX. The results are summarized (Table 6).
Reproducibility of Results. Several replicate pyrolysis
experiments were made with Aldrin in order to test the
reproducibility of the method. The results are summarized
(Table 7) .
These results indicate that the method was adequate for
determining significant changes in decomposition as the
composition of the sample was varied. Similar results were
obtained for replicate pyrolytic tests of Sevin and DDT.
Pyrolytic Degradation Products. DDT was the only pesticide
studied that showed significant amounts of degradation products
by gas chromatography that were not present in the chromatogram
of the reference DDT. When DDT was pyrolyzed alone, the
degradation products produced larger peaks than that for DDT
itself. These unknown peaks were, however, greatly reduced in
size in the gas chromatograms of the pyrolytic products of DDT
plus either mineral oil or potassium chlorate.
35
-------
vo
TABLE 6
AMOUNT OF PESTICIDE RECOVERED IN DRY ICE/ETHANOL COLD
TRAP AFTER PYROLYSIS AT 300 C ;'
Pesticide
alone (%)
Pesticide Pesticide Pesticide plus
plus plus mineral oil
mineral potassium and potassium
oil (%) chlorate (%) chlorate (%)
Gas chromatฉgraphic
conditions
Sevin 50
PCNB .50
Aldrin 20
Diazinon 5
DDT 10
Malathion 5
Atrazine 5
5
5
10
5
5
5
5
25
25
25
5
1
5
5
5
25
10
5
5
5
5
Aerograph 1520-
Aerograph 1520-
Aerograph 1520-
Aerograph 1520-
Aerograph 705-
Aerograph 705-
Aerograph 1520-
-column at 135
-colxunn at 135
-column at 145
-column at 155
-column at 190
-column.at 160
-column at 140
-------
TABLE 7
PERCENT OF ALDRIN RECOVERED IN DRY ICE/ETHANOL COLD TRAP
AFTER PYROLYSIS AT 300 C
Aldrin plus
Aldrin Aldrin plus Aldrin plus mineral oil and
alone mineral oil potassium chlorate potassium chlorate
1st
2nd
3rd
4th
60
17
20
20
15
10
0
0
30
24
0
0
10
0
0
0
37
-------
Conclusions
The addition of mineral oil to, either Sevin, Aldrin, PCNB,
or DDT significantly increased the amount of pesticide that
decomposed when heated at 300 C. The mineral, oil did not have
a significant effect on the decomposition of either Diazinon,
Malathion, or Atrazine at 300 C. These three pesticides were,
however, largely decomposed by heat alone.
The addition of potassium chlorate to either Sevin, PCNB,
or DDT increased the amount of pesticide that was decomposed
at 300 C; it did not affect either Aldrin, Diazinon, Malathion,
or Atrazine. In general, the addition of potassium chlorate to
the pesticide had less effect than the addition of mineral oil.
The addition of both mineral oil and potassium chlorate to
the pesticide had no greater effect than that of the addition of
mineral oil alone. The addition of either mineral oil or ,
potassium chlorate to DDT reduced the amount of gas chromatographable
pyrolytic products of DDT.
38
-------
THERMAL INVESTIGATION
OF CONTAINER MATERIALS
Container Materials Study
Apparatus. A large tripod was set up and a wire screen
placed over it. The ignition characteristics of container
materials were observed by igniting the materials with a Bunsen
burner until they were burning satisfactorily. The maximum
temperature reached was measured by a pyrometer by moving it
about in the burning mass and combustion gases throughout the
combustion period. The temperature depended in part on the
quantity of burning material but more on the rate of combustion
and rate of loss of combustion products.
Materials Investigated
Kraft paper bag
Corrugated box
Paper-coated cardboard box
Fiberboard carton (small drum)
Corrugated sheet
Cotton cloth (diaper material)
Waxed paper bag
Polyethylene bag
Polystyrene cushion container
Plywood (1/8 in.)
Burlap bag
Cardboard carton
39
-------
Multiwall paper.bag
Aluminum foil inside coated, paper bag used
for packaging Diazinon
Aluminum foil inside coated multiwall Kraft
paper bag used for packaging Diazinon
Coated double-wall Kraft paper bag used for
packaging Igran
Multiwall coated :Kraft paper bag used for
, packaging Altratol
Experimental Data
Burning Characteristics
A. The Kraft paper bag was crumpled before ignition.
It was easily ignited, burned rapidly and well, and left a
light, fluffy ash. When the bag was not crumpled;and was
left open, it was easily ignited, burned more rapidly than
before, and left a light, fluffy ash. .
b. A corrugated box (8 x 12 x 14 in.) was ignited at
a corner. It burned.with some smoke, rapidly and .well, and
left a large amount of ash.
c. A paper-coated cardboard carton was igni-ted fairly
easily. It burned with a slow, steady flame and left a fair
amount of residue.
d. A fiberboard carton (small drum) (2 in. high x 8 in.
diameter) took some time to ignite. It burned slowly and
steadily once ignited, smoked considerably, and1 left a large
amount of ash. After the flame ceased, it glowed for some
time.
e. A corrugated sheet ignited readily, smoked initially,
but after it was burning well, the smoke ceased. There was a
fair amount of ash.
f. The cotton cloth was crumpled. It ignited easily,
burned steadily but not rapidly. As the flame decreased,
the smoke increased. A black residue remained. When burned
without crumpling, it burned much more rapidly.
g. A waxed paper bag ignited very easily and burned
rapidly to completion.
40
-------
h. A lightweight polyethylene bag burned slowly with a
blue and yellow flame, melted, and dripped as it burned. It
was initially difficult to ignite, but once the melt was
obtained, it continued steadily on its own. A heavier gauge
bag was even more resistant to initial ignition, but once
melted, it likewise maintained its own combustion for a long
period.
1. A polystyrene cushion container ignited easily,
burned rapidly, but produced a great amount of black smoke and
soot. It dripped as it burned and produced much styrene
monomer, detected by odor, which also burned.
j. A plywood panel was difficult to ignite. It burned
slowly but not completely and left a large amount of charred
wood.
k. A burlap bag (dual layer) burned rapidly, producing
much white smoke and leaving a fair amount of ash.
1. A cardboard carton was slow to ignite, but once
ignited, burned at a slow, steady rate. It left considerable
ash, leafy residue, and tarry residue. Once the flame had
died out and it had been reignited, it did not burn well.
m. A multiwall paper bag ignited readily and burned well
and rapidly with very little smoke. It left only a small ash.
n. An aluminum-foil-coated bag burned rapidly with a
moderate amount of smoke and left much ash and aluminum residue
o. An aluminum-foil-coated, multiwall bag burned at a
moderate rate, gave a moderate amount of smoke, and left a
large amount of ash.
p. A coated, double-wall Kraft paper bag burned at a
moderate rate with some smoking and left a fair amount of
residue.
q. A multiwall, coated Kraft paper bag burned rapidly
with little smoke and left a small amount of residue.
41
-------
Maximum Combustion Temperature*
Item . Temp (C) : , Temp (F)
a
b
C '
d
e
f
g
h
i
j .
k.
1
m
n
0
P
q
,542
.-.-,.. 62.7
621
496
627
691
579
607
593
638
.593
621
621
579
579
579
593
1,025
1,160,
1,150
925;
1,160
1,275
1,075
1,125
1,100.
1,180
1,100
1,150
1,150
1,075
1,075
1,075
1,100
Pesticide Combustion Apparatus
A series of experiments was carried out to determine the
best arrangement for burning pesticides in packaging containers
and collecting the gases for analysis. The equipment had to
imitate open-air combustion as. closely as possible. By allowing
free access of air in the-absence of drafts, it was possible to
arrange for free combustion and yet collect the off-gases and
still avoid possibly being poisoned by vaporized pesticide.
'.This was accomplished by installing the setup in a hood,
operating with the fan off, and having the operators use gas
masks.
An aluminum pan was placed on a wire gauze on a ring held
on a large stand. A 14-in. diameter, galvanized funnel was
42
-------
inverted and suspended 1 in. above the aluminum pan. The stem
of the funnel was connected to pyrex connectors that led by a
glass system, joined by ^Teflon to a gas-scrubbing bottle with
fritted disc containing 200 ml ethanol, then to a trap, and
then to an air.suction pump.
Trial experiments showed that a successful combustion
could be carried out in this apparatus with multiwall Kraft
paper.
43
-------
THERMAL E)ESTRUCTIQN OF ..
PESTICrc>ESUiti 'CONTAINERS '
A Practical System For Pesticide Combus.tion .
Work previously discussed has indicated that mineral oil
is a very satisfactory binding agent. Other data showed that
chlorate was the most suitable oxidizer. When the data thus
obtained by differential scanning calorimetry were .applied to
pryrolysis experiments, it was found that the oxidizer was not
necessary.
The mineral oil is very important since it holds the
pesticide until it can be decomposed by heat before volatilizing.
It was felt that thoroughly wetting all particles of pesticide
could not be accomplished in a practical way, and so a scheme
was devised to accomplish the same result.
Mineral oil essentially consists of hydrocarbons having
chains of moderate length. Polyethylene is a polymer of ethylene
that consists of very long-chain hydrocarbons.. When polyethylene
is heated it partially depolymerizes to shorter chain
t
hydrocarbons that are roughly similar to mineral oil It was
felt that, by using polyethylene bags as liners to contain the
pesticide, the same result obtained by using mineral oil as a
binder could be achieved.
44
-------
Experiments were carried out in the apparatus for
collecting combustion gases, as described under Pesticide
Combustion Apparatus. The results are given in the next
section. As a consequence of the work, a system for practical
combustion of waste pesticides can now be described.
Pesticides should be shipped in containers having an inner
polyethylene bag to hold the pesticide. When the pesticide is
used or the container emptied, the bag should be left in place.
When it is desired to destroy the container and avoid air or
ground contamination by the residue of pesticide, the entire
carton or bag may be burned if it is combustible. If it is not
combustible, the bag containing the residue should be removed
and placed on top of other combustibles at the desired location
for burning. The other combustibles may be a sufficient supply
of paper, cardboard cartons, or wood.
In either case, the polyethylene bag should be flattened
or closed in such a way as to avoid enclosing any considerable
amount of air. This should be done because air will tend to
inflate it, and when the flame and heat melt it, a hole will
appear and the gases will carry residue away. In contrast by
collapsing the bag, the polyethylene melts when heat reaches it,
and breaks down' to a sticky, gummy mass that successfully holds
the residue until it is completely consumed.
It is important to have sufficient other combustible
material present to keep the polyethylene ignited in the early
45
-------
stages. When it is finally melted downvthoroughly to a molten
mass, it will continue to burn for a considerable period and.
destroy all residue. '....
It appears that the most satisfactory container for residue
- :'' '' z '" .' " '"'. '" .' ' '' .' , .
destruction is ,a multiwall bag containing a .polyethylene inner
bag. The inner bag should not be simply a polyethylene coating
but a separate container. ,It is preferable not to'use aluminum
foil or coating,* since .this hampers combustion and ,heat transfer.
Where shipments are to be made in cartons or combustible
drums, the same polyethylene liner should be used. If the drum
r f .".'*" '
is to be saved, the bag can be removed and burned on top of
other combustibles, as stated before. . '
l '.'' ' ' ' . w ' " ' ' . : .'.,'.
.' " ' . ' J.
The polyethylene liner should not be of too heavy gauge,
since this hampers closing or folding it to exclude air, and
it takes too long to melt it, and hence, if a hole is burned in
'.--'. \ '.;' .
it, some residue may escape by volatilization before being held
and destroyed. A gauge of 1 to 10 mils appears suitable.
"'' '".-" '" '' ' ' \ ' "'"
If the pesticide is a liquid, it could be shipped in
packages consisting of a flexible polyethylene inner container
-' - . .-"'.,'.'..' ' ' .' ' ' . '' .. * '"
encased in a corrugated carton (Poly Pac type). This would be
suitable for 1- to 5-gal quantities, and it could be destroyed in
._" ^ j
the manner previously described. The polyethylene container
would of necessity be of heavier gauge, than the usual lightweight
bags or liners. It would still, however, be flexible and could
be flattened before combustion in ,its carton.
46-
-------
If the pesticide cannot be shipped in polyethylene but can
be shipped in a combustible container, then mineral oil should
be used to wet the pesticide residue before combustion. Of
course, this can also be done, if desired, when the container is
polyethylene. ;
"-'',-
Pesticide Combustion Gases
Initial experiments to set up and test the combustion and
collection equipment were all performed with DDT. The final
arrangement for the laboratory tests for simulating a practical
- " ^ * - ' '"".
procedure consisted:in placing the pesticide in.a polyethylene
bag, folding or crumpling the bag .together, to .eliminate air,
and placing it on torn pieces of inultiwall bag in an aluminum
pan beneath an inverted funnel. The multiwall bag sections were
ignited with a .Bunsen burner and the gases drawn by .the vacuum
pump into 200 ml of ethanol. After the combustion was completed,
any residues that may have condensed in the equipment were
washed off with alcohol and the alcoholic portions combined.
The alcohol solution volume was measured and then, where
suitable, subjected to gas chromatographic analysis for
determining the presence of the pesticide or decomposition
products collected.
It would have been preferable to have perforations in the
bottom of the"aluminum dish to aid combustion. -This could not
be done, since the melted polyethylehe ran through and the gases
47
-------
escaped the-funnel* In practice> thisi wouldnot be a problem,
since gases would not: be collected.
Experimental Data
Legend
258A 1.0 g DDT in polyethylene on multiwall Kraft
258B 1.0 g DDT plus mineral oil in polyethylene
on multiwall Kraft
258C 1.0 g DDT on multiwall Kraft
258D 1.0 g DDT burned alone
Combustion stopped intentionally before complete:
Recovered as residue (no DDT present) . '. . 32.6
DDT recovered,in alcohol 0.5
Decomposition products recovered in
alcohol 12.5
DDT totally, destroyed 54.4
260A 1.0 g Aldrin on
.multiwall Kraft
260B 1.0 g Aldrin in polyethylene on multiwall Kraft
Incomplete combustion due to insufficient air
261A 2.0rg Diazinon SOW (50% wettable powder) in
polyethylene on multiwall,Kraft
261B 6.5 gPCNB in polyethylene on multiwall'Kraft
261C 0.5 g Sevin in polyethylene on multiwall Kraft
261E 0.5 g Atra'zine in polyethylene on multiwall Kraft
2611 0.5 g Malathion in polyethylene on multiwall
Kraft
261D 0.5 g 3-amino-l,.2,4 triazole in polyethylene on
multiwail Kraft
261F 0.5 g 2,4-D acid in polyethylene on multiwall
' ''-'." " Kraft 'l; ''''
261G 0.5 g MH-30 (maleic hydrazide) in polyethylene on
multiwall Kraft
261H 0.5 g Dalapon in polyethylene on multiwall Kraft
In the cases of 261D, F., G,, and H, the pesticide itself was
not detectable by gas chromatpgraphy. The method was applied to
search for volatile decomposition products/ but none,were found.
48
-------
Recovered Minimum Decomposition
Pesticide Run in alcohol (%) detectable (%) products
DDT 258A NF 0.5 NF*
DDT 258B NF 0.5 NF
DDT 258C NF 0.5 NF
DDT 258D 0.5 0.5 12.5
Aldrin 260A NF 0.1 NF
Aldrin 260B 0.3 0.1 NF
Diazinon 261A 0.2 0.2 NF
PCNB 261B 0.5 0.5 NF
Sevin 261C NF 1.0 NF
Atrazine 261E NF 0.5 NF
Malathion 2611 NF 0.5 NF
Amino triazole 261D NF
2,4-D 261F NF
MH-30 261G NF
Dalapon 261H NF
*NF denotes Not Found.
Analysis for 26ID/ F, G/ and H. Since four of the pesticides
were not detectable by gas liquid chromatography, the alcoholic
solutions of each were analyzed by thin-layer chromatography.
Thin layer plates: silica gel F254
(Brinkman Instruments, Inc)
Irrigant: n-butanol, acetic acid,
"water-60/15/25
Visualizing agents:
Short-wave ultraviolet light
Sodium salt of dichloroindophenol
49
-------
Test plates Minimum amount
Pesticide Rf detectable (yg)
Amino triazole 0.40 ' 30
2,4-D 0.65 30
MH-30 : 0.60 30
Dalapon ' 0.55 ( 60 ,
' - ' '
When first tested, each of the alcohol solutions gave a
negative test for the sought pesticide. In order to increase
the sensitivity of the tests, 100-ml portions of the alcohol
solutions were concentrated by evaporation, under nitrogen on
a hot water bath. The concentrates were tested at two stages,
20-fold and 200-fold concentrates. ,
The maximum amount of pesticide the solutions cpuld have
contained was 0.5 g or 2.5 yg/yl. For 20 x concentration this
is 50 yg/yl. When 12 yl was spotted, each application contained
600 yg. The minimum sensitivity was 30 yg 30/600 x. 100 = 5
percent except for Dalapon. This method could detect 5 percent
of the maximum amount that could be present. For^ 200 x
concentration 0.5 percent could be detected.
All the concentrates gave.a negative test for the sought
pesticide. In addition, there were no spots on the TLC plates,
and this finding indicated absence of breakdown products of the
pesticides.
50
-------
Amount
Amount detected
pesticide alcohol in Minimum amount
Pesticide burned (g) trap detectable
Amino triazole 0.500 NF 0.0025 g (0.5%)
2,4-D 0.500 NF 0.0025 g (0.5%)
NH-30 0.500 NF 0.0025 g (0.5%)
Dalapon 0.500 NF ,0.0050 g (1.0%)
The data obtained showed that no more than 0.5 percent
(in the case of Dalapon, 1.0 percent) of any of the pesticides
teated by the preferred procedure escaped as undecomposed vapor.
In a practical situation the proportion of pesticide to
combustibles would be much smaller than was employed here (1:7).
The likelihood of loss by vaporization would then be much lower.
End Product Gases. It is known that carbon monoxide and
carbon dioxide are formed by burning cellulose or polyethylene,
and this can be easily shown. Omitting these gases from
consideration, the following tabulation shows the simple gases
that might be formed by burning the pesticides and is based on
their respective structural formulas. The pesticides were burned
in polyethylene bags and the gases analyzed with the results
shown.
51
-------
Gaseous Products
Pesticide
Possible
Found
Not
found
DDT
Aldrin
Dalapon
Diazinon
Malathion
3-amino 1,2
4-triazole
Sevin
Maleic
hydrazide
diethanolamine
salt (MH-30)
PCNB
Hydrogen chloride
Chlorine
Chlorine dioxide
Phosgene
Hydrogen chloride
Chlorine
Chlorine dioxide
Phosgene
Hydrogen chloride
Chlorine
Chlorine dioxide
Phosgene
Hydrogen sulfide
Sulfur dioxide
Ammonia
Nitrogen dioxide
Hydrogen sulfide
Sulfur dioxide
Ammonia
Nitrogen dioxide
Ammonia
Nitrogen dioxide
Ammonia
Nitrogen dioxide
Hydrogen chloride
Chlorine
Chlorine dioxide
Phosgene
Ammonia
Nitrogen dioxide
x
x
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
52
-------
CONCLUSIONS AND RECOMMENDATIONS
' '''' .'' ' ''"' ' . t
1. Pesticides may be destroyed by combustion at the
temperatures normally achieved by burning wood, paper,
cardboard, or plastics.
2. The combustion products are mainly end.products of
combustion such as carbon dioxide, carbon monoxide, sulfur
dioxide, chlorine, ammonia, hydrogen sulfide, hydrogen chloride,
and phosgene. ..'.:."''.. . ^ :::;/; ..V : .-/
3. Only small or negligible amounts of intermediate products
of combustion are formed. . .
4. The original pesticide;, is more than 99. percent destroyed.
5. Pollution by end products such as .sulfur dioxide and
hydrogen chloride would depend on whether or not they are .'formed
by the pesticide and on the quantity of pesticide destroyed.
Since only residues are being burned and only a fractional amount
of pollutant is formed, normal burning of a few containers would
involve negligible pollution. This would not apply to collection
centers where the volume might be great and absorption arrangements
necessary. :
6. Binding agents perform an important service in retaining
: *
the pesticide in order to complete its combustion.
53
-------
7. Oxidizing agents perform an dfmportaht service in
lowering the temperatures required for completing combustion
and in aiding oxidation.
8. Oxidizing agents appear unnecessary,in the presence
of binding agents.
9. Mineral oil is a satisfactory binding agent.
1 ' i . j .. ^
10. Polyethylene serves the same purpose as mineral oil
in acting as a binding agent and serving as a combustible. It
has the further advantage of serving as a suitable liner for
most pesticide containers.
11. It is recommended that combustible pesticides be
packaged in light polyethylene packs or lightweight polyethylene
bags surrounded by;a combustible container such as a corrugated
package or fiber carton.
12. It is further recommended that future work.be carried
out in the following areas:
a. The design of polyethylene .containers \for most
efficient small-scale combustion (where he^vy-wall
polyethylene bags or containers are to be .used, the use
of pleated accordion type or jointed style 'to permit easy
folding could involve a patentable concept)
b. The use of other plastics
c. In large-scale combustion, the presence of a large
quantity of polymer may cause problems due to incomplete
combustion, carbon formation, and gum formation. Work
should be performed to investigate these possibilities
54
-------
and to develop solutions to such problems should thev
arise.
55
-------
REFERENCES
1. Walpole, J. L. Improvements in or relating to fumigating compositions.
British Patent 801,659, Sept. 17, 1958.
2. Rosser, W. A., H. Wise, and J. Miller. Mechanism of combustion inhibition
by compounds containing halogen. Ill Seventh Symposium (International)
on Combustion, London and Oxford, Aug. 28-Sept. 3, 1958. London,
Butterworths Scientific Publications, 1959. p. 175-182.
3. Woodland, R. G., M. C. Hall, and R. R. Russell. Process for disposal of
chlorinated organic residues. Journal of the Air Pollution Control
Association, 15(2):56-58, Feb. 1965.
4. Jonas, H. Zum thermischen Verhalten von Kontaktinsektiziden auf der
Basis l.l-Bis-(4-chlor-phenyl)-2-chlor-aethane (DDT-bzw. DDD-Wirkstoff).
[The thermal behavior of contact insecticide based on DDT and ODD.]
Zeitschrift fuer Natufforschung,7b(2):132-133, 1952.
5. Gunther, F. A. Thermal decomposition of DDT and benzene hexachloride
mixtures. Journal of Economic Entomology, 40(6);874-877, Dec. 1947.
6. Crowder, J. A., and E. E. Gilbert. Pyrolysis of benzene hexachloride.
U.S. Patent 2,895,998, July 21, 1959.
7. Kennedy, M. V., B. J. Stojanovic, and F. L. Shuman, Jr. Chemical and
thermal methods for disposal of pesticides. In^ F. A. Gunther, ed.
Residue reviews; residues of pesticides and other foreign chemicals
in foods and feeds, v. 29. New York, Springer-Verlaig, 1969. p. 89*104.
56
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CURVE LXXXV .
Sevin (Standard-no pyrolysis)
Solvent
141
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CURVE LXXXVI
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142
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CURVE LXXXVII
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Solvent
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CURVE LXXXVIH
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144
-------
CURVE LXXXIX
(Sevin - pyrolyzed with mineral oil
and KC1O3)
145
-------
CURVE XC
(PCNB - -standard
no pyrolysis)
146
-------
(PCNB -
pyrolyzed
alone)
147
-------
CURVE XCI1
(PCNB - pyrolyzed with
mineral oil)
148
I-.. '. ฃ&-*&ฃ'<.* .'^^tU.i.iL'.i.^ia^s;: ' .'f~&<
-------
i!
CURVE XCIII
(PCNB - pyrolyzed with KC1O3)
/ Solvent
\
PCNB
149
-------
CURVE XCIV
OPCNB - pyrolyzed with
. i KClOg and mineral oil)
150
-------
CURVE XCV
(Aldrin - standard - not pyrolyzed)
151
-------
CURVE XCV
(Aldriri, - pyrolyzed alone):
152
-------
CURVE XCVD
i ...
(Aldrin - pyrolyzed with
mineral oil)
153
-------
(Aldrin - pyrolyzed
! withKClOo)
154
-------
CURVE 1C
(Aldrin - pyrolyzed with mineral oil and
155
-------
(Diazinon - pyrolyzed
156
-------
CURVE Cl
(Diazinon - pyrolyzed alone)
/ SQlyent_
. L
157
-------
CURVE CII
- pyrolyzed with
mineral oil)
NOT
f ^PRODUCIBLE .
158
',! .'ป.
-------
4
CURVE GUI
(Diazinon - pyrolyzed with KC1CX)
Solvent
Diazinon
159
-------
CURVE CIV
(Diazinon - pyrolyzed with mineral oil
and KC1O0) -
Solvent
Diazinon
KP.1
160
-------
CURVE CV
(DDT - not pyrolyzed)
.. Solvent
NOT REPRODUCIBLE
161
-------
CURVE CV1
(DDT - pyrolyzed alone)
162
-------
CURVE CVII
(DDT - pyrolyzed with mineral oil)
f
Solvent
163
-------
CURVE CVIII
'(DDT - pyrolyzed with
Solvent
164
-------
CURVE CIX
(DDT - pyrolyzed with mineral oil and
KC1O )
3 ;
Solvent
211-384-C
(DDT
. Pyrolysis of (KC1O3
; (Mineral Oil
; Jan. 12, 1970
165
-------
t
CURVE CX
not
(Malathion - pyrolyzed}
s Solvent
\ Malathio
I
166>
-------
CURVE CXI
(Malathion - pyrolyzed alone)
Solvent
167
-------
CURVE CXII
(Malathipn - pyrolyzed with
mineral oil)
Solvent
168
-------
CURVE CXIII
(Malathion - pyrolyzed with KC1O )
. Solvent
i Malathion
)*ซซ.
169
-------
CURVE CXIV
- pyrolyzed with mineral oil
andKC1OJ
O - '
170;-
-------
ซl
CURVE CXV
not
(Atrazine - pyrolyzed )
Solvent
171
-------
CURVE CXVI
- pyrolyzed alone)
172
-------
CURVE CXVII
(Atrazine - pyrolyzed with mineral oil)
Solvent
173
-------
CURVE CXVlil
(Atrazine - .pyrolyzed with KC1O )
174
-------
CURVE CXIX
(Atrizine - pyrolyzed with mineral oil and
: = KCIOJ
* o .
175
------- |