EPA-600/2-75-041
December 1975 Environmental Protection Technology Series
DETERMINATION OF
INCINERATOR OPERATING CONDITIONS
NECESSARY FOR SAFE DISPOSAL OF PESTICIDES
Municipal Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agencv
Cincinnati, Ohio 45208
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EPA-600/2-75-041
December 1975
DETERMINATION OF INCINERATOR OPERATING CONDITIONS
NECESSARY FOR SAFE DISPOSAL OF PESTICIDES
by
Thomas L. Ferguson, Fred J. Bergman,
Gary R. Cooper, Raymond T. Li, and Frank I. Honea
Midwest Research Institute
Kansas City, Missouri 64110
Contract No. 68-03-0286
Project Officers
Donald A. Oberacker and Richard A. Games
Solid and Hazardous Waste Research Division
Municipal Environmental Research Laboratory
Cincinnati, Ohio 45268
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This report has been reviewed by the Municipal Environmental Research
Laboratory, U.S. Environmental Protection Agency, and approved for publi-
cation. Approval does not signify that the contents necessarily reflect
the views and policies of the U.S. Environmental Protection Agency, nor
does mention of trade names or commercial products constitute endorsement
or recommendation for use.
ii
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FOREWORD
Man and his environment must be protected from the adverse effects of
pesticides, radiation, noise, and other forms of pollution, and the unwise
management of solid waste. Efforts to protect the environment require a
focus that recognizes the interplay between the components of our physical
environment—air, water, and land. The Municipal Environmental Research
Laboratory contributes to this multidisciplinary focus through programs
engaged in
• studies on the effects of environmental contaminants on the
biosphere, and
• a search for ways to prevent contamination and to recycle
valuable resources.
Surplus and unwanted pesticide and pesticide containers pose safety
hazards to the public and are potential sources of environmental contami-
nation. In this study data have been developed that define the operating
conditions needed for the safe disposal of organic pesticides by
incineration.
Louis W. Lefke
Acting Director
Municipal Environmental
Research Laboratory
iii
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ABSTRACT
This research program was initiated with the overall objective of
determining design and operational criteria for incinerators that can
effect complete thermal degradation of pesticides.
An experimental incineration system was designed and constructed to
evaluate the effect of operational variables (rate of pesticide injection,
percent excess air, operating temperature, and retention time) on the effi-
ciency with which organic pesticides can be incinerated. This system
included a pilot-scale incinerator (45.4 kg/hr (100 Ib/hr) Type 1 waste
capacity), a three-stage scrubber, and a scrubber water treatment system.
Nine pesticides in 15 liquid and solid formulations were tested by injection
into the primary combustion chamber. The pesticides studied were DDT, aldrin,
picloram, malathion, toxaphene, atrazine, captan, zineb, and mirex.
Results of the incineration test were evaluated in terms of the effi-
ciency of active ingredient destruction, i.e., the percent of the pesticide
destroyed. Efficiencies of greater than 99.99% were achieved for all pesti-
cides tested except mirex over a range of combustion chamber retention time-
temperature combinations. Test results were used to estimate stack emission
rates for the subject pesticides when incinerated at 1000°C (1832°F) with
2 sec retention time.
A set of operating conditions (temperature, retention time, and excess
air rate) was developed from comparable results for all 15 formulations which
is believed to be applicable to the incineration of all organic pesticides.
Analysis of the incinerator effluents also showed that high concentra-
tions of sulfur dioxide and cyanide were present when organosulfur and organo-
nitrogen pesticides, respectively, were incinerated under certain operating
conditions. Particulate loadings in the effluent gases during the incinera-
tion of solid pesticide formulations (dusts, wettable powders, granules, and
pellets) were above federal limits established for new stationary sources
having a capacity of or greater than 45,000 kg/day (50 tons/day). Thus,
emission control devices will be required for pesticide incinerators.
Additional research is required before operating guidelines can be
developed for the incineration of all organic pesticides and pesticide-
containing solid wastes.
This report was submitted in fulfillment of Contract No. 68-03-0286
by Midwest Research Institute under the sponsorship of the Environmental
Protection Agency. Work was completed as of 28 February 1975.
iv
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CONTENTS
Disclaimer ••
Foreword iii
Abstract iv
List of Figures vii
List of Tables xi
Acknowledgements xvii
Summary 1
Sections
I Conclusions 7
II Recommendations 9
III Introduction 11
Objectives and Scope 12
Pesticide Selection 14
Report Organization 14
IV Experimental Methods and Equipment 19
Experimental Facilities 20
Sampling and Analysis 25
Experimental Design 30
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CONTENTS (Concluded)
V Results 35
Specific Results 36
DDT 36
Aldrin 43
Picloram 45
Malathion 51
Toxaphene 55
Atrazine 59
Captan 63
Zineb 65
Mirex 67
General Findings 70
System Performance 71
Problem Areas 71
VI Discussion 73
Significance of Test Results 79
Pesticide Incineration System Design Analysis ... 79
Incinerator 79
Air Pollution Control Considerations 80
Research Needs 83
VII References 85
Appendix A - Experimental Equipment 89
Appendix B - Test Results 113
Appendix C - Sampling and Analysis 335
Appendix D - Calculations 389
VI
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FIGURES
No. Title Page
1 Experimental incineration system 21
2 Incinerator configuration. ... 22
3 Solid pesticide formulation injection system 24
4 Scrubber system 26
5 Sample point, thermocouple, and manometer locations 27
6 Gas sampling train 29
7 Ranges of total species output ratios for the 15 formula-
tions tests 74
8 Ranges of total species off-gas emissions for the 15 formu-
lations tests 76
9 Estimated total species off-gas emission rates at 2 sec
retention time and 1000°C 77
10 Time-temperature zones for pesticide incineration 78
11 Incinerator thermocouple locations 91
12 Liquid pesticide feed system - fuel oil miscible formula-
tions 94
13 Diagram 0.6 to 3.0 gal/hr fuel oil burner 95
14 Diagram 3.0 to 8.0 gal/hr fuel oil burner 96
15 Liquid pesticide feed system - water based formulations. . • 97
vii
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FIGURES (Continued)
No. Title Page
16 Modified injection nozzle • .
17 Solid formulation injection system .
18 Dust injection nozzle
19 Scrubber water treatment system ...... 108
20 Representative chromatogram of 25% EC DDT formulation .... 123
21 DTA analysis of recrystallized aldrin 149
22 TGA analysis of recrystallized aldrin 150
23 DTA analysis of 19% aldrin granules 151
24 TGA analysis of 19% aldrin granules 152
25 Chromatogram of 41.2% aldrin EC formulation 155
26 DTA of picloram pellets 173
27 TGA of picloram pellets 174
28 DTA of recrystallized picloram 175
29 TGA of recrystallized picloram 176
30 Representative picloram chromatograms .... 179
31 Picloram pellets and residue 193
32 Primary chamber residue sampler 196
33 DTA of malathion powder 206
34 TGA of malathion powder 207
35 DTA of malathion 209
36 TGA of malathion 210
viii
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FIGURES (Continued)
No. Title Page
999
37 DTA of technical toxaphene .................
38 TGA of technical toxaphene ................. 23°
39 DTA of ~ 20% toxaphene dust ................. 231
40 TGA of ~ 20% toxaphene dust ................. 232
734
41 DTA of recrystallized toxaphene ...............
235
42 TGA of recrystallized toxaphene ...............
237
43 Representative toxaphene chromatograms ...........
44 Interior of plugged incinerator ............... 249
9 S6
45 DTA of technical atrazine .................. "D
9"57
46 TGA of technical atrazine ..................
47 DTA of dried liquid atrazine formulation ........ • • 258
48 TGA of dried liquid atrazine formulation .......... 259
49 DTA of «' 80% atrazine wettable powder ............ 26°
50 TGA of -' 80% atrazine wettable powder ............
O A*}
51 Representative atrazine chromatograms ............
52 Liquid atrazine formulation injection system ........ 267
285
53 DTA of technical captan ...................
286
54 TGA of technical captan ...................
OQ *7
55 DTA of a 50% captan wettable powder .............
n Q Q
56 TGA of 50% captan wettable powder ..............
302
57 DTA of technical zineb ...................
ix
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FIGURES (continued)
No. Title Page
58 TGA of technical zineb 303
59 DTA of 757o zineb wettable powder 304
60 TGA of 75% zineb wettable powder 305
61 Particulate discharge during zineb incineration 317
62 DTA of technical mirex 322
63 TGA of technical mirex 323
64 Gas sampling train 337
65 Particulate-sampling train 342
66 Particulate field,data 345
67 Preliminary moisture determination data 349
68 Particulate clean-up and analysis data 350
69 Gas sampling train 355
70 SO sampling train 353
71 Sampling train, flask valve, and flask ..... 353
72 Moisture sampling train 375
73 Cyanide sampling train . . ^ 384
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TABLES
No. Title Page
1 Chemical structures of test pesticide 15
2 Classification of pesticides by chemical structure . . 16
3 Summary of test results—25% DDT EC formulations ... 39
4 Summary of test results--10% DDT dust formulations . . 42
5 Summary of test results—41.2% aldrin EC formulation . 44
6 Summary of test results--19% aldrin granular
formulation 46
7 Summary of test results—21.57» picloram liquid
formulation 48
8 Summary of test results—10% picloram pellet
formulation 50
9 Summary of test results—57% malathion EC formulation . 53
10 Summary of test results—257o malathion WP formulation . 54
11 Summary of test results--60% toxaphene EC formulation . 57
12 Summary of test results—207o toxaphene dust
formulation 58
xi
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TABLES (continued)
No.
13
14
15
16
17
1ft
AO
14
JL s
90
£.\f
91
£. J.
22
*.£.
23
*.*/
24
fc*T
25
26
27
28
29
Title
Summary of test results — 4 Ib/gal atrazine liquid
Summary of test results — 80% atrazine WP formulation
Summary of test results — 50% captan WP formulation . .
Summary of test results — 75% zineb WP formulation . . .
Summary of test results — 0.37, mirex bait formulation .
Incinerator efficiency — 25% DDT EC formulation ....
Off-Gas composition — 25% DDT EC liquid incineration . .
Operational data sunnnary--257, DDT EC experiments . . .
Residue and off-gas characteristics--10% DDT dust
Pagj
61
62
64
66
69
81
83
93
102
110
125
J- f—^
128
129
130
experiments 138
30 Off-Gas composition—10% DDT dust incineration .... 139
xii
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TABLES (continued)
No. Title Page
31 Particulate sampling summary--107» DDT dust
experiments 140
32 Operational data summary—10% DDT dust experiments . . 141
33 Summary of 41.2% aldrin EC experiments 157
34 Incineration efficiency—41.2% aldrin EC formulation . 158
35 Off-Gas composition—41.2% aldrin EC incineration . . . 159
36 Operational data summary—41.2% aldrin EC experiment . 160
37 Summary of 19% aldrin granule experiments 162
38 Residue and off-gas characteristics —19% aldrin
granule experiments 163
39 Off-Gas composition—19% aldrin granule incineration . 164
40 Particulate sampling summary—19% aldrin granule
experiments 165
41 Operational data summary—19% aldrin granule
experiments 166
42 Summary of 21.5% picloram liquid experiments 182
43 Incineration efficiency—21.5% picloram liquid
formulation 183
44 Off-gas composition--21.57o picloram liquid
incineration 184
45 Operational data summary—21.5% picloram liquid
experiments 185
46 Summary of 10% picloram pellet experiments 188
47 Residue and off-gas characteristics—10% picloram
pellet experiments
189
xiii
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TABLES (continued)
No. Title Page
48 Off-gas composition — 107, picloram pellet incineration . 190
49 Particulate sampling summary — 10% picloram pellet
experiments ................ • • « • •
50 Operational data summary — 10% picloram pellet
experiments ..................... 192
51 Summary of 57% malathion EC experiments ........ 213
52 Incineration efficiency — 57% malathion EC experiments . 214
53 Off-gas composition — 57% malathion EC incineration . . 215
54 Operational data summary — 57% malathion EC
experiments ................ ..... 216
55 Summary of 25% malathion wettable powder experiments . 218
56 Residue and off-gas characteristics — 25% malathion
vettable powder experiments ...... . ...... 219
57 Off -gas composition — 25% malathion dust incineration . 220
58 Particulate sampling summary — 25% malathion wettable
powder experiments ................. 221
59 Operational data summary — 25% malathion wettable
powder experiments ................. 222
60 Summary of 60% toxaphene EC experiments ........ 239
61 Off-gas composition — 60% toxaphene EC incineration . . 240
62 Operational data summary — 60% toxaphene EC
experiments ...... ........ ....... 241
63 Summary of 20% toxaphene dust experiments ....... 243
xiv
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TABLES (continued)
No. Title
64 Residue and off-gas characteristics—20% toxaphene
dust experiments 244
65 Off-gas composition—207« toxaphene dust incineration . 245
66 Particulate sampling summary--20% toxaphene dust
experiments 246
67 Operational data summary—60% toxaphene dust
experiments ................ 247
68 Summary of 40.87» atrazine flowable concentrate
experiments 268
69 Incineration efficiency—40.87<> atrazine flovable
concentration experiments ... „... 269
70 Off-Gas composition--40.87o atrazine flowable
concentrate incineration 270
71 Operational data summary--40.87o atrazine flowable
concentrate experiments 271
72 Summary of 8070 atrazine wettable powder experiments . . 272
73 Residue and off-gas characteristics—8070 atrazine
wettable powder incineration . 273
74 Off-Gas composition—807° atrazine wettable powder
incineration 274
75 Particulate sampling summary—807« atrazine wettable
powder experiments 275
76 Operational data summary—807o atrazine wettable
powder experiments 276
77 Summary of 507« captan wettable powder experiments . . . 291
xv
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TABLES (concluded)
No. Title
78 Incineration efficiency—50% captan wettable powder
experiments 292
79 Off-gas composition—50% captan wettable powder
incineration ..... 293
80 Particulate sampling summary—50% captan wettable
powder experiments 294
81 Operational data suramary--50% captan wettable powder
experiments 295
82 Summary of 75% zineb wettable powder experiments . . . 310
83 Residue characteristics—75% zineb wettable powder
experiments 311
84 Off-gas composition—75% zineb wettable powder
incineration 312
85 Operational data summary~75% zineb wettable powder
experiments ..... ........ 313
86 Particulate sampling summary—75% zineb wettable
powder experiments ........ 314
87 Summary of 0.3% mirex bait experiments 326
88 Residue and off-gas characteristics—0.3% mirex bait
experiments 327
89 Off-gas composition—0.3% mirex bait experiments . . . 328
90 Operational data summary—0.3% mirex bait experiments . 329
91 Particulate sampling summary—0.3% mirex bait
experiments 331
92 Solvent selection 339
xvi
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ACKNOWLEDGEMENTS
This report presents the results of a study of the pilot-scale in-
cineration of pesticides conducted by Midwest Research Institute, under
EPA Contract No. 68-03-0286, MRI Project No. 3813-C. The work was per-
formed in the Physical Sciences Division of Midwest Research Institute,
Dr. H. M. Hubbard, Director. Dr. Larry J. Shannon, Head of the Environ-
mental Systems Section, Physical Sciences Division, was administratively
responsible for this program. This report was written by Mr. Thomas L.
Ferguson and Mr. Fred J. Bergman (Principal Investigators), Mr. Gary G.
Cooper, Dr. Raymond T. Li, and Dr. Frank I. Honea.
Project officers for the Environmental Protection Agency were
Messrs. Donald A. Oberacker and Richard A. Carnes.
xvii
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SUMMARY
The problem of how to dispose of unwanted pesticides and
pesticide-containing solid waste has been recognized for some
time. Only recently, however, has the development of environ-
mentally acceptable methods of disposal for these materials
been fully addressed. The U.S. Environmental Protection Agency
(EPA), under authority of the "Federal Insecticide, Fungicide,
and Rodenticide Act" as amended by the "Federal Environmental
Pesticide Control Act of 1972," has recommended procedures for
the disposal and storage of pesticides and pesticide containers.
The procedure recommended for the disposal of organic pesticides
is incineration at a temperature of 1000°C (1832°F) for 2 sec
retention time, or at other temperature-retention time combina-
tions that effect complete destruction of the pesticide. The
available data on pesticide incineration, however, are not suf-
ficient to determine specific operating guidelines for full-
scale incineration of unwanted organic pesticides and pesticide
containers.
This research study was initiated with the overall objec-
tive of determining design and operational criteria for the
incineration of pesticides, combustible pesticide containers,
and washings from pesticide containers. Efforts were focused
on the development of combustion data for a number of representa-
tive pesticides (active ingredients). An experimental pilot-
scale incineration system (45.4 kg/hr (100 Ib/hr) Type 1 waste*
capacity) was designed and constructed to evaluate the effect of
Type 1 waste is defined as rubbish, a mixture of combustible
waste such as paper, cardboard cartons, wood scrap, foliage
and combustible floor sweepings, from domestic, commercial
and industrial activities. This type of waste contains
257o moisture, 107» incombustible solids and has a heating
value of 1.51 x 107 J/kg (6,500 Btu/lb).
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operating variables (pesticide injection rate, operating temperature,
retention time, turbulence, and excess air rate) on the efficiency of
pesticide destruction. Injection nozzles were provided in the primary
combustion chamber for both liquid and solid pesticide formulations.
Nine representative active ingredients were selected for study by
EPA from the major classes of organic pesticides, i.e., chlorinated
organic, organophosphate, organonitrogen, and organosulfur. These pesti-
cides (DDT, aldrin, picloram, malathion, toxaphene, atrazine, captan,
zineb, and mirex) were tested using 15 commercial formulations, in-
cluding emulsifiable concentrates, wettable powders, dusts, a granule,
a pellet, and a bait.
Major emphasis was given to quantification of the active ingredient
(plus all closely related partially degraded chemical species) not de-
stroyed by the incineration process. To this end, nine sample points
were established in the experimental apparatus.
The measure of performance that has been used to evaluate test re-
sults is the efficiency to which the active ingredient was decomposed
within the incinerator during a period of steady state operation. This
efficiency, expressed as a percentage, equals [l - Slif2LlZ-~= 1 x 100.
L Quantity in J
The Quantity jln (the amount of active ingredient fed into the incinera-
tor) has been determined by volumetric measurement and quantitative
analysis of the pesticide-containing mixture injected into the inciner-
ator. Representative samples of the undiluted incinerator off-gas were
analyzed and, in combination with a determination of the total volume
of undiluted gas, were used to determine the amount of pesticide in the
effluent gas. Analogous determinations were made for any solid residue
left in the incinerator, e.g., from tests involving dust, wettable pow-
der, pellet, bait, or granular formulations. The amount of active in-
gredient plus related chemical species remaining in the incinerator
off-gas and solid residues was defined as the Quantity out. For DDT as
an example, the Quantity out included DDT* plus all other chlorinated
hydrocarbons detected.
"DDT" has been defined to include four major isomers commonly found
in the technical material, i.e., p,p'-DDT, o,p'-DDT, p,p'-DDE, and
o,p'-DDE.
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The efficiency of pesticide incineration was generally uniformly
high over the complete ranges of operating variables investigated. The
only exception was the 0.3% mirex bait formulation. The range of re-
sults for each formulation, expressed as pounds of the respective pes-
ticide plus all related chemical species detected in the incinerator
off-gas and solid residues per 1,000 Ib of active ingredient inciner-
ated, were as follows:
I
J
c
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\
100—
10—
0.01—
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a
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57% Molorhion EC"
25% Molothion WP**
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*The respective pesticide plus all related chemical species
detected in the incinerator off gas and solid residues.
"Based an Molothion detection limit.
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The ranges reported for the two malathion formulations are not
strictly comparable to the other results because they are calculated from
analytical detection limits for malathion (no malathion was detected in
the effluent from most tests) rather than from actual emission data.
The test data indicate that most organic pesticides can be destroyed
(i.e., greater than 99.99% of the active ingredient destroyed) over a
range of retention time-temperature combinations. Estimates were made
of the emissions (active ingredient plus related chemical species) in
the incinerator off-gas when the subject pesticides are incinerated at
2-sec retention at 1000°C (1832°F). (The 0.3% mirex formulation was ex-
cluded from this analysis because of the limited data in the time-
temperature area of interest.) These estimates, again expressed as
pounds of active ingredient plus related chemical species per 1,000 Ib
of active ingredient incinerated, are as follows:
?
•
'i
— 1 0—
I 0.1-
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0.01-
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* The respective pesticide plus all related chemical
species in the incinerator off-gas.
** Based on malathion detection limit.
-------
An evaluation was also made of comparable results for all 15 formula-
tions tested in an attempt to hypothesize operating conditions (retention
time-temperature combinations) generally applicable to the incineration of
organic pesticides when similarly injected. The result of this evaluation
is shown in the following diagram:
1200
u
0
I
1000
i
£ 800
600t
0
ZONE B
£&&&
•ZONE A
Retention Time, sec
Zone A represents operating conditions at which less than 99.99% ef-
ficiency may result, the Operating Zone represents conditions at which
efficiencies of at least 99.99% are expected, and Zone B represents con-
ditions at which greater than 99.99% are anticipated. The acceptable
range for excess air is estimated to be 80 to 160%.
Samples of solid formulations removed from the combustion chamber
after about 2-sec residence were found to contain significant levels of
pesticide. Approximately 10 and 30% of the active ingredient in 10%
picloram pellets and 0.3% mirex bait, respectively, was still present.
These findings demonstrate (a) the need to insure adequate retention of
solid residues in the combustion chamber, and (b) the inadequacy of
conventional retention time calculations (based on the volume of off-gas)
in defining solid residue retention time.
The stack gases from all incineration tests were also analyzed for
SC>2, NOX, CO, C02, CH^, total hydrocarbons, and for particulate emissions.
In addition, analyses were conducted for cyanide (as CN~) and total pyro-
phosphates when organonitrogen and organophosphate pesticides, respec-
tively, were tested.
-------
The organonitrogen pesticides generated measurable quantities of
cyanide (CN~) at the temperatures tested (640 to 1040°C). The cyanide
concentration of the incinerator off-gas, however, could generally be
controlled by increasing the operating temperature and percent excess
air above that required for pesticide destruction (greater than 99.99%
degradation).
Particulate loadings in the effluent gases during the incineration
of solid pesticide formulations (dusts, wettable powders, granules, and
pellets) were above federal limits established for new stationary sources
having a capacity of or greater than 45,000 kg/day (50 tons/day).
The results of these tests show that emission control devices will
be required for pesticide incineration. Emissions potentially requiring
control include particulates from solid formulations, P2^5 from phosphorus
based pesticides, HC1 from chlorinated hydrocarbons, CN~ from nitrogen-
containing organics, and SC>2 from organosulfur compounds. Odor is also a
problem, particularly during the incineration of organosulfur pesticides.
Additional research is required in three areas before operating
guidelines applicable to all organic pesticides as well as pesticide-
containing solid waste can be developed. These include (a) work at the
pilot scale to determine necessary combustion conditions for additional
representative pesticides and for pesticide-containing solid wastes,
(b) verification or revision of the generalized time-temperature-excess
air guidelines, utilizing the additional data, and (c) further charac-
terization of the effluents from pesticide incineration in order to
specify adequate emission devices.
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SECTION I
CONCLUSIONS
The following conclusions have been drawn from this study of the
incineration of pesticides.
1. Most organic pesticides can be destroyed, i.e., > 99.99% of
the active ingredient degraded, by incineration.
2. A range of retention time-temperatures exists at which these
pesticides can be > 99.99% destroyed.
3. The two most important operating variables are temperature and
retention time (dwell time) in the combustion chamber.
4. Conventional waste incinerators having adequate retention time
and operating temperature are potential facilities for pesticide incin-
eration using the injection methods described herein. However, modifica-
tions would probably be required because of the corrosive nature of the ef-
fluent gas from pesticide incineration and the need for emission control
devices.
5. Incineration of organonitrogen pesticides at the temperatures
tested (640 to 1040°C) generates measurable quantities of cyanide (CN~).
The cyanide concentration of the incinerator off-gas can generally be
controlled by increasing the operating temperature and percent excess
air above that required for pesticide destruction (> 99.99% degradation).
6. Emission control devices will be required for pesticide incinera-
tion. Emissions potentially requiring control include particulates from
solid formulations, ^2^5 from phosphorus-based pesticides, HC1 from
chlorinated hydrocarbons, CN~ from nitrogen-containing organics, and S0?.
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7. The solid residues left from the incineration of only pesticide
formulations generally contain very low levels of the pesticide, e.g.,
< 20 ppm.
8. Odor is a potential operational problem for pesticide inciner-
ation, particularly during the destruction of organosulfur pesticides.
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SECTION II
RECOMMENDATIONS
The feasibility for the destruction of unwanted organic pesticides
by incineration at the pilot scale has been demonstrated. There are
several areas, however, in which further study is needed. Recommended
activities include:
1. Development of operating condition data for the incineration of
additional representative pesticides and pesticide formulations.
2. Full-scale testing of representative pesticide incineration in
order to confirm the design and operational guidelines that have been
developed and to test their scale-up.
3. Pilot-scale testing of the incineration of pesticide-containing
solid wastes.
4. Development of guidelines for the incineration of pesticide-
containing solid wastes based on the above pilot-scale investigation
and confirmation by a limited number of large-scale tests.
5. Pilot-scale investigation of the "bake-out" principle of pesti-
cide incineration, i.e., the combustion of bulk pesticides (bags, car-
tons, etc.) using a long retention time in the combustion chamber, as a
possible alternative to particulate emissions control, and the effect of
longer test periods on the pesticide content of solid residues.
6. Investigation of particulate control devices for use during
solid pesticide formulation incineration.
7. Determination of the physical state and properties, i.e., par-
ticle size distribution of the pesticide-containing particulate emis-
sions in order to better assess their environmental significance.
8. Investigation of pesticide and pesticide-containing solid waste
feeding systems for pesticide incineration.
-------
9. Investigation of solid residue removal and handling methods for
pesticide incineration.
10. Development of improved analytical techniques to determine the
composition of incinerator emissions for the specific pesticides tested.
11. Additional investigations of the chemical species generated,
i.e., partial degraded pesticides, from pesticide incineration.
12. Characterization of the scope and geographic distribution of
the pesticide disposal problem.
10
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SECTION III
INTRODUCTION
The problem of how to dispose of unwanted pesticides and pesticide
containers has been recognized for several years.1*-' The development of
environmentally acceptable methods for disposal of these materials, how-
ever, has not been fully addressed until rather recently..£j_t' Pesticides
improperly disposed of, even in small quantities, may damage the local
environment or pose a hazard to individuals. Large quantities of improp-
erly disposed of pesticides would have undesirable local impact as well
as add to global environmental pollution.
The "Federal Insecticide, Fungicide, and Rodenticide Act," as amend-
ed by the "Federal Environmental Pesticide Control Act of 1972,"I/ requires
the Administrator of the U.S. Environmental Protection Agency to establish
regulations and procedures for the disposal and storage of pesticides
and pesticide containers. However, adequate disposal sites and facili-
ties are not readily available nationwide, and significant information
gaps exist which make it infeasible to write specific criteria for dis-
posal methods and procedures. Alternatively, the Agency has issued recom-
mended procedures for the disposal and storage of pesticides and pesticide
containers.—*—
The recommended procedure for organic pesticide disposal is incinera-
tion at a temperature of 1000°C (1832°F) for 2 sec retention (dwell) time
in the combustion zone, or at other temperature-retention time combina-
tions that effect complete destruction of the pesticide.
The thermal degradation of pesticides, i.e., conversion of the pesti-
cide to other organic and inorganic substances by heating in an oxygen-
sufficient (combustion) or oxygen-deficient (pyrolysis) atmosphere, has
been the subject of several research studies. Hanneman and Porter—' dem-
onstrated that certain dithiophosphates could be pyrolyzed at 2 215°C to
form volatile olefins structurally related to the alkyl group in the
original phosphate compound. Anthony and ShumanZ' have shown that mala-
thion can be successfully incinerated in a specially designed model in-
cinerator.
11
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Studies by Putnam et al.— have shown that, in gram quantities,
many pesticides can be destroyed (99% combustion) by open burning in a
flattened polyethylene bag surrounded by other combustible materials.
While oxidizing agents and binders were found to aid destruction, the
combination of oxidants and binders was found to be no more effective
than binders alone.
The incineration of DDT in a kerosene carrier has been studied by
Whaley et al.—' at the Canadian Combustion Research Laboratories in
Ottawa. Their work has shown that a DDT-kerosene formulation can be
destroyed in an incinerator utilizing a commercially available blue-
flame burner. This study provided the design data from which the Canadian
Department of National Defence built and operated a special incineration
system to destroy 107,000 gal. of a DDT-kerosene formulation. Further
study by Lee et al.JJ:' has shown that a DDT dust formulation can be sim-
ilarly destroyed.
Thermal degradation of pesticides also has been studied at the
laboratory scale by several investigators at Mississippi State Univer-
sity .i2rl2/ Their results indicate that the minimum temperature re-
quired for complete incineration is dependent on the specific pesticide,
and can range from 250°C to more than 600°C.JL1'
These earlier studies, however, failed to yield sufficient data to
determine design and operation guidelines for full-scale incineration of
unwanted pesticides and pesticide containers. The subject study was ini-
tiated in order to develop these data.
OBJECTIVES AND SCOPE
This research program was initiated with the overall objective of
determining design and operational criteria for incinerators that can ef-
fect complete thermal degradation of pesticides, combustible pesticide
containers, and washings from containers.
Specific objectives to be accomplished during the program were:
1. Determination of optimum combustion conditions for selected
pesticide formulations in a pilot scale incinerator. Representatives of
four major classes of pesticides (organochlorine, phosphorus, nitrogen,
and sulphur) were to be investigated.
2. Determination of the effect of selected materials on combustion
of pesticides. The materials were to include combustible container mate-
rials, sewage sludge, municipal refuse, waste industrial liquids, and
liquids used to clean noncombustible pesticide containers.
12
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3. Development of guidelines for design and use of incinerators
for pesticide destruction. The guidelines were to encompass conventional
incinerators as well as new incinerators designed specifically to handle
pesticides.
Work was initiated toward these objectives using a three phase re-
search plan.
Phase I was the determination of incinerator operating conditions
which would most effectively degrade specific pesticides. It was planned
that representative pesticides (one from each of four major chemical
classes--chlorinated organic, organophosphate, organonitrogen, and or-
ganosulfur) would be extensively investigated in statistically designed
tests to determine their respective optimum incineration conditions.
Phase II was the determination of the effect of other waste mate-
rials on the efficiencies of incineration for the four representative
pesticides obtained in Phase I.
The third and final phase under the original research plan was the
development of guidelines for the design and selection of pesticide in-
cinerators. Using the results from the two initial phases, minimum val-
ues for operating conditions necessary to achieve complete destruction
of the specific pesticides were to be established. These conditions were
then to be used in developing guidelines for determining the suitability
of existing incinerators and conventional municipal incinerator design
parameters for pesticide disposal.
However, only one pesticide (DDT) was studied using these initial
objectives and research plan. After completion of the DDT experiments,
efforts were focused on the development of combustion data for a number
of pesticides. Included in the pesticides studied were those represent-
ing acute disposal problems because of actual or potential registration
cancellation, and those representative of various chemical classes of
pesticides.
The modified research plan used for the remainder of the program
included a two-phased study of each pesticide. First, preliminary thermal
analyses (differential thermal analysis (DTA) and thermal gravimetric
analysis (TGA)) were conducted to identify temperatures at which the re-
spective pesticides could be expected to decompose. Following this identi-
fication, a limited number of experiments were made within the favorable
temperature range in order to determine the completeness of destruction
that could be achieved.
13
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PESTICIDE SELECTION
The pesticides studied during this research program were: DDT,
aldrin, malathion, picloram, toxaphene, atrazine, captan, zineb, and
mirex (see Table 1). The classification of these pesticides by chem-
ical structure is given in Table 2.
DDT was the first pesticide studied and the only one extensively
investigated. The combustion of DDT, a pesticide that currently repre-
sents an acute disposal problem, has been the subject of several other
research studies. The experiment with DDT, then, not only provided data
on its combustion, but also provided a means for relating our findings
to those from other programs.
The eight additional pesticides were subsequently selected by EPA
based on the suggestions of the Office of Solid Waste Management Pro-
grams (OSWMP) and Midwest Research Institute (MRI), as well as other
divisions of EPA.
REPORT ORRANTZATTfTN
The following subsections of this report (Sections IV through VII
and Appendices A through D) give the results of the experiments conducted
with the nine pesticides.
Section IV - Experimental Methods and Equipment, briefly describes
the experimental facilities, methods of sampling and analysis, and experi-
mental design used during the study. Complete detail of the facilities
design is given in Appendix A, while details of sampling and standard
analytical methods are given in Appendix C.
Section V - Results, briefly summarizes the experimental results,
general findings, and problem areas from the experimental phase of the
study. Detailed test results are presented in Appendix B. The last ap-
pendix to the report (Appendix D) gives details of calculation methods
used to derive the results reported in Section V.
Section VI - Discussion, includes an overall discussion of the sig-
nificance of the study as well as a brief analysis of system requirements
for pesticide incineration.
The final section of the report (Section VII) contains a listing of
all references cited in the text. (References pertaining to the specific
pesticides tested have been cited in the appropriate subsections of
Appendix B.)
14
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Table 1. CHEMICAL STRUCTURES OF TEST PESTICIDES
Cl-C-Cl
DDT
(A mixture of p.p'-isomers (75 to 807.),
o.p'-isomers (15 to 207.), as well as
related chlorinated compounds.)
ALDRIN
CH,
MALATHION
PICLORAM
(Tested as the potassium salt.)
8(C1
TOXAPHENE
(Mixed isomers of chlorinated catnphene,
67 to 69% chlorine.)
N-#N)
ATRAZINE
.CH,
^CH,
[-S-CC1,
-c
"2 0
,-NH-C-S,
Zn
CH0-NH-C-S
CAFTAN
ZINEB
cic-
MIREX
15
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Table 2. CLASSIFICATION OF PESTICIDES BY CHEMICAL STRUCTURE^'
Classification Pesticides tested
Inorganic and Metallo-Organic Pesticides
Mercury Compounds
Arsenic Compounds
Copper Compounds
Other Heavy-Metal Compounds
Cyanides, Phosphides and Related Compounds
Other Inorganic Compounds
Phosphorus-Containing Pesticides
Phosphates and Phosphonates
Phosphorothioates and Phosphonothioates
Phosphorodithioates and Phosphonodithioates Malathion
Phosphorus-Nitrogen Compounds
Other Phosphorus Compounds
Nitrogen-Containing Pesticides
Carbamates and Related Compounds
Thiocarbamates
Dithiocarbamatesa/ Zineb
Anilides
Imides and Hydrazides Captan
Amides
Ureas and Uracils
Triazines Atrazine
Amines, Heterocyclic (without sulfur) Picloram
Amines, Heterocyclic (sulfur-containing)
Nitro Compounds
Quaternary Ammonium Compounds
Other Nitrogen-Containing Compounds
16
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Table 2. (concluded)
Classification Pesticides tested
Halogen-Containing Pesticides
DDT DDT
DDT Relatives
Chlorophenoxy Compounds
Aldrin-Toxaphene Group Aldrin, Toxaphene,
Mirex
Aliphatic and Alicyclic Chlorinated Hydrocarbons
Aliphatic Brominated Hydrocarbons
Dihaloaromatic Compounds
Highly Halogenated Aromatic Compounds
Other Chlorinated Compounds
Sulfur-Containing Pesticides
Sulfides, Sulfoxides and Sulfones
Sulfites and Xanthates
Sulfonic Acids and Derivatives
Thiocyanates
Other Sulfur-Containing Compounds
Botanical and Microbiological Pesticides
Organic Pesticides. Not Elsewhere Classified
Carbon Compounds (< 9 carbon atoms)
Carbon Compounds (> 9 carbon atoms)
Anticoagulants
a/ Ten of the 13 pesticides in this category (including zineb) would be
classed as matallo-organic according to EPA disposal procedures.2-*2./
17
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SECTION IV
EXPERIMENTAL METHODS AND EQUIPMENT
The selection of experimental methods and facilities used during
this study was based on the initial objectives and scope as have been
outlined above. At the inception of the project, it was decided that
maximum flexibility be provided in the experimental system in order
that no mechanical restraints prevent the determination of optimum in-
cinerator operating conditions. For this reason, a commercial incinera-
tion unit was not used. Rather, a two-chambered experimental incinerator
of pilot scale (i.e., 45.4 kg/hr (100 Ib/hr) of Type 1 waste* capacity)
was constructed and used. The secondary combustion chamber of the ex-
perimental incinerator was designed following Incinerator Institute of
America (IIA) standards and constructed as a permanent installation.12'
The primary chamber was constructed of insulating firebrick layered up
with mortar. This system was designed to allow for rapid changes in ge-
ometry (turbulence) and length (retention time) with a minimum of effort
and lost time.
The following three subsections (Experimental Facilities, Sampling
and Analysis, and Experimental Design) briefly describe the facilities
and methods used to study the effects of incinerator operating condi-
tions on the efficiency with which selected pesticides could be de-
stroyed.
* Type I waste is defined as rubbish, a mixture of combustible waste
such as paper, cardboard cartons, wood scrap, foliage and combusti-
ble floor sweepings, from domestic, commercial and industrial ac-
tivities. The mixture contains up to 20% by weight of restaurant
or cafeteria waste, but contains little or no treated papers, plas-
tic or rubber wastes.
This type of waste contains 25% moisture, 107. incombustible solids
and has a heating value of 1.51 x 107 J/kg (6,500 Btu/lb) as fired.
Thus, the design capacity of the pilot scale incinerator was 6.86 x
108 J/hr (650,000 Btu/hr).
19
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EXPERIMENTAL FACILITIES
An overall schematic of the experimental apparatus used is given in
Figure 1. The experimental incinerator was located on a concrete pad im-
mediately adjacent to a laboratory building which housed the three-stage
scrubber system. The entire facility was located at MRI's Deramus Field
Station which is used for research projects involving potentially hazard-
ous materials or operations.
The following discussion summarizes the major characteristics of the
experimental apparatus. Complete information on the system has been in-
cluded as Appendix A.
Incinerator
The pi lot-scale incinerator was constructed of standard (Morex®)
firebrick using IIA design standards for a 45.4 kg/hr (100 Ib/hr) Type 1
waste incinerator-Lx' An outer shell was constructed using concrete
blocks, and the void between the firebrick and concrete walls was filled
with perlite. The primary chamber was initially provided with both front
(primary) and side (alternate) burner positions, as shown in Figure 2.
Pesticide Injection Systems
Separate injection systems were provided for liquid and solid for-
mulations. In addition, modification of the initial liquid formulation
injection system was made in order to accommodate water-based formula-
tions not compatible (miscible) with fuel oil. The liquid injection sys-
tem, the modified liquid injection system, and the solid formulation
injection system are briefly described as follows, while detailed infor-
mation is given in Appendix A.
Solid Formulations
All solid pesticide formulations tested were injected through a
system similar to that used for earlier studies of DDT dust incinera-
tionJL2/
The formulation was metered at a uniform rate by a variable speed
vibrating screw feeder and fed into a stream of compressed air which in-
jected the pesticide into the primary chamber of the incinerator through
a water-cooled injection nozzle. The dust injection nozzle and the fuel
oil burner were positioned in the primary burner position so that the
flame and dust stream impinged on a horizontal plane at an angle of 30
degrees, and at a point approximately 8 cm (3 in.) from the front wall
20
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Exhaust
clnerator
ed
Burner
1
V
Lr
-»x
x
Reheat
U
D
[
— A
4
1 ^
r
*-**^.
)}
*.
-
\
/
s — \
L^ \ —
-•— ••
\
-j
A
^^
300 SCFM
Ir from '
Building
V
S
Incinerator
entiiation
ystem
1 S
1
\N
\\
I
t— -
s£
;
/•
Vt —
7
Water
*\
-^x
4, 2gpm
Nozzles
Dampers
for Flow
Contra
fn
Trap
i*
i-c-j
Blia
"*•*.(")
A
o^Ros
!°o?Rin
._•«»
&H2°
r-
2, 1 gpm-<^
Water ^V
Nozzles ^\-
^-
chig
9'
L_J
--
-
Scrubber
ff ^
)
4, 2gpm
Nozzles
ji
I
j*0
H
&L^
f Ti
mM f ^\
^n r"~ Si|_
O • cj ft B
o° Raschig .
",<• Rings Marble
,.0.^--.. Bed ',
\ dj)
fTk
--
-------
Figure 2. Incinerator configuration
22
-------
of the primary chamber. A picture of the dust injection system in this
configuration is shown in Figure 3. (See also Figure 17, p. 100).
An alternate configuration was used during the DDT experiments,
where the oil burner was located in the primary burner position, and the
pesticide injection nozzle was located in the alternate (side) burner
position (see Figure 2). Thus, the flame and pesticide stream impinged
at 90 degrees on a horizontal plane at the geometric center of the pri-
mary chamber.
Liquid Injection System
All liquid pesticide formulations miscible with No. 2 fuel oil were
injected as pesticide fuel oil mixtures using standard fuel oil burners.
The mixtures were gravity fed from batch holding tanks at a height of
2.4m (8 ft) above the burner nozzle. Two burners with design capacities
of 11.3 to 30.3 liters/hr (3 to 8 gal/hr), and 2.3 to 11.3 liters/hr (0.6
to 3 gal/hr), respectively, were used to inject the pesticide-fuel oil
mixtures at the desired rate through the two burner positions provided
in the primary chamber (see Figure 12, p. 94).
Modified Liquid Injection System
For those liquid formulations not compatible with No. 2 fuel oil,
a dual injection system was used. Supplemental fuel (No. 2 fuel oil) was
injected at the desired rate using the standard fuel oil burner equipped
with the appropriately sized nozzle. The liquid formulation was pumped
into the incinerator through a fuel oil nozzle of the same type being
used in the oil burner. The liquid formulation and fuel oil were both
fed to the respective pumps by gravity from batch holding tanks located
2.4 m (8 ft) above the injection nozzles.
The two injection systems were positioned in the primary burner
position (see Figure 2) so that the liquid formulation and the flame from
the fuel oil burner impinged on a horizontal plane at an angle of 30 de-
grees and at a point about 8 cm (3 in.) from the front wall of the pri-
mary chamber. This configuration, as described above, is the same used
for injection of solid formulations (see Figure 15, p. 97).
A further modification was made to prevent plugging of the pesticide
injection nozzle. This consisted of using the dust injection nozzle water
jacket to cool the pesticide injection nozzle. (See Figure 16, p. 98.)
23
-------
Figure 3. Solid pesticide formulation injection system
24
-------
Scrubber System
A three-stage system was installed to scrub the incinerator off-
gas prior to discharge to the atmosphere (see Figure l). Water, hexylene
glycol, and water, respectively, were used as the scrubber liquids.
Scrubber waters from the first and third stage scrubbers were accumu-
lated in separate storage tanks during each test. Subsequently, they were
processed through a sand filter and activated charcoal columns before
being discharged into the facility's septic tank system. The hexylene
glycol from the second stage scrubber was recirculated during the test
periods. A picture of the scrubber system is shown in Figure 4.
Protective Equipment
The experimental facility required two operating personnel when
testing liquid pesticide formulations, and four when incinerating solid
formulations. All personnel involved with the operation of the facility
were provided with hard hats, disposable gloves, safety shoes, work
clothes, and disposable coveralls.
During the experimental phase of the facility's operation, i.e.,
whenever a pesticide was being incinerated, all personnel were supplied
with bottled breathing air through demand-flow respirators.
SAMPLING AND ANALYSTS
The major emphasis was given to characterization and quantification
of the pesticide (and closely related chemical species) not destroyed by
the incineration process so that the efficiency of incineration could be
evaluated. To this end, nine sample points were established in the exper-
imental apparatus. These sample points (as well as manometer and thermo-
couple locations) are shown in Figure 5.
Efficiency of incineration, which was evaluated about the incinera-
tor, was based on analysis of samples from three points (Sample Points
Nos. (l) , the incinerator feed; (2) , the incinerator off-gas; and fs),
any solid residues left in the incinerator chambers).
The incinerator off-gas (Sample Point No. (2J ) was also character-
ized according to more conventioanl discharge measurements, including
SC>2, NOX, moisture, Orsat analysis for excess air determination, total
hydrocarbons, and certain additional special analyses. The additional
tests included cyanide analysis (as CN~) for all nitrogen-containing
pesticides (picloram, atrazine, captan, and zineb), and total pyrophos-
phate analysis of the phosphorus-based pesticide (malathion).
25
-------
Figure 4. Scrubber system
-------
Exhaust
NJ
\^y Sample Point
\—f Thermocouple
L A Manometer
Figure 5. Sample point, thermocouple, and manometer locations
-------
The following two subsections briefly describe the sampling and
methods of analysis used during the study. A detailed discussion of the
sampling procedures and methods of analysis (excluding methods for active
ingredient analysis) is given in Appendix C. The methods of active in-
gredient analysis are reviewed in detail in the appropriate subsection
of Appendix B - Test Results.
Sampling Methods
For liquid pesticide formulations, the method used to obtain gas
samples for active ingredient analysis utilized sampling "trains" con-
sisting of mini-impingers, an 0.8 \i filter, a liquid nitrogen cold trap
(at Sample Point No. (~2\ (Figure 5) only), and a critical orifice at-
tached to a vacuum system. The first two impingers were filled with 20
ml of the appropriate pesticide grade solvent, while the last impinger
was left empty in order to trap any significant carry-over and prevent
wetting of the filter element. A 26G x 0.95 cm (3/8-in.) hypodermic
needle was used as the critical orifice in each of the four gas sampling
trains (Sample Points Nos. (^), (3) , ^?) , and ^9_) ) used for all li-
quid formulation experiments to continuously sample the gas stream during
a steady state period of about 30 min. The train used for the undiluted
incinerator off-gas (Sample Point No. (2) ) is shown in Figure 6.
For solid pesticide formulations, the potential for losing pesticide-
containing dust from the stack made it necessary to determine the stack
particulate loading. Sampling the incinerator effluent using only the
vapor sampling technique as outlined above for liquid formulation would
not reflect the pesticide content of dust emitted.
It was decided that the most accurate evaluation would be obtained
by utilizing Method 5 as published in the Federal Register-iQ' to deter-
mine the particulate loading in the stack. This technique, specified by
EPA for use in such determinations, gives the total particulate dis-
charged from the incinerator stack. The particulate samples, after col-
lection, were then analyzed for residual pesticides.
Two modifications were made to facilitate the analysis of the sample
for pesticide content. First, the appropriate solvent was used in the
impingers rather than water. The second modification was to add a liquid
nitrogen cold trap to the sample train in order to collect condensibles
for active ingredient analysis. After particulate analysis had been com-
pleted, all samples were analyzed for active ingredient and related chem-
ical species content.
28
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VO
SAMPLE PROBE
WATER OR.
ICE BATH
FILTER /-CRITICAL ORIFICE
IMPINGERS
COLD TRAP
GLASS WOOL
'TO
VACUUM
PUMP
Figure 6. Gas sampling train
-------
Sampling methods for SO , NO , moisture, and Orsat analysis followed
those specified in the Federal Register^-' Detailed descriptions of these
methods, as well as those used for obtaining representative samples of
solid residues and scrubber liquids are described in Appendix C.
Methods of Analysis
Samples from the nine sampling points were analyzed for active in-
gredient content, and for all other chemically similar, partially de-
graded species. Active ingredient and total species analyses were per-
formed using the specific method of analysis for each of the pesticides
tested. (Details of each method have been included in the appropriate
subsection of Appendix B - Test Results.)
Method of analysis used for SC>2, NOX, moisture, and Orsat determina-
tion were those specified in the Federal Register^0./ for such determina-
tions. These methods, as well as those for total hydrocarbons, cyanide
(as CN"), and total pyrophosphate content are detailed in Appendix C.
RyPRRTMRNTAT. DRSTfiN
DDT, the first pesticide tested, was the only one investigated using
the initial concept of statistically designed experiments in order to de-
fine optimum incinerator operating conditions. Pesticide injection rate,
excess air rate, operating temperature, and turbulence were selected as
the operating conditions to be independently varied during experiments
using a 43% DDT emulsifiable concentrate (EC) formulation. Retention time
and supplemental fuel rate, therefore, were dependent (concomitant) var-
iables. A modified fractional experiment was designed using 16 combina-
tions (high and low levels) of the four independently varied conditions.
This initial experiment was then followed with a limited number of tests
using a solid (dust) formulation in order to evaluate the effect of
physical form on the efficiency with which DDT could be incinerated.
The eight pesticides tested after DDT were evaluated using a two-
step approach. First, preliminary laboratory thermal analyses (differ-
ential thermal analysis (DTA), and thermal gravimetric analysis (TGA))
were conducted to identify temperatures at which the respective pesti-
cide could be expected to decompose. Following this definition, tests
were made in the favorable temperature range utilizing a liquid and a
solid formulation. For pesticides commercially available in only solid
forms, a minimum of eight tests were conducted using a major solid formu-
lation. The rate of pesticide injection, percent excess air, and operat-
ing temperature were varied between two nominal values, i.e., a high and
low level.
30
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Test Cycle
The following test cycles were used for all liquid and solid pesti-
cide formulation experiments conducted during the study.
Liquid Formulations___Test - The incinerator was preheated prior to the
test for approximately 6 hr. During the first 3 to 4 hr, an 11.3 or 13.2
liters/hr (3.0 or 3.5 gal/hr) nozzle was used, depending on: (a) the
desired test temperature; and (b) the temperature of the incinerator
prior to firing. For the last 2 to 3 hr, the incinerator was preheated
with the nozzle that was to be used for the test in order to (a) sta-
bilize the incinerator temperatures; and (b) determine the approximate
nozzle feed rate.
During the incinerator warm-up, further preparation was made for the
test. Sampling trains were made ready and installed, i.e., pesticide sam-
pling trains, moisture, S02, NOX, CN~ and total pyrophosphate as appro-
priate to the specific test. The Orsat analyzer, the total hydrocarbons
analyzer, and the manometers were standardized. The pesticide formulation
was then mixed and weighed.
Approximately 15 min prior to starting pesticide injection, the
scrubber system was started by turning on the blower, starting scrubber
water and hexylene glycol circulation, and closing the stack bypass (see
Figure 1, p. 21). After starting the system, the draft and burner fan
openings were adjusted for the anticipated percent excess air. Flow rate
tests were run on the sampling trains with a rotometer and Orsat anal-
ysis was run on the stack gas. Scrubbers 1 and 3 tanks were pumped out-
side, and Scrubbers 1, 2, and 3 were measured and sampled just prior to
initiating pesticide injection.
After pesticide injection was started, the system was run 15 min
before starting the sample trains in order to stabilize the system. An
initial sample was taken of the pesticide-fuel oil mixture.
During the sampling time (30 min) the following procedure was fol-
lowed. Readings were taken each 5 min on temperatures, manometers, fuel
oil and pesticide levels, S02, and pesticide sampling trains. Three Orsat
samples were taken, the exhaust plume was observed as appropriate, and
the second sample of the pesticide feed was taken.
Immediately after the 30 min sampling period, pyrometer readings were
taken and the second NO and incinerator feed samples were collected.
31
-------
The burner feed was then switched from the pesticide containing mix-
ture to fuel oil and allowed to run for an additional 5 min. During this
time, the pesticide feed line was cleaned out, flow rates were again
checked on the sampling trains, and the SC^ train was purged.
The stack bypass was then opened and the blower turned off. The
burner continued to operate another 10 to 30 min on fuel oil.
Immediately after the experimental test, Scrubbers 1 and 3 were
drained, the fuel oil line was allowed to run dry, the burner was re-
moved from the incinerator, and the sample trains were recovered. Orsat
samples were then analyzed, the pesticide drum was reweighed, the tanks
of Scrubbers 1, 2, and 3 were measured and sampled, the tanks of Scrub-
bers 1 and 3 were pumped out, and the stack bypass was closed.
Solid Formulations Test - Prior to beginning the incinerator warm-up,
residues from the prior run were cleaned out of the primary and second-
ary chambers. The residues were weighed, sampled, and the excess residue
labeled and stored.
The incinerator was fired approximately 6 hr prior to the test.
During the first 3 to 4 hr, the incinerator was operated with a 11.3 or
13.2 liters/hr (3.0 or 3.5 gal/hr) nozzle, depending on the anticipated
test temperatures and the temperature of the incinerator prior to firing.
During the last 2 to 3 hr, the warm-up was conducted with the intended
test nozzle.
During the incinerator warm-up, further preparation was made for the
test. Sampling trains were made ready and installed, i.e., pesticide sam-
pling train(s), moisture, S0_, NOX, and CN~ or pyrophosphate, as appro-
priate. The Orsat analyzer, the total hydrocarbons analyzer, and the man-
ometers were standardized. The pesticide formulation was then weighed out,
and the feed rate was set and checked.
Prior to starting the pesticide injection, the scrubber system was
started for approximately 15 min by turning on the blower, starting the
scrubber water and hexylene glycol circulation, and closing the stack by-
pass. After starting the system, the draft and burner fan openings were
adjusted for the anticipated percent excess air, and flow rate tests were
run on the sampling trains. Orsat analysis was run on the stack gas, and
the particulate sampling train (Sample Point No. (T) ) was leak checked.
After the pesticide injection was started, the system was run 15 to
30 min before starting the sample trains. During this time, final adjust-
ments of the draft were made, an Orsat analysis was run, and an NOX sample
32
-------
was taken. Scrubbers 1 and 3 tanks were pumped outside just prior to
starting the sampling. A sample of the pesticide formulation was taken.
During the sampling period (60 min), a number of measurements were
made. Scrubbers 1, 2, and 3 tanks were measured and sampled immediately
after the start of sampling, as appropriate. Readings were taken each 5
min on temperatures, manometers, fuel oil level, SC^ and pesticide sam-
pling train(s). During the test, four Orsat samples were taken, and the
exhaust plume was observed. Pyrometer readings were taken midway of the
sampling period (after 30 min).
After the 60 min sampling period, another NOX sample was taken and
the system was allowed to run 5 to 10 min on fuel oil during which time
the second pesticide sample was taken, the excess pesticide was cleaned
out of the vibrating screw feeder and weighed, flow rates were again run
on the sampling trains, the S02 train was purged, and Scrubbers 1 and 3
tanks were measured and sampled.
The stack bypass was then opened and the blower turned off. The
burner continued another 10 to 30 min.
After the experimental test, the burner was removed from the incin-
erator, sample trains were recovered, and the Orsat samples were anal-
yzed. Scrubbers 1 and 3 tanks were pumped out.
33
-------
SECTION V
RESULTS
This section summarizes the major findings from the pilot-scale in-
cineration of DDT, aldrin, picloram, malathion, toxaphene, atrazine, cap-
tan, zineb, and mirex. The measure of performance that has been used to
evaluate test results is the extent (efficiency) to which the pesticid-
ally active chemical species (active ingredient) was decomposed within
the incinerator during a period of steady state operation. This effi-
Quantity out ,„„ „.
ciency, expressed as a percentage, equals 1 - — x 100. The
Quantity in
Quantity in (the amount of active ingredient fed into the incinerator)
has been determined by volumetric measurement and quantitative analysis
of the pesticide-containing mixture injected into the incinerator (Sam-
ple Point No. (T) , Figure 5, page 27). Representative samples of the
undiluted incinerator off-gas (Sample Point No. (T) ) were analyzed,
and in combination with a determination of the total volume of undiluted
gas, were used to determine the amount of pesticide in the effluent gas.
Analogous determinations were made for any solid residue (Sample Point
No. ($} ) left in the incinerator, e.g., from tests involving dust,
wettable powder, pellet, bait, or granular formulations. The amount of
pesticide remaining in the incinerator off-gas and residues was defined
as the Quantity out.
Whenever possible, a second efficiency was calculated using the
same equation, but where the Quantity out included not only the unburned
pesticide as such, but also all other closely related, partially decom-
posed chemical species detected; this quantity has been termed total
species. Thus, for DDT as an example, the Quantity out (total species)
included DDT plus all other chlorinated hydrocarbon species detected in
the incinerator off-gas and any solid residues.
Other constituents of the incinerator off-gas, i.e., S02> NOX> CO,
C02> total hydrocarbons, CH^, and (where applicable) CN~, were not in-
cluded in the efficiency calculations.
35
-------
The results from the incineration tests are presented in four fol-
lowing subsections: Specific Results, General Findings, System Perform-
ance, and Problem Areas.
The specific results subsection briefly summarizes the major test
results for each of the nine pesticides in the chronological order of
their investigation. Complete details of the test conditions and results
are given in Appendix B.
The general findings subsection reviews the overall efficiencies of
incineration for the subject pesticides as well as general problem areas
that were encountered.
The last two subsections (Systems Performance and Problem Areas)
address the adequacy of the experimental apparatus used for the tests as
well as problems associated in its operation.
SPECIFIC RESULTS
DDT
DDT was specified by the EPA project officers as the first pesti-
cide to be studied because it not only represents existing disposal
problems but also has been the subject of other research studies. The
DDT experiments, therefore, provided data on its combustion as well as
a means for relating our findings to those from other research.
There are a number of operating conditions that can influence the
performance of an incinerator used for pesticide disposal. These include
pesticide injection rate, operating temperature, excess air rate, turbu-
lence, auxiliary fuel rate, and retention time. The interaction of many
of these factors, however, is such that they cannot all be independently
varied. Pesticide injection rate, excess air rate, operating temperature,
and turbulence were selected as the operating conditions to be indepen-
dently varied during the DDT experiments. Retention time and supplemental
fuel rate were dependent (concomitant) variables.
A modified fractional factorial experiment was designed to study
the combustion of a 25% DDT emulsifiable concentrate (EC) formulation
in order to determine optimum incineration conditions. The four con-
trolled variables (each at two levels) were to be run in 16 combina-
tions.
36
-------
The 25% EC formulation was initially injected at a nominal rate of
3.4 kg (7.5 Ib) DDT* per hour, while the second level of injection was
one-half of the initial rate. A standard fuel oil burner was used as the
injection system (see the subsection of Experimental Facilities, page 20
for a more detailed description of the feed system).
Air was injected at approximately 50 and 150% excess (calculated
according to Method 3 of "Standards of Performance for New Stationary
Sources, ").£?/ and the incinerator temperature was varied from approxi-
mately 950°C (1750°F) to 1090°G (2000°F), the nominal operating range of
the experimental incinerator with the available fuel oil burner. The
temperature was obtained by injecting the desired amounts of DDT (in the
EC formulation) mixed with the appropriate amount of supplemental fuel
(No. 2 fuel oil).
Turbulence within the ignition chamber was influenced by changing
the location of the pesticide injector. The two levels of turbulence
were studied by injecting the EC-fuel oil mixture through the fuel oil
burner in the front (primary) and in the side (alternate) position of the
primary combustion chamber (see Figure 2, page 22).
Thus, the fractional factorial experiment was as shown on the fol-
lowing page.
A total of 21 tests were conducted to fit the 16 points of a mod-
ified fractional factorial analysis of these four parameters.
The results of the 21 tests made using the 25% EC formulation are
summarized in Table 3. For all but four tests, the efficiency of incin-
eration was > 99.99%, based on either DDT or total species detected. The
operational data show that we were not able to operate the incinerator
precisely at the desired levels for each independent variable, e.g., 50
and 150% excess air. For this reason, the data could not be strictly
evaluated as representing a fractional factorial experiment. Therefore,
the data were evaluated using multiple regression analysis, which is the
more appropriate statistical technique in this instance because of the
uniformly high combustion efficiencies observed. Regressions of the four
* For purposes of thil report, "DDT" has been defined to include four
major isomers commonly found in the technical material, i.e., p,p -
DDT o,p'-DDT, p,p'-DDE, and o,p'-DDE. Both o,p'-DDD and p,p'-DDD
have been arbitrarily included with the "other" chlorinated hydro-
carbon species.
37
-------
Experiment
designation
a
b
c
d
e
f
g
h
A
B
C
D
E
F
G
H
I
J
K
L
M
N
0
P
Pesticide
injection
Operating
Turbulence rate temperature
a
a
a
a
a
a
a
a
b
b
b
b
b
b
b
b
c
c
c
c
d
d
d
d
c
c
c
c
d
d
d
d
e
e
f
f
e
e
f
f
e
e
f
f
e
e
f
f
Excess
air
rate
g
h
g
h
g
h
g
h
g
h
g
h
g
h
g
h
= frontal injection
= side injection
= 1.70 kg
= 3.4 kg
(3.75 Ib)
DDT per hour
(7.5 Ib) DDT per hour
= 950°C (1750°F)
= 1090°C
= 50%
= 1507.
(2000°F)
38
-------
Table 3. SUMMARY OF TEST RESULTS —25% DDT EC FORMULATIONS
Experiment
designation
A
B
C
D
E
F
G
u
I
J
K
L
M
N
0
P
DDT
rate
K/hr (Ib/hr)
1,090 (2.42)
1,910 (4.23)
1,950 (4.27)
1,770 (3.88)
1,630 (3.59)
1,320 (2.90)
4,630 (10.25)
2,400 (5.29)
2,400 (5.34)
1,450 (3.16)
1,220 (2.74)
1,130 (2.53)
1,450 (3.21)
1,500 (3.34)
500 (1.09)
730 (1.62)
1,860 (4.11)
1,810 (3.96)
3,220 (7.08)
3,360 (7.36)
1,810 (4.03)
Primary
chamber
temperature
Turbulence -'
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
•c
1040
940
1140
1170
1040
1050
930
1150
1050
1070
980
980
1170
1050
1100
1090
1030
940
1190
1030
1050
(°F)
(1900)
(1730)
(2090)
(2130)
(1900)
(1930)
(1700)
(2110)
(1920)
(1950)
(1800)
(1800)
(2140)
(1930)
(2010)
(2000)
(1890)
(1730)
(2180)
(1890)
(1930)
Excess
air
7.
92
162
88
100
120
85
143
116
135
83
138
128
64
151
137
163
96
166
80
164
130
Retention time
sec
Primary
chamber
2.5
1.3
1.6
1.5
0.9
2.4
1.0
2.2
0.9
2.9
3.1
2.5
1.4
1.4
1.6
1.3
1.5
3.0
1.7
1.3
1.5
Second
chamber
2.7
1.2
1.8
1.6
0.7
2.4
0.8
2.3
0.7
3.0
3.2
2.9
1.4
1.3
1.4
1.3
1.6
3.1
1.6
1.2
1.3
Ratio of DDT
in off-gas
to DDT fed
5 x 10"6
1.8 x 10-5
4.9 x 10-6
9 x ID"6
1.1 x 10-*
5 x 10-6
5 x lO-5
2.8 x 10-5
4 x 10-5
2.8 x 10-5
6 x 10-5
1.2 x 10-5
3.5 x 10-5
3.8 x 10-5
5 x 10-5
5 x 10-5
3.4 x 10-5
4.4 x 10-5
7 x 10-6
2.4 x 1C"5
3.0 x 10-5
Ratio of
total species
content of
off-gas to
DDT fed
2.9 x ID"5
2.7 x 10-5
1.2 X 10-5
2.1 x lO-5
1.7 x 10-*
3.0 x 10-5
5 x 10-5
7 x 10-5
5 x 10-5
6 x 10-5
1.4 x 10-4
2.3 x 10-5
9 x 10-5
1.2 x 10-*
6 x 10-5
6 x 10-5
9 x 10-5
1.6 x 10-4
1.8 x 10-5
2.6 x 10-5
4.9 x 10-5
Incinerator efficiency
DDT
> 99.99
> 99.99
> 99.99
> 99.99
> 99.98
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
7.
Total species
> 99.99
> 99.99
> 99.99
> 99.99
> 99.98
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.98
> 99.99
> 99.99
> 99.98
> 99.99
> 99.99
> 99.99
> 99.98
> 99.99
> 99.99
> 99.99
£/ 1 = Frontal injection
2 = Side injection
-------
quantitative variables (DDT injection rate, retention time, temperature,
and excess air) were run using: (a) the relative amount of DDT not de-
stroyed ("Ratio of DDT in Off-Gas to DDT Fed" column of Table 3); and (b)
the relative amount of total chlorinated hydrocarbon species not de-
stroyed ("Ratio of Total Species Content of Off-Gas to DDT Fed" column
of Table 3) as the dependent variable (y.)-
A multiple regression model, yi = aQ + a-X^ + o/2x-2i + Q^Si +
o/4^4i 4- G£ , was used to perform an Analysis jof variance (ANOVA) in or-
der to furnish values (F-values) which could be used to decide whether
or not predicting y.. (relative efficiencies of combustion, based on
either the DDT or total chlorinated species left undestroyed) by using
the model results in significantly more accurate results than "predict-
ing" y. by random choices from the y^ distribution.
In neither case was the regression found to be significant, nor were
any of the individual regression coefficients found to be significant.
Thus, knowledge of the DDT feed rate, primary chamber temperature, ex-
cess air, and retention time, over the ranges investigated did not mate-
rially aid in predicting the incineration efficiency.
The DDT efficiencies determined from these experiments are not un-
like those reported in an earlier study by the Defence Research Estab-
lishment of Canada. Their report showed that no more than 0.0002% of the
?l 7
DDT entering their incinerator remained unburned.— Our results, reported
to the same number of decimal points, indicate 0.0005% DDT remained un-
burned (Experiments A and C, Table 3).
Upon completion of experiments with the 25% DDT EC formulation, eight
tests were made using a 10% dust formulation. These limited additional
tests were made in order to evaluate the effect of physical form on the
previously established efficiency of DDT combustion.
Turbulence was varied for the dust experiments by injecting the dust
horizontally from two positions. For Configuration 1, both the dust in-
jection nozzle and the fuel oil burner were located in the front burner
position (see Figure 2, page 22). The dust was injected horizontally at
a 30-degree angle to the fuel oil burner, as shown in Figure 3, page 24.
For Configuration 2, the oil burner was located in the front (primary)
position, while the dust injection nozzle was located in the side (al-
ternate) position. Thus, the centerlines of the burner flame and dust
stream in Configuration 2 impinged at 90 degrees on a horizontal plane
at the geometric center of the primary chamber.
40
-------
Data from the eight 10% DDT dust experiments are summarized in Table
4. The incineration efficiency figures reported in the last two columns
of the table are based on (a) the total unburned DDT and (b) total species
found in the effluent gas and the solid residue deposited on the walls
and in the bottom of the incinerator. Thus, the Quantity out values used
to calculate the two efficiencies include the amount of material in the
gas evolved during the 60-min sampling period, plus the appropriate frac-
tion of the content of the total solid residue recovered from the incin-
erator. These efficiencies are comparable to those obtained from the in-
cineration of the 25% DDT EC formulation. Thus, the physical form of the
DDT formulation had no significant effect on the efficiency with which
DDT was incinerated.
Method 5 of "Standards of Performance for New Stationary Sources,"—'
was used to determine the particulate loading in the stack. This technique,
specified by EPA for use in such determinations, gave the total dust par-
ticulate discharged from the incinerator stack. The particulate samples,
after collection, were then analyzed for residual DDT and total species
content.
Two modifications of the standard particulate sampling train were
made to facilitate the analysis of the sample for DDT content. First,
pesticide grade benzene was used in the impingers rather than water. (The
substitution of an appropriate solvent was made for all of the pesticides
tested.) The second modification was to add a liquid nitrogen cold trap
to the sample train in order to collect condensibles for DDT and total
chlorinated hydrocarbon analysis. After particulate analysis had been
completed, all samples were analyzed for DDT content.
The results of the particulate loading analyses for the 10% DDT dust
adjusted to 12% CC>2, are also given in Table 4. The value for particulate
loading, according to Title 40, CFR (Part 60, Subpart 60.50), must not
exceed 183 mg/m^ (0.08 gr/dscf) on any new facility with a capacity 2 4.5
x 10 kg/day (50 tons/day). This indicates that an incinerator, if re-
quired to meet these federal regulations while incinerating the 10% DDT
dust formulation, would require emission control.
Significant corrosion was noted during the system cleanup after com-
pletion of the DDT experiments, primarily in the first water scrubber
(see Figure 1, page 21). Both the concial reducer nozzle and the demister
pad (constructed of 304 stainless steel) had been almost entirely cor-
roded out. Corrosion was also noted on the tank section of the first
scrubber, on the vertical piping leading down to the first water scrub-
ber, and on two water nozzles in that section of pipe.
41
-------
Table 4. SUMMARY OF TEST RESULTS—107. DDT DUST FORMULATIONS
DDT
Experiment rate
declination f/hr (Ib/hr)
A 1010 (2.22)
. 9SO (2.10)
C 980 (2.16)
0 1020 (2.24)
S 1720 (3.80)
t 2230 (4.91)
0 2230 (4.91)
R 1010 (2.22)
Turbulence
2
1
1
1
1
1
1
2
Primary
chanber
tenperaeure
•c cri
1210 (2210)
1140 (2080)
930 (1710)
1030 (1880)
1010 (1850)
1120 (2050)
1020 (I860)
1030 (1880)
EKcete
79
58
164
84
128
111
156
124
Retention tine
Primary
chamber
1.4
1.9
1.4
2.4
1.3
2.0
1.6
2.1
Second
chamber
1.4
2.0
1.2
2.S
1.2
2.0
1.6
2.2
Parttculaca
loeding
(tr/decC)
23,700 (10.3)
23,600 (10.2)
29,000 (12.6)
SI. 000 (22.1)
41,000 (17.8)
63,000 (27.3)
71,000 (30.8)
J3.000 (34.0)
Ratio of DDT
in otf-gaa to
V>fal DOT l«4
1.
6
9
7
9
9
7
1,
7 x 10-5
x 10-5
x W*
x 10-*
x 10-'
x 10-*
x 10-*
,2 x 10-5
Ratio of total
epeciee in off-
gaa to total
DD? ted
2.3 X 10-5
1.0 x 10-*
1.7 x 10-5
1.0 x 10-5
1.0 x ID'5
1.2 x 10-5
9 x 10-«
1.7 x 10-5
Incinerator efficiency
I
> 99.99
> 99.99
> 99.99
> 99.99
> 99,99
> 99.99
> 99.99
> 99.99
Tot«l macie>
> 99.99
> 99.98
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
-------
Aldrin
The experimentation with aldrin (and the seven additional pesticides
subsequently studied) involved two phases. First, differential thermal
analysis (DTA) and thermal gravimetric analysis (TGA) were made to iden-
tify potentially favorable combustion temperatures for each pesticide.
Experiments were then conducted in the pilot-scale incinerator to verify
the efficiency of combustion in the range of potentially favorable op-
erating temperatures. A minimum of eight experiments utilizing a liquid
formulation and four utilizing the solid formulation were made. For pes-
ticides commercially available in only solid forms, a minimum of eight
tests were conducted using a major solid formulation. Rate of pesticide
incineration, percent excess air, and operating temperature were varied
between two nominal values, i.e., a "high" and "low" level.
DTA of a sample of recrystallized aldrin obtained by evaporation of
a sample of the EC formulation showed two endotherms, one at 60 to 66°C,
and the other at 210 to 250°C. The first endotherm indicates a phase
change (TGA data showed no significant weight loss at 60 to 70°C). The
latter endotherm could very well be the vaporization of the liquid. Sig-
nificant weight loss was observed at this temperature from the TGA data.
Beyond 250°C, however, an exothermic process was observed which indicated
that the sample was undergoing decomposition. This was substantiated by
TGA which showed continued weight loss all the way to about 570°C. At
this temperature, virtually no sample remained.
DTA analyses of the 19% granular formulation of aldrin data showed
two decomposition processes--one at ~' 175 C and the other at •»' 370 C.
This was substantiated by the TGA which showed continuous weight loss as
temperature increased. At about 270°C almost 25% of the original weight
was gone, which exceeds the ~' 19% aldrin content of the formulation. As
the heating of the formulation continued to 700°C, another 10% was lost.
From 700° to 1000°C, essentially no weight loss was recorded. These data
indicate that the aldrin in this formulation would be destroyed at 700°C.
Initially, eight tests were made using the EC formulation of aldrin.
The results of these tests (as well as two subsequent tests) are given
in Table 5. Efficiencies of combustion was again defined in terms of the
incinerator, i.e., aldrin charged into the system (Quantity In) versus
aldrin (and total chlorinated species) not destroyed in the incinerator
(Quantity out) . The efficiencies for the eight initial tests were all
>99.99%, based on either aldrin, or total chlorinated hydrocarbon species
detected. However, all of the initial eight tests were made at temperatures
significantly above those indicated (by DTA and TGA) as being potentially
favorable for aldrin degradation. This was due to the operating limit of
the available fuel oil burner, which was designed to burn from 11.3 to
30.3 liter/hr (3.0 to 8.0 gal/hr) of No. 2 fuel oil.
43
-------
Table 5. SUMMARY OF TEST RESULTS—41.2% ALDRIN EC FORMULATION
Run
No.
1
2
3
4
5
6
7
8
9
10
Aldrin
rate
g/hr (Ib/hr)
2,310 (5.09)
3,480 (7.67)
2,470 (5.44)
1,610 (3.56)
1,650 (3.63)
660 (1.45)
2,260 (4.98)
1,350 (2.98)
1,010 (2.23)
620 (1.36)
Primary
chamber
temperature
°C (°F)
940 (1730)
1020 (1870)
1020 (1870)
920 (1690)
830- (1530)
850 (1560)
1050 (1920)
1140 (2080)
680 (1250)
600 (1120)
Excess
air
209
128
144
230
203
158
149
70
332
380
Retention time
sec
Primary
chamber
2.5
1.9
2.0
4.8
4.3
4.2
1.2
2.2
4.8
6.9
Second
chamber
2.3
1.6
1.9
5.1
4.6
4.5
1.2
2.2
5.3
7.6
Ratio of
aldrin content
of off-gas to
aldrin fed
1.2 x
1.5 x
2.4 x
2 x
2 x
3 x
1.1 x
1.7 x
1 x
6 x
10-7
10-7
10-7
10-7
10-7
10-7
10-7
10-7
ID'6
10-7
Ratio of total
species content
of off-gas to
aldrin fed
6
9
4.4
3
5
3
3
2.6
3
2
x 10'6
x 10- 6
x 10'6
x 10'6
x 10"6
x 10- 6
x ID*6
x 10- 6
x 10-5
x 10-5
Incineration efficiency
7.
Aldrin
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
Total species
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
-------
Subsequently, two additional tests (Nos. 9 and 10) were made using
a new fuel oil burner capable of operating at lower feed rates than the
burner previously used; the lower rates were used to conduct the two ad-
ditional runs at much lower temperatures. Runs Nos. 9 and 10, although
conducted at primary chamber temperatures 400 to 500°C (800 to 900°F)
lower than the initial eight runs, also showed an efficiency of aldrin
incineration of > 99.99%, based on aldrin or the total chlorinated species
detected. The relative amounts of chlorinated species generated during
Runs Nos. 9 and 10 (as shown by the "Ratio of Total Species Content of
Off-Gas to Aldrin Fed" column in Table 5), however, were significantly
higher than that for the tests conducted at higher temperatures. The
relative aldrin content of the off-gas was also somewhat higher for the
last two tests (see Table 5). Thus, incineration of aldrin at •»' 650°C
(1200°F) is virtually as efficient as incineration at «' 1090°C (2000°F)
in terms of actual aldrin content, but is less efficient in terms of
chlorinated hydrocarbons in the incinerator effluent.
A granular formulation of aldrin was used to evaluate the effect of
physical form on the efficiency of aldrin incineration. The results of
these tests, which are summarized in Table 6, also showed an efficiency
of > 99.99% in all cases.
The particulate emission rates, corrected to 12% CC^, were above
the standard of 183 mg/m • Incineration of the aldrin granular formula-
tion, if required to meet federal regulations, would require emission
control.
Upon completion of the aldrin experiments, the interior surfaces of
the incinerator and duct work were inspected for deposits. Samples were
taken of a thin layer of residue that had deposited on the walls of the
stack from the incinerator and in the horizontal run of duct leading to
the scrubber system. Neither aldrin nor any of the major components of
technical grade DDT (p,p'-DDT, o,p'-DDT, p,p'-DDE, o,p'-DDE, p,p'-DDD,
and o,p'-DDD) were detected in these samples.
No problems were encountered with the incineration of aldrin. The
solid residue left in the primary chamber of the incinerator when incin-
erating the granular formulation at the higher temperatures, however,
became very hard and compacted. In fact, these residues had to be chipped
out of the incinerator and ground before being analyzed.
Picloram
DTA of picloram (4-amino-3,5,6-trichloropicolinic acid as the potas-
sium salt) pellets showed one endotherm at about 90 C. Beyond 90 C, the
sample showed a continuous decomposition process all the way to the
-------
Table 6. SUMMARY OF TEST RESULTS—19% ALDRIN GRANULAR FORMULATION
Run
A
8
C
D
E
F
Aldrln
feed rate
g/hr (Ib/hr)
1,860 (4.09)
1,690 (3.73)
3,630 (8.01)
3,740 (8.24)
3,630 (8.00)
1,830 (4.03)
Primary
chamber
temperature
*C (V)
1150 (2100)
980 (1800)
890 (1630)
1030 (1890)
1100 (2020)
860 (1580)
Excoa
air
48
155
81
120
118
113
Retention time
aec
Primary
chamber
2.5
2.2
3.2
2.0
1.4
3.0
Second
chamber
2.7
2.6
3.6
2.2
1.4
3.2
Partlculata
loading
mg/o3
(gr/d«cf)
1,830 (0.79)
1,420 (0.62)
2,450 (1.06)
1,560 (0.68)
1,970 (0.85)
1,380 (0.60)
Ratio of aldrln
In off-gaa to
total aldrln fed
2.1 x 10" 7
1.
2.
7
3.
1.
6 x 10-5
3 x 10"7
x ID"8
3 x 1C'7
9 x 10"8
Ratio of total
•peclei In off-
gaa to total
aldrln fed
1.8
2.0
1.4
1.0
9
8
x 10'*
x 10-5
x ID'6
x 10-*
x lO'7
x 10- 7
Incineration efficiency
Aldrln
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
Total ipeclei
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
-------
instrument operational limit (400°C). This decomposition process was sup-
ported by the weight loss shown by TGA. The total weight loss up to 400°C
was approximately 127» compared to the nominal 11.6% picloram salt content
of the pellets.
DTA of a sample of recrystallized picloram obtained by the evapora-
tion of the 21.5% potassium salt formulation showed endotherms at 68 to
80°C, and 144 to 154°C. Once past the second endotherm, decomposition
started and exotherms at 222, 302, and 353°C were observed. The decom-
position process continued to the instrument operational limit (400°C).
The TGA data showed no significant weight loss at the two endotherm tem-
perature ranges, thus indicating possible phase changes. However, from
180 to 360°C, about 607o weight loss was observed. Weight loss continued
from 360 to 500°C and about 800 to 900°C. At 900°C virtually no sample
remained. These laboratory data indicated that picloram would be de-
stroyed before 900°C.
Kennedy et al.— also conducted DTA of picloram. Based on their lab-
oratory analyses, Kennedy et al. concluded that the temperatures for com-
plete combustion of a picloram reference standard and 11.67o picloram so-
lution were 550°C (1022°F) and 640°C (1184°F), respectively.
Initially, seven experiments were made using a water based liquid
formulation of picloram (24.9% as the potassium salt, 21.5% acid equiva-
lent). Because this formulation was not miscible with No. 2 fuel oil, a
modification of the incinerator feed system was required. (All miscible
pesticide formulations were mixed in the appropriate ratio with fuel oil
and injected through the primary burner position of the incinerator with
an oil burner.) Two separate systems were used to inject fuel oil and the
picloram formulation into the primary chamber of the incinerator on a
horizontal plane. A standard oil burner was used for the fuel oil. The
undiluted picloram was pumped into the incinerator through a fuel oil
nozzle of the same type being used in the oil burner. These injection
systems were positioned so that the picloram and the flame from the fuel
oil burner impinged at an angle of 30 degrees and at a point about 9 cm
(3 in.) from the front wall of the incinerator. This is the same config-
uration that is used to inject solid pesticide formulations (see Appendix
A for a more detailed description of the pesticide feed systems). The
results of the seven initial tests (as well as two subsequent tests)
have been summarized in Table 7.
Two efficiencies of combustion have been calculated to evaluate the
results of the picloram tests. The first considered only the picloram in
the incinerator input and discharge. This efficiency calculation shox^s
that > 99.99% of the picloram injected into the incinerator was at least
47
-------
Table 7. SUMMARY OF TEST RESULTS--21.5% PICLORAM LIQUID FORMULATION
oo
Run
No.
1
2
3
4
5
6
7
8
9
Picloram
rate
8/hr (Ib/hr)
1,870 (4.12)
1,380 (3.05)
1,510 (3.33)
1,290 (2.84)
1,110 (2.45)
3,470 (7.64)
2,230 (4.92)
3,270 (7.22)
2,450 (5.40)
Primary
chamber
temperature
•C (°F)
530 (990)
600 (1120)
630 (1160)
930 (1700)
1010 (1850)
1030 (1880)
800 (1470)
1000 (1840)
1010 (1850)
Excess
air
298
193
187
62
130
116
77
114
50
Retention time
sec
Primary
chamber
7.6
6.7
6.6
3.9
1.4
1.2
6.0
1.9
2.6
Second
chamber
8.0
6.9
6.8
4.0
1.4
1.2
5.8
1.8
2.5
Ratio of picloram
in off-gas to
picloram fed
2
1
3
2
2.3
2.0
4
9
3.7
x 10"6
x 10"6
x KT7
x 10'6
x 10-5
x 10'6
x 10- 7
x 10-6
x 10-5
Ratio of total
species in off-
gas to total
picloram fed
2
4
4
2
3.6
1.3
2
1.1
4.1
x ID' 3
x 10"*
x 10"3
x 10-4
x 10-5
x 10'5
x 10'3
x 10-5
x 10-5
Incineration efficiency
7.
Ficloram
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
Total species
> 99.83
> 99.95
> 99.63
> 99.98
> 99.99
> 99.99
> 99.78
> 99.99
> 99.99
-------
partially degraded at all temperatures tested, 530 to 1030°C (990 to
1880°F). This is not unexpected as piclorara has been reported to decom-
pose at about 216°C (420°F).12/
The second efficiency calculation includes not only the picloram
that is left in the incinerator effluent but also the other chemical
species trapped in the sample collection system. Using this calculation,
only the two tests (of the seven initial tests) conducted at 1010 and
1030°C showed an efficiency of > 99.99%. As will be discussed later,
these two tests also showed significantly lower concentrations (and
quantities) of cyanide (CN~) in the incinerator effluent.
In order to evaluate the effect of physical form on the efficiency
with which picloram can be incinerated, five tests were made using a
pellet formulation (~ 11.67<, picloram as the potassium salt, 107o as the
acid equivalent). Results from these five experiments (as well as two
subsequent additional tests) are summarized in Table 8.
As was done for the experiments using the liquid formulation, two
efficiencies of combustion were calculated. The first considers only the
quantity of picloram in the incinerator input and discharge. This effi-
ciency calculation shows that > 99.99% of the picloram injected into the
incinerator was at least partially degraded during the first five tests,
conducted at temperatures of 640 to 1020°C and primary chamber retention
times of 6.9 to 1.3 sec.
The second efficiency calculation includes not only the picloram
that is left but also other chemical species (volatile chlorinated hy-
drocarbons). Using this calculation, only the two tests conducted at the
higher temperatures (930 and 1020°C) showed an efficiency of > 99.99%.
These initial tests, as well as those using the liquid formulation, in-
dicate that temperatures of about 1000°C and primary retention time of
about 1.5 sec are required to satisfactorily incinerate picloram.
The results of the particulate sampling conducted on the picloram
pellet tests showed that the grain loadings for all tests exceeded what
can be considered low emissions and indicate the need for a particulate
control device when incinerating picloram pellets.
Subsequently, four additional tests were conducted to better define
the temperature required to reduce cyanide concentration in the inciner-
ator effluent gas to < 1 mg/m3. Two additional tests were made using the
liquid formulation (Runs Nos. 8 and 9, Table 7), and two were made using
the pellet formulation (Runs Nos. F and G, Table 8).
49
-------
Table 8. SUMMARY OF TEST RESULTS—107. PICLORAM PELLET FORMULATION
Run
*i
A
B
C
in
0 D
E
1
C
Picloram
rate
g/hr (Ib/hr)
1,270 (2.8)
1,270 (2.8)
1,180 (2.6)
2,360 (3.2)
2,360 (3.2)
2,350 (5.2)
2,270 (5.0)
Primary
chamber
temperature
•C CF)
1020 (1870)
930 (1710)
640 (1190)
710 U310)
930 (1700)
950 (1750)
920 (1680)
Excaaa
air
93
170
226
227
72
75
145
Retention
•ec
Primary
chamber
1.3
2.1
6.9
6.7
4.6
2.6
1.9
time
Second
chamber
1.4
2.2
7.4
7.3
4.9
2.6
1.7
Pirttculate
loading
mg/m
(gr/dicf)
357 (0.155)
1,060 (0.46)
2,900 (1.26)
7,800 (3.4)
20,100 (8.7)
2,750 (1.19)
1,600 (0.69)
Ratio of picloram
in off-gat to
picloram fed
< 8 x 10-9
< 5 x ID'8
< 6 x lO-«
2 x 10"8
3 x 10-6
4.7 x 10'7
4.8 x 10-7
Ratio of total
ip«cie* in off-
gas to total
picloram fed
2.5 x 10'6
2.3 x ID'5
2 x 10-*
2 x 10-*
2 x 10-*
1.9 x 10-*
1.3 x 10-6
Incineration efficiency
%
Plcloram
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
^otal speciea
> 99.99
> 99.99
> 99.96
> 99.93
> 99.97
> 99.99
> 99.99
-------
For the liquid formulation tests, only those experiments conducted
in the higher temperature ranges, 1000 to 1030°C (1840 to 1880°F), produced
low concentrations (and quantities) of cyanide in the off-gas. Low concen-
trations (< 1 mg/m^) and quantities of cyanide (as CN") were generally also
produced from the pellet formulation tests conducted at the higher temper-
ature, 930 and 950°C (1710 and 1750°F). These data indicate that a tem-
perature of about 1000°C for 1.5 sec and sufficient excess air (*' 100%) are
required to reduce cyanide generation to < 1 mg/m^.
Additional samples were also taken during the supplemental pellet
formulation experiments (Runs Nos. F and G, Table 8), using a special
sampler designed to "catch" pellets as they fell through the combustion
chamber in order to approximate the degree of decomposition actually oc-
curring during the first few seconds.
These samples showed that > 90% of the picloram (as well as the
other chlorinated species) was "removed" from the pellet during the first
2 sec residence time in the primary chamber. The ••' 10% of the picloram
left in the pellets after 2 sec demonstrates (a) the need to insure ade-
quate retention of solid residues in the primary combustion chamber and
(b) the inadequacy of conventional retention time calculations (based on
the volume of gas) in defining solid residue retention.
The incineration of picloram in both the liquid and the pellet for-
mulations can be classified as giving relatively dirty burns. A dark
(bluish) exhaust plume was discharged from the experimental system during
most of the tests.
The dirtiness of the burns caused minor plugging problems with the
demister pad in the first stage water scrubber. This problem was particu-
larly noticeable when operating the incinerator at low draft.
Malathion
DTA and TGA of 25% malathion wettable powder (WP) formulation indi-
cated that a rather slow decomposition of malathion took place. The DTA
data showed no prominent exotherms or endotherms; TGA data indicated slow
weight loss as temperature increased. At about 650°C, almost 30% of the
original weight was gone; essentially no more weight loss was observed
from 650 to 1000°C.
DTA of malathion obtained by evaporation of a sample of the 57% EC
formulation showed no prominent exotherms or endotherms. However, a marked
decomposition process occurred from about 338 C and on to the instrument
limit of 400°C. This decomposition process was substantiated by the slow
51
-------
weight loss observed from the TGA data as temperature increased. At
about 700° C, almost 80% of the original weight was gone. From 700 to
1000°C, another 10% of the original weight disappeared.
Kennedy et al .J/ also conducted DTA on malathion. Based on their
laboratory analyses, Kennedy et al. concluded that the temperatures of
complete combustion of the malathion reference standard and the 57%,
liquid formulation were 663°C (1225°F) and 715°C (1319°F), respectively.
A total of 11 tests were conducted using the 57% malathion EC for-
mulation; the results of these tests are summarized in Table 9.
Initially, nine tests were made using the EC formulation (Runs Nos.
1 through 9). Neither malathion nor any other sulfur containing organic
phosphates were detected at Sample Point No. C2j (the incinerator off-
gas) for any of these experiments. (The values given in Table 9 are the
detection limits for malathion in the respective samples.) Further,
neither malathion nor any other sulfur-containing phosphates were de-
tected at any other point in the experimental system except at Sample
Point No. ff) (the incinerator feed).
Relatively high quantities of total pyrophosphates, however, were
detected in the incinerator effluent from those runs using concentrated
feed (350 to 590 mg malathion per milliliter) (Runs Nos. 5 through 9).
Two additional tests (Runs Nos. 10 and 11) were then made using lower
concentrations of malathion. As had been the case with Runs Nos. 1 through
9, no malathion was detected in the incinerator effluent. Runs Nos. 10
and 11, however, failed to parallel earlier results in which detectable
levels of total pyrophosphates were found only in tests in which rela-
tively high concentrations of malathion (350 to 590 rag/ml) were burned.
Thus, a definite correlation could not be made between total pyrophos-
phate generation and either operating temperature or incinerator feed
concentration .
In order to evaluate the effect of physical form on the efficiency
with which malathion can be incinerated, five tests were made using an
~ 25% dust formulation. Results from these experiments are summarized in
Table 10. Two efficiencies of combustion have been calculated. The first
considered only the potential quantity of malathion (based on its detec-
tion limit) in the incinerator input and discharge. This efficiency cal-
culation showed that > 99.99% of the malathion injected into the incin-
erator was at least partially degraded at all temperatures tested.
52
-------
Table 9. SUMMARY OF TEST RESULTS—577, MALATHION EC FORMULATION
u>
Run
No.
1
2
3
4
5
6
7
8
9
10
11
Malathion
rate
g/hr (Ib/hr)
1,760 (3.89)
2,630 (5.80)
1,470 (3.24)
930 (2.04)
1,170 (2.58)
1,970 (4.35)
1,990 (4.38)
1,650 (3.62)
3,630 (8.00)
660 (1.45)
630 (1.39)
Primary
chamber
temperature
°C (°F)
1050 (1930)
1060 (1940)
1000 (1840)
1080 (1980)
620 (1140)
640 (1190)
690 (1270)
700 (1290)
960 (1760)
620 (1150)
600 (1110)
Excess
air
130
74
44
122
176
188
114
114
95
197
311
Retention time
sec
Primary
chamber
2.2
3.6
4.8
2.2
6.8
6.6
6.2
6.0
3.9
5.1
4.6
Second
chamber
2.2
3.7
5.0
2.6
6.5
6.5
6.2
6.1
3.9
5.1
4.3
Ratio of malathion
in the off-gas to
malathion fed
< 1
< 5
< 8
< 2.
< 1
< 6
< 6
< 8
< 4
< 3
< 3.
.9 x ID"5
x 10-6
x 10"6
.6 x 10'5
x 10-5
x 10-6
x ID"6
x 10-6
x 10-6
x 10-5
2 x 10-5
Ratio of total
species content
of the off-gas to
malathion fed
< 6
< 3
< 2
< 5
< 3
< 1
< 1
< 2
< 9
< 5
< 6
x ID"5
x 10-5
x ID"5
x 10'5
x 10-5
x 10-5
x 10-5
x 10-5
x 10-6
x 10-5
x 10-5
Incinerator efficiency
7.
Malathion
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
Total species
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
-------
Table 10. SUMMARY OF TEST RESULTS--257. MALATHION WP FORMULATION
Run
Mo.
A
B
C
D
E
Malathion
rate
g/hr (lb/hr)
3,310 (7.33)
4,580 (10.08)
3,130 (6.90)
3,290 (7.25)
1,100 (2.42)
Primary
temperature
•c CP>
810 (1490)
1040 (1900)
730 (1340)
930 (1710)
630 (1170)
air
%
43
37
113
156
157
Retention
Primary
chamber
4.2
3.8
5.7
1.9
4.2
time
Second
chamber
4.5
3.9
5.6
1.8
4.0
P«rtlcul«te
mg/rc3
(nr/dscf)
37,000 (16.1)
36,800 (16.0)
35,100 (15.2)
29,300 (12.7)
26,900 (11.7)
In the off-ga« to
malathlon fed
< 4.5 x 10-7
4.6 x ID"7
< 4.8 x 10-7
< 4.3 x 10-'
< 1.4 x 10-6
Ratio of total
of the off-gas to
malathion fed
< 4.5 x 10-7
4.6 x 10-7
< 1.2 x 10-5
2.4 x 10-*
< 1.4 x 10-«
I
Malathlon
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
Total species
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
-------
The second efficiency calculation included not only the malathion
that was left, but also all other organic phosphate species detected.
Using this calculation, all five tests showed an efficiency of > 99.99%
for the incinerator effluent gas.
Particulate loading for all five tests exceeded established emis-
sion rates, indicating the need for a particulate control device when
incinerating malathion dust formulations.
Minor operating problems were encountered during the 57% malathion
EC tests. Plugging of the demister in the first stage water scrubber was
observed, primarily during tests conducted at low draft. In addition, a
visible white plume was noted emitting from the scrubber system exhaust.
These same problems, i.e., inability to remove P205 from the effluent gas
stream and plugging of filter elements, had also been encountered during
recent studies of the incineration of organophosphorus chemical war-
00 /
fare agents.—'
Toxaphene
DTA of technical grade toxaphene showed no prominent endotherm or
exotherm at lower temperatures. However, as the temperature reached about
290°C, sharp decomposition was observed and continued to 400°C (instru-
ment limit). This decomposition process was substantiated by the TGA data
which indicated almost 95% of the initial weight was lost when the temper-
ature reached 300°C.
DTA and TGA of the 20% toxaphene dust formulation indicated a slow
decomposition process, while TGA indicated slow weight loss all the way
to about 700°C. The weight loss took place mainly at two temperature
ranges, one quite abruptly at about 190 to 260°C (about 20% weight loss).
At 710°C about 35% of the original weight was gone, compared to the nomi-
nal 20% toxaphene content of the formulation. No further weight loss was
observed from 710 to 1000°C.
DTA of a sample of recrystallized toxaphene obtained by evaporation
of a sample of the 60% EC formulation showed an endotherm at about 306°C,
which may have been only a phase change; TGA data showed no significant
weight loss at this temperature. However, prior to this endotherm, decom-
position was observed which was substantiated by the abrupt weight loss
from 180 to 280°C in the TGA. About 95% of the original weight was gone
at 280°C. Essentially no more than 3% additional weight loss was observed
from 280 to 1000°C.
55
-------
Eleven tests were made using the 60% EC toxaphene formulation. The
temperature of the primary chamber was varied between the lower operating
limit of the incinerator, i.e., -' 650°C (1200°F), and 1000°C (1830°F).
The results of these 11 tests are shown in Table 11. Because tech-
nical grade toxaphene consists of a number of chlorinated hydrocarbons
(including at least 175 polychlorinated 10-carbon compounds), the effici-
ency of toxaphene incineration was evaluated based on actual toxaphene
content of the incinerator feed (Sample Point No. (T)), versus the total
chlorinated hydrocarbon species detected in the incinerator effluent
(Sample Point No. (?)). The percent efficiency calculations showed that
> 99.99% of the toxaphene injected into the incinerator was degraded for
all 11 experiments, i.e., over the ranges of excess air, operating tem-
perature, and incinerator feed rate investigated.
There was no correlation between operating temperature and the rel-
ative amount of unburned "toxaphene" discharged (as shown by the "Ratio
of Chlorinated Hydrocarbon Content of the Off-Gas to Toxaphene Fed" col-
umn of Table 11). Significantly higher levels were discharged, however,
from Runs Nos. 5 and 7. These two tests also had the shortest retention
times in the primary chamber (2.4 and 2.2 sec, respectively).
Six tests were made using an ~ 20% dust formulation of toxaphene in
order to evaluate the effect of physical form on incineration efficiency.
The results of the six tests are summarized in Table 12. The efficiency
of toxaphene incineration for all six tests was > 99.99%.
The particulate loadings for the toxaphene dust experiments fol-
lowed the previously established trend of high particulate emission levels
for dust formulations. The incineration of toxaphene dust formulation
would therefore require a particulate emissions control system.
Operating difficulties were encountered on all four dust tests made
at the higher temperature of ~ 1000°C (1830°F), i.e., Runs Nos. C through
F. In fact, Run No. C was terminated when only half completed (30 min of
sampling) because of loss of draft within the incinerator. Inspection of
the incinerator disclosed that the six 11.4 cm x 11.4 cm (4-1/2 in x 4-1/2
in.) openings in the wall between the primary and secondary chamber (see
Figure 2, p. 22) had been completely plugged. The interior of the "plugged
incinerator" is shown in Figure 44, p. 249.
Feeding problems were also encountered with the toxaphene dust. The
dust tended to bridge in the feed line to the injection nozzle.
56
-------
Table 11. SUMMARY OF TEST RESULTS--60% TOXAPHENE EC FORMULATION
Run
No.
1
2
3
4
5
6
7
8
9
10
11
Toxaphene
rate
g/hr (Ib/hr)
1,250
1,220
1,540
1,520
1,250
3,240
2,340
2,220
1,090
2,110
1,070
(2.75)
(2.70)
(3.40)
(3.35)
(2.75)
(7.15)
(5.15)
(4.90)
(2.40)
(2.65)
(2.35)
Primary
chamber
temperature
"C (°F)
620
630
680
1040
980
1040
990
670
660
680
650
(1150)
(1160)
(1260)
(1900)
(1800)
(1900)
(1820)
(1240)
(1220)
(1260)
(1200)
Excess
air
7,
349
198
160
47
124
71
128
212
154
228
150
Retention time
sec
Primary
chamber
5.3
5.0
4.6
3.4
2.4
3.8
2.2
5.2
6.6
6.5
6.7
Second
chamber
4
4
4
3
2
3
2
5
6
6
6
.9
.6
.4
.5
.4
.9
.2
.1
.2
.4
.5
Ratio of chlorinated
hydrocarbon content
of the off-gas to
toxaphene fed
3
2
9
3
3.3
2
1.7
4
9
2
1
x 10-6
x 10-6
x 10" 7
x 10-7
x 10-5
x 10-8
x 10-5
x 10- 6
x 10-9
x 10-6
x 10-8
Efficiency
7.
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99,99
> 99.99
> 99.99
-------
Table 12. SUMMARY OF TEST RESULTS--20% TOXAPHENE DUST FORMULATION
Primary
Toxaphene
Run
No.
A
B
Ul
oo
c
D
E
F
rate
chamber
temperature
R/hr (Ib/hr)
3,520 (7.
2,750 (6.
3,060 (6.
3,850 (8.
3,430 (7.
3,310 (7.
76)
06)
75)
,49)
56)
30)
°C
670
670
1010
1030
970
1010
CF)
(1240)
(1240)
,(1850)
(1880)
(1770)
(1850)
Exceaa
air
T,
94
166
53
44
122
121
Retention time
sec
Primary
chamber
7.7
5.3
2.9
3.4
2.5
2.4
Second
chamber
8.3
5.7
3.2
4.1
2.8
2.8
Paniculate
loading
mg/m
(gr/dscf)
73,000 (31.2)
37,000 (16.1)
4,620 (2.01)
7,900 (3.43)
2,640 (1.15)
7,900 (3.43)
Ratio of total
chlorinated hydro-
carbons in the
off-gas to total
toxaphene fed
3.1 x 10-6
2.0 x 10'6
3.6 x 10-5
1.8 x 10-°
1.6 x 10'6
3.0 x 10"5
Incineration
%
> 99
> 99
> 99
> 99
> 99
> 99
efficiency
.99
.99
.99
.99
.99
.99
-------
Bridging problems have been encountered by others in formulation of
dusts using the same attapulgite clay as was used for the toxaphene dust
formulation tested. Grounding of the screens used in the formulation
process reported overcame the difficulty, indicating that a static elec-
trical charge on the dust particles was the cause.
Atrazine
DTA of technical grade atrazine (conducted on an instrument having
a higher temperature limit than had previously been used) showed that
decomposition of the compound started at about 180°C with two distinct
endotherms at 185 and 240°C, and exotherms at about 350, "450, and 470°C.
The decomposition process are substantiated by TGA data which indicated
that almost 957= of the sample weight was lost at about 300°C, and at
about 600°C, no sample was left.
DTA and TGA were also made of an atrazine sample obtained by evap-
oration of a sample of a 4 Ib/gal liquid formulation. DTA data showed
that as temperature increased, decomposition of the sample started, and
at about 185 and 245°C, two prominent endotherms were observed. As tem-
perature reached 350 and 440°C, distinct exotherms were observed. The
decomposition process was again substantiated by the TGA data which show
that from 200 to 220°C about 907, of the sample was lost, and at about
600°C, practically all the sample was gone.
DTA data for the 80% wettable powder atrazine formulation showed
endotherms and exotherms in addition to those observed from the techni-
cal material. These endotherms and exotherms could well be attributed to
the additives in the formulation. Decomposition was completed at about
600°C, as substantiated by TGA data which show that at 600°C over 90%
of the sample was gone.
13/
Kennedy et al.— also conducted DTA analysis of atrazine. Based on
their analyses, Kennedy et al. concluded that the temperatures of com-
plete combustion of the atrazine reference standard and an 80% wettable
powder formulation were 650°C (1202°F) and 600°C (1112°F), respectively.
Nine tests were conducted using the 4 Ib/gal liquid formulation of
atrazine. Nominal operating conditions for these tests were "high" and
"low" feed rates [3.40 kg (7.5 Ib) and 1.70 kg (3.75 Ib) active ingred-
ient per hour], excess air rates (150 and 50%), and operating tempera-
tures of 1000°C (1830°F) and 650°C (1200°F).
59
-------
Liquid atrazine, like the water based picloram formulation, was not
miscible with No. 2 fuel oil and therefore, was pumped into the incinera-
tor using a separate injector system. The liquid atrazine injector system
utilized a standard fuel oil burner nozzle of the appropriate size, and
the nozzle adapter and oil pipe from a fuel oil burner. Preliminary tests,
however, showed that the liquid atrazine would plug the nozzle and nozzle
adapter almost immediately after insertion into the incineration chamber.
For this reason, the nozzle adapter was modified so that it would be
cooled by the water-jacketed injection nozzle used for dust injection
(see Figure 52, p. 266). This modification eliminated the problem of plug-
ging during the test period.
Results of tests using the 4 Ib/gal liquid formulation are given in
Table 13. Two efficiencies of combustion were calculated for the atrazine
liquid tests. The first was based on atrazine only, while the second in-
cluded consideration of all nitrogenous organic species (including atra-
zine) detected in the effluent gas. Both of these efficiencies were
> 99.997= for all tests. Thus, the efficiency of liquid atrazine incinera-
tion was found to be > 99.99% over the temperature range of 550°C (1030°F)
to 1040°C (1900°F).
The relative quantity of atrazine (and total nitrogenous organic
species) not decomposed, however, does appear to be related to operating
temperature. The highest quantity of atrazine (and total nitrogenous or-
ganic species) as shown in Columns 7 and 8, respectively, of Table 13,
was emitted from Run No. 6 which was conducted at the lowest primary cham-
ber temperature (550°C) and 7.8 sec. The lowest quantities detected were
from Run No. 9, which was conducted at the highest temperature (1040°C)
and 2.7 sec.
Five additional tests were made using an 80% wettable powder formu-
lation of atrazine in order to determine the effect of physical form on
efficiency. Operational data and analytical results for the ~ 80%, atra-
zine wettable powder formulation tests are summarized in Table 14. The
results of these five tests parallel those of the nine tests using the
liquid atrazine formulation. Both efficiencies for all five tests were
> 99.99%.
Incineration of atrazine at the lower temperatures, «-• 650°C (1200°F),
yielded high levels of cyanide (CN~) in the effluent, i.e., 198 to 5,740
mg/nr*. The higher temperatures, ~ 1000°C (1830°F), generally yielded much
lower concentrations. However, only those tests conducted at the higher tem-
peratures and relatively high excess air rates (> 75%) routinely yield con-
centrations of < 1 mg/m3. Thus, temperatures of about 1000°C (1830°F),
for 2 sec retention time and excess air of > 75% are required to incin-
erate atrazine and obtain cyanide concentration in the undiluted off-gas
of < 1 mg/nr*.
60
-------
Table 13. SUMMARY OF TEST RESULTS--4 LB/GAL ATRAZINE LIQUID FORMULATION
Run
No.
1
2
3
4
5
6
7
8
9
Atrazine
rate
g/hr (Ib/hr)
1,470 (3.25)
1,470
1,320
1,600
3,420
3,410
4,470
3,290
1,480
(3.25)
(2.92)
(3.52)
(7.54)
(7.51)
(9.85)
(7.25)
(3-26)
Primary
chamber
temperature
*C (°F)
1020
1020
730
700
970
550
700
940
1040
(1860)
(1860)
(1340)
(1290)
(1780)
(1030)
(1300)
(1720)
(1900)
Excess
air
%
79
123
138
90
76
93
143
140
52
Retention time
sec
Primary
chamber
2.6
2.1
4.0
5.0
2.0
7.8
3.6
1.6
2.7
Second
chamber
2.5
2.0
3.6
4.6
1.8
6.9
3.3
1.3
2.8
Ratio of atrazine
in off-gas to
atrazine fed
< 1.1
< 1.1
< 8
< 6
< 9
< 5
< 2.9
< 9
< 8
x 10-5
x 10- 5
x 10-6
x 10"6
x 10"6
x ID'5
x 10"6
x 10" 6
x ID'6
Ratio of total
species content
of off-gas to
atrazine fed
< 2,
< 2,
< 4
< 3
< 5
< 7
< 6
< 2.
< 1.
.6 x 10-5
.1 x 10-5
x 10-5
x 10-5
x 10"5
x 10-5
x lO"6
,5 x ID'5
,6 x 10-5
Incineration efficiency
7.
Atrazine
> 99.99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
.99
.99
.99
.99
.99
.99
.99
.99
Total species
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
-------
Table 14. SUMMARY OF TEST RESULTS--80% ATRAZINE WP FORMULATION
N>
Run
So..
A
B
C
D
E
Atrazine
rate
g/hr (Ib/hr)
2,630 (5.8)
3,080 (6.8)
2,130 (4.7)
2,590 (5.7)
3,220 (7.1)
Primary
chamber
temperature
•C C?)
1070 (1960)
970 (1770)
600 (1120)
970 (1780)
650 (1200)
Excess
air
7.
43
125
146
71
111
Retention
sec
Primary
chamber
2.7
2.2
5.6
2.7
6.8
time
Second
chamber
2.8
3.9
5.2
3.8
6.4
Particulate
loading
mg/m3
(Rr/dscf)
2,060 (0.89)
1,750 (0.76)
4,700 (2.04)
3,790 (1.64)
7,500 (3.26)
Ratio
in
total
4
1
2
3
3
of atrazine
off-gas to
atrazine fed
.6 x 10"7
.8 x 10"7
.5 x 10"7
.0 x 10" 7
x 10"8
Ratio of total
species In off-
gas to total
atrazine fed
5 x 10'7
6 x 10'7
1.1 x 10'6
8 x 10'7
3 x ID"7
Incineration efficiency
Z
Atrazine
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
Total species
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
-------
The particulate loadings for the wettable powder formulation of
atrazine followed the previous trend, although not as high, of particu-
late emission levels which exceed established limits. The incineration
of atrazine wettable powder formulations would require a particulate
emissions control system.
The only operational problem encountered with atrazine incineration
was the plugging of the liquid formulation injection nozzle. Insulation
of this nozzle with the water jacketed dust nozzle, as discussed above,
overcame this problem.
The high concentration of active ingredients in the dust formula-
tion (80%) made the desired active ingredient injection rate more diffi-
cult to attain.
Captan
DTA of technical grade captan showed a distinct endotherm at about
185°C which approximately corresponds to the reported melting point of
pure captan (m.p. range 172 to 178°C). In additon, the data showed two
distinct exotherms at about 250 and 550°C, indicating decomposition of
the compound. The decomposition process was substantiated by the TGA data
which indicated that about 75% of the compound is lost at about 250°C,
and almost all of the compound is lost at 600 C.
DTA and TGA were also conducted on a 50% captan wettable powder for-
mulation. DTA data of this powder formulation showed a pattern of endo-
therm and exotherms similar to that of technical captan, i.e., an endo-
therm at about 185°C (indicating possible melting), and two exotherms at
about 220 and 530°G, respectively (indicating decomposition). The decom-
position process was again substantiated by the TGA data which indicated
approximately 50% lost in sample weight at 250°C and 60% loss at the com-
pletion of the experiment (at 1000°C). The weight loss due to decomposi-
tion corresponded (within experimental error) to the amount of captan (50%)
in the formulation.
Eight tests were made using the 50% captan wettable powder formulation.
The results of these tests are summarized in Table 15. The efficiency of
combustion was > 99.99% for all eight tests, whether based on captan or
total chlorinated species detected in the off-gas and incinerator resi-
dues. No correlation was found between the relative rate of captan and
total chlorinated species in the incinerator off-gas and specific operat-
ing conditions.
63
-------
Table 15. SUMMARY OF TEST RESULTS—50% CAFTAN WP FORMULATION
Run
No.
A
B
C
D
E
F
G
H
Captan
rate
g/hr (Ib/hr)
2,880 (6.35)
2,850 (6.28)
1,640 (3.62)
1,110 (2.45)
1,250 (2.76)
1,410 (3.11)
2,230 (4.92)
2,040 (4.50)
Primary
chamber
temperature
•C CF)
1000 (1830)
920 (1690)
1010 (1850)
980 (1790)
660 (1220)
670 (1230)
650 (1200)
690 (1280)
Exceas
air
137
94
76
135
192
130
252
99
Retention time
sec
Primary
chamber
1.8
3.2
2.5
2.0
4.2
5.3
6.8
6.7
Second
chamber
1.8
3.2
2.5
1.9
3.9
5.1
6.4
6.5
Partlculate
loading
mg/ra3
(gr/dscf)
8,500 (3.7)
14,500 (6.3)
4,800 (2.08)
6,500 (2.82)
14,100 (6.1)
16,100 (7.0)
65.000 (28)
31,600 (13.7)
Ratio of captan
In off-gas to
total captan fed
< 2.6 x
< 9 x
< 8 x
2.2 x
< 2.6 x
< 1.6 x
3 x
< 5 x
lo-7
ID"8
10-9
10-8
10-8
10-9
io-7
ID'9
Ratio of total
species In off-
gas to total
captan fed
< 1.4
< 1.7
< 1.2
1.1
< 2.0
< 3.8
2
< 3
x 10-6
x 10-'
x 10-6
x 10-6
x 10-6
x ID'6
x ID'6
xlO-7
Incineration efficiency
7.
Captan
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
Total species
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
-------
Analysis of the off-gas for cyanide (CN~) content showed that sig-
nificant concentrations (and amounts) were generated on all tests (27 to
133 mg/m^). No correlation has been found between the relative rate of
cyanide generation (rate of cyanide generated to rate of captan incin-
erated) and any of the operating variables being investigated (rate of
pesticide injection, percent excess air, and operating temperature).
Particulate loadings for all seven wettable powder tests were above
established limits. Particulate emission control devices would be required
for captan incineration.
No operational problems were encountered during the incineration
of captan. However, an l^S-like odor was quite evident during experi-
mental runs.
Zineb
DTA data for technical grade (85%) zineb showed that decomposition
of the sample started at about 150°C, with two endotherms at about 160
and 290°C, and exotherms at about 190, 440, 530, and 600°C. The de-
composition process was substantiated by the TGA data which indicate that
about 80% of the sample weight is lost at 800°C.
DTA data for the 75% zineb wettable powder formulation showed a de-
composition pattern similar to that of the technical grade zineb, with
characteristic endotherms at 170 and 260°C, and exotherms at 200, 440,
530, and 610°C. The decomposition process was substantiated by the TGA
data which indicated that about 75% of the sample weight is lost at 800°C.
Kennedy et al. (1969)-^' also conducted DTA analysis of zineb and
based on their laboratory analyses, they concluded that the temperatures
of complete combustion of the zineb reference standard and the 75% wet-
table powder formulation were 840°C (1544°F) and 690°C (1274°F), re-
respectively.
A total of 11 tests were conducted using the 75% zineb wettable pow-
der. The results of these tests are given in Table 16.
The zineb analyses, however, are not comparable to those of the
eight other pesticides tested because of limitations in the available
zineb analytical methods and the inability to analyze the filter ele-
ment of the off-gas sampling train (see Appendix B, p. 113). However,
an approximation of the zineb content of the particulates trapped on
the filter element was made by utilizing the analyses for other residue
samples obtained after the completion of each test. These additional
65
-------
Table 16. SUMMARY OF TEST RESULTS—75% ZINEB WP FORMULATION
Run
NO.
A
B
C
D
E
F
C
H
I
J
K
Zineb rate
g/hr (Ib/hrj
3540 (7.8)
3180 (7.0)
3220 (7.1)
2540 (5.6)
1590 (3.5)
1720 (3.8)
1680 (3.7)
1720 (3.8)
3040 (6.7)
3580 (7.9)
2130 (4.7)
Primary
chamber
temperature
•C CF)
890 (1630)
970 (1770)
680 (1260)
710 (1310)
690 (1270)
650 (1200)
980 (1790)
940 (1730)
1000 (1830)
930 (1710)
710 (1310)
Excen
air
69
106
102
153
111
165
67
151
62
129
85
Retention
•ec
Primary
chamber
3.3
1.9
5.2
3.4
5.0
4.4
2.5
1.8
2.4
1.9
5.1
time
Second
chamber
3.3
1.9
5.1
3.2
4.8
4.2
2.4
1.7
2.3
1.7
4.9
Particulate
loading
mg/m3
(gr/dicf)
13,200 (5.7)
9,400 (4.1)
15,400 (6.7)
14,800 (6.4)
7,200 (3.12)
13,600 (5.9)
7,200 (3.12)
8,400 (3.6)
10,600 (4.6)
11,100 (4.8)
13,700 (5.9)
Approximate ratio of
zineb in off-gas
to zineb fed
4 x 10-5
3 x lO'5
3 x ID'5
3 x ID'5
3 x 10-5
3 x ID"5
4 x 10-7
4 x 10-7
3 x 10-6
1 x 10-5
1 x 10-°
Incineration
efficiency
X
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
-------
samples were obtained from the walls of the horizontal and vertical sec-
tions of the incinerator stack preceding Sample Point No. (?), the normal
incinerator off-gas sampling point. Using this approximation, efficiencies
of combustion have been calculated as > 99.99% for all 11 tests.
High cyanide (CN~) levels were detected in the incinerator off-gas
for all zineb tests ranging in concentration from 138 to 1,260 mg/m .
The particulate loadings for zineb all exceed what can be consid-
ered low emissions and indicate the need for particulate control de-
vices when zineb wettable powder formulations are incinerated.
The most significant operational problem with the zineb incineration
was the inability of the off-gas scrubber system to clean up the effluent
gas. A white plume was discharged from the scrubber system exhaust, the
opacity of which ranged from 0 to 45%. The particulate material was also
deposited on interior surface areas throughout the scrubber system. Res-
idue deposition inside the scrubber system blower caused blower vibra-
tion during latter tests. (See Figure 61, p. 317.)
The deposition of particulate material also caused plugging of the
demister pads in the first and second stage scrubbers. The demister pad
was removed from the second stage (hexylene glycol) scrubber after Run
No. E in order to reduce plugging of the system.
The odor of SO^ was also noted during the incineration of zineb (S02
levels in the incinerator off-gas ranged from 6,670 to 22,900 mg/m3)-
Mirex
DTA and TGA were made of technical grade mirex (97%). DTA data showed
that decomposition started at about 130°C, with two endotherms at about
140° and 370°C, respectively, and an exotherm at about 570°C. The decom-
position process was substantiated by the TGA data which indicated that
about 95% of the sample weight was lost at about 350°C, and almost all
the sample was gone at 800 C.
No DTA and TGA experiments were performed on the bait formulation
tested because of the small amount of mirex present (0.3% mirex on ground
corncob grit).
Ten tests were made using an 0.3% mirex bait formulation. Because
of the size of the incinerator [designed for 45.4 kg/hr (100 Ib/hr) of
Type 1 waste, equivalent to 6.86 x IflS J/hr (650,000 Btu/hr)], the heat
of combustion of the mirex bait formulation 2.168 x 10 J/kg (9,329
Btu/lb), and the low concentration of mirex (~ 0.3%), low rates of active
67
-------
ingredient injection were used. Mirex (as the pure active ingredient) was
injected at nominal rates of 68 g/hr (0.15 Ib/hr) and 34 g/hr (0.075
Ib/hr), rather than the 3.40 kg/hr (7.5 Ib/hr) and 1.70 kg/hr (3.75
Ib/hr) rates used for all other pesticides studied.
The operational data for these 10 tests are summarized in Table 17.
Two efficiencies were calculated for the incineration of mirex, based on
(a) the mirex content of the effluent gas and solid residues, and (b)
the total chlorinated organic species (mirex plus all other chlorinated
organic species) detected in the effluent gas and solid residues. Effi-
ciency based on mirex content only ranged from > 98.21 to > 99.98%,
while efficiency based on total chlorinated organic species detected
ranged from > 97.78 to > 99.96%. Both of these ranges were significantly
lower than those for the other pesticides studied.
Additional samples were taken during the mirex tests using a special
sampler designed to catch the mirex bait particles as they fell through
the combustion chamber in order to approximate the degree of decomposi-
tion occurring during the first few seconds.
The average mirex content of the bait formulation used for these
tests was 2,710 pptn (based on 17 samples, ranging from 1,940 to 4,130
ppm) while the average conentration of mirex in the "grab" sample was
770 ppm. Although the data showed no strong correlation with any par-
ticular operating condition, they did indicate that a substantial por-
tion of the mirex (> 70%) was "removed" from the bait formulation during
the first 2 sec residence in the primary chamber. These results parallel
those from grab sampling of picloram pellets, and reiterate the need
to insure adequate retention of solid residues in the primary combustion
chamber.
The test data did not show what operating conditions would be re-
quired to effect mirex decomposition comparable to that which has been
achieved for the other pesticides studied (i.e., an incineration effi-
ciency of > 99.99%). Either higher temperatures than those investigated
with the appropriate retention time or secondary combustion (or possibly
both) would be required.
The particulate loadings for four of the mirex tests were within
the established limit, while the other six were of the same order of
magnitude. Thus, it appears that the 0.3% mirex bait formulation when
incinerated to an acceptable level (> 99.99% destruction) would not re-
quire particulate control devices.
68
-------
Table 17. SUMMARY OF TEST RESULTS—0.3% MI REX BAIT FORMULATION
Run
A
B
C
D
E
t
G
H
I
J
Contained
72
70
69
32
32
33
35
70
68
33
Primary
chamber
*C (°F)
900 (1650)
870 (1600)
930 (1710)
590 (1090)
700 (1290)
820 (1510)
940 (1730)
880 (1620)
740 (1400)
920 (1690)
Excess
57
85
82
225
79
48
118
123
149
141
Retention time
aec
chamber
2.8
2.6
2.0
2.8
6.0
5.3
2.0
1,7
2.2
1.8
chamber
3.0
2.8
2.0
3.4
6.2
5.5
2.0
1.6
2.2
1.5
Participate
loading
mg/m
(Rr/d»cf)
426 (0.185)
222 (0.096)
213 (0.092)
570 (0.247)
205 (0.089)
251 (0.109)
168 (0.073)
180 (0.078)
179 (0.078)
150 (0.065)
Ratio of mirex
in off'gas to
fed
1.0 x ID"4
3.4 x 10-4
3.5 x lO"4
1.8 x 10'2
2.9 x 10"3
8 x ID'4
1.2 x lO'3
1.4 x 10-*
1.2 x 10"3
2.3 x 10-*
Ratio of total
speclea in the
mlrex fed
1.3
5
8
2.2
5
2.4
3.1
5
1.4
3.9
x 10-2
x 10-4
x 10-*
x 10'2
x W 3
x 10"3
x ID'3
x 10-*
x 10- 3
x 10-*
Incinerator efficiency
f.
Mirex
> 99.98
> 99.96
> 99.96
> 98.21
> 99.70
> 99.91
> 99.87
> 99.98
> 99.88
99.97
Total apeclea
> 98.70
> 99.94
> 99.91
> 97.78
> 99.50
> 99.75
> 99.68
> 99.95
> 99.85
99.96
-------
There were no specific operational problems with mirex. The fact that
the mirex bait was formulated on a combustible inert carrier, however,
resulted in the continued burning of the solid residue in the bottom of
the primary combustion chamber throughout the experiments.
GENERAL FINDINGS
The efficiency of pesticide combustion was generally uniformly high
over the complete ranges of operating conditions investigated. The only
exception, as noted above, was the 0.3% mirex bait formulation.
The mirex bait experiments differed from all other tests in that
this was the only formulation tested that contained a combustible mate-
rial as the inert carrier, the active ingredient content was low (0.3%
versus 10 to 80% for the other formulations tested), and a lower range
of primary chamber temperatures was evaluated.
The particulate emissions from the solid formulations tested (i.e.,
pellets, granules, wettable powders, and dusts) were generally higher
than the standards established for large (* 4.5 x 104 kg/day (50 tons/
day)), new emission sources. Thus, the incineration of the major pesti-
cide formulations will require particulate control devices if these emis-
sion standards are to be met.
Odors were frequently detected during the tests, even though the ef-
ficiency of incineration was quite high. This potential problem area
exists whenever sulfur-containing pesticides are being incinerated.
Visible plumes were discharged from the experimental apparatus during
the incineration of picloram, malathion, and zineb; e.g., after the off-
gas had been scrubbed by a three stage scrubber system. Experiments during
which such plumes were discharged also generally involved difficulty in
operating the scrubber systems due to particulate buildup (plugging) of
the three demister pads in the three scrubbers.
Detectable levels of cyanide (as CN") were found in the incinerator
off-gas during tests with all four of the nitrogen-containing pesticides
studied (picloram, atrazine, captan, and zineb).
The available methods for specific pesticide analysis pose major
limitations on the type and significance of data that can be obtained
regarding pesticide incineration. For many pesticides (such as the chlori-
nated hydrocarbons DDT and aldrin), and the organic phosphate (malathion),
adequate techniques are available for quantification and identification
of the active ingredient and related compounds in the incinerator off-
gas and residues. For other pesticides, such as zineb, the only techniques
70
-------
available are either not applicable to the residue matrix, or are based
on the analysis of certain degradation products rather than on the active
ingredient.
SYSTEM PERFORMANCE
The experimental apparatus used to conduct the tests discussed above
functioned satisfactorily throughout the course of the study.
Minor modifications of the pesticide feed system were required in
order to inject water-based formulations. This modification included a
separate injection system for the pesticide formulation, consisting of
a water jacketed fuel oil burner nozzle of the appropriate size and an
adequate pump.
High pressure drops were encountered across the demister pads of the
first two scrubbers during some of the experiments. This operational prob-
lem was generally encountered when operating at low incinerator feed rates
and draft.
Extensive corrosion was noted during the course of the study. Most
seriously affected, as one would expect, were the internal and ancillary
piping of the first stage water scrubber. The entire first scrubber was
rebuilt (replaced) near the midpoint of the experimental phase of the
study. The demister pad (constructed of 304 stainless steel) and the re-
ducer cone on the first stage scrubber influent line were replaced twice
during the study. The most extensive corrosion appeared to result from
the DDT and toxaphene experiments.
PROBLEM AREAS
The major problem in the operation of the experimental facility was
associated with its operation at lower than design rates. As was discussed
in some detail in the subsection entitled Experimental Facilities, page
20 the experimental incinerator was designed to operate at 45.4 kg/hr
(100 Ib/hr) of Type 1 waste (equivalent to 6.86 x 10b J/hr (650,000 Btu/
hr)), which corresponds to a No. 2 fuel oil firing rate of approximately
23 liters/hr (6 gal/hr). Most of the experiments conducted subsequent to
the DDT tests were conducted at 20 to 50% of this design rate in order
to obtain lower primary chamber temperatures.
These low rates tended to amplify operational difficulties that would
have been less acute at design conditions, e.g., the plugging of the scrub-
ber demister pads while operating at low draft.
71
-------
The removal of solid residue from the primary chamber after aldrin
granule and picloram pellet tests conducted at high temperature (~ 1000°C)
caused minor problems. A major portion of the front wall of the primary
combustion chamber had to be removed after each test in order to provide
adequate access for removal of the hardened residue.
Large quantities of solid residue accumulated in the long horizon-
tal section of the incinerator stack (see Figure 1, p. 21), which neces-
sitated its frequent dismounting and cleanout. These deposits were par-
ticularly heavy after tests with solid formulations containing low con-
centrations of active ingredients, i.e., the 10% DDT dust and the 20%
toxaphene dust.
72
-------
SECTION VI
DISCUSSION
The results of this study show that the organic pesticides in 14
of the 15 formulations tested were effectively incinerated, i.e.,
> 99.99% degradation, over a range of time-temperature conditions. Of
the 137 experiments conducted at primary-chamber retention times and
temperatures ranging from 1.5 sec at 1200°C to 7 sec at 600°C, only 23
tests had an efficiency of < 99.99%. Ten of these 23 were tests using
the 0.3% mirex bait formulation, and only six of the remaining 13 tests
were conducted within a normal range of excess air (50 to 150%).
[Quantity out]
The total species output ratios == as discussed on page
[Quantity in J
35), were used to evaluate incinerator performance at various operating
conditions. These output ratios were the total amount of pesticide plus
all related chemical species detected (total species) in the off-gas
and solid residues per unit weight of active ingredient incinerated.
The ranges of total species output ratios for all 15 formulations (137
tests) expressed as pounds total species in the off-gas and solid res-
idues per 1,000 Ib of active ingredient incinerated, are given in Fig-
ure 7.
The output ratios were tabulated in a matrix with the key inciner-
ator operating variables—chamber temperature, flame temperature, re-
tention time, percent excess air, fuel/feed ratio and off-gas rate. As
expected, data comparisons showed that the operating variables were in-
terrelated and could not be evaluated separately.
The matrix for each series of pesticide tests was then analyzed to
determine the combinations and limits of the operating variables which
yielded the lowest and highest values for the output ratios, i.e., best
and worst conditions. This method of analysis showed the two most criti-
cal operating variables to be the retention time and primary chamber
temperature. The excess air was not as critical but best results occurred
at about 120%, with a range from 80 to 1607o.
73
-------
inft-
10-
1
I 1.0-
1
1
*0 ft 1
g
J
§
o
i
*; O.oi -
"f
J
*
1
S 0.001 -
•w
0.0001-
o.noooi-
&
o
«
C4
!—»»»¥
O
s
Q
O
41.2% Aldrin EC
19% Aldrin Granular
2
"5
o
u
cC
.2
0
_0
u
£
o
*
O
UJ
c
o
IE
^
ft
25%MolorhionWP**
60% Toxaphene EC
"5;
o
1
1
S
S
40.8% Alrazine Liquid
-
80% Atroiine WP
50% Copton WP
75%ZinebWP
£
X
S
CO
o
X
u
c
V
^o
£
C
2
1
t
1
*
1
"u
*£
UJ
^.
C
«
h- ^
* The respective pesticide plus all related chemical species detected
in the incinerator off-gas and solid residues.
** The range for malathion off-gas emissions is based on its detection
Unit.
Figure 7. Ranges or total species output ratios for the
15 formulations tests
74
-------
An evaluation was then made of the characteristics of the off-gas
from the pesticide incineration tests. The ranges of total species emis-
sions in the incinerator off-gas, expressed as pounds of total species
in the off-gas per 1,000 Ib of active ingredients incinerated, are shown
in Figure 8.
The results of tests conducted for each pesticide in proximity to
primary chamber time-temperatures of 2 sec at 1000°C were compared. (The
0.3% mirex formulation was excluded from this analysis because of the
limited data in the time-temperature area of interest.) Interpolation of
these data was used to estimate the total species emissions in the off-
gas when incinerating at 2-sec retention at 1000°C and within the excess
air range of 80 to 160%. These estimates, expressed as pounds of total
species in the off-gas per 1,000 Ib of active ingredients incinerated,
are given in Figure 9.
An evaluation was made of comparable results for all 15 formula-
tions tested in an attempt to hypothesize operating conditions (reten-
tion time and temperature) applicable to organic pesticides in general.
Reference to Figure 7 shows that the point of greatest commonality in
output ratios is 0.01, which corresponds to an incineration efficiency
of one order of magnitude "better" than 99.99%. Output ratios for all
tests having a nominal value of 0.01 were plotted as shown in Figure
lOa. Data points in Figure lOa representing essentially the same value
for a given pesticide formulation have been connected; these multiple
points indicate the magnitude of the range over which essentially the
same results have been obtained.
Figure lOb has been based on the data in Figure lOa and shows
three areas of incinerator operations: Zone A represents operating
conditions at which < 99.99% efficiency may result; the Operating Zone
represents conditions at which efficiencies of at least 99.99% are
expected; and Zone B represents conditions at which efficiencies of
> 99.99% are anticipated. Thus, the acceptable operating zones from
Figure lOb, in combination with lower temperature limits determined
from DTA and TGA, can be used to estimate necessary operating con-
ditions for the incineration of a given organic pesticide.
The preceding analysis of incineration efficiency has considered
only the unburned and partially decomposed pesticide in the effluents.
Additional factors that must be considered include the other potential
off-gas pollutants generated, such as particulates, cyanide, pyrophos-
phates, sulfur dioxide, and oxides of nitrogen. Particulate emissions,
as shown in Section V, exceeded the federal new source standard of 183
mg/m^ for all of the solid formulations tested. (The 0.3% mirex formula-
tion on a combustible corncob-grit base met the standard for four of 10
tests.)
75
-------
100
10-
1.0-
i
7 o.oi-
£
f
I
4
£ 0.001
S
a
0.0001-
O
£
0.00001-
* The respective pesticide plus all related chemical species detected
In the incinerator off-gas.
** The range for malathion is based on its detection limits.
Figure 8. Ranges of total species off-gas emissions for
15 formulations tests
76
-------
100
10-
1
1 '-°-
t>
2 0.1-
1
t: o.oi-
*
4
&
| 0.001-
_8
1
J
0.0001-
n nonoi —
Q
o
JR
m
—
3
Q
I—
O
O
^
0
u
UJ
c
^
CM
•^
^^m
Aldrin Gronula
gS
Os.
—
TJ
"5
% Piclorom Liqi
«•>
C«4
_
Piclorom Pellet
gS
o
I^H
U
LU
C
o
!c
"o
gS
tx.
"•• '
Molathion WP
gS
in
CM
"^™
Toxophene EC
g?
o
*o
Toxophene Dusi
b°
CN
^
4)
C
N
s
CO
o
—
Atrozine WP
gS
^1—
Capton WP
0?
o
IO
^M
Zineb V/P
g5
in
rs
* The retpecllve pesticide plut all related chemical tpeciel
in the Incinerator off gas.
Figure 9. Estimated total species off-gas emission rates at
2 sec retention time and 1000°C
77
-------
1200
1000
-i
u 800
|
t£
600
_L
J_
JL
012345
Retention Time, sec
a. Output ratios of ~ 0.01 for all pesticides tested
.J
7
1200r-
2 1000 -
800 ~
ZONE B
34567
Retention Time, sec
b. Operating zones for pesticide incineration at 80 to 160% excess air.
Figure 10. Time-temperature zones for pesticide incineration.
78
-------
As might be expected, the off-gas measurements for incineration of
the nitrogen-containing pesticides (atrazine, captan, picloram, and zineb)
indicated some cyanide (CN~). The amount of cyanide generated was to some
extent a function of chamber temperature and excess air and can apparently
be minimized at the higher temperatures (1000°C or above with 120% excess
air). Pesticides containing sulfur (captan, zineb, and malathion) also
generate high levels of S02 in the off-gas (up to 8,000 mg/m3 for the 57%
malathion emulsifiable concentrate and 22,900 mg/m3 for 75% zineb wet-
table powder). Malathion also showed to 3 g/hr of pyrophosphates in the
off-gas. All of these off-gas products indicate the need for adequate
particulate removal and scrubbing devices in the exhaust systems of pes-
ticide incinerators.
SIGNIFICANCE OF TEST RESULTS
The test results and evaluated data have led to the hypothesized
primary chamber temperature-retention time curves and operating zones
shown in Figure lOb. These curves are related to the pesticides tested,
the incinerator type and size, and the method of pesticide injection.
Although the active ingredients and formulations tested represent a
broad spectrum, the curves can only be recommended as a guideline for
the incineration of other pesticides. The incinerator type and size do
not appear to present major design problems, as long as sufficient re-
tention time, mixing, and chamber temperature are maintained. However,
the method of injection is significant, especially for the liquid for-
mulation mixed with fuel oil prior to injection into the incinerator.
(Here the flame temperature was "seen" by all of the liquid pesticides
and, as a result, the primary chamber temperature may not be a good in-
dication of the required temperature.) Thus, testing of grate-type in-
cinerators with typical containers of liquid and solid pesticide formu-
lation is needed before attempting to burn bulk pesticides, i.e., pack-
ages, jugs, etc., in these incinerators. The results from this research
study cannot be extrapolated to the incineration of bulk pesticides or
pesticide-containing solid waste without additional testing. An oil
burner or auxiliary injection nozzle may be used in grate-type inciner-
ators to spray the pesticide into the chamber with the chamber operated
at conditions to meet time, temperature, and air requirements.
PESTICIDE TNfTTNFRATTnN SYSTEM DKSTON ANALYSTS
Incinerator
The retention time, chamber temperature, and excess air limits for
good incineration of the pesticide formulations tested during this pro-
gram have been indicated in Figure 10b. Based on these results, it ap-
pears that any type of incinerator capable of meeting the retention time
79
-------
and primary combustion chamber temperature requirements with 80 to 160%
excess air is a potential candidate for use in incineration of pesti-
cides. However, these guidelines have been developed from the results of
tests in which all pesticides were injected into the primary chamber
through nozzles; no tests were run with bulk containers of liquids or
powders. Because of this limitation, only incinerators having similar
provisions for injection of the pesticides can be used. An alternative
is to modify existing incinerators by adding a suitable pesticide in-
jection nozzle into the primary chamber. The incineration of bulk
amounts of pesticides on grates cannot be recommended without further
tests.
Pesticide incinerators should be classified as a Class VII,* incin-
erators requiring special design for the waste to be incinerated. How-
ever, the Class IA (small) and Class V (municipal) incinerators should
be useable with appropriate feed nozzle additions since both classes
appear to include adequate retention time, temperature, and excess air.
Design information for pesticide incineration are included in Table
18. The capacity, heat release rate, and flue gas volume rate values (on
a unit primary chamber volume basis) are directly useable to calculate
the potential capacity, heat release rate, and flue gas volume rate for
use in design or for evaluating the capacity of an existing incinerator.
The fuel/pesticide ratio is also presented and can be useful as a guide
for supplemental fuel requirements to maintain adequate temperatures.
Additional considerations in the design of incinerators for pesti-
cides include mechanical design, instrumentation, materials handling and
safety. Proper materials of construction will be needed to prevent cor-
rosion, and the design must consider the affect of thermal cycling if the
facility is to be operated on an intermittent basis. At least minimum in-
strumentation must be provided to routinely determine primary combustion
chamber temperature and percent excess air. Adequate provision for stor-
age and handling of the pesticide and for the safety of the operating
personnel must also be included.
Air Pollution Control Considerations
The results of the incinerator off-gas sampling and analyses iden-
tified several types of emissions which must be considered in the design
and operation of a pesticide incineration system. Particulates and var-
ious gaseous pollutants in significant concentrations were measured at
levels which exceeded appropriate federal new source performance stan-
dards.
* Incinerator classification of the Incinerator Institute of America.iz/
80
-------
Table 18. DESIGN DATA FOR PESTICIDE INCINERATION
oo
Incinerator Information
Pesticide ,_. r -~.-_-~- ~
Peatlclde
Comnoii 1 1 1 on
Liquid formulations
DDT
Aldrln
F Ic lorflni
Malathlon
Toxaphene
Atrazlne
257. EC
41.27. EC
577. EC
607. EC
40.87. f lovable
formulation properties
Donslty Best of
kg/m combustion
(Ib/cu ft) J/kg (Btu/lb)
958 (59.8) 3.47 x 107
(14,920)
1,102 (68.8) 3.10 x 10
(13,330)
958 (59.8) 7.82 x 10
(3,360)
1,126 (70.3) 2.79 x 107
(12,020)
1,198 (74.8) 2.58 x 107
(11,190)
1,115 (69.6) 2.47 x 107
(10,630)
CapacityV
i/hr/m3
(nal/hr/cf)
28 (0.21)
11 (0.08)
19 (0.14)
9 (0.07)
8 (0.06)
23 (0.17)
rate
J/hr/m3
(Btu/hr/cf)
9.3 x 108
(25,100)
3.6 x 108
(9,800)
1.4 x 10
(3,800)
2.9 x 108
(7,900)
2.5 x 10°
(6,700)
6.3 x 10°
(16,800)
Flue gas"/
volume rate
dscfm/cf
15.2
10.4
10.0
3.5
2.6
4.7
Fuel/Pesticide
ratio
U/« or (gal/gal)
0-1.6
0.5-1.8
0.7-0.9
0
0.5-0.7
0.3
Solid formulations
DDT
Aldrln
Plcloram
Malathlon
Toxaphene
Atrazlne
Cap tan
Zlneb
Mlrex
107. dult
197. granules
107. pellets
207. dust
207. dust
807. WP
507. WP
757. WP
0.37. bait on corn-
cob grit
.
5.71 x 106
(2,460)
1.12 x 106
(480)
5.51 x 106
(2,370)
3.29 x 106
(1,410)
2.02 x 107
(8,690)
9.17 x 106
(3,940)
1.29 x 107
(5,550)
2.17 x 107
(9,330)
kg/hr/m3
(Ib/hr/cf)
52.4
(3.27)
27.7
(1.73)
43.9
(2.74)
26.6
(1.66)
25.5
(1.59)
6.4
(0.40)
9.0
(0.56)
6.6
(0.41)
32.0
(2.00)
_
1.6 x 108
(4,250)
4.9 x 107
(1,320)
1.5 x 108
(3,940)
8.4 x 10
(2,250)
1.3 x 108
(3,480)
8.2 x lO'
(2,210)
8.4 x 10
(2,250)
6.9 x 108
(18,600)
9.7
8.7
6.5
4.2
9.6
8.0
9.2
7.8
10.0
4/k« («al/kg)
0.26 (0.031)
0.47 (0.055)
0.28 (0.034)
0.44 (0.052)
1.70 (0.202)
0.54 (0.064)
1.01 (0.120)
1.60 (0.191)
0.25 (0.030)
s_/ Maximum capacity during teats with Incineration efficiencies of 99.
(25.6 cu ft).
b/ Based on maximum measured flow corrected to standard conditions of one stmosphere pressure snd 21.1"C (70'F) and divided by the primary chamber volume,
0.725 m3 (25.6 cu ft).
-------
Specific pollutants of concern for a given pesticide or generic
group of pesticides included the following:
1. Nitrogen-containing pesticides can emit significant concentra-
tions of cyanide (CN~) (captan, 49 mg/m3; zineb, 138 mg/m3).
2. Phosphorus-containing pesticides emit Po^S'
3. Sulfur-containing pesticides may emit sulfur dioxide (levels
as high as 8,000 mg/m3 from malathion and 22,900 mg/m3 for zineb).
4. Solid formulations (powders, dusts, granules, pellets) can emit
large quantities of particulates depending on the type and size of car-
rier medium (up to 71,000 mg/m3 for DDT; 73,000 mg/m3 for toxaphene).
5. Incineration of certain pesticides results in emission of other
gaseous pollutants such as HC1, C12, CO, NOX, etc.
The emission levels of the above pollutants for any incinerator will
be a function of the pesticide fed, feed rate, excess air, combustion
chamber temperature, and retention time. However, the fact that signifi-
cant emission levels were recorded during the course of this work indi-
cates the need of providing stack gas cleanup equipment to remove poten-
tially harmful gases and to meet incinerator effluent standards.
The design of an air pollution abatement system for a pesticide in-
cinerator will be highly dependent on the specific purposes for which
the incinerator will be used, i.e., type and formulations fed. There is
insufficient information from this work to delineate specific control
equipment design data, but some generalized design considerations can be
suggested.
Applications with high particulate concentrations in the effluent
(as have been measured for most of the solid formulation tests) will
probably require equipment with high mass and fractional collection ef-
ficiencies. Depending on the moisture content of the flue gas stream and
flue gas temperature, potential control devices include cyclones, fabric
filters or electrostatic precipitators.
If a cyclone collector is used, it would probably be included as a
precollector, followed by a collector with better efficiency potential.
As an extreme example of the possible collection efficiency required, the
maximum particulate loading measured was 73,000 mg/m3 for 20% toxaphene
dust. In order to meet a particulate effluent standard of 183 mg/m3,
the mass efficiency of the control system would need to be in excess of
99.75%. Depending on the particle size distribution of the particulate
82
-------
(which was not determined), a cyclone collector may have difficulty
achieving this level of collection. Fabric filters and electrostatic
precipitators are much more efficient; however, they are both sensi-
tive to gas conditions, gas composition and other particulate proper-
ties (resistivity, chemical composition, etc.).
The collection equipment of choice for the gaseous pollutants would
be a wet scrubber. There are a wide variety of possible scrubber types
which might be used. Table 19 is a listing of scrubber systems which
have been applied to combustion processes and for removal of gaseous
pollutants.lft' Some of these systems may prove to be adequate for par-
ticulate collection as well.
Table 19. SCRUBBER TYPES AND APPLICATIONS
Scrubber type Application!/
Plate p> G
Packed tower G
Fiber bed G
Spray tower G
Venturi P
Centrifugal p
Moving bed p» G
aj P = Particulate removal
G = Gaseous pollutant removal
83
-------
The particular gaseous pollutant of interest may require scrubbing
with a medium specific for the pollutant. Water is adequate for a gas
such as HC1, but other scrubber media may be required for SC^, NOX, etc.
In some cases, multiple stages will be required to efficiently remove a
combination of gaseous pollutants, with each stage specific for a given
pollutant.
Several other design considerations are worthy of note. Proper mate-
rials of construction will be necessary to prevent corrosion of duct work,
scrubber vessels, pumps, piping and nozzles. Proper design techniques for
duct velocities will be necessary to prevent settling of particulate in
horizontal duct runs. Scrubber x
-------
SECTION VII
REFERENCES
1. Working Group on Pesticides, "Proceedings of the National Working
Conference on Pesticide Disposal," at the National Agricultural
Library, Beltsville, Maryland, 30 June and 1 July 1970, NTIS No.
PB 197 145 (September 1970).
2. Federal Working Group on Pest Management, "Proceedings of the
National Conference on Pesticide Containers," New Orleans,
Louisiana, 28-30 November 1972 (December 1972).
3. Working Group on Pesticides, "Summary of Interim Guidelines for
Disposal of Surplus or Waste Pesticides and Pesticide Containers,"
NTIS No. AD 720 391 (December 1970).
4. Lawless, E. W., T. L. Ferguson, and A. F. Meiners, "Guidelines for
the Disposal of Small Quantities of Unused Pesticides," (Draft
Final Report), EPA Contract No. 68-01-0098 (August 1974).
5. 7 USC 135 et seq. The Federal Insecticide, Fungicide, and Rodenticide
Act, Section 2, as amended Public Law 92-516, "Federal Environ-
mental Pesticide Control Act of 1972" (21 October 1972).
6. Environmental Protection Agency, "Pesticides and Pesticide Contain-
ers: Regulations for Acceptance and Recommended Procedures for
Disposal and Storage," Federal Register. 3JK85): 15236-15241 (1
May 1974).
7. Environmental Protection Agency, "Pesticides and Pesticide Contain-
ers: Proposed Regulations for Prohibition of Certain Acts Re-
garding Disposal and Storage," Federal Register, .39(200): 36867-
36870 (15 October 1974).
8. Hanneman, W. W., and R. S. Porter, "The Thermal Decomposition of
Dialkyl Phosphates and 0,0-Dialkyl Dithiophosphates," J. Organic
Chem., 29:2996 (October 1964).
85
-------
9. Anthony, W. S., and F. L. Shuman, Jr., "Disposal of Liquid Pesti-
cides by Incineration," Paper No. 71-148, 1971 Annual Meeting
American Society of Agricultural Engineers, Pullman, Washington
(27-30 June 1971).
10. Putnam, R. C., F. Ellison, R. Protzmann, and J. Hilovsky, "Organic
Pesticides and Pesticide Containers," Report No. EPA-SW-21C-71,
Foster D. Snell, Inc., Florham Park, New Jersey (1971).
11. Whaley, H., G. K. Lee, R. K. Jeffery, and E. R. Mitchell, "Thermal
Destruction of DDT in an Oil Carrier," Canadian Combustion Re-
search Laboratory, Ottawa, Canada, Mines Br. Res. Rep., R225 (1970).
12. Lee, G. K., F. D. Friedrich, B. C. Post, and H. Whaley, "Thermal
Destruction of DDT-Bearing Powders," Mines Br. Res. Rep., R234
(1971).
13. Kennedy, M. V., B. J. Stojanovic, and F. L. Shuman, Jr., "Chemical
and Thermal Methods for Disposal of Pesticides, Res. Rev., .2,9:89
(1969).
14. Stojanovic, B. J., M. V. Kennedy, and F. L. Shuman, Jr., "Edaphic
Aspects of the Disposal of Unused Pesticides, Pesticide Wastes,
and Pesticide Containers," J. Environ. Quality. Hi): 54 (1972).
15. Kennedy, M. V., B. J. Stojanovic, and F. L. Shuman, Jr., "Chemical
and Thermal Aspects of Pesticide Disposal," J. Environ. Quality,
Hi):63 (January-March 1972).
16. Shuman, F. L., Jr., B. J. Stojanovic, and M. V. Kennedy, "Engineer-
ing Aspects of the Disposal of Unused Pesticides, Pesticide Wastes,
and Pesticide Containers," J. Environ. Quality, _Hl):66 (January-
March 1972).
17. Kennedy, M. V., B. J. Stojanovic, and F. L. Shuman, Jr., "Analysis
of Decomposition Products of Pesticides," J. Agr. Food Chem.,
_20(2):341 (1972).
18. Stojanovic, B. J., F. Hutto, M. V. Kennedy, and F. L. Shuman, Jr.,
"Mild Thermal Degradation of Pesticides," J. Environ. Quality,
J.(4):397 (1972).
19. I.I.A. Incinerator Standards, Incinerator Institute of America,
Inc., Arlington, Virginia (March 1970).
86
-------
20. "Standards of Performance for New Stationary Sources," Federal
Register, 3_6(247): 24876-24895 (23 December 1971).
21. Games, R. A., EPA/NERC-SHWRL, Personal Communication to Mr. T. L.
Ferguson (30 January 1974).
22< Herbicide Handbook of the Weed Science Society of America, 2nd ed.,
W. F. Humphrey Press, Inc., Geneva, New York (1970).
23. Capasso, N. S., L. Buckles, P. Cavey, F. Hildebrandt, and I. I.
Stevens, U.S. Army Munitions Command, Edgewood Arsenal, Maryland,
Personal Communication to Mr. T. L. Ferguson and Mr. Fred J.
Bergman (14 September 1973).
24. Calvert, S., J. Goldshmid, D. Leith, and D. Mehta, "Scrubber Hand-
book," A.P.T., Inc., EPA Contract No. CPA-70-95 (July 1972).
87
-------
APPENDIX A
EXPERIMENTAL EQUIPMENT
CONTENTS
Page
90
Incinerator. ......... .... .
Pesticide Injection System .... .... 92
Liquid Pesticides 92
Solid Pesticides • 99
Scrubber System. . ....... • 99
Scrubber Water Treatment System 107
Ancillary Equipment 109
89
-------
The experimental system was built at MRI's Deramus Field Station
in Grandview, Missouri.
Facilities at the experimental site consisted of Laboratory Build-
ings Nos. 1 and 2. The incinerator was constructed adjacent to Building
No. 1, which housed the scrubber and water treatment systems. Laboratory
Building No. 2 provided storage and special laboratory facilities removed
from the test area.
The overall system (Figure 1, p. 21) consisted of an incinerator
(Figures 2, p. 22 and 11), a pesticide feed system (Figures 12 through
18), three scrubbers (Figure 1, p. 21) and a wastewater treatment system
(Figure 19). Specific details on these components (in the actual system
of units used for their design) follow under separate headings.
INCINERATOR
The experimental incinerator (Figures 2, p. 22 and 11) was constructed
on a concrete pad adjacent to Laboratory Building No. 1.
The incinerator was constructed with an outer wall of concrete blocks
and a liner of insulating firebrick. The void between the walls was filled
with perlite insulation.
The incinerator was a two-chamber design separated by a checker wall.
The primary chamber volume was approximately 25.6 ft3 and the secondary
chamber volume 20.6 ft3. The design capacity was 100 Ib/hr of Type I
waste,* equivalent to 650,000 Btu/hr.
The primary chamber was constructed with two burner positions, one
in front and an alternate on the side. Also in the front wall were a view
port and near the bottom a sample port for collecting a grab sample of
solid pesticides during incineration. Another port was located in the top
of the primary chamber to facilitate pyrometer readings. The underfire
air opening was located beneath the front burner opening.
A door was provided near the rear of the second chamber for cleaning
out solid residues.
Five thermocouples (Figure 11) were installed in the incinerator,
three in the primary chamber and two in the secondary chamber. Manometer
I.I.A. Incinerator Standards, Incinerator Institute of America, Arlington,
Virginia (March 1970).
90
-------
TC3
1
1
13"
1
1
6-3/4
L
T
6-3/4
*
t '
8-1/2"
6-1/4" 1 I7~
1
PRIMARY '
CHAMBER
17-
U 12-1/2" ».
(
1
(„ 12-1/2" -
"
/<••
|« 12-1/2" »
6-1/4"
A" I* *'
t
8-1/2"
. 1
TC5
TC4
•TC2
FRONT
TOP
VIEW
SIDE
VIEW
INCINERATOR THERMOCOUPLE LOCATIONS
Figure 11. Incinerator thermocouple locations
-------
connections for determining the differential pressure of the chamber dur-
ing incineration were located adjacent to the front wall of each chamber
(see Figure 5, p. 27).
Transition from the incinerator to the vertical stack was made by
a square stack constructed from 1/8 in. sheet metal. Two openings were
located in the square stack, one in the side near the front and one in
the rear. These openings provided entrance for inspection cleaning.
The incinerator was covered with a roof serving as a partial pro-
tection from the weather and as a platform for particulate sampling.
The original design of the incinerator was made according to IIA
standards for 100 Ib/hr of Type I waste. Requirements and values for the
design are given in Table 20. The elimination of the grating from the
primary chamber resulted in the effective volume of the primary chamber
being changed to 25.6 ft3.
During the experimental tests the incinerator operated under induced
draft provided by a blower (Figure 1, p. 21). During warm-up periods when
only fuel oil was being burned, the incinerator was operated by natural
draft by opening the stack bypass and venting to the atmosphere.
PESTICIDE INJECTION SYSTEMS
Liquid Pesticides
For liquid formulations, two types of injection systems were used,
one for fuel oil miscible liquids and the second for water-based pesti-
cides.
The injection method used with fuel oil miscible liquid pesticides
(Figure 12) was to mix the pesticide with fuel oil feeding the burner
(Figures 13 and 14).
For water based liquid pesticides, a separate system was used which
consisted of a pump and a fuel oil burner nozzle (Figure 15). The pesti-
cide nozzle and the fuel oil burner were located on a horizontal plane
and at a 30 degree angle to each other in the primary burner position
(see Figure 2, p. 22). The pesticide was passed through a water-cooled
jacket and then through a conventional fuel oil nozzle (Figure 16). The
water-cooled jacket prevented the pesticide injection system from plug-
ging when exposed to the heat of the incinerator.
92
-------
Table 20. INCINERATOR DESIGN PARAMETERS^/
Basic Ratio: 100 Ib/hr of Type I waste = 650,000 Btu/hr maximum
Stack velocity = 165 ft/min
= 18 ft3/sec at 1400°F
Settling chamber velocity = 9 ft/sec
Cross-section in secondary chamber = 1.56 ft^
Grate area equivalent = 5.25 ft^
Primary chamber = 20 ft^
Secondary chamber = 24 ft^
Surface area =71 ft2
Radiation rate = 9,155 Btu/ft2/hr
Stack = 12 in. diameter
No. 2 fuel oil at 18,900 Btu/lb
= 110,000 Btu/gal
Air required at 100% excess
7.0 lb/10,000 Btu = 455 Ib/hr
£/ Based on I.I.A. Incinerator Standards, Incinerator Institute of
America, Arlington, Virginia (March 1970).
93
-------
vO
r
Vent
Level
Gauge
20 Gal
Pesticide
Drum
No 2
20 Gal
Pesticide
Drum
Nol
20 Gal
Fuel Oil
Drum
Level Gauge
I . . j^sj- i__ — ,
Sight ^
t
— f'vT'/y/TTjTri— ^
' UU(rvv ^^X
,, Glass with JL
Glass , Heat Tape A (j\)(p\\
Burner
Figure 12. Liquid pesticide feed system - fuel oil miscible formulations
-------
-21-1 X „ 3t
ITEM
SO.
DESCRIPTION
1 Motor, 1/8 HP
2 Motor Mt'g. Fll. Hd. Mich. Screw
3 Fir.
Fan Set Screw
Tranaformer
Hinge Clip
Self Tipping Screw
Id. Hd. Screw
Fan Homing
10 Air Ad}. Band - Inner
11 Air Adj. Band - Outer
12 Air Band Fll. Hd. Mach. Screw
13 Tlnnernan Speed Nut
14 oil Line Adj. Slot Cover
15 Oil Line Slot Cover Screw
16 Oil Line Locknut
17 Pump Coupling
18 Pump Coupling Set Screw 34
19 Oil Line Aatembly 35
20 Oil Line Elbow 36
21 Fuel Unit
22 Fuel Unit Mt'g. Fll. Hd. Mach. Screw 38
23 Oil Line Fitting
24 Oil Pipe
25 Buaa Bar 40
26 Hex Nut 41
27 Waahar *2
28 Inaulator Buahlng '3
29-1 Electrode Support 44
29-2 Stabilizer 45
30 Rd. Hd. Mach. Screw 46
31 Baffle Plate *7
32 Rd. Hd. Mach. Screw 48
Nozzle Adapter
Inaulator
Electrode Steal and Unher
Air Tube
Air Cone Mt'g. Fll. Kd. Mach. Screw
jo Air Cone
39-1 Large Flange - 9 In. 0. D.
39-2 Snail Flange - 6-1/4 in. 0. D.
Flange Mt'g. Fll. Hd. Mach. Screw
Caaket
Adj. Flange
Fll. Hd. Kach. Screw
Square Hut
Support Bracket
Vt* Hd. Hach. Screw
Uaaher
Hex Nut
Figure 13. Diagram of 0.6 to 3.0 gal/hr fuel oil burner.
95
-------
12) TAILPIECE ASSEMBLY
ON
ITEM
NO.
1.
4.
I.
I.
1.
I.
I.
10.
II.
12.
13.
14.
15.
It.
17.
II.
19.
20.
21.
NAME OF
PART OR ASSEMBLY
Blower CM*
Pedestal Assembly
a. P*d*stal Column
b. H«x lam Nut
c. P*d*slal
Motor. G. E. '/I H.P.. Typ* K.H.
ran—Torringlon 37 Had* —Typ* No. I. « Had*
Fuel Pump. W.b.c.r
Air Shutter Housing
Air Shutter
Air Shull.r Retaining Spring
Thumb Scr«w
rivxibl* Coupling
Tranilormir (Glr« >ollag<>. crcl««). Car4n«l
Tail Pi*c« A**«mbtr
a. NonU Tip (Sp>clly capacilr. angulotlon)
b. No»l« Adapter
c. Air D«n.clor 4 EUcliod* Held«r
d. El.ctiod. (Right)
.. El.clrod. (L.ll)
f. Ignition Gobi*
g. Ignition Cabl* Spacer
b. Tailpl.c. Collar
I. Tailpioc*
). Tailpitc* Gtau Rftlainor
IT Tailpi>c< Glau
I, Imperial Elbow Tilting
m. ru«l Tubo
Blower Tub* A»«mbly
a. Air Dilluler
b. Tailpi«c« Support
c. Blowtr Tub*
d. Air DirJui«r Adjustment Rod (not shown)
•. Wing Nul (not shown)
Junction Box
function Box Cover
ru«l Teed Pip* Assembly
BX Conduit
BX Connector
Anti Short
Burner Bracket Mounting Auomblr
a.Burner Mounting Stud
b.Bumer Mounting Rod
c. Burner Mounting Washer (2)
d. Burner Mounting Washer
••Rubber Mounting
Burner Bracket Assembly
Figure 14. Diagram of 3.0 to 8.0 gal/hr fuel oil burner
-------
Vent
VD
20 Gal
Fuel Oil
Drum
20 Gal
Pesticide
Drum
No 1
20 Gal
Pesticide
Drum
No 2
Level Gauge
Glass with
Heat Tape
Sight
Glass
Figure 15. Liquid pesticide feed system-water based formulations
-------
00
NOZZLE-,
ft
/
/
/
NOZZLE ADAPTER
1/4 IN. PIPE-^.
_ 2 IN. PIPE 3/4 IN,
V///////////// //////////////< U //////.
'' L»
/>
y//////////////////////////y? '
* 2 1, 2 IN. H 3/4)N
12 IN. 1/4 IN. PIPE -^
^
xA-
->>.
N
:*/
^
^
^
H«—
s
s
'/>
\
's
1
s
s
k
1 IN ».
//////
S
'f
V
//////
-1 IN.-*
1/2 IN. PIPE
SAV/SA1S1
ijSsssafcia _-.
^VOID PACKED
WITH WET
INSULATION
B. MODIFIED,WATERCOOLED INJECTION NOZZLE
NOZZLE
•NOZZLE ADAPTER
1/8 IN.
"OIL PIPE
A. STANDARD BURNER NOZZLE
Figure 16. Modified injection nozzle
-------
Both liquid pesticide injection systems were fed from drums situ-
ated on a platform inside Laboratory Building No. 1. The platform was
8 ft above the center line of injection. The feed drums were vented out-
side the building.
The feed line to the burner was equipped with an electrical heat tape
for use during cold weather. (Heating of the water-based pesticide feed
line was unnecessary because all of the water based liquid pesticides
were incinerated during the summer months.)
Pressure gauges were installed on both the fuel oil burner and the
water base pesticide pumps. The burner also had an oil temperature in-
dicator.
The feed drums for both the fuel oil and pesticide mixture had level
gauges for use in determining the flow rate.
Solid Pesticides
The solid pesticide injection system is shown in Figure 17. The pesti-
cide was fed into a flexible hose from a vibrating screw feeder. Compressed
air was injected into the feed line, forcing the pesticide through a water
cooled injection nozzle (Figure 18).
The fuel oil burner and the water cooled injection nozzle were loca-
ted in the primary burner position and on a horizontal plane and at a
30 degree angle to one another.
The vibrating screw feeder was equipped with a variable speed drive
allowing the delivery rate to be changed. This feature also adapted well
to the different active ingredient contents and particle sizes of the
various solid pesticide formulations.
The compressed air passed through two water traps before entering
the injection system to prevent plugging problems with dust formulations.
SCRUBBER SYSTEM
The purpose for installing a scrubber system was to prevent poten-
tial emissions of pesticides into the environment.
The experimental scrubber system (see Figure 1, p. 21) consisted of
three separate scrubbers; the first and third used water as the scrubbing
liquid and the second, hexylene glycol. Design criteria for the scrubber
system appear in Table 21.
99
-------
Solid Pesticide
Formulation
Vibrating Screw
Feeder
Compressed I I
Air
Pressure
Regulator
Funnel
3/4" I.D. Flexible
Tubing
Injection Nozzle-
I
Cooling
Water
Out
Figure 17. Solid formulation injection system
Incinerator
Wall
I
100
-------
•2 IN. PIPE
IN
.-^J
v-1/4 IN. PIPE
1/2 IN. PIPE
*-2-1/2 IN.-»-|
-12 IN.
Figure 18. Dust injection nozzle
-------
Table 21. DESIGN OF SCRUBBING SYSTEM
1. Scrubber No. 1
Calculate cross-sectional area of the marble bed
Use superficial velocity of 500 ft/min
Gas flow is *» 300 acfm
- 0.60
500 ft/min
Area = JL d2
4
0.60 = -H-d2
4
d2 = 0.765
d = 0.875 ft = 10.5 in.
.*. use 1 ft diameter
H20 spray onto the marble bed
Use 10 gal/1,000 cf x 300 cfm = 3 gal/min of H20
Estimated AP will be about 4 in. H20
Quenching
Use gas velocity of 500-700 fpm—
Gas flow 840 acfm at 1400°F
Desire cooling to « 225°F
Enthalpy of air at 1400°F =342 Btu/lb I ^ = 302 Btu/lb
Enthalpy of air at 225°F = 40 Btu/lb (
Avg. Cp of air (1400-200°F) ~ 0.244 Btu/lb °F
(840 acf/min)(.021 Ib/acf) = 18 Ib/min of air
Cooling reqd. = (18 Ib air/min)(302 Btu/lb) = 5,500 Btu/min
Heat absorbed by water «* 1,100 Btu/lb H20
.'. Water reqd. = 5.500 Btu/min = 5 Ib/min of H20
1,100 Btu/lb H20
.«. Use 1 gal/min H20
102
-------
Table 21. (Continued)
Velocity of gas entering quench section (12 in. pipe) is:
Area of 12 in. pipe =0.78 ft2
840 acf/min = 1,100 ft/min .*. that avg. velocity through
0.78 ft2 Quench section using 12-in.
pipe will be o.k. compared to
Velocity out: 300 acf/min = 390 ft/min desired 500-700 fpm above.
0.78
Calculate diameter of demisters
/PL - PG
Optimum design velocity = 0.35 \/
. 0.35./62.4 - 0.07
V 0.07
= 0.35A /890
PG
V
= 0.35 (29.8) = 10.4 ft/sec x 60 = 600 ft/min optimum design
velocity
300 cfm/3 ft2 = 100 ft/min
Gas flow design basis = 300 acfm
Use demister pad dia. of 12 in.
.*. Face velocity st 300 ft3/min = 300 ft/min
2. Scrubber No. 2
Design of second stage scrubber (hexylene glycol)
Density of hexylene glycol = 0.97; assume viscosity ~ that of
ethylene glycol
Use liquid flow of 8 gpm
' ' G\/PG = °'10 then> Read f(c1)2 = o.ios/
v^r
103
-------
Table 21. (Continued)
U2 = ethylene glycol 15 cp (15)°*2 = 1.7
a
0.10 = (G1)2 E3 U0>2
8C PG PL
12 =
(G1)^ = 0.10 RC PG PL
^ U'2
E PG PR
(G1)2 = (0.10)(32.2)(0.07)(60) = 0.020
(400)(1.7)
1 9
G = 0.141 Ib/sec ftz gas flow at flooding
gas flow - 0.38 Ib/sec
Area reqd. = 0.38 Ib/sec =2.7 ft2 at flooding
0.141 Ib/sec ft2
Use 4.0 ft2 to be below flooding
/. 27 in. diameter
3. Scrubber No. 3
Design of third stage H20 scrubber
Basis: 250 acfm at 100°F
Not possible to calculate the quantity of water required to remove
carry-over of hexylene glycol, therefore, use 8-10 gal/1,000 cf or 2 gpm.
Calculate tower diameter required
'p \ 0 _ a/
PL /
L1 = 2 gal/min x 60 x (8.34 Ib/gal) = 1,000 Ib/hr
V1 = (18 Ib air/min + 5 Ib/min H20)(60) = 1,400 Ib/hr
104
-------
Table 21. (Continued)
Area reqd. = 0.38 ft/sec _ = 1<4 fl-2 at flooding
0.276 Ib/sec ftz
Est use 2.0 ft2 21 in. 0
-V— =0-025 (pg3)
G VPL
For 1/2 in Raschig rings —
Irrigation rate =0.9 gal/min ft
2 gal/min = 2.2 ft2
0.9 gal/min ft2
2
2
Considering recommended value of 3-5 gpm/ft recalculate tower dia.
Increase from 2 gpm up to 8 gpm
•*• ii\ /!!G = °-10 y
G VPL
Read new value of 0.10—' compared to 0.20—
2 = (0.10)(32.2)(0.07)(62.4)
(400)(0.93)
2 = 0.038
G1 = 0.195 Ib/sec ft gas flow at flooding
gas flow =0.38 Ib/sec-'
Area reqd. = 0.38 Ib/sec =2.0 ft2 at flood
0.195 Ib/sec ft2
2
Use 3.0 ft to be below flooding
2 ft 0 or 24 in.
Use 24 in. dia. vessel with 4 spray nozzles, each of which
deliver 2 gpm for a total water flow of 8 gpm.
105
-------
Table 21. (Concluded)
satrd. air at 100°F = 15 ft3/lb dry air
0.04 Ib H20/lb air
15 ft3/!.04 Ib .'. pG = 0.070 lb/ft3
p_ = 62.4 lb/ft3
0.5 = 3
1,400 V 624 1,400
Bead value of 0.209-'
- Q.20S/
G1 - gas flow Ib/sec ft2
T - 400
E3
Uj " liquid viscosity cp - 0.70 cp (0.70)0.2 = 0.93
gc - 32.2
p = 0.07 lb/ft3
G
p - 62.4 lb/ft3
I*
(G1)2 = (0.20)(gc PG PL) - (0.20) (32. 2) (0.07) (62. 4)
(a )(l>£)0.2 (400)(0.93)
£
(G1)2 - 0.076
1 2
G - 0.276 Ib/sec ft gas flow at flooding point
gas flow = (23 Ib/min) (min/60 sec) = 0.38 Ib/sec
a/ Danielson, John A., Air Pollution Engineering Manual. U.S. Department
of Health, Education, and Welfare, Public Health Service, Publica-
tion No. 999-AP-40, Cincinnati, Ohio (1967).
b/ Clarke, Loyal, Manual for Process Engineering Calculations, McGraw-Hill
Book Company, Inc., New York, New York (1947).
106
-------
Scrubber No. 1 was a water scrubber designed to cool the stack gases
and remove the contained particulate matter. Located above the collection
tank in the downcoming stack were two 1 gpm nozzles. The gas then passed
through a marble bed with a third nozzle washing the bottom of the bed.
The marble bed had eight downcomers, with outlets beneath the collected
water surface. The downcomers were used to eliminate foam above the marble
bed. Just before exiting Scrubber No. 1, the gases passed through a 12-
in. diameter, 4 in. thick 304 stainless steel demister pad. Water collected
in the main body of the scrubber, a 2 ft by 4 ft oval tank, and drained
by gravity through a water trap to a sump pump. The sump pump transferred
the water to a temporary holding tank for sampling.
The main body of hexylene glycol Scrubber No. 2 was a 28 in. diameter
by 8 ft high. The gases from Scrubber No. 1 entered beneath a 2 ft deep
bed of 1/2 in. raschig rings. Four spray nozzles of 2 gpm each sprayed
down on the rasching rings. Gases from Scrubber No. 2 passed through
another demister pad located as in the first scrubber. The hexylene glycol
collected in the bottom of the scrubber for recycle through the spray sys-
tem.
Scrubber No. 3 was similar to Scrubber No. 2. The raschig ring bed
was 1 ft deep and water was used as the scrubbing liquid. Water collected
in the bottom of the scrubber for removal by gravity to a sump pump trans-
ferring the water to a temporary hold tank. Water collected in the hold
tank was sampled and analyzed. The main body of Scrubber No. 3 was 24 in.
in diameter and 7 ft high.
SCRUBBER WATER TREATMENT SYSTEM
The system used to treat the scrubber waters is shown in Figure 19.
Water from Scrubbers Nos. 1 and 3 was collected during the experimental
test in separate hold tanks inside Building No. 1 for sampling and analy-
sis. This water was then pumped outside to larger hold tank before treat-
ment and disposal. Approximately 800 gal. were collected during each ex-
perimental test.
From the outside hold tank, the scrubber water was pumped to a sand
filter for removal of particulate matter. Flow to the sand filter was con-
trolled by two float switches, one on the outside hold tank and another
on the sand filter.
107
-------
Outside Hold
Tank
Scrubber No.l
Hold Tank
Venf
Scrubber No. 3
Hold Tank
Activated
Carbon
Columns
Sand
Filter
o
00
To Septic
Tank
Figure 19. Scrubber water treatment system
-------
Water flowed by gravity through a filter composed of two layers of
media; the top was filter sand 6 in. in depth and the bottom, limestone
chat, 1/4 in. nominal diameter, 6 in. deep.
The filtered water then passed through two parallel columns 8 in.
in diameter and 4 ft high. These columns contained approximately 25 Ib
(dry weight) each of 6 to 8 mesh activated carbon.
Effluent from the carbon columns was discharged into the facility
septic tank system.
ANCILLARY EQUIPMENT
Table 22 lists other equipment used as part of the experimental
system.
109
-------
Table 22. ANCILLARY EQUIPMENT
Designation
Make
Model
Fuel oil pump American Gear 77
Burner
Burner
Burner
Firebrick
Thermocouples
Manometer
Manometer
Spray nozzles
Demister pad
Sump pumps
Hexylene glycol
pump
Raschig rings
Blower
Ray (Monarch and 1XPJ
Steinen nozzles)
Wondaire (Monarch OE
and Steinen nozzles)
Wondaire
Kaiser Re-
fractories
PG-260B
Morex
Chrome1-Alumel 22 gauge
Dwyer 172
Dwyer 171
Spraying Systems 1/2 GG3030
3/8 GG15
1/8 GG5
York
Little Giant
Weinman
Knight
304 stainless
steel
8 CIA
5ACK-10P
ceramic
New York Blower Size 12
Liquid pesticide Oberdorfer
pump
C-6287
-110-
Purpose
Transfer fuel oil from
storage to the feed
system
Fuel oil burner 3.0
to 8.0 gal/hr
Fuel oil burner 0.6
to 3.0 gal/hr
Natural gas burner
Manometer No.
Manometer No. /2\
2 gal/min
3 gal/min
1 gal/min
4-in. thickness
12-in. diameter
Transfer water from
the scrubbers to
the hold tanks
Recycle the hexylene
glycol
1/2-in. diameter
I/2-in. length
Induce draft
Inject water-based
liquid pesticides
-------
Table 22. (Concluded)
Designation
Make
Vibrating screw Vibra Screw
feeder
Temperature
recorder
Total hydrocar-
bons analyzer
Total hydrocar-
bons recorder
Particulate sam-
pling consol
Leeds and
Northrup
Beckman
Leeds and
Northrup
Research Appli-
ance Corp.
Discharge pump Meyers
Outside hold
tank pump
Scales
Stayrite
Model
Speedomax W
6800
601
2343-10
100M1/2
JH1B
Fairbanks-Morse 0-500 Ib
Purpose
Feed solid pesti-
cides
12 points variable
chart speed
Transfer water from
the scrubber hold
tanks
Transfer water to
the filter
Weighing and mixing
pesticide formula-
tions
111
-------
APPENDIX B
TEST RESULTS
CONTENTS
I. DDT 117
Pesticide Description 117
Formulations Tested 119
Preliminary Thermal Analyses 120
Methods of Analysis. .................. 121
Test Conditions and Results 124
Discussion ........ .......... 143
References 144
II. Aldrin 145
Pesticide Description. ........ 145
Formulations Tested 146
Preliminary Thermal Analysis . 148
Methods of Analysis 153
Test Conditions and Results 154
Discussion .......•••••••«•••••••• 167
References 168
III Picloram 169
Pesticide Description. .. .......... 169
Formulations Tested. 170
Preliminary Thermal Analysis 171
Methods of Analysis 177
Test Conditions and Results 180
Discussion ........ 197
References 198
113
-------
CONTENTS (Continued)
IV. Malathion 199
Pesticide Description 199
Formulations Tested 204
Preliminary Thermal Analysis ..... 205
Methods of Analysis 208
Test Conditions and Results. 212
Discussion ..... ............. 223
References 224
V. Toxaphene 225
Pesticide Description. ............. 225
Formulations Tested 227
Preliminary Thermal Analysis 228
Methods of Analysis 233
Test Conditions and Results 238
Discussion • 250
References 251
VI. Atrazine 252
Pesticide Description 252
Formulations Tested 253
Preliminary Thermal Analysis 254
Methods of Analysis 262
Test Conditions and Results 265
Discussion • 278
References ........ 279
VII. Captan 280
Pesticide Description 280
Formulations Tested 283
Preliminary Thermal Analysis 283
Methods of Analysis ' 284
Test Conditions and Results 290
Discussion •
References »
114
-------
CONTENTS (Concluded)
VIII. Zineb 298
Pesticide Description «• 298
Formulations Tested. • 299
Preliminary Thermal Analysis 300
Methods of Analysis 306
Test Conditions and Results 309
Discussion • 316
References ......••••• ... 318
IX. Mirex 319
Pesticide Description 319
Formulations Tested 320
Preliminary Thermal Analysis 321
Methods of Analysis 321
Test Conditions and Results 325
Discussion ......••••••••«•»•»••• 333
References . ........... 334
115
-------
This appendix contains a summarization of data from the pilot scale
incineration of representative commercial formulations of nine pesticides.
The rationale for the pesticides' selection, as well as the experimental
design used for their study, have been discussed in detail in Sections III
and IV, respectively, of the main text of the report.
The experimental facilities used for these tests have been reviewed
in Appendix A, and are shown in Figure 1, p. 21. The sample points,
thermocouple positions, and manometer locations referenced in the following
discussions are shown in Figure 5, p. 27*
116
-------
I. DDT
PESTICIDE DESCRIPTION
Physical Properties
Chemical Name; 1,1,l-Trichloro-2,2-bis(£-chlorophenyl)ethane;
dichloro diphenyl trichloroethane
Common Name; DDT
Trade Names; Anofex®, Chlorophenotane®, Dedelo®, Dicophane®,
Genitox®, Gesapon®, Gesarex®, Gesarol®, Gyron®,
Ixodex®, Kopsol®, Neocid®, Pentachlorin®,
Rukseam®, Zerdane®
Pesticide Class; Broad spectrum insecticide; chlorinated hydro-
carbon
Structural Formula:
Empirical Formula;
Molecular Weight; 354.3
Physical State; White, crystalline solid
Characteristics:
Technical grade DDT contains a mixture of p,p'-
isomers, o,p*-isomers, as well as related
chlorinated compounds. Domestically produced
technical grade DDT contains 75 to 80% p,p'-
isomers, and 15 to 20% o,p!-isomers (Lawless
et al.i/). FAO specifications (of the Food and
Agriculture Organization of the United Nations)
require a minimum p,pf-DDT content of 70%
(von Rvimker and Horay.2/).
For purposes of this report, "DDT" has been de-
fined to include four major isomers commonly
found in the technical material; i.e., p,p'-
DDT, o,p'-DDT, p,p'-DDE, and o,p'-DDE. Both
o,p'-DDD and p,p'-DDD have been arbitrarily
included with the "other" chlorinated hydro-
carbon species.
117
-------
Melting Point: 108.5 C (p,p'-DDT)
Boiling Point; Decomposes at 110° C (von Rumker and Horay)— '
Specific Gravity; 1.38 (technical grade); 1.6 (p,p '-isomer)
Vapor Pressure; 1.9 x 10~7 mm Hg at 20° C (p,p'-DDT)
Chemical Properties
ZeidlerJ/ discovered that DDT undergoes a dehydrochlorination reac-
tion in strongly basic solution, i.e., caustic alkali in alcohol, to
give a product now known as DDE.
(ClC6H4)2CH-CCl3 " (ClC6H4)2C=CCl2 + HCl-Base
Dehydrochlorination was shown to be complete in 30 to 60 min at
room temperature in 0.1N alkali solution by Wain and Martinet/ and also
to occur with organic bases such as amines by Lord.A'
DDT is quite resistant to oxidation and is not oxidized by chromic
oxide in glacial acetic acid or by nitric acid, although the latter ni-
trates the aromatic rings, according to Fleck£/ and Beilstein's Handbuch
der Organischen Chemie.Z/ Similarly, attempted oxidation by permanganate,
persulfate, chlorine or hypochorite has given poor results.—'
The reduction of DDT by active metals has been known for several years.
For example, a mixture with zinc granules and HC1 in aqueous ethanol gives
a mixture of partially dechlorinated products; (C1C6H4)2CH-CH3, (0105114)2-
CH-CHC12, and C1C6H4-CH=CH-C6H4C1, as referenced in Beilstein's Handbuch
der Qrganischen Chemie.Z/
Putnam et al.-/ reported DDT to be stable up to about 300°C, and at
this temperature at least 10% of the DDT distilled without decomposition.
Only 5% of the DDT distilled when the pyrolysis was conducted in the pres-
ence of mineral oil and only 1% with -potassium chlorate, but unfortunately
the decomposition products, some of which appear to be chlorinated hydro-
carbons, were not identified.
Molten DDT is subject to catalytic dehydrochlorination by impurities,
such as certain metals as shown by Fleck.6./
118
-------
The incineration of DDT in a kerosene carrier has been studied by
Whaley et al.iP./ at the Canadian Combustion Research Laboratories in
Ottawa. Whaley's work has shown that a DDT-kerosene formulation can be
"completely" destroyed in an incinerator utilizing a commercially avail-
able blue-flame burner. This study provided the design data from which
the Canadian Department of National Defense built and operated a special
incineration system to destroy 107,000 gal. of a kerosene-based DDT
formulation.!!/ Further, study by Lee et al.IZ/ has shown that a DDT
dust formulation can be similarly destroyed.
Production and Use
The registrations for essentially all domestic uses of DDT have
been cancelled. However, DDT is still being manufactured in the United
States by one company, primarily for export to other countries. The
estimated annual production rate in 1972 was 45 million pounds (Lawless
et al.l/).
FORMULATIONS TESTED
Two major formulations of DDT were tested: a 2 Ib/gal (25%) emul-
sifiable concentrate (EC), and a 10% DDT dust.
4 Ib/gal EC
Name: AMOCO® elm spray emulsifiable DDT concentrate
Manufacturer; American Oil Company, Chicago, Illinois
Composition; Active ingredients (by weight)
Dichloro diphenyl trichloroethane (DDT) 25%
Petroleum oil (a paraffinic horticultural
oil) 18%
Xylene (boiling range 270-290°F) 55%
Inert ingredients (by weight) _2%
Total 100%
Registration: USDA Reg. No. 1145-8
Lot No.; F-039-013-26B
10% Dust
Name: Tobacco States Brand 10% DDT Ready Mixed Dust
Manufacturer; Tobacco States Chemical Company, Lexington, Kentucky
119
-------
Composition: Active ingredient
Dichloro diphenyl trichloroethane (DDT) 10.00%
Inert ingredients 90.00%
Registration; USDA Reg. No. 226-59
Particle Size Specifications; Manufactured from a mixture of 20
parts (by weight) of a 50% DDT
dust (10 parts technical DDT and
10 parts attapulgite ground to
< 44 u, (325 mesh) and 80 parts
soap stone (< 74 u. (200 mesh)).
PRELIMINARY THERMAL ANALYSES
The heat of combustion of the 25% EC formulation was determined at
the outset of the study. The results were as follows:
Heat of combustion 3.4676 x 107 J/kg (14,921 Btu/lb)
Sulfur 1.16%
Differential thermal analysis (DTA) and thermal gravimetric analysis
(TGA) were not conducted for DDT. Other investigations, however, have
reported the results of such analyses. Kennedy et al.JL^' reported tem-
peratures at which endothermic and exothermic peaks were observed for
analytical standard and technical flake DDT. The results of their tests
were as follows:
Endotherms Exotherms
Reference standard 60, 110, 180 and 350°C 545°C
Technical flake DDT 70, 110, 240, 275 375, 578, and 825°C
and 355°C
Sensitivity = 25%.
Based on these and other laboratory analyses, Kennedy et al. concluded
that the temperature of complete combustion for the DDT reference stand-
ard and technical material were 560°C (1040°F) and 850°C (1560°F),
respectively.
120
-------
Putnam et al.—' also studied the combustion of DDT in a closed sys-
tem, i.e., samples encapsulated in a volatile sample pan, using differen-
tial scanning calorimetry (DSC). These tests showed decomposition over
the range of 305 to 325°C. DSC of DDT open to the air, however, did not
show exotherms. The authors concluded that their test results indicate
that pesticides heated in an open system apparently do not decompose, but
vaporize or sublime (combustion of DDT was reported to have been observed
at 182°C).
METHODS OF ANALYSIS
Apparatus
A Micro-Tek 2000R gas chromatograph equipped with a 3-ft, 4 mm
I.D. glass column (packed with 1.5% OV-17 + 1.95% QF-1 on 80/100 mesh
Supelcoport from Supelco, Inc., Bellefonte, Pennsylvania) and a tritium
electron capture detector, maintained at a voltage of 15 V DC, was used
for gas chromatographic analysis. Chromatographic operating conditions
were: injection temperature 225°C; column temperature, 200°C; detector
temperature, 180°C; carrier flow rate, 100 ml/min, N£? and purge gas
flow rate, 200 ml/min, N2.
A Honeywell strip chart recorder was used to record the chromato-
grams.
Reagents and Materials
The solid standards o,p'-DDT (99+%), p,p'-DDT (99+%), o,p'-DDE
(99%), p,p'-DDE (99%), o,p'-DDD (99%), and p,p'-DDD (99%) used for pre-
paring stock standard solutions (as well as standards for all other
pesticides tested) were obtained from the Pesticides and Toxic Substances
Effects Laboratory, USEPA, Research Triangle Park, North Carolina, sol-
vents used were pesticide grade benzene (Fisher Scientific) for standard
solutions and extraction of water samples and residues, and pesticide
grade hexane (Matheson, Coleman, and Bell) for extraction of hexylene
glycol samples (from the second stage scrubber). All laboratory glass-
ware (beakers, vials, pipettes, etc.) was washed in Alconox detergent
(Scientific Products) and rinsed with deionized, distilled water and
reagent grade acetone (Fisher Scientific).
121
-------
Standards and Calibration Curves
The solid standards o,pf-DDT, p,p'-DDT, o,p'-DDE, p,p«-DDE, o,p'-
DDD, and p,p'-DDD obtained from USEPA, were used to prepare separate
stock standards of 100 ^g/ml each and appropriate dilutions were made
of each to produce a linear curve (linear range used on each: 0 to
500 pg).
Procedure for Sample Preparation
In all tests involving the 25% EC formulation, the samples collected
in water were extracted with two 5-ml portions each of benzene; 10 ml of
the hexylene glycol samples (second stage scrubber) were extracted with
two 5-ml portions of hexane. Appropriate amounts (1 to 5 p,l) of the ex-
tracted samples and the samples collected in benzene impingers were in-
jected into the gas chromatograph.
The mass of collected particulate was determined for all samples
collected from incineration of DDT dust (Runs A through H) as follows:
samples were taken to dryness in clean, dessicated, tared 250-ml beak-
ers and dessicated 2 days before final weighing. The residues were ex-
tracted with benzene (10 or 20 ml depending on amount of residue) and
appropriate portions of these extracts were injected for analysis. The
silica gel impinger was extracted with known volume of benzene to cover
the solid and a portion of the extract was analyzed. Benzene blanks
were analyzed directly as they came from the field. A portion of water
blanks was extracted with known volume of benzene and the extract was
analyzed by gas chromatography.
Portions of all the cleanout samples (primary chamber, secondary
chamber, etc.) were weighed out, extracted and the extracts analyzed
for DDT and its isomers.
Analysis and Discussion
All samples were analyzed for DDT, and its isomers. Unidentified
chromatographic peaks were quantitated against the p,p'-DDT calibra-
tion curves. A representative chromatogram for the 25% EC DDT formula-
tion is shown in Figure 20.
The sensitivities of the instrument for DDT and its isomers were:
5 pg for p,p'-DDT, 5 pg for o,p'-DDT, 2 pg for p,p«-DDE, 5 pg for o,pf-
DDE, 10 pg for p,p'-DDD, and 10 pg for o,p'-DDD. Based on these sensi-
tivity values, and with a 5 u.1 sample injection for each analysis, the
122
-------
1 - Unknown
2 - o.p'-DDE
3 - p,p'-DDE
4 - o.p'-DDD
5 - o.p'-DDT
6 - p,p'-DDD
7 -
INJECTION
I
Figure 20. Representative chromatogram of 25% EC DDT formulation
123
-------
minimum detectable values for a 20-ml sample solution were 20 ng for p,p'-
DDT, 20 ng for o,p'-DDT, 8 ng for p,p'-DDE, 20 ng for o,p'DDE, 40 ng for
p,p'-DDD and 40 ng for o,p'-DDD. However, during the analysis, samples
were very often concentrated down to 1 ml, which resulted in minimum
detectable quantities of 1 ng for p,p'-DDT, 1 ng for o,p'-DDT, 0.4 ng
for p,p'-DDE, 1 ng for o,p'-DDE, 2 ng for p,p'DDD, and 2 ng for o,p'-
DDD.
TEST CONDITIONS AND RESULTS
DDT was specified as the first pesticide to be studied. The combus-
tion of DDT, which represents one of the most acute disposal problems,
has been the subject of several research studies. The first experiment,
therefore, was intended not only to provide data on combustion of this
pesticide, but also to provide a means for relating our findings to those
from other research programs.
There are a number of factors that can influence the operation of an
incinerator. These include pesticide injection rate, operating temperature,
air flow rate, turbulence, auxiliary fuel rate, and retention time. The
interaction of many of these factors, however, is such that they cannot
all be independently varied. Pesticide injection rate, excess air rate,
operating temperature, and turbulence were selected as the variables to
be independently varied during the DDT experiments. Retention time and
supplemental fuel rate, therefore, were dependent (concomitant) variables.
A modified fractional factorial experiment was designed to study
the combustion of liquid (25% EC) formulation. The four controlled vari-
ables (each at two levels) were run in 16 combinations (see Table 23).
Pesticide Injection Rate
The 25% EC formulation was initially injected at a nominal rate of
3.4 kg (7.5 Ib) DDT per hour. The second level of DDT injection was one-
half of the initial rate. A standard fuel oil burner was used as the
pesticide injection system.
Excess Air
Air was injected at approximately 50 and 150% excess, calculated
according to Method 3 of "Standards of Performance for New Stationary
Sources," Federal Register, 36(247):24876-24895, 23 December 1971.
124
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Table 23. FACTORIAL DESIGN FOR 25% DDT EC EXPERIMENT
Experiment
Designation
A
B
C
D
E
F
G
H
I
J
K
L
M
N
0
P
Turbulence
a
a
a
a
a
a
a
a
b
b
b
b
b
b
b
b
Pesticide
Injection
Rate
c
c
c
c
d
d
d
d
c
c
c
c
d
d
d
d
Operating
Temperature
e
e
f
f
e
e
f
f
e
e
f
f
e
e
f
f
Excess
Air
Rate
g
h
g
h
g
h
g
h
g
h
g
h
g
h
g
h
a - frontal configuration
b - side configuration
c - 1.70 kg (3.75 lb) DDT per hour
d - 3.4 kg (7.5 lb) DDT per hour
e - 950°C (1750°F)
f - 1090°C (2000°F)
g - 507,
h - 1507.
125
-------
Temperature
The incinerator temperature was to be varied from approximately
950°C (1750°F) to 1090°C (2000°F), i.e., the nominal operating range
of the experimental incinerator with the available fuel oil burner. The
temperature was obtained by injecting the desired amount of DDT (in the
EC formulation) mixed with the appropriate amount of supplemental fuel
(No. 2 fuel oil).
Turbulence
Turbulence within the ignition chamber is influenced by the lo-
cation and orientation of the supplemental fuel and pesticide injector
as well as by any internal baffling. Two levels of "turbulence" were
studied by injecting the EC formulation through the fuel oil burner in
the front (primary) and in the side (alternate) position of the pri-
mary combustion chamber (see Figure 1, p. 21).
A total of 21 tests were conducted to fit the 16 points of a modi-
fied fractional factorial analysis of the parameters (combustion chamber
turbulence, rate of operation, operating temperature, and excess air
rate).
Results of these tests are summarized in Tables 24 through 27. The
incineration efficiencies given in Table 25 are those for the incinerator
portion of the pilot scale system only, i.e., DDT discharged from the
incinerator stack (Sample Point No. (5) ), versus DDT charged into the
incinerator (Sample Point No. (I) , Figure 5, p.27). Samples from Sample
Point No. (3) (solid residue in the combustion chambers) do not enter
into the efficiency calculations because no solid residue was generated
by the liquid formulations.
Two efficiencies were calculated in order to better evaluate the
completeness of combustion. The first, shown in the next to last column
of Table 25, is based only on the four major constituents of technical
"DDT," which for purposes of this report, have been defined as DDT, i.e.,
p,p'-DDT, o,p'-DDT, p,p'-DDE, o,p'-DDE. The second efficiency includes
not only these four constituents but also all "other" species collected
in the respective samples. This "other" category includes various chlor-
inated hydrocarbons having a lower molecular weight and higher volatility
than p,p'-DDT, including p,p'-DDD and o,p'-DDD.
The data in Table 24 clearly show that we were not able to operate
the incinerator at the desired levels for each independent variable.
For this reason, the data could not be strictly evaluated as representing
a fractional-factorial experiment.
126
-------
Table 24. SUMMARY OF 25% DDT EC EXPERIMENTS
designation
b/
c/
d/
J/
fl
A
B
C
D
E
F
G
H
I
J
K
L
M
N
0
P
Nominal Total
i/hr (cal/hr) X/hr (gal/hr) K/hr (Ib/tir)1"^ x/hr (gol/hr)1^'
11.3 (3.0) 9.39 (2.48) 1,090 (2.42)
13.2 (3.5) 15.59 (4.12) 1,910 (4.23)
13.2 (3.5) 15.44 (4.08) 1,950 (4.27)
13.2 (3.5) 11.66 (3.08) 1,770 (3.88)
24.6 (6.5) 24.07 (6.36) 1,630 (3.59)
11.3 (3.0) 9.39 (2.48) 1,320 (2.90)
18.9 (5.0) 20.36 (5.38) 4,630 (10.25)
13.2 (3.5) 13.32 (3.52) 2,400 (5.29)
24.6 (6.5) 23.88 (6.31) 2,400 (5.34)
11.3 (3.0) 9.73 (2.57) 1,450 (3.16)
11.3 (3.0) 9.92 (2.62) 1,220 (2.74)
11.3 (3.0) 9.16 (2.42) 1,130 (2.53)
13.2 (3.5) 15.67 (4.14) 1,450 (3.21)
13.2 (3.5) 14.76 (3.90) 1,500 (3.34)
18.9 (5.0) 14.15 (3.74) 500 (1.09)
18.9 (5.0) 16.43 (4.34) 730 (1.62)
11.3 (3.0) 9.54 (2.52) 1,860 (4.11)
11.3 (3.0) 9.73 (2.57) 1,810 (3.96)
13.2 (3.5) 13.59 (3.59) 3,220 (7.08)
13.2 (3.5) 14.12 (3.73) 3,360 (7.36)
18.9 (5.0) 19.42 (5.13) 1,810 (4.03)
Actual DDT content of the incinerator feed.
Volume of ~ 257. EC formulation in the fuel oil-pesticide
1 • Front
burner location; 2 » side burner location.
4.47 (1.18)
7.91 (2.09)
7.99 (2.11)
7.23 (1.91)
6.70 (1.77)
5.41 (1.43)
20.36 (5.38)
9.88 (2.61)
9.95 (2.63)
5.90 (1.56)
5.11 (1.35)
4.73 (1.25)
5.98 (1.58)
6.24 (1.65)
2.04 (0.54)
3.03 (0.80)
9.54 (2.52)
9.73 (2.57)
13.59 (3.59)
14.12 (3.73)
7.53 (1.99)
mixture.
No. 2 fuel
llhr (gal/hr)
4.92 (1.30)
7.68 (2.03)
7.46 (1.97)
4.43 (1.17)
17.37 (4.59)
3.97 (1.05)
-0-
3.44 (0.91)
13.93 (3.68)
3.82 (I. 01)
4.81 (1.27)
4.43 (1.17)
9.69 (2.56)
8.52 (2.25)
12.11 (3.20)
13.40 (3.54)
-0-
-0-
-0-
-0-
11.88 (3.14)
Calculated according to Method 3 of "Standards of Performance for New Stationary Sources,"
Retention
volume
time is defined as ^ , where v is the wet ofC-gas flow rate from
of that chamber.
Primary
c hambe r
lenceE/ °C (°F)
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
Federal
the incinerator at the
1040 (1900)
940 (1730)
1140 (2090)
1170 (2130)
1040 (1900)
1050 (1930)
930 (1700)
1150 (2110)
1050 (1920)
1070 (1950)
980 (1800)
980 (1800)
1170 (2140)
1050 (1930)
1100 (2010)
1090 (2000)
1030 (1890)
940 (1730)
1190 (2180)
1030 (1890)
1050 (1930)
Register, 36(247):
Retention time
Excess seel/ Sampling Off-eas
7, chamber chamber
92
162
88
100
120
8S
143
116
135
83
138
128
64
151
137
163
96
166
80
164
130
; 24876-24895,
2.5
1.3
1.6
1.5
0.9
2.4
1.0
2.2
0.9
2.9
3.1
2.5
1.4
1.4
1.6
1.3
1.5
3.0
1.7
1.3
1.5
2.7
1.2
1.8
1.6
0.7
2.4
0.8
2.3
0.7
3.0
3.2
2.9
1.4
1.3
1.4
1.3
1.6
3.1
1.6
1.2
1.3
LI.UJV LI^W caL.e,jL' ur~/nc
min (1,000's of SCFH)
30
28
30
30
30
30
30
32.5
30
30
30
30
30
31
30
30
30
30
30
30
30
218 (7.7)
419 (14.8)
326 (11.5)
343 (12.1)
643 (22.7)
229 (8.1)
663 (23.4)
218 (7.7)
648 (22.9)
193 (6.8)
190 (6.7)
187 (6.6)
351 (12.4)
425 (15.0)
368 (13.0)
405 (14.3)
371 (13.1)
201 (7.1)
275 (9.7)
442 (15.6)
394 (13.9)
23 December 1971.
respective chamber temperature and
pressure, and
V is the
-------
Table 25. INCINERATION EFFICIENCY--257. DDT EC FORMULATION
00
Experiment
designation
A
B
C
D
E
F
G
H
I
J
K
L
M
M
0
P
DDT
feed rate*'
g/hr
1,090
1,910
1,950
1,770
1,630
1,320
4,630
2,400
2,400
1,450
1,220
1,130
1,450
1,500
500
730
1,860
1,810
3,220
3,360
1,810
DDT
content of
off-gas
B/hr
5 x IO"3
3.4 x 10"2
1.0 x 10"2
1.5 x IO"2
1.7 x 10- x
7 x 10"3
2.3 x 10"1
7 x 10"2
9 x IO"2
4 x 10"2
8 x ID"2
1.3 x 10"2
5 x ID"2
6 x IO"2
2.6 x 10"2
3.6 x ID'2
6 x ID"2
8 x 10"2
2.1 x lO"2
8 x 10"2
5 x ID"2
£/ Actual DDT content of the incinerator feed.
b_/ DDT plus all other chlorinated hydrocarbon sj
c/ Efficiency is
defined as
1 quantity out i
Ratio of DDT
in off-gas
to DDT fed
5 x
1.8 x
4.9 x
9 x
1.1 x
5 x
5 x
2.8 x
4 x
2.8 x
6 x
1.2 x
3.5 x
3.8 x
5 x
5 x
3.4 x
4.4 x
7 x
2.4 x
3.0 x
io-6
10-5
10"6
io-6
io-4
io-6
10-5
ID"5
ID'5
10-5
10-5
ID'5
10-5
10"5
lO-5
10-5
10-5
10-5
io-6
ID'5
ID'5
Ratio of
Total species^ total species^'
content of content of
off-gas
g/hr
3.2 x ID'2
5 x 10"2
2.5 x IO"2
3.8 x 10"2
2.9 x 10"1
3.9 x IO"2
2.5 x IO"1
1.7 x IO"1
1.2 x IO"1
9 x 10'2
1.7 x 10"1
2.6 x 10"2
1.3 x 10"1
1.8 x IO"1
3.0 x 10"2
4.1 x 10"2
1.8 x 10"1
3.0 x 10' x
6 x 10"2
9 x 10"2
9 x IO"2
Incinerator efficiency^'
off-gas to
2
2
1
2
1
3
5
7
5
6
1
2
9
1
6
6
9
1
1
2
4
DDT fed
.9 x ID'5
.7 x ID"5
.2 x 10"5
.1 x ID"5
.7 x 10"4
.0 x ID"5
x 10"5
x lO"5
x ID'5
x ID"5
.4 x 10"4
.3 x ID"5
x ID"5
.2 x 10"4
x 10-5
x ID'5
.6 x 10'4
.8 x 10"5
.6 x 10"5
.9 x ID"5
DDT
•> 99
5. 99
* 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
•> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
.99
.99
.99
.99
.98
.99
.99
.99
.99
.99
.99
.99
.99
.99
.99
.99
.99
.99
.99
.99
.99
7.
Total species-'
•> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
.99
.99
.99
.99
.98
.99
.99
.99
.99
.99
.98
.99
.99
.98
.99
.99
.99
.98
.99
.99
.99
jecies detected.
x 100.
where the a
uantltv out is
evaluated
at Samole
Point No. (2
) fth
e effluent EI
as).
L quantity in J
and the quantity in is evaluated at Sample Point No.Q) (the incinerator feed). Efficiencies have been calculated based on (a)
DDT only, and (b) the total chlorinated hydrocarbons detected at Sample Point No.(2).
-------
Table 26. OFF-GAS COMPOSITION--25% DDT EC LIQUID INCINERATION^/
Total hydrocarbons analyzer
Experiment
designation
A
B
C
D
E
F
G
H
I
J
K
L
M
N
0
P
DDT
mK/m3
2.4 x 10"2
8.1 x 10"2
3.0 x 10'2
4.5 x 10"2
2.7 x 10"1
2.9 x 10"2
3.5 x 10"1
3.0 x 10'1
1.4 x 10" x
2.1 x 10"1
4.1 x 10- 1
7.0 x 10'2
1.4 x 10"1
1.4 x 10"1
7.2 x 10"2
8.9 x 10"2
1.7 x 10"1
4.1 x 10"1
7.8 x 10"2
1.8 x 10"1
1.3 x 10"1
Total
species]!/
mg/m3
1.4 x 10"1
1.3 x 10" l
7.7 x 10"2
1.1 x 10" l
4.5 x 10" 1
1.7 x 10"1
3.8 x 10" l
7.6 x 10"1
1.9 x 10"1
4.7 x 10"1
8.8 x 10"1
1.4 x 10" l
3.8 x 10"1
4.2 x 10"1
8.2 x 10'2
9.9 x 10"2
4.7 x 10"1
1.4
2.1 x 10"1
2.0 x 10"1
2.3 x 10" 1
a_/ As dry gas at one atmosphere pressure, and
b/ nnT olua all othpr chlorinated hydrocarbon
S02
mg/in3
180
78
220
110
93
110
31
78
93
170
89
250
180
100
150
330
92
34
50
20
95
21. 1°C
NOX^
mg/m
80
7
ra>dy
ND
9
ND
81
3
110
290
80
6
64
110
80
120
200
56
95
78
20
(70°F).
l detected.
Total
hydrocarbons
ppra
NAe/
NA
NA
NA
66
NA
43
NA
51
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Orsat analyzer
CO
pprc
NA
NA
NA
NA
32
NA
127
NA
18
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
CH,
ppm
NA
NA
NA
NA
42
NA
27
NA
29
NA
NA '
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
°2
vol. 7,
10.3
13.2
10.1
10.7
11.7
9.9
12.6
11.6
12.3
9.8
12.4
12.0
8.5
12.5
12.5
13.2
10.6
13.2
9.5
13.2
12.1
C02
vol. 7.
8.4
6.0
8.5
8.2
7.1
9.0
6.9
7.5
6.7
8.9
6.9
7.1
9.9
6.8
6.4
6.2
8.4
6.2
9.5
6.4
6.9
CO
vol. 7.
0.0
0.0
0.1
0.0
0.0
0.0
0.1
0.2
0.0
0.1
0.0
0.0
0.0
0.0
0.0
0.0
0.1
0.0
0.0
0.0
0.0
Moisture
vol. 7,
4.0
14.6
3.5
3.5
4.0
6.3
0.0
6.8
5.4
3.5
2.5
22.7
5.4
7.0
5.3
9.8
6.8
3.5
13.9
8.6
3.9
c_/ Calculated as
d_/ Not detected.
e_/ No analysis.
-------
Table 27. OPERATIONAL DATA SUMMARY--25% DDT EC EXPERIMENTS
w
o
Run No.
Temperature *C CD
Primary chamber (Thermocouple Ho. (l) )
Primary chamber (Thermocouple No. {^ )
Primary chamber (Thermocouple No. ?3} )
Second chamber (Thermocouple No. ($5 )
Second chamber (Thermocouple No. ^ )
Sample Point No. © (Thermocouple No. ^6)
Pressures
Draft (Manometer No. A ), paacala
(In. H2<>) gauge
Burner operation pressure, paacala (pal)
gauge
Scrubber liquids*/
lat Stage 1^0 scrubber
Volume, I (gal.)
DDT cone., mg/£
K /
Total species cone.,-' mg/Z
2nd Stage hexalene glycol scrubber
Volume, t (gal.)
DDT cone, change, mg/jt
Total species^' cone, change, mg/i
3rd Stage H20 scrubber
Volume, I (gal.)
DDT cone. , mg/£
Total species-/ cone., mg/Z
^L.
1010 (1850)
990 (1820)
1040 (1900)
850 (1570)
570 (1060)
) 330 (620)
17 (0.070)
7.9 x 105 (114)
1230 (325)
3 x 10'3
3 x 10"3
115 (30.3)
ND
ND
1990 (525)
5 x 10-3
5 x 10°
B
900 (1660)
740 (1360)
940 (1730)
850 (1560)
670 (1240)
490 (920)
46 (0.185)
NA£/
990 (262)
3 x lO'3
3 x ID'3
138 (36.4)
3 x 10"2
2.1 x 10"1
1680 (445)
5 x ID'3
5 x ID'3
C
1120 (2050)
wi/
1140 (2090)
950 (1740)
530 (990)
390 (740)
25 (0.100)
NA£/
1150 (304)
ND«'
ND
134 (35.4)
ND
ND
1890 (500)
4 x ID'3
4 x 1C-3
1170 (2130)
NA!/
1170 (2130)
990 (1820)
620 (1150)
470 (880)
26 (0.105)
NA£/
1140 (302)
5 x 10'3
5 x 10
134 (35.4)
6 x 10'2
8 x ID"2
1760 (465)
1 x 10'3
1 x ID'3
D
1000 (1840)
920 (1690)
1040 (1900)
990 (1820)
870 (1590)
650 (1210)
88 (0.355)
NA£/
1030 (273)
3 x ID"3
3 x 10"3
137 (36.1)
5 x ID'3
5 x 10"3
1910 f505)
ND
ND
E
1030 (1890)
1000 (1830)
1050 (1930)
870 (1600)
600 (1120)
390 (740)
10 (0.040)
7.9 x 105 (115)
1300 (343)
1 x ID'3
1 x 10'3
119 (31.4)
ND
ND
1970 (520)
2 x ID'3
2 x 10"3
F
890 (1640)
640 (1190)
930 (1700)
920 (1680)
770 (1420)
590 (1100)
58 (0.235)
7.9 x 105 (115)
1050 (277)
4 x ID"3
4 x 10"3
126 O3.4)
ND
ND
1820 (480)
< 1 x ID'3
< 1 x lO'3
-------
Table 27. (Continued)
Run No.
Temperature °C (°F)
Primary chamber (Thermocouple No. (T,
Primary chamber (Thermocouple No,
Primary chamber (Thermocouple No
Second chamber (Thermocouple No.
Second chamber (Thermocouple No.
Sample Point No.
Pressures
(Thermocouple No.
)
)
)
)
)
p. (1
1140 (2080)
1150 (2100)
1150 (2110)
980 (1800)
640 (1190)
) ) 440 (820)
1000 (1840)
760 (1400)
1050 (1920)
1020 (1860)
880 (1620)
670 (1230)
1030 (1880)
970 (1780)
1070 (1950)
850 (1560)
630 (1170)
330 (620)
950 (1740)
890 (1640)
980 (1800)
810 (1490)
580 (1070)
350 (670)
940 (1730)
890 (1630)
980 (1800)
740 (1360)
420 (790)
290 (560)
1100 (2020)
1030 (1890)
1170 (2140)
980 (1800)
730 (1340)
450 (840)
890 (1630)
700 (1300)
1050 (1930)
800 (1470)
660 (1220)
440 (830)
Draft (Manometer No. /Ti. ), pascals
!_, (in. H20) gauge
W Burner operation pressure, pascals (psi)
1-1 gauge
Scrubber liquids8./
1st Stage H20 scrubber
Volume, l (gal.)
DDT cone., mg/t
Total species cone.,£' mg/X
2nd Stage hexalene glycol scrubber
Volume, I (gal.)
DDT cone, change, mg/i
Total species^' cone, change, mg/jt
3rd Stage H20 scrubber
Volume, l (gal.)
DDT cone., mg/£
Total species!*' cone., mg/£
22 (0.090)
93 (0.375)
15 (0.060)
27 (0.110)
7.4 x 105 (108) NA£/ 7.7 x 105 (112) 7.7 x 105 (112)
12 (0.050) 27 (0.110) 31 (0.125)
7.9 x 105 (115) 7.7 x 105 (112)
1070 (284)
7 x 10-3
7 x ID'3
134 (35.4)
4 x 10'2
1.0 x 10'1
1910 (505)
4 x 10'2
4 x 10'2
1080 (286)
5 x 10-3
5 x ID"3
132 (34.9)
1.0 x KT1
1.0 x KT1
2010 (530)
1 x 10'3
1 x ID"3
1290 (340)
< 1 x ID'3
< 1 x ID'3
121 (31.9)
2.9 x 10- !
3.0 x 10'1
1990 (525)
WS.'
ND
1120 (297)
mS.'
ND
121 (31.9)
1.3 x HT1
1.5 x 10'1
1930 (510)
ND£/
ND
1240 (327)
6 x ID"3
2.0 x 10"2
132 (34.9)
6 x 10"2
1.0 x 10" 1
2010 (530)
6 x ID'3
6 x ID'3
1140 (300)
5 x 10-3
5 x 10"3
123 (32.6)
1.5 x 10'1
2.7 x 10'1
1930 (510)
2 x ID'3
2 x ID"3
1180 (313)
5 x 10-3
6 x ID'3
125 (32.9)
ND£/
ND
2010 (530)
2 x ID'3
2 x ID-3
-------
Table 27. (Concluded)
NJ
Run No.
Temperature *C CD
Primary chamber (Thermocouple No. UJ )
Primary chamber (Thermocouple No. (2} )
Primary chamber (Thermocouple No. J3} )
Second chamber (Thermocouple No. ftY )
Second chamber (Thermocouple No. (5) )
Sample Point No, (5) (Thermocouple No, @
Pressure!
JL
950
800
1100
880
740
» 540
(1750)
(1480)
(2010)
(1620)
(1370)
(1000)
960
840
1090
850
730
540
(1760)
(1540)
(2000)
(1560)
(1350)
(1000)
990
940
1030
820
520
320
(1820)
(1720)
(1890)
( 1500)
(960)
(600)
N
900 (1660)
840 (1550)
940 (1730)
780 (1440)
540 (1000)
340 (640)
0
1100 (2010)
1050 (1920)
1190 (2180)
1000 (1840)
760 (1400)
490 (920)
F
890
750
1030
800
660
440
(1640)
(1380)
(1890)
(1470)
(1220)
(820)
950 (1740)
780 (1440)
1050 (1930)
930 (1700)
770 (1410)
570 (1060)
Draft (Manometer No. ), paacala
(In. HjO) gauge
Burner operation pressure, pascal* (pal)
gauge
Scrubber liquids-^
lit Stage H20 icrubber
Volume, t (gal.)
DDT cone., mg//
Total species cone.,—' mg/jt
2nd Stage hexalene glycol scrubber
Volume, I (gal.)
DDT cone, change, mg/j
Total species^' cone, change, mg/Jt
3rd Stage H20 scrubber
Volume, jt (gal.)
DDT cone., mg/l
Total species]!/ cone., tng/Jt
40 (0.160) 45 (0.180) 15 (0.060) 30 (0.120) 22 (0.090) 36 (0.145) 45 (0.180)
7.6 x 105 (110) 7.6 x 105 (110) 7.6 x 105 (111) 7.7 x 105 (112) 7.9 x 105 (114) 7.6 x VO5 (110) 7.6 x 105 (110)
1190 (315)
3 x 10-3
3 x ID'3
126 (33.4)
1.2 x lO-l
1.6 x ur1
2010 (530)
ND
ND
1160 (307)
7 x 10" 3
4 x 10-2
133 (35.2)
1.4 x 10-1
2.0 x ID'1
2010 (530)
2 x 10"3
6 x 10'3
1200 (316)
ND
128 (33.7)
1 x
1 x
1890 (500)
1 x ID*3
5 x 10'3
1240 (327)
5 x ID'3
1 x 10"2
128 (33.7)
8 x 10"3
5 x 10"2
2020 (535)
I x 10'3
6 x 10" 3
1230 (325)
2 x
2 x
124 (32.7)
3.1
10
5.1 x 10'1
1990 (525)
2 x 10'3
3 x UT3
1290 (340)
3 x 10"3
5 x ID'3
125 (32.9)
2.8 x
4.8 x
1910 (505)
2 x 10"3
4 x 10'4
1140 (300)
5 x 10'3
5 x 10'3
131 (34.7)
5.0 x 10'1
5.8 x 10'1
1930 (510)
1 x
1 x
a/ Scrubber water (Scrubbers Nos. 1 and 3) was used once through, while the hexylene glycol (Scrubber No. 2) was recycled.
for hexylene glycol, therefore, are the concentration changes (Increases) detected during the respective tests.
W DDT plus all other chlorinated hydrocarbon species detected.
c_/ Pressure gauge broken.
d/ Thermocouple not working.
e/ Not detected.
The concentrations reported
-------
Therefore, these data were evaluated using multiple regression analysis,
which is the more appropriate statistical technique in this instance
because of the uniformly high combustion efficiencies observed in our
experiments. Regressions of the four quantitative variables (pesticide
injection rate, retention time, temperature, and excess air) were run
using: (a) the relative amount of DDT not destroyed ("Ratio of DDT in
Off-Gas to Total DDT Fed" column of Table 25); and (b) the relative
amount of chlorinated hydrocarbon species not destroyed ("Ratio of Total
Species Content of Off-Gas to DDT Fed" column of Table 25).
A multiple regression model, such as y.^ =
-------
The results of these multiple regression analyses can be summarized
as follows.
Y! = (DDT in of f-gas)/(DDT fed)
Variable Regression coefficient t -value
Xi = DDT rate - 1.026 not significant
X2 = primary chamber temp. - 0.881 not significant
X3 = excess air percent 0.526 not significant
X, = retention time - 1.48 not significant
F-value for regression = 1.28 (not significant)
Y2 = (Total chlorinated hydrocarbon species in off-gas)/(DDT fed)
X, = DDT rate - 0.900 not significant
X? = primary chamber temp. - 0.653 not significant
X3 = excess air percent 0.498 not significant
XA = retention time 0.206 not significant
F-value for regression = 0.73 (not significant)
Two additional multiple regression models of the same form Y^ =
ffO "*" ffl Xli + * * * were estimated where:
Y = i DDT content of off -gas (g/hr),
Y. = i total species content of off -gas (g/hr),
X = ith DDT feed rate (Ib/hr),
X = i primary chamber temperature ( F),
X = i excess air (7.),
X = i primary chamber retention time (sec).
134
-------
Another variable that is potentially influential is turbulence; turbu-
lence exists only at "levels" 1 and 2. Therefore turbulence is not of a
good form to include as an independent variable in a regression analysis,
and the effects of turbulence on Y^1) and Y^2) were evaluated by the Mann-
Whitney U test.
The original experimental design was a fractional factorial design,
so the two levels of turbulence "see" virtually the same combination of
the other independent variables. Thus the Mann-Whitney U test is a suit-
able technique with which to examine turbulence effects.
Neither the mean Y nor the mean Y was significantly affected
by the turbulence level (Z^1^ = 0.36, Z<2) = 0.50). However, the vari-
ance of Y'1' was affected by turbulence level (Z = 2.35, a < 0.05); i.e.,
DDT content was more erratic at turbulence level 1 than at turbulence
level 2. This influence does not apply to Y^2^ (total species content).
For the response Y' (total chlorinated hydrocarbons species content)
neither the regression as a whole nor any individual term was significant,
i.e., the independent variables do not significantly influence the chlor-
inated hydrocarbons content of the incinerator off -gas.
For the DDT content f Y^M , however, the regression was signifi-
cant (F(4,16) = 5.19), i.e., using a knowledge of the X's does allow one
to predict DDT content of the effluent gas more accurately. The only in-
dependent variable with a significant regression coefficient was X^, the
DDT feed rate (Ib/hr). However, the
-------
Finally, one should point out that the ratio of precision in
when predicted by Xj^ and X^ to precision in Y'^' without knowledge of
X^ or X, is 75%. Thus 75% of the uncertainty in DDT content remains even
after the influences of X]^ and X^ are accounted for.
The DDT efficiencies determined from these experiments are not un-
like those reported in an earlier study by the Defense Research Estab-
lishment of Canada. Their report showed that no more than 0.0002% of the
DDT entering their incinerator remained unbumed.ift' These test results,
reported to the same number of decimal points, indicate < 0.0005% DDT
remained unburned (Experiments A and C, Table 25).
Upon completion of experiments with the 25% DDT EC formulation,
eight tests were made using a 10%* dust formulation. These limited addi-
tional tests were made in order to evaluate the effect of physical form
on the previously established efficiency of DDT combustion.
Turbulence was varied for the dust experiments by injecting the dust
horizontally from two positions. For Configuration 1, both the dust in-
jection nozzle and the fuel oil burner were located in the front burner
position. The dust was injected horizontally at a 30-degree angle to the
fuel oil burner. For Configuration 2, the oil burner was located in the
front (primary) position, while the dust injection nozzle was located
in the side (alternate) position (see Figure 2, p. 22). Thus, the burner
flame and dust stream in Configuration 2 impinged at 90 degrees on a
horizontal plane at the geometric center of the primary chamber.
Data from the eight 107. DDT dust experiments are summarized in
Tables 28 through 32. The efficiency figures reported in the last two
columns of Table 29 are based on the total unburned DDT and total species,**
respectively, found in the effluent gas and the solid residue deposited
on the walls and in the bottom of the incinerator, i.e., the content of
the gas evolved during the 60-min sampling period, plus the appropriate
fraction of the content of the total solid residue recovered from the
system.
The possibility of emissions of dust-containing pesticide from the
stack makes it necessary to determine the stack dust loading for accurate
evaluation. Sampling the incinerator effluent using only the vapor sam-
pling technique that was employed for liquid formulation would not reflect
the pesticide content of dust emitted.
* Actual DDT content of the dust ranged from 5.5 to 6.3%.
** DDT plus all other chlorinated hydrocarbon species detected.
136
-------
Table 28. SUMMARY OF 10% DDT DUST EXPERIMENTS
No. 2 fuel oil rate Pesticide
No.
A
B
C
D
E
F
G
K
Nominal
J/hr (eal/hr)
13.2 (3.5)
13.2 (3.5)
13.2 (3.5)
11.3 (3.0)
13.2 (3.5)
11.3 (3.0)
11.3 (3.0)
11.3 (3.0)
_ 107. Dust
jt/hr (gal/hr) kg/hr (Ib/hr)
NA-' 17.14 (37.8)
NA 16.19 (35.7)
NA 16.69 (36.8)
9.73 (2.57) 16.10 (35.5)
13.25 (3.50) 29.75 (65.6)
9.88 (2.61) 37.91 (83.6)
9.73 (2.57) 37.91 (83.6)
10.48 (2.77) 17.10 (37.7)
feed rato
Contained
DDT Turbu-
1010 (2
950 (2
980 (2
1020 (2
.22) 2
.10) 1
.16) 1
.24) 1
1720 (3.80) 1
2230 (4
2230 (4,
1010 (2.
.91) 1
.91) 1
.22) 2
Primary chamber
temperature "C (°F)
1210 (2210)
1140 (2080)
930 (1710)
1030 (1880)
1010 (1850)
1120 (2050)
1020 (1860)
1030 (1880)
Excess
air-*/ X
79
58
164
84
128
111
156
124
Retention time±/
sec
Primary
chamber
1.4
1.9
1.4
2.4
1.3
2.0
1.6
2.1
Second
chamber
1.4
2.0
1.2
2.5
1.2
2.0
1.6
2.2
Sampling
tine
60
60
60
60
60
50
60
60
Off-gas flow rate-'
n3/hr (1.000's of SCFH)
360
263
462
227
422
283
362
272
(12.7)
(9.3)
(16.3)
(8.0)
(14.9)
(10.0)
(12.8)
(9.6)
a/ Not determined.
b/ Actual DDT content of the „ 107. dust formulation. Concentration of the DDT In this formulation ranged from 5.5 to 6.3%.
£/ 1 " Both fuel oil burner and dust nozzle in front burner position, at a 30-degree angle to one another.
2 • Fuel oil burner in front burner position and dust nozzle inside position at a 90-degree angle to one another.
d_/ Calculated according to Method 3 of "Standards of Performance for New Stationary Sources," Federal Register. 36(247):24876-24895 (23 December 1971).
e/ Retention time is defined as ¥ , where
-------
Table 29. RESIDUE AND OFF-GAS CHARACTERISTICS—107. DDT DUST EXPERIMENTS
u>
oo
Solid residues
Pesticide f«ed rate
Run
Ffli
A
B
C
D
E
T
0
H
Primary
chamber
Second chamber
107, Duit tormilatton Contained DOTS' Total DDT cone . Total specie*!' Total
Xi/hr_ClWhr)
17.14 (37
16.19 (35
16.69 (36
16.10 (35
29.75 (65
37.91 (83
37.91 (83
17.10 (37
DDT content
No,
A
B
r
D
E
P
G
H
I/
—
1
6
9
8
1
?
1
1
Actu
DDT
Eff 1
l/hr
.7 10"2
lO'2
lO'3
io-3
.5 IO"2
.0 10"2
.5 IO"2
,2 10"
.8)
.7)
.8)
.5)
.6)
.6)
.6)
.7)
t/hr Ki/hr (Ib/hr) POT
1,010 5.80
950 5.90
980 3.67
1,020 4.94
1,720 9.34
2,230 13.92
2,230 14.97
1,010 5.58
Total DDT
content of
DDT content of off-gas and
•olid residues aolld residues
e/hr
4.1 x 10"3
4.8 x 10°
4.5 x 10"3
3.7 x 10"3
6 x 10°
6 x 10°
1.6 x 10"2
3.8 x lO"2
R/hr
2.1 x ID'2
6 x IO"2
1.4 x 10"2
l.l x 10"2
2.1 x 10"2
2.6 x IO"2
3.1 x IO"2
5 x IO"2
(12.8) 0.55
(13.0) 0.64
(8.1) 0.60
(10.9) 0.32
(20.6) 0,12
(30.7) 0.18
(33.0) 0.42
(12.3) 5.56
Total species^
content of
off-gas
i/hr
2.3 x IO"2
1.0 x 10" l
1.7 x 10"2
1.0 x 10"Z
1.8 x 1C"2
2.6 x IO"2
2.0 x IO"2
1.7 x 10"2
al DDT content of the ~ 101 dust formulation.
plus all other chlorinated hydrocarbon species detected.
clency Is dtM~-H n. T t - quantity out -| „ ]0n. „(,„„ fhc iiiff-Uv
quantity JLn Is
L
evaluated at
quantity In 1
cone . . pprn
0.69
0.74
0.84
0.44
0.14
0.22
0.47
8.44
Total species^/
content of
•olid residues
K/hr
5 x lO"3
6 x IO-3
6 x 10°
4.6 x IO-3
6 x 10°
7 x 10"3
2.0 x 10"2
6 x ID"2
out Is evaluated at
. ..
Sample Point No. (T) (the Incinerator feed). Efficiencies
ta/hr (Ib/hr)
1.86 (4.1)
1.50 (3.3)
3.17 (7.0)
2.58 (5.7)
4.49 (».»)
3.76 (8.3)
5.17 (11.4)
2.27 (5.0)
Total specie*!'
content of
off-ga» and
•olid reilduel
i/hr
2.8 x 10"2
1.1 x W1
2.3 x IO"2
1.5 x 10"2
2.5 x 10":
3.3 x 10"2
4.0 x IO"2
7 x 10"2
Sample Point* No* .
have been calculated
DOT cone .
ppm
0.46
0.68
0.72
0.83
1.05
0.91
0.19
3.04
Ratio of DDT
in off-ga* to
to total
DDT fed
1.7 x 10'5
6 x lO"5
9 x 10"'
7 x 10"*
9 x lO"6
9 x 10"6
7 x 10"6
1.2 x 10"5
© (the Inclne
based on: (a)
Total ipecU«£'
cone., pptn
0.63
0.80
0.93
0.91
1.13
0.98
2.48
3.59
Ratio of total
species^/ In
off-gas to
total DDT fed
2.3 x 10"5
1.0 x 10'*
1.7 x 10"5
1.0 x IO"5
1.0 x 1C"5
1.2 x 10"5
9 x 10"'
1.7 x 10"5
rator off-gas) and
DDT only; and (b)
Ratio of residues
Primary chamber Total residue*
to
to
second chamber total dust fed
3.2
4.0
1.9
1.9
2.1
3.7
2.9
2.5
0.45
0.46
0.41
0.47
0.47
0.47
0.53
0.46
Incineration efficiency^'
DDT
>99.99
>99.99
>99.99
>99.99
>99.99
>99.99
>99.99
> 99.99
(3) (solid
the total
7.
Total speciesi'
> 99.99
> 99.98
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
residues), and the
chlorinated hydrocarbon
-------
Table 30. OFF-GAS COMPOSITION--10% DDT DUST INCINERATION*/
Total hydrocarbons analyzer
Run
No.
A
B
C
D
E
F
G
H
Total
DDT species)!'
mg/m3
4.7 x ID'2 6
2.2 x 10" 1 3
2.0 x ID"2 3
3.3 x ID"2 4
3.5 x ID'2 4
7.0 x 10" 2 9
4.1 x 10"2 5
4.4 x ID'2 6
mg/m3
.4 x ID"2
.8 x 10'1
.7 x ID'2
.4 x ID'2
.3 x ID"2
.2 x lO"2
.5 x lO"2
.3 x lO"2
Total
hydrocarbons
ppm
NA£/
NA
4
5
12
NA
NA
15
Orsat analyzer
CO
ppm
NA
NA
93
150
13
NA
NA
>47~X
CH4
ppm
NA
NA
5
32
3
NA
NA
26
02
vol. %
9.5
7.9
13.3
9.9
12.0
11.2
13.0
12.1
C02
vol
8
9
5
8
7
7
6
6
. 7.
.6
.8
.8
.4
.0
.6
.2
.6
CO
vol
0
0
0
0
0
0
0
0
. %
.0
.0
.0
.0
.0
.0
.0
.0
Moisture
vol. %
6.6
8.5
6.2
11.9
9.2
7.6
6.1
6.7
a/ As dry gas at one atmosphere pressure, and 21.1°C (70°F).
W DDT plus all other chlorinated hydrocarbon species detected
£/ No analysis.
d/ Analyzer attenuation setting too low.
-------
Table 31. PARTICULATE SAMPLING SUMMARY—10% DDT DUST EXPERIMENTS
Description
Vol. dry-gas - std. cond. , nnP
Percent moisture by vol.
Avg. stack temperature, "C
Stk. flow rate, dry, std. en., nm3/mtn
Actual stack flow rate, nP/mln
Percent Isokinetic
Percent excess air
Particulates - partial catch
Particulate wt. - partial, mg
Part, load - ptl., std. en., rag/ran3
Part, load - ptl., stk. en., mg/m3
Partic. emis. - partial, kg/hr
Particulates - total catch
Particulate wt. - total, mg
Part, load - ttl., std. en., mg/nnP
Part, load - ttl., std. en. and
127. C02, mg/nm3
Part, load - ttl., std. en., mg/nr
Partic. emis. - total, kg/hr
Percent impinger catch
A
0.511
6.6
468.5
6
16
81.6
76.7
8,681
16,968
6,302
6.10
8,700
17,005
23,700
6,315
6.11
0.21
B
0.413
8.5
385.2
4
11
90.0
58.4
7,948
19,213
7,783
5.06
7,971
19,268
23,600
7,805
5.08
0.29
C
0.757
6.2
480.3
8
21
94.0
165.1
10,638
14,021
5,099
6.49
10,643
14,027
29,000
5,101
6.49
0.04
0
0.427
11.9
343.8
4
9
108.3
83.1
15,393
36,012
15,300
8.14
15,401
36,031
51,000
15,308
8.15
0.05
_.,E
0.733
9.2
493.5
7
20
99.5
127.9
17,666
24,052
8,450
10.18
17,672
24,061
41,000
8,453
10.18
0.03
F
0.474
7.6
381.5
5
11
95.9
111.8
19,085
40,140
16,548
11,41
19,087
40,145
63,000
16,550
11.41
0.01
G
0.624
6.1
369.2
6
14
98.4
158.6
23,063
36,862
15,739
13.34
23,106
36,930
71,000
15,768
13.36
0.18
H
0.490
6.7
360.4
5
10
102.9
129.2
14,873
30,301
13,247
8.23
14,888
30,332
55,000
13,261
8.23
0.10
-------
Table 32. OPERATIONAL DATA SUMMARY—10% DDT DUST EXPERIMENTS
Run No .
Temperature "C ("FJ
Primary chamber (Thermocouple No. (I) )
Primary chamber (Thermocouple No. @ )
Primary chamber (Thermocouple No. {3} )
Second chamber (Thermocouple No. (& )
Second chamber (Thermocouple No. (^ )
Sample Point No. © (Thermocouple No. @ '.
Pressures
Draft (Manometer No. & ), pascals
(In. H20) gauge
gauge
Dust Injection air, pascals (psl) gauge
1180
1210
1210
1060
730
) 490
39
NA
6 x
&_
(2160)
(2210)
(2210)
(1940)
(1340)
(920)
(0.155)
»/
104 (9)
1090
1100
1140
950
640
400
22
7.4
6 x
B_
(2000)
(2020)
(2080)
(1740)
(1180)
(760)
(0.090)
x 105 (108)
104 (9)
880
600
930
860
700
520
52
7.4
6 x
C_
(1620)
(1120)
(1710)
(1580)
(1290)
(960)
(0.210)
x 105 (108)
104 (9)
1
990
1020
1030
850
580
350
12
7.7
6 x
D_
(1820)
(1870)
(1880)
(1560)
(1070)
(670)
(0.050)
x 105 (112)
104 (9)
E
980 (1800)
860 (1580)
1010 (1850)
920 (1680)
740 (1360)
530 (980)
46 (0.185)
NA2'
9 x 104 (13)
1050
1070
1120
940
530
400
32
7.4
1 x
F_
(1930)
(1950)
(2050)
(1720)
(980)
(760)
(0.130)
x 105 (108)
105 (14)
940
980
1020
870
510
380
42
7.5
1 x
2_
(1730)
(1800)
(1860)
(1600)
(950)
(720)
(0.170)
x 105 (109)
105 (15)
H
930 (1710)
920 (1690)
1030 (1880)
860 (1580;
520 (960)
360 (680)
19 (0.075)
7.5 x 105 (109)
6 x 104 (9)
£/ Pressure gauge broken.
-------
It was therefore decided that the most accurate evaluation would be
obtained by utilizing Method 5 of "Standard Performance for New Stationary
Sources," as published in the Federal Register, 3&(247):24876-24895,
23 December 1971, to determine the particulate loading in the stack. This
technique, specified by EPA for use in such determinations, will give
the total dust (particulate) discharged from the incinerator stack. The
particulate sample, after collection, can then be analyzed for residual
pesticide content.
Two modifications were made to facilitate the analysis of the sam-
ple for DDT content. First, pesticide grade benzene was used in the im-
pingers rather than water. The second modification was to add a liquid
nitrogen cold trap to the sample train in order to collect condensibles
for DDT analysis. After particulate analysis had been completed, all
samples were analyzed for DDT content (see Section IV and Appendix C
of this report for a detailed description of the sampling method).
The total residual DDT was determined by the sum of: (a) the ap-
propriate fraction of the DDT contained in the residue remaining in the
incinerator, based on the ratio of sampling period to total pesticide
injection period; (b) the pesticide content and particulate loading of
the stack; and (c) the pesticide in the vapor form in the stack.
A summary of the particulate loading results obtained in the eight
tests is shown in Table 31. Line 6 of this table reports the value for
percent isokinetic. This value reflects the degree of isokinetic sampling
that was maintained during the test. Method 5 requires, for compliance
testing, maintaining percent isokinetic within 90 to 110. These limits
were maintained during the tests in all except Run A. We can, there-
fore, state that we obtained a representative sample of the particu-
lates in all but Run A. In Run A, since the value was less than 100%,
the sampling velocity was less than isokinetic, and a larger fraction
of the smaller particles was sampled. This would make the indicated
particle loading value somewhat lower than the true value.
The other values of particular importance to the program are lines
14 and 16, Particle Load-Total at standard condition (dry gas at one
atmosphere pressure, and 21.1°C (70°F)) and Particle Emission Total. The
particle loading is reported in mg/ra3. This value, according to Title 40,
CFR, (Part 60, Subpart 60.50), must not exceed 183 mg/m3 on a new facil-
ity wity a capacity * 4.5 x 104 kg/day (50 tons/day). This indicates that
an incinerator, if required to meet federal regulations while combust-
ing dust-pesticide formulation, would probably require emission control.
142
-------
The particle emission-total reports emission in kg/hr. The measure
is sometimes used in control regulations, but does not reflect the size
of the operating unit. A small unit could have a relatively high particle
density and still meet this type of emission criteria.
The only other data of direct importance are shown in the last line,
Percent Impinger Catch. The impinger catch consists of particles which
pass through the sample filter (less than 0.8 u.) and organic vapors col-
lected in the impinger solvent. The impinger catch data for the 10% DDT
dust experiment indicate that only a small fraction of the total discharge
consists of organic volatiles and very fine particulates.
DISCUSSION
Significant corrosion was noted during the system cleanup, primarily
in the first water scrubber (see Figure 1, p. 21). Both the conical re-
ducer nozzle, (12 in.) diameter to (6 in.) diameter, and the demister
pad (constructed of 304 stainless steel) had been almost entirely corroded
out. Corrosion was also noted on the tank section of the first scrubber.
Both the reducer nozzle and the tank section of this scrubber were re-
placed. Corrosion was also noted on the vertical piping leading down
to the first water scrubber as well as to the two water nozzles in this
section of pipe.
143
-------
References
1. Lawless, E. W., R. von Rumker, and T. L. Ferguson, "The Pollution
Potential in Pesticide Manufacturing," EPA Contract No. 68-01-0042
(June 1972).
2. von Riimker, R., and F. Horay, Pesticide Manual, Contract No. AID/csd
3296, Agency for International Development, U.S. Department of State
(September 1972).
3. Zeidler, 0., Ber., Ti1180 (1874).
4. Wain, R. L., and A. E. Martin, Analyst, 72.:! (1947).
5. Lord, K. A., J. Chem. Soc., 1657 (1948).
6. Fleck, E. E., Ind. Eng. Chem., 40:706 (1948).
7. Beilstein's Handbuch der Organischen Chemie, 4th ed., E III 5, Syst.
No. 479 (p. 1833), and Syst. No. 480 (p. 1981), Springer, Berlin.
8. Leigh, G., "Degradation of Selected Chlorinated Hydrocarbon Insecti-
cides," i_WPC_F> 41:R450 (1969).
9. Putnam, R. C., F. Ellison, R. Protzmann, and J. Hilovsky, "Organic
Pesticides and Pesticide Containers—A Study of Their Decontami-
nation and Combustion," Foster D. Small, Inc., Final Report on
Contract No. CPE 69-140 (1971).
10. Whaley, H., G. K. Lee, R. K. Jeffrey, and E. R. Mitchell, "Thermal
Destruction of DDT in an Oil Carrier," Can. Mines Br., Res. Rep.,
R225 (1970).
11. Montgomery, W. L., B. G. Cameron, and R. S. Weaver, "The Thermal
Destructor," Report No. 270, Defence Research Establishment Suffield,
Ralston, Alberta (Canada) (October 1971).
12. Lee, G. K., F. D. Friedrich, B. C. Post, and H. Whaley, "Thermal
Destruction of DDT-Bearing Powders," Can. Mines Br., Res. Rep.,
R234 (1971).
13. Kennedy, M. V., B. J. Stojanovic, and F. L. Shuman, Jr., "Chemical
and Thermal Methods for Disposal of Pesticides," Res. Rev., 29:89
(1969).
14. Games, R. A., EPA/NERC-SHWRL, Personal communication to Mr. T. L.
Ferguson (January 30, 1974).
144
-------
II. ALDRIN
PESTICIDE DESCRIPTION
Physical Properties
Chemical Name; 1,2,3,4,10,10-Hexachloro-1,4,4a,5,8,8a-hexahydro-
l,4-endoexo-5,6-dimethanonaphthalene; hexachloro-
hexahydro-endo,exo-dimethanonaphthalene; HHDN
Common Name; Aldrin (technical material containing not less than
95% of HHDN)
Trade Names; Aldrosol®, Aldrite®, Drinox®, Octalene®, Seedrin®
Pesticide Class; Broad spectrum insecticide; chlorinated hydro-
carbon
Cl
Structural Formula:
Cl
Empirical Formula; CioHoCl
Molecular Weight; 364.93
Physical State; Solid (at 25°C)
Solubility in;
Water at 20°C: 11 ppb
Organic Solvents: At 25°C moderately soluble in paraffins,
aromatics, halogenated solvents, esters
and ketones; sparingly soluble in alco-
hols.
Lipids, Fats: Soluble
Melting Point; Setting range 54 to 66°C (130 to 150°F)
Boiling Point; 34°C at 1 x 10"5 mm Hg
Vapor Pressure; 6 x 10~6 mm Hg at 25°C
Flammability; Not flammable
145
-------
Stability; Slowly forms hydrochloric acid on storage and may,
therefore, be corrosive to metal containers. Stable
to heat, alkali and dilute acids; reacts with acid
oxidizing agents, strong acids, phenols and active
metals.
Chemical Properties
Aldrin is reported to be"very stable thermally with no decomposi-
tion noted at 250°C.J;/ Aldrin (along with the structurally related
compounds dieldrin and isodrin) is stable to alkali (in contrast to
chlordane and heptachlor)—' and refluxing with aqueous or alcoholic
caustic has no effect.]J
Incineration has been recommended by the MCA Manual—' for aldrin
disposal. Putnam et al.ft/ found that combustion of aldrin in polyethylene
on a small scale gave more than 99% decomposition. Differential scanning
calorimetry (DSC) analysis of aldrin by Putnam et al. indicated minor
decomposition (based on exothermic peaks) over the range of 343 to
354° C and major decomposition from 383 to 403°C in a closed system
(i.e., a sealed sample). In an open system, very small evidence of
exothermic decomposition was detected over the range of 293 to 297°C.
Production and Use
Aldrin has been one of the most widely used soil insecticides.
However, its use is currently the subject of litigation, and aldrin
is not currently being produced in the United States. Estimated 1972
domestic production of aldrin was 13 million pounds (von Rumker et al.—.')«
Commercial formulations that have been available include: emulsi-
fiable concentrates (44.2% = 4 Ib/gal); wettable powder (25%), granules
(20%), dusts and dust concentrates, seed dressings, fertilizer mix-
tures, and oil solutions.
FORMULATIONS TESTED
Two aldrin formulations were tested, a 4 Ib/gal EC, and a 20%
granule.
4 Ib/gal EC
Name; Shell Aldrite®4
Manufacturer; Shell Chemical Company, Agricultural Chemicals
Division, New York, New York
146
-------
Composition; Active ingredient (by weight)
Aldrin 43.4%*
Petroleum hydrocarbons 50.6%
Inert ingredients (by weight) 6.0%
Total 100.0%
* Equivalent to 41.2% aldrin plus 2.2% related
compounds.
Registration; EPA Reg. No. 201-245-AA
Lot No.; 3-RCA-4306, 3-RCA-4319
20% Granules
Name; Shell Aldrin 20G
Manufacturer; Shell Chemical Company, Agricultural Chemicals
Division, New York, New York
Composition; Active ingredient (by weight)
Aldrin 20.0%*
Inert ingredients 80.0%'
Total 100.0%
* Equivalent to 19.0% aldrin and 1.0% related com-
pounds.
Registration; EPA Reg. No. 202-214-AA
Lot No.; H332804, H332805, H332807, and 52-1262
Particle Size Specification; Formulated on 20/40 attapulgite
clay (smaller than 841 u., larger
than 420 u. in size)
147
-------
PRELIMINARY THERMAL ANALYSIS
Bomb calorimetric analyses of aldrin gave the following results:
Samp 1e
41.2% Aldrin
Emulsifiable
Concentrate
19.0% Aldrin
(granular)
Aldrin
(technical grade)
Test Test method
Heat of combustion ASTM D-240
Sulfur
Calorific value
Calorific value
Sulfur
ASTM C-129
Result
3.098 x 10? J/kg
(13,331 Btu/lb)"
0.38%
ASTM D-2015 5.708 x 10 J/kg
(2,456 Btu/lb)
(no sulfur correction)
ASTM D-2015 1.786 x 10? J/kg
(7,684 Btu/lb)
ASTM D-129 0.70%
DTA and TGA were run using a Du Pont Model 900 differential ther-
mal analyzer, and a Perkin-Elmer Model TGS-1 Thermobalance (equipped
with Perkin-Elmer temperature program control UU1), respectively.
Figures 21 and 22 show the results of DTA and TGA of a sample of
recrystallized aldrin obtained by evaporation of a sample of the EC
formulation. The DTA data (Figure 21) on aldrin show two endotherms,
one at 60 to 66°C, and the other at 210 to 250°C. The first endotherm
indicates a phase change (TGA data in Figure 22 show no significant
weight loss at 60 to 70°C). The latter endotherm could very well be
the vaporization of the liquid. Significant weight loss is observed
at this temperature on the TGA data. Beyond 250°C, however, an exo-
thermic process is observed which indicates that the sample is under-
going decomposition. This is substantiated by TGA which shows continued
weight loss up to about 570°C. At this temperature, virtually no sam-
ple remained.
DTA and TGA analyses of the ~ 19% granular formulation of aldrin
are shown in Figures 23 and 24.'The DTA data show that there are two
decomposition processes—one at ~ 175°C and the other at ~ 370°C. This
is substantiated by the TGA which shows continuous weight loss as tem-
perature increases (Figure 24). At about 270°C almost 25% of the original
weight is gone, which corresponds to the nominal 20% aldrin content of
the formulation. As the heating of the formulation continues to 700°C,
another 10% is lost. From 700 to 1000°C there is essentially no weight
loss recorded. Thus, it is probable that the aldrin in this formulation
would be destroyed at 700°C.
148
-------
-I—I—I—I—I—I—I I I I I I I I I
J 1
o »
<0 K 100 HO 140 140 110 200 J» J40 !« no
TEMKUTUK 'C
J20 340 JJO
Reference: Glass beads
Prog, mode: Heat
Rate: 10°C/mln
Start: 28°C
Figure 21. DTA analysis of recrystallized aldrin
-------
I
0.4
0.8
1.2 1.6
WEIGHT LOSS, mg
I
I
I
I
2.0
I
10
20
30
40 50 60
WEIGHT LOSS. PERCENT
Heating rate: 20°C/min
Environment: ~ 20 ml/min air (20% 02, 807. N2)
70
80
90
Figure 22. TGA analysis of recrystallized aldrin
2.8
100
150
-------
I I I t I
20 40
t20 MO
200 220
tCMffWTWi 'C
MO MO 340 MO 400
Reference: Glass beads
Frog, mode: Heat
Rate: 100C/min
Start: 40°C
Figure 23. DTA analysis of 197. aldrin granules
-------
10001-
900 -
0.0 0.4 0.8 ).2 1.6 2.0 2.4 2.8
I I
I 1 I I I I
0 5 10 15 20 25 30 35 40 45
WEIGHT LOSS. PERCENT
Sample weight: 6.422 mg
Heating rate: 20°C/min
Environment: ~ 20 ml/min air (20% 02, 80% N2)
Figure 24. TGA analysis of 19% aldrin granules
152
-------
METHODS OF ANALYSIS
Apparatus
A Micro-Tek 2000 R gas chromatograph equipped with a 3-ft, 4 mm
I.D. glass column (packed with 1.5% OV-17 + 1.95% QF-1 on 80/100 mesh
Supelcoport from Supelco, Inc., Bellefonte, Pennsylvania) and a tri-
tium electron capture detector, maintained at a voltage of 15 V DC,
were used for gas chromatographic analysis. Chromatographic operating
conditions were: injector temperatue, 190°C; column temperature, 175°C;
detector temperature, 180°C; carrier flow rate, 80 ml/min, N£; and purge
gas flow rate, 200 ml/min, N2»
A Varian G-2000 strip chart recorder was used to record the chro-
matograms.
Reagents and Materials
The solid standard, aldrin (91% pure) used to prepare standard
solutions. Solvents used were pesticide grade 2,2,4-trimethylpentane
(Matheson, Coleman, Bell) for solution of standards and extraction of
all water-based samples and pesticide grade hexane (Matheson, Coleman,
Bell) for extraction of hexylene glycol traps from the second stage
scrubber. All laboratory glassware was washed in Alconox detergent
(Scientific Products) and rinsed in deionized distilled water and re-
agent grade acetone (Fisher Scientific).
Standards and Calibration Curves
The solid aldrin standard was used to prepare a stock solution of
100 u.g/m.1 and appropriate dilutions were made to produce a linear curve
(linear range used: 0 to 10 pg).
Procedure for Sample Preparation
All samples collected in water from the liquid aldrin formula-
tion tests were extracted with two 5-ml portions of 2,2,4-trimethyl-
pentane. Twenty milliliters of the hexylene glycol samples (from the
second stage scrubber) were extracted with two 5-ml portions of hexane.
Appropriate amounts (1 to 5 u-1) of these extracted samples and the sam-
ples collected in 2,2,4-trimethylpentane were injected into the gas
chromatograph.
The mass of collected particulates was determined for all samples
from incineration of granular aldrin tests as follows. Samples were
taken to dryness in clean, dessicated, tared 250-ml beakers and dessi-
cated 2 days before final weighing. The residues were extracted with
2,2,4-trimethylpentane (10 or 20 ml depending on amount of residue)
and appropriate portions of these extracts were injected for GC analysis.
153
-------
Blank impinger samples were analyzed directly as they came from the
field. The silica gel was extracted with enough 2,2,4-trimethylpentane
to cover the silica gel and a portion analyzed by gas chromatography.
Portions of all solid residues (primary chamber, secondary cham-
ber, etc.) were weighed out, extracted, and the extracts analyzed for
aldrin.
Analysis and Discussion
A chromatogram of the liquid aldrin formulation diluted to 5 x
10-* times in 2,2,4-trimethylpentane showed a total of nine peaks (see
Figure 25). Peaks 7 and 9 are identified as aldrin and dieldrin, re-
spectively, based on relative retention time of standards. Peaks 5, 6,
and 8 were at first thought to be lindane, heptachlor, and heptachlor
epoxide, respectively. However, comparison with the relative retention
time of the standards showed differences of 0.1 min for lindane, 0.1
min for heptachlor, and 0.5 min for heptachlor epoxide. All of these
unidentifiable peaks were termed as unknowns, and their respective
concentration present in each sample collected from the incinerator
system for analyses was calculated based on the aldrin calibration
curve.
The sensitivity of the instrument for aldrin is 1 pg. Based on
this sensitivity, and with a 5 u-1 sample injection for each analysis,
the minimum detectable value for a 20-ml sample solution is 4 ng. How-
ever, during the analysis samples were very often concentrated to 1 ml,
giving a minimum detectable value of < 1 ng.
TEST CONDITIONS AND RESULTS
The experimentation with aldrin, and for all other pesticides
subsequently studied, involved two phases. First, laboratory studies
were made to determine potentially favorable combustion conditions for
each pesticide. Experiments were then conducted in the pilot-scale in-
cinerator to verify the efficiency of combustion in the range of po-
tentially favorable operating conditions.
For each pesticide studied, representative formulations and tech-
nical grade material were obtained. These materials were analyzed by
differential thermal analysis, thermal gravimetric analysis, and bomb
154
-------
Figure 25. Chromatogram of 41.27» aldrin EC formulation
155
-------
calorimetry. These thermal analyses were used to determine the tem-
perature range at which the respective pesticide could be expected to
decompose.
Following this definition, at least eight experiments utilizing
a liquid formulation and four utilizing the solid formulation were
made. For pesticides commercially available in only solid forms, a
minimum of eight tests were conducted using a major solid formulation.
Rate of pesticide incineration, percent excess air, and operating tem-
perature were varied between two nominal values, i.e., a "high" and
"low" level.
Initially, eight tests were made using the EC formulation of
aldrin. The results of these tests (as well as two subsequent tests)
are given in Tables 33 through 36. Efficiency of combustion was again
defined in terms of a mass balance, i.e., aldrin charged into the sys-
tem versus aldrin not destroyed in the incinerator (aldrin out). Ref-
erence to Figure 5, p. 27, will make this definition more evident.
Aldrin in was determined by volumetric measurement and GC analysis of
the mixture charged into the incinerator (Sample Point No. (T) ).
Representative gas samples were collected at Sample Point No. @) (the
undiluted, cooled incinerator effluent), and in combination with a
volumetric determination of the total undiluted incinerator effluent,
yielded the quantity of aldrin (and other chlorinated hydrocarbons)
out. No solid residue (Sample Point No. (V) was generated during the
incineration of the liquid formulation, and, therefore, Sample Point
No. (3) did not enter into the efficiency calculation.
The efficiencies for the eight initial tests were all > 99.99%,
based on either aldrin, or total chlorinated hydrocarbon species de-
tected. However, all of the initial eight tests were made at temperatures
significantly above those indicated (by differential thermal and thermal
gravimetric analyses) as being required for aldrin degradation. This
was due to the operating limit of the available fuel oil burner, which
was designed to burn from 3.0 to 8.0 gal/hr of fuel.
Subsequently, two additional tests (Nos. 9 and 10) were made using
a new fuel oil burner capable of operating at lower feed rates than
the burner previously used. The lower rates enabled us to conduct these
two additional runs at much lower temperatures. Runs 9 and 10, although
conducted at primary chamber temperatures 440 to 500°C (800 to 900°F)
lower than the initial eight runs also showed an efficiency of aldrin
incineration of > 99.99%, based on aldrin or the total chlorinated
species detected.
156
-------
Table 33. SUMMARY OF 41.2% ALDRIN EC EXPERIMENTS
Run
1
2
3
4
5
6
7
8
9
10
W
£/
d/
Nomina i
burner nlze
If\\r (p.al/hr)
13.2 (3.5)
15.1 (4.
15.1 (4.
7.6 (2.
5.7 (I.
5.7 (1
15.1 (4,
13.2 (3.
3.8 (1.
2.8 (0
Volume of ~
.0)
,0)
0)
.5)
.5)
.0)
.5)
.0)
.75)
tnci
Total
feed rote
t/lir (p.al/hr)
12.64
18.70
14.57
5.22
5.49
5.07
13.78
11.77
3.48
2.69
(3.14)
(4.94)
(3.85)
(1.38)
(1.45)
(1.34)
(3.64)
(3.11)
(0.92)
(0.71)
len.l rat
r./lir (In/Mr)-1!'
2,310
3,480
2,470
1,610
1,650
660
2,260
1,350
1,010
620
•ator fee
(5.09)
(7.67)
(5.44)
(3.56)
(3.63)
(1.45)
(4.98)
(2.98)
(2.23)
(1.36)
5.07
7.65
5.41
3.56
3.63
1.44
4.96
2.95
3.48
2.69
No. 1 fuel
«l/hr)i' l/hr (>'.al/hr)
(1.34) 7.57 (2.00)
(2.02) 11.05 (2.97)
(1.43) 9.16 (2.42)
(0.94) 1.66 (0.44)
(0.96) 1.86 (0.49)
(0.38) 3.63 (0.96)
(1.31) 8.82 (2.33)
(0.78) 8.82 (2.33)
(0.92) 0
(0.71) 0
Prlm/iry
chamber Flat**
•c rn •<: CFJ
940 (1730)
1020 (1870)
1020 (1870)
920 (1690)
830 (1530)
850 (1560) 1380 (2510)
1050 (1920) 1400 (2560)
1140 (2080) 1440 (2630)
680 (1250)
600 (1120) 1100 (2020)
Retention tlmep'
Excess
.
209
128
144
230
203
158
149
70
332
380
sec
chamber
2.5
1.9
2.0
4.8
4.3
4.2
1.2
2.2
4.8
6.9
(23 December
chamber
2.3
1.6
1.9
5.1
4.6
4.5
1.2
2.2
5.3
7.6
1971).
Sampll
time
30
30
30
30
30
30
30
30
30
30
Is the v<
Off-gas
ng (lou rate-^'
(1,000's of SCFH)
229
283
252
119
156
159
450
224
153
113
olume of that
(8.1)
(10.0)
(8.9)
(4.2)
(5.5)
(5.6)
(15.9)
(7.9)
(5.4)
(4.0)
chamber.
-------
Table 34. INCINERATION EFFICIENCY—41.2% ALDRIN EC FORMULATION
AMrln Ratio of
Aldrln content aldrln content of Total species^-' Ratio of total Incineration efflcicncy£
Run feed rate-' of off-gas off-yon to content of off-pas species^ content of 7,
a_/ Actual aldrln content of the Incinerator feed.
b/ Aldrln plus all other chlorinated hydrocarbon species detected.
5 1,650 3 x 10 2 x 10 9 x 10 5 x 10 > 99.99 > 99.99
6 660 2 x lo" 3 x 10* 2 x 10 3 x 10" > 99.99 > 99.99
-7
7 2,260 2.4 x 10 1.1 x 10 8 x 10 3 x 10 > 99.99 > 99.99
9 1,010 1 x 10 1 x 10 3 x 10 3 x 10 > 99.99 > 99.99
Ho. R/hr K/lir aldrln fed R/hr off-Kn» to aldrln ted Alilrln Trial s
t 2,310 2.8 x lo"4 1.2 x 10'7 1.3 x 10"2 6 x 10 > 99.99 > 99.99
1 3,480 5 x 10 1.5 x 10-7 3.1 x 10'2 9 x 10 > 99.99 > 99.99
-4 -7 -2 -6
3 2,470 6 x 10 2.4 x 10 1.1 x 10 4.4 x 10 >'99.99 > 99.99
-4 "' •' h
4 1,610 4xrO 2x10 4x10 3x10° > 99.99 > 99.99
-4 -7 -3 -6
8 1,350 2.3 x 10 1.7 x 10 3.5 x 10 2.6 x 10 > 99.99 > 99.99
-7 -
10 620 4 x 10 6 x 10 1 x 10 2 x 10 > 99.99 > 99.99
b/ Aldrln plus all other chlorinated hydrocarbon species detected.
c/ Efficiency la defined as (". quantity out 1 x loo, where the quantity out Is evaluated as Sample Point No. (7) (the effluent gas), and the quantity Iji Is evaluated
L quantity ^n j
at Sample Point No. (?) (the incinerator feed). F.fficlencles have been calculated based on (a) aldrln only, and (b) the total chlorinated hydrocarbon species detected
at Sample Point No. (?) .
-------
Table 35. OFF-GAS COMPOSITION—41.2% ALDRIN EC INCINERATION*/
Total hydrocarbons analyzer
Run
No.
1
2
3
4
5
6
7
8
9
10
Aldrin
mg/m3
1.2 x 10"3
1.8 x 10"3
2.4 x 10"3
3.1 x 10"3
2.0 x 10"3
1.1 x 10"3
5.2 x 10"
1.0 x 10'3
9.0 x 10'3
3.2 x 10'3
Total
. b/
species—'
5.5 x 10"2
1.1 x Uf1
4.5 x 10"2
3.7 x 10'2
5.5 x 10"2
1.3 x 10"z
1.7 x 10"2
1.6 x 10"2
1.8 x 10"1
1.1 x 10'1
S02
ms/m
17
83
140
50
95
100
94
190
27
ND£/
mg/m
69
ND£/
52
64
260
140
ND
ND
ND
ND
Total
hydrocarbons
ppm
9
9
13
9
10
4
9
9
35
52
CO
6
33
8
12
47
28
25
11
204
1,670
CH4
ppm
> S*'
2
2
1
3
2
2
3
9
6
Orsat analyzer
°2
vol. 7.
14.4
12.0
12.7
14.7
14.1
13.1
12.8
8.9
16.3
16.5
C02
vol. 7.
4.9
6.7
6.4
5.1
5.9
6.2
6.2
9.6
3.7
4.6
CO
vol. 7.
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
Mositure
vol. 7,
6.7
12.3
12.4
9.6
3.5
3.5
4.9
7.7
5.6
7.0
*/ As dry gas at one atmosphere pressure, and 21.1"C (70°F).
_b/ Aldrin plus all other chlorinated hydrocarbon species detected.
£/ Not detected.
d/ Calculated as N02.
£/ Analyzer attenuation setting too low.
-------
Table 36. OPERATIONAL DATA SUMMARY--41.27. ALDRIN EC EXPERIMENT
Run No.
Temperature *C (T>
Primary chamber (Thermocouple No. (_D )
Primary chamber (Thcraocouple No. J£ )
Primary chamber (Tlieraocouple No. ^3) )
Second chamber (Thermocouple No. <^y )
Second chamber (Thermocouple No. ,5) )
Sample Point No. (V) (Thermocouple No. ® )
Prffriiureji
Draft (Manometer No. /1\ ), paecale
(tn K20) gauge
(pil) gauge
Scrubber liquid*!'
lit Stage, HjO it rubber
Volume, t (gal-)
Aldrln cone . t m&/l
2nd Stag*, Hexalene glycol pc rubber
Volume, t (gal.)
Aldrln cone, change, mg/4
3rd Stage, H20 scrubber
Volume, I (gal. )
Aldrln cone . , onj/i
Scrubber lyittm
Effluent gat (Sample Point So. (?) )£
Aldrln tone., mg/n.3
Total ipecLes conc.,~ mg/ra
aV Scrubber water (Scrubber* 1 and 3) wai ua«?d
concentration changes (Increaaea) detected
£/ Not detected.
-L
920 (1680)
840 (1560)
910 (1730)
900 (1650)
640 (1.90)
'.80 (900)
45 (0.180)
7.6 x 10^
(110)
1200 (318)
Nt£/
108 (28.6)
m&f
1 1 x 10"2
1850 (490)
NT£/
ND
1 x 10-3
3 x 10-3
once through
2
990 (1810)
760 (1400)
1020 (1870)
990 (1820)
840 (1350)
600 (1120)
50 (0.200)
7.4 x 10^
(108)
950 (250)
ND
114 (30.1)
"*' .3
1950 (515)
ND
NO
ND
1 X lO'2
_L
980 (1800)
930 (1700)
1020 (1870)
970 (1780)
660 (1220)
530 (990)
41 (0.165)
7.4 x 10^
(108)
1070 (284)
ND
114 (30.1)
1 x 10-3
1950 (515)
ND
ND
2 x 10-3
2 x 10'2
, while the hexylene glycol
4
900 (1650)
900 (1660)
920 (1690)
790 (1460)
440 (830)
270 (520)
12 (0.050)
7.6 x 10^
(111)
1050 (277)
ND
2 x 10" 3
108 (28.6)
Nr4 ^
1890 (500)
ND
ND
2 x 10-3
6 x 10-3
(Scrubber 2) waa
_L
820 (1500)
800 (1480)
830 (1530)
690 (1280)
390 (740)
250 (480)
14 (0 055)
8. 1 x 10^
(118)
890 (234)
ND
100 (26.4)
2 x 10-3
2 2 x 10"^
1760 (465)
ND
ND
ND
2 x ID'3
recycled. The
6
830 (1520)
820 (1500)
850 (1560)
710 (1310)
400 (750)
260 (500)
14 (0.055)
8.1 x 10^
(118)
940 (248)
NO
ND
97 (25.6)
I x 10-3
1 x 10"^
1780 (470)
ND
1 x 10"^
ND
2 x 10-3
concentracto
7
1050 (1920)
1020 (1860)
1030 (1920)
970 (1780)
660 (1220)
540 (1000)
47 (0.190)
8.0 x 10^
(116)
1080 (286)
ND
103 (27.1)
I x 10-3
2 1 x 10"2
2020 (535)
ND
ND
ND
6 X ID'3
na reported for
8
1120 (2040)
1090 (1990)
1140 (2080)
960 (1760)
680 (1260)
400 (760)
12 (0.050)
8 0 x 10^
(116)
920 (243)
NO
ND
99 (26.1)
-2
1740 (460)
SD
1 x 10"3
ND
2 x lO'2
hexylene glycol,
9
680 (1250)
620 (1140)
670 (1230)
540 (1000)
260 (500)
170 (330)
17 (0.070)
n
1150 (304)
ND
3 x 10*3
94 (24.8)
1 x 10-3
1890 (500)
ND
>VD
8 x 10'4
3 x 10-3
, therefore.
JO
600 (1120)
540 (1000)
600 (1110)
480 (890)
230 (450)
160 (320)
16 (0.065)
NA
1090 (289)
ND
2 x 10"3
91 (24.1)
1 x 10-3
1 X 10"3
1780 (470)
ND
S'D
2 x 10-3
1 x 10--
are the
during the reapectlve teata.
-------
The relative amount of chlorinated species generated during Runs Nos.
9 and 10 (as shown by the "Ratio of Total Species Content of Off-Gas
to Aldrin Fed" column in Table 34) was significantly higher than that
for the tests conducted at higher temperatures. The relative aldrin
content of the off-gas was also somewhat higher in the last two tests
(see Table 34). Thus, it appears that incineration of aldrin at ~ 650°C
(1200°F) is virtually as efficient as incineration at <~ 1090°C (2000°F)
in terms of actual aldrin content, but is less efficient in terms of
total chlorinated hydrocarbons detected in the incinerator effluent.
A granular formulation of aldrin was used to evaluate the effect
of physical form on the efficiency of aldrin incineration.
The operation and analytical results for the six granule runs are
summarized in Tables 37 through 41. All efficiencies of aldrin incin-
eration are > 99.99%. The relatively high level of aldrin recovered
at Sample Point No. (T) on Run No. B, however, is suspect. Total pesti-
cide recovery from the sample train at Sample Point No. \2J is deter-
mined by summing that found in the probe cyclone, the filter element,
the impinger contents, the impinger rinses, and the cold trap. While
the levels of aldrin found in all other elements of the sample train
were of normal magnitude, the aldrin level on the filter element for
Run No. B was quite high, i.e., 162 times the next highest filter con-
centration. Thus, it is highly probable that the filter element was
contaminated.
Method 5, as published in the Federal Register,!/ was used to de-
termine the particulate loading in the stack at Sampling Point No. {2J
(see Figure 5, p. 27). Two modifications were made to facilitate the
analysis of the sample for aldrin content. First, pesticide grade 2,2,4-
trimethylpentane was used in the impingers rather than water. The second
modification was to add a liquid nitrogen cold trap to the sample train
in order to collect condensibles for aldrin analysis. After particulate
analysis had been completed, all samples were analyzed for aldrin con-
tent.
The total residual aldrin was determined by the sum of: (a) the
appropriate fraction of the aldrin contained in the residue remaining
in the incinerator, based on the ratio of sampling period to total
pesticide injection period; (b) the pesticide content and particulate
loading of the stack; and (c) the aldrin in the vapor form in the stack.
161
-------
Table 37. SUMMARY OF 19% ALDRIN GRANULE EXPERIMENTS
NJ
No. 2 Fuel oil rate
Run
F°t
A
B
C
D
E
F
Nominal
burner size
£/hr (gal/hr)
13.2 (3.5)
7.6 (2.0)
5.7 (1.5)
9.5 (2.5)
11.3 (3.0)
5.7 (1.5)
Actual rate
l/hr (gal/hr)
12.15 (3.21)
9.20 (2.43)
5.83 (1.54)
9.42 (2.49)
11.81 (3.12)
5.83 (1.54)
Pesticide
•• 197. Granule
formulation
kg/hr (Ibytir)
9.98 (22.0)
9.12 (20.1)
19.55 (43.1)
20.09 (44.3)
19.50 (43.0)
9.84 (21.7)
feed rate
Contained
aldrlnl/
g/hr (Ib/hr)
1,860 (4.09)
1,690 (3.73)
3,630 (8.01)
3,740 (8.24)
3,630 (8.00)
1,830 (4.03)
Primary
chamber Flame
temperature temperature^-'
"C
1150
980
890
1030
1100
860
(°F) "C (°F)
(2100)
(1800)
(1630)
(1890)
(2020) 1280 (2330)
(1580) 1280 (2340)
Excess
air
%
48
155
81
120
118
113
Retention time-/
sec
Primary
chamber
2.5
2.2
3.2
2.0
1.4
3.0
Second
chamber
2.7
2.6
3.6
2.2
1.4
3.2
Sampling
time
mln
60
60
60
60
60
60
Off-gas
flow
rate
m3/hr
(1,000's
210
266
198
278
377
215
of SCFH)£/
(7.4)
(9.4)
(7.0)
(9.8)
(13.3)
(7.6)
t_l Aldrln content of the ~ 197. granule formulation, baaed on an average aldrln concentration of 18.77..
b/ The flame temperature was observed at a point ~ 15 cm (6 In.) In from the front wall of the incinerator.
c./ Calculated according to Method 3 of "Standards of Performance for New Stationary Sources," Federal Register, 36(247):24876-24895, 23 December 1971.
if Retention time Is defined as 1L , where v Is the wet off-gas flow rate from the Incinerator at the respective chamber temperature and pressure, and V Is
the volume of that chamber.v
e_/ As dry gas at one atmosphere pressure, and 21.1'C (70*F).
-------
Table 38. RESIDUE AND OFF-GAS CHARACTERISTICS--19% ALDRIN GRANULE EXPERIMENTS
03
Run
No.
A
B
C
D
E
F
Run
No.
A
B
C
D
E
F
• 1
b/
Pestle Id
- 197. Granule
formulation
kg/hr (Ib/hr)
9.98 (22.0)
9.12 (20.1)
19.55 (43.1)
20.09 (44.3)
19.50 (43.0)
9.84 (21.7)
Aldrln
content
Solid residues
Contained
aldrlni' Total
K/hr
1,870
1,700
3,660
3,760
3,650
1,840
Aldrln
content of
of off-gas solid residues
jt/hr
3.9 x 10'4
2.7 x 10"2
8 x 10'4
2.7 x 10'4
1.2 x 10"3
3.5 x 10'5
g/hr
2.8 x 10'3
1.8 x 10'4
1.0 x 10"2
7 x 10'4
1.0 x 10
1.4 x 10'5
kg/hr (Ib/hr)
5.53 (12.2)
5.31 (11.7)
12.15 (26.8)
12.29 (27.1)
11.25 (24.8)
5.99 (13.2)
Total
aldrln
Aldrln Total species*'
cone.
ppm
0.50
0.02
0.80
0.05
N.D4'
N.D.
content of Total species^
off-gas and
solid residues
e/hr
3.2 x 10°
2.7 x 10'2
1.0 x 10'2
9 x 10"*
2.1 x 1CT3
4.9 x 10"5
content of
off-gas
B/hr
3.3 x lO'3
3.4 x 10'2
5 x 10"3
3.6 x 10'3
3.4 x 10"3
1.5 x 10'3
cone .
ppm
0.54
0.02
0.83
0.65
0.05
0.20
Total species^/
content of
solid residues
e/hr
3.1 x 10'3
3.0 x 10"4
1.0 x 10'2
8 x 10"3
1.6 x 10°
1.3 x 10'3
Total
g/hr
190
190
280
330
390
280
Total speclesV
content of
off-gas and
solid residues
l/hr
6 x 10'3
3.4 x 10"2
1.5 x 10'2
1.2 x ID' 2
5 x 10'3
2.8 x 10'3
Aldrln Total species^'
cone .
ppin
0.40
0.40
0.10
0.12
2.50
0.05
Ratio of
aldrln
in off-gas to
to total
aldrln fed
2.1 x 10"7
1.6 x 10'5
2.3 x 10'7
7 x 10'8
3.3 x 10'7
1.9 x 10"8
cone .
ppm
0.40
1.00
0.14
0.13
2.81
0.25
Ratio of
total species^/
In off-gas
to total
aldrln fed
1.8 x 10'6
2.0 x 10'5
1.4 x 10"6
1.0 x 10*6
9 x 10'7
8 x 10'7
Primary chamber Total residue
28.7 0.57
28.5 0.60
43.2 0.64
37.1 0.63
28.9 0.60
21.5 0.64
Incineration efficiency—/
7.
Aldrln Total species^'
99.99 > 99.99
99.99 > 99.99
99.99 -~ 99.99
99.99 > 99.99
99.99 > 99.99
99.99 > 99.99
c/ Efficiency Is defined as T quantltv outl /—\ s~\
~ 1 - —sssfff x 100, where the quantity £ut Is evaluated at Sample Points Hoa. [2J (the Incinerator off-gas) and (3J (solid residues), and the
quantity in Is evaluated at Sample Point No. (^(the Incinerator fetd). Efficiencies have been calculated based on (a) aldrtn only and (b) the total chlorinated hydro-
and (T) .
carbon spec leu detected at Sample Points Nos. (2
d/ Not detected.
-------
Table 39. OFF-GAS COMPOSITION--19% ALDRIN GRANULE INCINERATION^
Total hydrocarbons analyzer
Run
No.
A
B
C
D
E
F
Adrin
2.0 x
1.1 x
4.5 x
1.0 x
Total species—
mg/m3
io-3
io-1
io-3
io-3
3.4 x IO"3
1.7 x
io-4
1.7
1.4
2.7
1.3
9.5
7.3
-2
x 10
x IO"1
x 10
x 10
XIO'3
x 10
Total
hydrocarbons
ppm
187
6
18
28
4
< 1
Orsat analyzer
CO CH4
ppm pptn
2,970 103
249 2
1,490 12
313 3
241 2
13 < 1
°2
vol. 7.
7.1
13.0
9.7
11.6
11.6
11.4
co2
vol. %
10.
6.
8.
7.
7.
7.
2
0
8
3
2
3
CO
vol. 7.
0.0
0.0
0.0
0.0
0.0
0.0
Moisture
vol. 7.
3.0
12.5
7.2
5.9
8.0
4.5
a/ As dry gas at one atmosphere pressure, and Zl.l'C (70'F).
b/ Aldrin plus all other chlorinated hydrocarbon species detected.
-------
Table 40. PARTICULATE SAMPLING SUMMARY—19% ALDRIN GRANULE EXPERIMENTS
Ul
Description
Vol. dry gas - std. cond., nra^
Percent moisture by vol.
Avg. stack temperature, °C
Stk. flow rate, dry, std. en., nm-Vmin
Actual stack flow rate, m3/min
Percent isokinetic
Percent excess air
Particulates - partial catch
Particulate wt. - partial, rag
Part, load - ptl., std. en., mg/nnr
Part, load - ptl., stk. en., mg/nr'
Partic. emis. - partial, kg/hr
Particulates - total catch
0.421
3.0
283.5
3.5
6.9
116.2
48
0.518
8.5
270.8
4.5
9.0
111.1
155
0.395
7.2
206.5
3.3
5.7
114.6
80
0.391
5.9
320.6
4.6
10.0
80.4
119
0.638
8.0
378.9
6.3
15.3
97.4
118
0.576
4.5
242.4
3.6
6.6
98.5
114
635
1,500
760
0.313
310
598
297
0.160
645
1,630
935
0.322
285
727
339
0.203
629
983
404
0.370
417
722
390
0.155
Particulate wt. - total, mg
Part, load - ttl., std. en., mg/nm3
Part, load - ttl., std. en., corrected to
127. CC>2, mg/nm3
Part, load - ttl., stk. en., rag/m-*
Partic. emis. - total, kg/hr
Percent impinger catch
656
1,550
1,830
786
0.323
3.30
368
709
1,420
351
0.189
15.59
712
1,800
2,450
1,030
0.356
9.41
370
946
1,560
441
0.264
23.13
757
1,180
1,970
486
0.445
16.88
487
842
1,380
455
0.181
14.27
-------
Table 41. OPERATIONAL DATA SUMMARY—19% ALDRIN GRANULE EXPERIMENTS
Run No.
Temperature *C (*F)
Primary chamber (Thermocouple No. (T) )
Primary chamber (Thermocouple No. (I) )
primary chamber (Thermocouple No. {5> )
Second chamber (Thermocouple No. (£> )
Second chamber (Thermocouple No. /_?) )
Sample Point No. Q) (Thermocouple Mo. ® )
Pressures
Draft (Manometer No. /fry ), pascals (in H20)
gauge
Burner operation pressure, pascals (p«i)
gauge
Pesticide injection air, pascals (psl) gauge
A
1100 (2020)
1140 (2080)
1150 (2100)
960 (1760)
590 (1100)
340 (650)
12 (0.050)
7.4 x 105 (108)
6 x 10* (9)
_§-
940 (1730)
970 (1780)
980 (1800)
780 (1440)
410 (770)
290 (560)
29 (0.115)
7.6 x 105 (110)
6 x 10* (9)
C
850 (1560)
850 (1560)
890 (1630)
700 (1300)
390 (730)
240 (470)
14 (0.055)
8.1 x 105 (117)
6 x 10* (8)
D
960 (1760)
990 (1820)
1030 (1890)
830 (1520)
520 (960)
340 (650)
37 (0.150)
8.0 x 105 (116)
6 x 10* (9)
JL
1050 (1930)
1100 (2020)
1090 (1990)
920 (1680)
630 (1160)
390 (740)
51 (0.205)
8.0 x 105 (116)
7 x 10* (10)
F
850 (1560)
860 (1580)
860 (1580)
730 (1350)
440 (830)
290 (560)
12 (0.050)
8.1 x 105 (
6 x 10* (9)
-------
Stack velocities are normally higher than those existing in the
pilot-scale incinerator, especially for those tests conducted at low
feed rates. Because the Method 5 train is designed for sampling stacks
with typical velocities, it is difficult to maintain isokinetic sam-
pling.
Runs A, B, and C were sampled at rates higher than isokinetic.
This would increase the proportion of large particles and increase the
grain loading. Run D was lower than isokinetic which would decrease
the large particles and lower the apparent grain loading. Runs E and
F were in the acceptable range and should be representative of the
actual loadings. This is consistent with the grain loading reported in
Table 40. The particle loading is reported in mg/m3 (gr/dscf). The
data indicate that the true grain loading on the system is in the 1,300
to 1,900 mg/nP (0.6 to 0.8 gr/dscf) range and is not affected by the
fuel oil feed rate. Grain loadings in this range are typical of those
normally found in a well operated incinerator without control devices.
These results indicate that an incinerator, if required to meet
federal regulations while combusting this granular aldrin formulation,
would require emission control.
The last item of direct importance to this program is shown in
the last line, Percent Impinger Catch. The impinger catch consists of
particles which pass through the sample filter (less than 0.8 u.) and
organic vapors collected in the impinger solvent. The impinger catch
indicates that a much larger fraction of the total discharge from aldrin
granular incineration consists of organic volatiles and very fine par-
ticulates than from incineration of DDT dust (see Table 41).
Upon completion of the aldrin experiments the interior surfaces
of the incinerator and duck work were inspected for any significant
deposits. Samples were taken of a thin layer of residue that had de-
posited on the walls of the stack from the incinerator and in the
horizontal run of duct leading to the scrubber system. Neither aldrin
nor any of the major components of DDT (p,p'-DDT, o, p'-DDT, p,p'-DDE,
o,p'-DDE, p,p'-DDD, and o,p'-DDD) were detected in these samples.
DISCUSSION
No problems were encountered with the incineration of aldrin. It
should be noted, however, that the solid residue left in the primary
chamber of the incinerator when incinerating the granular formulation
at the higher temperatures became very hard and compacted. In fact,
it had to be chipped out of the incinerator and ground before being
analyzed.
167
-------
References
1. Zweig, G., (ed.)» Analytical Methods for Pesticides, Plant Growth
Regulators, and Food Additives, Vol. II, Insecticides, Vol. Ill,
Fungicides, Nematocides and Soil Fumigants, Rodenticides and
Food and Feed Additives, and Vol. IV, Herbicides, Academic Press,
New York (1964).
2. Riemschneider, R., "The Chemistry of the Insecticides of the Diene
Group," World Review of Pest Control, 4_(29): 29-61 (1963).
3. Manufacturing Chemists Association, Laboratory Waste Disposal
Manual, 2nd ed. (September 1969).
4. Putnam, R. C., F. Ellison, R. Protzmann, and J. Hilovsky, "Organic
Pesticides and Pesticide Containers--A Study of Their Decontami-
nation and Combustion," Foster D. Small, Inc., Final Report on
Contract No. CPE 69-140 (1971).
5. von Rlhnker, R., E. W. Lawless, and A. F. Meiners, "Production,
Distribution, Use and Environmental Impact Potential of Selected
Pesticides," Final Report, Contract No. EQC-311 for Council on
Environmental Quality, Washington, D.C. (1974).
6. Federal Register, 36(247): 24876-24895 (23 December 1971).
168
-------
III. PICLORAM
PESTICIDE DESCRIPTION
Physical Properties
Chemical Name; 4-Amino-3,5,6-trichloropicolinic acid
Common Name; Picloram
Trade Names; Tordon®, 101 Mixture®, Tordon®10K, Tordoi®22K»
Borolin®
Pesticide Class; Systemic herbicide
Structural Formula; NH2
Cl I. Cl
Empirical Formula; C^H-jCl-j^C^
Molecular Weight; 241.5
Melting Point; Decomposes at 215°C
Boiling Point; Decomposes
Vapor Pressure; at 35°C, 6.16 x 10~7 mm Hg
Solubility; ppm at 25°C, water - 430; isopropyl alcohol - 5,500,
acetone - 20,000; xylene - 160; kerosene - 10.
Physical State; Powder
Color; White
Odor; Chlorine like
Stability; Stable
Corrosive Action: Low
169
-------
Chemical Properties—
Incineration at 1000°C for 2 sec is suggested for thermal decom-
position. Alternatively, the free acid can be precipitated from its
solutions by addition of a mineral acid. The concentrated acid can then
be incinerated and the dilute residual solution disposed of in an area
where several years'persistence in the soil can be tolerated.
Production and Use
Picloram is effective against a wide variety of herbaceous weeds
and woody plants, although most grasses are resistant. Estimated 1972
domestic production was 3 million pounds (Lawless et al.—').
Picloram has been available as pellets, as a liquid concentrate,
as well as in combination with 2,4-D and 2,4,5-T.
FORMULATIONS TESTED
Picloram was tested using both liquid and solid formulations: a
21.5% pic loram liquid and a 10% pellet formulation.
21.5% Liquid Formulation
Name; Tordon® 22K Weed Killer
Manufacturer; The Dow Chemical Company, Midland, Michigan
Composition; Active ingredients (by weight)
Picloram (4-amino-3,5,6-trichloropicolinic
acid as the potassium salt 24.9%*
Inert ingredient 75.17.
Total 100.0%
* Acid equivalent 21.5% (2 Ib/gal).
Registration; EPA Reg. No. 464-323-AA
Lot No.; MM 810764
170
-------
10% Pellet formulation
Name; Tordon 10K Pellets
Manufacturer; The Dow Chemical Company, Midland, Michigan
Composition; Active ingredient (by weight)
Picloram (4-amino-3,5,6-trichloropicolinic
acid as the potassium salt) 11.6%*
Inert ingredients 88• 4%
Total 100.0%
* Acid equivalent 10%.
Registration; EPA Reg. No. 464-320-AA
Lot No.; F-12083B, F-12303A, F-10223C
Particle Size Specifications; Extruded on bentonite clay, 4 mm
(5/32 in.) in diameter x 8 mm
(5/16 in.) long
PRELIMINARY THERMAL ANALYSIS
The laboratory thermal analyses of picloram gave the following
results:
Sample Test Test method Result
Picloram Calorific value ASTM D-2015 1.392 x 10 J/kg
(technical (5,990 Btu/lb)
grade) Sulfur ASTM D-129 0.82%
Picloram Calorific value ASTM D-2015 1.120 x 10 J/kg
Pellet t482 Btu/lb)
(10% acid
equivalent)
-------
Differential thermal analysis (DTA) of the picloram pellets showed
one endotherm at about 90°C (see Figure 26). Beyond 90°C, the sample
showed a continuous decomposition process all the way to the instru-
ment operational limit (400°C). This decomposition process was sup-
ported by the weight loss shown by thermal gravimetric analysis (TGA).
The total weight loss up to 400°C was approximately 12%, which corre-
sponds to the ~ 11.6% picloram salt content of the pellets (see Figure
27).
DTA of a sample of recrystallized picloram obtained by the evapora-
tion of the 21.5% potassium salt formulation showed endotherms at 68 to
80°C, and 144 to 154°C (see Figure 28). Once past the second endotherm,
decomposition started and exotherms at 222, 302, and 353°G were observed.
The decomposition process continued to the instrument operational limit
(400°C). A check on the TGA data showed no significant weight loss at
the two endotherm temperature ranges, thus, indicating possible phase
changes. However, from 180 to 360°C, about 60% weight loss was observed.
Weight loss continued from 360 to 500°C and about 800 to 900°C. At 900°C
virtually no sample remained. Therefore, it is very probable that picloram
would be destroyed before 900°C (see Figure 29).
Kennedy et al.!/ also conducted DTA of picloram. The results of
their analyses were as follows:
Endotherms Exotherms
Reference standard 225, 270 and 482°C None reported
11.6% Picloram solution 145, 160, 171, 173 190, 386, 475 and
334, and 355°C 580°C
Sensitivity = 25%.
Based on these and other laboratory analyses, Kennedy et al. concluded
that the temperatures for complete combustion of the picloram reference
standard and solution were 550°C (1022°F) and 640°C (1184°F), re-
spectively.
172
-------
U)
J ( I I I I I 1 1 1 1 1 1 L-
J I I 1 1
0 20 40 00
100 120 140 160
IN 200 220
TEMPERATURE. "C
240 260 210 300 320 340 360 3W 400
Reference: Empty pan
Prog. mode: Heat
Rate: 10°C/min
Start: 28°C
Figure 26. DTA. of picloram pellets.
-------
5
UJ
a.
O.I
0.2
0.3 0.4 0.5
WEIGHT LOSS, mg
0.6
10 15
WEIGHT LOSS. PERCENT
Sample weight: 3.610 mg
Heating rate: 20°C/min
Environment: ~ 20 ml/min air (20% 02, 80% N2)
Figure 27. TGA of picloram pellets.
0.7
0.8
20
174
-------
Ln
J L
J I I I I I 1 I I I I I 1 1 1 L.
10 40 « 80 100 120 140 100 180 200 220 240 260 280 300 320 340 MO UO 400
TEMPERATUHE, *C
Reference: Empty pan
Prog, mode: Heat
Rate: 10°C/min
Start: 30°C
Figure 28. DTA of recrystallized picloram.
-------
1000
950
900
850
800
750
700
650
600
550
500
450
400
350
300
250
200
150
100
50
0.5
1.0
1.5 2.0
WEIGHT LOSS, mg
I L
2.5
3.0
3.5
10
20 30 40 50 60 70
WEIGHT LOSS. PERCENT
80
100
Sample weight: 3.354 mg
Heating rate: 20°C/min
Environment: ~ 20 ml/min air (20% 02, 80% N2)
Figure 29. TGA of recrystallized picloram.
176
-------
ram
METHODS OF ANALYSIS
Apparatus
A Micro-Tek 2000R gas chroma tog raph equipped with a 3-ft, 4 .....
I.D. glass column (packed with 1.5% OV-17 + 1.95% QF-1 on 80/100 mesh
Supelcoport from Supelco, Inc., Bellefonte, Pennsylvania), and a tri-
tium electron capture detector, maintained at a voltage of 15 V DC,
were used for gas chromatographic analysis. Chromatographic operating
conditions were: injector temperature, 225°C; column temperature,
190°C; detector temperature, 180°C; carrier flow rate, 100 ml/min, N2;
and purge flow rate, 200 ml/min, N2.
A Varian G-2000 strip chart recorder was used to record the chro-
matograms.
Reagents and Materials
The picloram standard used was obtained from the Pesticides and
Toxic Substances Effects Laboratory, USEPA, Research Triangle Park,
North Carolina. The solid standard, 4-amino-3,5,6-trichloro-2-picolinic
acid, methyl ester (picloram methyl ester), used for preparing stand-
ards for gas chromatographic analysis was obtained from Dow Chemical
Company, Midland, Michigan. N-methyl-N-nitroso-N1-nitroquanidine used
for preparing diazomethane for methylation of samples was procured
from Pfaltz and Bauer, Flushing, New York. Solvents used were pesti-
cide grade diethyl ether (Fisher Scientific) in preparing diazomethane,
pesticide grade 2,2,4-trimethylpentane (Mallinckrodt) for standard
solutions, pesticide grade hexane (Matheson, Coleman, Bell) for ex-
traction of hexylene glycol traps from the second stage scrubber, and
pesticide grade benzene (Fisher Scientific) for all samples after
methylation.
Diazomethane, used for methylation of picloram, was prepared in
the following manner: 2.3 g of analytical reagent grade potassium hy-
droxide (Fisher Scientific) was dissolved in 2.3 g deionized distilled
water and added to 25 ml of ether, 1.5 g of N-methyl-N-nitroso-N1-
nitroguanidine (ether washed) was added very slowly to the KOH-ether
in an Erlennmeyer flask. The guanidine went through the ether layer
and dissolved in the KOH layer, releasing diazomethane into the ether.
The ether layer was carefully decanted and saved and the KOH layer
properly disposed. (Note: Diazomethane and N-methyl-N-nitroso-N'-
nitroguanidine are carcinogenic and explosive; due care was and must
be exercised.)
177
-------
Standards and Calibration Curve
The solid standards, picloram methyl ester, obtained from Dow
Chemical Company, was used to prepare stock standard of 100 p,g/ml and
appropriate dilutions were made to produce a linear curve (linear range
used: 0 to 100 pg).
Procedure for Sample Preparation
All samples from liquid formulation tests, excluding the hexylene
glycol samples from the second stage scrubber, were taken just to dry-
ness. One milliliter of diazomethane was added to each dried sample and
allowed to sit uncovered (in a hood) for at least 2 hr, so the ether
could evaporate, and then capped. Ten milliliters of the hexylene glycol
samples were extracted with hexane, the extract was dried, and methylated
as above.
The mass of collected particulate was determined for all samples
collected from incineration of picloram pellets as follows. Samples
were taken to dryness in clean, dessicated, tared 250-ml beakers and
dessicated 2 days before final weighing. The residue was extracted and
the extract was taken just to dryness and methylated. Twenty milli-
liters of each of the blank solutions were pipetted into a vial, taken
to dryness and methylated. The silica gel impinger was extracted with
reagent grade 2-propanol (Fisher Scientific); 10 ml of this extract was
taken to dryness and methylated.
All samples were taken up in 5 ml of benzene just prior to gas
chromatographic analysis.
Portions of all the residue samples (primary chamber, secondary
chamber, etc.) were weighed out, extracted, and the extracts were
methylated and analyzed for picloram methyl ester.
Analysis and Discussion
All samples were analyzed for the picloram methyl ester. Unidenti-
fied chromatographic peaks were quantitated against the picloram methyl
ester calibration curve. (Representative chromatograms are shown in
Figure 30).
The sensitivity of the instrument for picloram methyl ester is
10 pg. Based on this sensitivity value and with a 5 \il sample injec-
tion for each analysis, the minimum detectable value for a 20-ml sam-
ple solution is 40 ng. However, during the analysis samples were very
often concentrated to 1 ml, which resulted in a minimum detectable
quantity of 2 ng.
178
-------
.PICLORAM
INJECTION
•
PICLORAM
INJECTION-
l/ilx32
10% Picloram
Formulation
PICLORAM
Incinerator
Effluent
(Sample Point
No.
Figure 30. Representative picloram chrotnatograms.
-------
Prior to adopting the diazomethane esterification of picloram and
followed by GC analysis, two other methods of analysis were also examined.
The first method was to analyze the silylation product of picloram by
gas chromatography. Silylation reagent Trizil "Z" (N-tri-methylsilyl-
imidazole) was used, and reaction products were analyzed with electron
capture GC. This method of analysis was given up because of interferences
due to a large number of peaks from the samples and the reagent, and
also because of lengthy retention times.
The second method examined was analysis of picloram by a lumines-
cence technique. An Aminco Bowman spectrophotofluorometer was used to
measure the excitation and emission spectra. Unfortunately, picloram
does not show any natural fluorescence at 298 and 77°K; however, strong
phosphorescence was observed at 77°K. The phosphorescence method was
not employed because quantitative phosphorescence data are difficult
to obtain unless specially designed sample cells are used._Lt£'
Before using the diazomethane technique of forming methyl picloram
ester, esterification with boron trichloride 2-chloroethanol reagent
at elevated temperature was examined. The esterification yield by this
approach was so low that this method was not employed.
In order to check if there were organic acids or alcohols, be-
sides residual picloram formed after incineration, chromatograms were
collected for selected samples before and after the esterification. No
differences, except the picloram ester peak, were observed in these
chromatograms which indicates that the volatile unidentified species
were probably chlorinated hydrocarbons formed from incineration of
picloram.
Esterification of picloram with diazomethane employed in this
study generally gave a yield of over 90%.
TEST CONDITIONS AND RESULTS
Initially, seven experiments were made using a water-based liquid
formulation of picloram (24.9% 4-amino-3,5,6-trichloropicolinic acid
as the potassium salt, 21.5% acid equivalent). Because this formula-
tion was not miscible with No. 2 fuel oil, a modification of the in-
cinerator feed system was required (all miscible pesticide formula-
tions were mixed in the appropriate ratio with fuel oil and injected
through the primary burner position of the incinerator with an oil
burner). Two separate systems were used to inject fuel oil and the
picloram formulation into the primary chamber of the incinerator on
a horizontal plane. A standard oil burner was used for the fuel oil.
180
-------
The undiluted picloram was pumped into the incinerator through a fuel
oil nozzle of the same type being used in the oil burner. These injection
systems were positioned so that the picloram and the flame from the
fuel oil burner impinged at an angle of 30 degrees and at a point about
8 cm (3 in.) from the front wall of the incinerator. This is the same
configuration that is used to inject solid pesticide formulations.
The results of the seven initial tests (as well as two subsequent
tests) have been summarized in Tables 42 through 45.
Two efficiencies of combustion were calculated to evaluate the
results of these tests. The first considered only the picloram in the
incinerator input and discharge. This efficiency calculation showed
that > 99.99% of the picloram injected into the incinerator was at
least partially degraded at all temperatures tested, 530 to 1030°C
(990 to 1880°F); see Table 43. This is not unexpected, as picloram has
been reported to decompose at about 216°C (420°F).—/
The second efficiency calculation includes not only the picloram
that is left in the incinerator effluent but also the other chemical
species trapped in the sample collection system. Using this calcula-
tion, only the two tests (of the seven initial tests) conducted at 1010
and 1030°C (1850 and 1880°F) showed an efficiency of > 99.99%. As will
be discussed later, these two tests also showed significantly lower
concentrations (and quantities) of cyanide in the incinerator effluent.
Small quantities of residue were found in the primary and second-
ary chambers of the incinerator after each of the four tests conducted
at lower temperatures, 530 to 800°C (990 to 1470°C). Analyses of these
residues gave the following results:
Primary chamber residue Second chamber residue
Run
No.
1
2
3
Total
£/hr
21
397
298
Picloram
ppm
ND*'
1.7
ND
Total .
. a/
species"
ppm
0.2
3.0
0.8
Total
g/hr
_
43
29
Picloram
ppm
—
0.1
ND
Total
species
ppm
mm
6.9
4.2
4 -
5 -
6 -
7 628 1.1 7.1 460 < 0.1 < 4.5
77Picloram plus all other chlorinated hydrocarbon species detected.
t>/ Not detected.
181
-------
Table 42. SUMMARY OF 21.57. PICLORAM LIQUID EXPERIMENTS
co
Run
No.
1
2
3
it
i
6
7
6
9
w
c/
^
?/
Fuel oil rate
Nominal Actual
l7hr UalAir) l/hr (gal/hr)
2.8 (0.75) 2.57 (0.68)
3.« (1.0) 3.60 (0.95) .
5.7 (1.5) 5.72 (1.51)
11.4 (3.0) 9.08 (2.40)
13.2 (3.5) 12.49 (3.30)
13.2 (3.5) 12.30 (3.25)
11.4 (3.0) 8.36 (2.21)
9.5 (2.5) 9.08 (2.40)
9.5 (2.5) 9.16 (2.42)
Nominal
1/hr (Ml/hrl
11.4 (3.0)
9.5 (2.5)
18.9 (5.0)
9.5 (2.5)
9.5 (2.5)
20.8 (5.5)
20.8 (5.5)
20.8 (5.5)
Plcloram
rate
Actual
focd rate
1 (/hr (gsl/hr)
8.78
6.43
7.31
5.72
5.56
13.59
13.51
13.10
20.8 (5.5) 13.25
Actual plcloram content of the Incinerator feed.
The flame temperature was observed at a point approximately 15
Calculated according to Method 3 of "Standards of Performance
Retention time Is defined as * , where v Is the wet off-gas
As dry gas at one atmosphere pressure, and 21.1"C (70'F).
Not determined.
(2.32)
(1.70)
(1.93)
(1.51)
(1.47)
(3-59)
(3.57)
(3.46)
*/hr Ub/hr)
1,870 (4.12)
1,380 (3.05)
1,510 (3.33)
1,290 (2.84)
1,110 (2.45)
3,470 (7.64)
2,230 (4.92)
3,270 (7.22)
(3.50) 2,450 (5.40)
cm (6 In.) In from the front
for New Stationary Sources,"
flow rate from the Inclnerato
Prljwry
chamber
330 (9'(0)
600 (1120)
630 (1160)
930 (1700)
1010 (1810)
1030 (1880)
800 (1470)
1000 (1840)
Flame Excess
•C CD 7,
HA!'
KA
NA
HA
NA
KA
NA
1090 (2000)
1010 (1850) 1150 (2110)
wall of the Incinerator (
Federal Register, 36(247):
298
193
187
62
130
116
77
114
Retention time-'
sec
Chamber chamber
7.6 8.0
6.7 6.9
6.6 6.8
3.9 4.0
1.4 1.4
1.2 1.2
6.0 5.8
1.9 1.8
50 2.6 2.5
see Figure B- 1) .
24876-24895, 23 December 1971.
r at the respective chamber temperature and pressure, and V
Sampling
tin
mln (1
30
30
30
30
30
28.5
30
28.5
30
Is' the volume of
Off-gas
flow ratei'
m3/hr
.OOO's of SCFH)
116 (4.1)
110 (3.9)
113 (4.0)
150 (5.3)
391 (13.8)
433 (15.3)
108 (3.8)
303 (10.7)
204 (7.2)
that chamber.
-------
Table 43. INCINERATION EFFICIENCY--21.57. PICLORAM LIQUID FORMULATION
Run
No.
1
2
3
4
5
£
u>
7
8
9
a/
>>/
r/
Picloram
feed rate!/
K/hr
1,870
1,380
1,510
1,290
1,110
3,470
2,230
3,270
2,450
Actual plcloram content
Flcloram plus all other
Picloram
content
of off-gas
g/hr
3
2
5
2
2.6
7
1
3.0
9
x 10"3
x 10'3
x ID'4
x 10" 3
x 10"2
x 10"3
x 10-3
x 10-2
x 10"2
Ratio of
picloram in Total speicesi'
off-gas to content of off-gas
piclorara fed g/hr
2
1
3
2
2.
2.
4
9
3.
x ID'6 3
x 10"6 0.6
x 10-7 6
x 10"6 0.3
,3 x 10" 5 0.040
0 x 10'6 0.044
x 10'7 5
x 10"6 0.035
,7 x 10"5 0.10
Ratio of
total species— in Incineration efficiency^.'
off-gas to total %
picloram fed Picloram
2 x 10~3 > 99.99
4 x 10"4 > 99.99
4 x 10"3 > 99.99
2 x 10'4 > 99.99
3.6 x 10'5 > 99.99
1.3 x ID"5 > 99.99
2 x 10'3 > 99.99
1.1 x 10'5 > 99.99
4.1 x 10"5 > 99.99
Total species^/
> 99.83
> 99.95
> 99.63
> 99.98
> 99.99
> 99.99
> 99.78
> 99.99
> 99.99
of the Incinerator feed.
chlorinated organic species detected.
|~ quantity out"] _^
the quantity in is evaluated at Sample Point No. \IJ (the incinerator feed). Efficiencies have been calculated based on (a) picloram
only, and (b) the total chlorinated organic species detected at Sample Point No. (2) .
-------
Table 44. OFF-GAS COMPOSITION—21.57. PICLORAM LIQUID INCINERATIONi/
co
Total hydrocarbons analyzer
Run
No.
1
2
3
4
5
6
7
8
9
Pichloram
mc/m
2.7 x 10"2
1.5 x 10"2
< 4.3 x 10'3-
1.7 x 10"2
6.6 x 10-2
V.6 x 10'2
< 9 x 10" 3~
1.0 x 10'v
4.4 x 10"1
Total »pecles£'
mR/m
26
5.6
49 '
1.7
0.10
0.10
44
0.12
0.49
CN-
mg/m3
689
906
211
98
< I
< I
967
< 1
2
S02
mg/m-1
20
mi'
5
9
ND
9
3
162
253
NO/7
mg/in
no
48
95
ND
310
1,860
553
«*£'
36
Total
hydrocarbon's
ppm
708
732
712
625
686
37
704
13
8
Orsat analyzer
CO CH^
ppm ppm
3,230 > 842&/
> 4. 630s' > 875^'
3,510 > 851&/
3,660 > 943fc/
1,490 244
< 1 4
3,680 > 962i7
< 1 < 1
18 < 1
°2
vol. 7,
16.1
14.3
14.2
8.4
12.2
11.7
10.5
11.4
7.2
co2
vol. 7,
2.8
3.6
3.3
8.1
6.5
6.7
6.1
7.2
10.4
CO
vol. 7,
0.0
0.0
0.0
0.0
0.0
0.0
2.6
0.0
0.0
Moisture
vol. 7.
4.6
8.3
7.1
3.2
4.6
5.8
5.1
5.8
11.2
»./ A» dry gas at one »trno»phere pressure and 21.1°C (70"F).
£/ Plcloratn was not detected. The value given represents the detection limit for picloram in the respective sample.
c_/ Picloram plus all other chlorinated organic species detected.
AJ Not detected.
fl Calculated as N0?,
it No analysis.
g/ Upper detection limit.
-------
Table 45. OPERATIONAL DATA SUMMARY--21.57. PICLORAM LIQUID EXPERIMENTS
oo
Ln
Run No.
Temperature °C (°F)
Primary chamber (Thermocouple No. Q )
Primary chamber (Thermocouple No. <]y )
Primary chamber (Thermocouple No. \3) )
Second chamber (Thermocouple No. ^4) )
Second chamber (Thermocouple No. (^ )
Sample Point No. (T) (Thermocouple
No. (6) )
Pressures
Draft (Manometer No. /1\ ), pascals
(In. H20) gauge
Fuel oil burner pressure, pascals
(psl) gauge
Pesticide injection air pressure, pascals
(psi) gauge
Scrubber liquids^/
1st Stage, H20 scrubber
Volume, i (gal.)
Picloram cone., mg/i
Total species cone.,—' mgA4
2nd Stage, hexalene glycol scrubber
Volume, I (gal. )
Picloram cone, change, mg/£
Total species cone, change ,£.' mg/i
3rd Stage, H20 scrubber
Volume , f, (gal. )
Picloram cone., mg/2
Total species conc.,£/ mg/i
Scrubber system
Effluent gas (Sample Point No. (?) )!/
Picloram cone., mg/m3
Total species cone. ,£' mg/m3
1
530 (990)
400 (760)
490 (920)
400 (760)
220 (430)
150 (300)
12 (0.050)
NAf/
4.0 x 105 (58)
1120 (297)
< 2 x 10-32/
2
84 (22.1)
< 2 x lO-3^'
9 x 10-1
1990 (526)
< 2 x 10-32'
3 x 10'1
< 2 x lO"2^
< 8 x 10- 1
2
590 (1100)
590 (1090)
600 (1120)
530 (990)
280 (540)
170 (340)
11 (0.045)
NA
4.1 x 105 (60)
1290 (340)
< 2 x 10-32'
2
83 (21.9)
< 2 x 10-32'
2
2030 (537)
< 2 x 10-32'
7 x 10-1
< 6 x 10-3*'
< 8 x 10'2
3
610 (1130)
600 (1110)
630 (1160)
550 (1030)
290 (560)
180 (350)
12 (0.050)
NA
4.4 x 105 (64)
1230 (325)
< 2 x 10-32'
6
84 (22.1)
< 2 x 10-32'
2
1840 (486)
< 2 x 10-32/
5 x ID'1
< 7 x W&
< 2 x ID"1
4
890 (1640)
920 (1680)
930 (1700)
800 (1480)
490 (910)
290 (560)
12 (0.050)
NA
4.5 x 105 (65)
1240 (327)
2 x 10-3
4
84 (22.1)
< 3 x 10-32'
ND£/
1880 (497)
2 x 10"3
2 x 10-1
< 7 x 10-3*7
< 5 x 10'2
5
900 (1660)
940 (1730)
1010 (1850)
840 (1540)
600 (1120)
420 (790)
46 (0.185)
8.0 x 105 (116)
4.4 x 105 (64)-
1180 (313)
1 x 10-2
2
83 (21.8)
< 3 x 10-32'
ND
1990 (526)
< 2 x 10-32/
4 x 10"1
< 6 x 10-3*'
< 7 x 10~2
-------
Table 45. (Concluded)
co
Run No.
Temperature *C ("F)
Primary chamber (Thermocouple No. ()J )
Primary chamber (Thermocouple No. 'Tij )
Primary chamber (Thermocouple No. (\ )
Second chamber (Thermocouple No. 'i )
Second chamber (Thermocouple No. '1f> )
Sample Point No. \2 } (Thermocouple
No. '£• )
Pjrejmirejii
Draft (Manometer No. A ), pascals
(In H20) gauge
(psl) gauge
(p»l) gauge
Scrubber llqulde*-/
lat Stage, H20 acrubber
Volume, t (gal.)
Picloram cone., mg/f
Total specie* conc.,£' og/i
2nd Stage, hexalene glycol aerubber
Volume, I (gal.)
Picloram cone, change, rag/f
3rd Stage, H20 acrubber
Volume, / (gal.)
Picloram cone., mg/i
Scrubber ayatcm
Effluent gai (Sample Point No. (5) ).-'
Picloram cone., mg/m3
Total apeclea conc.,£'
A
950 (1740)
940 (1730)
1030 (1880)
920 (1690)
680 (1260)
500 (930)
50 (0.200)
91 v 1 f)5 / 1 15 N
. 1 X iU \ Lj£ )
NA
1230 (325)
< 2 x 10'3S'
5 x 10" l
90 (23.9)
2 x 10'3
ND
1820 (480)
< 2 x 10'3i/
6 x 10"2
< 8 x 10-3a/
<• 3 x 10' z
JL
770 (1410)
780 (1430)
800 (1470)
750 (1390)
470 (870)
250 (480)
12 (0.050)
5
9>1 x 10 ( 132 )
4,6 x 10 (66)
1120 (295)
2 x W*
7 x 10"1
86 (22.8)
2 x 10'3
6 x 10"
1730 (457)
3 x ID'3
7 x 10*
< 3 x ID'2*'
< 4 x 10" '
JL
920 (1680)
910 (1670)
1000 (1840)
900 (1660)
640 (1180)
420 (780)
63 (0.255)
7 Q v in* / i i i\
f . 7 X IV ( 1 1 J )
4.1 x 10 (60)
1140 (302)
NA
NA
99 (26.1)
NA
NA
1780 (469)
NA
Mk
NA
NA
JL
950 (1740)
890 (1640)
1010 (1850)
890 (1630)
650 (1200)
380 (710)
39 (0.155)
5
7.4 x 10 ( 108)
3.7 x 10 (54)
1060 (280)
NA
NA
99 (26.1)
NA
NA
1730 (457)
NA
HA
PIA
NA
NA
a/ Not determined.
b/ Scrubber water (Scrubber* 1 and 3) waa uaed once through, while the hexylene glycol (Scrubber 2) was recycled. The concentrations reported for hexylene glycol, therefore, are the
concentration changes (Increases) detected during the respective teats.
£/ Picloram plus all other chlorinated organic species detected.
d/ As the wet gas at one atmosphere pressure and 20*C.
e/ Picloram not detected. The values given represent the detection limit for plcloram In the respective sample.
i_l No Increase detected.
][/ Picloram not detected In all components (I.e. Implnfiers) of gas sampling train. The value given mrl-Mes the detectable limit for ptcloram In these components.
-------
The inclusion (or exclusion) of these residues has no effect on the
efficiency of combustion as shown in Table 43.
In order to evaluate the effect of physical form on the efficiency
with which picloram can be incinerated, five tests were made using a
pellet formulation (~ 11.6% picloram as the potassium salt, 107. as the
acid equivalent). Results from these five experiments (as well as sub-
sequent additional tests) are summarized in Tables 46 through 50.
The last of the five initial tests conducted (Run No. E) was made
with ground picloram pellets. Approximate size distribution of the
ground material was:
Particle size Distribution
(u.) (%)
> 1,680 1.1
1,680 to 1,410 0.8
1,410 to 1,190 6.7
1,190 to 53 78.4
53 to 44 1.0
< 44 12.0
Pictures of the original picloram pellets, as well as residues recovered
from the primary chamber of the incinerator after Run No. B, are shown
in Figure 31. Residue A is representative of the majority of material
found in the primary chamber. Residue B is representative of the top
layer of residue found in the primary chamber after the two high-temperature
runs (Nos. A and B). Picloram content of Residues A and B from Run No. B
was 0.2 and < 0.1 ppm, respectively.
As was done for the experiments using the liquid formulation, two
efficiencies of combustion were calculated. The first considers only the
quantity of picloram in the incinerator input and discharge. This effi-
ency calculation showed that > 99.99% of the picloram injected into the
incinerator was at least partially degraded at all temperatures tested
during the first five tests, 930 to 1020°C (1710 to 1870 F).
187
-------
Table 46. SUMMARY OF 10% PICLORAM PELLET EXPERIMENTS
No. 2 fuel oil rate
Run
No.
A
B
C
D
H*
00 E
00
F
G
a/
b/
c/
Pesticide feed rate Primary
Nominal ~ 107. Pellet Contained chamber Flame Exce
burner size Actual rate formulation ptcloramS.' temperature temperature"-' air
i/hr (gal/hr) i/hr (gal/hr) ku/hr (Ib/hr) R/hr (Ib/hr) °C (°F) "C CF) 7.
11.4 (3.0)
11.4 (3.0)
3.8 (1.0)
3.8 (1.0)
11.4 (3.0)
9.5 (2.5)
9.5 (2.5)
9.01
9.46
3.60
3.44
9.08
9.35
9.58
(2.38)
(2.50)
(0.95)
(0.91)
(2.40)
(2.47)
(2.53)
17.42 (38.4) 1,270 (2.8) 1020 (1870) 1140 (2080)
17.24 (38.0) 1,270 (2.8) 930 (1710) 1270 (2320)
16.51 (36.4) 1,180 (2.6) 640 (1190) 1020 (1860)
32.75 (72.2) 2,360 (5.2) 710 (1310) 980 (1800)
32.21 (71.0) 2,360 (5.2) 930 (1700) 870 (1590)
31.84 (70.2) 2,350 (5.2)i/ 950 (1750) 1180 (2160)
30.66 (67.6) 2,270 (5.0)i/ 920 (1680) 1150 (2110)
Actual content of picloram in the ~ 107. (acid equivalent) pellet formulation.
The flame temperature was observed at a point approximately 15 cm (6 In. ) In from the front
Calculated according to Method 3 of "Standards of Performance for New Stationary Sources,"
93
170
226
227
72
75
145
wall of
Federal
Retention timed/
ss sec Sampling
-' Primary Second time
chamber chamber min
1.3
2.1
6.9
6.7
4.6
2.6
1.9
the incinerator
Register, 36_(247)
1.4 60
2.2 60
7.4 60
7.3 60
4.9 60
2.6 60
1.7 60
(see Figure B-l).
:24876-24895, 23
Off-gas
flow rate!/
m3/hr
(1,000's of SCFH)
408
300
119
113
125
232
334
December
(14.4)
(10.6)
(4.2)
(4.0)
(4.4)
(8.2)
(11.8)
1971.
-------
Table 47. RESIDUE AND OFF-GAS CHARACTERISTICS—107, PICLORAM PELLET EXPERIMENTS
00
Run
A
8
C
D
E
F
G
A
E
T
Solid residue
~107. Picloram Contained Picloram Total species-'
formulation picloram!/ Total cone. cone.
kp/hr (Ib/hrj R/hr kn/hr (Ib/hrl nvm ppm
17.42 (38.4)
17.24 (38
16.51 (36
32.75 (72
32.21 (71
31.84 (70
30.66 (67
Picloram
content
f ff
8,/hr
< 1 x 10-5^
< 6 x 10- 5^
< 4 x 10' 5-
8 x 10-3
1.1 x 10"3
0)
4)
2)
.0)
.2)
6)
Ficloran
content of
e/hr
1.4 x 10"2
1 x 10-3
1 x 10"2
2 x 10"3
Z.4 x 10- *aV
•/ Actual pi. do run content of the
t./
Picloram plu. all
1,270 13
1,270 12
1,180 13
2,360 26
2,360 25
2,360d./ 23
2,270d/ 23
picloram content
of off-gaa and
8/hr
1.4 x 10-2
< 1 x 10-3
1 x lO"2
1 x 10"2 ,
1.3 x 10- 3£',
i n . in-2£'
15 (29.0)
61 (27.8)
70 (30.2)
48 (58.4)
08 (55.3)
63 (52.1)
13 (51.0)
Total opecleat/
content of
off-ga.
«/hr
< 3.2 x 10-3
2 x 10-1
4 x 10"1
5 x 10-1
4.6 x ID'3
» 10% pellet formulation.
other chlorinated organic apeclea
quantity "SH ..
detected.
1.1
0.07
0.08
0.5
0.06
0.01
0.4
Total «peclea£/
content of
solid reslduea
u/hr
1.1 x 10-1
1 x 10-1
1
1 x 10-2
6 x 10-2&'
5 x 10- **/
7.1
3.0
9.0
41.1
0.3
2.5
1.9
content of
off-gaa and
aolld residue.
n/hr
1.1 x 10-1
4 x lO"1
2
5 x 10-1
6 x 10-2*'
at Sample Polnta
Total
R/hr
38
43
57
54
658
98
73
picloran
in off-gaa
to total
picloraffl fed
< 8 x 10-'
<6 x 10'8
2 x 10-'
3 x 10~6
4.7 x 10-'
Noa. © (the
Plclortun Total speclesJi'
cone . cone .
0.08
1.4
0.3
1.1
0.6
NA£/
NA
total apecleaV
in off-gaa
to total
picloran fed
2.5 x 10"6
2 x lO'4
2 x 10-4
2 x 10"4
1.9 x 10-6
1 3 x 10**
Incinerator off-gaa) and
4.4
5.3
84.9
89.7
4.6
NA
NA
incinerator
residue to
total charge
0.76
0.73
0.83
0.81
0.81
0.74
0.76
Incineration efficiencyS'
Flcloram
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99&'
> 99.99*'
ff) (aolld
I
Total apeclea£/
> 99.99
99 99
99.96
99.93
99.97
99.99S'
99 . 99S/
raaiduaa) and
the
quantity in la evaluated at Sample Point No. (^
-------
Table 48. OFF-GAS COMPOSITION—107. PICLORAM PELLET INCINERATION^/
Total hydrocarbons analyzer
Run
No.
A
B
C
D
g
F
G
Plcloram
< 1.4 x 10"4-
< 4.7 x 10**^'
< 5.6 x lO'4^
< 7.4 x 10~*~
7.0 x 10'2
4.7 x ID'3
3.3 x 10-3
Total species^/ CN'
i 3 j 1
wt/nr "R'™
< 8.6 x 10-3 NA!/
9.9 x 10'2 < 1
2.2 178
3.9 278
4.4 NA
2.0 x 10'2 < 1
9.0 x 10-3 4
4/m3
NA
NA
NA
NA
NA
234
127
mg/m3
NA
NA
NA
NA
NA
59
21
Total
hydrocarbons
ppm
304
46
52
53
740
4
8
Orsat analyzer
CO
ppm
37
20
262
4,360
4,010
16
ND&/
CH4 02
ppm vo 1 . 7.
1 10.6
7 13.5
3 14.8
2 14.7
> 1,040^'' 9.4
ND 9.2
ND 12,6
co2
vol. 7.
7.7
5.5
4.6
4.8
8.0
9.2
6.4
CO
vol. 7.
0.0
0.0
0.0
0.0
0.8
0.0
0.0
Moisture
8.2
3.0
9.1
10.2
10.1
8.6
7.2
•/ A» dry gas at one atmosphere pressure, and 21.1'c (70°F).
y Plcloram was not detected In all components (i.e., Imptngers) of the sampling train. The value given includes the detection limit for picloram in
t-h«<9A rpsneetlve elements.
these respective elements.
<:/ Plcloram plus all other chlorinated hydrocarbon species detected.
d/ No analysts.
~i_l calculated as N02.
f/ Upper detection limit.
&/ Not detected.
-------
Table 49. PARTICUIATE SAMPLING SUMMARY—10% PICLORAM PELLET EXPERIMENTS
Description
Vol. dry gas - std. cond. , nm^
Percent moisture by vol.
Avg. stack temperature, "C
Stk. flow rate, dry., std. en., nm^/min
Actual stack flow rate, m-Vmin
Percent isokinetic
Percent excess air
Particulates - partial catch
Particulate wt. - partial, mg
Part, load - ptl., std. en., rag/run
Part, load - ptl., stk. en., mg/m
Partic. emis. - partial, kg/hr
Particulates - total catch
Particulate wt. - total, mg
Part, load - ttl. , std. en., rag/nm
Part, load - ttl., std. en., corrected
to 12% CO , mg/nm3
Part, load - ttl., stk. en., ing/m-*
Partic. emis. - total, kg/hr
Percent impinger catch
A
1.034
8.2
316.0
6.8
15.5
92.8
95
201
194
85
0.079
237
229
357
101
0.094
15.32
B
0.511
3.0
334.0
5.0
10.6
97.6
172
203
397
188
0.119
248
484
1,060
229
0.145
18.12
C
0.215
9.1
177.8
2.0
3.3
105.1
229
198
920
551
0.108
242
1,120
2,900
672
0.132
18.07
D
0.203
10.2
176.6
1.9
3.2
102.4
231
577
2,840
1,680
0.322
632
3,110
7,800
1,840
0.353
8.71
E
0.202
10.1
260.0
2.1
4.2
100.7
71
2,680
13,300
6,540
1.665
2,710
13,400
20,100
6,590
1.680
0.89
F
0.398
8.6
303.0
3.8
8.2
99.2
75
800
2,000
939
0.464
843
2,110
2,750
990
0.489
5.13
G
0.516
7.2
351.2
5.6
12.8
88.4
147
285
551
240
0.185
442
855
1,600
372
0.288
35.53
-------
Table 50. OPERATIONAL DATA SUMMARY--107. PICLORAM PELLET EXPERIMENTS
vo
Run No.
Temperature "C (*F)
Primary chamber (Thermocouple No. (]^ )
Primary chamber (Thermocouple No. (^ )
Primary chamber (Thermocouple No. J^ )
Second chamber (Thermocouple No. (^ )
Second chamber (Thermocouple No. <3) )
Sample Point No. (2) (Thermocouple No. (D I
Pressures
Draft (Manometer No. /f\ ), pascals
(in. H20) gauge
Burner operation pressure, pascals
(psi) gauge
Pesticide injection air, pascals (psi)
gauge
A
1000 (1840)
1020 (1860)
1020 (1870)
840 (1550)
500 (930)
1 340 (650)
21 (0.085)
NAi/
6 x 10* (9)
B
900 (1660)
920 (1680)
930 (1710)
800 (1480)
520 (960)
370 (690)
35 (0.140)
NA
7 x 10* (10)
640
530
600
500
250
180
12
NA
6 x
C
(1190)
(990)
(1120)
(930)
(490)
(360)
(0.050)
10* (9)
710
520
630
530
280
190
12
NA
6 x
D
(1310)
(970)
(1160)
(980)
(530)
(370)
(0.050)
10* (9)
920
900
930
790
450
180
14
NA
6 x
E
(1680)
(1650)
(1700)
(1450)
(850)
(360)
(0.55)
10* (9)
900
850
950
810
580
260
31
7.4 x
6 x
F
(1660)
(1570)
(1750)
(1490)
(1070)
(500)
(0.125)
103 (108)
10* (9)
C
830 (1520)
770 (1410)
920 (1680)
830 (1520)
620 (1140)
420 (780)
54 (0.215)
7.4 x 103 (108)
7 x 10* (10)
a_/ No analysis, gauge broken.
-------
VO
I , I a
[WPIWPIW
121 ' 13
151
RESIDUE
A
RESIDUE
B
10% PIC LOR AM
PELLETS
Figure 31. Picloram pellets and residue.
-------
The second efficiency calculation includes not only the piclorara
that is left, but also other chemical species (volatile chlorinated hy-
drocarbons). Using this calculation, only the two tests conducted at the
higher temperatures (930 and 1020°C) showed an efficiency of > 99.99%.
Thus, these initial tests, as well as those using the liquid formu-
lation, indicate that temperatures of about 1000°C appear to be re-
quired to satisfactorily incinerate picloram.
The results of the particulate sampling conducted on the picloram
runs are shown in Table 49. Two modifications were made to facilitate
the analysis of the sample for picloram content; 2-propanol was used in
the impingers rather than water and a liquid nitrogen cold trap was
added to the sample train in order to collect condensibles for picloram
analysis. Acceptable isokinetic conditions were achieved in all of the
initial five runs. The loadings all exceed what can be considered low
emission and indicate the need for a particulate control device when
incinerating picloram pellets.
Subsequently, four additional tests were conducted at the request
of the project officers in order to better define the temperature re-
quired to reduce cyanide (CN~) concentration in the incinerator effluent
gas to < 1 mg/m . Two additional tests were made using the liquid form-
ulation (Runs Nos. 8 and 9, Tables 42 through 45), and two using the 10%
pellets (Runs Nos. F and G, Tables 46 through 50). The results of cyanide
analysis of the incinerator effluent for all picloram tests are summarized
as follows:
Liquid formulation
Primary chamber Excess Cyanide content of .
Run temperature air incineration off-gas~
No. °C (°F) % mg/m3 g/hr
1 530 ( 990) 298
2 600 (1120) 193
3 630 (1160) 187
4 930 (1700) 62
5 1010 (1850) 130
6 1030 (1880) 116
7 800 (1470) 77
8 1000 (1840) 114
9 1010 (1850) 50
a/ Calculated as CN~.
194
-------
Pellet formulation
A
B
C
D
E
F
G
1020 (1870)
930 (1710)
640 (1190)
710 (1310)
930 (1700)
950 (1750)
920 (1680)
93
170
226
227
72
75
145
NA-
< 1
178
278
NA
< 1
4
b/
NA
< 0.3
21.2
31.4
NA
< 0.2
1.3
Is/ No analyses.
For the liquid formulation tests, only those experiments conducted
in the higher temperature ranges, 1000 to 1030°C (1840 to 1880°F), pro-
duced low concentrations (and quantities) of cyanide in the off-gas.
Low concentrations (<; 1 mg/m ) and quantities of cyanide were generally
also produced from the pellet formulation tests conducted at the higher
temperature, 930 and 950°C (1710 and 1750°F). Thus, these data indicate
that a temperature of about 1000°C and sufficient excess air (»' 1007o)
are required to minimize cyanide generation.
Additional samples were also taken during the supplemental pellet
formulation experiments (Runs Nos. F and G, Tables 46 through 50), using
a special sampler installed in the bottom of the primary combustion cham-
ber (see Figure 32). This sampler was used to "catch" pellets as they
fell through the combustion chamber in order to approximate the degree
of decomposition actually occurring while the pellet was falling. The
sampler was inserted upside down, rotated, and immediately (-»• 3 sec)
extracted to obtain grab sample with a nominal retention time in the
primary combustion chamber of about 2 sec. The grab samples (two and
three per run, respectively) were analyzed for the picloram content, and
gave the following results:
195
-------
Figure 32. Primary chamber residue sampler
196
-------
Total
Picloram species^'
ppm ppm
Run No. F
Primary chamber residue composition 0.01 2.5
Average "grab" sample composition 124 1,041
Run No. G
Primary chamber residue composition 0.4 1.9
Average "grab" sample composition 65.3 265
aj Picloram plus all other chlorinated organic species detected.
These values when compared to the nominal picloram content of the feed
(•^ 74,000 ppm) indicate that the vast majority of the picloram (as well
as the other chlorinated species) are "removed" from the pellet during
the first 2 sec residence time in the primary chamber.
DISCUSSION
Several minor operational problems were encountered during the in-
cineration of picloram. The first of these, as alluded to earlier, was
the pumping of the water-based liquid picloram formulation. This material
would neither stay in suspension as a fuel oil mixture, nor be success-
fully pumped through a system designed to handle only hydrocarbons. This
problem was overcome by injecting the undiluted picloram formulation
through a separate injection system consisting of a gear pump designed
to handle aqueous systems and a standard burner nozzle of the appropriate
size
The incineration of picloram in both the liquid and the pellet formu-
lation can be classified as giving relatively dirty burns. A dark (bluish)
exhaust plume was discharged from the experimental system (i.e., at Sam-
ple Point No. f9J , Figure 5, p. 27) during most of the tests.
The dirtiness of the burns caused minor plugging problems with the
demister pad in the first stage water scrubber. This problem was particu-
larly noticable when operating the incinerator at low draft (see Table
50).
197
-------
References
1. Lawless, E. W., T. L. Ferguson, and A. Meiners, "Guidelines for
the Disposal of Small Quantities of Unused or Spilled Pesticides"
(Draft), EPA Contract No. 68-01-0098 (1974).
2. Lawless, E. W., R. von RUmker, and T. L. Ferguson, "The Pollution
Potential in Pesticide Manufacturing," EPA Technical Studies
Report No. TS-00-72-04 (June 1972).
3. Kennedy, M. V., B. J. Stojanovic, and F. L. Shuman, Jr., "Chemical
and Thermal Methods for Disposal of Pesticides," Res. Rev., 2£:89
(1969).
4. Li, R., and E. C. Lim, J. Chem. Phys., 5£(2):605 (1972).
5. Zweidinger, R., and J. D. Winfordner, Anal. Chem., <42(6):639 (1970).
6. Herbicide Handbook of the Weed Science Society of America, 2nd ed.,
W. F. Humphrey Press, Inc., Geneva, New York (1970).
198
-------
IV. MALATHION
PESTICIDE DESCRIPTION
Physical Properties
Chemical Name; S-[l,2-bis(ethoxycarbonyl)ethyl]0,0-dimethyl phos-
phorodithioate; 0,0-dimethyl phosphorodithioate
of diethylmercaptosuccinate
Common Name; Malathion
Trade Names; Cythion®, Enmatos®, Emmatos Extra®, Fyfanon®, Karbofos®,
Kop-Thion®, Kypfos®, Malaspray®, Malamar®, MLT,
Zithiol®, Mercaptothion®, Carbofos®, Maldison®
Pesticide Glass: Nonsystemic insecticide and acaricide; organophos-
phate
Structural Formula; ^3°^ //s
P\ ?i
CH30/' S-CH-C-OC2H5
CH2-C-OC2H5
0
Empirical Formula; CioH19°6PS2
Molecular Weight; 330.36
Analysis; C 36.35%} H 5.80%; P 9.38%; S 19.41%; 0 29.06%
Physical State; Clear liquid, may be colorless, yellow, amber or brown
Characteristics; Technical grade material is a minimum 95% purity.
It has a slight characteristic mercaptan-like
odor, but has a maximum 30 ppm methyl mercaptan.
Malathion insecticide concentrates may gel if
stored in contact with iron, terneplate, or tin
plate for a prolonged period. No gelation has
been observed in finished malathion insecticide
aerosols or other formulations containing 5% or
less of the insecticide. Malathion insecticide
concentrates may solidify if stored at tempera-
tures ranging around 0°C (32°F); the product will
increase in viscosity. Normal viscosity can be
restored by allowing drums of malathion to warm
up to 4.5° C(40°F). (Cyanamid International un-
dated).!/
199
-------
Melting Point; 2.85°C
Boiling Point; 156 to 157°C at 0.7 mm Hg (slight decomposition)
Vapor Pressure; 0.00004 mm Hg at 30°C
Specific Gravity; 1.2315 at 25°C
Density; 1.2 kg/liter (10.25 Ib/gal)
Refractive Index; n25 1.4985
D
Viscosity; At 40°G, 0.176 dyne/sec/cm2 (17.57 centipoises)
At 25°C, 0.368 dyne/sec/cm2 (36.78 centipoises)
Flash Point (Tag Open Cup); Greater than 160°C (320°F)
Solubility; In water at 25°C, approximately 145 ppm. Completely solu-
ble in most alcohols, esters, high aromatic solvents,
ketones and vegetable oils. Poor solubility in ali-
phatic hydrocarbons.
Chemical Properties
Hydrolysis is the most important decomposition reaction of mala-
thion and has received intense investigation. Depending upon the reac-
tion conditions, hydrolysis can occur via several different pathways
leading to a variety of products. The thermal decomposition of mala-
thion has also been investigated, but relatively little is known con-
cerning the decomposition products. Malathion is readily oxidized to
malaoxon, a reaction typical of other sulfur-containing organophosphate
pesticides. Malathion is degraded by ultraviolet radiation, but little
is known concerning this reaction. The chemical reactions of malathion
are described in the following paragraphs.
Malathion is a reasonably stable compound that undergoes some de-
composition when held much above room temperature. Heating the purified,
nearly colorless liquid for 24 hr at 150°C resulted in the formation of
an orange-brown, viscous liquid and some colorless cloudy material which
was immiscible (Metcalf and March)..2/ This treatment resulted in the
isomerization of approximately 90% of the original material. No decom-
position products were identified.
McPherson and Johnson!/ examined the variation of decomposition time
with temperature and, for malathion, obtained the following results.
200
-------
Temperature (° C) Decomposition time (days)
115 5
100 20
80 163
65 925
The burning of malathion solutions was investigated by Smith and
Ledbetter.—' Malathion solutions (1 g/10 ml) in xylene and kerosene
were burned and gases collected above the fire were analyzed. Samples
were collected at various intervals after the ignition of the solutions.
The maximum malathion found from the burning malathion-xylene solutions
was 10 y,g/m3 at 4.5 min after ignition, and that from the kerosene mix-
ture was 4 u.g/m3 at 2.5 min. Smith and Ledbetter noted that these quite
low concentrations could result from either a high efficiency of com-
bustion or a failure of the malathion to evaporate during the burning.
Some of the decomposition products of malathion were identified
during the experiments. Diethyl fumarate was separated and positively
identified by infrared spectrophotometry. Some other compounds were
tentatively identified by their retention times in gas chromatography.
Compounds tentatively identified by Smith and Ledbetter were:
Methanol
Ethano1
Ethyl acetate
Diethyl fumarate
Isomers of dimethyl dithiophosphate
Malathion isomers
Smith and Ledbetterft/ concluded that several factors tend to re-
duce the hazards from organophosphate (e.g., malathion) insecticides in
fires. First, most of the pesticide is destroyed by decomposition before
it can evaporate. Second, over 90% of the evaporating insecticide is
destroyed by the flames. Third, the evaporating portion is considerably
diluted by the time it reaches anyone.
201
-------
Differential thermal analysis of malathion by Kennedy et al.2' pro-
vided the following data.
Product Endotherms Exotherms
Reference standard 500°C 250, 308, 333, and 422°C
Commercial product 145, 441, and 475°C 261 and 308°C
(5 Ib/gal)
Sensitivity = 25%.
Based on these and other laboratory analyses, Kennedy et al. concluded
that the temperature of complete combustion of the malathion -reference
standard and the 57% liquid formulation were 663°C (1225°F) and 715°C
(1319°F), respectively.
According to Melnikov,!/ malathion, on prolonged heating at 150°C,
is isomerized to the corresponding thiolo isomer:
S CHoO^ 0
(CH30)2PSCHCOOC2H5 > PSCHCOOC2H5
| CT3S I
'--- -j CH2COOC2H5
At a higher temperature, this reaction proceeds violently and a consid-
erable amount of the product is decomposed, sometimes even explosively.
The thermal decomposition of a commercial malathion formulation
(5 Ib/gal) at various temperatures was also investigated by Kennedy
et al.,1/ Extensive decomposition would have been expected at the high
temperatures reported; thus the contact time, which was not reported,
must have been very short, or the reported loss was equivalent to total
decomposition. The results from this study are summarized as follows.
Temperature (°C) Percent loss
600 95.3
700 96.0
800 96.3
900 96.4
1000 96.7
202
-------
Kennedy et al.l/ further investigated the thermal decomposition of
malathion (analytical grade). The observed effects of heating on weight
loss, color and physical appearance were as follows.
Heating time Temperature Weight loss Physical
(min) (°C) (%) Color appearance
30 200 58.7 Dark-brown Liquid
30 250 72.9 Dark-brown Liquid, jelly-
like on cooling
30 300 76.2 Dark-brown Silk flakes
30 350 80.3 Dark-brown Silk flakes
30 400 80.3 Dark-brown Silk flakes
30 500 80.3 Dark-brown Silk flakes
30 600 80.3 Dark-brown Silk flakes
Additional data on the decomposition of malathion were reported by
Stojanovic et al.Z.' In general, the same physical changes previously re-
ported were observed when malathion was heated. Diethyl succinate, diethyl
malate and diethyl fumarate were tentatively identified as decomposition
products on the basis of infrared spectra.
8/
In another study of pesticide combustion (Putnam et al.),—' it was
reported that malathion decomposed over the temperature range of 277 to
326°C.
Production and Use
Malathion has a very broad spectrum of effectiveness against insects
and mites. It is registered and recommended in the United States for use
on about 130 different crops, on livestock and pets, and on agricultural
premises such as barns (including dairy barns and milk rooms), feedlots,
holding pens, poultry houses, feed rooms, and grain bins. The foregoing
count of 130 crops includes several dozen minor vegetables counted as only
one crop. Tolerances for malathion residues have been established on at
least 127 raw agricultural commodities (EPA).—'
It is estimated that about 16.2 million pounds of malathion (as ac-
tive ingredient) were used in the United States in 1972.—' Consumption
of malathion by category of use in 1972 is estimated to have been:
agriculture - 5 million pounds; industrial and commercial uses - 4 mil-
lion pounds; government agencies - 2.2 million pounds; and home and gar-
den uses - 5 million pounds.
203
-------
Malathion is available to users in the United States in a variety
of different formulations including emulsifiable liquids, wettable pow-
ders, dusts, solutions, concentrates for low volume (LV) and ultra-low
volume (ULV) applications, and manufacturing concentrates.
FORMULATIONS TESTED
Two malathion formulations were tested: a 57% emulsifiable concen-
trate; and a 25% wettable powder. The available information on these for-
mulations is summarized as follows.
57% Emulsifiable Concentrate
Name; Crown Malathion 57%
Manufacturer; Crown Chemicals, Rockford, Illinois
Compo s it ion; Active Ingredients
Malathion* 57.00%.
Aromatic Petroleum
Derived Solvent 33.09%
Inert Ingredients 9,91%
Total 100.00%
* 0,0-dimethyl dithiophosphate of diethyl
mercaptosuccinate
Registration; EPA Reg. No. 7273-59
Lot No.; 16646
25% Wettable Powder
Name; Niagara Malathion 25 Wettable
Manufacturer; Niagara Chemical Division, FMC Corporation,
Middleport, New York
204
-------
Composition; Active Ingredients
Malathion*
Inert Ingredients
Total
25.0%
75.07,
100.0%
* 0,0-dimethyl dithiophosphate of diethyl
mercaptosuccnate
Registration; USDA Reg. No. 279-761
Lot No.; A650 AY, A650 PX, M6524 ET
Particle Size Specifications; At least 99% pass through a 44 p,
(325 mesh) sieve.
PRELIMINARY THERMAL ANALYSIS
Bomb calorimetric analyses of the two formulations gave the following:
Sample
Test
25% Malathion powder Sulfur
formulation
Calorific value
57% Malathion liquid Sulfur
formulation
Calorific value
Test Method
ASTM D-1552
ASTM D-240
ASTM D-1552
Result
5.21%
5.510 x 106 J/kg
(2,371 Btu/lb)
11.57%
ASTM D-240 2.793 x 10 J/kg
(12,017 Btu/lb)
Figures 33 and 34 show the results of DTA and TGA of the 25% mala-
thion powder formulation. The DTA data do not show any prominent exotherms
or endotherms. Rather, a slow decomposition process is indicated. Such
a process is substantiated by the TGA data that indicate slow weight loss
as temperature increases. At about 650°C almost 30% of the original weight
is gone; nominal malathion content of the formulation is 25%. Essentially
no more weight loss is observed from 650 to 1000°C.
205
-------
I j I
I I I I 1 1. I 1 1 1 1 . I I I I I
W 210 190 300 310 320 330 340 350 360 370 3K> 3*0 400
a—»
70 - K - » - 100 110 'O )» '« l» '«>
TlMPKAtuN "C
Reference: Empty pan
Prog, mode: Heat
Rate: 10°C/min
Start: 24°C
Figure 33. DTA of malathlon powder
-------
1000 r-
900 -
800 -
700 -
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
20
WEIGHT tOSS. PERCENT
Sample weight: 2.434 mg
Heating rate: 20°C/min
Environment: ~ 20 ml/min air (20% 0, 80%
Figure 34. TGA of malathion powder
207
-------
Figures 35 and 36 show the results of DTA and TGA of a sample of
malathion obtained by evaporation of a sample of the 577o EC formulation.
DTA data show no prominent exotherms or endotherms. However, a marked de-
composition process occurs from about 338°C and on to the instrument
limit of 400°C. This decomposition process is substantiated by the slow
weight loss observed on the TGA data (Figure 36) as temperature increases.
At about 700°C, almost 80% of the original weight is gone. From 700 to
1000°C, another 10% of the original weight disappears.
METHODS OF ANALYSIS
Apparatus
For gas chromatographic analysis a Tracer 550 gas chromatograph
equipped with FPD 200 AT sulfur and phosphorus flame photometric detectors
(Meloy, Inc., Springfield, Virginia) and a 6-ft, 4 mm I.D. glass column
(packed with 1.5% OV-17 + 1.957. QF-1 on 80/100 mesh Supelcoport from
Supelco, Inc., Bellefonte, Pennsylvania) were used. Chromatographic
operating conditions were: injector temperature, 240°C; column tempera-
ture, 200°Cj detector temperature, 235°C; carrier flow rate, 100 ml/min,
N£J detector flow rate, 30 ml/min, 02; 175 ml/min, ^j and 34 ml/min,
air.
A Tracer Westronics Model MT 22 dual pen strip chart recorder was
used to record the chromatograms.
Reagents and Materials
Solvents used were pesticide grade benzene (Fisher Scientific) for
extraction of water samples and for standard solutions, and pesticide
grade hexane (Matheson, Coleman, Bell) for extraction of hexylene glycol
(second stage scrubber samples). All laboratory glassware was thoroughly
rinsed in dilute hydrochloric acid (Fisher Scientific), deionized dis-
tilled water and reagent grade acetone (Fisher Scientific).
Standard and Calibration Curves
The solid malathion standard obtained from EPA, was used to prepare
a stock standard of 100 jig/ml and appropriate dilutions were made to
produce a linear curve (linear range used: 0 to 50 ng).
208
-------
O
VD
—I 1 1 1 1 1 1 1 * 1 1 I I I ' ' I i i i i i i i i i i I I i t i i r i . i i . i
10 *° 30 *0 50 40 70 SO 90 100 110 120 130 UO 150 140 170 180 (TO 100 HO 220 130 240 250 260 270 280 290 300 310 320 330 340 3M 370 340 380 390 400
TEMPERATU*[ *C
Reference: Glass beads
Prog, mode: Heat
Rate: 10°C/min
Start: 30°C
Figure 35. DTA of malathion
-------
1000
900
0^ Ol TO 1.2 1.4 1.6 1.8 2.0
40 SO
WEIGHT LOSS, CfBCfNT
Sample weight: 2.15/rag
Heating rate: 20°C/min
Environment: ~20 ml/min water pumped air
Figure 36. TGA of malathion
210
-------
Procedure for Sample Preparation
All samples collected in water were extracted with 10 ml benzene
(includes samples in dilute sulfuric acid) and appropriate amounts (2 to
5 u-1) were injected into the G.C. On all other samples (which were col-
lected in acetone or benzene) the volumes were measured and appropriate
amounts were injected into the G.C. Twenty milliliters of the hexylene
glycol samples (from second stage scrubber) were extracted with two 5 ml
portions of hexane, and appropriate amounts of the hexane extracts were
injected for analysis. The volume of liquid in the ^ cold trap and the
glass wool plug in the trap were each extracted with 10 ml of benzene and
a portion of this extract was analyzed for malathion. Filter elements
from all gas sample points were extracted with two 5 ml portions of
benzene and the benzene extract analyzed for malathion.
The mass of collected particulates was determined for all samples
collected from incineration of malathion dust as follows. All samples of
impinger solutions were evaporated in clean, dessicated, tared 250 ml
beakers and dessicated 2 days before final weighing. The residues were
extracted (using an ultrasonic mixer) with known volume of benzene and
portions of the extracts were analyzed by G.C. The cold trap solutions
were extracted with two 5 ml portions of benzene and the benzene extract
analyzed. Blank acetone and benzene samples were analyzed as received.
The silica gel was extracted with a known volume of benzene and an ap-
propriate amount was injected for analysis.
Portions of all solid residue samples (from the primary chamber,
secondary chamber, etc.) were weighed out, extracted, and the extracts
were analyzed for malathion.
Analysis and Discussion
All samples were analyzed for malathion. Unidentified chromatographic
peaks were quantitated against the phosphorus response of standard malathion.
The sensitivity of the instrument for malathion is 1 ng. Based on
this sensitivity value and with a 5 \i,l sample injection for each analysis,
the minimum detectable quantity for a 20 ml sample solution is 4 p,g. How-
ever, during the analysis, samples were very often concentrated down to
1 ml which resulted in a minimum detectable quantity of 0.02 p,g.
211
-------
The detection limit for each sample point as reported in the follow-
ing subsection on "Test Conditions and Results," is dependent on not only
the sensitivity of the instrument as has been outlined, but also on the
size of the sample analyzed, e.g., the volume of incinerator off-gas drawn
through the sampling train, or the size of the solid residue extracted.
The detection limits reported in the following, therefore represent the
limits for detection in the specific samples analyzed and vary from test
to test.
TEST CONDITIONS AND RESULTS
A total of 11 tests were conducted using the 57% malathion emulsi-
fiable concentrate (EC) formulation. The results of these tests are sum-
marized in Tables 51 through 54.
Initially, nine tests were made using the EC formulation (Runs Nos.
1 through 9). Neither malathion nor any other sulfur-containing organic
phosphates were detected at Sample Point No.(2)(the incinerator off-gas)
for any of these experiments. Further, neither malathion nor any other
sulfur-containing phosphates were detected at any other point in the ex-
perimental system except at Sample Point No.(T) (the incinerator feed).
Relatively high quantities of total pyrophosphates, however, were
detected in the incinerator effluent from those runs using concentrated
feed (350 to 590 mg malathion per milliliter) (Runs Nos. 5 through 9).
Two additional tests (Runs Nos. 10 and 11) were then made using lower
concentrations of malathion. As had been the case with Runs Nos. 1 through
9, no malathion was detected in the incinerator effluent. Runs Nos. 10
and 11, however, failed to parallel earlier results in which detectable
levels of total pyrophosphates were found only in tests where relatively
high concentrations of malathion (350 to 590 rag/ml) were burned. Thus,
a definite correlation could not be made between pyrophosphate generation
and either operating temperature or incinerator feed concentration.
212
-------
Table 51. SUMMARY OF 57% MALATHION EC EXPERIMENTS
No.
1
2
3
4
5
6
7
8
9
10
11
a/
b/
c/
-------
Table 52. INCINERATION EFFICIENCY--57% MALATHION EC EXPERIMENTS
Run
£2*
1
2
3
4
5
6
7
8
9
10
11
a/
b/
If
Al
Malathion Total species^/
Malathion content of content of
feed ratefi' off-gasV off-gas
8/hr g/hr g/hr
1,760
2,630
1,470
9?0
1,170
1,970
1,990
1,640
3,630
660
630
< 3.
< 1
< 1
< 2.
< 1
< 1
< 1
< 1
< 2
< 2
< 2.
Actual malathion content
Malathion was
Malathion (Its
Pffielrntw Is
3 x IO'2
x ID'2
x ID'2
4 x 10"2
xlO-2
xlO-2
x ID'2
x IO"2
x ID'2
x 10
0 x ID'2
of the
< 1.0
< 7
<2
< 4.8
< 3
<3
< 3
< 3
< 3
< 3
x 1C' l
x ID"2
x ID'2
x ID'2
x ID"2
x ID"2
x 10"2
x ID"2
x ID'2
x lO'2
< 4.0 x lO"2
incinerator feed.
not detected In any effluent gas
detection
defined aa
limit)
plus all other
T. quantity outl
Ratio of
Ratio of total speclesS/
malathton content of Incinerator efficiency^/
In the off-gas- the off-gas to 7,
to malathion fed to malathion fed Malathion
< 1.9 x ID'5
< 5 x 10'6
< 8 x 10"6
< 2.6 x ID"5
< 1 x ID"5
< 6 x 10"6
< 6 x 10"6
< 8 x 10"6
< 4 x ID'6
< 3 x ID"5
< 3.2 x ID"5
The values shown represent
organic
100. whel
<6
< 3
< 2
<5
<3
< 1
< 1
< 2
< 9
< 5
< 6
the detection
x 10"5 > 99.99
x lO"5 > 99.99
x 10"5 > 99.99
x ID"5 > 99.99
x 10"5 > 99.99
x 10"5 > 99.99
x ID"5 > 99.99
x IO"5 > 99.99
x 10"6 > 99.99
x ID'5 > 99.99
x 10"5 > 99.99
limit for each test.
Total species^.'
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
phosphate species detected.
•e the atianM tv out is
evaluated at
Satnnle Point- No. (yi Mnclnpraf
TIT rtf f -oac. \ an A
the quantity j.n is evaluated at Sample Point No. (l) (the incinerator feed). Efficiencies have been calculated based on: (a) the malathion
detection limit only; and (b) malathion plus all other organic phosphate species detected.
-------
Table 53. OFF-GAS COMPOSITION—577, MALATHION EC INCINERATION^/
NO
Total hydrocarbons analyzer
Run
No.
1
2
3
4
5
6
7
8
9
10
11
Malathionb/
n«/m3
< 1.3 x
< 1.0 x
< 1.1 x
< 1.1 X
< 1.0 x
< 1.0 x
< 1.0 x
< 1.1 x
< 1.0 x
< 1.1 x
< 1.1 x
10'1
10-1
10-1
ID'1
ID'1
10-1
10-1
10-1
10-1
10-1
ID'1
Total
species—'
< 4.0 x 10-1
< 4.9 x 10-1
< 2.2 x 10-1
< 2.1 x 10*1
< 2.7 x 10-1
< 2.5 x 10"1
< 2.4 x 10"!
< 2.8 x 10"!
< 2.3 x 10"1
<2.1x 10-1
< 2.2 x 10"1
mg/m^
3,430
8,080
5,540
2,180
5,360
7,910
8,210
5,210
6,050
1,580
631
mg/nr
677
1,050
33
35
23
22
45
19
130
182
141
Total
hydrocarbons
ppm
242
15
27
698
5
3
18
NDS'
87
26
14
Orsat analyzer
CO
PPm
2,790
4,380
3,340
ND
ND
1
ND
ND
ND
< 1
ND
CH4
ppm
160
< 1
23
< 1
1
2
< 1
< 1
< 1
14
7
°2
vol. 7.
12.2
9.2
6.7
11.9
13.6
13.9
11.4
11.5
10.6
14.1
16.0
C02
vol. 7.
6.5
9.1
10.4
6.8
5.6
5.3
7.4
7.1
7.8
5.1
3.7
CO
vol. %
0.2
0.1
0.1
0.1
0.0
0.0
0.1
0.0
0,1
0.0
0.1
Moisture
vol. 1,.
0.0
10.5
8.1
4.1
5.2
8.4
9.7
4.6
4.3
5.0
4.5
a/ As dry gas at one atmosphere pressure, and 21.1*C (70*F).
b/ Malathlon was not detected In any effluent gas. The values shown represent the detection limit for each test.
c/ Malathion (its detection limit) plus all other organic phosphage species detected.
&/ Calculated as N02.
e/ Not detected.
-------
Table 54. OPERATIONAL DATA SUMMARY--577, MALATHION EC EXPERIMENTS
N>
I-"
ON
Run No.
Temperature *C (*F)
Primary chamber (Thermocouple No. \)J )
Primary chamber (Thermocouple No. Q) )
Primary chamber (Thermocouple No. Q) )
Second chamber (Thermocouple No. K) )
Second chamber (Thermocouple No. oS )
Sample Point No. (2) (Thermocouple No. (5)
Pressures
Draft (Manometer No. /Ti ), pascals
(in. H20) gauge
Burner operation pressure, pascals (pal)
gauge
1
1050 (1930)
1030 (1880)
1060 (1940)
980 (1800)
620 (1150)
) 350 (660)
22 (0.090)
9.0 x 105 (130
2
1070 (1950)
1050 (1930)
1060 (1940)
900 (1650)
610 (1130)
310 (590)
21 (0.085)
I) 9.1 x 105 (132)
_L
1020 (1860)
1000 (1840)
1000 (1830)
890 (1630)
540 (1010)
230 (450)
12 (0.050)
- HA*/
4
990 (1810)
960 (1760)
980 (1800)
830 (1530)
570 (1060)
330 (630)
35 (0.140)
6.3 x 105 (92)
5
620 (1140)
560 (1040)
650 (1200)
580 (1070)
380 (720)
170 (330)
2 (0.010)
6.6 x 105 (95)
6
640 (1190)
590 (1100)
680 (1250)
580 (1080)
370 (700)
180 (350)
19 (0.075)
6.9 x 105 (100
7
680 (1260)
640 (1180)
720 (1330)
620 (1140)
390 (740)
170 (340)
19 (0.075)
i) 6.8 x 105 (9
Run No.
Temperature *C (°F)
Primary chamber (Thermocouple No.
Primary chamber (Thermocouple No.
Primary chamber (Thermocouple No.
Second chamber (Thermocouple No.
Second chamber (Thermocouple No.
10
11
Sample Point No.
Pressures
(Thermocouple No.
), pascals
) 690 (1280)
) 650 (1200)
) 730 (1350)
) 600 (1120)
) 390 (730)
. (§) ) 160 (320)
950 (1750)
930 (1700)
970 (1780)
840 (1540)
570 (1050)
290 (560)
590 (1100)
490 (910)
620 (1150)
520 (970)
300 (570)
190 (370)
580 (1070)
470 (880)
600 (1110)
550 (1020)
350 (670)
240 (460)
Draft (Manometer No.
(In. H20) gauge
Burner operating pressure, pascals (psi)
gauge
16 (0.065) 22 (0.090) 15 (0.060) 35 (0.140)
5.9 x 105 (85) 9.3 x 105 (135) 7.3 x 105 (105) 7.2 x 105 (105)
a/ Not determined.
-------
The results of total pyrophosphate analysis for these 11 experiments
were as follows:
a/
Pyrophosphates—'
Run No. (gr/hr)
2 ND
3 ND
4 ND
5 3.21
6 2.14
7 2.46
8 2.14
9 0.62
10 2.01
11 ND
aj Expressed as phosphorus.
b/ Not detected.
In order to evaluate the effect of physical form on the efficiency
with which malathion can be incinerated, five tests were made using an
~ 25% dust formulation. Results from these experiments are summarized in
Tables 55 through 59. Two efficiencies of combustion have been calculated
(see Table 56). The first considers only the quantity of actual malathion
in the incinerator input and discharge. This efficiency calculation shows
that > 99.99% of the malathion injected into the incinerator was at least
partially degraded at all temperatures tested, 630 to 1040°C (1170 to
1900°F).
The second efficiency calculation includes not only the malathion
that was left, but also all other organic phosphate species detected.
Using this calculation, all five tests showed an efficiency of > 99.99%
for the incinerator effluent gas.
Measurable quantities of total pyrophosphates were not detected in
either the residues or the effluent gas from the incineration of 257*
malathion dust. The colorimetric method being used for total pyrophosphate
determination is based on the difference between ortho- and total phos-
phate content.
217
-------
Table 55. SUMMARY OF 257. MALATHION WETTABLE POWDER EXPERIMENTS
00
No. 2 fuel oil rate
Nominal
Run burner size
No. Z/hr (gal/hr)
A 4.7
B 9.5
C 4.7
D 11.4
E 3.8
(1.25)
(2.5)
(1.25)
(3.0)
(1.0)
Pesticide feed rate
Actual _ 257. Malathlon Contained
rate formulation malathlon
Z/hr (gal/hr) kg/hr (Ib/hr) g/hr (lb/hr)-'
4.05 (1.07)
8.52 (2.25)
4.09 (1.08)
10.48 (2.77)
3.63 (0.96)
• / Actual malathlon content of the -
b/ Calculated according to Method 3
14.02 (30.9) 3,310 (7.33)
19.23 (42.4) 4,580 (10.08)
13.15 (29.0) 3,130 (6.90)
13.83 (30.5) 3,290 (7.25)
6.30 (13.9) 1,100 (2.42)
> 257. wettable powder formulation.
of "Standards of Performance for New
Primary
chamber
temperature Excess
810
1040
730
930
(1490)
(1900)
(1340)
(1710)
630 (1170)
Stationary Sources
43
37
113
156
157
," Federal
Retention tlme£/
sec
Primary
chamber
4.2
3.8
5.7
1.9
4.2
Regis ter ,
Secon
chamb
4.5
3.9
5.6
1.8
Sampli
d tinw
er min
60
60
60
60
4.0 60
36(247) :24876-24895,
Off -gas
Lng flow rate^/
: m3/hr
(1.000's of SCFH)
201
184
167
408
(7.1)
(6.5)
(5.9)
(14.4)
246 (8.7)
23 December 1971.
£/ Retention time is defined as — , where v Is the wet off-gas flow rate from the incinerator at the respective chamber temperature and pressure, and
V is the volume of that chamber.
d_/ As dry gas at one atmosphere pressure, and 21.1*C (70°F).
-------
Table 56. RESIDUE AND OFF-GAS CHARACTERISTICS—25% MALATHION WETTABLE POWDER EXPERIMENTS
S3
•M 257* Malathlon Contained
Run
No.
A
B
C
D
E
Run
No.
A
B
C
D
E
formulation
kit/hr (Ib/hr)
14.02 (30.9)
19.23 (42.4)
13.15 (29.0)
13.83 (30.5)
6.30 (13.9)
of off-gaa
< 1.5 x 10-^'
2.1 * 10" 3 ..
<1.5x 10-3 2
< 1.4 x 10"3-:.
<1.5x ID"3 -'
malathlon^'
g/hr
3,310
4,580
3,130
3,290
1,100
•olid reslduea
K/hr
1.7 x 10'2
2.7 x 10"3
2.6 x 10"3
< 8 x 10"4
2.5 x 10'3
Total
kg/hr (Ib/hr)
2.68 (5.9)
2.04 (4.5)
2.77 (6.1)
2.04 (4.5)
1.18 (2.6)
Total
malathlon
aolld realduea
c/hr
< 1.8 x HT2
4.8 x KT3
< 4.1 x 10"3
<2.2 x 10' 3
<4.0 x 10'3
Primary chamber
Malathlon cone.
ppm
5.6
0.6
0.4
< 0.3i'
1.5
off-gas
K/hr
< 1.5 x 10'3
2.1 x 10'3
< 3.7 x 10"2
< 8 x 10"3
< 1.5 x 10'3
Solid
Total species':'
cone . , ppm
5.6
1.3
0.4
<0.3
1.5
•olid residues
K/hr
1.8 x 1CT2
3.9 x 10'3
2.6 x lO'3
< 8 x lO'4
2.5 x iO'3
residue
Total
kg/hr (Ib/hr)
1.22 (2.7)
0.73 (1.6)
0.63 (1.4)
0.68 (1.5)
0.68 (1.5)
Total •peclesS.'
solid residues
K/hr
< 2.0 x 10'2
6 x 1(T3
<4.0 x 10'2
< 9 x 10'3
< 4.0 x 10'3
Second chamber
ppm
1.2
1.9
2.4
< O.lfe/
1.1
Ratio of
to total
malathlon fed
<4.5 x lO'7-'
4.6 x 10-7d/
< 4.8 x 10'7j/
< 4.3 x 10'73/
< 1.4 x 10"6~
Total species^'
cone., ppm
1.2
1.9
2.4
< 0.3
1.1
Ration of
to total
malathlon fed
< 4.5 x UT7
4.6 x 10'7
< 1.2 x 10'5
2.4 x W6
< 1.4 x 10'6
Ratio of total
formulation
0.28
0.14
0.26
0.20
0.29
7.
fed
efficiency*/
Malathlon Total species^'
> 99.99
•> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
a/ Actual malathion content of the — 257, wettable powder formulation.
W Malathion was not detected in this residue. The value shown represents the detection limit for malathlon in this sample.
c/ Malathion as well as all other organic phosphate species detected.
d/ Malathlon was not detected in this off-gas. The value shown representa the detection limit for malathlon in the respective sample.
e/ Efficiency is defined as^ _ ^"^ ^] x LOO, where the Sample Points Nos. © (the incinerator off-gas) and
Sample Point No. (T) (the incinerator feed). Efficiencies have been calculated based on (a) malathlon only and (b) the total organic phosphate species detected at
at Sample Points Nos. (?) and (3) .
(solid residues) and the quantity in is evaluated at
-------
Table 57. OFF-GAS COMPOSITION—257. MALATHION DUST INCINERATION5-/
KJ
K)
0
Run Malathion
No. mg/m3
A < 7.0 x 10'3-
_o
B 1.0 x 10 ^
C < 8.4 x 10"3-
/
D < 3.2 x 10' 3~
E < 5.6 x 10"
Total^
species
/ 3
< 7.0 x 10"3
1.0 x 10"12
< 2.1 x 10"1
< 1.8 x 10'2
<• 5.6 x 10"3
Total hydrocarbons analyzer
.. Total Orsat analyzer
S02 N0x hydrocarbons CO CH^ 02 C02 CO
mg/m3 mS/m PPm PP™ PPm vol. "/, vol. 7, vol. 7
17,650 36 0 02 6.6 10.9 0.2
6,890 17 < 1 < 1 2 6.0 10.8 0.2
8,910 220 14 132 3 11.3 7.5 0.1
2,880 1,550 3 10 < 1 12.9 6.1 0.0
2,450 46 4 < 1 2 13.1 5.9 0.1
Moisture
vo 1 . ','•
7.1
7.9
7.0
7.8
7.5
»/ As dry gas at one atmosphere pressure, and 21.1°C (70°F).
b/ Malathion was not detected in this off-gas. The value shown represents the detection limit for malathion in the respective sample.
c/ Malathion plus all other organic phosphate species detected.
£/ Calculated as N02.
-------
Table 58. PARTICULATE SAMPLING SUMMARY--25% MALATHION WETTABLE POWDER EXPERIMENTS
Description
Vol. dry-gas - std. cond., nm
Percent moisture by vol.
Avg. stack temperature, °C
Stk. flow rate, dry, std. cond., nm /min
Actual stack flow rate, m /min
Percent isokinetic
Percent excess air
Particulates - partial catch
Particulate wt. - partial, mg
Part, load - ptl, std. en., mg/nm
Part, load - ptl., stk. en, mg/nr'
Partic . emis . - partial, kg/hr
Particulates - total catch
Particulate wt. - total, mg
Part, load - ttl. , std. en., mg/nm^
Part, load - ttl., std. en., corrected to
127. C02, mg/nm3
Part, load - ttl., stk. en., mg/rn^
Partic. emis. - total, kg/hr
Percent implnger catch
A
0.335
7.1
204.4
3.3
5.8
95.9
43
11,200
33,500
19,300
6.714
11,300
33,600
37,000
19,400
6.733
0.29
B
0.305
7.9
303.3
3.1
6.5
94.3
37
10,100
33,000
15,600
6.134
10,100
33,100
36,800
15,700
6.152
0.30
C
0.280
7.0
246.2
2.8
5.3
96.3
113
5,520
19,700
10,400
3.281
6,160
22,000
35,100
11,600
3.664
10.44
D
0.723
7.8
477.0
6.8
18.8
101.5
156
10,800
14,900
5,390
6.065
10.800
14,900
29,300
5,400
6.081
0.27
E
0.418
7.5
209.7
4.1
7.3
97.7
157
5,500
13,100
7,390
3.223
5,550
13,200
26,900
7,460
3.253
0.93
-------
Table 59. OPERATIONAL DATA SUMMARY—25% MALATHION WETTABLE POWDER EXPERIMENTS
ro
NS
NJ
Run No.
Temperatures, "C (°F)
Primary chamber (Thermocouple No. (D )
Primary chamber (Thermocouple No. \2) )
Primary chamber (Thermocouple No. (3) )
Second chamber (Thermocouple No. \M )
Second chamber (Thermocouple No. \5) )
Sample Point No. @ (Thermocouple No. \§) )
0
A
800 (1480)
810 (1490\
NA-7
650 (1210)
420 (790)
220 (430)
B
1000 (1840)
1040 (1900)
1040 (1900)
920 (1680)
560 (1040)
320 (600)
_C_
670 (1230)
680 (1260)
730 (1340)
600 (1120)
410 (770)
250 (490)
0
890 (1630)
840 (1540)
930 (1710)
800 (1480)
600 (1120)
470 (870)
E
610 (1130)
540 (1010)
630 (1170)
550 (1030)
350 (670)
230 (450)
Draft (Manometer No. ), pascals
(in. H20) gauge
Burner operation pressure pascals (psi)
gauge
Pesticide injection air, pascals (psi)
gauge
151 (0.060) 27 (0.110) 16 (0.065) 62 (0.250) 29 (0.115)
7.6 x 105 (110) 7.6 x 105 (110) 7.4 x 105 (107) 9.1 x 105 (132) 7.4 x 105 (108)
6 x 104 (9) 6 x 104 (9) 6 x 104 (9) 8 x 104 (12) 6 x 104 (9)
a/ Thermocouple burned out during the test.
-------
In general, results of the ortho- and total phosphate analyses for a given
sample were equal (within experimental error); and therefore indicated
no measurable total pyrophosphate. However, a few samples showed a higher
value for ortho- than for total phosphates. This inconsistency can be at-
tributed to positive interference during the color formation step of the
orthophosphate test. During subsequent nitric acid digestion for total
phosphate analysis, it is very probable that the interfering substances
were destroyed, thus giving a lower absorbance for the spectrophoto-
metric measurement.
The results of the particulate sampling conducted on the malathion
tests are shown in Table 58. Two modifications of the standard sampling
method were made to facilitate the analysis of the sample for malathion
content; benzene was used in the impingers rather than water, and a liquid
nitrogen cold trap was added to the sample train in order to collect con-
densibles for malathion analysis. Acceptable isokinetic conditions were
achieved in all runs. The loadings all exceed what can be considered low
emission and indicate the need for a particulate control device when in-
cinerating malathion dust formulations.
Upon completion of the experiments with malathion, the experimental
apparatus was inspected for any deposits or residues of pesticide contain-
ing materials. Wall scrapings from the horizontal section of the incinerator
stack, the first water scrubber, and the demister pad in the first water
scrubber contained no detectable levels of malathion, or of any other
organic phosphorus compound. Wall scrapings from the vertical section of
the incinerator stack contained 0.5 ppm malathion. Thus, there was apparently
no significant deposition of malathion or any other organic phosphorus
compound in the experimental apparatus.
DISCUSSION
Minor operating problems were encountered during the 57% malathion
EC tests. Plugging of the demister in the first stage water scrubber
(Manometer No./^ , Figure 5, p. 27) was observed, primarily during
tests conducted at low draft (see Table 54). In addition, a visible white
plume was noted emitting from the scrubber system exhaust. These same
problems, i.e., inability to remove P2(-I5 from tne effluent gas stream
and plugging of filter elements had also been encountered during recent
studies of the incineration of the organophosphorus chemical warfare agents
GB and VX (Wynneii/ and Capasso et al.H/).
223
-------
References
1. Cyanamid International, Malathion Insecticide for Adult Mosquito
Control (Bulletin), Wayne, New Jersey (undated).
2. Metcalf, R. L., and R. B. March, "The Isomerization of Organic Thio-
phosphate Insecticides." J. Econ. Entomol., 46:288-294 (April 1953).
3. McPherson, J. B., Jr., and G. A. Johnson, "Thermal Decomposition of
Some Phosphorothioate Insecticides," J. Agr. Food Ghem., ,4(1): 42-49
(January 1956).
4. Smith, W. M., Jr., and J. 0. Ledbetter, "Hazards from Fires Involving
Organophosphorus Insecticides," Amer. Ind. Hyg. Assoc. J., 32^(7):
468-474 (July 1971).
5. Kennedy, M. V., B. J. Stojanovic, and F. L. Shuman, Jr., "Chemical
and Thermal Methods for Disposal of Pesticides," Res. Rev.,
29:89-104 (1969).
6. Melnikov, N. N., Chemistry of Pesticides, Springer-Verlag, New York,
pp. 357-359 (1971).
7. Stojanovic, B. J., F. Hutto, M. V. Kennedy, and F. L. Shuman, Jr.,
"Mild Thermal Degradation of Pesticides," J. Environ. Quality,
J.(4): 397-401 (1972).
8. Putnam, R. C., F. Ellison, R. Protzmann, and J. Hilovsky, "Organic
Pesticides and Pesticide Containers—A Study of their Decontamina-
tion and Combustion," EPA-SW-21C-71 (PB 202 202) (1971).
9. EPA Compendium of Registered Pesticides, Vol. Ill, U.S. Environmental
Protection Agency (1973).
10. Midwest Research Institute, "Initial Scientific and Minieconomic Review
of Malathion" (Draft), EPA Contract No. 68-01-2448 (September 1974).
11. Wynne, D. J., "Pilot-Scale Incineration of GB and VX and the Containment
of Gaseous Products," Edgewood Arsenal Technical Report No. EATR
4734, U.S. Army Munitions Command, Edgewood Arsenal, Maryland (May
1973).
12. Capasso, N. S., L. Buckles, P. Cavey, F. Hildebrandt, and I. I. Stevens,
U.S. Army Munitions Command, Edgewood Arsenal, Maryland; personal
communication to Mr. Thomas L. Ferguson and Mr. Fred J. Bergman
(14 September 1973).
224
-------
V. TOXAPHENE
PESTICIDE DESCRIPTION
Physical Properties
Chemical Name; Chlorinated camphene, octachlorocamphene
Common Name; Toxaphene
Trade Names; Agricide® Maggott Killer, Alltox®, Chem-Phene®,
Estonox®, Phenacide®, ChlorChem T-590, Motox,
Phenatox®, Strobane-T@, Toxakil®
Pesticide Class; Insecticide, chlorinated hydrocarbon
Structural Formula;
XVL-CH3
8(ci)4- rLcH3
\^X
-------
Viscosity; Temperature
100
110
120
130
SayboIt-Universal
(sec) Poises
400 1.4
260 0.9
174 0.6
120 0.4
Solubility; SoIvent
Acetone
Benzene
Carbon tetrachloride
Ethylene dichloride
Toluene
Xylene
Hexane
Turpentine
Kerosene
Fuel oil
Isopropyl alcohol
957. Ethyl alcohol
Water at 25°C
Chemical Properties
Grams/100 ml at 27°C
all proportions
all proportions
all proportions
all proportions
all proportions
all proportions
all proportions
below 350
above 280
below 250
below 15
below 10
0.4 ppm
Toxaphene is reported to dehydrochlorinate in the presence of alkali
upon prolonged exposure to sunlight and at temperatures of about 155°C.2/
Reduction with sodium in isopropyl alcohol is the analytical method for
total chloride.
Production and Use
Toxaphene is a broad-spectrum insecticide (contact and stomach poison)
which is used on a large number of agricultural crops, livestock, and orna-
mentals.
It has been estimated that the 1972 domestic production of toxaphene
was 70 to 95 million pounds (von Rumker et al.).—/
The toxaphene is formulated as 10 and 15% granular, 20% dust, and
6 and 8 Ib/gal emulsifiable concentrates. Other formulations are low-
volume concentrates, wettable powders, solutions, and combination formula-
tions with other insecticides. These formulations are available under dif-
ferent brand names and in varying concentrations of active ingredient.
226
-------
FORMULATIONS TESTED
The two toxaphene formulations tested were a 60% EC and a 207<> dust.
60% EG
Name; Arcadian® Toxaphene EM-6
Manufacturer; Allied Chemical Corporation, Morristown, New Jersey
Composition; Active Ingredients
Toxaphene (technical chlorinated camphene,
67 to 69% chlorine) 60.00%
Petroleum Distillate (minimum
unsulfonated residue 97%) 30.34%
Xylene 6.66%
Inert Ingredients 3.00%
Total 100.00%
Registration; EPA Reg. No. 218-643
Lot No.; SO-108022
20% Dust
Name; Cotton States Toxaphene 207o Dust
Manufacturer; Cotton States Chemical Co., Inc., Monroe, Louisiana
Composition; Active Ingredients
Toxaphene* 20.00%
Inert Ingredients 80.00%
Total 100.00%
* Technical chlorinated camphene (chlorine content
67 to 69%)
227
-------
Registration; EPA Reg. No. 1339-6
Pesticide Size Specifications; Formulated in attapulgite clay such
that at least 90% passes through
a 44 ^ (325 mesh) sieve
PRELIMINARY THERMAL ANALYSIS
Laboratory thermal analyses of toxaphene gave the following results:
Sample Test Test Method Result
Toxaphene Sulfur ASTM D-129 3.27%
20% dust Calorific value ASTM D-240 3.286 x 106 J/kg
(1,414 Etu/lb)
Toxaphene Sulfur ASTM D-129 2.35%
60% liquid form Calorific value ASTM D-240 2.577 x 107 J/kg
(11,089 Btu/lb)
Figures 37 and 38 show the results of DTA and TGA of the technical
grade toxaphene. DTA data show no prominent endotherm or exotherm at
lower temperatures. However, as the temperature reaches about 290°C,
sharp decomposition is observed and continues to 400 C (instrument limit).
This decomposition process is substantiated by the TGA data which indicate
almost 95% of the initial weight is lost when temperature reaches 300°C.
Figures 39 and 40 show the results of DTA and TGA of the 20% toxa-
phene dust formulation. The DTA data show no significant exotherms or
endotherms; however, a slow decomposition process is observed. This de-
composition process is substantiated by the TGA which indicates slow
weight loss all the way to about 700°C. The weight loss takes place mainly
at two temperature ranges, one quite abruptly at about 190 to 260°C (about
20% weight loss), and the other, rather gradually, from 260 to 710°C (about
15% weight loss). At 710°C about 35% of the original weight is gone, compared
to the nominal 20% toxaphene content of the formulation. No further weight
loss is observed from 710 to 1000°C.
228
-------
o
x
NJ
O
Q
z
0 24 40
Reference: Empty pan
Prog, mode: Heat
Rate: 10°C/min
Start: 24°C
80
120
160
200
TEMPERATURE °C
240
280
320
360
400
Figure 37. DTA of technical toxaphene
-------
1000
900
800
700
600
500
400
300
200
100
_L
JL
I L
1.0
JL.
J_
2.0 3.0
WEIGHT LOSS, ing
I I I L
JL
4.0
_L
5.0
J
10 20 30 40 50 60 70 80 90 100
WEIGHT LOSS. PERCENT
Sanple weight: 4.404 rag
Heating rate: 20°C/min
Environment: — 20 ml/min air (20TL 02> 801 1^)
Figure 38. TGA of technical toxaphene
230
-------
i i i i i i i i i i i i i i i i i \ 1 1 1 1 1 i i 1 i 1 1 i i i i i i i i j i
10 20 30 40 SO 60 70 BO 90 100 110 120 130 140 150 160 170 ISO 190 200 210 220 230 240 250 260 270 280 290 300 310 320 330 340 350 360 370 380 390 400
TEMPERATURE "C
Reference: Empty pan
Prog, mode: Heat
Rate: 10°C/min
Start: 26°C
Figure 39. DTA of ~ 20% toxaphene dust
-------
1000 r-
0.0
0.1
0.2
0.3 0.4 0.5
WEIGHT LOSS, mg
J_
0.6
_L
10
20 30
WEIGHT LOSS, PERCENT
Sample weight: 1.878 mg
Heating rate: 20°C/min
Environment: ~ 20 ml/min air (20% 02, 80% N2)
Figure 40. TGA of ~ 207, toxaphene dust
0.8
40
232
-------
Figures 41 and 42 show the results of DTA and TGA of a sample of
recrystallized toxaphene obtained by evaporation of a sample of the liquid
formulation. The DTA data (Figure 41) show an endotherm at about 306°C,
which may be only a phase change, as TGA data in Figure 42 show no sig-
nificant weight loss at this temperature. However, prior to this endotherm,
decomposition is observed which is substantiated by the abrupt weight loss
from 180 to 280° G in the TGA. About 95% of the original weight is gone
at 280°C. Essentially no more than 3% additional weight loss is observed
from 280 to 1000°
METHODS OF ANALYSIS
Apparatus
A Micro-Tek 2000R gas chromatograph equipped with a 3-ft, 4 mm I.D.
glass column (packed with 1.5% OV-17 + 1.95% QF-1 on 80/100 mesh Supelco-
port from Supelco, Inc., Bellefonte, Pennsylvania) and a tritium electron
capture detector, maintained at a voltage of 20 V DC, was used for gas
chromatographic analysis. The chromatographic operating conditions were:
injector temperature, 210°C; column temperature, 195°Cj detector temper-
ature, 180°C; carrier flow rate, 80 ml/min, N2; and a purge gas flow rate,
120 ml/min, N2.
A Hewlett-Packard 3380A Integrator was used for peak quantification.
Reagents and Materials
Analytical reagents toxaphene (68.9% Cl") and aldrin (97% pure), were
used for preparing standards. Solvents used were pesticide grade 2,2,4-
trimethylpentane (Mallinckrodt) for standard preparation and all impingers,
and pesticide grade hexane (Matheson, Coleman, and Bell) for extraction
of hexylene glycol traps from the second stage scrubber. All laboratory
glassware (beakers, vials, etc.) was washed in Alconox detergent (Scien-
tific Products) and rinsed with deionized distilled water and reagent grade
acetone (Fisher Scientific).
Standards and Calibration Curves
The solid standard, aldrin, provided by USEPA, was used to prepare
a stock solution of 100 p,g/ml and appropriate dilutions were made to ob-
tain linear results (linear range used: 0 to 200 pg). A toxaphene stan-
dard was made up in the same manner and used for a standard curve for the
incinerator feed samples.
233
-------
NJ
. I I . I I 1 1 I 1 I I 1 I I I 1 I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ' I I I I
I 20 j5 Jo» 60 70 60 90 W HO 120 130 140 ISO 160 170 180 190 200 210 220 230 240 2SO 2«0 270 280 290 300 310 320 330 340 3iO 360 370 380 390 400
T!MPf«AtU»f 'C
Reference: Glass beads
Prog, mode: Heat
Rate: 10°C/min
Start: 26°C
Figure 41. DTA of recrystallized toxaphene
-------
1000
900
800
700
600
D
<
C*L
LU
5 500
400
300
20C
10
5
J L
_L
J_
0.0 0.1 0.2
0.4 0.5 0.6 0.7 0.8 0.9 1.0
WEIGHT LOSS, mg
I I I 1
K2K3 1.4 1.5 1.6 1.7
10
20
30
40 50 60
WEIGHT LOSS, PERCENT
70
80
100
Sample weight: 1.674 mg
Heating rate: 20°C/min
Environment: ~ 20 ml/min air (207» 02, 80% N2)
Figure 42. TGA of recrystallized toxaphene
235
-------
Procedure for Sample Preparation
All impingers, washes, and blank solutions, except the hexylene
glycol samples from the second stage scrubber, were taken just to dry-
ness in their original French Square, sample bottles. Ten milliliters of
the hexylene glycol samples were extracted with n-hexane and the extract
was taken just to dryness. All samples were taken up again in appropriate
amounts of 2,2,4trimethylpentane just prior to gas chromatography.
The mass of collected particulates was determined for all samples
collected from incineration of toxaphene dust as follows: samples were
taken to dryness under a hood in clean, dessicated, tared 250-ml beakers
and dessicated 2 days before final weighing. The residue was extracted
with 2,2,4-trimethylpentane (two 10 to 15 ml portions) and the extract
was taken just to dryness. The silica gel was extracted with sufficient
2,2,4-trimethylpentane to cover the silica gel and a 20 ml portion
pipetted out and taken to dryness. Twenty milliliter portions of the
blank impinger solutions (2,2,4-trimethylpentane and acetone) were pipetted
out into vials and taken to dryness. All samples were then taken up again
in appropriate amounts of 2,2,4-trimethylpentane just prior to gas chro-
matography.
Portions of all cleanout samples (primary chamber, secondary cham-
ber, etc.) were weighed out and extracted and the extracts were analyzed
for toxaphene (chlorinated hydrocarbons).
Analysis and Discussion
The complexity of the toxaphene chromatogram has been illustrated
in the literature, including at least 175 polychlorinated id-carbon com-
pounds.!/ (Representative chromatograms for both the liquid toxaphene for-
mulation and the incinerator effluent are given in Figure 43). For this
reason, it is virtually impossible to pick out toxaphene as such from the
samples collected after each incineration. Therefore, it was decided to
quantitate all the chromatographic peaks based on an aldrin standard curve.
However, incinerator feed samples were quantitated relative to the actual
toxaphene response. This was accomplished by using four of the most
prominent and reproducible peaks in the toxaphene mixture.
The sensitivity of the instrument for aldrin is 1 pg. The sensitivity
for the toxaphene standard, based on the four most prominent peaks, is
0.5 ng. Since the feed samples consist of 60% toxaphene, appropriate dilu-
tions were necessary to bring its concentration to the calibration range.
236
-------
N3
-Reference Peaks
a - 60% Toxaphene Formulation
b - Incinerator Effluent
(Sample Point No. ©
Figure 5, p. 27)
Figure 43. Representative toxaphene chromatograms
-------
(External calibration method: Hewlett-Packard Integrator Model 3380A in-
struction manual, pp. 3-18.)
During the course of the toxaphene analysis, frequent ghosting was
observed in the chromatogram, which necessitated rerunning of several
samples where ghosts interfered. The detector required cleaning twice, and
consequently there was considerable down time on the instrument used for
toxaphene analysis.
TEST CONDITIONS AND RESULTS
Eleven tests were made using the 60% EC toxaphene formulation. The
temperature of the primary chamber was varied between the lower operating
limit of the incinerator, ~ 650°C (1200°F), and 1000°C (1830°F).
The results of these 11 tests are shown in Tables Nos. 60 through
62. As has been discussed above, technical grade toxaphene consists of
a number of chlorinated hydrocarbons, including at least 175 polychlori-
nated 10-carbon compounds..!' For this reason, the efficiency of toxaphene
incineration was evaluated based on actual toxaphene content of the in-
cinerator feed (Sample Point No.(T)) versus the total chlorinated hy-
drocarbons detected in the incinerator effluent (Sample Point No. (?))•
No solid residues were formed during the incineration of liquid toxaphene,
and therefore, do not enter into the efficiency calculation. The percent
efficiency calculations show that > 99.99% of the toxaphene injected into
the incinerator was degraded for all 11 experiments, i.e., over the ranges
of excess air, operating temperature, and incinerator feed rate investi-
gated.
There is no correlation between operating temperature and the rela-
tive amount of unburned "toxaphene" discharged (as shown by the "Ratio
of Chlorinated Hydrocarbon Content of the Off-Gas to Toxaphene Fed" column
of Table 60. Significantly higher levels were discharged, however, from
Tests 5 and 7. These two tests also had the shortest retention times in
the primary chamber (2.4 and 2.2 sec, respectively).
Six tests were made using an <~ 20% dust formulation of toxaphene in
order to evaluate the effect of physical form on incineration efficiency.
The results of the six tests are summarized in Tables 63 through 67.
Nominal conditions were the high feed rate (7.5 Ib active ingredient/hr),
"high" and "low temperature" 1000°C (1830°F) and 650°C (1200°F), respec-
tively, tively, and "high" and "low" excess air (150 and 50%, respectively)
238
-------
Table 60. SUMMARY OF 60% TOXAPHENE EC EXPERIMENTS
t-o
LO
Incinerator feed
Run
No.
1
2
3
4
5
6
7
8
9
10
11
Run
No.
1
2
3
4
5
6
7
8
9
10
11
Nominal
burner size
Total
fepd rate
Toxaphene rate
//hr (Ral/hr) i/hr (gal/hr) K/hr (lb/hr)a/
3.8 (1.0)
3.8 (1.0)
4.7 (1.25)
11.3 (3.0)
11.3 (3.0)
11.3 (3.0)
11.3 (3.0)
4.7 (1.25)
3.8 (1.0)
4.7 (1.25)
3.8 (1.0)
Retention
sec
Primary
chamber
5.3
5.0
4.6
3.4
2.4
3.8
2.2
5.2
6.6
6.5
6.7
3.41
3.71
4.16
9.16
9.16
8.74
10.14
4.20
2.84
4.01
3.67
e/
time"
Second
chamber
4.9
4.6
4.4
3.5
2.4
3.9
2.2
5.1
6.2
6.4
6.5
a/ Actual toxaphene content o
W
c/
d/
e/
£/
£/
Volume per hour
(0.90) 1
(0.98) 1
(1.10) 1
(2.42) 1
(2.42) 1
(2.31) 3
(2.68) 2
(1.11) 2
(0.75) 1
(1.06) 2
(0.97) 1
Sampling
time
min
30
30
30
30
30
30
30
30
30
30
30
,250 (2.75)
,220 (2.70)
,540 (3.40)
,520 (3.35)
,250 (2.75)
,240 (7.15)
,340 (5.15)
,220 (4.90)
,090 (2.40)
,110 (2.65)
,070 (2.35)
Off-gas f
flow rate""
m3/hr
Toxaphene No. 2 fuel
conct>nr r.ir i nn oil rate
i/hr (gal/rir)^/ m
2.38
2.31
2.91
2.84
2.35
6.09
4.43
4.20
2.08
4.01
2.01
/
(1,000's of SCFH)
156 (5.5)
159 (5.6)
156 (5.5)
156 (5.5)
232 (8.2)
136 (4.8)
249 (8.8)
144 (5.1)
116 (4.1)
113 (4.0)
110 (3.9)
(0.63)
(0.61)
(0.77)
(0.75)
(0.62)
(1.61)
(1.17)
(1.11)
(0.55)
(1.06)
(0.53)
Chlorinated
hydrocarbon
content of
off-gas
R/hr
4 x 10"3
2 x 10"3
1 x 10"3
4 x 10~*
4.1 x 10"^
8 x 10 ~^
4.0 x 10"
9 x 10~3
1 x 10
5 x lO^j
1 x lo"
R/ml «/hr (Ral/hr)
370 1.02
330 1.40
375 1.25
165 6.32
135 6.81
370 2.65
230 5.71
530
385 0.76
525
290 1.66
(0.
(0.
(0.
(1.
(1.
(0.
(1.
0 -
(0.
0 -
(0.
27)
37)
33)
67)
80)
70)
51)
20)
44)
Primary
chamber Flame
"C (°F) °c (°F)
620 (1150)
630 (1160)
680 (1260)
1040 (1900) 1040 (1910)
980 (1800)
1040 (1900) 1140 (2090)
990 (1820) 1160 (2120)
670 (1240)
660 (1220)
680 (1260) 1140 (2080)
650 (1200)
Excess^'
air
7
349
198
160
47
124
71
128
212
154
228
150
Ratio of chlorinated
hydrocarbon content
of the off-gas
to toxflphene
fed
3 x 10"6
2 x lO"6
9 x 10"7
i v in"7
J X. I"
3.3 x 10
2 x 10
1.7 x 10"5
4 x 10"6
_q
9 x 10 *
? V 1 0
-8
1 x 10
Efficiency*'
%
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
f the incinerator feed.
of the liquid toxaphene formulation.
The flame temperature was
observed at
a point approximately 15
Calculated according to Method 3 o£ "Standards of Performance
(23 December
Retention time
ond pressure,
1971).
is defined
and V is
y
as ~ , where v is the wet
the volume
As dry gas at one atmosphere pressure,
Efficiency is defined as:
of that chamber
anvl21.1°C (70
[~~ quantity outl
off-gas
°F).
cm (6 in.) in
from the fron wall
of
the
for New Stationary Sources," Federal Reg:
flow rate from
here quantity out is the
the incinerator at
amount of chlorin;
incinerator.
later, 36(247) : 24876-24895
the respective chamber temperature
sted hy<
irocarbons detected at
Sample Point No. (2*) (incinerator off-gas), and amount in is the amount
\ / f—v —
of toxaphene detected at Sample Point No. (1) (incinerator feed).
-------
Table 61. OFF-GAS COMPOSITION--607. TOXAPHENE EC INCINERATION^
Total hydrocarbons analyzer
Run
No.
1
2
3
4
5
ISJ
0 *
7
8
9
10
11
Chlorinated
hydrocarbons^'
mg/m3
2.6 x
1.3 x
9.0 x
2.8 x
1.8 x
5.7 x
1.6 x
6.0 x
8.6 x
4.1 x
1.0 x
ID'2
10-2
10-3
10-3
lO'1
lo-^
10-1
ID'2
10"5
ID'2
10-*
S02 NO-vi/
me/m3 me/m3
ND^ 439
672 257
30 392
240 ND2-/
72 ND
205 133
122 2,490
85 ND
114 11
59 322
110 ND
Total
hydrocarbons
ppm
13
7
6
222
11
9
ND
< 1
124
435
53
Orsat analyzer
CO
ppm
> 201-'
194
17
3,440
2
ND
34
12
4,000
2,220
107
CH4
ppm
3
1
3
35
< 1
1
3
5
5
62
3
°2
vol. 7,
16.4
14.5
13.3
7.1
11.9
9.0
12.0
14.5
13.0
14.9
12.9
co2
vol. %
4.1
4.5
5.5
10.0
6.8
8.9
6.5
4.8
6.1
4.4
6.0
CO
vol. %
0.4
0.3
0.0
0.3
0.0
0.0
0.0
0.1
0.0
0.1
0.0
Moisture
vol. 7,
3.9
6.6
7.4
11.9
5.9
10.4
7.3
7.6
6.8
8.5
9.8
a/ As dry gas at one atmosphere pressure, and 21.1°C (70°F).
b/ Total chlorinated hydrocarbon species detected.
£/ Not detected.
d/ Calculated as N02-
e/ Analyzer attenuation setting too low.
-------
Table 62. OPERATIONAL DATA SUMMARY--60% TOXAPHENE EC EXPERIMENTS
Run No.
Temperature °C (°F)
Primary chamber (Thermocouple No. (I) )
Primary chamber (Thermocouple No. (2) )
Primary chamber (Thermocouple No. /3) )
Second chamber (Thermocouple No. f& )
Second chamber (Thermocouple No. /5\ )
Sample Point No. Qf) (Thermocouple No. (6^ )
Pressures
Draft (Manometer No. /j\ ), pascals
(in H20) gauge
Burner operation pressure, pascals
(psi) gauge
Scrubber liquids^/
1st Stage, H20 scrubber
Volume, i (gal.)
Total species cone.,—' mg/4
2nd Stage, hexalene glycol scrubber
Volume, I (gal. )
Total species cone, change ,£/ mgAt
3rd Stage, 1I20 scrubber
Volume, I (gal. )
Scrubber system
Effluent gas (Sample Point No. f?))
1
580 (1080)
530 (980)
620 (1150)
570 (1050)
370 (690)
220 (430)
21 (0.085)
7.6 x 105 (110)
1200 (318)
5 x 10'4
109 (28.8)
9 x 10'2
1880 (497)
2 x 10"4
1 x 10'1
2
590 (1100)
540 (1000)
630 (1160)
570 (1060)
390 (740)
200 (400)
19 (0.075)
7.6 x 105 (110)
1120 (295)
6 x 10-4
109 (28.8)
5 x ID' 3
1750 (463)
4 x 10~4
7 x 10"2
_3_
650 (1200)
590 (1100)
680 (1260)
620 (1140)
420 (780)
200 (400)
19 (0.075)
7.6 x 105 (110)
1190 (315)
1 x 10"3
109 (28.8)
6 x 10'2
1750 (463)
2 x 10~3
6 x 10" 2
4
1010 (1850)
980 (1800)
1040 (1900)
890 (1640)
550 (1020)
260 (500)
20 (0.080)
9.3 x 105 (135)
1160 (306)
7 x 10'4
110 (29.1)
trod/
1750 (463)
1 x 10' 3
f \ x ID'2
5
940 (1730)
900 (1660)
980 (1800)
860 (1580)
590 (1100)
380 (710)
37 (0.150)
9.3 x 105 (135)
1170 T309)
6 x ID'4
111 (29.3)
ND
1750 (463)
8 x 10"^
1
6
1010 (1850)
990 (1310)
1040 (1900)
870 (1590)
600 (1110)
330 (620)
21 (0.085)
9.3 x 105 (135)
1140 (302)
4 x 10'3
111 (29.3)
2 x 10' '
1730 (457)
2 x iQ-4
3 x 10'2
Total species cone., mg/m
-------
Table 62. (Concluded)
K>
Run No.
Temperature *C I't)
Primary chamber (Thermocouple Ho. (p )
Primary chamber (Thermocouple No. (2) )
Primary chamber (Thermocouple No. {iy )
Second chamber (Thermocouple No. ^ )
Second chamber (Thermocouple No. /JS )
Sample Point No. (7) (Thermocouple No. (S) )
Pressures
), pascal*
Draft (Manometer No.
(In HjO) gauge
Burner operation pressure, pascals
(psl) gauge
Scrubber liquids^
1st Stage, H20 scrubber
Volume, I (gal.)
Total species cone.,—' mg/Z
2nd Stage, hexalenc glycol scrubber
Volume, i (gal.)
Total species cone, change,li' rag//
3rd Stage, H20 scrubber
Volume, t (gal.)
Total species conc.,£/
Scrubber system
Effluent gas (Sample Point No. )t-
Total species cone., mg/m
c/
10
11
990 (1820)
960 (1760)
1000 (1830)
860 (1580)
600 (1120)
390 (730)
41 (0.165)
9.3 x 105 (135)
1160 (306)
4 x 10'2
110 (29.1)
2 x 10'1
1790 (474)
NA^
< 1 x 10"2
650 (1200)
600 (1120)
680 (1250)
580 (1080)
370 (700)
220 (420)
24 (0.095)
7.4 x 105 (108)
1140 (302)
3 x 10'3
109 (28.9)
NA
1750 (463)
2 x 10'4
< 1 x 10"2
640 (1190)
550 (1030)
660 (1220)
590 (1100)
400 (750)
190 (370)
15 (0.060)
7.9 x 105 (115)
1230 (324)
2 x 10"3
108 (28.6)
ND
1950 (514)
4 x 10"3
< 2 x 10"2
660 (1220)
620 (1140)
680 (1260)
590 (1090)
390 (730)
190 (370)
16 (0.065)
8.1 x 105 (117)
1200 (318)
1 x 10
106 (28.1)
7 x T.O'2
1900 (503)
3 x 10
5 x 10* I
640 (1180)
540 (1000)
650 (1210)
580 (1070)
370 (700)
190 (370)
16 (0.065)
8.1 x 105 (118)
1180 (311)
2 x 10'4
104 (27.6)
ND
1820 (480)
2 x 10"3
< 1 x 10"2
a/ Scrubber water (Scrubbers 1 and 3) was used once through, while the hexylene glycol (Scrubber 2) was recycled. The concentrations reported for
~ hexylene glycol, therefore, are the concentration changes (Increases) detected during the respective tests.
b/ Total chlorinated hydrocarbon species detected.
c/ As the wet gas at 1 atm pressure and 21.70°C (70*F). Chlorinated hydrocarbons were not detected In all major elements of the sample train
(I.e., ImplngersV, the values given Include the detection limits for chlorinated hydrocarbons In these elements.
d/ No Increase In concentration detected.
e/ No analysis.
-------
Table 63. SUMMARY OF 20% TOXAPHENE DUST EXPERIMENTS
No. 2 fuel oil rate
Pesticide
Nominal ~ 207, Toxaphene
Run burner size Actual rate formulation
No. i/hr (gal/hr) i/hr (Ral/hr) kg/hr (Ib/hr)
A
B
C
D
E
F
a/
b/
c/
3.8 (1.0) 3.86 (1.02)
4.7 (1.25) 4.05 (1.07)
9.5 (2.5) 8.71 (2.30)
9.5 (2.5) 8.78 (2.32)
11.4 (3.0) 9.69 (2.56)
9.5 (2.5) 3.89 (2.35)
feed rate
Contained
toxaphene—
R/hr (Ib/hr)
14.92 (32.9) 3,520 (7.76)
16.47 (36.3) 2.750 (6.06)
18.42 (40.6) 3,060 (6.75)
18.51 (40.8) 3,850 (8.49)
16.51 (36.4) 3,430 (7.56)
14.47 (31.9) 3,310 (7.30)
Actual toxaphene content of the ~ 207. toxaphene dust formulation.
The flame temperature was observed at a point approximately 15 cm
Calculated according to Method 3 of "Standards of Performance for
Primary
chamber
temperature
°C (°F)
Flame
temperature—
°C (°F)
Excess
Retention time Off-gas
sec!/ Sampling flow rate£/
airr-' Primary
7. chamber
670 (1240) 900 (1650) 94 7.7
670 (1240) 970 (1770) 166 5.3
1010 (1850) -- — 53 2.9
1030 (1880) 920 (1690) 44 3.4
970 (1770) 1050 (1920) 122 2.5
1010 (1850) 1040 (1900) 121 2.4
The concentration ranged from 16.7 to 23.6%.
(6 in.) in from the front wall of the incinerator
New Stationary Sources," Federal Register, 36(247)
Second
chamber
8.3
5.7
3.2
4.1
2.8
2.8
(see Figure
:24876-24895
time
min
60
60
30
60
60
60
B-l),
, 23
m3/hr
(1,000's of SCFH)
195 (6.9)
283 (10.0)
337 (11.9)
278 (9.8)
416 (14.7)
399 (14.1)
December 1971.
d/ Retention time is defined as — , where v is the wet off-gas flow rate from the incinerator at the respective chamber temperature and pressure, and
V is the volume of that chamber.
e/ As dry gas at one atmosphere pressure, and 21.1°C (70°F).
-------
Table 64. RESIDUE AND OFF-GAS CHARACTERISTICS—20% TOXAPHENE DUST EXPERIMENTS
Run
No.
A
B
C
D
E
F
Run
No.
A
B
C
D
E
F
Feed rate
207. Toxaphene
formulation
kg/hr (Ib/hr)
14.92 (32.9)
16.47 (36.3)
18.42 (40.6)
18.51 (40.8)
16.51 (36.4)
14.47 (31.9)
Chlorinated
hydrocarbons^'
content of
off-gas
2/hr
1.1 x 10"2
5 x Hf3
1.1 x 10
7 x 10"3
5 x 10"3
1.0 x 10
• — — — — — — ^—
Contained
toxapheneS'
Solid
Primary chamber
Chlorinated
hydrocarbons".'
Total content
g/hr kg/hr (Ib/hr) ppm
3,520
2,750
3,060
3,850
3,430
3,310
Chlorinated
hydrocarbons]"'
content of
solid residues
8/hr
9 x 10"4
2.5 x 10"*
3.1 x 10"*
4.4 x 10"*
2.1 x 10
1.7 x 10
3.26 (7.2) 0.14
4.58 (10.1) 0.02
6.71 (14.8) 0.04
5.71 (12.6) 0.07
6.26 (13.8) 0.03
5.17 (11.4) 0.02
Total chlorinated
hydrocarbon^.'
content of
off -gas and
solid residues R/hr
1.2 x 10"2
6 x 10"3
1.1 x 10"1
7 x 10
6 x 10"3
1.0 x 10
residue
Second chamber
Total
kg/hr (Ib/hr)
1.72 (3.8)
1.09 (2.4)
1.18 (2.6)
1.27 (2.8)
2.27 (5.0)
2.13 (4.7)
Ratio of total
chlorinated
hydrocarbons^'
In the off-gas
to total
toxaphene fed
3.1 x 10"6
2.0 x 10
3.6 x 10
1.8 x 10
1.6 x 10
3.0 x 10"
hydrocarbons^'
content
ppm
0.27
0.15
0.04
0.03
0.01
0.03
Ratio of total
incinerator
residue to
total charge
0.34
0.34
0.43
0.38
0.51
0.51
Incineration efficiency^'
7.
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
£/ Actual toxaphene content of the formulation.
b/ Total chlorinated hydrocarbon species detected.
£/ Efficiency is defined as:
1 - 3^32 x 100, where quantities of chlorinated hydrocarbons out is evaluated at Sample Points
L Quantity .ln_j
Nos. (2) (incinerator off-gas) and Ml (solid residues). The quantity of toxaphene ^n Is evaluated at Sample Point No. (l ; (incinerator feed).
-------
Table 65. OFF-GAS COMPOSITION--207<, TOXAPHENE DUST INCINERATION^
Total hydrocarbon analyzer
Run
No.
A
B
C
D
E
F
Chlorinated
hydrocarbons^/ S02 NO*?./
nig / TO TOE / ro inE/in1^
5.6 x 10-2 299 74
1.9 x ID"2 NA£/ NA
3.3 x 10"1 ND!/ ND
2.4 x ID'2 < t ],
1.3 x 10'2 3 28
2.5 x 10'1 97 6
Total
Orsat analyzer
hydrocarbons CO CH, 02
ppm ppm ppm vol. %
78
46
NA
20
18
< 1
> 5,340^ 18 10.5
4,530 5 13.3
NA NA 7.6
105 2 7.2
ND 2 11.8
176 7 11.9
C02
vol. '/,
8.3
6.1
10.3
9.5
6.6
6.8
CO
vol. %
0.2
0.1
0.1
1.1
0.0
0.0
Moisture
vol. 7.
8.4
8.6
7.0
8.1
6.8
8.2
a/ As dry gas at one atmosphere pressure, and 21.1°C (70°F).
b/ Total chlorinated hydrocarbon species detected.
£/ No analysis.
d/ Not detected.
ej Calaculated as N02-
f/ Upper detection limit.
-------
Table 66. PARTICULATE SAMPLING SUMMARY—20% TOXAPHENE DUST EXPERIMENTS
t-o
Description
Vol. dry gas - std. cond., nn>3
Percent moisture by vol.
Avg. stack temperature, °C
Stk. flow rate, dry., std. cond., nnrVmin
Actual stack flow rate, m-Vmin
Percent isokinetic
Percent excess air
Particulates - partial catch
Particulate wt. - partial, mg
Part, load - ptl., std. en., mg/nnP
Part, load - ptl., stk. en., mg/m3
Partic. emis. - partial, kg/hr
Particulates - total catch
Particulate wt. - total, mg
Part, load - ttl., std. en., mg/nm3
Part, load - ttl., std. en., corrected
to 127. C02, rag/ run3
Part, load - ttl., stk. en., mg/m3
Partic. emis. - total, kg/hr
Percent impinger catch
A
0.321
8.4
195.6
3.0
5.2
102.4
96
10,700
33,100
19,000
5.959
16,400
50,800
73,000
29,200
9.142
34.81
B
0.444
8.6
194.0
4.3
7.5
98.7
166
8,230
18,500
10,700
4.772
8,270
18,600
37,000
10,700
4.800
0.58
C
0.319
7.0
259.5
5.2
10.1
116.6
54
1,240
3,890
2,020
1.223
1,270
3,960
4,620
2,060
1.247
1.91
_D_
0.427
8.1
271.8
4.3
8.5
96.0
44
2,570
6,010
3,000
1.533
2,660
6,230
7,900
3,110
1.590
3.55
E
0.659
6.8
363.0
6.5
15.1
97.3
124
873
1,320
567
0.513
958
1,450
2,640
622
0.564
8.95
F
0.644
8.2
330.1
6.1
13.7
100.8
125
2,780
4,310
1,920
1.580
2,880
4,460
7,900
1,990
1.636
3.45
-------
Table 67. OPERATIONAL DATA SUMMARY--60% TOXAPHENE DUST EXPERIMENTS
N5
JN
Run No.
Temperature "C (°F)
Primary chamber (Thermocouple No
Primary chamber (Thermocouple No
Primary chamber (Thermocouple No
Second chamber (Thermocouple No.
Second chamber (Thermocouple No.
Sample Point No. (2j (Thermocouple No.
Pressures
), pascals
Draft (Manometer No.
(in. H20) gauge
Burner operation pressure, pascals
(psi) gauge
Pesticide injection air, pascals (psi) gauge
640 (1180)
550 (1020)
670 (1240)
560 (1040)
370 (700)
190 (380)
640 (1180)
560 (1040)
670 (1240)
580 (1070)
380 (710)
240 (460)
970 (1780)
990 (1810)
1010 (1850)
850 (1570)
570 (1050)
280 (530)
1010 (1850)
1030 (1880)
1030 (1880)
850 (1570)
500 (930)
290 (560)
930 (1710)
910 (1670)
970 (1770)
820 (1500)
510 (950)
380 (710)
990 (1820)
990 (1810)
1010 (1850)
840 (1540)
510 (950)
370 (690)
16 (0.065) 26 (0.105) 32 (0.130) 32 (0.130)
7.6 x 105 (110) 7.6 x U>5 (110) 7.6 x 105 (110) 7.6 x U>5 (110)
6 x 10* (9) 6 x 104 (9) 6 x 10* (9) 6 x 104 (9)
52 (0.210) 50 (0.200)
9.3 x 105 (135) 9.3 x 105 (135)
6 x 104 (9) 6 x 104 (9)
-------
The efficiency of combustion has been calculated on the basis of total
chlorinated hydrocarbons in the off-gas and solid residues versus the toxa-
phene injected into the incinerator. The efficiency of toxaphene incinera-
tion for all six tests was > 99.99%. Inclusion (or exclusion) of the chlori-
nated hydrocarbons content of the solid residues left in the primary and
secondary chambers of the incinerator is too small to change the above
percent efficiency.
An unusually high level of chlorinated hydrocarbon was reported in
the liquid nitrogen trap in the Sample Point No. @ sample train from
Run No. F. In fact, the amount of chlorinated hydrocarbons reported in
this trap for Run No. F were more than 50 times that of the next highest
value. Thus, it seems probably that the high chlorinated hydrocarbon level
shown for the off-gas from Run No. F is the result of a contaminated sam-
ple. The results of Run No. C, as discussed below, are also somewhat sus-
pect.
Particulate sampling results are summarized in Table 66. All runs
with the exception of G were within acceptable isokinetic limits. The dust
formulations of toxaphene have followed the previously established trend
of high particulate emission levels for dust formulations. The incinera-
tion of toxaphene dust formulation will require a particulate emissions
control system to meet established limits.
Runs A and B have grain loadings considerably higher than the re-
mainder of the toxaphene dust series. This was partly the result of the
production of an oily material which was collected in the impingers and
cryogenic trap of the sampling train. The source of this material is un-
known, but it is possible that it is the result of poor combustion of the
supplementary fuel. It has been determined that the oil does not contain
chlorinated hydrocarbons.
Operating difficulties were encountered on all four tests made at
the higher temperature of ~ 1000°C (1830°F), i.e., Runs C through F. In
fact, Run No. C was terminated when only half completed (30 min of sam-
pling) because of loss of draft within the incinerator. Inspection of the
incinerator disclosed that the six 11.4 cm x 11.4 cm (4-1/2 in. x 4-1/2 in.)
openings in the wall between the primary and secondary chamber (see
Figure 2, p. 22) had been completely plugged. The interior of the "plugged
incinerator" is shown in Figure 44. During the remaining tests (Runs Nos.
D, E, and F) the three lower openings were kept open by means of periodic
clearing with a rod inserted through the view port in the front wall of
the primary chamber.
248
-------
I 3
4
-
Center Line
of Flame Cone
Center Line of
Dust Injection
Figure 44. Interior of plugged incinerator
-------
Upon completion of the tests with toxaphene, the experimental ap-
paratus was inspected for any deposits or residues of pesticide contain-
ing materials. Scrapings from the wall of the horizontal section of the
incinerator stack, the bottom of the first water scrubber, and the demister
pad in the first water scrubber contained 0.05, 0.17, and 2.3 ppm of chlo-
rinated hydrocarbons, respectively. Wall scrapings from the vertical sec-
tion of the incinerator stack contained 0.2 ppm of chlorinated hydrocarbons.
Thus, there was apparently no significant deposition of chlorinated hy-
drocarbon compounds in the experimental apparatus.
DISCUSSION
Problems were encountered with the feeding as well as with the in-
cineration of the 20% dust formulation. The dust tended to bridge in the
feed line to the injection nozzle upstream of the point of air injec-
tion (see Appendix A for details of the dust injection system).
As has already been pointed out, plugging of the checker work be-
tween the primary and secondary chambers when operating at the higher
temperature was a major problem*
Bridging problems have been encountered by others using dust for-
mulations using attapulgite clay as the inert carrier; grounding of the
screens overcame the difficulty, indicating that a static electrical
charge on the dust particles was the caused/ It is quite possible that
static charges contributed to the toxaphene dust plugging problems. The
"whiskering" effect shown in the residue (see Figure 44) tend to support
this theory.
250
-------
References
1. Casida, J. E., R. L. Holmstead, S. Khalifa, J. R. Knox, T. Ohsawa,
K. J. Palmer, and R. Y. Wong, "Toxaphene Insecticide: A Complex
Biodegradable Mixture," Science, ,183:520-521 (8 February 1974).
2. Metcalf, R. L., Organic Insecticides, Interscience Publishers, New York,
New York (1955).
3. von RUmker, R., E. W. Lawless, and A. F. Meiners, "Production, Distri-
bution, Use and Environmental Impact Potential of Selected Pesticides,"
Final Report, Contract No. EQC-311, for Council on Environmental
Quality, Washington, B.C. (1974).
4. Bell, W. L., Consultant, Arlington Blending and Packaging Co., Personal
Communication to Mr. Thomas L. Ferguson (10 April 1975).
251
-------
VI. ATRAZINE
PESTICIDE DESCRIPTION
Physical Properties
Chemical Name; 2-Chloro-4-ethylamino-6-isopropylamino-S-triazine
Common Name; Atrazine
Trade Names; Atranex®, AAtrex®, Gesaprim®, G-30027, Primatol A®,
Atra-Bor®, Atratol®
Pesticide Glass; Herbicide
Cl
Structural Formula; i
/S
i N
0 V
\/
Empirical Formula; CgH
Molecular Weight; 215.7
Physical State; Colorless crystals
Melting Point; 173 to 175°C
Vapor Pressure; 3.0 x 10"7 mm Hg at 20°C
Solubility; SoIvent Temperature C Solubility (ppmw)
Dimethyl sulfoxide 27 183,000
Chloroform 27 52,000
Ethyl acetate 27 28,000
Methanol 27 18,000
Diethylether 27 12,000
N-Pentane 27 360
Water 27 33
252
-------
Chemical Properties
Atrazine is reportedly hydrolyzed by either acid or base as shown:—
Cl OH
ji 1 strong acid > jj I
C2H ™/NlX\NHCH(CH )2 °r alkali C l^NH^lT^
Putnam et al.—' reported that > 99% of atrazine underwent decompo-
sition when burned in polyethylene or multiwall Kraft bags (a 0.5 g atra-
zine sample).
Production and Use
Atrazine is the most widely used herbicide in the United States. Major
crops on which it is used are corn, sorghum and sugarcane; minor uses in-
clude nonselective control. The estimated 1972 domestic consumption was
75 million pounds (von Rvimker et al.3./).
Available formulations include an 807o wettable powder, and a 4 Ib/gal
flowable concentrate. Atrazine is also formulated in combination with other
active ingredients including propachlor, amitrole, and fenac.
FORMULATIONS TESTED
The two principal atrazine formulations, the 80% wettable powder and
the 4 Ib/gal flowable concentrate, were tested.
4 Lb/Gal Flowable Concentrate
Name ; AAtrex®4L Herbicide
Manufacturer; Agricultural Division, CIBA-GEIGY Corporation,
Greensboro, North Carolina
Composition; Active Ingredients 43%
Atrazine (2-chloro-4-ethylamino-6-
i sop ropy lamino-S-triazine) 40.8%
Related Compounds 2.27o
Inert Ingredients 57%
Total 100.0%
253
-------
Registration; EPA Reg. No. 100-497 AA
80% Wettable Powder
Name; AAtrex® SOW Herbicide
Manufacturer; Agricultural Division, CIBA-GEIGY Corporation,
Greensboro, North Carolina
Composition; Active Ingredients
80%
Atrazine (2-chloro-4-ethylamino-6-
isopropylamino-S-triazine) 76%
Related Compounds 4%
Inert Ingredients
Total
20%
100%
Registration; EPA Reg. No. 100-439ZA
Particle Size Specifications; Formulated on kaolinite clay such that
a maximum of 0.02% is larger than
297 \i,t and a maximum of 3.0% larger
than 44 p,.
PRELIMINARY THERMAL ANALYSIS
Bomb calorimetric analysis of atrazine gave the following results.
Sample
Test
a/
Liquid formulation— Sulfur
Test Method
ASTM D-129
Result
0.77%.
Calorific value ASTM D-2015 2.471 x 10 J/kg
(10,634 Btu/lb)
80% wettable powder Sulfur
ASTM D-129
0.96%.
Calorific value ASTM D-2015 2.020 x 10 J/kg
(8,692 Btu/lb)
Technical grade
Sulfur
ASTM D-129
0.69%.
Calorific value ASTM D-2015 2.328 x 10 J/kg
(10,018 Btu/lb)
aj The liquid was oven-dried and the analysis performed on the residue.
254
-------
Figures 45 and 46 show the results of DTA and TGA of the technical
grade atrazine. DTA data show that decomposition of the compound starts
at about 180°C with two distinct endotherms at about 185 and 240°C, and
exotherms at about 350, 450, and 470°C. The decomposition process is sub-
stantiated by the TGA data which indicate that almost 95% of the sample
weight is lost at about 300° C, and at about 600°C, no sample is left.
Figures 47 and 48 show the results of DTA and TGA of a sample, of
atrazine obtained by evaporation of a sample of the liquid formulation.
DTA data show that as temperature increases decomposition of the sample
starts, and at about 185 and 245°C, two prominent endotherms are observed.
As temperature reaches to about 350 and 440°C, respectively, distinct
exotherms are observed. The decomposition process is again substantiated
by the TGA data which show that from 200 to 220°C about 90% of the sample
is lost, and at about 600°C, practically all the sample is gone.
Figures 49 and 50 show the results of DTA and TGA data of atrazine
wettable powder formulation. DTA data show that, aside from the familiar
pattern of endotherms (at 185 and 225° C) and exotherms (at 350 and 550° G),
additional endotherms and exotherms are observed. These endotherms and
exotherms could very well be attributed to the additives in the dust formu-
lation. The decomposition is completed at about 600°C. This is substanti-
ated by TGA data which show that at 600°C over 90% of the sample is gone.
Kennedy et al.— also conducted DTA analysis of atrazine. The results
of their analyses were as follows:
Endotherms Exotherms
Reference Standard 210, 308, 334, 360, 400 290, 385, and
and 480°C 582°C
80% Wettable Powder 182 and 280° C 250, 315, and
Formulation 550°C
Sensitivity = 25%
Based on these and other laboratory analyses, Kennedy et al. concluded
that the temperatures of complete combustion of the atrazine reference
standard and the 80% wettable powder formulation were 650°C (1202°F) and
600°C (1112°F), respectively.
255
-------
o
x
O
o
tu
I
I I I
100
200
300 400
TEMPERATURE. 8C
500
600
700
Reference: Al^O-j + Kaolinite
Frog, mode: Heat
Rate: 20°C/min
Figure 45. DTA of technical atrazine.
256
-------
lOOOp
950
900
850
800
750
700
650
600
0.4
0.8 1.2
WEIGHT LOSS, mg
I I I I
1.6
2.0
20 40 60
WEIGHT LOSS, PERCENT
60
100
Sample weight: 1.764 mg
Heating rate: 20°C/min
Environment: ~ 20 ml/min air (20% 02> 80% N2)
Figure 46. TGA of technical atrazine.
257
-------
I I
I I
I I I I
50 100
200 300 400
TEMPERATURE °C
500
600
Reference: Al^O-j + Kaolinite
Prog mode: Heat
Rate: 20°C/min
Figure 47. DTA of dried liquid atrazine formulation.
258
-------
L
_L
0.4
_L
0.8 1.2
WEIGHT LOSS, ma
_L
J_
J_
20
80
1.6
2.0
100
40 60
WEIGHT LOSS. PERCENT
Sample weight: 1.866 mg
Heating rate: 20°C/min
Environment: ~ 20 ml/min air (20% 02, 80% N2)
Figure 48. TGA of dried liquid atrazine formulation.
259
-------
I I
100
200
300 400
TEMKKATURC. *C
500
400
700
Reference: Al2C>3 + Kaolinite
Prog, mode: Heat
Rate: 20°C/min
Figure 49. DTA of ~ 8070 atrazine wettable powder.
260
-------
1000
950
900
850
800
750
700
650
600
550
0.4
0.8 1.2
WEIGHT LOSS, mg
1.6
20
80
100
40 60
WEIGHT LOSS, PERCENT
Sample weight: 1.854 mg
Heating rate: 20°C/min
Environment: ~ 20 ml/min air (20% 02, 80% N2)
Figure 50. TGA of ~ 80% atrazine wettable powder
261
-------
METHODS OF ANALYSIS
Direct gas chromatographic analysis of atrazine with electron capture
detector is not feasible due to the low response of single chlorine atom
in the atrazine molecule. In addition, atrazine1s major metabolite, hy-
dro xyatrazine, is not detectable by electron capture. However, the hy-
drogens attached to the nitrogen atoms (of atrazine and hydroxyatrazine)
and the hydroxyl group in hydroxyatrazine should be susceptible to acyla-
tion. Therefore, halogenated-acyl derivatives can be formed by using a
reagent, such as N-heptafluorobutyrylimidazole, to form derivatives suit-
able for electron capture detection. This procedure, as reported in the
literature, will improve the response of atrazine and hydroxyatrazine to
electron capture detection 10-fold to 100-fold. Three halogenated reagents,
pentafluorobenzoyl chloride, N-heptafluorobutyrylimizole, and 4-chloro-
3-nitro-benzotrifluoride were evaluated for use.
This method was successfully applied to standard atrazine solutions.
Efforts to adapt this technique to the analysis of incinerator effluent
samples, however, were not successful.
Figures 51a and 51b show a blank and a 10.9 mg atrazine solution,
respectively. The peak eluted at 4.7 min in Figure 51b is derivated
atrazine. However, when this method was applied to a series of representa-
tive incinerator effluent samples in which residual atrazine was most prob-
ably present, chromatograms showed a relatively high background plus a
broad peak that covered the area where atrazine is expected to elute.
Figure 51c shows the chromatogram of a representative incinerator effluent
gas sample from a liquid atrazine formulation test. Analysis of atrazine
by this method, therefore, was not feasible.
An alkaline flame detector was obtained in order to allow more accurate
analysis of the atrazine samples.
Apparatus
A Perkin-Elmer 3920 gas chromatograph equipped with a phosphorus-
nitrogen thermionic detector (bead setting 500, polarizing voltage X3)
and a 6 ft, 2 mm I.D. stainless steel column (packed with 1.5% OV-17 +
1.95% QF-1 on 100/120 mesh Supelcoport from Supelco, Inc., Bellefonte,
Pennsylvania) was used for gas chromatographic analysis. Chromatographic
operating conditions were: injector and detector temperature, 235°C;
column temperature, 200°C; flow rate, 40 ml/min, He; detector gas flow
rates, 6 ml/min, H2 and 75 ml/min, air.
A Perkin-Elmer No. 56 strip chart recorder was used to record the
chromatograms.
262
-------
4.7 min.
a. Derivatized Blank
b. Derivatized Atrazine
e. Derivatized Incinerator Sample
Figure 51. Representative atrazine chromatograms
-------
Reagents and Materials
Solvents used were pesticide grade benzene (Fisher Scientific) for
all samples (except the hexylene glycol from the second stage scrubber)
and all standard solutions; and reagent grade methanol (Fisher Scientific)
for initial extraction of the Sample Point No. (2.J train, and to prepare
solutions of hexylene glycol. (Note that pesticide grade solvents are not
absolutely imperative because of the high specificity of the phosphorus-
nitrogen thermionic detector.) All laboratory glassware (vials, beakers,
pipettes, etc.) was washed with Alconox detergent (Scientific Products)
and rinsed with deionized distilled water water and reagent grade acetone
(Fisher Scientific).
Standard and Calibration Curves
The atrazine standard, obtained from USEPA, was used to prepare a
stock solution of 27.2 u.g/ml atrazine, from which appropriate dilutions
were made to produce linear results (linear range utilized: subnanogram
to 1 yg atrazine).
Procedure for Sample Preparation
The mass of collected particulates was determined for the incineration
of solid atrazine as follows. All samples were taken to dryness in clean,
dessicated, tared 250 ml beakers and were dessicated 2 days before final
weighing. The residue was extracted with methanol and this was taken just
to dryness and tightly capped. The methanol extract from the silica gel
and all other solutions, as well as liquid samples collected from incinera-
tion of atrazine liquid formulation (except the hexylene glycol from the
second stage scrubber) were taken to dryness in the French Squares bottles
as received. One milliliter each of the hexylene glycol samples was pipetted
into vials and made up to 10 ml with methanol. These samples were run di-
rectly and all other impinger, blank and wash samples were taken up in
appropriate amounts of benzene just prior to gas chromatographic analysis.
Some samples with heavy particulate interference were filtered and taken
just to dryness again; the filter and particulate matter was washed thor-
oughly with benzene after filtration of the sample itself.
Portions of all cleanout samples (primary chamber, secondary chamber,
etc.) were weighed out and extracted and the extracts were analyzed for
atrazine.
264
-------
Analysis and Discussion
All samples were analyzed for atrazine. Unidentified chromatographic
peaks were quantitated against the atrazine calibration curve.
The sensitivity of the instrument for atrazine is 300 pg. Based on
this sensitivity, and with a 5-yJ sample injection for each analysis, the
minimum detectable value for a 20-ml sample solution is 1.2 y,g. However,
during the analysis, samples were concentrated down to 1 ml, which resulted
in a minimum detectable quantity of 60 ng.
The first step in method development for atrazine analysis involved
an attempt to derivitize atrazine with three halogenated reagents, namely
pentafluorobenzol chloride, 4-chloro-3-nitro-benzotrifluoride, and N-hepta-
fluorobutyrylimidazole, and subsequent analysis with electron-capture GC.
Interferences were encountered due to large number of peaks from nonnitrogen-
containing materials in the samples and the reagents. Furthermore, no
methods were available in the literature dealing with nanogram to subnano-
gram levels of detection of atrazine without extensive sample cleanup.
After the delivery of the Perkin-Elmer instrument, extensive time
was spent to obtain optimum instrumental parameters for the analysis of
atrazine in the incineration samples with minimum sample clean-up.
TEST CONDITIONS AND RESULTS
Nine tests were conducted using the 4 Ib/gal liquid formulation of
atrazine. An additional five tests were conducted using an 80% wettable
powder formulation of atrazine in order to evaluate the effect of physi-
cal form on the efficiency of atrazine incineration.
Nominal operating conditions for these tests were "high" and "low"
feed rates 3.40 kg ((7.5) and 1.70 kg (3.75 Ib) active ingredient/hr),
excess air rates (150 and 50%), and operating temperatures, 1000°C (1830°F)
and 650°C (1200°F). These operating temperatures were based on DTA and
TGA of atrazine samples which indicated that this pesticide could be ex-
pected to decompose at a temperature of 650°C (-' 1200°F).
Liquid atrazine, like the water-based picloram formulation, is not
miscible with No. 2 fuel oil, and therefore, was pumped into the incinera-
tor using a separate injector system. The liquid atrazine injector system
utilized standard fuel oil burner nozzles of the appropriate size, and
the nozzle adapter and oil pipe from a fuel oil burner (Part Nos. 33 and
24, respectively, Figure 13, p. 95). Preliminary tests, however, showed
265
-------
that the liquid atrazine would plug the nozzle and nozzle adapter almost
immediately after insertion into the incinerator chamber. For this reason,
the nozzle adapter was modified so that it would be cooled by the water
jacketed injection nozzle used for dust injection, as shown in Figure 52.
This modification eliminated the problem of plugging during the test period.
Results of tests using the 4 Ib/gal liquid formulation are given in
Tables 68 through 71. Two efficiencies of combustion were calculated for the
atrazine liquid tests, as defined in Table 69. The first was based on
atrazine only, while the second included consideration of all nitrogenous
organic species (including atrazine) detected in the effluent gas. Both
of these efficiencies were > 99.99% for all tests. Thus, the efficiency
of liquid atrazine incineration was found to be > 99.99% over the tem-
perature range of 550°C (1030°F) to 1040°C (1900°F).
The relative quantity of atrazine (and total nitrogenous organic
species) not decomposed, however, does appear to be related to operating
temperature. The highest quantity of atrazine (and total nitrogenous or-
ganic species) as shown in Columns 3 and 5, respectively, of Table 69,
was emitted from Run No. 6, which was conducted at the lowest primary
chamber temperature (550°C). The lowest quantities detected were from Run
No. 9, which was conducted at the highest temperature (1040°C).
Five additional tests were made using an 80% wettable powder formula-
tion of atrazine in order to determine the effect of physical form on the
efficiency. Operational data and analytical results for the ~ 80% atrazine
wettable powder formulation tests are summarized in Tables 72 through 76.
The results of these five tests parallel those of the nine tests using the
liquid atrazine formulation. Both efficiencies for all five tests were >
99.99%.
The results of cyanide analysis for all 14 atrazine tests (nine
liquid and five dust) are summarized on page 277.
266
-------
M
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X
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X
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WITH WET
INSULATION
B. MODIFIED.WATERCOOLED INJECTION NOZZLE
NOZZLE-
-NOZZLE ADAPTER
1/8 IN.
"OIL PIPE
A. STANDARD BURNER NOZZLE
Figure 52. Liquid atrazine formulation injection system
-------
Table 68. SUMMARY OF 40.8% ATRAZINE FLOWABLE CONCENTRATE EXPERIMENTS
K3
(^
00
No.
1
2
3
4
5
6
7
8
9
W
c/
I/
T/
Fuel
Nominal
oil rate
Actual
i/ht (jtal/hr) //hr (cal/hr)
11.4
11.4
4. 7
3.8
11.4
2.8
4.7
13.3
11.4
(3.0)
(3.0)
(1.25)
(1.0)
(3.0)
(0.75)
(1.25)
(3.5)
(3.0)
Volume per hour
9.84 (2.60)
9.84 (2.60)
4.31 (1.14)
3.33 (0.88)
9.08 (2.40)
2.73 (0.72)
4.35 (1.15)
11.39 (3.01)
8.97 (2.37)
Nominal
Actual
//hr (p.al/hr) i/hr (Kal/hr)!'
9.5 (2.5)
9.5 (2.5)
9.5 (2.5)
9.5 (2.5)
22.7 (6.0)
22.7 (6.0)
22.7 (6.0)
22.7 (6.0)
9.5 (2.5)
of the diluted formulation.
Calculated according to Method 3
7.15 (1.89)
7.53 (1.99)
6.40 (1.69)
7.15 (1.89)
16.54 (4.37)
16.09 (4.25)
16.20 (4.28)
15.90 (4.20)
6.55 (1.73)
of "Standards of Performance [or New S
(70'F).
i/hr db/hrji'
1,470 (3.25)
1,470 (3.25)
1,320 (2.92)
1,600 (3.52)
3,420 (7.54)
3,410 (7.51)
4,470 (9.85)
3,290 (7.25)
1.480 (3.26)
tatlonary Sourcea,"
chamber
„„«, ,,«,«,,
1020 (1860)
730 (1340)
700 (1290)
970 (1780)
550 (1030)
700 (1300)
940 (1720)
1040 (1900)
Retention time
Flam Exceaa aecE'
•C (*F) 7. chamber
1070 (1960)
1130 (2060)
1100 (2020)
1080 (1980)
1090 (1990)
960 (1760)
1040 (1900)
1050 (1920)
1080 (1980)
Federal KeRliter, 36:24876-24895,
79 2.6
123 2.1
138 4.0
90 5.0
76 2.0
93 7.8
143 3.6
140 1.6
52 2.7
23 December 1971.
0[f-ga»
' Sampling [low rate!'
chamber mln
2.5 30
2.0 30
3.6 30
4.6 30
1.8 30
6.9 30
3.3 30
1.3 30
2.8 30
(1.000'j of SCFH)
207 (7.3)
269 (9.5)
181 (6.4)
144 (5.1)
272 (9.6)
108 (3.8)
204 (7.2)
360 (12.7)
195 (6.9)
-------
Table 69. INCINERATION EFFICIENCY--40.8% ATRAZINE FLOWABLE CONCENTRATE EXPERIMENTS
Run
No.
1
2
3
4
5
NJ
S 6
7
8
9
Atrazine feed
rate*/
8/hr
1,470
1,470
1,320
1,600
3,420
3,410
4,470
3,290
1,480
Atrazine content of
the off-gasV
R/hr
< 1.6
< 1.6
< 1.1
< 9
< 3.1
< 2
< 1.3
< 2.9
< 1.2
x 10" 2
x 10"2
x IO'2
x IO"3
x IO"2
x 10-1
x 10"2
x 10"2
x IO-2
Ratio of atrazine in
off-gas to atrazine fed
< 1.1 x
< 1.1 x
< 8 x
< 6 x
< 9 x
< 5 x
< 2.9 x
< 9 x
< 8 x
10-5
10-5
ID"6
10-6
ID'6
10-5
IO-6
ID"6
10-6
Ratio of total
Total speciesS' content species^' content
of the off -gas of off-gas to
8/hr atrazine fed
< 3.8 x lO"2
< 3.1 x ID"2
< 5 x 10"2
< 5 x ID'2
< 1.8 x lO'l
< 2 x 10-1
< 2.5 x ID'2
< B x 10"2
< 2.4 x 10-2
< 2
< 2
< 4
< 3
< 5
< 7
< 6
< 2.
< 1.
.6 x ID'5
. 1 x ID"5
x 10"5
x ID'5
x ID"5
x 10-5
x 10-6
,5 x 10"5
6 x 10-5
Incineration efficiency^'
Atrazine
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
Total speciesS'
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
a/ Actual atrazine content of the incinerator feed.
b/ Atrazine was not detected in all major elements (e.g., impingera) of the gas sampling train. The values given, therefore, include the lower
detectable limit for atrazine in these elements.
£/ Atrazine plus all other nitrogenous organic species detected.
f~ Quantity out ~1 *~\
&l Efficiency ia defined as: jl - tit I— X 100> where quantity out is evaluated at Sample Point No. (2) (incinerator off-gas), and
amount l^n is evaluated at Sample Point No. Ql (the incinerator feed). Efficiencies have been calculated based on (a) atrazine only,
and (b) the total nirrogenous organic species detected.
-------
Table 70. OFF-GAS COMPOSITION--40.8% ATRAZINE FLOWABLE CONCENTRATE INCINERATION^
Total hydrocarbons analyzer
Run
No.
1
2
3
4
5
NJ
ij 6
O
7
8
9
Atrazinek/
ntE/m3
< 7.7 x
< 5.9 x
< 6.1 x
< 6.4 x
< 1.1 x
< 1.5
< 6.4 x
< 8.1 x
< 6.2 x
10-2
10-2
10-2
10-2
10-1
10-2
10-2
10-2
Total species!/
mg/m3
< 1.8 x
< 1.2 x
< 2.6 x
< 3.5 x
< 6.6 x
< 2.1
< 1.2 x
< 2.3 x
< 1.2 x
10-1
10-1
10-1
10-1
10-1
10-1
10-1
10-1
CN"
mg/m3
**£.'
< 1
198
264
< 1
5,740
635
< 1
81
S02
rag/in3
155
122
106
144
200
190
77
308
219
NOxS/
me/m3
306
512
7
29
171
126
76
278
64
Total
hydrocarbons CO
ppm ppm
40
24
132
54
42
350
57
47
41
NDl/
Nnf/
348
223
591
972
> 7.780&/
102
> 7,670
Orsat analyzer
Ch^
ppm
< 1
< 1
3
25
22
177
19
32
22
°2
vol. '/.
9.6
11.8
12.4
10.2
9.4
10.8
12.6
12.5
7.6
C02
vol. 7.
8.3
6.8
6.2
7.8
8.4
6.7
6.0
6.2
9.6
CO
vol. 7.
0.0
0.0
0.0
0.0
0.0
0.7
0.0
0.0
0.1
Moisture
vol. 7.
12.0
4.6
8.7
8.3
11.7
13.3
9.4
7.6
8.1
a/ As dry gas at one atmosphere pressure, and 21.1"C (70°F).
b/ Atrazlne was not detected In all major elements (e.g., Implngers) of the gas sampling train. The values given, therefore, include the lower
detectable limit for atrazine in these elements.
£/ Atrazine plus all other nitrogenous organic species detected.
d/ No analysis.
e/ Calculated as N02-
£_/ Not detected.
R/ Upper detection limit.
-------
Table 71. OPERATIONAL DATA SUMMARY--40.8% ATRAZINE FLOWABLE CONCENTRATE EXPERIMENTS
Run No.
Primary chamber (Thermocouple No- (D )
Primary chamber (Thermocouple No. (f> )
Primary chamber (Thermocouple No. (3} )
Second chamber (Thermocouple No. ^+) )
Second chamber (Thermocouple No. £§) )
San-vie Point No. (T) (Thermocouple No. -(6)
Pressures
Dratt (Manometer No. /i\ ), pascals
(in H^O) gauge
Burner operation pressure, pascals
(psi) gauge
Scrubber liquids*'
1st Stage, H2Q scrubber
Volume, I (gal.)
Atrazine cone. , mR/i
2nd Stage, hexalene glycol scrubber
Volume , * (gal . )
Atrazine cone.,-' mg/ I
Total species cone. , change," mg/i
3rd Stage, H2Q scrubber
Volume, L (gal.)
•
Total species cone.,- mg/i
Scrubber system
Effluent gas (Sample Point No. (?) )-'
/ 3
1
950 (1750)
900 (1650)
1020 (1860)
850 (1570)
630 (1160)
) 350 (660)
32 (0.130)
9.1 x 105
(132)
1070 (284)
< 5 x 10-3*'
< 9 x 10
100 (26.4)
< 5 x 10-3
< 5 x 10-3
1710 (451)
3 x 10"2
4 x 10-2
7 x ID'2
2
940 (1730)
920 (1680)
1020 (1860)
890 (1630)
680 (1260)
390 (740)
45 (0.180)
9.1 x 105
(132)
1030 (273)
< 5 x 10-3V
< 5 x 10
105 (27.8)
< 5 x 10-3
< 5 x 10-3
1690 (446)
, . .-,-3
3 x 10-2
< 2 x 10-2V
3
670 (1230)
560 (1050)
730 (1340)
650 (1200)
480 (900)
260 (500)
22 (0.090)
7.4 x 105
(107)
1090 (288)
< 5 x 10-3V
< 2 x 10
104 (27.4)
< 5 x 10-3
< 5 x 10-3
1790 (474)
7 x 10~3
2 x ID"2
< 2 x 10- 2V
4
650 (1200)
540 (1010)
700 (1290)
620 (1150)
440 (820)
210 (410)
19 (0.075)
7.2 x 105
(105)
1040 (275)
1 x 10-2
4 x 10
101 (26.8)
< 5 x 10-3
< 5 x 10-3
1670 (440)
< 5 x 1Q-3V
7 x 10-2
< 2 x 10- 2V
5
900 (1660)
850 (1560)
940 (1730)
850 (1570)
680 (1250)
390 (740)
34 (0.135)
7.4 x 105
(107)
950 (252)
< 5 x 10- 3V
< 7 x 10"^
103 (27.1)
< 5 x 10-3
< 5 x 10-3
1840 (486)
1 x 10"2
4 x 10-2
< 2 x 10- 2V
6
520 (970)
400 (760)
550 (1030)
520 (970)
360 (680)
190 (370)
15 (0.060)
7.3 x 105
(106)
1090 (289)
< 5 x 10-3V
< 1 x 10
103 (27.1)
< 5 x 10-3
< 5 x 10-3
1750 (463)
< 5 x 10"3V
8 x ID'2
< 2 x 10- 2V
7
650 (1200)
540 (1000)
700 (1300)
640 (1180)
450 (850)
260 (500)
44 (0.175)
7.4 x 105
(108)
1060 (279)
j c .. in" 3—'
104 (27.4)
< 5 x 10-3
< 5 x 10-3
1780 (469)
< 5 x 10- 3V
5 x 10-2
< 2 x 10-2V
—
890 (1630)
750 (1380)
940 (1730)
900 (1650)
730 (1350)
500 (940)
61 (0.245)
9.1 x 105
(132)
1160 (307)
< 5 x 10-3V
109 (28.9)
< 5 x 10-3
< 5 x 10-3
1820 (480)
3 x 10"2
1 x 10- i
< 2 x 10-2V
9
1020 (1860)
1030 (1880)
1040 (1900)
880 (1610)
560 (1040)
330 (630)
39 (0.155)
7.4 x 105
(107)
1090 (288)
< 5 x 10-3V
1 x 10
106 (28.1)
< 5 x 10-3
< 5 x 10-3
1710 (451)
< 5 x 10-3V
5 x 10"2
< 2 x 10- 2V
a/ Scrubber water (Scrubbers 1 and 3) was used once through, while the hexylene glycol (Scrubber 2) was recycled. The concentrations reported for hexylene glycol, therefore, are
the concentration changes (increases) detected during the respective tests
b/ Atrazine was not detected. The values given represent the lower detection limit for atrazine in the respective sample.
c/ Atrazine plus all other nitrogenous organic species detected.
d/ Aj the wet gas at one atmosphere pressure, and 21.1°C (70°F).
-------
Table 72. SUMMARY OF 80% ATRAZINE WETTABLE POWDER EXPERIMENTS
to
^i
N5
Run
No, 2 fuel oil rate
Nominal
burner size Actual rate
Pesticide feed rate
~ 807. Atrazlne
formulation
Contained
atrazlnoS/
2.8 (0.75)
7.6 (2.0)
2.8 (0.75)
2.69 (0.71)
6.89 (1.82)
2.54 (0.67)
4.67 (10.3) 3,220 (7.1)
Primary
chamber
Retention time
Flame
Excess
No.. i/hr (gal/hr) i/hr (gal/hr) kg/hr (lb/hr> g/hr (Ib/hr)
A 9.5 (2.5) 8.33 (2.20) 3.63 (8.0) 2,630 (5.8) 1070 (1960)
11.4 (3.0) 8.52 (2.25) 4.45 (9.8) 3,080 (6.8)
3.40 (7.5) 2,130 (4.7)
4.26 (9.4) 2,590 (5.7)
temperature temperature^ air£/ Primary Second
°C CF) °C CF) 7.
1050 (1920)
1080 (1970)
940 (1720)
970 (1770)
600 (1120)
970 (1780) 1070 (1950)
650 (1200) 980 (1800)
43
125
146
71
111
Sampling
time
min
Off-gas
flow rate£'
m3/hr
(l.OOO'a of SCFH)
a_/ Actual atrazlne content of the ~ 807. atrazine vettablc powder formulation.
b/ The flame temperature was observed at a point ~ 15 cm (6 in.) In from the front wall of the incinerator (see Figure B-l).
cV Calculated according to Method 3 of "Standards of Performance for New Stationary Sources," Federal Register. .36(247):24876-24895, 23 December 1971.
"it Retention time is defined aa - , where v Is the wet off-gas flow rate from the Incinerator at the respective chamber temperature and pressure,
and V Is the volume of that chamber.
e/ A» dry gas at one atmosphere pressure, and 21.1°C (70°F).
-------
Table 73. RESIDUE AND OFF-GAS CHARACTERISTICS--807o ATRAZINE WETTABLE POWDER INCINERATION
Pesticide feed rate
Run
No.
A
B
C
D
E
~ 807. Atrazlne
formulation
kg/hr (Ib/hr)
3.63 (6.0)
4.45 (9.8)
3.40 (7.5)
4.26 (9.4)
4.67 (10.3)
Contained
atrazlne£/
2
3
2
2
3
R/hr
,630
,080
,130
,590
,220
Solid
residue
Primary chamber
Total
g/hr
54
79
58
75
123
Atrazine
cone.
10.4
18.9
14.0
2.3
14.0
Total species!/
cone.
10
20
15
2.
14
ppm
.4
.8
.2
.3
.0
Total
101
23
61
23
29
Second chamber
Atrazine
cone.
PPm
8.4
6.5
2.4
6.2
5.2
Total species"/
cone .
ppm
8.4
6.5
4.6
9.0
5.2
Ratio of total
Incinerator
residue to
total charge
0.042
0.023
0.035
0.023
0.032
N3
Run
No.
A
B
C
D
E
b/
c/
Atrazine
content of
off-gas
1.
6
5
8
1
g/hr
2 x 10'3
x IO-4
x 10"4
x ID'4
x 10-4
Atrazlne
content of
solid residue
R/hr
1.2
1.6
1
3.2
2
Actual atrazlne content
Atrazlne plua all other
Efficiency is defined a
x
X
X
x
X
10- 3
10- 3
io-3
ID'4
10- 3
of the ..
nltrogeno
8 Ti - ""•
Atrazlne
content of
off-gas and
solid residue
Total
species content!/
of off-gas
R/hr
2.4
2.1
1.5
1.1
2
X
X
X
x
X
10- 3
io-3
10- 3
10- 3
10- 3
807. wettable powder
us organic species
:ntlty ouT]
1
2
2
R/hr
.4 x
.0 x
.3 x
2.2 x
1
x
formulation
detected.
where the au
10- 3
ID"3
io-3
lO'3
io-3
antitv 01
Total
•pec lea!/
content of
solid residues
1.2 x 10- 3
1.8
1.2
3.8
2
x 10- 3
x 1C'3
x 1C'4
x 10- 3
Total species!/
content
off-gas
of
and
solid residues
2.6 x
3.8 x
3.5 x
2.6 x
3 x
io-3
10- 3
10-3
10- 3
io-3
Ratio of
atrazlne
In off-gas to
to total
4.6 x 10"7
1.8 x 10- 7
2.5 x 10'7
3.0 x 1
>
>
11
99
99
99
99
99
99
99
99
99
^
E- -_•zrrr I x 100, where the quantity out is evaluated at Sample Points NOB. (2j (Incinerator off-gas) and f3j (incinerator residues) and the
quantity .ln_| ^^^ ^"^
quantity iri is evaluated at Sample Point No. fljfthe Incinerator feed). Efficiencies have been calculated based on (a) atrazloe only, and (b) the total nitrogenous organic
species detected at Sample Points Nos. (2J and
-------
Table 74. OFF-GAS COMPOSITION--807. ATRAZINE WETTABLE POWDER INCINERATION^
Total hydrocarbons analyzer
Run
No.
A
B
C
D
E
At ratine
mg/
4.8 x
1.6 x
2.8 x
2.9 x
6.8 x
'm3
10-3
10-3
10-3
io-3
10-*
Total species]!/
rng/m3
5.6 x ID"3
5.8 x 1C"3
1.2 x 10"2
8.2 x ID"3
7.5 x ID'3
CN-
"S/1"3
38
< 1
919
1
316
S02
491
241
332
304
455
Total
Orsat analyzer
NOjf hydrocarbons CO CH^
mg/m3
218
333
77
517
86
ppm
38
26
37
20
55
ppm
> 7,970^
441
127
357
160
ppm
35
26
53
26
83
°2
6.6
12.0
12.7
9.1
11.4
co2
10.4
6.7
6.3
8.7
6.9
CO
vol. 7.
0.0
0.0
0.0
0.0
0.0
Moisture
yol .._ 7L_
11.6
7.2
5.3
7.9
5.0
£/ As dry gas at one atmosphere pressure, and 21.1*C (70T).
b/ Atrazlne plus all other nitrogenous organic species detected.
c./ Calculated as N02.
d/ Upper detection limit.
-------
Table 75. PARTICULATE SAMPLING SUMMARY--807, ATRAZINE WETTABLE POWDER EXPERIMENTS
K>
Ln
Description
Vol. dry gas - std. cond. , nm3
Percent moisture by vol.
Avg. stack temperature, °C
Stk. flow rate, dry., std. en., nnr/min
Actual stack flow rate, m3/min
Percent isokinetic
Percent excess air
Particulates - partial catch
Particulate wt. - partial, nig
Part, load - ptl., std. en., rag/run
Part, load - ptl., stk. en., mg/m3
Partic. emis. - partial, kg/hr
Particulates - total catch
Particulate wt. - total, mg
Part, load - ttl., std. en., mg/nm3
Part, load - ttl., std. en., corrected
to 127, C02, mg/nm3
Part, load - ttl., stk. en., mg/m3
Partic. emis. - total, kg/hr
Percent impinger catch
A
0.440
8.6
280.8
4.2
8.6
99.6
43
763
1,730
852
0.439
790
1,790
2,060
883
0.454
3.42
B
0.589
6.2
372.0
5.7
13.3
98.2
124
704
1,190
513
0.410
577
977
1,750
420
0.336
22.04
C
0.334
9.5
173.9
3.2
5.3
100.4
143
762
2,280
1,360
0.435
820
2,450
4,700
1,470
0.468
7.13
D
0.465
8.5
297.5
4.5
9.4
99.4
72
968
2,080
988
0.558
1,280
2,750
3,790
1,310
0.739
24.53
E
0.254
9.6
210.0
2.4
4.4
100.4
112
993
3,800
2,170
0.567
1,100
4,330
7,500
2,400
0.629
9.92
-------
Table 76. OPERATIONAL DATA SUMMARY—80% ATRAZINE WETTABLE POWDER EXPERIMENTS
Description
Vol. dry gas - std. cond., nm-'
Percent moisture by vol.
Avg. stack temperature, °C
Stk. flov rate, dry., std. en., nm3/min
Actual stack flow rate, m /min
Percent isokinetic
Percent excess air
Particulates - partial catch
Particulate wt. - partial, mg
Part, load - ptl., std. en., rag/ran3
Part, load - ptl., stk. en., mg/m3
Partic. emis. - partial, kg/hr
Particulates - total catch
Particulate vt. - total, mg
Part, load - ttl., std. en., mg/nm3
Part, load - ttl., stk. en., mg/m3
Partic. emis. - total, kg/hr
Percent impinger catch
A
0.440
8.6
280.8
4.2
8.6
99.6
43
762.60
1,727.67
852.49
0.439
789.60
1,788.84
882.67
0.454
3.42
B
0.589
6.2
372.0
5.7
13.3
98.2
124
703.80
1,192.60
512.94
0.410
576.70
977.23
420.31
0.336
22.04
C
0.334
9.5
173.9
3.2
5.3
100.4
143
761.70
2,277.26
1,363.32
0.435
820.20
2,452.15
1,468.03
0.468
7.13
D
0.465
8.5
297.5
4.5
9.4
99.4
72
968.00
2,075.87
987.51
0.558
1,282.70
2,750.74
1,308.56
0.739
24.53
E
0.254
9.6
210.0
2.i
4.4
100.4
112
993.00
3,897.91
2,165.02
0.567
1,102.30
4,326.96
2,403.32
0.629
9.92
-------
Liquid formulation
Primary chamber
temperature
Run no.
1
2
3
4
5
6
7
8
9
Dust formulation
Run no .
A
B
G
D
E
°C (°F)
1020 (1860)
1020 (1860)
730 (1340)
700 (1290)
970 (1780)
550 (1030)
700 (1300)
940 (1720)
1040 (1900)
1070 (1960)
970 (1770)
600 (1120)
970 (1780)
650 (1200)
Excess air
a/
Cyanide content"
R/hr
m
79
123
138
90
76
93
143
140
52
< 1
198
264
< 1
5,740
635
< 1
81
NA
< 0.3
36
38
< 0.3
620
130
< 0.4
16
43
125
146
71
111
38
< 1
919
1
316
10
< 0.3
175
0.3
46
al Calculated as CN~.
_b/ No analysis.
Incineration of atrazine at the lower temperature, ~ 650°C (1200°F),
yielded high levels of cyanide in the effluent, i.e., 198 to 5,738 mg/m .
The higher temperatures, ~ 1000°C (1830°F), generally yielded much lower
concentrations. However, only those tests conducted at the higher tempera-
ture and relatively high excess air rates (> 75%) routinely yield con-
centrations of < 1 mg/m3. . Thus, it appears that temperatures of about
1000°C (1830°F) and excess air of > 75% are required to incinerate
atrazine and obtain cyanide concentration in the undiluted effluent of
< 1 mg/m3.
The results from particulate sampling are shown in Table 75. All
runs were within acceptable isokinetic limits (100 + 10%). The wettable
powder formulation of atrazine followed the previous trend, although not
as high, of particulate emission levels which exceed established limits.
The incineration of atrazine wettable powder formulations will therefore
require a particulate emissions control system.
277
-------
DISCUSSION
The only operational problem encountered with atrazine incineration
was the plugging of the liquid formulation injection nozzle. Insulation
of this nozzle with the water-jacketed dust nozzle, as discussed above,
overcame this problem.
It should be noted that the high concentration of active ingredients
in the dust formulation (80%) made the desired active ingredient injection
rate more difficult to attain.
278
-------
References
1. Lawless, E. W., T. L. Ferguson, and A. F. Meiners, "Guidelines for
the Disposal of Small Quantities of Unused Pesticides," (Draft),
EPA Contract No. 68-01-0098 (1974).
2. Putnam, R. C., F. Ellison, R. Protzmann, and J. Hilovsky, "Organic
Pesticides and Pesticide Containers--A Study of Their Decontamination
and Combustion," Foster D. Small, Inc., Final Report on Contract
No. CPE 69-140 (1971).
3. von Rlimker, R., E. W. Lawless, and A. F. Meiners, "Production,
Distribution, Use and Environmental Impact Potential of Selected
Pesticides," Contract No. EQC-311 (1974).
4. Kennedy, M. V., B. J. Stojanovic, and F. L. Shuman, Jr., "Chemical
and Thermal Methods for Disposal of Pesticides," Res. Rev., 29:89
(1969).
279
-------
VII. CAPTAN
PESTICIDE DESCRIPTION
Physical Properties
Chemical Name; N-(trichloromethylthio)-4-cyclohexene-l,2-dicar-
boximide
Common Name; Captan
Trade Names; Merpan®, Orthocide®, SR-406, Vanicide
Pesticide Class; Fungicide; chlorinated organosulfur compound
Structural Formula; H 9>
——^—~—————^»——- no f\
HT^V \
31 T )-S-CCl3
V^C?
«2 g
Empirical Formula; CgHgCl-jNC^S
Molecular Weight; 300.61
Analysis; C, 35.96%; H, 2.69%; N, 4.67; Cl, 35.50%; S, 10.67%;
0, 10.65%
Physical State; Pure Technical
White crystals Yellow to buff-colored amor-
phous powder
Odor; Odorless Pungent
Melting Point; 178°C (Martin)!/ 160 to 170°C (Martin)
174 to 176°C (Stauffer)-'
172 to 173°C (Merck)!/ 158 to 164°C (Stauffer)
Boiling Point; Decomposes near melting point
Specific Gravity (20/20°C); 1.73 1.62
280
-------
Pure
Technical
Bulk Density; 25 to 30 lb/ft3
Vapor Pressure; 6 x 10~5 mm Hg at 25°C
pH; Typically 8.0 to 8.3
Particle Size; 9 to 13 p, surface average diameter by air permeation
2 /
Captan Content in Technical Product (Stauffer)-' ; 92% Typical,
seldom less than 90% or more than 94%.
21
Noncaptan Chlorine (Stauffer)— ; Analysis by chlorine content
typically gives results almost 2% too high when calculated as
captan.
2/
Solubility of Gaptan in Various Solvents (Stauffer)- ;
Substance
Tetrachloroethane
Chloroform
Xylene
Dioxolane
Cyclohexanone
Dioxane
Ethyl acetate
Benzonitrile
Acetonitrile
Chlorobenzene
Methyl chloride
Acetone
Ethylene chloride
Nitrotne thane
Velsicol AR-50
Benzene
Isopropyl alcohol
Toluene
Methyl alcohol
Ethanol
Diethyl ether
Heptane
Stove oil
Carbitol
Water
Grams/100 ml of solvent
(25°C)
8.15
8.0
6.5
5.0
4.96
4.7
4.5
4.0 (12°C)
3.6 (12°C)
3.3
3.0
3.0
2.85
2.0
Less than 2
1.8
0.8
0.7
0.5
0.29
0.25
0.04
Less than 0.5 ppm
3.3 ppm (Chevron)—
4/
281
-------
Chemical Properties
The chemistry of captan reported in the literature primarily con-
cerns degradation reactions. Captan is reported to be decomposed by hy-
drolysis (essentially complete hydrolysis of a 2% slurry at 100°C in
2-1/2 hr); thermal decomposition; and photolysis.
von Rumker and Horay^' state that dry captan is stable to heat but
aqueous suspensions are quickly decomposed at 100°C or in alkaline media.
The following thermal stabilities for dry captan are given:
Half-life at 80°C 213 weeks
Half-life at 120°C 14-1/4 days
At temperatures above the melting point dry captan is reported to be
rapidly decomposed (Melnikov).—'
Pyrolysis of captan by dry distillation at 200°C is reported to re-
sult in the formation of thiophosgene, tetrahydrophthalimide and "other
related products" (California Spray-Chemical Corporation!/).
Production and Use
Captan is a contact fungicide that is effective against a fairly
broad spectrum of plant-pathogenic fungi. It is registered and recom-
mended in the United States for use on more than 70 different crops
(EPA).I/
An estimated 16 million pounds of captan were used in the United
States in 1972—about 10 million pounds in agriculture and 6 million by
home gardeners (Midwest Research Institute) JL/
Captan is domestically available in a great variety of dry form-
ulations, i.e., wettable powders and dusts of various concentrations.
Because of its physical and chemical properties, captan active ingredi-
ent cannot readily be dissolved or formulated into liquids. No emulsi-
fiable captan formulations are currently available.
282
-------
FORMULATIONS TESTED
Because captan is available only in solid forms, only one form-
ulation was tested--a 50% wettable powder.
Name: Ortho Orthocide®50 Wettable
Manufacturer; Chevron Chemical Company, Ortho Division, San
Francisco, California
Composition: Active ingredient (by weight)
Captan*
Inert ingredients
50%
50%
* N-(trichloromethylthio)-4-cyclohexene-l,2-
dicarboximide.
Registration; EPA Reg. No. 239-533
Lot No.: M30943 CK 90
Particle Size Specifications;
Formulated from 544 parts by weight
technical material (92% captan)
424 parts clay, and 32 parts other
inert material such that > 99.9%
passes a 44 y, (325 mesh) sieve
with brushing.
PRELIMINARY THERMAL ANALYSIS
Laboratory thermal analysis of the powder as well as technical
captan gave the following results:
Sample
Technical captan
Captan wettable
powder (50%)
.Test
Sulfur
Test method
ASTM D-129
Calorific value ASTM D-2015
Sulfur ASTM D-129
Calorific value ASTM D-2015
Result
11.69%
1.619 x 10? J/kg
(6,966 Btu/lb)
6.84%
9.166 x 106 J/kg
(3,944 Btu/lb)
283
-------
Figures 53 and 54 show the results of DTA and TGA of the technical
grade captan. DTA data show a distinct endotherm at about 185°C which
approximately corresponds to the reported melting point of pure captan
(m.p. range 172 to 178°C). In addition, the data show two distinct exo-
therms at about 250 and 550°C indicating decomposition of the compound.
The decomposition process is substantiated by the TGA data which indicate
that about 75% of the compound is lost at about 250°C, and almost all
of the compound is lost at 600°C.
Figures 55 and 56 show the results of DTA and TGA data on a 50%
captan wettable powder formulation. DTA data of this powder formula-
tion show a similar pattern of endotherm and exotherms as that of the
technical grade, i.e., an endotherm at about 185°C (indicating pos-
sible melting), and two exotherms at about 220 and 530°C, respectively
(indicating decomposition). Again, the decomposition process is sub-
stantiated by the TGA data which indicate approximately 50% lost in
sample weight at 250°C and 60% less at the completion of the experi-
ment (at 1000°C). The weight loss due to decomposition corresponds (within
experimental error) to the amount of captan (50%), in the formulation.
METHODS OF ANALYSIS
Apparatus
Two instruments were used for captan analysis. One, a Micro-Tek
2000R gas chromatograph equipped with an 18-in., 4 mm I.D. glass column
(packed with 1.5% OV-17 + 1.95% QF-1 on 100/120 mesh Supelcoport from
Supelco, Inc., Bellefonte, Pennsylvania), and a tritium electron cap-
ture detector, maintained at a voltage of 10 V DC was used for gas chro-
matographic analysis of all impinger samples collected at Sample Point
No. (2) of the incinerator. Chromatographic operating conditions were:
injector temperature, 155°C; column temperature, 150°C; detector tem-
perature, 180°C; carrier flow rate, 125 ml/min, N2; and purge gas flow
rate, 2?5 ml/min, N2«
A Hewlett-Packard 3380A integrator was utilized for peak identi-
fication and quantification.
284
-------
50
100 150 200 250 300 350 400 450 500 550 400 650
TEMPERATURE *C
Reference:
Prog, mode: Heat
Rate: 20°C/min
Start: 25 °C
Kaolinite
Figure 53. DTA. of technical captan
285
-------
u
cc
LU
1000
950
900
850
800
750
700
650
600
550
500
400
350
300
250
200
150
100
50
0
0
I
0.4 0.8 1.2 1.6
WEIGHT LOSS, mg
I I I I I I
2.0
2.4
20
40 60
WEIGHT LOSS. PERCENT
80
100
Sample weight: 2.340 mg
Heating rate: 20°C/min
Environment: ~ 20 ml/min air (20% 02, 80% N2)
Figure 54. TGA of technical captan.
286
-------
o
x
I
O
Q
z
0 50 100 150 200 250 300 350 400 450 500 550 600 650
TEMPERATURE °C
Reference: Al-203 + Kaolinite
Prog, mode: Heat
Rate: 20°C/min
Figure 55. DTA of a 50% captan wettable powder
287
-------
-------
The other instrument used was a Varian 1400 gas chromatograph equipped
with an Aerograph Scandium Tritide electron capture detector (polarizing
voltage: -90 V DC) and a 6-ft, 4 mm I.D. glass column (packed with 1.5%
OV-17 + 1.9% QF-1 on 100/120 mesh Supelcoport from Supelco, Inc.). This
instrument was used for the analysis of all samples other than those col-
lected at Sample Point No. @ . Chromatographic operating conditions
were: injector temperature, 180°C; column temperature, 190°C; detector
temperature, 200°C; carrier flow rate, 35 ml/min, N2; and no purge flow
(as per manufacturer's recommendations).
A Heath-Schlumberger Model SR-255B strip chart recorder was used
to record the chromatograms.
Reagents and Materials
Two standard materials, captan (98.6% pure) and aldrin (97% pure)
were used. Solvents used were pesticide grade benzene (Fisher Scientific)
for all impingers and standard captan samples, pesticide grade 2,2,4-
trimethylpentane (Mallinckrodt) for standard aldrin solutions and pesti-
cide grade hexane (Matheson, Coleman, Bell) for extraction of hexylene
glycol traps from the second stage scrubber. All laboratory glassware
(vials, beakers, pipettes, etc.) was washed in Alconox detergent (Scien-
tific Products) and rinsed with deionized distilled water and reagent
grade acetone (Fisher Scientific).
Standards and Calibration Curves
The solid standards, captan and aldrin, provided by USEPA, were used
to prepare stock standard solutions of 100 g/ml each. On the Micro-Tek
2000R, separate captan and aldrin calibration curves were obtained by dilu-
tions of various amounts of stock solutions (captan range used: 0.0 to
2.0 ng; aldrin range used: 0.0 to 200 pg). On the Varian 1400 the aldrin
and captan standards were combined and linear calibration curves were
obtained from this composite standard (captan range used: 0 to 800 pg;
aldrin range used: 0 to 100 pg). In the samples captan peaks were quan-
tified against the captan calibration curve and all other peaks were
quantified according to the aldrin curve.
Procedure for Sample Preparation
The mass of collected particulates was determined for all elements
of the sample train at Sample Point No. (?) as follows. All samples were
taken to dryness under a hood in clean, dessicated, tared 250-ml beakers
and dessicated 2 days before final weighing. The residue was extracted
with benzene (two 10-to 15—ml portions) and the extract taken just to
dryness and capped tightly. The silica gel was extracted with a known
volume of benzene to cover and a 20-ml portion pipetted into vials and
taken just to dryness. All other impinger, wash and blank solutions,
289
-------
were taken just to dryness in the French Square bottles as they were
received. Ten milliliters of the hexylene glycol traps from the second
stage scrubber were extracted with n-hexane and the extract was taken just
to dryness. All samples were taken up in appropriate amounts of benzene
just prior to GC analysis.
Portions of all cleanout samples (primary chamber, secondary cham-
ber, etc.) were weighed out and extracted and the extracts were analyzed
for captan.
Analysis and Discussion
All samples were analyzed for captan. Unidentified chromatographic
peaks were quantitated against the aldrin calibration curve because the
response range of captan was not low enough to include many of these
unidentified peaks.
The sensitivity of the instrument is 50 pg for captan and 1 pg for
aldrin. Based on these sensitivity values, and with a 5-y.l sample injec-
tion for each analysis, the minimum detectable quantities for a 20-ml
sample solution are 0.2 ^g for captan and 4 ng for aldrin. However, dur-
ing the analysis, samples were very often concentrated down to 1 ml,
resulting in minimum detectable quantities of 10 ng for captan and 0.2
ng for aldrin.
Major problems were encountered on the Micro-Tek 2000R while run-
ning captan. It appeared initially that sensitivity was low; and a new
column was packed. It then became apparent that the captan was degrading
between the injector and the detector. Resolution of this problem involved
working at lower column and inlet temperatures and silanization of all
pieces of the chromatograph through which the sample traveled.
TEST CONDITIONS AND RESULTS
Eight tests were made using the 50% captan wettable powder formula-
tion. The results of these tests are summarized in Tables 77 through 81.
As is shown in Table 78, the efficiency of combustion was > 99.99%
for all eight tests, whether based on captan or total chlorinated species
detected in the off-gas and incinerator residues. No correlation has been
found between the relative rate of captan and total chlorinated species
in the incinerator off-gas (fourth and third to last columns in Table 78)
and specific operating conditions.
290
-------
Table 77. SUMMARY OF 50% CAPTAN WETTABLE POWDER EXPERIMENTS
Run
No.
A
B
C
D
t-o
£ E
F
G
H
a/
b/
C/
No. 2 fuel
Nominal
burner size
i/hr (gal/hr)
7.6 (2.0)
7.6 (2.0)
9.5 (2.5)
9.5 (2.5)
3.8 (1.0)
3.8 (1.0)
2.8 (0.75)
3.8 (1.0)
oil rate
Actual rate
jt/hr (gal/hr)
8.71 (2.30)
5.75 (1.52)
8.82 (2.33)
9.24 (2.44)
3.56 (0.94)
3.82 (1.01)
2.73 (0.72)
3.71 (0.98)
Actual captan content of the ~ 507.
The flame temperature was observed
Pesticide
~ 507. Captan
formulation
ks/hr (Ib/hr)
6.44 (14.2)
6.49 (14.3)
3.58 (7.9)
3.54 (7.8)
3.54 (7.8)
3.49 (7.7)
6.35 (14.0)
6.17 (13.6)
feed rate
Contained
captani'
g/hr (Ib/hr)
2,880 (6.35)
2,850 (6.28)
1,640 (3.62)
1,110 (2.45)
1,250 (2.76)
1,410 (3.11)
2,230 (4.92)
2,040 (4.50)
Primary
chamber
temperature
°C (°F)
1000 (1830)
920 (1690)
1010 (1850)
980 (1790)
660 (1220)
670 (1230)
650 (1200)
690 (1280)
captan wettable powder formulation.
at a point approximately 15 cm (6 in.) In from
Calculated according to Method 3 of "Standards of
Performance for
New Stationary
Flame Excess
temperature^'
°C (°F)
1160 (2120)
1120 (2040)
1180 (2160)
1190 (2170)
1120 (2040)
1100 (2010)
1040 (1900)
1080 (1980)
the front wall of
Sources," Federal I
air£'
7.
137
94
76
135
192
130
252
99
Retention
ser
Primary
chamber
1.8
3.2
2.5
2.0
4.2
5.3
6.8
6.7
the incinerator (see
legister,
ti«i/
Sampling
Second
chamber
1.8
3.2
2.5
1.9
3.9
5.1
6.4
6.5
Figure B-l).
36(247):24876-24895, 23
time
min
60
60
60
60
60
60
60
60
December
Off-gas
flow rate^
m3/hr
(1,000's of SCFH)
391 (13.8)
241 (8.5)
278 (9.8)
396 (14.0)
235 (8.3)
187 (6.6)
150 (5.3)
144 (5.1)
1971.
^/ Retention time is defined as ~ , where v is the wet off-gas flow rate from the incinerator at the respective chamber temperature and pressure, and V is
the volume of that chamber.
e/ As dry gas at one atmosphere pressure, and 21.1*C (70°F).
-------
Table 78. INCINERATION EFFICIENCY—50% CAPTAN WETTABLE POWDER EXPERIMENTS
N3
VO
IsJ
Pesticide feed rate
~ 507. Captan
Run
No.
A
B
C
D
E
r
c
H
Run
A
B
C
D
E
F
C
H
formulation '
kit/hr (Ib/hr)
Contained
captanS'' Total
g/hr (Ib/hr) g/hr
6.44 (14.2) 2,880 (6.35) 540
6.49 (14.3) 2,850 (6.28) 957
3.58 (7.9) 1,640 (3.62) 301
3.54 (7.8) 1,110 (2.45) 370
3.54 (7.8) 1,250 (2.76) 342
3.49 (7.7) 1,410 (3.11) 353
6.35 (14.0) 2,230 (4.92) 713
6.17 (13.6) 2,040 (4.50) 625
Captan content of
Captan content Captan content of off-gas and solid
of off-gas
< 7 x 10-4£/
< 2.6
< 1.4
2.5
< 3.2
< 2.3
6
< 1
x
x
X
X
X
X
X
10-4S/
10-5
10- 5£/
ig-65/
l°"*d/
solid residues
o/hf
1
7
1
ft
2
7
5
0 x 10-4
5 x
4 x
x
•> x
X
X
10-4
10-4
10-5
10-5
10-6
10-5
residues
< 8 x 10-4
< 5 x 10-4
< 1.5 x 10-4
1.0 x 10-4
< 6 x ID"5
< 9 x lO-6
7 x 10-4
Solid
residue
Primary chamber
Captan cone.
0.06
0.11
0.15
0.12
0.01
0.01
0.04
0.73
Total apeciesk'
content of
off-gas
o/hr
< 4.0
< 4.9
< 1.9
1.2
< 2.5
< 5
5
x 10-3
x 10-3
x 10-3
x 10-3
x 10-3
x ID"3
x ID'3
Total species^'
cone. , ppm
0.14
0.21
0.22
0.16
0.02
0.02
0.07
0.83
Total specieak/
content of
•olid residues
B/hr
< 1.7 x
< 3.8
< 1.9
1.1
< 2.9
< 2.3
6
x
X
X
X
X
X
10-4
10-*
io-4
10-4
10-5
10-5
10-5
Total
g/hr
Second
chamber
Captan cone. Total species^'
ppm cone . , ppm
358
205
172
115
146
120
319
453
Total species!/
content of off-
gas and solid
residue
ff/hr
4
5
2
1
2
5
5
2 x 10-3
X
1 X
3 x
5 x
x
X
10-3
10-3
10-3
10-3
10-3
10-3
in-3
0.20
0.69
0.54
0.28
0.15
0.03
0.06
0.08
Ratio of captan
in off-gas to
< 2.6 x ID"7
< 9
< 8
2.2
< 2.6
< 1.6
3
x 10-8
x ID'9
x 10-8
x ID"8
x 10-9
x lO"7
0.27
0.88
0.74
0.46
0.15
0.13
0.02
1.12
Ratio of
species]*/
< 1.4 x
< i
< 1
1
< 2
< 3
2
7 x
2 x
1 X
0 x
8 x
x
total
in off-
fed
10-6
10-6
10-6
10-6
10-6
10-6
ID"6
in-7
residue to total charge
0.14
0.18
0.13
0.14
0.14
0.14
0.16
0.18
Incineration efficiency^
7.
> 99.99
> 99.99
99.99
99.99
99.99
99.99
99.99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
99
99
99
99
99
99
99
&/ Captan content of the - 307. captan wet table powder formulation.
J>/ Captan as well as other chlorinated hydrocarbon species detected.
c/ Captan was not detected in all elements (e.g., impingera) of the gas sampling train, the value given, therefore, includes the lover detectable limit for captan in these
elements.
d/ Captan not detected. The value given represents the captan detection limit for the particular sample.
e/ Efficiency is defined as 1 - t unm«\ x 100, where the quantity out is evaluated at Sample Points Nos. @ (incinerator off-gas) and (5) (incinerator residues),
and the quantity ,in is evaluated at Sample Point No. (T) (the incinerator feed). Efficiencies have been calculated based on (a) captan only, and (b) the total chlorinated
hydrocarbon species detected at Sample Points Nos. (2) and (5).
-------
Table 79. OFF-GAS COMPOSITION--5070 CAPTAN WETTABLE POWDER INCINERATION*/
NJ
Total hydrocarbons analyzer
Run
No.
A
B
C
D
E
F
G
H
Captan
< 1.9 x 10"3-
< 1.1 x 10"3-
< 5.0 x 10"5"
6.0 x 10"5
< 1.2 x 10"4"
< 1.1 x lO"5-'
4.0 x KT3
< 6.9 x lO"5-'
Total species^/
mg/m3
< 1.0
< 2.0
< 6.8
2.9
< 9.8
< 2.6
2.9
< 4.0
x 10"2
x 10' 2
xlO-3
x 10"3
x 10"3
x 10" 2
x 10"2
x 10-3
CN"
mg/m3
77
129
46
49
NA!/
27
107
133
SO i
mg/m3
2,050
3,540
1,960
1,'JjQ
2,090
2,970
5,780
5,020
mg/m3
138
165
536
175
109
208
130
39
Total
hydrocarbon;
ppm
18
3
38
15
15
23
12
7
Orsat analyzer
5 CO CH4
ppm ppm
NA NA
16 2
8 < 1
10 < 1
3'j'i >
217 14
1,340 3
1,100 2
°2
vol. %
12.4
10.5
9.4
12.3
14.0
12.2
15.2
10.7
C02
vol. '/.
6.4
8.0
8.7
6.5
5.3
6.6
4.4
8.0
CO
vol. '/.
0.0
0.0
0.1
0.0
0.0
0.1
0.0
0.1
Moisture
vol. '/.
8.1
8.5
9.2
4.6
7.6
8.4
7.7
8.3
aj As dry gas at one atmospheric pressure, and 21.1'C (70°!').
b_/ Captan was not detected in all elements (e.g., impingers) of the gas sampling train. The values given, therefore, includes the lower detectable
limit for captan in these elements.
cY Captan not detected. The value given represents the captar. detection limit for the particular sample.
&/ Captan plus all other chlorinated hydrocarbon species detected.
e7 No analysis.
i_l Calculated as N02-
-------
Table 80. PARTICU1ATE SAMPLING SUMMARY--507. CAPTAN WETTABLE POWDER EXPERIMENTS
N)
VO
JS
Description
Vol. dry gas - std. , cond., nm
Percent moisture by vol.
Avg. stack temperature, °C
Stk. flow rate, dry, std. cond., nm
Actual stack flow rate, nrVmin
Percent isoklnetic
Percent excess air
Participates - partial catch
Partlculate wt. - partial, ntg
Part, load - ptl., std. en., mg/nnP
Part, load - ptl., stk. en., mg/nfl
Partlc. emls. - partial, kg/hr
Partlculates - total catch
Partlculate wt. - total, ng
Part, load - ttl., std. en., mg/nnP
A
0.670
8.1
311.8
/mln6.5
13.9
98.5
137
2,760
4,110
1,920
1.604
3,050
4,540
B
0.419
8.5
252.1
4.0
7.8
100.6
95
3,130
7,460
3,800
1.783
4,060
9,690
C
0.488
9.2
328.9
4.6
10.5
100.3
77
1,530
3,120
1,380
0.872
1,690
3,450
D
0.672
4.6
333.6
6.6
14.2
97.2
135
2,140
3,180
1,480
1.263
2,370
3,520
E
0.405
7.6
193.8
3.9
6.8
98.3
192
2,060
5,070
2,940
1.200
2,520
6,210
F
0.323
8.4
171.1
3.1
5.1
99.2
132
2,420
7,470
4,540
1.394
2,870
8,870
G
0.257
7.7
196.1
2.5
4.3
98.4
252
5,600
21,800
12,600
3.262
6,090
23,700
H
0.251
8.3
218.3
2.4
4.4
99.2
99
5,240
20,900
11,500
3.026
5,290
21,000
Part, load - ttl., std. en., corrected
to 127. C02, mg/nm3
Fart, load - ttl., stk. en., mg/nr
Partic. emis. - total, kg/hr
Percent Implnger catch
8,500
2,120
1.771
9.45
14,500
4,930
2.314
22.97
4,800
1,530
0.963
9.55
6,500
1,640
1.398
9.68
14,100
3,610
1.471
18.42
16,100
5,390
1.655
15.77
65,000
13,700
3.545
7.98
31,600
11,600
3.051
0.84
-------
Table 81. OPERATIONAL DATA SUMMARY--50% CAFTAN WETTABLE POWDER EXPERIMENTS
Run No .
Temperature *C (°F)
Primary chamber (Thermocouple No. (D )
Primary chamber (Thermocouple No. (2) )
Primary chamber (Thermocouple No. (3) )
Second chamber (Thermocouple No. \4) )
Second chamber (Thermocouple No. (5) )
Sample Point No. © (Thermocouple No. (5) )
A
940
940
1000
900
640
390
(1730)
(1730)
(1830)
(1650)
(1180)
(740)
890
910
920
790
530
290
B
(1640)
(1670)
(1690)
(1450)
(990)
(550)
970
950
1010
880
630
370
C_
(1770)
(1740)
(1850)
(1620)
(1160)
(690)
930
950
980
870
620
380
n
(1700)
(1750)
(1790)
(1590)
(1150)
(720)
630
570
660
600
430
240
E
(1170)
(1060)
(1220)
(1110)
(810)
(470)
640
550
670
580
390
210
F
(1180)
(1020)
(1230)
(1080)
(740)
(410)
630
560
650
580
390
210
C
(1160)
(1040)
(1200)
(1070)
(730)
(410)
670
590
690
600
390
210
H
(1240)
(1100)
(1280)
(1110)
(740)
(410)
58 (0.235) 27 (0.110) 30 (0.120) 51 (0.205)
7.4 x 105 (108) 7.5 x 105 (109) 7 '.4 x 105 (107) 7.7 x 105 (Ml)
6 x 10* (9) 6 x 104 (9) 6 x 10* (9) 6 x 104 (9)
Pressures
Draft (Manometer No. A ), pascals
(in HjO) gauge
Burner operation pressure, pascals
(psi) gauge
Pesticide injection air, pascals (psi) gauge
Scrubber liquid^'
1st Stage, ffjO scrubber
Volume, i (gal.)
Captan cone., mg/i
Total species cone.,—' mg/i
2nd Stage hexalene glycol scrubber
Volume, t (gal.)
Captan cone., mg/£
Total species cone, change,—' mg/i
3rd Stage 1^0 scrubber
Volume, £, (gal.)
Captan cone., mg/i
Total species cone.,— mg/£
Scrubber system
Effluent gas (Sample Point No. @ )-'
Captan cone., rng/m^
Total species conc.,-^ mg/m
a/ Scrubber water (Scrubbers 1 and 3) was used once through, while the hexylene glycol (Scrubber 2) was recycled.
are the concentration changes (increases) detected during the respective tests.
W Captan plus all other chlorinated hydrocarbons species detected.
c/ As the wet gas at one atmosphere pressure, and 21.1°C (70*F).
d/ No captan detected. The values given represents the limit of detection for captan in the particular sample.
e_/ No analysis.
f/ No increase detected.
25 (0.100) 16 (0.065) 16 (0.065) 16 (0.065)
7-4 * 1°5 (107) 7.4 x 105 (107) 7.4 x 105 (108) 7.4 x 105 (109)
6 x 104 (9) 6 x 10* (9) 6 x 104 (9) 6 x 104 (9)
1010 (268)
< 2 x 10-24'
2 x 10-2
104 (27.4)
< 7 x 10-32'
4 x ID'2
1950 (514)
< 2 x 10-44'
1 x 10-3
< 3 x 10" -1-
4 x ID"2
1060 (279)
< 2 x 10-34'
1 x 10"1
100 (26.4)
NA
1950 (514)
< 2 x 10-44'
6 x 10-3
< 2 x 10"3—
2 x 10-2
1080 (286)
< 2 x 10-34'
4 x ID"2
101 (26.8)
< 7 x 10-32'
4 x ID'1
1900 (503)
< 2 x 10-34'
3 x 10-2
< 3 x 10-34'
1 x 10-2
1020 (270)
NA
NA
103 (27.1)
ND!/
ND
1730 («7)
< 2 x 10-34/
6 x 10-3
< 3 x 10-34'
2 x 10-2
1080 (286)
< 2 x 10-34'
9 x ID"2
99 (26.1)
< 7 x 10-35'
9 x 10"1
2030 (537)
< 2 x 10-34'
6 x 10-3
< 2 x 10-34'
2 x 10-2
1100
NA
NA
98
< 7 x
ND
1900
NA
NA
< 3 x
2 x
(291)
(25.8)
10-34'
(503)
io-34'
10-2
1100 (291)
< 2 x 10-34/
2 x 10- !
104 (27.6)
< 7 x 10- 34/
2 x ID"1
1860 (491)
< 2 x 10- 34/
6 x 10-3
< 2 x 10-34'
1 x iO'1
980 (259)
NA
NA
93 (24.6),
< 7 x 10-34'
2 x 10" '
1730 (457)
NA
NA
< 2 x 10-34'
1 x ID"2
£. K IV ~ t. X IV ~ J. X i\f IX IV *•
The concentrations reported for hexylene glycol, therefore.
-------
A
B
C
D
E
F
G
H
1000 (1830)
920 (1690)
1010 (1850)
980 (1790)
660 (1220)
670 (1230)
650 (1200)
690 (1280)
The results of cyanide (CN~) analysis of the incinerator off-gas
are summarized as follows:
Primary chamber /
temperature Excess air Cyanide content"
Run No. °C (°F) % tng/m3 R/hr
137 77 30
94 129 31
76 46 13
135 49 19
192 NA~ NA
130 27 5
252 107 16
99 133 19
aj Calculated as CN~.
b/ No analysis.
These results show that significant amounts of cyanide were apparently
generated* on all eight tests. No correlation has been found between the
relative rate of cyanide generation (rate of cyanide generated to rate
of captan incinerated) and any of the operating conditions being investi-
gated (rate of pesticide injection, percent excess air, and operating
temperature).
The results from particulate sampling of the captan tests are summar-
ized in Table 80. All eight runs were within acceptable isokinetic limits.
The 50% wettable powder formulation of captan follows the previously estab-
lished trend of particulate emissions, which exceed established incinerator
limits. The incineration of the captan formulation will, therefore, re-
quire a particulate emission control system.
DISCUSSION
No problems were encountered during the incineration of captan. It
should be noted, however, that the H2s~like odor was
-------
References
1. Martin, H., Pesticide Manual, 2nd ed., British Crop Protection Council,
Worcester, England (1971).
2. Stauffer Chemical Company, "Technical Captan Data Sheet" (1965).
3. Merck Index, The, P. G. Strecher (ed.), 8th ed., Merck and Company,
Rahway, New Jersey (1968).
4. Chevron Chemical Company, Ortho Technical Information Bulletin (April
1974).
5. von Rlimker, R., and F. Moray, Pesticide Manual, Vol. I, Department
of State, Agency for International Development (1972).
6. Melnikov, N. N., "Chemistry of Pesticides," Res. Rev., 3J3_: 247 (1971).
7. California Spray-Chemical Corporation, The Chemistry of Gaptan (31
March 1955).
8. U.S. Environmental Protection Agency, EPA Compendium of Registered
Pesticides, Vol. Ill, Washington, D.C. (1973).
9. Midwest Research Institute, "Initial Scientific and Minieconomic Review
of Captan" (Draft) EPA Contract No. 68-01-2448 (September 1974).
297
-------
VIII. ZINEB
PESTICIDE DESCRIPTION
Physical Properties
Chemical Name; Zinc ethylene bisdithiocarbamate
Common Name; Zineb
Trade Name; Aspor®, Chem Zineb®, Dithane® Z-78, Hexathane®, Kypzin®,
Lonacol®, Pamosol 2 Forte®, Parzate® C, Polyram@Z,
Tiezene®, Tritofterol®, Zebtox®, Zidan®, Zinosan®
Pesticide Glass; Fungicide
fi
Structural Formula; ONHCSv
Zn
CH2NHCS
S
Empirical Formula; C^H^^S^Zn
Molecular Weight; 275.8
Physical State; Off-white solid
Solubility in;
Water; 10 ppm
Organic Solvents; Soluble in pyridine
Lipids, Fats; Negligible
Melting Point; Decomposes before melting
Vapor Pressure; Negligible at 15° C
Flammability; Flash point (open cup) between 138 and 143° C (280 and
290° F)
298
-------
Stability; Decomposes gradually, accelerated by exposure to moisture,
heat or air
Chemical Properties
Zineb is reported to be unstable toward moisture; acid hydrolysis
yields CS2.J:' Heating above 120° C is also reported to cause decomposition
to a carbonaceous product.—' Zineb is said to be the most stable of the
metallic dithiocarbamates.ji'
Production and Use
Zineb is a fungicide used extensively on vegetable crops as well as
on a few fruit crops.
Zineb is available commercially in wettable powder formulations vary-
ing in strength from 75 to 96% active ingredient.
Unpublished MRI estimates of domestic pesticide usage for 1972 include
an estimate of 8 million pounds for zineb.
FORMULATIONS TESTED
A 75% wettable powder WP formulation was the only form tested. The
WP was obtained from two manufacturers.
Zineb Wettable
Manufacturer; Ortho Division, Chevron Chemical Company, San Francisco,
California
Composition: Active Ingredient
Zineb* 75%
Inert Ingredients 25%
Total 100%
Zinc expressed as metallic: 17.7%
* Zinc ethylene bisdithiocarbamate
299
-------
Registration; EPA Reg. No. 239-523-AA
Lot No.: M21122-CK96
Particle Size Specification;
Formulated from 882 parts technical
material (85% zineb), 98 parts clay,
and 20 parts dispersing agents such
that > 99.9% pass a 149 p, (100 mesh)
sieve with brushing
Zineb 75 Wettable Powder Fungicide
Manufacturer; Niagara Chemical Division, FMC Corporation, Middleport,
New York
Composition; Active Ingredient
Zineb (zinc ethylene bisdithiocarbamate)
(total zinc as metallic: 17.7)
Inert Ingredients
Total
75.0%
25.0%
100.0%
Particle Size Specification; At least 99% of the particles pass through
a 44 ji (325 mesh) sieve
Registration; USDA Reg. No. 279-1387
PRELIMINARY THERMAL ANALYSIS
Bomb calorimetric analyses gave the following results.
Sample
Technical
Zineb
Zineb Wettable
Powder (75%)
Test
Sulfur
Heat of Combustion
Sulfur
Heat of Combustion
Test Method
ASTM D-129
ASTM D-2015
ASTM D-129
ASTM D-2015
Results
1.91%
1.058 x 107 J/kg (4,554 Btu/lb)
1.05%
2.168 x 107 J/kg (9,329 Btu/lb)
300
-------
Figures 57 and 58 the results of DTA and TGA of the technical grade
zineb (85%). DTA data show that decomposition of the sample starts at
about 150° C, with two endotherms at about 160 and 290° C, respectively,
and exotherms at about 190, 440, 530, and 600°C, respectively. The decom-
position process is substantiated by the TGA data which indicate that
about 80% of the sample weight is lost at 800°C. The weight loss agrees,
within experimental error, with the percent composition of the technical
grade zineb.
Figures 59 and 60 show the results of DTA and TGA data of the 75%
wettable powder. DTA data show a similar decomposition pattern as that
of the technical grade zineb, with characteristic endotherms at 170 and
260° respectively, and exotherms at 200, 440, 530, and 610°C, respectively.
The decomposition process is substantiated by the TGA data which indi-
cate that about 75% of the sample weight is lost at 800° C. The weight
loss agrees very well with the percent composition of zineb in the formu-
lation.
Kennedy et al. (1969)—' also conducted DTA analysis of zineb. The
results of their analyses were as follows:
Endotherms Exotherms
Reference Standard 185 and 496°C 196, 245, 525,
675, 690, 749,
767 and 795°C
75% WP Zineb 187, 290, 390, 452 215, 232,
formulation and 550°C and 620°C
Sensitivity = 25%
4/
Based on these and other laboratory analyses, Kennedy et al.— con-
cluded that the temperature of complete combustion of the zineb reference
standard and the 75% wettable powder formulation were 840°C (1544°F) and
690°C (1274°F), respectively.
301
-------
600
650
TEMPERATURE °C
Reference: Al^O-j
Prog, mode: Heat
Rate: 20°C/min
Start: 30°C
+ Kaolinite
Figure 57. DTA of technical zineb
302
-------
0.4 0.8
WEIGHT LOSS, mg
I II I I I
20 40 60
WEIGHT LOSS, PERCENT
.2
80
Sample weight: 1.504 mg
Heating rate: 20°C/min
Environment: ~ 20 ml/min air (20% 02, 80% N2)
Figure 58. TGA of technical zineb
303
-------
o
Q
z
o
X
UJ
50
100 150 200
Reference: Al^C^
Prog, mode: Heat
Rate: 20°C/min
Start: 40°C
300 350
TEMPERATURE °C
+ Kaolinite
450
500 550
600
Figure 59. DTA of 75% zineb wettable powder
304
-------
0.4 0.8
WEIGHT LOSS, mg
I I I I i
1.2
I
20 40 60 80
WEIGHT LOSS, PERCENT
Sample weight: 1.540 mg
Heating rate: 20°C/min
Environment: ~ 20 ml/min air (20% 02, 80% N2)
Figure 60. TGA of 75% zineb wettable powder
305
-------
METHODS OF ANALYSIS
Dithiocarbamate fungicides, e.g., maneb, nabam, and zineb, are non-
volatile compounds and are not subject to gas chromatographic analysis
intact.^./ There are no published methods of analyses for trace quantities
of zineb in the presence of extremely high quantities of ZnO as encountered
in the incinerator sampling train. Existing methods of analysis for zineb
rely on the analysis of degradation products resulting from the following
reaction:
H
H-^-N-C-S
H-G-N-G-S
i ii
H S
Zn
H2S°4
Zn
2CS,
Zineb
The problem with this approach when analyzing incinerator effluents
and residues is obvious—the incinerated sample can be expected to con-
tain trace quantities of zineb and a wide range of various degradation
products, depending on the efficiency of incineration.
After searching the literature and consulting EPA scientists at two
laboratories, it was concluded that direct measurement of intact zineb
at useful concentration levels was not possible within the time and cost
limitations of this program. The most useful information that could be
obtained concerning the effectiveness of incineration was the amount of
organically bound zinc present in the various samples.
The approach used was to attempt to separate trace quantities of organic
zinc by solvent extraction from high quantities of inorganic zinc, which
resulted from incineration. The solubility of zineb in organic solvents
is quite limited. Pyridine was selected as the solvent which might pref-
erentially extract zineb in the presence of zinc oxide.
Synthetic mixtures of zineb and varying quantities of zinc oxide were
extracted with pyridine. The pyridine extracts were evaporated to dryness,
digested in acid, and the zinc determined by atomic absorption spectrom-
etry (AAS). In the absence of zinc oxide, zineb could be determined quan-
titatively by this method. However, the excess zinc oxide resulted in a
high, inconsistent background due to the extraction of this species into
the pyridine.
306
-------
Because zineb is soluble in relatively polar solvents, it is not likely
that other solvents that would dissolve zineb would not dissolve zinc oxide
also. Therefore, this approach was not investigated further.
The next approach investigated was to analyze for ethylenediamine
(EDA) by gas chromatography (GC). Zineb standards could be quantitatively
determined by GC of EDA but, similar to the AAS method, excess zinc oxide
interfered. The interference was probably due to chelation of the EDA by
the excess zinc. The resulting zinc/EDA complex could not be analyzed by
GC.
Several methods were attempted to release the EDA for GC analysis.
All were unsuccessful. Several of the methods are described below.
Destruction of the Complex with Heat
Samples were injected into the gas chromatograph at an elevated in-
jection port temperature (up to 350°C).
Distillation
Distillation from basic aqueous solution was attempted in the hope
of separating the EDA from the zinc. Although 1^0 boils lower than EDA
(116.5°C), EDA was recovered (at least 25%) from a synthetic EDA/Zn oxide
mixture. Ten filter samples were analyzed without success. The residues
from the aqueous distillation were taken up in xylene which has a boil-
ing point similar to EDA (116°C). No EDA was detected in the distillate.
Displacement with Chelating Agents
Displacement of EDA using 8-hydroxyquinoline (Oxine—8-hydroxyquinoline)
as a chelating agent was attempted in the hope that the zinc would be re-
moved from EDA and the free EDA would be available for GC analysis. Both
acidic and basic samples were extracted with 8-hydroxyquinoline in benzene.
A yellow precipitate was formed indicating the formation of zinc oxinate.
However, GC analysis of both layers gave negative results for EDA.
Addition of Arsenate
Zinc arsenate has a very low solubility product. Arsenate was added
to the aqueous solution of the 10 filter samples in an attempt to precipi-
tate zinc arsenate and free the EDA for GC analysis. EDA was not detected
in any of the 10 samples treated with arsenate.
307
-------
When all attempts to analyze for EDA failed, carbon disulfide, evolved
by the addition of sulfuric acid, was analyzed. The headspace analysis
technique for carbon disulfide was not attempted before the methods dis-
cussed above because other workers, who had successfully applied the method
to ferbam and nabam, reported problems with the analysis of zineb.67
Although a number of problems were encountered with the headspace
method, a satisfactory method for zineb was developed. Unfortunately,
the CSo in the filter samples that were used for EDA method was lost
during the development effort and these samples could not be analyzed.
All other samples were analyzed by the headspace procedure described below.
Apparatus
For gas chromatographic analysis a Tracer 550 gas chromatograph
equipped with dual mode (sulfur and phosphorus) flame photometric detectors
(Meloy, Inc., Springfield, Virginia) and a 6-ft,>4 mm I.D. stainless
steel column (packed with 3% OV-1 on 100/110 mesh Gas Chrom Q from Supelco,
Inc., Beliefonte, Pennsylvania) was used. Chromatographic operating con-
ditions were: injector temperature, 160°C; column temperature, ambient;
detector temperature, 170°C; carrier flow rate, 45 ral/min ^j detector
flow rate, 30 ml/min, 021 120 ml/min, ^j and 40 ml/min, air.
A Hewlett-Packard 3380A integrator recorder was used to record the
chromatograms.
Reagents and Materials
A 1.1 N H2S04 solution (prepared by dilution of concentrated re-
agent grade from Mallinckrodt) was used for hydrolysis of zineb. Pesti-
cide grade toluene (matheson, Coleman, Bell) was used to prepare stan-
dard carbon disulfide solutions (Fisher Certified Reagent). Headspace
gases were measured in Pierce Hypo-vials stoppered with gray Hycar septa
(Pierce Chemical Company, Rockford, Illinois). Standard zineb (86.9%)
was used to evaluate the yield of carbon disulfide.
Procedure for Sample Preparation
Sample preparation depended on the types of sample. Water impingers
were taken to dryness with a stream of air. The residue was extracted
with pyridine which was taken to dryness in a Pierce Hypo-vial. The vial
was stoppered, and 1 ml of 1.1 N ^SO, was injected. The sample was placed
in a steam bath and heated for 1 hr, after which the solutions were placed
in a temperature bath at 52 + 1°C. Just prior to analysis, the headspace
pressure was equilibrated by puncturing the septa, and measuring the gas-
water displacement from an inverted burette. While still in the temperature
bath, a volume of the headspace was sampled with a gas-tight syringe and
injected into the chromatograph.
308
-------
The mass of collected particulates was determined for all elements
of the sample train at Sample Point No. (T) as follows. All were taken
to dryness under a hood in clean, desiccated, tared 250 ml beakers and
desiccated 2 days before final weighing. The residue was extracted with
pyridine and taken to dryness in a Pierce Hypo-vial. Following this step,
sample preparation and analysis were the same as that used for water
solutions.
Hexylene glycol solutions (from the second stage scrubber) were
treated as follows: 1 ml of the hexylene glycol solution was acidified
with enough 1.1 N H2SC>4 (approximately 1 ml) and then treated the same
as water samples mentioned earlier.
Analysis and Discussion
The method for determination of zineb is based on headspace carbon
disulfide analysis. At 100° C in 1.1 N l^SC^ the following reaction occurs:
Zineb _ _ > 2 CS2 + NI^Ct^C^Nl^ + Zn""
Standard zineb treated as indicated yielded 85 to 95% of the theoretical
amount of carbon disulfide.
The sensitivity of the instrument for carbon disulfide is 10 ng.
Since 2 moles of carbon disulfide are generated for every mole of zineb,
the sensitivity of the instrument for zineb is 5 ng.
Prior to adopting the headspace technique, determination of the
ethyl enediamine generated by the hydrolysis of zineb was investigated.
A Perkin-Elmer 3920 gas chromatograph equipped with a phosphorus-nitrogen
thermionic detector was used to follow the ethylenediamine peak. Zineb
was detected at low nanogram levels from standard solutions. However, high
zinc content in the incinerator samples prohibited use of this method
(probably due to chelation of the ethylenediamine with zinc).
TEST CONDITIONS AND RESULTS
A total of 11 tests were conducted using the 75% zineb wettable powder.
The results of these tests are given in Tables 82 through 86.
309
-------
Table 82. SUMMARY OF 75% ZINEB WETTABLE POWDER EXPERIMENTS
No. 2 fuel oil rate
Run
No.
A.
B
C
D
E
F
C
H
I
J
K
a/
b/
c/
Nominal
burner size Actual rate
i/hr (jul/hr) i/hr (eal/hr)
7.6 (2.0)
11.4 (3.0)
3.8 (1.0)
3.8 (1.0)
3.8 (1.0)
3.8 (1.0)
9.5 (2.5)
9.5 (2.5)
9.5 (2.5)
9.5 (2.5)
4.7 (1.25)
5.90 (1.56)
9.42 (2.49)
3.90 (1.03)
3.79 (1.00)
3.86 (1.02)
3.79 (1.00)
9.08 (2.40)
9.27 (2.45)
8.67 (2.29)
9.42 (2.49)
4.43 (1.17)
Nominal zineb content of the ~ 75%
The flame temperature was observed
Calculated according
Pesticide feed rate
~ 757. Zincb Contained
formulation zinebi/
ku/hr (Ib/hr) g^hr (Ib/hr)
4.72 (10.4) 3540 (7.8)
4.22 (9.3) 3180 (7.0)
4.31 (9.5) 3220 (7.1)
3.40 (7.5) 2540 (5.6)
2.13 (4.7) 1590 (3.5)
2.31 (5.1) 1720 (3.8)
2.27 (5.0) 1680 (3.7)
2.31 (5.1) 1720 (3.8)
4.08 (9.0) 3040 (6.7)
4.76 (10.5) 3580 (7.9)
2.81 (6.2) 2130 (4.7)
ilneb uettable povder formulation.
at a point approximately 15 cm (6
to Method 3 of "Standards of Performance for New
Primary
chamber
°C CF)
890 (1630)
970 (1770)
680 (1260)
710 (1310)
690 (1270)
650 (1200)
980 (1790)
940 (1730)
1000 (1830)
930 (1710)
710 (1310)
in.) in from
Retention timed/
Flame fc/
•c (
1000
1080
930
930
980
990
1060
1090
1050
990
990
the front
Stationary Sources,"
•F)
(1830)
(1980)
(1700)
(1700)
(1790)
(1820)
(1940)
(1990)
(1920)
(1820)
(1810)
wall of
Federal
Excess
alr-
69
106
102
153
111
165
67
151
62
129^
85
sec
chamber
3.3
1.9
5.2
3.4
5.0
4.4
2.5
1.8
2.4
1.9
5.1
Second
chamber
3.3
1.9
5.1
3.2
4.8
4.2
2.4
1.7
2.3
1.7
4.9
Sampling
time
min
60
60
60
60
60
60
60
60
60
60
60
Off-gas
flow rateS'
3/1.
(1.000's of SCFH)
193 (6.8)
303 (10.7)
150 (5.3)
218 (7.7)
156 (5.5)
184 (6.5)
235 (8.3)
340 (12.0)
235 (8.3)
337 (11.9)
150 (5.3)
the incinerator.
Register,
36(247):
24876-24895,
23 December
1971.
d/ Retention time Is defined as — , vhere v is the wet off-gas flow rate from the Incinerator at the respective chamber temperature and pressure,
and V is the volume of that chamber.
e_/ A« dry gas at one atmosphere pressure, and 21.1°C (70°F) .
-------
Table 83. RESIDUE CHARACTERISTICS--75% ZINEB WETTABLE POWDER EXPERIMENTS
Run
No.
A
B
C
D
E
F
G
H
I
J
K
a/
b/
c/
jl
Pesticide feed
~ 75% WP C
formulation
kR/hr (Ib/hr)
4.72 (10.4)
4.22 (9.3)
4.31 (9.5)
3.40 (7.5)
2.13 (4.7)
2.31 (5.1)
2.27 (5.0)
2.31 (5.1)
4.08 (9.0)
4.76 (10.5)
2.81 (6.2)
Nominal zineb content
No analysis.
Does not include any
rate
ontained
zineb*''
g/hr
3,540
3,180
3,220
2,540
1,590
1,720
1,680
1,720
3,040
3,580
2,130
of the ~
Solid residues
Primary chamber
Ratio
of total
Second chamber incinerator
Total Zineb cone. Total Zineb cone. residue to
R/hr ppm 8/hr ppm total charge
200
122
124
97
57
55
54
38
28
25
40
757. wettable
14.8
11
16
14.5
34
< 2
< 1
0.8
1.2
< 1.2
8.3
powder
116
79
56
34
26
47
20
25
40
76
24
formulation.
15 0.
NAk/ 0.
19.2 0.
13.1 0.
< 0.2 0.
< 1 0.
4.6 0.
< 0.2 0.
< 0.9 0.
5.4 0.
16.1 0.
067
048
042
038
039
044
033
027
017
021
023
Zineb content of Approximate ratio Incineration
the solid residues of zineb in off-gas efficiency^'
g/hr to zineb fed '/.
4.7 x ID"3
1.3 x 10-3£/
3.1 x 10-3
1.8 x ID"3
1.9 x 10-3
< 1.6 x ID'3
< 1.5 x 10-4
3.5 x 10'5
7.0 x ID'5
4.4 x 10-4
7.2 x 10-4
4
3
3
3
3
3
4
4
3
1
1
x ID"3
x 10-5
x 10-5
x 10"5
x ID"5
x 1C'5
x lO"7
xlO-7
x 10'6
x ID"5
x 10"6
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
> 99.99
zineb present in the second chamber residue.
a<= 1 -
quantity out"
x 100
. where the auant
itv out is evaluated at Samp]
Le Points Nos. (T) i
[incinerator
off-eas:
I and (3) ^incinerator
residues), and the quantity in is evaluated at Sample Point No. (T) (the incinerator feed).
-------
Table 84. OFF-GAS COMPOSITION--757. ZINEB WETTABLE POWDER INCINERATION^
Total hydrocarbons analyzer
Run
No.
A
B
C
D
E
OJ
E
G
H
1
J
K
Zinebk/
1
0.3
0.7
0.4
0.3
0.3
0.003
0.002
0.04
0.1
0.07
CN'
mg/m3
1,260
617
1,100
703
668
835
707
138
569
768
1,080
S02
ing/nv*
21,800
8,330
22,900
14,500
13,100
12,500
8,140
6,670
12,900
10,300
20,500
37
185
21
13
19
9
113
125
96
321
68
Total
hydrocarbons
ppm
5
2
< 1
5
5
10
2
4
4
4
5
Orsat analyzer
CO CHi 02
ppm ppm vol. 7.
6 < I 8
ND^/ < i H
2 < 1 10
< 1 < 1 12
< 1 < 1 11
< 1 < 1 13
< 1 ND 8
ND ND 12
ND ND 8
< 1 < 1 12
ND < 1 9
.8
.2
.9
.9
.4
.3
.7
.9
.3
.1
.9
CO 2
vol. 7.
8.9
6.7
7.3
5.9
7.0
5.7
9.0
5.9
9.2
6.4
8.2
CO
vol .
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0,
7.
0
0
0
0
0
0
0
0
,0
,0
.0
Moisture
vol. '/,
6.9
6.7
6.7
8.5
6.3
5.3
6.4
6.4
8.4
6.7
6.4
a/ As dry gas at one atmosphere pressure, and 21.1°C (70°F).
b/ Approximated value.
c/ Calculated as N02-
d/ Not detected.
-------
Table 85. OPERATIONAL DATA SUMMARY--757o ZINEB WETTABLE POWDER EXPERIMENTS
Run No.
Temperature *C ^°F)
Primary chamber (Thermocouple No. CjU )
Primary chamber (Thermocouple No. (?) )
Primary chamber (Thermocouple No. jTT) )
Second chamber (Thermocouple No. (Vf )
Second chamber (Thermocouple No. f5j )
Sample Point No. \2J (Thermocouple No. Q>) )
860
850
890
750
520
260
A
(1580)
(1570)
(1630)
(1390)
(970)
(500)
930
900
970
850
610
370
B
(1710)
(1660)
(1770)
(1560)
(1130)
(690)
650
590
680
590
380
200
C
(1200)
(HOO)
(1260)
(1090)
(720)
(400)
670
600
710
630
430
230
D
(1240)
(1110)
(1310)
(1160)
(800)
(450)
670
620
690
600
400
190
_E_
(1240)
(1140)
(1270)
(1120)
(760)
(380)
F
630 (1170)
570 (1050)
650 (1200)
580 (1080)
390 (730)
210 (410)
Pressures
Draft (Manometer No, ^ ), pascals
(in. H20) gauge
Burner operation pressure, pascals (psi)
gauge
Pesticide injection air, pascals (psi)
gauge
16 (0.065) 42 (0.170) 12 (0.050) 24 (0.095) 12 (0.050) 24 (0.095)
7.4 x 105 (108) 7.4 x 105 (108) 7.5 x 10^ (109) 7.7 x 105 (112) 7.4 x 105 (108) 7.4 x 105 (108)
6 x 104 (9) 6 x 104 (9) 6 x 104 (9) 6 x 104 (9) 6 x 104 (9) 6 x 104 (9)
OJ
Temperature *C (°F)
Primary chamber (Thermocouple No. UJ )
Primary chamber (Thermocouple No.
Primary chamber (Thermocouple No. f3) )
Second chamber (Thermocouple No.
Second chamber (Thermocouple No.
Sample Point No. C 2 J (Thermocouple No .
Pressures
), pascals
Draft (Manometer No.
(in. H20) gauge
Burner operation pressure, pascals (psi)
gauge
Pesticide injection air, pascals (psi)
gauge
940 (1720)
920 (1690)
980 (1790)
870 (1590)
640 (1190)
350 (660)
890 (1640)
850 (1560)
940 (1730)
870 (1600)
640 (1190)
380 (710)
950 (1740)
930 (1710)
1000 (1830)
890 (1630)
630 (1160)
340 (650)
880 (1620)
850 (1570)
930 (1710)
850 (1560)
600 (1110)
380 (710)
690 (1270)
590 (1100)
710 (1310)
630 (1170)
420 (780)
210 (410)
24 (0.095) 56 (0.225) 24 (0.095) 51 (0.205) 12 (0.050)
7.4 x 105 (108) 7.4 x 103 (107) 7.4 x 10^ (107) 7.4 x 105 (108) 7.4 x IflS (107)
6 x 10^ (9) 6 x 104 (9) 6 x 104 (9) 6 x 104 (9) 6 x 104 (9)
-------
Table 86. PARTICULATE SAMPLING SUMMARY—75% ZINEB WETTABLE POWDER EXPERIMENTS
OJ
Description
Vol. dry gai - «td. cond., nnP
Percent moisture by vol.
Avg. stack temperature, "C
Stk. flow rate, dry, ltd. cond., nm3/nin
Actual stack flow rate, mVnln
Percent isokinetlc
Percent excess air
Particulars - partial catch
Parttculate wt. - partial, mg
Part, load - ptl., std. cond., mg/mn3
Part, load - ptl., itk. cond., mg/m3
Partic. emis. - partial, kg/hr
Partlculates - total catch
Particulate wt. - total, mg
Part, load - ttl., std. cond., ing/ ran3
Part, load - ttl., std. en., corrected
to 127. CO., ng/ron3
Part, load - ttl., stk. cond., mg/m3
Partic. emit. - total, kg/hr
Percent irapinger catch
A
0.343
6.9
243.8
3.2
6.0
101.8
70
2,860
8,320
4,430
1.608
3,350
9,760
13,200
5,190
1.885
14.70
B
0.521
6.7
356.7
5.0
11.7
98.7
107
2,501
4,790
2,070
1.452
2,730
5,240
9,400
2,260
1,587
8.53
C
0.260
6.7
191.5
2.5
4.2
98.1
102
2,000
7,680
4,580
1.166
2,440
9,370
15,400
5,590
1.423
18.09
JL
0.392
8.5
191.5
3.6
6.2
103.0
155
2,200
5,590
3,260
1.221
2,860
7,270
14,800
4,240
1.589
23.19
JL
0.262
6.3
175.3
2.6
4.2
97.3
112
793
3,030
1,860
0.467
1,100
4,210
7,200
2,580
0.651
28.19
..r
0.310
5.3
202.1
3.1
5.3
97.0
165
1,360
4,380
2,540
0.804
2,020
6,480
13,600
3,760
1.190
32.41
G
0.413
6.4
354.9
3.9
8.9
100.8
67
1,470
3,550
1,570
0.835
2,220
5,380
b
7,200
2,380
1.264
33.97
H
0.587
6.4
377.1
5.7
13.3
99.4
151
1,600
2,710
1,150
0.920
2,430
4,130
8,400
1,760
1.401
34.32
I
0.423
8.4
354.4
3.9
9.2
102.7
62
2,580
6,090
2,600
1.441
3,450
8,130
10,600
3,480
1.924
25.10
J
0.577
6.7
351.6
5.6
12.6
98.6
129
2,310
4,000
1,780
1.344
3,420
5,910
11,100
2,630
1.984
32.26
K
0.255
6.4
203.5
2.5
4.3
97.7
85
1,740
6,810
3,940
1.019
2,400
9,390
13,700
5,430
1.404
27.43
-------
As has been discussed in the preceding subsection on analytical methods,
the zineb analyses are not comparable to those of the eight other pesticides
tested. This is due in general to the limitations in the available zineb
analytical methods, and in particular to the inability to analyze the fil-
ter element of the off-gas sampling train. However, an approximation of
the zineb content of the particulates trapped on the filter element can
be made by utilizing the analyses for other residue samples obtained after
the completion of each test. These additional samples were obtained from
the walls of the horizontal and vertical sections of the incinerator stack
preceding Sample Point No. (T), the normal incinerator off-gas sampling
point. Values of the zineb content of the residues deposited in this sec-
tion of the stack (average value of 55 ppm, ranging from < 0.2 to 109 ppm
for the 11 tests) have been substituted for the filter element analyses
in order to develop the estimated zineb quantities and concentrations given
in Tables 83 and 84. Using this approximation, efficiencies of combustion
have been calculated as > 99.99% for all 11 tests. It should be noted that
the actual zineb content of the particulate material on the filter ele-
ment of the off-gas sampling train would have to be greater than twice
the highest incinerator-stack-residue zineb concentration detected (i.e.,
2 x 109 or 218 ppm) before the efficiency of combustion would be less than
that indicated, i.e., > 99.99%.
High cyanide levels were detected in the incinerator off-gas (Sample
Point No. (^)> for all zineb tests. The results of cyanide analyses, expressed
as CN~, are summarized as follows:
Primary chamber Excess
temperature air Cyanide content
Run No. (°F) (%) (g/hr) (mg/m3)
A 890 (1630) 69 243 1,260
B 970 (1770) 106 187 617
C 680 (1260) 102 165 1,100
D 710 (1310) 153 153 703
E 690 (1270) 111 104 668
F 650 (1200) 165 154 835
G 980 (1790) 67 166 707
H 940 (1730) 151 469 138
I 1000 (1830) 62 134 569
J 930 (1710) 129 259 768
K 710 (1310) 85 162 1,080
315
-------
The results of the particulate sampling conducted on the zineb tests
are given in Table 86. Acceptable isokinetic conditions were achieved
on all runs. The particulate loadings all exceed what can be considered
low emissions and indicate the need for particulate control devices when
zineb wettable powder formulations are incinerated.
DISCUSSION
The most significant operational problem with the zineb incinerator
was the inability of the off-gas scrubber system to clean up the effluent
gas. A white plume was discharged from the scrubber system exhaust (Sample
Point No. (?), the opacity of which ranged from 0 to 45%, based on random
observations (see Figure 61a). The particulate material was also deposited
on interior surface areas throughout the scrubber system. Residue deposi-
tion inside the scrubber system blower, as shown in Figure 61b, caused
blower vibration during the latter tests.
The deposition of particulate material also caused plugging of the
deraister pads in the first and second stage scrubbers. The demister pad
was removed from the second stage hexylene glycol scrubber after Run No.
E in order to reduce plugging of the system. (The opacities of the ex-
haust plume for Runs Nos. A through E ranged from 0 to 20%, while those
for Runs Nos. F through K ranged from 5 to 45%.)
The odor of SOo was also noted during the incineration of zineb.
316
-------
a. Effluent plume (35% opacity)
b. Residue deposition in blower
Figure 61. Particulate discharge during zineb incineration
317
-------
References
1. Martin, H., Pesticide Manual, British Crop Protection Council,
Worcester, England (1971).
2. Melnikov, N. N., Chemistry of Pesticides, Springer-Verlag, New York,
New York (1971).
3. 1975 Farm Chemicals Handbook, Meister Publishing Company, Willoughby,
(1975).
4. Kennedy, M. V., B. J. Stojanovic, and F. L. Shuman, Jr., "Chemical
and Thermal Methods for Disposal of Pesticides," Residue Reviews,
£9:95 (1969).
5. Zweig, G., and J. Sherma, "Analytical Methods for Pesticides and Plant
Growth Regulators," Gas Chromatographic Analysis, Vol. VI, G. Zweig,
ed., Academic Press, New York (1972).
6. McLeod, H. A., and K. A. McCully, J. AOAC, 52(6): 1226 (1969).
318
-------
IX. MIREX
PESTICIDE DESCRIPTION
Physical Properties
Chemical Name; Dodecachlorooctahydro-l,3,4-metheno-2H-cyclobuta (cd)
pentalene
Common Name; Mirex
Trade Name; Dechlorane®, GC-1283
Pesticide Class; Stomach insecticide
Structural Formula;
C1C-J CC1
C1C-
-CC1
.C1C
Empirical Formula; ^10^12
Molecular Weight; 545.6
Physical State; White crystalline solid
Melting Point; ~ 485°C
Flash Point; Nonflammable
Solubility; Insoluble in water; reasonably soluble dioxane, xylene,
benzene, and carbon tetrachloride.
Chemical Properties
This highly chlorinated compound is reported to be unaffected by
mineral acids (HC1, HN03 and H2S04).!/ Lawless et al.-' stated that mirex
would be expected to be extremely resistant to oxidation except at the
high temperature of an efficient incinerator.
319
-------
Production and Use
Mirex is a stomach insecticide toxic to grass-feeding insects, espe-
cially ants. It is available in a limited number of solid bait formula-
tions, the most important of which is a 0.3% mirex bait for Imported Fire
Ant control. The use of mirex in the Fire Ant eradication program in the
southeastern United States is currently the subject of review of EPA and
USDA.
Unpublished MRI estimates of 1972 domestic pesticide use include an
estimated 0.3 million pounds of mirex (as active ingredient).
FORMULATIONS TESTED
Mirex is commercially available in only solid formulations. A 0.370
bait, the principal form in which mirex is marketed, was the only formula-
tion tested.
0.3% Mirex Bait
Name; Mirex Granulated Bait 4X
Manufacturer; Allied Chemical Corporation, Agricultural Division,
Morristown, New Jersey
Composition; Active Ingredient
Dodecachlorooctahydro-l,3,4-metheno- 0.3%
2H-cyclobuta(cd)pentalene*
Inert Ingredients 99.7%
Total 100.0%
* Mirex
Registration; EPA Reg. No. 218-565
Lot No.; 2J1037
Particle Size Distribution; Mirex in soybean oil on 12/30 corncob
grit ( < 1.41 mm, > 595 ^ )
320
-------
PRELIMINARY THERMAL ANALYSIS
Laboratory thermal analyses were conducted on the 0.3% bait formula-
tion as well as on technical mirex. Bomb caloriraetric analyses gave the
following results:
Sample Test Test Method Result
Technical mirex Heat of combustion ASTM D-2015 1.058 x 10 J/kg
(4,554 Btu/lb)
Sulfur ASTM D-129 1.91%
0.3% mirex bait Heat of combustion ASTM D-2015 2.168 x 10 J/kg
formulation (9,329 Btu/lb)
Sulfur ASTM D-129 1.05%
Figures 62 and 63 show the results of DTA and TGA of the technical
grade mirex (97%). DTA data show that decomposition of the sample starts
at about 130°C, with two endotherms at about 140 and 370°C, respectively,
and an exotherm at about 570°C. The decomposition process is substan-
tiated by the TGA data which indicate that about 95% of the sample weight
is lost at about 350°C, and almost all the sample is gone at 800°C.
No DTA and TGA experiments were performed on the bait formulation
because of the small amount of mirex present (0.3%).
METHODS OF ANALYSIS
Apparatus
A Micro-Tek 2000R gas chromatograph equipped with a 3-ft, 4 mm I.D.
glass column (packed with 1.5% OV-17 + 1.95% QF 1 on 80/100 mesh Supelcoport
from Supelco, Inc., Bellefonte, Pennsylvania) and a tritium electron capture
detector, maintained at a voltage of 18 V DC was used for gas chromato-
graphic analysis. Chromatographic operating conditions were: injector
temperature, 235°C; column temperature, 220°C; detector temperature, 180°C;
carrier flow rate, 125 ml/min, N2; and purge gas flow rate, 200 ml/min,
N2.
A Hewlett-Packard 3380A Integrator was used for peak identification
and quantification.
321
-------
o
Q
z
LU
OJ
O
X
LU
_L
0 50 100
J L
J L
200
300 400
TEMPERATURE °C
500
600
Reference: Al^O^
Prog, mode: Heat
Rate: 20°C/min
Start: 0°C
Kaoltnite
Figure 62. DTA of technical mirex
-------
1
114
Q.
1000
950
900
850
800
750
700
650
600
550
500
450
400
350
300
250
200
150
100
50
0
1 1 1 1 1
1 1 1 1 1
0.4
0.8 1.2
WEIGHT LOSS, mg
I I I I
1.6
2.0
0 20 40 60 80
WEIGHT LOSS, PERCENT
Sample Weight: 1.518 mg
Heating Rate: 20"C/min
Environment: ~ 20 ml/min air (207. 02, 80Z ^
Figure 63. TGA of technical mirex
100
323
-------
Reagents and Materials
The analytical reagent mirex (99.9%) was used for preparing standard
solutions. Solvents used were pesticide grade benzene (Fisher Scientific)
for all impingers and standard mirex solutions, and pesticide grade hexane
(Matheson, Coleman, Bell) for extraction of hexylene glycol traps (from
the second stage scrubber). All glassware coming from the laboratory
(vials, beakers, etc.) was washed with Alconox Detergent (Scientific
Products) and rinsed with deionized distilled water and reagent grade
acetone (Fisher Scientific).
Standards and Calibration Curve
The solid standard, mirex, provided by USEPA, was used to prepare
a stock solution of 100 u-g/ml mirex and various dilutions were made to
obtain linear results (linear range used: 0 to 2.50 ng).
Procedure for Sample Preparation
The mass of collected particulates was determined for all components
of the Sample Point No.fSntrain as follows. All samples were taken to
dryness under a hood in clean, dessicated, tared 250-ml beakers and
desiccated 2 days before final weighing. The residue was extracted with
benzene (two 10- to 15-ral portions) and the extract taken just to dryness
and capped tightly. Silica gel was extracted with just enough benzene to
cover silica gel and a 20-ml portion pipetted out and taken just to dry-
ness. Twenty milliliter portions of blank impinger solutions (benzene and
acetone) were also pipetted into vials and taken just to dryness. All
other impinger, wash and blank solutions, were taken just to dryness in
the French Squares bottles as received. Ten milliliters of the hexylene
glycol were extracted with ri-hexane and the extract was taken just to
dryness. All samples were taken up in appropriate amounts of benzene just
prior to GC analysis.
Portions of all cleanout samples labeled (primary chamber, secondary
chamber, etc.) were weighed out and extracted and the extracts were analyzed
for mirex.
Analysis and Discussion
All samples were analyzed for mirex. Unidentified chromatographic
peaks were quantitated against the mirex calibration curve.
324
-------
The sensitivity of the instrument for mirex is 50 pg. Based on this
sensitivity, and with a 5 u-1 sample injection for each analysis, the mini-
mum detectable quantity for a 20-ml sample solution is 0.2 p,g. However,
during the analysis, samples were very often concentrated down to 1 ml
which resulted in a minimum detectable quantity of 10 ng.
TEST CONDITIONS AND RESULTS
Ten tests were made using a 0.37o mirex bait formulation. This bait,
the primary form in which mirex is used, is formulated on a combustible,
granular carrier (i.e., corncob grit). Because of the size of the incinerator
[designed for 45.4 kg/hr (100 Ib/hr) of Type 1 waste, equivalent to 6.86
108 J/hr (650,000 Btu/hr)], the heat of combustion of the mirex bait for-
mulation 2.168 x 107 J/kg (9,329 Btu/lb), and the low concentration of
mirex («« 0.37o), low rates of active ingredient injection were used. Mirex
(as the pure active ingredient) was injected at nominal rates of 68 g/hr
(0.15 Ib/hr) and 34 g/hr (0.075 Ib/hr), rather than the 3.40 kg/hr (7.5
Ib/hr) and 1.70 kg/hr (3.75 Ib/hr) rates used for all other pesticides
studied.
The operational data for these 10 tests are summarized in Tables 87
through 91. Two efficiencies were calculated for the incineration of
mirex, based on (a) the mirex content of the effluent gas and solid resi-
dues, and (b) the total chlorinated organic species (mirex plus all other
chlorinated organic species) detected in the effluent gas and solid resi-
dues (see Table 88). Efficiency based on mirex content only ranged from
> 98.21 to > 99.987o while efficiency based on total chlorinated organic
species detected ranged from > 97.78 to > 99.967o. Both of these ranges
are significantly lower than those for the other pesticides studied.
The temperature reported in Table 87 is the higher temperature in
the upper portion of the primary chamber, i.e., Thermocouples Nos. 1 or
3 (see Figure 11, p. 91). Reference to the data in Table 90 will show that
the temperature for Thermocouple No. 2 (located approximately 15 cm (6 in.)
above the center of the primary chamber floor) was normally higher than
either Thermocouples Nos. 1 or 3. This temperature (Thermocouple No. 2),
however, is not representative of the chamber temperature. The mirex for-
mulation, upon injection into the chamber, was observed to drop to the
floor and continue to burn in close proximity of Thermocouple No. 2,
thus giving a high temperature reading.
325
-------
Table 87. SUMMARY OF 0.3% MIREX BAIT EXPERIMENTS
N3
Run
A
B
C
0
E
F
G
H
I
J
No. 2 fuel
Nominal
burner size
f/hr (gal/hr)
3.8 (1.0)
2.8 (0.75)
5.7 (1.5)
2.8 (0.75)
2.8 (0.75)
7.6 (2.0)
9.5 (2.5)
5.7 (1.5)
2.8 (0.75)
9is (2.5)
oil rate
Actual rate
t/hr (ital/hr)
3.94 (1.04)
2.73 (0.72)
5.75 (1.52)
2.80 (0.74)
2.34 (0.75)
5.75 (1.52)
9.50 (2.51)
5.87 (1.55)
2.84 (0.75)
9.46 (2.50)
Pesticide feed rate
~ 0.3% Mlrex
bait
kg/hr (Ib/hr)
23.95 (52.8)
23.36 (51.5)
23.00 (50.7)
10.61 (23.4)
10.80 (23.8)
11.02 (24.3)
11.52 (25.4)
23.18 (51.1)
22.59 (49.8)
10.84 (23.9)
Contained
Mlrexi/
72
70
69
32
32
33
35
70
68
33
Primary
chamber
temperature
•C CF)
900 (1650)
870 (1600)
930 (1710)
590 (1090)
700 (1290)
820 (1510)
940 (1730)
880 (1620)
760 (1400)
920 (1690)
Flame
temperature^/
•C CF)
1020 (1860)
990 (1820)
1020 (1860)
1020 (1860)
1020 (I860)
1070 (1960)
1090 (2000)
1060 (1940)
1020 (1860)
1100 (2020)
Excess
57
85
82
225
79
48
118
123
149
141
Retention time
sec*/
Primary
chamber
2.8
2.6
2.0
2.8
6.0
5.3
2.0
1.7
2.2
1.8
Second
chamber
3.0
2.8
2.0
3.4
6.2
5.5
2.0
1.6
2.2
1.5
Sampling
time
min
60
60
60
60
60
60
60
60
60
60
Off-gas
flow rate*/
(1,000's of SCFH)
263
300
382
297
161
167
388
456
394
428
(9.3)
(10.6)
(13.5)
(10.5)
(5.7)
(5.9)
(13.7)
(16.1)
(13.9)
(15.1)
a/ Analysis of grab samples of the bait formulation showed mlrex content ranging from 0.21 to 0.411. Becaus"e of the difficulty In obtaining representative
~ samples of the material burned during each test (I.e., ~ 45.4 kg (100 Ib) of a rather heterogeneous mixture), the nominal value of 0.37, mlrex was used
to calculate the quantity of contained mlrex.
b/ The flame temperature was observed at a point approximately 15 en (6 In.) In from the front wall of the Incinerator (see Figure B-l).
c/ Calculated according to Method 3 of "Standards of Performance for New Stationary Sources," Federal Register. 36(247):24876-24895, 23 December 1971.
d/ Retention time Is defined as - , where v Is the off-gas flow rate from the Incinerator at the respective chamber temperature and pressure, and V Is
the volume of that chamber.
e/ As dry gas at one atmosphere pressure, and 21.1°C (70°F).
-------
Table 88. RESIDUE AND OFF-GAS CHARACTERISTICS--0.37. MIREX BAIT EXPERIMENTS
CO
Pesticide feed rate
0.37. Mirex
Run
No.
A
B
C
D
E
F
G
H
I
J
bait Contained
formulation mtrcx£'
kc/hr (Ib/hr) K/hr
23.95 (52.8) 72
23.36 (51.5) 70
23.00 (50.7) 69
10.61 (23.4) 32
10.80 (23.8) 32
11.02 (24.3) 33
11.52 (25.4) 35
23.18 (51.1) 70
22.59 (49.8) 68
10.84 (23.9) 33
Run
No.
A
B
C
D
E
F
C
H
I
J
of off-gas
R/hr
7
2.4
2.4
6
9
2.7
4.3
1
8
8
x 10
x ID' 2
x 10-2
x 10-1
x ID"2
X ID"2
X ID"2
x ID'2
x ID"2
x 10-3
solid residues
R/hr
1.8 x ID"3
2.6 x ID'5
7 x 10-6
2.8 x ID"4
2.4 x ID'5
4 x ID'5
< 1, x W-M
< l.l x 10-5-'
3.4 x IO-6
1.7 x 10-5
Primary
Solid residue
chamber
Total Mirex cone.
K/hr PP™
284
247
210
170
139
121
80
197
231
56
solid residues
f
9
2.4
2.4
6
9
2.7
4.3
1
8
8
1/hr
x ID"3
x 10
x 10-2
x 10-1
x ID"2
x 10" 2
x ID'2
x ID'2
x 10-2
x 10-3
4.2
< 0.05S/
1.6
0.05
0.2
< 0.05£/
« 0.05£/
0.3
Total species]!/
cone . , ppm
... b/
off-gas
K/hr
9
3.7
6
7
1.6
8
1.1
3.5
9
1.3
x
x
X
X
X
X
X
X
X
10-1
ID'2
10-2
10-1
10-1
10-2
10-1
IO-2
10-2
10-2
51.5
< 0.05
0.2
1.8
< 0.3
3.9
23.3
0.5
12.4
1.3
o a spec es-
solid residues
Total
E/hr
Second chamber
Mirex cone.
ppm
60 10.8
32 0.8
37 0.2
20 0.6
17 0.6
21 0.5
33 < 0.05S/
30 < 0.05S/
34 0.1
18 < 0.05S/
Total species^'
con en o o
residues
R/hr
1.4 x
5 x
6 x
3.2 x
7 x
5 x
< 2.7 x
< 1.2 x
3.0 x
1.0 x
10" 2
io-5
10-5
io-4
10-5
ID'4
10-3
io-4
10-3
io-4
9
3.
6
7
1.
8
1.
3.
1
1.
R/hr
x
7 x
x
X
6 x
X
1 X
5 x
X
3 x
10-1
10-2
10-2
10-1
10-1
10-2
10-1
10-2
10-1
10-2
Total
cone
11.6
0.8
0.4
0.9
1.5
1.4
25.6
0.7
2.9
1.5
totai mirex
fed
1.0
3.4
3.5
1.8
2.9
8
1.2
1.4
1.2
2.3
x 10'4
x ID'4
x IO-4
x ID'2
x 10-3
x ID'4
x 10-3
x ID'4
x 10-3
x ID'4
0.014
0.012
0.011
0.018
0.014
0.013
0.010
0.010
0.012
0.006
off-gas to total
mirex fed
1.3 x ID"2
5 x IO-4
8 x 10-4
2.2 x lO-2
5 x 10-3
2.4 x 10"3
3.1 x ID'3
5 x ID"4
1.4 x 10-3
3.9 x ID"4
I
Mirex Total species]"/
> 99
> 99
> 99
> 98
> 99
> 99
> 99
> 99
> 99
> 99
.98
.96
.96
.21
.70
.91
.S7
.98
.88
.97
> 98.70
> 99.94
> 99.91
> 97.78
> 99.50
> 99.75
> 99.68
> 99.95
> 99.85
> 99.96
a/ Analysis of grab samples of the bait formulation showed mirex content ranging from 0.21 to 0.417.. Because of the difficulty in obtaining representative samples of the
material burned during each test (i.e., ~ 45-4 kg (100 Ib) of a rather heterogeneous mixture), the nominal value of 0.37* mirex was used to calculate the quantity of
contained mtrex.
b/ Mirex plus all other chlorinated organic species detected.
c/ Mirex was not detected. The value given represents the detection limit for mirex in the particulatc sample.
£/ Efficiency is defined as 1 - ,^...^r—. x 100> where the quantity otit is evaluated at Sample Points Nos. (?) (incinerator off-gas) and (3) (incine
idues),
and the quantity in is evaluated at Sample Point No. (T) (the incinerator feed). Et'iicicneics have been calculated based on (a) mirex only, and (b) the total chlorinated
organic species detected at Sample Points Nos. (2) and (3) .
-------
Table 89. OFF-GAS COMPOSITION--0.3% MIREX BAIT EXPERIMENTS!/
oo
Total hydrocarbons analyzer
Run
No.
A
B
C
D
E
F
C
H
I
J
Mirex Total specie&k/
mg/m3 TO/m3
2.8
8.0
6.3
5.8
1.6
1.1
2.1
2.0
1.8
x 10-2 35
x ID"2 ! 2 x 10-1
x 10-2 l-5 x 10-1
1.9 2.4
x 10-1 9.9 „ 10-1
x 10'1 4.8 x 10'1
x 10"1 2.8 x 10"1
x UT2 7.7 x 10'2
x 10'1 2.4 x 10'1
x ID'2 3.0 x ID'2
S02
mg/m3
74
74
87
44
119
199
129
71
50
131
T/rni
13
39
32
59
26
45
52
52
54
55
Total
hydrocarbons
ppm
76
31
43
93
55
24
29
31
35
20
Orsat analyzer
CO
ppm
65
ND*'
ND
63
5
20
4
ND
26
ND
Cl<4 02
ppm vol. 7.
f K
< 1 7
< 1 9
< 1 9
< 1 14,
< 1 9,
< 1 7.
< 1 11.
< 1 11,
< 1 12.
< 1 12.
- '•
.8
.7
.6
.6
,4
,0
,6
.7
6
5
C02
vol. 7.
11.4
9.6
9.6
5.2
9.6
11.4
7.6
7.9
7.2
6.8
CO
vol. 7,
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
Moisture
vo 1 . 7.
11.6
7.2
5.3
7.9
5.0
3.0
7.0
7.4
7.5
7.3
a/ A» dry gas at one atmosphere pressure, and 21.1'C (70°F).
b/ Mlrex plus all other chlorinated organic species detected.
£/ Calculated as NO^.
dV Not detected.
-------
Table 90. OPERATIONAL DATA SUMMARY--0.3% MIREX BAIT EXPERIMENTS
OJ
Run No.
Temperature "C (*F)
Primary chamber (Thermocouple No. \l) )
Primary chamber (Thermocouple No. (2} )
Primary chamber (Thermocouple No. ^3i )
Second chamber (Thermocouple No. (4) )
Second chamber (Thermocouple No. ^Tj )
Sample Point No. (T) (Thermocouple No. ^6y )
Pressures
Draft (Manometer No. /1\ ), pascals
(in H20) gauge
(psi) gauge
Pesticide Injection air, pascals (psi) gauge
Scrubber liquids^/
1st Stage, 1120 scrubber
Volume, J (gal.)
Mirex cone . , tng/£
Total species cone.,—' mg/i
2nd Stage, hexalene glycol scrubber
Volume, I (gal.)
Mirex cone, change, mg/l
Total species cone, change,— mg/jt
3rd Stage, 11^0 scrubber
Volume, I (gal.)
Mirex cone., mg/£
Total species cone.,—' mg/2
Scrubber syKtrm
Effluent gas (Sample Point No. @ )£/
Total species cone.,— mg/m3
A
850 (1570)
970 (1780)
900 (1650)
700 (1300)
500 (930)
310 (590)
36 (0.145)
7.4 x 10^ (108)
8 x 104 (11)
1110 (293)
1 x 10- :
5 x 10"1
100 (26.3)
ND£/
ND
2030 (537)
2 x ID"3
5 x ID'2
4 x 10-3
2 x 10-1
B
820 (1510)
940 (1720)
870 (1600)
670 (1230)
490 (920)
310 (590)
54 (0.215)
7.5 x 105 (1C9)
7 x 104 (10)
1070 (282)
1
2
99 (26.1)
NA<1/
NA
2010 (531)
3 x ID'2
3 x 10-2
1 x 10"2
2 x ID"2
880
1050
930
730
620
400
62 (
7 .4
8 x
1100
4 x
8 x
101
7 x
1 x
1950
6 x
8 x
2 x
3 x
C_
(1610)
(1930)
(1710)
(1440)
(1150)
(760)
0.250)
x 105 (108)
104 (12)
(291)
ID'2
10-2
(26.8)
10-2
10-1
(514)
10-3
10-3
10-3
10-3
570
690
590
510
390
270
42
7.6
8 x
126i
7 x
7 x
96
9 x
2
102i
HA!
NA
2 x
2 x
0
(1050)
(1270)
(1090)
(950)
(730)
(510)
(0.170)
x 105 (110)
104 (12)
0 (334)
10-1
10-1
(25.4)
10-1
0 (269)
/
10-1
10-1
E
700 (1290)
720 (1320)
690 (1280)
570 (1060)
390 (730)
230 (450)
17 (0.070)
7.4 x 105 (108)
6 x 104 (9)
1020 (270)
6 x ID"2
7 x ID'2
94 (24.8)
ND£/
ND
1820 (480)
9 x ID'3
1 x 10-2
9 x 10-3
7 x ID'2
810
790
820
680
440
270
19
7.4
6 x
103
2 x
2 x
93
4 x
1
184<
NA
6 x
3 x
F
(1490)
(1460)
(1510)
(1250)
(830)
(520)
(0.075)
x 105 (108)
104 (9)
3 (273)
10- 2
io-2
(24.6)
10-1
0 (486)
/
10-3
io-2
890
950
940
830
650
420
62
7.4
6 x
103'
96
1
7
182'
2 x
8 x
3 x
7 x
C
(1640)
(1750)
(1730)
(1520)
(1210)
(790)
(0.250)
x IO5 (108)
IO4 (9)
0 (271)
/
/
(25.4)
0 (480)
10-3
10-3
10-3
10-3
-------
Table 90. (Concluded)
co
10
O
Run Ko.
Temperature *C (*F)
Primary chamber (TtieroocoupU No. (ft )
Primary chamber (Thermocouple No. (f) )
Primary chamber (Thermocouple No.^J\ )
Second chamber (Thermocouple No. ("«"' )
Second chamber (Thermocouple No. )*!v )
Sample Point No. 0 (Thermocouple No. (t) )
Pressures
Draft (Manometer Ko. /^ ), pascals
(in HjO) gauge
Burner operation pressure, pascals
(pal) gauge
Scrubber liquids!/
lat Staga, H20 scrubber
Volume, i (gal.)
Mirex cone. , mg/jf
K/
Total species cone., 5' WQ/t
2nd Stage, hexalrno glycol scrubber
Volume, t (gal.)
Mlrex cone, change, mg/i
3rd Stage, H20 scrubber
Volume, / (gal.)
Mlrex cone. , m?,H
Total species cone.,—' mg/4
Scrubber system
Effluent gai (Sample Point No. (?) )£'
Mlrex cone., mg/m3
Total speclei com . ,£/ mg/W
a/ Scrubber vater (Scrubbers 1 and 3) was used
recycled. The concentrations reported for
(Increases) detected during the respective
-11_
830 (1530)
980 (1800)
880 (1620)
790 (1450)
650 (1200)
430 (800)
60 (0.240)
7.6 x ID' (110)
8 X 10" (12)
1140 (300)
1 x 10"2
2 x 10'2
97 (23.6)
2 x 10-'
2
1930 (509)
2 x 10-3
6 x 10'3
< 4 x 10-^'
7 x 10-3
-i.
7ZO (1330)
890 (1630)
760 (1400)
630 (1160)
320 (960)
340 (640)
51 (0.205)
7.4 x 105 (108)
8 x 104 (12)
1040 (275)
7 x 10"2
1 x 10"1
94 (24.8)
2
5
1730 (457)
1 x 10"3
2 x 10'2
< 4 x 10'3-'
3.5 x 1C'1
J
890 (1630)
960 (1760)
920 (1690)
840 (1540)
680 (1260)
450 (850)
57 (0.230)
7.4 x 10* (108)
8 x 104 (12)
1020 (270)
2 x 10"2
4 x 10"4
96 (25.3)
9 x 10" '
1790 (474)
1 x 10"3
2 x 10'2
5 x 10'3
9 x 10'J
once through, while the hexylene glyco! (Scrubber 2) was
hexylene glycol, therefore, are the concentration changes
tests.
b_/ Mlrex plus all other chlorinated organic species detected.
c_/ No Increase in concentration detected.
d_/ No analysis.
e/ As the wet gas at one atmosphere pressure, and Jl.l'c (70'f>.
U Mlrex not delected. The value reported repr
this particular sample.
t-'B-.-'il ; the limit of
detection for
-------
Table 91. PARTICULATE SAMPLING SUMMARY—0.3% MIREX BAIT EXPERIMENTS
co
Description
Vol. dry gas - std. cond., nm^
Percent moisture by vol.
Avg. stack temperature, °C
Stk. flow rate, dry, std. cond., nm^/min
Actual stack flow rate, m^/min
Percent isokinetic
Percent excess air
Particulates - partial catch
Particulate wt. - partial, mg
Part, load - ptl., std. en., ing/nn>3
Part, load - ptl., stk. en., rag/m-*
Partic. emis. - partial, kg/hr
Particulates - total catch
Particulate wt. - total, mg
Part, load - ttl., std. en., mg/nm^
Part, load - ttl., std. en., corrected
to 127. C02, mg/nm3
Part, load -.ttl., stk. en., mg/m3
Partic. emis. - total, kg/hr
Percent impinger catch
A
0.429
11.6
307.2
4.4
9.8
93.6
58
86
199
89
0.052
174
405
426
182
0.106
50.78
B
0.537
7.2
296.1
5.0
10.6
102.3
86
64
119
56
0.036
95
177
222
84
0.053
33.00
C
0.650
5.3
402.6
6.4
15.5
97.4
82
73
112
46
0.043
111
171
213
70
0.065
34.13
D
0.501
7.9
256.7
5.0
9.7
96.5
229
69
138
70
0.041
124
246
570
126
0.073
43.86
£
0.279
5.0
242.4
2.7
4.9
99.3
80
23
82
45
0.013
46
164
205
90
0.027
49.85
F
0.258
3.0
305.3
2.8
5.6
88.6
48
31
120
60
0.020
62
238
251
118
0.040
49.76
G
0.592
7.0
476.4
6.5
17.7
87.2
57
45
77
28
0.030
63
106
168
39
0.041
28.04
H
0.707
7.4
432.9
7.6
19.6
88.7
123
78
111
43
0.051
84
118
180
46
0.054
6.55
I
0.674
7.5
364.1
6.5
15.4
98.5
150
58
86
36
0.034
72
107
179
46
0.042
20.09
J
0.731
7.3
468.7
7.1
19.6
98.4
142
51
70
25
0.030
62
85
150
31
0.036
17.86
-------
Additional samples were taken during the mirex tests using a special
sampler installed in the bottom of the primary combustion chamber (see
Figure 32, p.196). This sampler was used to catch the mirex bait particles
as they fell through the combustion chamber in order to approximate the
degree of decomposition actually occurring while the particle was falling.
The sampler was inserted upside down, rotated, and immediately (^ 3 sec)
extracted to obtain grab samples with a nominal retention time in the pri-
mary combustion chamber of about 2 sec. The grab samples were analyzed
for mirex and total chlorinated species content and gave the following
results:
Grab Sample Composition
a/
Run No. Mirex (ppm) Total Species (ppm)—
A
B
C
D
E
F
G
H
I
J
Average 770 900
aj Mirex plus all other chlorinated organic species detected.
The average mirex content of the bait formulation used for these tests
was 2,710 ppm (based on 17 samples, ranging from 1,940 to 4,130 ppm). Al-
though the above data show no strong correlation with any particular
operating parameter, they do indicate that a substantial portion of the
mirex (~ 70%) is "removed" from the bait formulation during the first 2
sec residence in the primary chamber.
332
-------
The data do not show what operating conditions would be required to
effect mirex decomposition comparable to that which has been achieved for
the other pesticides studied (i.e., an incineration efficiency of > 99.99%).
It appears that temperatures higher than those tested (above 940°C
(1730°F)) both will be required.
The results from particulate sampling of the mirex test are sum-
marized in Table 91.* Seven of the 10 runs were within acceptable iso-
kinetic limits (100 + 10%). Runs Nos. F, G, and H, although not accept-
able, were close enough to being isokinetic as to provide valuable in-
formation. Four of the runs (G, H, I, and J) had particulate emissions
rates within established incinerator limits.
DISCUSSION
There were no specific operational problems with mirex. As was noted
above, however, the fact that the mirex bait was formulated on a combust-
ible inert carrier resulted in the continued burning of the solid residue
in the bottom of the primary combustion chamber throughout the experi-
ments.
Initial analysis of the particulate emission samples showed an unrea-
sonably high particulate catch in the liquid nitrogen cold trap for
Runs Nos. E, F, G, and H, equal to 90 to 98% of the apparent total
particulate emission. These values were not included in the values
reported in Table 91.
333
-------
References
1. Martin, H., Pesticide Manual, 2nd Edition, British Crop Protection
Council, Worcester, England (1971).
2. Lawless, E. W., T. L. Ferguson, and A. F. Meiners, "Guidelines for
the Disposal of Small Quantities of Unused Pesticides," (Draft),
EPA Contract No. 68-01-0098 (1974).
334
-------
APPENDIX C
SAMPLING AND ANALYSIS
CONTENTS
Page
I. Active Ingredient and Related Chemical Compounds. .... 336
Incinerator Feed. ................... 336
Incinerator Effluent - Liquid Pesticide Formulations. . 336
Incinerator Effluent - Solid Pesticide Formulations . . 341
Scrubbed Gas 354
Scrubber Liquids. . ........... 357
Solid Residues. 358
II. Other Sampling and Analysis .......... 362
Sulfur Dioxide 362
Nitrogen Oxides .................... 367
Moisture. ................ 373
Excess Air 378
Total Hydrocarbons 380
III. Special Analysis . 382
Cyanide 382
Total Phrophosphates 386
335
-------
I. ACTIVE INGREDIENT AND RELATED CHEMICAL COMPOUNDS
A. INCINERATOR FEED
1. Liquid Formulations
a. Samples of the liquid formulation were collected through a valve
on the burner between the pump and the nozzle.
b. The method of sample collection consisted of the following:
(1) Purge the sample valve and line with approximately 75 ml of
the liquid formulation mix.
(2) Fill the sample bottle.
(3) Purging the sample line and collecting the sample should be
done slowly so that the flow to the nozzle is not affected.
2. Solid Formulations
a. Solid formulation samples were collected from the delivery spout
of the vibrating screw feeder before the test and at the conclusion of
the test.
b. The samples were weighed and the net weight subtracted from the
weight of the charge.
B. INCINERATOR EFFLUENT - LIQUID PESTICIDE FORMULATIONS
1. Apparatus (see Figure 64)
a. Sampling
(1) Probe - Pyrex® glass probe 7 mm I.D. and of sufficient
length for the inlet to be at midstream (centroid) of the stack.
(2) Midget impingers - Three.
(3) Filters and casing - Millepore, Type AA, 0.8 p, opening with
a fiberglass filter for support.
(4) Critical orifice - 26G-3/8 in. needle allowing a flow rate
of about 0.3 liters/min.
336
-------
SAMPLE PROBE
U)
u>
-J
WATER OR.
ICE BATH
FILTER /-CRITICAL ORIFICE
IMPINGERS
COLD TRAP
GLASS WOOL
*TO
VACUUM
PUMP
Figure 64. Gas sampling train
-------
(5) Cold trap.
(6) Vacuum pump - To pull stack gas through the train.
(7) Rotometer - For checking the dry gas flow rate through the
sampling train, 0 to 0.5 liter/rain.
(8) Dewer flask - 1-qt capacity.
(9) Glass wool.
(10) Automatic pipette - Delivery capacity of 20 ml.
(11) Septum - 7 mm.
b. Sample Recovery
(1) Glass wash bottles - Two.
(2) Sample containers - 1-oz French Squares, and one 3-oz bottle.
2. Reagents
a. Solvent - Pesticide grade as appropriate to the pesticide being
tested, see Table 92.
b. Water - Distilled deionized.
c. Acetone - Reagent grade.
d. Chromic acid - 160 ml concentrated sulfuric acid added to 100 ml
saturated potassium dichromate.
e. Liquid nitrogen.
3. Procedure
a. Wash procedure - For sample bottles and caps, probe, impingers,
filter casing and cold trap.
(1) Detergent and water.
(2) Rinse twice in tap water.
(3) Chromic acid rinse.
(4) Deionized, distilled water rinse twice.
(5) Acetone rinse - Except filter casings.
(6) Oven dry - 110°C.
338
-------
Table 92. SOLVENT SELECTION
Pesticide
First
impinger
Second
impinger
DDT
Aldrin
Picloram
Malathion
Toxaphene
Atrazine
Captan
Zineb
Mir ex
Benzene
2,2,4-Trimethylpentane
Distilled, deionized
water
Benzene
2,2,4-Trimethylpentane
Benzene
Benzene
Distilled, deionized
water
Benzene
Benzene
2,2,4-Dimethylpentane
2-Propanol
pH 4 Sulfuric acid
2,2,4-Trimethylpentane
2-Propanol
Benzene
Distilled, deionized
water
Benzene
339
-------
b. Train Preparation
(1) Pipette 20 ml of solvent into each of two impingers.
(2) Transfer a fiberglass filter and a Type AA Millepore filter
to the casing with clean tongs. Assemble the filter casing and tape closed,
(3) Assemble the cold trap.
(4) Assemble the train as shown in Figure 64.
(5) Tape the probe and the cold trap closed with masking tape
to prevent contamination during transport and installation.
c. Sampling
(1) Install the train at Sampling Point No. (T) with the inlet
of the sample probe at midstream.
(2) Check the gas flow rate with a rotometer. The probe should
be temporarily disconnected.
(3) Sample the stack gas 30 min.
(4) Again check the gas flow rate, as above, at the end of the
experimental test.
d. Sample Recovery
(1) Transfer the contents of the impingers into separate sample
bottles.
(2) Tape the cold trap closed for shipment intact.
(3) Tape the filter casing closed for shipment intact.
(4) Rinse the probe, the impingers and the connecting glassware
with the solvent of the test and transfer the rinsings to the 3-OE sample
bottle.
(5) Send as blanks, samples of solvent, acetone and deionized,
distilled water in separate bottles.
(6) Send as a blank an assembled filter and casing taped closed.
340
-------
C. INCINERATOR EFFLUENT - SOLID PESTICIDE FORMULATIONS
1. Principle
Particulate matter is withdrawn isokinetically from the source and
its weight is determined gravimetrically after removal of uncombined water.
2. Apparatus
a. Sampling train - The design specifications of the particulate
sampling train used by EPA (Figure 65) are described in APTD-0581. Com-
mercial models of this train are available.
(1) Nozzle - Stainless steel (316) with sharp, tapered leading
edge.
(2) Probe - Pyrex®glass 3 ft in length, with a heating system
capable of maintaining a minimum gas temperature of 250 F at the exit end
during sampling to prevent condensation from occurring.
(3) Pitot tube- Type S attached to probe to monitor stack gas
velocity.
(4) Filter holder - Pyrex® glass with heating system capable
of maintaining minimum temperature of 225 F.
(5) Impingers/condenser - Five impingers connected in series
with glass ball joint fittings. The first, third, fourth, and fifth im-
pingers are of the Greenburg-Smith design, modified by replacing the tip
with a 1/2-in. I.D. glass tube extending to 1/2-in. from the bottom of
the flask. The second impinger is of the Greenburg-Smith design with the
standard tip.
(6) Metering system - Vacuum gauge, leak-free pump, thermometers
capable of measuring temperature to within 5°F, dry gas meter with 2%
accuracy, and related equipment, or equivalent, as required to maintain
an isokinetic sampling rate and to determine sample volume.
(7) Barometer - To measure atmospheric pressure to + 0.1 in.
Hg.
(8) Dewar flask - Four liters capacity.
(9) 125 ml cyclone flask - One.
341
-------
Heated Area Filter Holder
Thermometer
Probe
Reverse-Type
Pi tot Tube
Liquid Nitrogen
xCold Trap
NJ
Pitot Manometer
Thermometers
Orifice
Impingers'
By-Pass Valve
-Vacuum
Gauge
Main Valve
Dry Test Meter Air-Tight
Pump
Check Valve
Vacuum Line
Figure 65. Particulate-sampling train
-------
b. Sample Recovery
(1) Probe brush - At least as long as probe.
(2) Glass wash bottles - Two.
(3) Glass sample storage containers.
(4) Graduated cylinder - 250 ml.
c. Analysis
(1) Glass weighing dishes.
(2) Desiccator.
(3) Analytical balance - To measure to ± 0.1 mg.
(4) Trip balance - 300 g capacity, to measure to ± 0.05 g.
3. Reagents
a. Sampling
(1) Filters - Glass fiber, MSA 1106 BH, or equivalent, numbered
for identification and preweighed.
(2) Silica gel - Indicating type, 6 to 16 mesh, dried at 175°C
(350°F) for 2 hr.
(3) Water.
(4) Crushed ice.
(5) Appropriate solvent(s). (See Table 92.)
(6) Liquid nitrogen.
b. Sample Recovery
(1) Acetone - Reagent grade.
c. Analysis
(1) Water.
(2) Desiccant - Drierite®, indicating.
343
-------
4. Procedure
a. Sampling
(1) Preparation of collection train - Weight to the nearest gram
approximately 200 g of silica gel. Label a filter of proper diameter,
desiccate* for at least 24 hr and weigh to the nearest 0.5 mg in a room
where the relative humidity is less than 50%. Place 100 ml of solvent
in each of the first two impingers, leave the third impinger empty, and
place approximately 200 g of preweighed silica gel in the fourth impinger.
Set up the train without the probe as in Figure 65. Leak check the sam-
pling train at the sampling site by plugging up the inlet to the filter
holder and pulling a 15-in. Hg vacuum. A leakage rate not in excess of
0.02 cfm at a vacuum of 15 in. Hg is acceptable. Attach the probe and
adjust the heater to provide a gas temperature of about 250°F, at the
probe outlet. Turn on the filter heating system. 'Place crushed ice
around the impingers. Add more ice during the run to keep the tempera-
ture of the gases leaving the last impinger as low as possible and prefer-
ably at 70°F, or less. Temperatures above 70°F may result in damage to the
dry gas meter from either moisture condensation or excessive heat.
(2) Determine the stack pressure, temperature, moisture, and
range of velocity head.
(3) Particulate train operation - For each run, record the data
required on the example sheet shown in Figure 66. Take readings at each
sampling point every 5 min, and when significant changes in stack con-
ditions necessitate additional adjustments in flow rate. To begin sampling,
position the nozzle at the first traverse point with the tip pointing di-
rectly into the gas stream. Immediately start the pump and adjust the
flow to isokinetic conditions. Sample for 5 min at each of the 12 traverse
points; sampling time must be the same for each point. Maintain isokinetic
sampling throughout the sampling period. Nomographs are available which
aid in the rapid adjustment of the sampling rate without other computations.
APTD-0576 details the procedure for using these nomographs. Turn off the
pump at the conclusion of each run and record the final readings. Remove
the probe and nozzle from the stack and handle in accordance with the sam-
ple recovery process described in Section 4-b.
b. Sample recovery - Exercise care in moving the collection train from
the test site to the sample recovery area to minimize the loss of collected
sample or the gain of extraneous particulate matter. Set aside a portion
of the acetone used in the sample recovery as a blank for analysis. Mea-
sure the volume of water from the first three impingers. Place the samples
in containers as follows:
* Dry using Drierite®at 70°F + 10°F.
344
-------
FIELD DATA
PLANT.
DATE_
SAMPLING LOCATION.
SAMPLE TYPE
RUN NUMBER
OPERATOR
AB8IENT TEMPERATURE .
BAROMETRIC PRESSURE .
STATIC PRESSURE. (P,l_
FILTER NUMBER It)
PROBE LENGTH AND TYPE.
NOZZLE 1.0
ASSUMED MOISTURE.'.
SAMPLE BOX NUMBER.
METER BOX NUMBER.
METER 4M6
C FACTOR.
PROBE HEATER SETTING.
HEATER BOX SETTING
REFERENCE 4p
SCHEMATIC OF TRAVERSE POINT LAYOUT
READ AND RECORD ALL DATA EVERY.
MINUTES
U)
4>
Ln
TRAVERSE
POINT
NUMBER
f
\. CLOCK TIME
S**!LIKG X^LOCKI
TIME, mm X^
— .
GAS METER READING
-------
Container No. 1 - Remove the filter from its holder, place in this
container, and seal.
Container No. 2 - Place loose particulate matter and acetone washings
from all sample-exposed surfaces prior to the filter in this container and
seal. Use a razor blade, brush, or rubber policeman to loosen adhering par-
ticles.
Container No. 3 - Measure the volume of water in Impinger No. 1, and
record. Transfer the contents of Impinger No. 1 and a solvent rinse into
Container No. 3.
Container No. 4 - Measure the volume of water in Impinger No. 2 and
record. Transfer the contents and a solvent rinse into Container No. 4.
Container No. 5 - Measure the volume of water in Impinger No. 3 and
record. Transfer the contents of Impinger No. 3 and a solvent rinse into
Container No. 5.
Container No. 6 - Weigh and transfer the silica gel from the fourth
impinger to Container No. 6 and seal. Use a rubber policeman as
an aid in removing silica gel from the impinger.
Container No. 7 - Rinse all four impingers and all connecting glass after
the filter and before Impinger No. 4 with solvent. Transfer the above
into Container No. 7.
Container No. 8 - Transfer the contents of the cold trap and a solvent
rinse into Container No. 8.
Container No. 9 - Rinse Impingers 1, 2, 3, 4, the cold trap and all
connecting glass after the filter and before the cold trap with acetone.
Transfer into Container No. 9.
Container No. 10 - Solvent blank.
Container No. 11 - Acetone blank.
c. Analysis - Record the data required on the example sheet shown in
Figure 66. Handle each sample container as follows:
Container No. 1 - Transfer the filter and any loose particulate matter
from the sample container to a tared glass weighing dish, desiccate, and
dry to a constant weight. Report results to the nearest 0.5 mg.
346
-------
Container No. 2 - Transfer the acetone washings to a tared beaker and
evaporate to dryness at ambient temperature and pressure. Desiccate and
dry to a constant weight. Report results to the nearest 0.5 mg.
Containers Nos. 3, 4, 5, 7, 8, 9 - Transfer the contents of each of the
Containers Nos. 3, 4, 5, 7, 8, 9 into separate tared beakers. Evaporate to
dryness at ambient temperature and pressure. Desiccate and dry to a
constant weight. Weigh and report results to the nearest 0.5 mg.
5. Calibration
Use methods and equipment which have been approved to calibrate the
orifice meter, pitot tube, dry gas meter, and probe heater. Recalibrate
after each test series.
6. Calculations
a. Average dry gas -?ter temperature and average orifice pressure
drop. See data sheet (F re 66).
b. Dry Gas Volume - Correct the sample volume measured by the dry gas
meter to standard conditions 70°F, 29.92 in. Hg) by using Eq. C-l.
"m
;std
= V,
m
T \
std
M
f Pbar +
AH
13.6
Pstd
/
= 17.71
\
°R 1
in. Hg
Vm
/ \
p + AH
bar 13.6
Tm
i
(C-l)
where
Vm , = Volume of gas sample through the dry gas meter (standard
conditions) cubic feet
Vm = Volume of gas sample through the dry gas meter (meter
conditions) cubic feet
Tst(j = Absolute temperature at standard conditions, 530°R
TJJJ = Average dry gas meter temperature, °R
Pbar = Barometric pressure at the orifice meter, inches Hg
AH = Average pressure drop across the orifice meter, inches Ho
13.6 = Specific gravity of Hg.
347
-------
P = Absolute pressure at standard conditions, 29.92 in. Hg.
std
c. Volume of Water Vapor
v = Vl —- —^ = 0.0474 ±±J±\ v, (C-2)
-std lo MH90 Pstd ml Mo
where V = Volume of water vapor in the gas sample (standard condi-
std tions), cubic feet
V-i = Total volume of liquid collected in impingers and silica
° gel (see Figure 67), milliliters
pHoO = Density of water, 1 g/ml
Mu Q = Molecular weight of water, 18 Ib/lb-mole
R = Ideal gas constant, 21.83 in. Hg--cubic feet/pound--
mole °R
T td = Absolute temperature at standard conditions, 530°R
p t, = Absolute pressure at standard conditions, 29.92 in. Hg
d. Moisture Content
vw
B = §td (C-3)
Dwo v + v
mstd wstd
where B., = Proportion by volume of water vapor in the gas stream,
dimensionless.
V = Volume of water in the gas sample (standard conditions),
T-T
std cubic feet.
= Volume of gas sample through the dry gas meter (standard
w
conditions), cubic feet
e. Partial particulate weight (Mnp) - Determine the partial partic-
ulate catch from the sum of the weights of Containers Nos. 1 and 2 on the
analysis data sheet (Figure 68).
348
-------
MIDWEST RESEARCH INSTITUTE
Run Number
Date
Recorded by
Assisted by
NOTE: Same as Run No..
A. Condensor and/or Silica Gel Method
Barometric Pressure, Pg =
D Barometer Location
Reading Time
Q Elevation
in. Hg
by
Final
Initial
Difference
Clock
Time
Dry Gas
Meter
Reading(cf)
Vm =
Flowmeter
Setting
Dry Gas
Meter
Temp (°F)
Impinger
Water Volume
(ml)
We =
Tube No.
Weight (Grams)
Final
Initial
Total Moisture Adsorbed;
Di fference
Wa =
Meter Pressure, Pg ** Pm
Average Meter Temperature, Tm
Total Weight of Moisture
Collected, We + Wa = V|
in. Hg
op
Moisture Content =
'o
100
gm
% by Volume
I +375
PmVm
(Tm+460)V|
B. Wet/Dry Bulb Method
Dry Bulb Temperature =
Wet Bulb Temperature =
Moisture Content (from Ref. Table) =
C. Predetermined Value
% Moisture Basis
% by Volume
MRI - Form P4 (10/72)
Figure 67. Preliminary moisture determination data
349
-------
MIDWEST RESEARCH INSTITUTE
Run No.
Date
FIELD ANALYSIS
1 2 3
Impinger Sequence
Impinger Type*
Final Volume**
Initial Volume**
Difference
* S = Greenburg-Smith standard, M = modified, O - Other
** Indicate value and units (ml or gm)
MRI LAfr ANALYSIS
Comments: Codes:
1. Ether-chloroform extraction of impinger water
2. Impinger water residue
3. Impingers and back half of filter, acetone wash
4. Dry probe and cyclone catch (generally no data)
5. Probe, cyclone, flask and front half of filter, acetone wash
6. Filter
7. Ether blank
8. Chloroform blank
9. Water blank
10. Acetone blank
MRI-FormPIO (10/72)
Figure 68. Particulate clean-up and analysis data
350
-------
f. Total participate weight 0%j) - Determine the total particulate
catch from the sum of the weights of container Nos. 1-5, 7-9 on the analy-
sis data sheet (Figure 68).
g. Concentration
(1) Concentration in grains/standard cubic foot, partial.
M
0.0154
_np_
mg V
(C-4)
mstd/
where C*1 = Partial concentration of particulate matter in stack gas,
grains/standard cubic foot, dry basis
M = Partial amount of particulate matter collected, milligrams
V,
mstd
Volume of gas sample through dry gas meter (standard
conditions), cubic feet
(2) Concentration in grains/standard cubic foot, total
0.0154
(C-5)
mstd/
where
Cs
M,
1NT
mstd
= Total concentration of particulate matter in stack gas,
grains/standard cubic foot, dry basis
= Total amount of particulate matter collected, milligrams
Volume of gas sample through dry gas meter (standard
conditions), cubic feet
(3) Concentration in pounds/standard cubic foot, total
/" 1 jLb^N
= 1453,600 ing JMMT = 2.205 x 10-5 J%T_ (c_6)
V»Btd mstd
351
-------
where C = Concentration of particulate matter in stack gas,
pounds/standard cubic foot, dry basis, total
453,600 = Milligrams/pound
MNT = Total amount of particulate matter collected, milligrams
Vm = Volume of gas sample through dry gas meter (standard
conditions), cubic feet
(4) Concentration normalized to 12% C02, grains/standard cubic
foot, total.
12 C1
^^^^ IS
7. C0
where CN = Concentration of particulate matter in the stack gas
normalized to 12% C02> grains/standard cubic foot,
dry basis, total
% COo = Actual concentration of CCU in the stack gas as deter-
mined by Orsat analysis, percent
C' = Total concentration of particulate matter in the stack
gas, grains/standard cubic foot, dry basis
h. Isokinetic Variation
..
(C-8)
(l.667 |§) [ (°.0°267 t..
352
-------
where I = Percent of isokinetic sampling
Vi = Total volume of liquid collected in impingers and silica
o
gel (see "Figure 67), milliliters
PH20 = Density of water, 1 g/ml
R = Ideal gas constant, 21.83 in. Hg-cubic feet/pound mole, °R
M,, n = Molecular weight of water, 18 Ib/lb-mole
V = Volume of gas sample through the dry gas meter (meter
conditions), cubic feet
T = Absolute average dry gas meter temperature (see Figure
66), °R
p, = Barometric pressure at sampling site, inches Hg
AH = Average pressure drop across the orifice (see Figure 66),
inches H20
To = Absolute average stack gas temperature (see Figure 66), °R
O
0 = Total sampling time, minutes
V = Stack gas velocity calculated by Eq. D-14, Appendix D, ft/ sec
s
P <= Absolute stack gas pressure, inches Hg
s
A = Cross-sectional area of nozzle, square feet
i. Acceptable Results - The following range sets the limit on accep-
table isokinetic sampling results:
If 90% <; I £ 110%, the results are acceptable; otherwise, reject the
results and repeat the test.
Adapted from Federal Register, Vol. 36, No. 247, Thursday, 23 December 1971.
353
-------
D. SCRUBBED GAS
1. Apparatus (see Figure 69)
a. Sampling
(1) Probe - Pyrex® glass probe 7 mm I.D. and of sufficient
length for the inlet to be at midstream (centroid) of the stack.
(2) Midget impingers - two.
(3) Filters and casing - millepore. Type AA, 0.8 p, opening
with a fiberglass filter for support.
(4) Critical orifice - 26G-3/8 in. needle allowing a flow rate
of about 0.3 liter/min.
(5) Vacuum pump - To pull stack gas through the train.
(6) Rotometer - For checking the dry gas flow rate through the
sampling train, 0 to 0.5 liter/min.
(7) Septum - Seven millimeters.
(8) Automatic pipette - Delivery capacity 20 ml.
b. Sample Recovery
(1) Glass wash bottles - two.
(2) Sample containers - One ounce French Squares.
354
-------
Oi
Ln
•SAMPLE PROBE
FILTER
~o
Water or Ice
Bath
IMPINGERS
•CRITICAL ORIFICE
TO
VACUUM
PUMP
Figure 69. Gas sampling train
-------
2. Reagents
a. Solvent(s) - Pesticide grade as appropriate to the pesticide being
tested, see Table 92.
b. Water - Distilled, deionized.
c. Acetone - Reagent grade.
d. Chromic acid - 160 ml concentrated sulfuric acid added to 100 ml
saturated potassium dichromate.
3. Procedure
a. Wash Procedure - For sample bottles and caps, probe, impingers,
and filters.
(1) Detergent and water.
(2) Rinse twice in tap water.
(3) Chromic acid rinse.
(4) Deionized, distilled water rinse twice.
(5) Acetone rinse - Except filter casings.
(6) Oven dry - 110°C.
b. Train Preparation
(1) Pipette 20 ml of solvent into each of two impingers.
(2) Transfer a fiberglass filter and a Type AA millepore filter to
the casing with clean tongs. Assemble the filter casing and tape closed with
masking tape.
(3) Assemble the trains as shown in Figure 69.
(4) Tape the probe closed with masking tape to prevent contamina-
tion during transport and installation.
c. Sampling
(1) Install the trains at Sampling Points Nos. \5J , No. (V) , and
No. (IT) , see Figure 5, p. 27.
356
-------
(2) Check the gas flow rate with a rotometer. The probe should
be temporarily disconnected.
(3) Sample the stack gas 30 min.
(4) Again check the gas flow rate, as above, at the end of the
experimental test.
d. Sample Recovery
(1) Transfer the contents of the impingers into separate sample
bottles.
(2) Tape the filter casing closed for shipment intact,
(3) Send as blanks, samples of solvent, acetone and deionized,
distilled water in separate bottles.
(4) Send as a blank an assembled filter and casing properly
taped closed.
E. SCRUBBER LIQUIDS
1. Scrubber No. 1 - Hold Tank
a. Initial Sample
(1) Pump to the outside hold tank the water collected during the
warm-up phases of the experimental test, leaving approximately 3 in. in the
tank.
(2) Rinse twice the weighted sampling bottle with water from the
tank.
(3) Collect a sample of Scrubber No. 1 hold tank with the weighted
sampling bottle.
(4) Measure the level of water in Scrubber No. 1 hold tank.
B. Final Sample
(1) Rinse the weighted sampling bottle twice with water from Scrub-
ber No. 1 hold tank.
(2) Collect a sample.
357
-------
(3) Measure the final level of water in the tank.
2. Scrubber No. 2 - Initial and Final Samples
a. Allow the pump to circulate the hexylene glycol in Scrubber No. 2
at least 15 min.
b. Determine the level of Scrubber No. 2 in the sight glass.
c. Purge the sample line and valve by draining and collecting approxi-
mately 1 pint of the hexylene glycol.
d. Fill the sample bottle.
3. Scrubber No. 3 - Hold Tank
a. Initial Sample
(1) Pump outside the water collected during the preliminary steps
of the test to a level of approximately 1-1/2 in.
(2) Rinse the weighted sampling bottle, reserved for Scrubber No.
3, twice with the water being sampled.
(3) Collect a sample.
(4) Measure the water level of Scrubber No. 3 hold tank.
b. Final Sample
(1) Rinse the weighted sampling bottle twice.
(2) Collect a sample of the Scrubber No. 3 hold tank.
(3) Measure the final water level.
F. SOLID RESIDUES
1. Primary Chamber
a. Remove Thermocouples Nos. 1, 2, and 3
b. Remove the bricks from the underfire air opening.
c. Using a foxtail brush reserved for cleaning out the incinerator,
sweep all residue from the front of the chamber to the back of the chamber.
Repeat this step as necessary.
358
-------
d. Remove the residue from the chamber with a vacuum cleaner reserved
for cleaning the incinerator only.
e. Transfer the residue from the vacuum cleaner to a tared container(s).
f. Weigh the residue and container(s) and record the weight of the residue.
g. Sample the residue, obtaining representative residue from the top,
middle, and bottom portions of the container.
h. Label the container(s) and store.
i. Repeat this procedure after each solid formulation experimental test.
2. Secondary Chamber
a. With compressed air, blow all loose residue from the square stack
into the second chamber,,
b. Remove the bricks from the door opening in the secondary chamber.
c. Using a foxtail brush reserved for cleaning out the incinerator,
sweep all residue from the walls of the chamber to the back of the chamber.
Repeat this step as necessary.
d. Remove the residue from the chamber with a vacuum cleaner reserved
for cleaning the incinerator only.
e. Transfer the residue from the vacuum cleaner to a tared container.
f. Weigh the residue and container and record the weight of the residue.
g. Sample the residue, obtaining representative residue from the top,
middle, and bottom portions of the container.
h. Label the container and store.
i. Repeat this procedure after each solid formulation experimental test.
3. Square Stack
a. With compressed air, blow all loose residue from the bottom of the
square stack.
b. Gently tap the outside walls of the square stack with a rubber hammer.
359
-------
c. With a long brush reserved for cleaning the square stack, pull the
residue out into a tared sample container.
d. Weigh the residue, record and label the sample.
e. Repeat this procedure after each solid formulation experimental
test.
4. Vertical Stack
a. Clean the primary and secondary chambers and the square stack.
b. Starting at the top of the vertical stack, force a compressed air
hose down the stack. Twist the hose back and forth to direct compressed
air at the entire circumference of the stack. Repeat this step as neces-
sary.
c. Gently tap the top portion of the vertical stack with a rubber
hammer.
d. Blow the residue from the square stack into the secondary chamber.
e. Clean the primary and secondary chambers as previously described.
f. Weigh the residue in a tared container and record.
g. Sample the residue, label and store.
h. Sample the vertical stack only after the concluding pesticide solid
formulation experimental test.
5. Horizontal Stack
a. Clean and sample Scrubber No. 1 tank as described below.
b. Take the horizontal stack apart at the seam near the pitot tube.
c. Vacuum in both directions from the seam, using the rigid extentions
on the vacuum cleaner.
d. With compressed air, blow any remaining residue from the horizontal
stack into either the vertical stack or into Scrubber No. 1 as appropriate.
e. Clean the incinerator and Scrubber No. 1.
f. Weigh the residue, sample, label and store.
360
-------
g. Sample the horizontal stack after concluding the respective solid
formulation tests.
6. Scrubber No. 1
a. Drain Scrubber No. 1.
b. Remove the outlet section containing the demister pad,
c. If there is any residue either in the demister pad or on the walls
of the exit section, retain a sample of the residue and label as Exit Scrub-
ber No. 1.
d. Clean Scrubber No. 1 tank with a putty knife.
e. Sample the residue from Scrubber No0 1 tank, label the residue and
store.
f» Sample Scrubber No. 1 only after the concluding pesticide solid
formulation experimental test.
361
-------
II. OTHER SAMPLING AND ANALYSIS
A. Sulfur Dioxide
1. Principle
A gas sample is extracted from the sampling point in the stack (Sam-
ple Point No. (2)) and the acid mist including sulfur trioxide is separated
from the sulfur dioxide. The sulfur dioxide fraction is measured by the
barium-thorin titration method.
2. Apparatus
a. Sampling (see Figure 70)
(1) Probe - Pyrex® glass, approximately 5 to 6 mm I.D., with a
heating system to prevent condensation and a filter to remove particulate
matter including sulfuric acid mist.
(2) Midget bubbler - One, with glass wool packed in top to pre-
vent sulfuric acid mist carryover.
(3) Glass wool.
(4) Midge impingers - four.
(5) Silica gel - To dry the sample.
(6) Pump - Leak-free, vacuum type.
(7) Rate meter - Rotometer, or equivalent, to measure a 0 to
10 cubic ft2/hr flow range.
(8) Dry gas meter - Sufficiently accurate to measure the sam-
ple volume within 1%.
362
-------
Stack Wall
Midget Bubbler
Glass Wool / Midget Impingers
Ice Bath
Probe (End Packed
wuth Quartz or
Pyrex Wool )
Dry Gas Meter
Pump
Figure 70. S02 sampling train
363
-------
b. Sample Recovery
(1) Glass wash bottles - Two.
(2) Polyethylene storage bottles - To store impinger samples.
c. Analysis
(1) Pipettes - Transfer type, 5 ml and 10 ml sizes (0.1-ml divi-
sions) and 25-ml size (0.2-ml divisions).
(2) Volumetric flasks - 50 ml, 100 ml and 1,000 ml.
(3) Burettes - 5 ml and 50 ml.
(4) Erlenmeyer flask - 125 ml
3. Reagents
a. Sampling
(1) Water - Deionized, distilled.
(2) Isopropanol, 80% - Mix 80 ml of isopropanol with 20 ml of
distilled water.
(3) Hydrogen peroxide, 3% - Dilute 10 ml of 30% hydrogen per-
oxide with 90 ml of distilled water. Prepare fresh daily.
b. Sample Recovery
(1) Water - Deionized, distilled.
(2) Isopropanol, 80%.
c. Analysis
(1) Water - Deionized, distilled.
(2) Isopropanol.
(3) Thorin indicator - l-(p_-Arsonophenylazo)-2-naphthol-3,6-
disulfonic acid, disodium salt (or equivalent). Dissolve 0.20 g in 100
ml distilled water.
364
-------
(4) Barium perchlorate (0.01 N)- Dissolve 1.95 g of barium per-
chlorate [Ba(C104)23H20] in 200 ml distilled water and dilute to 1 liter
with isopropanol. Standarize with sulfuric acid.
(5) Sulfuric acid standard (0.01 ty - Purchase or standardize
against a primary standard to + 0.0002 N.
4. Procedure
a0 Sampling
(1) Preparation of collection train - Pour 15 ml of 80% isopro-
panol into the midget bubbler and 15 ml of 3% hydrogen peroxide to each of
the first two midget impingers. Leave the third midget impinger dry. In
the final impinger, place approximately 15 ml of silica gel. Assemble the
train as shown in Figure 70. Leak check the sampling train at the sampling
site by plugging the probe inlet and pulling a 10-in. Hg vacuum. A leakage
rate not in excess of 1% of the sampling rate is acceptable. Carefully re-
lease the probe inlet plug and turn off the pump. Place crushed ice around
the impingers. Add more ice during the run to keep the temperature of the
gases leaving the last impinger at 70°F or less.
(2) Sample collection - Adjust the sample flow rate to obtain ap-
proximately 1 cu ft in 30 or 60 min as determined by the experimental test.
Take readings every 5 min. At the conclusion of each run, turn off the pump
and record the final readings. Remove the probe from the stack and discon-
nect it from the train. Drain the ice bath and purge the remaining part of
the train by drawing clean ambient air through the system for 15 min.
b. Sample Recovery - Disconnect the impingers after the purging period.
Discard the contents of the midget bubbler. Pour the contents of the midget
impingers into a polyethylene shipment bottle. Rinse the three midget im-
pingers and the connecting tubes with distilled water and add these washings
to the same storage container.
c. Sample Analysis - Transfer the contents of the storage container
to a 50-ml volumetric flask. Dilute to the mark with deionized, distilled
water. Pipette a 10 ml aliquot of this solution to a 125-ml Erlenmeyer
flask. Add 40 ml of isopropanol and two to four drops of thorin indicator.
Titrate to a pink endpoint using 0.01 N barium perchlorate, Run a blank
with each series of samples.
5. Calibration
a. Use standard methods and equipment to calibrate the orifice
meter, pitot tube, dry gas meter, and probe heater.
365
-------
b. Standardize the sulfuric acid with potassium acid phthlate as a
primary standard. Standardize the barium perchlorate with 25 ml of stand-
ard sulfuric acid containing 100 ml of isopropanol.
6. Calculations
a. Dry gas volume - Correct the sample volume measured by the dry gas
meter to standard conditions (70°F and 29.92 in. Hg) by using Eq. C-9.
17.71
^Tm^Pstd/ \ in. Hg/ Tm
where ^tnetd = Volume °f 8as sample through the dry gas meter (standard
conditions), cubic feet
Vm = Volume of gas sample through the dry gas meter (meter
conditions), cubic feet
Tst(j = Absolute temperature at standard conditions, 530°R
Tm - Average dry gas meter temperature, °R
Pfcar = Barometric pressure at the orifice meter, in. Hg
Pst(j = Absolute pressure at standard conditions, 29.92 in. Hg
b. Sulfur Dioxide Concentration
7.05 x 10-5 l^f CVt-Vtb) (N) UJpiB (c.10)
CS02 ~
g-ml
where CCn = Concentration of sulfur dioxide at standard condi-
2 ^
tions, dry basis, lb/ftj
7.05 x 10-5 = Conversion factor including the number of grams per
gram equivalent of sulfur dioxide (32 g/g-eq.),
453.6 g/lb and 1,000 ml/I, lb-£/g-ml
Vt = Volume of barium perchlorate titrant used for the
sample, ml
366
-------
vtb ~ Vol1™6 °f barium perchlorate titrant used for the
blank, ml
N = Normality of barium perchlorate titrant, g-eq/liter
^soln = Total volume of sample, ml
V0 = Volume of sample aliquot titrated, ml
3L
Adapted from Federal Register, Vol. 36, No. 247, Thursday, 23 December
1971.
B. NITROGEN OXIDES
1. Principle - A grab sample is collected in an evacuated flask contain-
ing a dilute sulfuric acid-hydrogen peroxide absorbing solution, and the
nitrogen oxides, except nitrous oxide, are measured colorimetrically using
the phenoldisulfonic acid (PDS) procedure.
2. Apparatus
a. Sampling (See Figure 71)
(1) Probe - Pyrex® glass, heated, with filter to remove particulate
matter. Heating is unnecessary if the probe remains dry during the purging
period.
367
-------
EVACUATt
W36E
T
FILTER
GROUND-GLASS SOCI
3 NO. 12/S
8-WAY STOPCOCK;
T-60RE, Jt, PYREX,
2-mrn BORE, B-mm oo
FLASK VAL'
FLASK
FLASK SHIEUX>.\
GROUND-GLASS CONE.
STANDARD TAPER,
J SLEEVE NO. 24/40
GROUND-GLASS
SOCKET. § NO. 125
PVREK
THERMOMETER
6-'A In.
7 in.N
FOAM ENCASEMENT
»' XBOILING FLASK •
2- LITER. ROUND-BOTTOM, SHORT NECK.
WITH J SLEEVE NO. 24/40
Figure 71. Sampling train, flask valve, and flask
368
-------
(2) Collection flask - Two-liter, Pyrex® round bottom with short
neck and 24/40 standard taper opening, protected against implosion or break-
age.
(3) Flask valve - T-bore stopcock connected to a 24/40 standard
taper joint,
(4) Temperature gauge - Dial-type thermometer, or equivalent,
capable of measuring 2°F intervals from 25 to 125°F.
(5) Vacuum line - Tubing capable of withstanding a vacuum of 3-in.
Hg absolute pressure, with "T" connection and T-bore stopcock, or equivalent.
(6) Pressure gauge - U-tube manometer, 36 in., with 0.1-in. divi-
sions, or equivalent.
(7) Pump - Capable of producing a vacuum of 3-in. Hg absolute
pressure.
b. Sample Recovery
(1) Pipette or dropper.
(2) Glass storage containers - Cushioned for shipping.
(3) Glass wash bottle.
c. Analysis
(1) Steam bath.
(2) Beakers or casseroles - 250 ml, one for each sample and stand-
ard (blank).
(3) Volumetric pipettes - 1, 2, and 10 ml.
(4) Transfer pipette - 10 ml with 0.1-ml divisions.
(5) Volumetric flask - 100 ml, one for each sample, and 1,000 ml
for the standard (blank).
(6) Spectrophotometer - To measure absorbance at 420 mu.
369
-------
(7) Graduated cylinder - 100 ml with 1.0-ml divisions.
(8) Analytical balance - To measure to 0.1 mg.
3. Reagents
a. Sampling
(1) Absorbing solution - Add 2.8 ml of concentrated lUSO, to 1
liter of distilled water. Mix well and add 6 ml of 37o hydrogen peroxide.
Prepare a fresh solution weekly and do not expose to extreme heat or direct
sunlight.
b. Sample Recovery
(1) Sodium hydroxide (IN)- Dissolve 40 g NaOH in distilled water
and dilute to 1 liter.
(2) Red litmus paper.
(3) Water - Deionized, distilled.
c. Analysis
(1) Fuming sulfuric acid - 15 to 18 N by weight free sulfur tri-
oxide.
(2) Phenol - White solid reagent grade.
(3) Sulfuric acid - Concentrated reagent grade,
(4) Standard solution - Dissolve 0.5495 g potassium nitrate (KN03)
in distilled water and dilute to 1 liter. For the working standard solution,
dilute 10 ml of the resulting solution to 100 ml with distilled water. One
milliliter of the working standard solution is equivalent to 25 ug nitrogen
dioxide.
(5) Water - Deionized, distilled.
(6) Phenoldisulfonic acid solution - Dissolve 25 g of pure white
phenol in 150 ml concentrated sulfuric acid on a steam bath. Cool, add 75
ml fuming sulfuric acid, and heat at 100°C for 2 hr. Store in a dark stop-
pered bottle.
370
-------
4. Procedure
a. Sampling
(1) Pipette 25 ml of absorbing solution into a sample flask. In-
sert the flask valve stopper into the flask with the valve in the "purge"
position. Assemble the sampling train as shown in Figure 70 and place the
probe at the sampling point. Turn the flask valve and the pump valve to
their "evacuate" positions. Evacuate the flask to at least 3-in Hg absol-
ute pressure. Turn the pump valve to its "vent" position and turn off the
pump. Check the manometer for any fluctuation in the mercury level. If
there is a visible change over the span of 1 min, check for leaks. Record
the initial volume, temperature, and barometric pressure. Turn the flask
valve to its "purge" position, and then do the same with the pump valve.
If condensation occurs in the probe and flask valve area, heat the probe
and purge until the condensation disappears. Then turn the pump valve to
its "vent" position. Turn the flask valve to its "sample" position and
allow sample to enter the flask for about 15 sec. After collecting the
sample, turn the flask valve to its "purge" position and disconnect the
flask from the sampling train. Shake the flask for 5 min.
b. Sample Recovery
(1) Let the flask sit for a minimum of 16 hr and then shake the
contents for 2 min. Connect the flask to a mercury-filled U-tube mano-
meter, open the valve from the flask to the manometer, and record the
flask pressure and temperature along with the barometric pressure. Trans-
fer the flask contents to a container for shipment or to a 250-ml beaker
for analysis. Rinse the flask with two portions of water (approximately
10 ml) and add rinse water to the sample. For a blank use 25 ml of absorbing
solution and the same volume of distilled water as used in rinsing the flask.
Prior to shipping or analysis, add sodium hydroxide (IN) dropwise into
the sample and the blank until alkaline to litmus paper (about 25 to 35
drops in each).
c. Analysis
(1) If the sample has been shipped in a container, transfer the
contents to a 250-ml beaker using a small amount of water. Evaporate the
solution to dryness on a steam bath and then cool. Add 2 ml phenoldisul-
fonic acid solution to the dried residue and triturate thoroughly with a
glass rod. Make sure the solution contacts all the residue. Add 1 ml
water and 4 drops of concentrated sulfuric acid. Heat the solution on a
steam bath for 3 min with occasional stirring. Cool, add 20 ml water,
mix well by stirring, and add concentrated ammonium hydroxide dropwise
371
-------
with constant stirring until alkaline to litmus paper. Transfer the solu-
tion to a 100-ml volumetric flask and wash the beaker three times with 4-
to 5-ml portions of water. Dilute to the mark and mix thoroughly. If the
sample contains solids, transfer a portion of the solution to a clean, dry
centrifuge tube and centrifuge, or filter a portion of the solution. Meas-
ure the absorbance of each sample at 420 mu using the blank solution as a
zero. Dilute the sample and the blank with a suitable amount of distilled
water if absorbance falls outside the range of calibration.
5. Calibration
a. Flask Volume - Assemble the flask and flask valve and fill with
water to the stopcock. Measure the volume of water to +10 ml. Number and
record the volume on the flask.
b. Spectrophotometer - Add 0.0 to 16.0 ml of standard solution to a
series of beakers. To each beaker add 25 ml of absorbing solution and add
sodium hydroxide (1 N) dropwise until alkaline to litmus paper (about 25 to
35 drops). Follow the analysis procedure described in (c.) on the previous
page to collect enough data to draw a calibration curve of concentration in
micrograms, N02 Per sample versus absorbance.
6. Calculations
a. Sample Volume
(Vf—25ml) 1£ _ 11 (C-ll)
pstd
where Vsc = Sample volume at standard conditions (dry basis), ml
Tstd = Absolute temperature at standard conditions, 530°R
Pstd = Pressure at standard conditions, 29.92 in. Hg
Vf = Volume of flask and valve, ml
V"a = Volume of absorbing solution, 25 ml
Pf - Final absolute pressure of flask, in. Hg
P^ = Initial absolute pressure of flask, in. Hg
372
-------
Tf = Final absolute temperature of flask, °R
T- = Initial absolute temperature of flask, °R
b. Sample Concentration - Read ug N02 for each sample from the plot
ug NOo versus absorbance.
c - m 1 lb/cu ft \ = /6.2 x 10-5 lb/scf\ /_m_\ (C-12)
/ sc'
where c = Concentration of NOX as N02 (dry basis), Ib/scf
m = Mass of N02 in gas sample, ug
Vsc = Sample volume at standard conditions (dry basis), ml
Adapted from Federal Register, Vol. 36, No. 247, Thursday,
23 December 1971.
C. MOISTURE
1. Principle - Moisture is removed from the gas stream, consensed,
and determined gravimetrically.
373
-------
2. Apparatus (see Figure 72)
a. Probe - Pyrex® glass sufficiently heated to prevent condensation
and equipped with a filter to remove particulate matter.
b. Impingers - Three midget impingers, each with 30 ml capacity.
c. Ice Bath Container - To condense moisture in impingers.
d. Rotameter - To measure a flow range from 0 to 1.0 liters/min.
e. Critical Orifice - 22G-1 in. needle allowing a flow of approxi-
mately 0.8 liters of dry gas per minute.
f. Pump - Leak-free, diaphragm type, to pull gas through train.
g. Balance - Capable of measuring to the neatest 0.1 g.
h. Barometer - Sufficient to read to within 0.1 in. Hg.
i. Silica gel.
j. Millepore Filter - Type SC, 8.0 u-.
3. Procedure
a. Place about 5 ml distilled water in each of two impingers, and
about 15 ml of silica gel in the third impinger.
b. Assemble the train with the water impingers first and second and
the silica gel impinger third,
c. Weigh the impingers and contents to the nearest 0.1 g and record.
d. Place the train in the ice bath container.
e. Attach the critical orifice for flow control.
f. Attach the vacuum pump.
374
-------
HEATED
'SAMPLE PROBE
FILTER
•CRITICAL ORIFICE
TO
VACUUM
PUMP
Ln
ICE BATH
fvA
t
— 1
0
0
o
c>
_
O
O
o
D
•b
D0(
°0<
0 '
3I>°!
i
t> 0
0 6
00
0
* „
IMPINGERS
Figure 72. Moisture sampling train
-------
g. Measure the flow with the rotameter and record. Probe should not
be in place while checking the flow.
h. Attach the probe and sample the stack 30 or 60 min as appropriate
to the experimental test. Record the elapsed time of sampling.
i. After the experimental test, again check the flow as in (g.) above.
j. After collecting the sample, weigh the impingers and their contents
again to the nearest 0.1 g.
4. Calculations
a. Volume of Water Collected
v
we
PstdMw
= (0.0474 ffc3 [ (Wf—Wi) (C-13)
where Vw = Volume of water vapor collected (standard conditions), cu
ft
Wf = Final weight of impingers and contents, g
V. = Initial weight of impingers and contents, g
R = Ideal gas constant, 21.83-in. Hg - cu ft/lb mole-0 R
Tstd = Absolute temperature at standard conditions, 530°R
**std = Pressure at standard conditions, 29.92 in. Hg
My = Molecular weight of water, 18 Ib/lb-mole
b. Volume of Stack Gas
vm = F x M (C-14)
28.32 1/cu ft
where Vm = Dry gas volume measured by rotameter, cu ft
F = Average critical orifice flowrate, liters per minute
M = Elapsed time of the test, minutes
376
-------
c. Gas Volume
vm = v" Pm Tstd = 17.71
Pstd Tm in. Hg T,
m
where V = Dry gas volume through train at standard conditions, cu ft
Vm = Dry gas volume measured by rotameter, cu ft
Pm = Barometric pressure, in. Hg
Pstd = Pressure at standard conditions, 29.92 in. Hg
Tstd = Absolute temperature at standard conditions, 530°R
Tm = Absolute temperature at critical orifice, 510°R
d. Moisture Content
Vwc + IHra = Vwc + (0.025) (C-16)
Vwc + Vmc Vwc + Vmc
where BWQ = Proportion by volume of water vapor in the gas stream,
dimensionless
Vwc = Volume of water vapor collected (standard conditions), cu ft
Vmc = Dry gas volume through train (standard conditions) , cu ft
BWU! = Approximate volumetric proportion of water vapor in the gas
stream leaving the impingers, 0.025
e. Percent Moisture
% Moisture (Volume) = 100 x B^o (C-17)
where % Moisture = Percent of stack gas that is moisture, by volume
377
-------
Adapted from Federal Register^ Vol. 36, No. 247, Thursday, 23 December 1971.
D. EXCESS AIR
1. Principle - A grab gas sample is extracted from a sampling point and
analyzed for its components using an Orsat analyzer.
2. Apparatus
a. Grab Sample,
(1) Probe - Stainless steel or Pyrex®glass, equipped with a
filter to remove particulate matter.
(2) 500 cc-Tedlar®bags.
(3) Pump - One-way squeeze bulb to transport gas sample to
500-cc Tedlar®bags.
b. Analysis
(1) Orsat analyzer.
378
-------
3. Procedure
a. Grab Sampling
(1) Place the probe in the stack at the sampling point and purge
the sampling line.
(2) Draw sample into the Tedlar®bag.
b. Analysis
(1) Determine the COo, Oo, and CO concentrations as soon as possible,
Make as many passes as are necessary to give constant readings. If more
than 10 passes are necessary, replace the absorbing solution,
4. Calculations
a. Carbon dioxide - Average the three consecutive runs and report
result to the nearest 0.1% C02.
b. Excess air - Use Eq. C-18 to calculate excess air, and average
the runs. Report the result to the nearest 0.1% excess air.
% EA = (% 02)-0.5(% CO) x 100 (C-18)
0.264(% N2)-(7o 02) +0.5 (% CO)
where % EA = Percent excess air
% 02 = Percent oxygen by volume, dry basis
% N2 = Percent nitrogen by volume, dry basis
% CO = Percent carbon monoxide by volume, dry basis
0.264 = Ratio of oxygen to nitrogen in air by volume
Adapted from Federal Register. Vol. 36, No. 247, Thursday, 23 December 1971.
379
-------
c. Dry Molecular Weight - Use Eq. C-19 to calculate dry molecular
weight and average the runs. Report the result to the nearest 0.1%.
Md = 0.44(7, C02) + 0.32(7, 02) + 0.28(7, N2 + 7, CO) (C-19)
where Md = Dry molecular weight, pound per pound-mole
7, C02 = Percent carbon dioxide by volume, dry basis
7, 02 = Percent oxygen by volume, dry basis
% N2 = Percent nitrogen by volume, dry basis
0.44 = Molecular weight of carbon dioxide divided by 100
0.32 = Molecular weight of oxygen divided by 100
0.28 = Molecular weight of nitrogen divided by 100
Adapted from Federal Register, Vol. 36, No. 247, Thursday, 23 December 1971.
E. TOTAL HYDROCARBONS
1. Equipment
a. 1/4 in. O.D. stainless steel tubing.
b. Midget impinger.
c. Glass wool.
d. Beckman Model 6800 gas analyzer.
380
-------
e. Leeds and Northrup Model 601 recorder.
f. 1/4 in. O.D. stainless steel probe.
20 Reagents
a» Ultra pure hydrogen.
b. Ultra pure air.
c. Standard gas - 5.44 ppm CH4
1.04 ppm CO
d. Compressed air - Water pumped.
3. Procedure
a. Place the 1/4 in. O.D. stainless steel probe into midstream (centroid)
of the stack at Sample Point No. (T) .
b. Connect to the probe one end of the 1/4 in. O.D. stainless steel
tubing.
c. Connect the other end of the stainless steel tubing to the midget
impinger, filled vith glass wool. This midget impinger acts as a particu-
late trap to protect the gas analyzer.
d. Connect the particulate trap to the sample port of the gas analyzer
by means of 1/4 in0 OD. stainless steel tubing. The particulate trap should
be no more than 3 ft from the gas analyzer.
e. Sample and analyze the stack gas continuously and automatically
during the experimental test, using the gas analyzer vacuum pump.
f. Standardize the gas analyzer daily with the standard gas.
g. Record the results of the stack gas and the standard gas by means
of the Leeds and Northrup Model 601 recorder.
381
-------
III. SPECIAL ANALYSIS
Solid and liquid formulations of pesticides containing nitrogen
(piclorara, atrazine, captan and zineb) were analyzed for cyanide (CN~)
content in the off-gas.
Malathion was the only phosphorus-containing pesticide tested. The
off-gas of the malathion solid and liquid formulations were analyzed for
total pyrophosphate content.
A. CYANIDE (Calculated as CN~)
1. Apparatus
a. Sampling
(1) Pipette - 20 ml.
(2) Midget impinger - One.
(3) Filter - Millipore, Type AA 0.8 u. opening with fiberglass
filter for support.
(4) Critical orifice - 26G-3/8 in. needle allowing a flow rate
of about 0.32 liters/min.
(5) Rotameter - Calibrated to measure a flow rate of 0 to 0.5
liters/min.
(6) Connecting glassware.
(7) Wash bottle.
(8) Sample bottles - Three 30-cc French squares.
b. Analysis
(1) Pipette - 1 ml.
(2) Volumetric flask - 5 ml.
(3) Aminco - Bowman spectrophotofluorometer.
382
-------
2. Reagents
a. Sampling
(1) Sodium hydroxide - Reagent grade.
(2) Water - Deionized, distilled.
b. Sample Recovery - Deionized, distilled water.
c. Analysis
(1) Palladium chelate - Prepared from 8-hydroxy-5-quinoline-
sulfonic acid (Fisher Scientific) and palladous chloride (Fisher Scienti-
fic) as described in Hanker, Gelberg, and Witten.*
(2) Glycine solution - Prepared by dissolving glycine (reagent
grade, Fisher Scientific) and sodium chloride (reagent grade, Fisher Sci-
entific) in deionized distilled water.
(3) Sodium hydroxide solution - 0.5 N
(4) Magnesium chloride hexahydrate solution - 1% W/V in deionized
distilled water.
(5) Water - Deionized, distilled
(6) Standards - The solid standard, potassium cyanide (Merck) was
used to prepare a stock standard of 1,000 ug/ml cyanide and various amounts
were used and treated as the samples (below) to produce a linear curve (linear
range used: 0.02 to 1.0 ug/ml).
3. Procedure
a. Preparing the Train (Figure 73)
(1) Pipette 20-cc 0.5 N NaOH, discard.
(2) Pipette 20-cc 0.5 N NaOH into a clean 1-oz French square
sample bottle and label as the blank.
(3) Pipette 20-cc 0.5 N NaOH into the midget impinger.
(4) Install the cyanide sampling train at the sampling sight.
* Hanker, J. S., A. Gelberg, and B. Witten, Anal. Chem.. 3JK1):93 (1958).
383
-------
SAMPLE PROBE
IMP1NGER
FILTER ^-CRITICAL ORIFICE
TO
VACUUM
PUMP
Figure 73. Cyanide sampling train.
384
-------
(5) Check the needle flow rate by pulling ambient air through a
calibrated rotameter, record.
b. Sample the Stack - 30 to 60 min.
c. Sample Recovery
(1) Check the needle flow after the experimental run as in Step
(5) above.
(2) Transfer the contents of the impinger into a clean 1-oz French
Square sample bottle.
(3) Rinse the impinger with a small volume of distilled water and
transfer the rinse to the sample bottle, label.
d. Analysis
(1) Measure total volume of sample.
(2) Pipette into a 5-ml volumetric flask the following: 1 ml of
sample; 1 ml of deionized distilled water; 1 ml of glycine-sodium chloride
solution; 1 ml of palladium chelate; and 1 ml of magnesium chloride solution.
(3) Shake the volumetric flask vigorously.
(4) After 8 min read a portion on the fluorometer. Excit at 350 nm
and measure the fluorescence at 490 nm.
e. Standarization - The standards, which were made up in water contained
1 ml of 0.5 N sodium hydroxide instead of water and were treated identi-
cally to the samples.
CCN = QsmP1 xl (C-20)
Rc x Tsmpl
where CCN = Concentration of cyanide in the stack gas, dry basis,
standard conditions,
Qsmpl = Amount of cyanide in the sample, p,g
385
-------
Rc = Critical orifice flow rate, dry basis, liters per
minute
Tsmol = samPlin8 time, minutes
1 = rag * \
V-g • m3
B. TOTAL PYEOPHOSPHATES
1. Apparatus
a. Sampling - Sampling for total pyrophosphates was accomplished
as a part of the train sampling for active ingredient and total species
in the stack gases.
b. Sample Recovery - Same as for active ingredient and related chemical
species.
c. Analysis
(1) Cary 118 ultraviolet - Visible recording speetrophotometer.
(2) Volumetric flasks - Two 25 ml.
(3) Graduated cylinger - 10 ml
2. Reagents
a. Sampling and Sample Recovery
(1) Sulfuric acid - pH 4.
(2) Water - Deionized, distilled.
b. Analysis
(1) Ammonium molybdate - A 5% solution prepared in deionized dis-
tilled water.
(2) Ammonium vanadate - 0.25% solution prepared in 2% nitric acid.
(3) Ammonium peroxydisulfate - 7.5% solution prepared in deionized,
distilled water.
(4) Standard - 1,000 ug/ml PO^"^ prepared from potassium dihydrogen
phosphate in deionized, distilled water.
386
-------
3. Procedure
a. Sampling and Sample Recovery - Completed during sampling and re-
covery of the active ingredient and related chemical species train.
b. Analysis - Analysis was performed according to the colorimetric
phosphovanadomolybdate procedure first described by Kitson and Mellon.*
Two different forms of phosphorus were determined: orthophosphate and
total phosphorus (including ortho-, meta-, pyro-, tripoly- and organic
phosphates).
(1) Divide the sample into two equal portions, the first for
orthophosphate determination and the second for total phosphorus determin-
ation.
(2) Transfer the first portion to a 25-ml volumetric flask and
add in order: 5 ml of nitric acid (1:2 dilution); 5 ml of ammonium molyb-
date solution; 5 ml of ammonium vanadate solution; and water to dilute to
volume.
(3) Transfer the second portion to a 25-ml volumetric flask and
add: 5 ml nitric acid (1:2 dilution) and 5 ml ammonium peroxydisulfate
solution. Digest for 10 min on a hot plate. Treat identically to the
first portion except exclude the 5 ml addition of nitric acid.
(4) Various amounts of the standard were used to produce a linear
curve (linear range used: 0 to 7 ug/ml) when treated with ammonium molyb-
date and ammonium vanadate.
(5) Scan the samples and standards from 450 nm to 350 nm.
(6) Use water treated with ammonium molybdate and ammonium vana-
date as a reference.
* Kitson, R. E_, and M. G. Mellon, Ind. Eng. Chem. Anal. Ed., 1£:379 (1944),
387
-------
APPENDIX D
CALCULATIONS
CONTENTS
Page
I. Pesticide and Fuel Oil Rates 390
Liquid Pesticide Formulations 390
Solid Formulations 393
II. Off-Gas Flow Rate 394
Stack Gas Velocity 394
Off-Gas Flow Rate 394
III. Efficiency of Incineration 395
Liquid Formulations 395
Solid Formulations 396
IV. Retention Time 398
Primary Chamber 398
Secondary Chamber 399
V. Significant Figures 399
This appendix contains the important calculations used during the
experimental phase of the project and for reduction of the data generated.
These calculations are presented using the system of units actually mea-
sured, and have not been standardized to the metric system. Calculations
pertinent to sampling and analysis have been presented in Appendix C.
389
-------
I. PESTICIDE AND FUEL OIL RATES
A. LIQUID PESTICIDE FORMULATIONS
The liquid pesticide formulations were mixed with fuel oil (or water)
to give the approximate primary chamber temperature and active ingredient
injection rate desired.
1. Equations for Pesticide Mixing
a. Active ingredient requirement
A0 = 1.25 AD (D-
where AQ = Amount of contained active ingredient required, pounds
AD = Predetermined active ingredient injection rate (normally
7.5 or 3.75), pounds per hour
1.25 = Pesticide incineration period, hours
b. Weight of pesticide formulation
W = *2. x 100
Co
where WT - Weight of pesticide formulation required, pounds
P
A = Amount of weight of active ingredient required, pounds (see
(Eq. D-l))
C = Active ingredient content of pesticide formulation, percent
c. Volume of pesticide formulation
v !i (D-3)
P (Sp. Gr) x 8.34
where Vp = Volume of pesticide formulation in the mix, gallons
WT = Weight of pesticide formulation in the mix, pounds (see
* (Eq. D-2))
(SP. Gr)p - Specific gravity of the pesticide formulation
8.34 = Density of water (Sp. Gr = 1.00), pounds per gallon
390
-------
d. Volume of fuel oil required
VD=1.25RN-Vp (D-4)
where VD = Volume of fuel oil required in the pesticide- fuel oil mix-
ture, gallons
1.25 = Test period, hours
RN = Burner nozzle flow rate, gallons per hour
Vp = Volume of pesticide formulation in the mix, gallons
(see (Eq. D-3))
e. Weight of required fuel oil
WTD = VD x (Sp> Gr>D x 8.34 (D-5)
where W-£ = Weight of fuel oil, pounds
VD = Volume of fuel oil, gallons
(Sp. Gr)j} = Specific gravity of fuel oil
f . Volume fraction of pesticide formulation in total feed
V
Vp + VD
(D-6)
where Bp = Volume fraction of pesticide formulation in the pesticide-
fuel oil mixture, gallons per gallon
2. Pesticide and Fuel Oil Injection Rates
a. Total feed rate
(L-i-Lo) x 0.2516 x 60
-------
where Rjn = Rate of the pesticide-fuel oil mixture fed to the burner,
gallons per hour
Li = Initial level of the pesticide formation-fuel oil mixture
in the feed drum, centimeters
L£ = Final level of the pesticide formulation fuel oil mixture
in the feed drum, centimeters
0.2516 = Volume per unit height of the feed drum, gallons per centi-
meter
60 = Minutes per hour
ti = Time at Lj reading, minutes
t2 - Time at L£ reading, minutes
b. Pesticide formulation feed rate
Rp = Bp x ^ (D-8)
where Rp = Pesticide feed rate, gallons per hour
Rja = Total feed rate, gallons per hour (see (Eq. D-6))
B- = Volume fraction of pesticide formulation (see (Eq. D-6))
c. Fuel oil feed rate
RD - RH. - Rp d>9)
where RD = Fuel oil feed rate, gallons per hour
3. Active Ingredient Injection Rate
RAI = CAI x Rm x 3,785 (D-10)
where R^i = Pesticide active ingredient feed rate, grams per hour
CAI = Pesticide active ingredient concentration in the pesticide
fuel oil mixture, as determined by analysis, grams per
milliliter
Rjn - Rate of the pesticide-fuel oil mixture fed to the burner,
gallons per hour
3,785 = Milliliters per gallon
392
-------
B. SOLID FORMULATIONS
1. Weight of Solid Pesticide Formulation Burned
Net burned = (0^-62- smpl) (D-ll)
where Net burned = Net weight of the pesticide formulation burned during
the experimental test, pounds
G± = Gross weight charged into the feeder (including con-
tainers), pounds
G = Gross weight remaining in the feeder at the end of
the experimental test (including containers),
pounds
smpl = Net weight removed from the feeder as samples, pounds
2. Solid Pesticide Feed Rate
Net burned x 60
where Rp = Rate of solid pesticide fed into the incinerator, pounds per
hour
Net burned = Eq. D-10
60 = Minutes per hour
t~ = Time the feeder was stopped, minutes
ti = Time the feeder was started, minutes
3. Active Ingredient Feed Rate
RAI = CAI x Rp x 4.536 (D-13)
where RAi = Pesticide active ingredient feed irate, grams per hour
R^ = Rate of solid pesticide formulation feed, pounds per hour
CAi = Pesticide active ingredient concentration in the solid
formulation as determined by analysis, percent
, _„,. _ Grams per pound
100
393
-------
II. OFF-GAS FLOW RATE
A. STACK GAS VELOCITY
where (Vs)avg. = Stack &as velocity> feed per sec°nd (fps)
* = 85.48 ft/sec (pound per pound mole °R)1/2 when these
units are used
C = Pitot tube coefficient, dimensionless, 0.83
(X ) = Average absolute stack gas temperature, °R
fA ^ = Average velocity head of stack gas, inches H20
v"p'avg.
P = Absolute stack gas pressure, inches Hg
s
M = Molecular weight of stack gas (wet basis), pounds
per pound mole
= Md(l-Bwo) + 18 BWQ
M. = Dry molecular weight of stack gas
B^ = Proportion by volume of water vapor in the gas stream
F = Correction factor for the pitot tube in midstream,
dimensionless
B. OFF-GAS FLOW RATE
where Qs - Off-gas flow rate, dry basis, standard conditions, cubic
feet per hour
A = Cross-sectional area of stack, square feet
Tstd = Absolute temperature at standard conditions, 530°R
Pgtd = Absolute pressure at standard conditions, 29.92 in. Hg
3,600 = Seconds per hour
394
-------
III. EFFICIENCY OF INCINERATION
(ACTIVE INGREDIENT AND TOTAL SPECIES BASIS)
A. LIQUID FORMULATIONS
1. Relative Amount of Unburned Pesticide (or Total Species) in Off-Gas
Quantity out
RR - 7: : ^ (D-16)
* Quantity in
where RR = Relative amount of unburned pesticide (or total species)
in off-gas, grams/hour per gram/hour
WAT
a. Quantity out = ^ x Q0 x 28.32, grams per hour (D-17)
KC x ismpl s
W = Amount of active ingredient (or total species) in
A.T
the sample by analysis, grams
Qs = Off-gas flow rate (Eq. D-14), cubic feet per hour
28.32 = Liters per cubic foot
Rc = Critical orifice flow rate, liters per minute
Tsmpi = Sampling time, minutes
b. Quantity in = R^j (see (Eq. D-10)), grams per hour (D-18)
2. Efficiency
e = [1-%] x 100 (D-19)
where e = Efficiency of incineration (active ingredient or total
species basis), percent
•jr = Relative amount of unburned pesticide (or total
species) in the off gas (Eq. D-16)
3. Concentration of Pesticide (or Total Species) in the Off-Gas
CoM-gas - H
395
-------
where C0ff-eas = Concentration of active ingredient (or total species)
in off gas, milligrams per cubic meter
WAI = Ajnount of active ingredient (or total species) in
the sample by analysis, grams
1L, = Critical orifice flow rate, liters per minute
Tsmpl = Sampling time, minutes
10^ = Milligrams per gram
10 = Liters per cubic meters
B. SOLID FORMULATIONS
1. Efficiency
f quantity out!
= h _ 2 . y — x 100 (D-21)
L quantity in J
where e = Efficiency of incineration (active ingredient or total
species basis), percent
Quantity out = Total quantity of active ingredient (or total species) not
burned in the off gas and residue, grams/hour
_ Quantitysample x Qs + Qua (D-22)
„ residue
mstd
Quantity , = Total quantity of active ingredient (or total species) in
the particulate sampling train, grams
Qs = Off-gas flow rate (Eq. D-12), cubic feet per hour
Vm , = Gas volume sampled, cubic feet
Quantityresidue = Quantity of active ingredient (or total species) in the
primary and secondary chamber residues, grams per hour
Quantity in = R^ (see (Eq. D-13)), grams per hour (D-23)
396
-------
2. Relative Amount of Unburned Pesticide (or Total Species) in the Off-
Gas
Quantityoff-
K Quantity in v
where RR = Relative amount of unburned pesticide (or total species),
gram per hour per gram per hour
Quantityof£.gas x Qs
Quantxtyoff_gas = 5 (D-25)
Quantity ££_ = Total quantity of active ingredient
(or total species) in the incinerator
effluent sample, grams per hour
Qg = Off-gas flow rate (Eq. D-12), cubic feet
per hour
Vm fcj = Gas volume sampled, cubic feet
Quantity in = R (See (Eq. D-13) (D-26)
"~™ ™" A.J-
3. Concentration in Off -Gas
= Quantitysample x fn-27)
Coff-gas 7 x 0. 02832 *• '
mstd
where C0ff_gas = Concentration of active ingredient (or total species)
in the off-gas, milligrams per cubic meter
Quantitysample = Total quantity of active ingredient (or total species)
in the incinerator effluent sample, grams
10^ = Milligrams per gram
Vm = Gas volume sampled, standard conditions,
cubic feet
0.02832 = Cubic meters per cubic feet
397
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IV. RETENTION TIME
A. PRIMARY CHAMBER
1. Primary Chamber Temperature
2ti + to + 2to
TA - — ~^ + 460 (D-28)
where T» = Weighted average temperature of the primary chamber, °R
ti = Temperature of Thermocouple No. (T} , °F
t-2 - Temperature of Thermocouple No. {2) , °F
t3 = Temperature of Thermocouple No. ^3) , °F
2. Off-Gas Flow Rate
= (Vs)avg. x0.785xTA
A T7
where VA = Off-gas flow rate from the primary chamber at temperature
TA> wet basis, cubic feet per second
Ty = Temperature of the stack at the pitot tube, °R
(Vs)avg. = Average velocity of the stack gas at Ty feet per second
0.785 = Cross-sectional area of the stack, square feet
3. Retention Time
VA 25.6
RTA = 4= ~ (D~30)
where RT^ = Retention time of the primary chamber, seconds
VA = Volume of £lie Primary chamber, cubic feet
v = Off-gas flow rate (Eq. D-29), cubic feet per second
A
398
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B. SECONDARY CHAMBER
1. Secondary Chamber Temperature
TB = t4 + t5 + 460
2
where TR = Average temperature of the secondary chamber, R
t^ = Temperature of Thermocouple No. A^ , °F
tr = Temperature of Thermocouple No. (~5\ , °F
2. Off-Gas Flow Rate
v -
B
. * °-785 * TB (D.32)
T7
where VB = Off-gas flow rate from the secondary chamber at temperature
TB, wet basis, cubic feet per second
3. Retention Time
VR 20.6 , ,.,.,.
RTR = _£ = (D-33)
B VB VB
where RTB = Retention time in the secondary chamber, seconds
VB = Volume of the secondary chamber, cubic feet
VR = Off-gas flow rate from the secondary chamber at temperature
TB, wet basis, cubic feet per second (Eq. D-32).
V. SIGNIFICANT FIGURES
Particular attention has been given to the significant figures reported
for the relative amounts of unburned pesticides (and total species) and the
concentration of pesticides (and total species) in the incinerator off-gas.
The calculations used to generate these data for liquid and solid formula-
tions are shown in (Eq. D-16, D-20, D-24, and D-27), respectively. Proper
use of significant figures for these results involved a comparison of only
the relative uncertainties of the data involved. The rule followed in report-
ing these values has been that the relative uncertainty of the answer be
between 0.2 and 2.0 times the largest relative uncertainty of the data used.
Reference to (Eq. D-16) will show that the calculation of the rela-
tive amount of unburned pesticides from liquid formulation tests involves
measurements of the amount of pesticide found in the sample train, the
sampling rate and time, and the total quantity of incinerator off-gas.
In most cases, the greatest relative uncertainty of the measurements in-
volved in this calculation was approximately * 1070, and was usually
399
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associated with the AP measurement for total off-gas determination (see
(Eq. D-14)). The acceptable relative uncertainty range for reporting the
relative rates,therefore, was > 2 to < 20%. The same ranges are applicable
to calculations for solid formulation tests. Accordingly, the following
significant figures were used.
Percent
Value relative uncertainty
1.0 to 4.9 10 to 2.04
5 to 9 20 to 11.1
For those calculations involving data having a relative uncertainty
of > 10%, only one significant figure has been reported.
The calculations for pesticide (and total species) concentration in
the effluent gas from liquid and solid pesticide formulation tests are
given in (Eqs. D-20 and D-27), respectively. This calculation involves
the measurements of amount of pesticide in the sample train, sampling
time, and sampling rate (or the volume of gas sampled). The greatest
relative uncertainty in these measurements was generally about 5%, and was
associated with the volumetric measurements. The acceptable relative un-
certainty range for the concentration is between 1 and 10%. These re-
sults, therefore, have been reported to two significant figures, i.e.,
1.0 to 9.9.
400
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
REPORT NO.
EPA-600/2-75-041
3. RECIPIENT'S ACCESSION>NO.
4. TITLE AND SUBTITLE
DETERMINATION OF INCINERATOR OPERATING CONDITIONS
NECESSARY FOR SAFE DISPOSAL OF PESTICIDES
5. REPORT DATE
December 1975 (Issuing Date)
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Thomas L. Ferguson, Fred J. Bergman, Gary R. Cooper,
Raymond T. Li, and Frank I. Honea
8. PERFORMING ORGANIZATION REPORT NO.
3. PERFORMING ORGANIZATION NAME AND ADDRESS
Midwest Research Institute
425 Volker Boulevard
Kansas City, Missouri 64110
10. PROGRAM ELEMENT NO.
1DB311; ROAP 21BKV; Task 008
11.
68-03-0286
12. SPONSORING AGENCY NAME AND ADDRESS
Municipal Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA-ORD
15. SUPPLEMENTARY NOTES
Project Officers: Donald A. Oberacker and Richard A. Games
16. ABSTRACT
An experimental incineration system was designed and constructed to evaluate the
effect of operational variables (rate of pesticide injection, percent excess air,
operating temperature, and retention time) on the efficiency with which organic
pesticides can be incinerated. This system included a pilot-scale incinerator
(45.4 kg/hr (100 Ib/hr) Type 1 waste capacity), a three-stage scrubber, and a
scrubber water treatment system. Nine pesticides in 15 liquid and solid formulations
were tested by injection into the primary combustion chamber. The pesticides studied
were DDT, aldrin, picloram, malathion, toxaphene, atrazine, captan, zineb, and mirex.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COS AT I Field/Group
Detoxification
Incinerators
Pesticides
Temperature
Research
Residence time
Incinerator conditions
Pesticides destruction
Time/temperature
Surplus pesticides
13B
18. DISTRIBUTION STATEMEN1
RELEASE TO PUBLIC
19. SECURITY CLASS (ThisReport)
UNCLASSIFIED
419
2O. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
401
*USGPO: 1976 — 657-695/5360 Region 5-1
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