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

-------
                                         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

-------
                              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

-------
                                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

-------
                                 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

-------
                              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

-------
                        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

-------
                                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

-------
                          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

-------
                          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

-------
                          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

-------
                               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

-------
                          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

-------
                          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

-------
                         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

-------
                         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

-------
                         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

-------
                           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

-------
                              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).

-------
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.

-------
     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
JU
\

100—
10—









0.01—




0.001-

n nnni —
a
o
0
s



















a
o
0
0



















a
c
2



















J
1
O
2



















3
13
|
£
m



















u
£
O



















57% Molorhion EC"



















25% Molothion WP**



















U
UJ
1
1—
1



















O
1
s



















-o
1
Li
j
*N
CO
O



















a.
1
H
1



















a.
c
a
0.
o
U
8



















1
N
#
R



















ii
fO
O





















Fficiency
s
J
i
I
I
t

e
£
0?
8:
c
£
V
g
6

 I
 w
 *:
         *The respective pesticide plus all related chemical species
          detected in the incinerator off gas and solid residues.
         "Based an Molothion detection limit.

-------
     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-
§
0.01-
£
J
J 0.001-
c
O
8
tu
1 n nnui—
u
s
o
#
CM

^•MH




3
5
0
^
o






u
UJ
c
<
r>4
^


mmmm



Gronglof
2
^
o


«••••



-o
'5
ID
E
2

V)
OJ

^^^M




i
E
J
U
a.
#
o


MHHMM



•
*
U
UJ
c
o
0
1
^
!?>

— —




I
C
O
i
^
in


^•^•i



U
UJ
|
a.
o
j
^
s






0
c
•Q.
o
s
•>£
s






•o
"5
(T
1
*N
E
CO
§

mmmmt




a.
f
N
e
•*5
o
oo




"^""^

t
s
a.
05
o



	


a.
-D
M
^
£






       *  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.

-------
                               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?.

-------
     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.

-------
                               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

-------
                              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

-------
     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

-------
     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

-------
 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

-------
               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

-------
       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

-------
                           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

-------
                               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

-------
 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

-------
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

-------
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

-------
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

-------
          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
ON
            NOZZLE
             NOZZLE ADAPTER
1/4 1
2 IN. PIPE
<
'///////////////////////////// k
/ 1 \
^ i
i
_ji i i i — L i i . i ^r^T^y-yyr^pY sv^yv^r ? $ \-a-c\

/ f
/ 'x^xx^x'x'xT y
'////////////////////////////) J
-* T 1 /O |K| ^

^ 12 IN. 1/41
N. PIPE-v
t
3/4 IN.





x^-^0
///////>
t
3/4 1 N .
sj p|p£ 	 ^^
V
X
X
X
X
X
X
X
X


>
<<
\
x\
X
X
X
X
X
X
r
f


i

X,
^
N



i
•«—
X
X
X
X
X
X
X



\
<^
X
X
X
X
X
X
X
« —
1 IN._

////

"iTlMI 1 ""^



////


-1 IN.-
-»•

//
'',
^i

//




»•
».



	 1/2 IN. PIPE
/
-J^ ° - J^^^^XIO 1^^
^VOID PACKED
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

-------
                          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

-------
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

-------
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

-------
                                   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

-------