Prepublication issue for EPA libraries
and State Solid Waste Management Agencies
A STUDY OF PESTICIDE DISPOSAL IN A SEWAGE SLUDGE INCINERATOR
This final report (SW-116c) describes work performed
for the Federal solid waste management programs under contract No. 68-01-1587
and is reproduced as received from the contractor
Copies will be available from the
National Technical Information Service
U.S. Department of Commerce
Springfield, Virginia 22151
U.S. ENVIRONMENTAL PROTECTION AGENCY
1975
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This report has been reviewed by the U.S. Environmental Protection
Agency and approved for publication. Approval does not signify that
the contents necessarily reflect the views and policies of the U.S.
Environmental Protection Agency, nor does mention of commercial products
constitute endorsement by the U.S. Government.
An environmental protection publication (SW-116c) in the solid waste
management series.
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ACKNOWLEDGEMENTS
The authors wish to express their gratitude to Mr. Alfred W. Lindsey,
Mr. Arch C. Scurlock and Mr^ John Schaum of the Environmental Protection Agency
for their continued interest and enthusiastic support for this program. The
experimental tests carried out at the Brisbane Facility of Envirotech Corporation
were made possible by the continued support of Mr. Raymond D. Fox and Mr. Thomas
E. Carleson of that laboratory. Finally, we wish to express our sincerest thanks
to Mr. Ronald N. Doty, Superintendent of Water Quality of the City of Palo Alto,
California for his cooperation in allowing us to carry out the research at the
Palo Alto Municipal Incinerator.
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TABLE OF CONTENTS
Page
1.0 PROGRAM SUMMARY . 1
2.0 GLOSSARY 7
3.0 INTRODUCTION 8
3.1 Experimental Design 10
4.0 PROTOTYPE EXPERIMENTS 12
4.1 Experiments 12
4.2 Prototype Furnace Operations 15
4.2.1 Pesticides; Sources and Analysis 31
4.2.2 Pesticide Mixing and Feed 31
4.3 Gas Stream Sampling 32
4.3.1 Other Samples 34
4.4 Analytical Methods and Results - DDT and
Products 34
4.5 Results of the DDT Combustion Experiments 35
4.6 Analytical Results on 2,4,5-T Experiments 47
4.7 Results of 2,4,5-T Experiments 47
4,8 Summary of Prototype Experiments 49
4.9 Chloride Ion Measurements 54
5.0 FULL SCALE EXPERIMENTS 57
5.1 Furnace Operating Conditions 57
5.1.1 Pesticides and Feed Methods 58
5,2 Gas Stream Sampling 66
5.3 Analytical Methods and Results of DDT and
Products 66
5.4 Results of the DDT Combustion Experiments 67
5.5. Analytical Results of 2,4,5-T Experiments 77
5.6 Results of 2,4,5-T Experiments 77
5.7 Summary of Full-Scale Experiments 81
5.8 References 82
6.0 POSSIBLE APPLICATION OF MULTIPLE HEARTH COINCINERATION
OF PESTICIDES 83
6.1 Furnace and Feed Conditions 83
6.2 Applicability of MHF Coincineration to Other
Refractory Organic Compounds 84
iii
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TABLE OF CONTENTS (Con't)
6.3 Availability of Multiple Hearth Sewage Sludge
Incineration 35
6.4 Feed Arrangements for Large Scale Destruction
of Toxic Compounds 86
6.5 Safety Precautions qs
7.0 DISCUSSIONS AND RECOMMENDATIONS 88
8.0 CONCLUSIONS AND OBSERVATIONS 90
APPENDIX A: Determination of Particulate Emissions from Stationary
Sources 93
APPENDIX B: Method of Organochlorine Pesticides in Industrial
Effluents 109
APPENDIX C: Method for Chlorinated Phenoxy Acid Herbicides in Indus-
trial Effluents 149
APPENDIX D: Partial List of Operating Municipal Incinerators in the
Continental United States 183
APPENDIX E: Stack Sampling Procedures 193
IV
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LIST OF TABLES
Table # Page
1. Furnace Conditions - 2% DDT Solid Experiment . . 17
2. Fumaoe Conditions - 5% DDT Solid Experiment . . 18
3. Furnace Conditions - 2% DDT Solution Experiment. 19
4. Furnace Conditions - 5% DDT Solution Experiment. 20
5. Furnace Conditions - 2,4,5-T 2% Solution
Experiment 21
6. Furnace Conditions - 2,4,5-T 5% Solution
Experiment 22
1-A. Furnace Conditions - 2% DDT Solid Experiment . . 23
2-A. Furnace Conditions - 5% DDT Solid Experiment . . 24
3-A. Furnace Conditions - 2% DDT Solution Experiment. 25
4-A. Furnace Conditions - 5% DDT Solution Experiment. 26
5-A. Furnace Conditions - 2,4,5-T 2% Solution
Experiment 27
6-A. Furnace Conditions - 2,4,5-T 5% Solution
Experiment 28
7. Stack Sampling Data 35
8. DDT Concentration - Product (Ash) 37
9. DDT Concentration - Emergent Air Stream .... 33
10. DDT Concentrations - Scrubber Water 39
11. Summary of DDT Combustion Experiments 40
12. Production & Distribution of DDT Combustion
Product :DDD 41
13. Production & Distribution of DDT Combustion
ProductrDDE 42
14. Distribution of DDT Combustion Products .... 43
15. DDT & Combustion Products - Total Effluent
Streams Emission Bates 44
16. Summary DDT Combustion Experiments 45
17. Effluent Streams - 2,4,5-T Concentrations ... 49
18. Mass Balance 2,4,5-T Experiments 51
19. Summary 2,4,5-T Combustion Experiments 52
20. Furnace Operating Conditions 61
20-A. Furnace Operating Conditions 62
21. Furnace Operating Conditions 63
21-A. Furnace Operating Conditions 64
22. Gas Sampling Data 68
23. DDT Concentrations/Production in Stack Gases . . 69
24. ODD Concentrations/Production in Stack Gases . . 69
25. DDE Conoentrations/Production in Stack Gases . . 70
26. DDT Concentrations/Emission Rate in Product . . 71
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LIST OF TABLES
Table
27. ODD Conoentrations/^lmission Rate in Product ... 72
28. DDE Concentrations/Emission Rate in Product (Ash) 73
29. DDT Concentrations/Production in Scrubber .... 74
30. EDD Concentrations/Production in Scrubber .... 74
31. DDE Concentrations/Production in Scrubber .... 75
32. Summary of Palo Alto DDT Conbustion Experiments . 75
33. Efficiency of Destruction (DDT) ......... 76
34. 2,4,5-T Concentrations Various Effluent Streams . 78
35. Mass Balance 2,4,5-T Experiments ......... 79
36. Sumnary 2,4,5-T Experiments ........... 80
VI
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LIST OF FIGURES
Figure #
1. 30" I.D. X 6HTH Pilot Furnace System 16
2. Stack Sampler Schematic 33
3. Mass Balance DDT Combustion Experiments
Showing Effect of Various Afterburner (AB)
Temperatures for Prototype Experiments 46
4. Mass Balance 2,4,5-T Combustion Experiments
Showing Effect of Various Afterburner (AB)
Temperatures for Prototype Experiments 53
5. Flow Diagram of Palo Alto Sewage Treatment
Plant 59
6. Schematic Palo Alto Municipal Multiple Hearth
Furnace 60
B-l. Analytical Flow Scheme for DDT and Its
Degradation Products
B-2. Qircmatogram of Typical Non-Particulate Stack
Gas Sample (Full Scale DDT Burn) 127
B-3. Chrcmatogram of Typical Stack Gas Particulate
Sample (Full Scale DDT Burn) 128
B-4. Chromatogram of Typical Scrubber Water
Filtrate Sample (Full Scale DDT Burn) 129
B-5. Chrcmatogram of Typical Scrubber Water
Particulate Sample (Full Scale DDT Burn) 130
B-6. Chromatogram of Typical Product Sample
(Full Scale DDT Bum) 131
B-7. Chromatogram of Product Sample (Full Scale
DDT Burn) 132
B-8. Chromatogram of Typical Non-Particulate Stack
Gas Sample (Pilot Scale DDT Burn) 133
B-9. Chrcmatogram of Typical Stack Gas Particulate
Sample (Pilot Scale DDT Burn) 134
B-10. Chromatogram of Typical Scrubber Water
Filtrate Sample (Pilot Scale DDT Burn) 135
B-ll. Chrcmatogram of Scrubber Water Filtrate
Sample (Pilot Scale DDT Burn) 136
B-12. Chrcmatogram of Typical Scrubber Water
Particulate (Pilot Scale DDT Burn) : 137
B-13. Chrcmatogram of Scrubber Water Particulate
Sample (Pilot Scale DDT Burn) 138
B-14. Chromatogram of Typical Product Sample (Pilot
Scale DDT Burn) 139
B-15. Chromatcgram of Product Sample (Pilot Scale
DDT Burn) 140
B-16. Typical Chromatogram of Sewage Sludge Sample
(Pilot Scale DDT Burn) 141
B-17. Typical Chrcmatogram of Laboratory Blank 142
vii
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LIST OF FIGURES
Figure #
B-18. Chronatogram of Typical Pesticide Composite
Standard 143
B-19. Chromatogram of DDT Standard 144
B-20. Chranatogram of p-p1 - DDE Standard 145
B-21. Chranatogram of o-p' - DDE Standard 146
B-22. Chromatogram of o-p1 - ODD Standard 147
B-23. Chromatogram of p-p1 - ODD Standard 148
0-1. 2,4,5-T 164
C-2. Dickins 165
C-3. Chranatogram of Typical Non-Particulate Stack
Gas Sample (Full Scale 2,4,5-T Burn) 166
C-4. Chranatogram of Typical Stack Gas Particulate
Sample (Full Scale 2,4,5-T Burn) 167
C-5. Chromatogram of Typical Scrubber Water
Filtrate Sample (Full Scale 2,4,5^1 Burn)... 168
C-6. Chranatogram of Typical Scrubber Water
Particulate Samples (Full Scale 2,4,5-T
Burn) 169
C-7. Chranatogram of Typical Product Sample (Full
Scale 2,4,5-T Burn) 170
C-8. Laboratory Blank - 2,4,5-T 171
C-9. Chranatogram of 2,4,5-T Standard 172
viii
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1.0 PROGRAM SUMMARY
Removal from general use of certain refractory pesticide compounds
has resulted in large excess stocks of these materials. These stocks con-
stitute a potential hazard to the environment, and environmentally adequate
methods for their disposal are being sought by the United States Environmental
Protection Agency. A significant portion of the problem may be attributed to
DDT, millions of pounds of which are currently stored in military depots
throughout the United States. Conventional solid waste incineration methods
and other low-cost disposal methods do not appear to be environmentally ade-
quate because of the relative chemical stability of these types of materials
and the large amounts requiring disposal. Thus, less conventional methods
of disposal, having both high and low relative cost compared to conventional
incineration, are under study.
The rapidly accumulating evidence that a larger fraction of the omni-
present polychlorinated biphenyls (PCB) are effectively destroyed incident
to sewage sludge incineration suggests the possibility that co-incineration
of other refractory compounds with sewage sludge might provide effective
disposal. On the basis of this premise, the program was designed to demon-
strate that a modern sewage sludge incinerator, fitted with the appropriate
air pollution control devices, could be used to successfully destroy typical
organic pesticides under conditions that assure that the emissions from the
incirarator remain well within established effluent standards.
EPA selected 2,2, bis (p-chlorophenyl) 1,1,1-trichlorethane (DDT) and
2,4,5-trichlorophenoxy-acetic acid C2,4,5-T) as the primary test materials.
DDT was- selected because it represented a high priority- dispqs.al problem as
a result of the ban. The cancellation of the 2,4,5-T registration was being
considered at hearings during the planning stage of this contract and there-
1
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fore also appeared to represent a potentially high priority disposal problem.
[The hearings have since been concluded and the 2,4,5-T registration was not
cancelled).
In order to obtain the maximum amount of information the demonstration
program was conducted in two phases:
Phase 1 - prototype experiments on the Envirotech Corporation
76 cm. six-hearth furnace at Brisbane, California; and
Phase 2 - full scale experiments on the Palo Alto, California
municipal multiple hearth sewage sludge incinerator.
The Phase 1 experiments were designed to test the effect on destruction
of a range of variables including pesticide type, pesticide preparation
(powder or solution), feed rate, location of feed mechanism, hearth tem-
perature and afterburner temperature. The Phase 2 experiments were sub-
sequently designed to provide a field test to verify the results of the
Phase I study.
The six Phase 1 experiments utilized the following pesticide feeds:
Experiment Pesticide Feed Feed Ratio
1 L)DT powder, 75% active ingredient 2 g /100 g sludge solids
2 OUT powder, 75% active ingredient 5 g /100 g sludge solids
3 UUT in kerosene,20% active ingredient 2 g /100 g sludge solids
4 DDT in kerosene,20% active ingredient 5 g /100 g sludge solids
5 Weedon™ solution, 20% 2,4,5-T 2 g /100 g sludge solids
6 Weedon™ solution, 20% 2,4,5-T 5 g /100 g sludge solids
The above feed ratios were computed on the basis of the total
pesticide preparation per dry sludge. The sludge contained variable
*A11 experiments were originally planned such that the feed ratios would
be two and five percent. However, these varied slightly in some cases due to
changes in the solids content of the sludge and the lack of precision in the
feed mechanism.
2
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solids contents on the order of 20 per cent by weight. The total feed
rate of the sewage sludge was maintained at 45.4 kg/hr (100 Ib/hr) in all
six experiments.
For each prototype experiment, the furnace was allowed to reach steady
state with the afterburner at 760 C (1400 F), pesticide feed was initiated
and another hour was allowed for steady state conditions to be reestablished
before sampling. One hour elapsed between the first and the second set of
samples. Subsequently, the afterburner temperature was increased to 955 C
(1750 F), two sample sets were taken as per the above schedule, and then
the afterburner was shut down and two additional sample sets were taken at
the same one hour intervals. Each set of samples included product (ash),
scrubber water, sludge feed, exhaust particulates and exhaust gases.
Detailed laboratory studies were made to determine sample concentra-
tions and injection rates of the test materials into the various effluent
streams from the furnace. Since some concern had been expressed about the
possible conversion of DDT to 2-2-bis(p-chlorophenyl)-l,l-dichloroethane
(ODD) and 2-2-bis(p-chlorophenyl)-l,l-dichloroethylene (DDE), the analy-
tical studies included analyses for these compounds in addition to DDT. A
similar concern about the possible formation of significant amounts of tet-
rachlorodioxin during the combustion of 2,4,5-T, required that the 2,4,5-T
samples also be analysed for the dioxin. Analyses were, in every case,
carried out by standard methods and verified by the frequent interposition
of standard and calibration samples.
The results of the prototype experiments allowed the following con-
clusions to be drawn:
1. Detectable quantities of DDD and DDE were found in the incinera-
tion system, but no trace of the dioxin was found;
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2. The total of DDT, ODD and DDE in all of the effluent streams did
not exceed 0.4 per cent of the DDT feed under any operating con-
dition, and did not exceed 0.04 per cent of the feed with the af-
terburner on; destruction efficiencies for DDT were thus 99.96%
or greater with the afterburner operating;
3. Destruction efficiencies for 2,4,5-T were above 99.95% at all
operating conditions (even with the afterburner off) and above
99.99% in many cases with no detectable tetrachlorodioxin; and
4. Variations in feed type, pesticide feed rate and sludge solids
content did not affect the results over the ranges studied for
these variables.
In nearly all cases the highest pesticide losses were found in the
scrubber water. Since these waters are normally recycled through the fa-
cility, tne above destruction ratios appear to be conservatively low in
comparison to normal operating conditions.
In view of the results from the prototype experiments, large-scale
experiments were authorized at the municipal sewage sludge incinerator in
Palo Alto, California. The experiments carried out in this facility fol-
lowed a program similar to that of the prototype with the exception that
no attempt was made to alter the afterburner operating conditions or other
normal operations at the facility. In addition, only the solid formulation
of DDT was tested because the DDT/kerosene solution supplied for this ex-
periment was judged to be unfit for use in such tests.
The full-scale experiments produced results which agreed extremely well
with those from the prototype tests with the afterburner on. No dioxin was
found, but both DDD and DDE were formed from DDT in the process; in many
cases, the samples held higher concentrations of DDE than DDT. Destruction
4
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effeciencies were 99.97% or higher for DDT (including ODD and DDE) and
99.99% or higher for 2,4,5-T. No effect of pesticide feed ratio was found
over the range covered. These values, too, could be considered conservatively
low, since the scrubber water is returned to the treatment facility for recycling.
To simplify comparison of the prototype and full scale experiments, the
significant data are summarized in Tables A and B which follow:*
TABLE A
COT DESTRUCTION EFFICIENCY
PHOTOTYPE EXPERIMENTS
Preparation
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solution
Solution
Solution
Solution
Solution
Solution
Solution
Solution
Feed
Hearth
1st
1st
1st
1st
1st
1st
1st
1st
3rd
3rd
3rd
3rd
3rd
3rd
3rd
3rd
Feed
Ratio
(gm/gm)
0.02
0.02
0.02
0.02
0.05
0.05
0.05
0.05
0.02
0.02
0.02
0.02
0.05
0.05
0.05
0.05
Avg.
Hearth
Temp
(C°)
764
754
715
738
759
795
780
782
841
827
837
842
838
841
810
802
AB*
Tenp
TcT
733
738
900
182
733
716
800
221
672
716
983
204
705
727
830
182
%
Cest.
Eff.
7%r~
99.98
99.98
99.98
99.96
99.995
99.997
99.998
99.66
99.79
—
99.99
99.99
—
99.99
99.98
99.99
FULL SCALE EXPERIMENTS
Avg.
Feed Feed Hearth AB*
Preparation Hearth Ratio Tenp Temp
(io755) TcT" TcT
Dest.
Eff.
Solid
Solid
Solid
Solid
1st
1st
1st
1st
0.02
0.02
0.05
0.05
629
634
628
659
638
649
663
649
99.97
99.98
99.98
99.98
*A.B. - Afterburner
TABLE B
2,4,5-T DESTRUCTION EFFICIENCY
PROTOTYPE EXPERIMENTS
Avg. %
Feed Feed Hearth AB* Dest.
Preparation Hearth Ratio Tenp Tenp Eff.
~1cT" Tc*7 7%T~
FULL SCALE EXPERIMENTS
Avg.
Feed Feed Hearth AB*
Preparation Hearth Ratio- Tenp Tenp
(C») 75")
Solution
Solution
Solution
Solution
Solution
Solution
Solution
Solution
3rd
3rd
3rd
3rd
3rd
3rd
3rd
3rd
0.02
0.02
0.02
0.02
0.05
0.05
0.05
0.05
792
809
781
749
774
793
780
784
711
711
1005
216
694
727
1010
227
99.98
99.99
99.99
99.98
99.99
99.9<>
99.99
Solution
Solution
Solution
Solution
3rd
3rd
3rd
3rd
0.02
0.02
0.05
0.05
700
677
691
698
677
655
644
663
99.99
99.99
99.996
99.99
*A.B. - Afterburner
*The feed ratios varied slightly from the amounts shown above in some case:.
The feed ratios for the solid DDT in the prototype experiments were actually .026
and .066. The feed ratios for the liquid 2,4,5-T in the full-scale experiments
were actually .012 and .038.
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Several other observations should be made regarding the full-scale
experiments. A small amount of the finer particulates in the DDT powder did
escape during the feeding process. Members of the research team experienced
slight and temporary upper respiratory irritation, apparently from this
source. This, of course, could be prevented if the powder were fed in as a
prepared solution in kerosene. The test results indicate no loss of effec-
tiveness between top hearth feed of solids and third hearth feed of kerosene
solutions. The education of operating personnel would be very important to
the effective use of this method in municipal facilities. The Palo Alto op-
erating crew were uncooperative until they had been fully informed of the
purposes of and the minimal hazards from the tests.
The results of this study indicate that DDT and 2,4,5-T can be safely
destroyed by co-incineration with sewage sludge in a multiple hearth furnace.
It appears probable that other pesticides with a similar chemical nature to
DDT or^4,5-T could also be safely destroyed via this technique. The pos-
sible application of this co-incineration disposal method to other pesti-
cides and other MHF installations is discussed in Section 6 of this report.
The stack sampling procedures used during this study are described in
detail in Appendix E.
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2-0 GLOSSARy OF ABBREVIATIONS AND SYMBOIS
A.I. = active ingredient contained in preparation
ODD = dichlorodiphenyl-dichloroethane
DEE = dichlorodiphenyl-ethylene
DDT = dichlorodiphenyl-trichloroethane
2,4,5-T = 2,4,5-trichlorophenoxyacetic acid
C_,-(t) = chloride ion concentration at tine t (gm/gnO
C. = chloride ion concentration of make up feed (gm/gm)
C = chloride ion concentration at tine t = o (gm/gm)
M = make up water input rate (gm/miiO
M. = total mass of water in the scrubber (gm)
Q = rate of injection of Cl~ ions due to DDT combustion (gm/min)
t. = time at which DDT feed began
t = initial fire up time
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3.0 IMTRDDUCTION
Pesticide use has increased explosively in recent years, resulting in
greater yields and higher quality products from American agriculture. However,
these pesticides have also resulted in a legacy of pollution problems in addition
to these benefits. Most recently, the banning of seme persistent pesticides such
as DDT (dichlorodiphenyl-trichloroethane) and Herbicide Orange has focused atten-
tion on the problem of pesticide disposal. The amounts involved are large.
Approximately 100 pesticide manufacturers produce some 1000 basic chemicals for
use in registered commercial pesticide products, with production of these materials
in 1971 estimated at 600 million kilograms U320 million pounds}. In addition,
over 10 million kilograms (22 million pounds) are on hand for disposal by govern-
ment agencies, including pesticides involved in regulatory actions and surplus
military material. This problem has been investigated by the Federal Working
Group on Pesticide Management (FWGPM) and the EPA Task Force on Excess Chemicals
(TFEC).
Materials to be disposed of include the following general types:
(1) Inorganic pesticides in various forms;
(2) Organic pesticides in solid form;
(3) Organic pesticides in liquid form (solutions,
slurries, suspensions, emulsions, etc.); and
(4) Organic pesticides in aerosol cans containing
various propellents and other ingredients.
Organic pesticides (items 2 and 3 above) comprise the bulk of the disposal
problem at this time. For these materials incineration as reccratiended by
the TFEC is a very desirable form of disposal.
In analyzing how best to meet this requirement, Versar, in a paper to EPA,
Office of Solid Waste Management programs,, used th.e follovjing criteria;
(1) The disposal plan should utilize existing and available facilities,
if possible, or commercially-available equipment if appropriate
facilities do not exist;
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(2) The recommended type of facility and equipment should be capable
of disposing of the widest possible range of pesticides provided
product streams (to air, water, landfills, etc.) meet local
standards and codes;
(3) If an existing type of facility is chosen, such facilities should
be generally available throughout the contiguous 48 states; and
(4) If existing facilities appear to be unavailable, then the designated
equipments must be capable of being operated successfully and within
code in any of the contiguous 48 states.
The Versar study concluded that the most attractive general type of incinerator
for this purpose (providing high temperatures, long residence times, and
closed-cycle collection of effluent species) appears to be a rotary kiln or
a multiple-hearth furnace. Both of these are designed primarily for solid feeds
and provide mixing and turning of the charge during a relatively long residence
time. Additionally, both appear to have been used for the incineration of
pesticides. The rotary kiln, used primarily for calcining or roasting ores,
consists of a revolving tube inclined so that the material moves downward by
gravity as the hot combustion gases move through the tube (usually) counter-
current to the feed. The rotary motion stirs the solid materials and constantly
exposes new surfaces. Incineration is a relatively new, but growing, use for
rotary kilns.
Multiple hearth furnaces also provide counter-current exposure of solids
to the hot gases. Revolving rakes mix the charge and move it so that it falls
by gravity from one hearth to another. These furnaces are generally cylindrical,
and an air-cooled central shaft is revolved to provide the raking motion. This
type of furnace has been used to incinerate sewage sludge since the early 1930's.
The mixing and turning action is much more positive than that of the rotary kiln,
and semi-liquid tars, gums, etc., can be incinerated by controlled introduction
to avoid slugs which create hot spots. The rotating hearth furnace, employing
rotation of the hearth against a stationary rake, is a simpler but less effective
version of the same general technique used in the multiple hearth furnaces.
The multiple-hearth furnace incinerator appears to be the logical first
choice for an incineration system, with the rotary kiln second. The basis for
this selection was as follows:
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(1) Multiple hearth systems have been used for incineration for many
years, and thus would appear to be more available in a wide
geographical distribution; and
(2) The more positive mixing and turning action of the multiple hearth
furnace compared to the rotary kiln seems desirable.
This information, plus other investigations carried out by the TFEC,
indicate that a modem design sewage sludge incinerator may have the potential
to destroy organic pesticides, and thus formed the basis for the study dis-
cussed in this report.
The present program was designed to verify that a modern sewage sludge
incinerator, fitted with the appropriate air pollution control devices, could be
used to successfully destroy typical organic pesticides under conditions that
assure that the emissions from the incinerator remain well within established
effluent standards.
i^l Experimental Design
In order to determine the applicability and safety of co-incineration
as a method for disposing of refractory pesticides it was decided to conduct a
study using the banned pesticide DDT and the still approved 2,4,5-T (trichloro-
phenoxyaoetic acid) as test materials . A program was designed to determine the
effect of such parameters as pesticide feed rate, pesticide form (that is, as a
water wettable solid and as a normal hydrocarbon solution) and afterburner
temperature. In the original program it was proposed to also examine the effects
of below normal hearth temperatures, but the possible dangers of injecting large
amounts of pesticide into the environment prohibited such an experiment.
In order to allow the gathering of the maximum amount of information
in the least amount of time, it was further decided to conduct the parametric
variation experiments on a prototype multiple hearth furnace available in the
laboratories of Envirotech Corporation in Brisbane, California. Only after these
prototype experiments were completed and the results evaluated would a full scale
experiment be carried out.
10
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The experiments at Brisbane were designed as follows:
1. Powdered DDT preparation pre-mixed in dewatered sludge to
be fed into the top hearth. The emergent DDT to be measured
in each effluent stream under three afterburner conditions.
In addition, the concentration of DDT in the sludge was to
be 2 per cent and/or 5 per cent by weight.
2. Kerosene solution of DDT mixed with sludge to be injected
into the grease port (scum port) on the third hearth. The
DDT emergent in each of the effluent streams was to be measured
under three afterburner conditions. There were to be two
separate concentrations of DDT — 2 per cent and/or 5 per cent.
3. Standard preparation of 2,4,5-T solution mixed with sludge to
be injected into the grease port on the third hearth. The
emergent 2,4,5-T in each effluent stream was to be measured
under three afterburner conditions. There were to be two sep-
arate concentrations of pesticide preparation, 2 per cent
and/or 5 per cent.
4. In each of the above experiments sampling should be delayed
for a sufficient length of time after initial injection to allow
equilibrium to be established.
5. In order to insure greater accuracy and sensitivity, it was
decided that no attempt would be made to accomplish analyses
in the field, but that all samples would be returned to the
laboratory where only standard methods of sample treatment and
analysis would be used.
If the results of the prototype experiments showed successful inciner-
ation with effluent levels well below existing regulations, the experiments
would be repeated in a full scale operating multiple hearth incinerator. The
full scale experiments would be conducted in a manner similar to the prototype
experiitents except that no attempt would be made to alter the normal afterburner
temperature.
11
-------
4.Q PROTOTYPE EXPERIMENTS
The experiments conducted at the 76.2 cm. (30 in.) diameter pilot
multiple hearth furnace at Envirotech Corporation in Brisbane, California,
were designed to discover the effects of such variables as the formulation
of the test compound, method of feed, feed ratio and afterburner conditions
on the effectiveness of the destruction of the two representative pesti-
cides (DDT and 2,4,5-T). The tests were divided into six separate experi-
ments, each conducted with a specified pesticide, specified formulation
and feed method and a specified feed ratio. Each experiment involved
sampling at each of three temperature conditions of the afterburner —
normal temperature of 760 C (1400F), highest attainable temperature 955 C
(1750 F) and with the afterburner off. In all experiments the sludge feed
rate was maintained at 45.4 kg/hr (100 Ib/hr) throughout the experiment.
4.1 Experiments
Experiment A:
Dry DDT preparation (75 per cent active ingredient) mixed with
sludge feed in the ratio of 2 grams preparation per 100 grains of the sludge and
fed to the top hearth by screw pump.
Test 1§2 Taken with afterburner at 760 C (1400 F)
Test 3 Taken with afterburner at 955 C (1750 F)
Test 4 Taken with afterburner off
Experiment B:
Dry DDT preparation (75 per cent active ingredient) mixed with
sludge feed in the ratio of 5 grams preparation per 100 grains of the sludge and
fed to the top hearth by screw pump.
Test 5 § 6 Taken with afterburner at 760 C (1400 F)
12
-------
Test 7 Taken with afterburner at 955 C (1750 F)
Test 8 Taken with afterburner off
Experiment C;
DDT in kerosene solution (20 per cent active ingredient) mixed
with sludge feed at third hearth in the ratio of 2 grains preparation per
100 grains sludge.
Test 9 & 10 Taken with afterburner at 760 C (1400 F)
Test 11 Taken with afterburner at 955 C (1750 F)
Test 12 Taken with afterburner off
Experiment D:
DDT in kerosene solution (20 per cent active ingredient) mixed
with sludge feed at third hearth in the ratio of 5 grams preparation per
100 grains sludge.
Test 13 & 14 Taken with afterburner at 760 C (1400 F)
Test 15 Taken with afterburner at 955 C (1750 F)
Test 16 Taken with afterburner off
Experiment E:
2,4,5-T in polyalcohol solution (20 per cent active ingredient)
mixed with sludge feed at third hearth in the ratio of 2 grams preparation
per 100 grams sludge.
Test 17 & 18 Taken with afterburner at 760 C (1440 F)
Test 19 Taken with afterburner at 955 C (1750 F)
Test 20 Taken with afterburner off
Experiment F;
2,4,5-T in polyalcohol solution (20 per cent active ingredient)
mixed with sludge feed at third hearth in the ratio of 5 grams preparation
per 100 grams sludge.
Test 21 & 22 Taken with afterburner at 760 C (1400 F)
Test 23 Taken with afterburner at 955 C (1750 F)
Test 24 Taken with afterburner off
13
-------
As indicated above, all feed ratios were to have been .02 and .05.
However, due to changes in the solids content these varied slightly in some
cases. The feed ratios in the solid DDT experiments (A and B) were actually
.026 and .066 rather than .02 and .05.
14
-------
4.2 Prototype Furnace Operations
A schematic diagram of the Envirotech Corporation prototype 76.2 on.
(30 in.) multiple hearth furnace shewn in Figure 1 represents the normal con-
figuration of the system. For the purposes of this series of experiments, the
cyclone was by-passed and the scrubber was arranged for closed circuit operation
by the addition of a reservoir approximately 1.22 m x 0.91 m x 0.91 m (4 ft x
3 ft x 3 ft) fitted with a surface closure and an access port to allow periodic
sampling. The major purpose of recycling the scrubber water was to minimize
escape of unburned pesticide to the environment; however, it also provided samples
for a chloride production analysis.
Provisions were made to allow a continuous measurement of the in-
dividual hearth temperatures, the afterburner and exhaust temperatures and the
oxygen and carbon dioxide content of the emergent gas stream. Provisions were
also made to collect the product (ash) and to impound the scrubber water pending
the outcome of the analyses.
Tables 1 through 6 contain discrete hourly temperature and gas
analysis data taken during each experiment. These tables also show the time
intervals during which tire pesticide feed was continued and also tiiose time intervals
during which sampling was carried out. In the interests of the widest possible
utilization of the data within this report, Tables 1-A through 6-A are repetitious
of the corresponding Tables 1 through 6 except that the hearth temperatures are
given in degrees Fahrenheit — this seems appropriate since most current instru-
mentation in the field is calibrated in English units. In addition, these tables
indicate that sampling was delayed for one hour after initial injection of the
pesticide in order to allow equilibrium residence tine of the order of 45 minutes.
The combustion conditions within the furnace can be inferred by measure-
ment of the composition of the emergent exhaust gases. In the studies conducted
at the prototype furnace at Brisbane, it has been found that under conditions
wherein the 02 content of the stack gases is greater than several per cent and
the CD content very low (not detectable in the experiments reported herein)- The
conditions are such as to indicate excess air as per the following discussion.
15
-------
AFTERBURNER
FEEDER(S) SLUDGE
FEEDER 15) SAMPLI
\ 7 (Screw) *V
n
I/VWWWWWVWWWWM 1 1
^^ Jl
(Pump)
FURNACE
-i i ii
HTH 1
2
3.
4
5.
6
#
•VM
g
^
5
fl
f
rH-i '
CYCLONE
Y
ME/
^. SCREW
^.^^ CONVEYOR
PRODUCT
SAMPLE
;"
r
X
^
f \^
O^i COn ^ /
IXSUREMENT U
1^-J
Y
Scrubbe
Water Ou
n,. EMERGE
1 *~ AIR SAM
f^^> \ n FAN
•4- Scrubber
Wcter In
2- STAGE
SCRUBBER
SCRUBBER SAMPLE
r
t
FIGURE I
30" I.D. x 6 HTH PILOT FURNACE SYSTEM
-------
Table I
FURNACE CONDITIONS - 2% DDT SOLID EXPERIMENT
Feed Time T| T2 T3 T4 T5 T6 (°C) (°C) %02 %C02 %N2 Sample
Sludge only
Sludge & DDT
PROTOTYPE FURNACE
Hearth Temperature (°C)
Time
1050
1230
1320
1430
1555
1650
1705
1730
1830
1930
2010
2100
2150
2230
2300
2400
0040
T|
549
405
394
271
127
383
433
349
316
405
483
471
394
405
260
338
366
T2
805
633
738
572
527
771
783
733
761
705
749
744
777
683
677
694
688
TS
838
872
850
672
872
861
872
866
838
838
827
827
816
816
794
827
805
T4
861
894
838
838
872
861
872
894
861
872
838
844
827
850
838
861
827
T5
894
905
872
872
905
872
872
872
894
872
883
861
838
861
838
861
850
T6
861
861
827
827
894
872
872
872
872
866
872
883
872
883
883
861
894
A.B*
CC)
494
738
738
827
538
661
722
733
772
705
749
705
738
716
894
905
182
Stack
PC)
93
99
99
121
99
93
93
96
116
93
93
93
93
93
116
110
63
Stack
Gas Analysis
%°2
13.5
15
14
15.2
13.4
18.5
20
%C02
5
2.3
4.0
2.1
1.6
1.5
0.6
%N2
81.5
82.7
82.0
82.7
85
81
79.4
Notes:
a. Entire run plagued by clogging of #' drop hole.
b. Sludge feed @ rate of 45 kg/hr (100 Ib/hr).
c. DDT (solid) feed @ rate of 0.91 kg/hr (2 Ib/hr) began <& 1705.
d. Sludge/DDT fed to hearth #1.
* A.B. = Afterburner
#3
-------
Feed
Sludge
oo
Sludge & DDT
Table 2
FURNACE CONDITIONS - 5% DDT SOLID EXPERIMENT
PROTOTYPE FURNACE
Hearth Temperatures (°C)
Time
0900
1000
1030
1100
1130
1200
1220
1240
1340
1400
1430
1515
1600
1630
1645
1715
1800
1830
1900
Tl
538
427
427
515
583
560
583
405
371
394
327
338
271
316
399
366
416
427
427
T2
761
761
711
761
738
738
749
761
772
755
761
738
705
705
761
749
705
772
738
T3
816
838
827
794
788
772
794
833
850
850
850
855
905
905
927
927
905
905
905
T4
888
894
883
883
894
888
888
894
894
883
872
872
905
900
905
900
888
883
872
T5
894
900
894
894
905
916
916
916
905
894
883
894
894
894
905
894
900
872
872
T6
838
850
850
872
877
866
861
866
872
872
866
866
872
861
872
866
866
827
877
A.B*
(°C)
683
705
683
683
699
711
716
716
733
716
716
727
733
716
716
705
800
794
221
Stack
Stack Gas Analysis
(°C) %02
93
99
105
105
105
349
405
93
99
93 13.5
93
93
93 13.5
93
93 13.0
93
93 10.5
93
71 14.5
%C02 %N2
2.0 84.5
1.9 84.6
1.8 85.2
1.9 87.6
1.3 84.2
Notes:
a. Sludge feed began 0900 - completed 1900@rate of 45 kg/hr (100 Ib/hr).
b. DDT (solid) feed,§rate of 2.25 kg/hr (5 lb/hr> began @ |400 discontinued @ 1900.
c. Brief shut-down @ 1045 - 1200 to fix rake arm # 3 hearth.
d. Sludge/DDT fed to hearth #F.
* A.B. = Afterburner
Sample
-------
Table 3
FURNACE CONDITIONS - 2% DDT SOLUTION EXPERIMENT
Feed Time Tj T2 T3 T4 T5 T6 (°C) (°C) %02 %C02 %N2 Sample
Sludge 1140 727 716 622 761 872 865 143 38 10.5 4 85.5
Sludge & DDT
81.5
82.0 9
78
84 10
85
88 11
1925 772 850 705 905 905 871 850 93
Sludge Only
88 12
Note:
a. Sludge feed began 1140 @ rate of 45 kg/hr (100 Ib/hr), discontinued @2020. Fed on third hearth.
b. 2% DDT solution feed @L rate of 0.91 kg/hr (2 Ib/hr) of preparation began @ '1515 on third hearth - fped discontinued @ 1950.
c. Several minor leaks developed in the DDT feed line.
d. Sludge/DDT fed to hearth #3.
* A. B. = Afterburner
PROTOTYPE FURNACE
Hearth Temoerature (°C)
Time
1140
1415
1500
1530
1600
1630
1700
1715
1800
1830
1850
1925
1950
2040
Tl
727
733
727
772
783
777
760
783
772
772
783
772
794
783
T2
716
772
772
816
833
833
794
821
827
855
855
850
833
850
T3
622
516
583
722
699
694
649
677
694
716
683
705
722
738
T4
761
865
872
916
916
905
888
916
894
727
916
905
905
916
T5
872
894
883
950
939
916
894
894
916
905
911
905
905
900
T6
865
872
865
844
883
883
871
871
871
866
871
871
866
866
A.B.*
CC)
143
483
666
661
672
716
716
716
727
738
983
850
427
204
Stack
CC)
38
60
105
93
93
93
93
93
93
93
99
93
99
71
Gai
%02
10.5
13.5
13.0
19
13
11
10.5
10.5
Stack
s Anal'
%C02
4
5
5
3
3
4
1.5
1.5
-------
Table 4
FURNACE CONDITIONS - 5% DDT SOLUTION EXPERIMENT
Feed Time T, T? T3 T4 T5 T6 (°C) (°C) %02 %C02 %N2 Sample
Sludge Only
Sludge & DDT
PROTOTYPE FURNACE
Hearth Temperatures (°C)
Time
1115
1200
1230
1300
1320
1345
1400
1415
1435
1500
1525
1540
1600
1635
1640
1700
1730
1750
1830
Tl
772
772
777
816
783
761
749
755
749
749
755
749
722
716
716
705
705
711
705
T2
805
805
833
861
838
838
838
844
844
858
850
844
816
805
800
805
794
788
772
T3
638
638
672
699
738
761
738
761
788
783
794
761
722
672
649
694
672
672
649
T4
888
888
894
649
894
894
900
905
916
894
894
894
900
894
888
872
850
861
850
T5
894
900
916
671
883
883
883
888
872
883
883
888
900
900
894
894
894
888
894
T6
872
883
8/2
694
883
872
872
872
883
883
872
883
872
872
888
883
888
894
888
A.B.*
CC)
705
716
711
705
722
722
705
705
727
727
727
727
805
805
838
316
205
182
171
Stack
Stack Gas Analysis
(°C) %02
93
93
93
93
93 12.5
93 10.5
93
93
93 13.5
93
93
93
93 13
104
516**
116 19
82
71
60
%C02 %N2
6.1 81.4
4.0 85.5
5 81.5
5 82
1 80
Notes:
a. Sludge feed @ rate of 45 kg/hr (TOO Ib/hr) began® 1115. discontinued @ 1800. Fed on third hearth.
b. DDT feed @ rate of 2.25 kg/hr (5 Ib/hr) of solutionbegan @ 1200, discontinued 1725. Fed on third hearth.
c. Scrubber feed pump lost @ 1630 - replaced 1650.
d. A series of hearth bed temperatures vs nominal temperatures gave the following results:
Hearth Bed Nominal
6 677 °C 882 °C
5 860 °C 893 °C
4 849 °C 893 °C
3 449 °C 804 °C
* A.B. = Afterburner
** Scrubber water level control failed - immediately replaced
13
14
15
16
-------
Table 5
FURNACE CONDITIONS - 2, 4, 5-T 2% SOLUTION EXPERIMENT
PROTOTYPE FURNACE
Feed
Sludge
Sludge & Solvent
Sludge & 2,4,5-T
10
Hearth Temperatures (°C)
A.B* Stack
Stack
Gas Analysis
Time
1100
1130
1200
1300
1400
1430
1500
1530
1600
1625
1640
1700
1730
1800
788
850
761
766
755
761
761
761
749
749
749
705
705
705
783
794
738
816
777
794
805
822
761
772
772
761
727
783
683
716
632
694
694
572
644
583
588
572
572
538
538
588
816
816
805
838
844
844
844
850
816
816
805
827
788
805
933
888
894
872
888
911
894
900
872
883
888
872
844
861
861
850
872
872
872
872
816
872
872
894
894
872
894
316
583
705
683
694
705
711
711
738
861
1005
1061
216
216
193
99
116
93
88
93
77
88
93
99
96
105
60
60
60
%02
16.0
16.5
15.0
14
13
%C02
3.5
2.0
115
4
6
%N2
80.5
81.5
83.5
82.0
81.0
Sample
17
18
19
Sludge
Shut Down
Notes:
a. Sludge feed @rate of 45 kg/hr (100 Ib/hr) began® 1100, discontinued® 1725. Fed on third hearth.
b. Solvent only injection® rate of 0.91 kg/hr (2 Ib/hr) began @ 1130, discontinued® 1200. Fed on third hearth.
c. 2,4,5-T Solution injection @ rate of 0.91 kg/hr (2 Ib/hr) began® 1200, discontinued @ 1735. Fed on third hearth.
* A.B. = Afterburner
20
-------
Feed
Sludge Feed
Sludge & Solvent
Sludge & 2,4,5-T
to
to
Table 6
FURNACE CONDITIONS - 2. 4. 5-T 5% SOLUTION EXPERIMENT
Sludge
Notes:
a. Sludge feed @ rate of 45
b. Solvent only injection @
c. 2,4,5-T solution feed @
* A.B. = Afterburner
PROTOTYPE FURNACE
Hearth Conditions (°C)
Time
1110
1130
1145
1230
1330
1430
1510
1530
1555
1615
1630
1655
1700
1735
1800
Tl
638
705
711
733
727
716
727
738
749
761
747
749
749
749
983
T2
733
761
761
783
783
777
794
772
783
816
761
782
782
772
772
T3
672
594
594
594
555
577
605
616
627
661
638
588
599
622
616
T4
761
805
838
811
827
827
827
833
855
872
838
816
816
816
816
T5
872
872
916
872
872
872
877
872
872
883
872
872
872
872
872
T6
872
872
872
872
883
872
861
872
872
872
872
872
872
872
872
A.Bf
143
594
661
733
694
694
705
705
727
972
1010
788
761
227
205
Stack
49
77
93
93
93
82
93
88
88
88
88
93
93
71
49
Stack
Gas Analysis
%02 %C02 %N,
16 2 82
16 2 82
14 4.5 81.5
17 1 82
21
22
23
24
kg/hr (100 Ib/hr) began @ 1110, discontinued @ 1750. Fed on third hearth.
rate of 2.25 kg/hr (5 Ib/hr) began @ 1130, discontinued @ 1145. Fed on third hearth.
rate of 2.25 kg/hr (5 Ib/hr) began @ 1145, discontinued @ 1735. Fed on third hearth.
-------
Feed
Sludge only
Sludge & DDT
Table I -A
FURNACE CONDITIONS - 2% DDT SOLID EXPERIMENT
PROTOTYPE FURNACE
Hearth Temperature (°F )
Time
1050
1230
1320
1430
1555
1650
1705
1730
1830
1930
2010
2100
2150
2230
2300
2400
0040
T|
1020
760
740
520
260
720
810
660
600
760
900
880
740
760
500
640
690
T2
1480
1460
1360
1060
980
M20
1440
1350
1400
1300
1380
1370
1430
1260
1250
1280
1270
T3
1540
1600
1560
1240
1600
1580
1600
1590
1540
1540
1520
1520
1500
1500
1460
1520
1480
T4
1580
1640
1540
1540
1600
1580
1600
1640
1580
1600
1540
1550
1520
1560
1540
1580
1520
T5
1640
1660
1600
1600
1660
1600
1600
1600
1640
1600
1620
1580
1540
1580
1540
1580
1560
T6
1580
1580
1520
1520
1640
1600
1620
1600
1600
1590
1600
1620
1600
1620
1620
1580
1640
A.B*
(°F)
920
1360
1360
1520
1000
1220
1330
1350
1420
1300
1380
1300
1360
1320
1640
1660
360
Stack
(°F)
200
210
210
250
210
200
200
205
240
200
200
200
200
200
240
230
145
Stack
Gas Analysis
%o2
13.5
15
14
15.2
13.4
18.5
20'
%co2
5
2.3
4.0
2.1
1.6
1.5
0.6
%N2
81.5
82.7
82.0
82.7
85
81
79.4
Notes:
a. Entire run plagued by clogging of *l drop hole.
b. Sludge feed @ rate of 45 kg/hr (100 Ib/hr).
c. DDT (solid) feed @ rate of 0.91 kg/hr (2 Ib/hr) began
d. Sludge/DDT fed to hearth#1.
* A.B. = Afterburner
1705.
Sample
#2
#3
-------
Feed
Sludge
Sludge & DDT
Table 2-4
FURNACE CONDITIONS-5%DDT SOLID EXPERIMENT
PROTOTYPE FURNACE
Stack
Gas Analysis
Hearth Temperatures (°F) A.B.* Stack
T, T, T, T,
T, T (°F) (°F) %0, %CO. o,
Time
0900 1000 1400
1000 800 1400
1030 800 1310
1100 960 1400
1130 1080 1360
1200 1040 1360
1220 1080 1380
1240 760 1400
1340 700 1420
1400 740 1390
1430 620 1400
1515 640 1360
1600 520 1300
1630 600 1300
1645 750 1400
1715 690 1380
1800 780 1300
1830 800 1420
1900 800 1360
1500
1540
1520
1460
1450
1420
1460
1530
1560
1560
1560
1570
1660
1660
1700
1700
1660
1660
1660
1630
1640
1620
1620
1640
1630
1630
1640
1640
1620
1600
1600
1660
1650
1660
1650
1630
1620
1600
1640
1650
1640
1640
1660
1680
1680
1680
1660
1640
1620
1640
1640
1640
1660
1640
1650
1600
1600
1540
1560
1560
1600
1610
1590
1580
1590
1600
1600
1590
1590
1600
1580
1600
1590
1590
1520
1610
1260
1300
1260
1260
1290
1310
1320
1320
1350
1320
1320
1340
1350
1320
1320
1300
1470
1430
430
200
210
220
220
220
660
760
200
210
200
200
200
200
200
200
200
200
200
160
13.5 2.0 84.5
13.5
13.0
10.5
14.5
1.9
1.8
1.9
1.3
84.6
85.2
87.6
84.2
Sample
Notes:
a. Sludge feed began 0900 - completed 1900 @ rate of 45 kg/hr (100 Ib/hr).
b. DDT (solid) feed @ rate of 2.25 kg/ hr (5 Ib/hr) began @ 1400 discontinued (§1900.
c. Brief shut-down @ 1045 - 1200 to fix rake arm #3 hearth.
d. Sludge/DDT fed to hearth # 1.
* A.B. = Afterburner
-------
Table 3-A
FURNACE CONDITIONS-2% DDT SOLUTION EXPERIMENT
Feed
SI udge
ii
Sludge & DDT
Sludge Only
PROTOTYPE FURNACE
Hearth Temperature \"fy
Time
1140
1415
1500
1530
1600
1630
1700
1715
1800
1830
1850
1925
1950
2040
T.
1
1340
1350
1340
1420
1440
1430
1400
1440
1420
1420
1440
1420
1460
1440
T.
2
1320
1420
1420
1500
1530
1530
1460
1480
1520
1570
1570
1560
1530
1560
T0
3
1150
960
1080
1330
1290
1280
1200
1250
1280
1320
1260
1300
1330
1360
j
4
1400
1560
1600
1680
1680
1660
1630
1680
1640
1630
1680
1660
1660
1680
T_
5
1600
1640
1620
1740
1720
1680
1640
1640
1680
1660
1670
1660
1660
1650
T.
6
1560
1600
1560
1550
1620
1620
1600
1600
1600
1590
1600
1600
1590
1590
A.B*
C ^J
290
900
1230
1220
1240
1320
1320
1320
1340
1360
1800
1560
800
400
Stack
C 0
100
140
220
200
200
200
200
200
200
200
210
200
210
160
Stack
Gas Analysis
%0.
2
10.5
13.5
13.0
19
13
11
10.5
10.5
%CO, %N0
2 2
4
5
5
3
3
4
1.5
1.5
85.5
81.5
82.0
78
84
85
88
88
Sample
10
II
12
Notes:
a. Sludge feed begun 1140 @ rate of 45 kg/hr (100 Ib/hr), discontinued @ 2020. Fed on third hearth.
b. 2% DDT solution feed @ rate of 0.91 kg/hr (2 Ib/hr) of preparation began @ 1515 on third hearth - feed discontinued 81950.
c. Several minor leaks developed in the DDT feed line.
d. Sludge/DDT fed to hearth #3.
* A.B. = Afteburner
-------
Table 4-A
FURNACE CONDITIONS-5% DDT SOLUTION EXPERIMENT
PROTOTYPE
Hearth Temperatures ( F)
Feed
Sludge Only
Sludge & DDT
II
II
"
11
11
"
»
"
11
11
11
"
It
11
11
••
Time
1115
1200
1230
1300
1320
1345
1400
1415
1435
1500
1525
1540
1600
1635
1640
1700
1730
1750
1830
Tl
1420
1420
1430
1500
1440
1400
1380
1390
1380
1380
1390
1380
1330
1320
1320
1300
1300
1310
1300
T2
1480
1480
1530
1580
1540
1540
1540
1550
1550
1575
1560
1550
1500
1480
1470
1480
1460
1450
1420
T3
1180
1180
1240
1290
1360
1400
1360
1400
1450
1440
1460
1400
1330
1240
1200
1280
1240
1240
1200
T4
1630
1630
1640
1200
1640
1640
1650
1660
1680
1640
1640
1640
1650
1640
1630
1600
1560
1580
1560
T5
1640
1650
1680
1240
1620
1620
1620
1630
1600
1620
1620
1630
1650
1650
1640
1640
1640
1630
1640
T6
1600
1620
1600
1280
1620
1600
1600
1600
1620
1620
1600
1620
1600
1600
1630
1620
1630
1640
1630
FURNACE
A.B.*
(<*)
1300
1320
1310
1300
1330
1330
1300
1300
1340
1340
1340
1340
1480
1480
1540
600
400
360
340
Stack
Stack Gas Analysis
(°F) %02
200
200
200
200
200 12.5
200 10.5
200
200
200 13.5
200
200
200
200 13
220
960**
240 19
180
160
140
%C02 %N2
6.1 81.4
4.0 85.5
5 81.5
5 82
1 80
Sample
437-13
437-14
437-15
437-16
Notes:
a. Sludge feed @ rate of 45 kg/hr (100 Ib/hr) began @ 1115, discontinued @ 1800. Fed on third hearth.
b. DDT feed @ rate of 2.25 kg/hr (5 Ib/hr) of solution began @ 1200, discontinued 1725. Fed on third hearth.
c. Scrubber feed pump lost @ 1630 - replaced 1650.
d. A series of hearth bed temperatures vs nominal temperatures gave the following results.
Hearth
6
5
4
3
* A. B. = Afterburner
** Scrubber water leVel control failed - immediately replaced.
Bed
\25tf F
1580°F
1560°F
840°F
Nomine
1620°F
1640 F
1640°F
1480°F
-------
ro
Table 5-A
FURNACE CONDITIONS - 2, 4, 5-T 2% SOLUTION EXPERIMENT
PROTOTYPE FURNACE
Hearth Temperatures
Feed
Sludge
Sludge & Sol vent
Sludge & 2, 4,5-T
II
"
n
11
"
n
11
n
"
Sludge
Shut down
Time
1100
1130
1200
1300
1400
1430
1500
1530
1600
1625
1640
1700
1730
1800
Tl
1450
1560
1400
1410
1390
1400
1400
1400
1380
1380
1380
1300
1300
1300
T2
1440
1460
1360
1500
1430
1460
1480
1510
1400
1420
1420
1400
1340
1440
T3
1260
1320
1170
1280
1280
1060
1190
1080
1090
1060
1060
1000
1000
1090
(*)
T4
1500
1500
1480
1540
1550
1550
1550
1560
1500
1500
1480
1520
1450
1480
T5
1710
1630
1640
1600
1630
1670
1640
1650
1600
1620
1630
1600
1550
1580
T6
1580
1560
1600
1600
1600
1600
1500
1600
1600
1640
1640
1600
1640
1600
A.B*
(OP)
1080
1300
1260
1280
1300
1310
1310
1360
1580
1840
1940
420
420
380
Stack
Stack Gas Analysis
(°F) %02 %C02 %N2
210
240
200
190 16.0 3.5
200 16.5 2.0
170
190 15.0 115
200
210 14 4
205
220
140 13 6
140
140
80.5
81.5
83.5
82.0
81.0
Sample
17
18
19
20
Notes:
a. Sludge feed @ rate of 45 kg/hr (100 Ib/hr) began @ 1100, discontinued® 1725. Fed on third hearth.
b. Solvent only injection @ rate of 0.91 kg/hr ( 2 Ib/hr) began at 1130, discontinued @ 1200. Fed on third hearth.
c. 2,4,5-T Solution injection @ rate of 0.91 kg/hr (2*/hr) began® 1200, discontinued® 1735. Fed on third hearth.
-------
Table 6-A
FURNACE CONDITIONS - 2, 4, 5-T 5% SOLUTION EXPERIMENT
PROTOTYPE FURNACE
CO
Hearth Conditions f F)
Feed
Time
Sludge Feed 1110 1180 1350
Sludge & Sol vent 1130 1300 1400
Sludge&2,4,5-T 1145 1310 1400
1230 1350 1440
1330 1340 1440
1430 1320 1430
1510 1340 1460
1530 1360 1420
1555 1380 1440
1615 1400 1500
1630 1375 1400
1655 1380 1440
1700 1380 1440
1735 1380 1420
Sludge 1800 1340 1420
Stack
A.B* Stack Gas Analysis
%02 %C02 %N2
1240 1400 1600 1600
1100 1480 1600 1600
1100 1540 1680 1600
1100 1490 1600 1600
1030 1520 1600 1620
1070 1520 1600 1600
1120 1520 1610 1580
1140 1530 1600 1600
1600
1160 1570
1220 1600 1620 1600
1180 1540 1600 1600
290
1100
1220
1350
1280
1280
1300
1300
1600 1310
1780
1850
1090 1500 1600 1600 1450
1110 1500 1600 1600 1400
1150 1500 1600 1600 440
1140 1500 1600 1600 400
16
120
170
200
200
200
180
200
190 16
190
190
190 14
200
200
160
120 17
82
82
4.5 81.5
82
Sample
21
22
23
24
Notes:
a. Sludge feed
rate of 45 kg/hr (100 Ib/hr) began @ 1110, discontinued @ 1750. Fed on third hearth.
b. Solvent only injection @ rate of 2.25 kg/hr(5 fb/hr) began @ 1130, discontinued @ 1145. Fed on third hearth.
c. 2,4,5-T solution feed® rate of 2.25 kg/hr (5 Ib/hr) began @ 1145, discontinued @ 1735. Fed on third hearth.
* A.B. = Afterburner
-------
As a typical experiment involving the prototype furnace at Brisbane,
consider the 5 per cent solid DDT burn. The furnace and emergent air stream
analysis are given in Table 2(2A) along with the total run time of 10 hours.
During this experiment producer gas was consumed at an average rate of 4.4
m3/min (155 ft3/tun) [total gas consunption of 2.65 x 103 m3 (9.36 x 104 ft3)
in an elapsed tine of 600 minutes]. At the same tine, the dry sludge input rate
of 151 gms/min (dry weight) was maintained. If it is assumed that the sludge
contains approximately 20 per cent carbon as the most significant combustible
(the hydrogenous components would produce water which is removed by the scrubber)
contained within the sludge, and further,that the producer gas contains 60 per
cent nitrogen, then it is possible to compute the level of oxygen excess in the
system during this experiment. The flue gas analysis, from Table 2, is:
0>2 = 1.78%
02 = 13 %
N2 = 85.22%
conputed and measured on a dry basis. Following Baumeister , to totally com-
bust 4.4 m of producer gas requires the consunption of 4.4 x 0.198 = 0.87 m
00 and produces 4.4 x 0.31 = 1.36 m GCL in the process. Thus, taking the
3
volumetric composition of air to be 21 per cent O^, this requires 4.14 m /min
of air for total conbustion of the input producer gas.
From the data given above, the carbon input from sludge is 28 gm/min
which, for complete conbustion requires, according to the relation:
c + o2 -> co2
74 gms 0_/min which then requires a volune (STP) of 0. on the order of 1.85 m /min
3
and which produces 1.87 m /min of CD2. The air input for sludge decomposition is
then 1.87/0.21 =8.90 m3/min.
Thus, the total air input required is:
8.90 + 4.14 = 13.04 m3/min
The total C02 produced is 1.36 x 1.87 = 3.23 m /fain.
29
-------
Fran the N_ in stack gas we may compute the total input N0 from
33
all sources as 35.2 m /rain x 0.85 = 29.92 m /min which is derived partially
from the input air (79 per cent N_) and frcm the producer gas (60 per cent N)
as follows:
N- producer gas = 4.4 x 0.6 = 2.64 m /min
3
N_ from input air = 29.92 - 2.64 = 27.28 m /min
27 28 3
Input air volume rate = —'-=5 = 34.53 m /min
To compute the expected 0_ content of the emergent gases, the total 0 input =
3 3
34.53 x .21 = 7.25 m /min of which 0.87 + 1.85 = 2.72 m /min is consumed. Hence
residual 0_ in emergent stack gases should be 4.53 m /fain which suggests an 0_
concentration en the order of 13 per cent. On the other hand, the total C00 pro-
3
duced by the assumed model is 1.87 + 1.36 = 3.23 m /min which should correspond to
a concentration in the emergent stream on the order of 9 per cent. Several points
may be made dealing with the discrepancy between the computed G0_ concentration in
the exhaust gases and the actual measured values as given in Table 2 (2A).
If we add the nitrogen volume rate (29.92 m /min) plus the expected
0_ volume rate (4.53 m /min) and the CCL generation rate (3.23 m /min) the total
3 3
is 37.66 m /min which is to be compared to the measured 35.2 m /min. It is in-
teresting to note that if the difference of 2.46 m /min were assumed to be due to
the absorption of C0_ in the scrubber, then there remains 0.77 m /min C0_ in the
stack gases. This corresponds to a level of 2 per cent 00- which compares favor-
ably to the measured levels as shown in Table 2 (2A).
The average scrubber water temperature was en the order of 50 C (122 F)
and the average scrubber flow rate on the order of 150 1/min (40 gal/min) so that,
in order to absorb 2.46 m /min CO- which is 147 gm O02/nin, it is necessary that
the solubility of 00_ in water at 50 C be on the order of 0.98 gms/liter or 9.8 x
—4 -4
10 gm/ml ~ 9.8 x 10 gms/gm. From the table values (Reference 2), the solu-
-4
bility of (XL in water at 50 C is given as 7.61 x 10 gms/gm which compares
favorably with the computed value above.
In view of the discussion above and the fact that the 00_/02 ratio in
all the reported experiments is of the same order, one is safe in concluding that
the combustion conditions are in fact such that excess air is present in the system.
30
-------
4.2.1 Pesticides; Sources and Analysis
For the purposes of these experiments, a wettable DDT powder
preparation containing 75 per cent active ingredient was supplied by the Army
Material Command from the Sierra Base Depot in northern California. In addition,
a solution of 20 per cent DDT in kerosene was also supplied by the Army. Lab-
oratory analyses of both these preparations indicated that the labeled concentr-
ations were correct and further that the active ingredient was an exceptionally
pure DDT (ratio of o-p1 DDT to p-p1 DDT « 1 to 4) with no trace of such de-
composition products as ODD (dichlorodiphenyl-dichloroethane) or DDE
(dichlorodiphenyl-ethylene).
The 2,4,5-T was only available as a solution containing
20 per cent active ingredient. The preparation used in these experiments was
a commercial weed killer known as Weedon , which is available through commercial
channels. Analysis of the material used indicated very low (below detection
limits) levels of tetrachlorodioxin and further that the concentration of 2,4,5-T
was correctly given by the manufacturer.
4.2.2 Pesticide Mixing and Peed
In those experiments where the wettable powder preparation
was used, mixing was accomplished by adding the appropriate amount of the pre-
paration to a 207.9 liter (55 gallon) drum of sludge. Mixing was accomplished
using a slow speed paddle arrangement. The mixing operations were carried cut
within a plastic glove bag to avoid contamination of the area. The mixed
sludge-pesticide was introduced into a vibrator hopper which in turn fed a
screw pump. The resulting mixture was then introduced into the top hearth.
The solution feed was accomplished by metering the test
solution into a 5.1 cm. (2 in.) feedline with the sludge. The mixed sludge-
pesticide was then introduced into the third hearth. In these experiments the
upper two hearths served as additional afterburners.
In all the experiments conducted at the prototype furnace,
the sludge feed was regulated at 45.4 kg/hour (100 Ibs/hour) — a rate fixed by
the size of the inter-hearth drop holes within the prototype furnace.
31
-------
4.3 Gas Stream Sampling
The emergent gas stream was sampled at the output of the scrubber
(Figure 1) using the standard EPA Method 5 for air stream particulates (Appendix A
& E. The physical layout of the stack was such that it was not possible to con-
duct separate traverses of the stack along perpendicular paths so a single
traverse was conducted for each run. The heated probe (at 95 C or 203 F) was
inserted into the 7.6 cm. (3.0 in.) sampling port (see Figure 1 for location
of port) at the beginning of each sampling run. Toe collected sample was passed
through the 0.45 micron filter prior to its introduction into the bubbler
as shown in the schematic Figure 2. For DETT (and its combustion products) the
first two impinger tubes contained 100 ml spectre grade hexane each; for the
2,4,5-T, the first two impingers contained 100 ml ethylene glycol each. The
third impinger was empty while the fourth contained 150 grams Dryrite — the
whole train being maintained at ice temperatures.
Isckinetic sampling was accomplished by first calibrating the S
Pitot tube in the probe against a calibrated Dwyer Pitot tube with a slant guage
manometer. Adjustments were made in the pumping speed as needed to compensate
for variation in air stream velocity during a sampling run or when the sampling
probe was moved during a traverse. Each traverse was conducted so as to collect
approximately 0.15 m at each of four sampling points per traverse.
At the completion of each sampling run, the probe and the connected
sampling train assembly were removed from the stack, taken to a clean room and
the samples removed. In the case of EOT sampling, the filter, along with, the
hexane rinsings of the probe, cyclone and associated fittings were combined into
the particulate sample. The hexane impinger samples were combined with the
hexane rinsings of the first two impingers and their connecting fitting to
form the impinger sample. The same procedure was used for the 2,4,5-T samples,
except that ethylene glycol was used in the rinsing.
After each run, the sampling train, probe and associated glassware
were washed in hot detergent solution, rinsed with distilled water, rinsed with
de-ionized water, dried with anhydrous ethyl alcohol and finally rinsed with
spectro grade hexane.
32
-------
LJ
U>
/; PROBE
2) CYCLONE
3) FLASK
4) PARTICULATE FILTER
5) IMPINGERS (Grcenbug-
Smith)
6) THERMOMETER
7) CHECK VALVE
8) UMBILICAL CORD
9) VACUUM GAGE
IO) COURSE FLOW ADJUST VALVE
II) FINE FLOW ADJUST VALVE
12) OILER
13) VACUUM PUMP
14) FILTER
15) DRY GAS METER
16) ORIFICE TUBE
21
17) INCLINE MANOMETER
18) SOLENOID VALVES
19) PITOT
20) THERMOCOUPLE
21) PYROMETER
FIGURE 2
STACK SAMPLER SCHEMATIC
-------
The detailed data from each of the 24 runs are displayed in Table 7
after being converted to metric units (nearly all connercial sampling trains
still present data in English units). Also included in Table 7 is the corrected
(to standard conditions) sample volume and the calculated gas flow rate averaged
over each run (the method of correction is outlined in Appendix A).
4.3.1 Other Samples
At the end of each gas sanpling run representative samples
were taken of the scrubber water, the product (ash) and the input sludge.
During the experimental run, the total product was collected so that each pro-
duct sample, approximately 100 grams, was a composite of the product collected
over the period during which the gas stream sample was taken. As is indicated
in Section 4.2, the scrubber system was arranged to be a closed system in order
to attempt to measure the rate of HC1 production — an attempt that was not
successful as will be discussed below. Scrubber samples, approximately 1 liter,
were taken from the holding tank at the end of each gas sampling run. Be-
cause of the turbulence within the holding tank, it was assumed that adequate
uniformity would be assured and thus a simple surface sample was taken.
The sludge samples, taken at the end of each gas sampling
run, were taken from the vibratory feed hopper and stored in a refrigerator
until they were analyzed.
The sample bottles had been washed and rinsed according to
the same scheme outlined for the sampling train. When the cleaned bottles
were dry, they were sealed with teflon lined plastic caps and held in this
condition until the sample was introduced.
4.4 Analytical Methods and Results - DDT and Products
The samples, product, scrubber water with particulates and gas
stream samples were returned to the laboratory for analysis. Since some con-
cern had been expressed about the possible conversion of significant amounts
of DDT to the even more hazardous chlorinated hydrocarbons ODD and DDE,
analytical procedures were adopted to detect all three compounds. The methods
of analysis, which are described in detail in Appendix B, consisted primarily
34
-------
Table 7
STACK SAMPLING DATA
01
Sample
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
Collect
Time
(sec)
1200
900
1140
1140
960
840
900
600
900
1080
1020
1020
1080
1200
1200
1200
1080
1080
1140
1080
900
900
900
1140
Sample
Vol.(Meas)
(M3)
0.404
0.254
0.537
0.528
0.386
0.258
0.271
0.217
0.267
0.314
335
258
368
0.355
0.438
0.290
0.402
364
343
0.283
0.318
0.398
0.315
0.
0.
0.
0.
0.
0.312
Stack
Temp
CQ
102.2
107.8
107.8
85.
96.
96.
85.
85.
85.
85.
85.
85.
102.
102.
102.
102.2
93.9
93.9
.6
.7
.7
.6
.6
.6
.6
.6
.6
.2
.2
.2
93.
93.
96.
96.
96.
63.3
Prototype Experiment
AP
(imH20)
21.6
20.2
11.95
8.9
17.8
21.6
14.2
12.2
19.6
19.6
14.1
10.7
17.8
17.0
14.1
12.7
24.9
24.6
15.2
12.7
27.9
27.9
15.8
13.0
P
Stack
(cmHg) (
75.95
75.95
75.95
75.95
75.90
75.90
75.90
75.90
75.90
75.90
75.90
75.95
75.95
75.95
75.95
75.85
75.85
75.85
75.85
75.85
75.85
75.85
75.85
75.85
AH
faniH20)
31.3
56.0
112.0
96.6
61.0
52.6
45.7
30.5
48.3
47.5
45.7
32.0
45.7
45.7
35.6
30.5
58.5
58.5
38.1
30.5
63.5
73.6
35.5
30.5
Vel
Stack
(M/sec)
20.91
20.69
18.62
13.28
18.99
20.91
16.82
15.45
19.60
19.60
16.73
17.19
19.17
18.68
17.10
15.94
22.34
22.25
17.53
16.00
23.80
23.80
17.89
15.51
0=35.25
Corrected*
Sample
Vol.
(M3)
0.513
0.329
0.696
0.640
0.495
0.324
0.343
0.267
0.337
0.398
0.425
0.327
0.463
0.450
0.550
0.363
0.479
0.434
0.412
0.343
0.386
0.487
0.379
0.346
m /min
Q
Stack Flow
(MVmin)
40.78
40.26
36.35
25.82
37.04
40.78
32.79
30.07
38.23
38.23
32.62
33.47
37.38
36.36
33.30
31.09
43.66
43.32
34.15
31.26
46.38
46.38
34.83
30.07
NOreS; Average stack flow
*See Appendix A for correction formulae and for the identification of all symbols.
All data taken from the sampler are presented in English units which have been converted to metric units in this table.
Sample data form is included in Appendix A.
-------
of extraction of the hydrocarbons, chrcmatographic clean-up to remove inter-
fering conpounds and subsequent concentration and quantative determination using
an electron capture detector on a gas chromatograph. The frequent introduction of
reference solutions of known concentration of each of the compounds of interest
provided calibration.
The analytical results (analyses carried out by methods described
in detail in Appendix B) for the principal hazardous products, DOT, ODD and DDE,
in the individual emergent streams are displayed in Table 8-10, 12 and 13. These
data may be combined to allow the computation of the rates of emission of each
of the hazardous components and for each emergent stream; the results of these
computations are displayed in Tables 11 and 14 and summarized in Table 15.
4.5 Results of the DDT Combustion Experiments
In order to simplify the comparison of the results obtained under
various conditions of pesticide formulation, pesticide feed ratio and furnace
operation, it is appropriate to introduce the concept of the per cent destruction
efficiency using the following general definition:
% efficiency of destruction = pesticide feed rate -hazardous product emission rate x
*
which, for DDT takes the specific form:
% efficiency of destruction = DPT feed rate "™™ ****** rate x 10Q>
The % efficiency of DDT destruction is shown in Column 5 of Table 16 and diagram-
atically in Figure 3 wherein the effect of the various parametric variations is
illustrated. To better illustrate the significance of these data, recall that the
first eight tests were run using solid DDT fed on the top hearth. Further, note
the following:
a) Tests 1, 2, 5 and 6 were run with the afterburner at
760 C (1400 F) ;
b) Tests 3 and 7 were run with the afterburner at 955 C
(1950 F); and
c) Tests 4 and 8 were run with the afterburner off.
36
-------
Test
No.
I
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
P-P
DDT
(ppb)
6.1
7.5
9.5
5.35
2.1
.4
.4
10.
1,
5.6
2.5
2.7
13.6
4.1
2.0
4.5
9.2
9.7
o-p'
DDT
(ppb)
522
37
50,
33.
8.2
17.7
4.4
19.4
7.8
16.6
38.3
24.7
12.3
15.2
35.5
30.6
Table 8
DDT CONCENTRATION - PRODUCT (ASH)
Prototype Experiments
Total
(ppb)
528
44.5
60.0
39.2
10.3
28.1
5.8
25.0
10.3
19.3
51.9
28.8
14.3
19.7
44.7
40.3
Product (Ash)
Production
(grams/hr)
680
Total DDT
Emission
(groms/hr)
36*.
.30x10-4
.41x10-4
.27x10-4
.07x10-4
.19x10-4
.04x10-4
.17x10-4
.07x10-4
.13x10-4
.35x10-4
.195x10-4
.09x10-4
.13x10-4
.30x10-4
.28x10-4
DDT
Feed Rate
(gramsAO
908
2270
181.6
454
Notes:
a. Analytical methods described in Appendix B.
b. Test conditions described in Section 4.1, pp. 9 and 10.
DDT feed rate is reported on an active ingredient basis, rather than fhe total formulation.
"Questionable data point.
c.
37
-------
Table 9
DDT CONCENTRATION-EMERGENT AIR STREAM
Test
No.
•1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
1
o-p'
(ppb)
1122
40
103
83
288
267
155
230
4146
307
203
41
sample
258
224
58
mpinger
P-P1
(ppb)
2060
155
295
408
800
1335
322
2818
12423
1780
1043
168
lost
1437
758
199
Prototype Experiments
Particulate Total DDT
Total
(ppb)
3182
195
398
491
1088
1602
477
3049
16569
2087
1246
209
1694
982
257
o-p1
(ppb)
23
98
609
218
45
47
194
4666
87
451
72.5
62.5
8
100
349
40
p-p1
(Ppb)
227
450
2284
600
183
278
930
13376
447
1780
327.5
275
30
390
1308
148
Total Air Stream
(ppb) (ppb)
250 3422
548
2893
818
228
325
1124
48042
534
2231
400
337.5
38
490
1657
188
743
3291
1309
1316
1927
1601
55756
17103
4318
1646
546
2153
2839
445
Air Flow
Rate
M3/min.
36.3
36.3
36.3
36.3
36.3
36.3
36.3
36.3
36.3
36.3
36.3
36.3
36.3
36.3
36.3
36.3
Notes:
a. Analytical methods described in Appendix B.
b. Test conditions described in Section 4.1, pp. 9 and 10.
4.
2.
2.
5.
DDT in
Exit Air
gm/M3
6.7x10-6
2.26x10-6
.73x10-6
.05x10-6
.68x10-6
.97x10-6
4.69x10-6
211.1x10-6
50.8x10-6
10.7x10-6
3.88x10-6
2.37x10-6
8.22x10-6
5.15x10-6
2.08x10-6
38
-------
Table 10
DDT CONCENTRATIONS - SCRUBBER WATER
Prototype Experiments
Test
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Notes:
a. An<
Scrubber Water
o-p'
(ppb)
0.025
0.02
0.075
1.37
0.25
0.06
0.07
0.27
0.08
0.05
0.06
0.06
0.04
0.02
0.05
0.025
alytical
p-p1
(ppb)
0.10
0.12
0.13
4.50
0.63
0.13
0.25
1.01
0.23
0.32
0.10
0.19
0.10
0.12
0.17
Total
(Ppb)
0.125
0.140
0.21
5.87
0.88
0.19
0.32
1.28
0.31
0.37
0.16
0.25
0.14
0.14
0.22
0.102 0.127
methods
described in Apr
Scrubber Particulates
o-p1
(ppb)
0.125
0.075
0.07
146
0.08
0.73
2.0
210
0.4
0.14
0.1
0.1
0.026
0.115
0.15
0.02
>endix B.
P-P'
(ppb)
0.435
0.38
0.23
371
0.27
2.18
31.0
638.2
1.7
0.54
0.45
0.38
0.127
0.39
0.41
0.11
Total
(ppb)
0.56
0.46
0.307
517
0.35
2.91
33.0
859.4
2.1
0.68
0.55
0.48
0.153
0.500
0.56
0.129
Total DDT
in Scrubber
(ppb)
0.685
0.595
0.507
523
1
3
23
,09
33.3
860.0
2.41
1.05
0.71
0.74
0.29
0.64
0.76
0.255
b. Test conditions described in Section 4.1, pp. 9 and 10.
39
-------
Table 11
SUMMARY OF DDT COMBUSTION EXPERIMENTS*
*».
o
Test
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Prototype
Product
DDT (Total)
gm/hr
3.6x 10'3
0.3x 10-4
0.41 x 10-4
0.27x ID'4
0.07x ID'4
0.04x ID'4
0.04 x 10-4
0.17x 10-4
0.07x ID"4
0.13x 10-4
0.35x 10~4
0.195x ID"4
0.09x 10-4
0.13x ID-4
O.SOx 10-4
0.28x 10-4
Experiments — DDT Emission Rates
Air Stream
DDT (Total)
gm/hr
1.46x 10-2
0.49x 10-2
1.03x ID'2
0.45 x 10-2
0.58x ID'2
1.30x ID'2
1.02 x 10'2
4.59x 10-1
0.111
0.0234
0.84x 10~2
0.515x ID-2
(lost sample)
1.79x 10-2
1.12 x 10"2
0.45x 10-2
Scrubber
DDT (Total)
gm/hr
3.9x 10-4
3.4x ID'4
2.9x 10-4
0.3
2.05x ID'4
1.75x 10-3
1.90x ID'2
0.49
1.37x 10'3
6. Ox ID'4
4. Ox 10-4
4.30x 10-4
1.65x ID"4
3.64x ID"4
4.32x ID'4
1.45x ID'4
Various Stream:
Total Losses
DDT (Total)
gm/hr
1.86x 10'2
4.96 x 10"J
1.06x ID'2
0.340
6.5x 10-3
1.48x ID'2
2.92x 10-2
0.949
0.112
0.024
8.84x 10'3
5.6x lO'3
1.83x ID'2
1.16x ID'2
-.48x 10'2
DDT
Feed Rate
(gm/hr)
908 (Sol id)
2270 (Solid)
181.6 (Solution)
454 (Solution)
Notes:
a. Analytical methods described in Appendix B.
b. Test conditions described in Section 4.1, pp. 9 and 10.
c. DDT feed rate is reported on an active ingredient basis, rather than the totb+formuloHon.
* Product Emission Rate = Product DDT Concentration x Product Production Rate.
Air Stream Emission Rate = Air Stream DDT Concentration x Air Stream Flow Rate.
Scrubber Emission Rate = Scrubber DDT Concentration x Scrubber Flow Rate.
-------
Table 12
PRODUCTION & DISTRIBUTION OF DDT COMBUSTION PRODUCT: ODD
Air Stream
Impinger
op1 pp1
(ppb) (ppb)
32.5
108
20.5
325
133
11
53
2600
95
10.4
4.8
—
68
74
12
1315
108.0
127
165
2059
1050
104
262
12300
760
52.2
25
—
827
183
115
Filter
op1 pp1
(ppb) (ppb)
19
61.8
388
455
7.8
0.8
6.5
3774
13
—
5.2
17
7.0
69
202
15
33
125.5
2354
2300
159
53
205
25417
965
—
198
92
23.0
111
1076
42
Prototype Experiments
Scrubber
Total
(ppb)
2967
327.8
2977
2941
2551
1237
327
45383
15878
—
266
139
—
1075
1535
184
op1
(Ppb)
0.104
0.142
0.28
6.68
1.53
0.18
0.47
2.25
0.5
0.2114
0.058
0.28
0.21
0.16
0.19
0.20
PP1
(ppb)
0.70
0.118
0.119
O.-l
0.131
3.42
5.82
0.33
0.62
0.31
0.34
0.16
0.35
0.28
0.1«
0.08
Total
(ppb)
0.804
0.255
0.399
6.69
1.66
3.6
6.29
2.59
1.12
0.52
0.398
0.44
0.56
0.44
0.37
0.28
Product (Ash)
op'
(ppb)
__
1.18
7.30
1.10
0.43
0.59
0.36
4.17
0.85
0.28
9.87
0.63
0.79
1.45
1.29
2.30
PP1
(ppb)
413
1.18
45.4
2.67
2.92
6.29
1.85
33.6
3.19
1.97
84.0
1.59
8.37
4.25
69.2
51.8
Total
(ppb)
413
3.15
52.7
3.77
3.35
6.88
2.21
37.77
4.04
2.25
93.87
2.22
9.16
5.70
70.5
54.1
Test
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Notes:
a. Analytical methods described in Appendix B.
b. Test conditions described in Section 4.1, pp. 9 and 10.
-------
Table 13
PRODUCTION & DISTRIBUTION OF DDT COMBUSTION PRODUCTS: DDE
10
Test
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Air Stream
Impinger
o-p1 p-p1
(ppb) (ppb)
1850
45
165
386
338
1720
73
353
106
230
30
93
No
500
1630
188
1040
55
120
385
3155
3277
105
420
160
520
68
113
sample
552
2145
240
Filter
o-p1 p-p1
(ppb) (ppb)
60
113
1820
1050
190
232
103
6758
650
No
80
70
56
150
580
103
53
70
1308
265
255
338
160
11133
1240
sample
129
80
16
105
1265
54
Prototype Experiments
Scrubber
Total
(ppb)
3003
283
3413
2086
3938
5567
341
18664
2156
307
356
1307
5620
585
o-p1
(ppb)
.6
.56
.74
8.0
.89
4.1
7.7
1518
1.3
1.2
1.48
1.1
1.1
1.15
1.16
0.26
p-p1
(ppb)
3.75
1.92
3.88
4.2
3.2
4.2
4.3
1707
1.9
3.6
1.9
4.1
3.95
3.88
3.73
4.1
Total
(ppb)
4.35
2.48
4.62
12.2
4.09
8.3
12.0
3225
3.2
4.8
3.38
5.2
5.05
5.03
4.89
4.36
o-p1
(ppb)
6.1
3.9
45.5
2.5
1.02
6.29
1.99
27.3
2.42
0.98
60.8
1.65
5.18
1.77
3.11
6.84
Product
P-p1
(ppb)
39.3
14.4
78
11.4
2.6
1.2
3.98
15.8
17.3
9.03
43.7
10.3
5.34
3.90
6.48
1.09
Total
(ppb)
45.4
18.3
124
13.9
3.62
7.5
6.0
43.1
19.7
10.0
104.5
11.95
10.52
5.67
9.59
7.93
Notes:
a. Analytical methods described in Appendix B.
b. Test conditions described in Section 4.1, pp. 9 and 10.
-------
Table 14
DISTRIBUTION OF DDT COMBUSTION PRODUCTS*
u>
Test
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Product
T5T5T3
(gmAr)
-2
81 x 10
15 x 10"4
3.6x 10"3
2.57xlO'4
2.28x 10~4
69 x 10~4
51 x lO"4
2.57x 10'3
2.75x 10'4
1.53x 10'4
6.39x 10"3
1.51 x!0~4
6.24x 10-4
3.85x 10"4
4.8x 10'3
3.68x 10'3
DUE
(gmAr)
3.08x
1.24x 10
~3
"3
8.43x 10
9.45x lO^4
2.46x 10"4
5.1 x ID'4
4. Ox 10~4
2.93x 10~3
1.34x 10~3
6.8x 10'4
7.11 x 10"3
8.13x 10"4
7.15x 10"4
3.84x 10~4
6.52x 10'4
5.39x 10"4
DDT & DDE Emission Rates — Prototype
Air
DDD
(gmAr)
1.27x 10~2
2.17x 10~3
9.32x 10~3
1 x 10'2
1.2x 10'2
8.32x 10"3
2.10x 10~3
3.76x 10'1
1.03x 10'1
1.36x 10'3
0.93x 10"3
.__.
5.2x 10'3
6.08x 10~3
l.lOx 10'3
Stream
DDE
(gmAr)
1.28xlO~2
1.87x 10"3
1. OSxlO'2
7. 17xlO"3
1.73x 10~2
3.76x 10'2
2.l7x 10~3
1.53x 10'1
1.39x 10'2
1.57xlO'3
3.36 x 10"3
..._
1.09x 10~2
2.22xlO'2
5.92x 10'3
Experiments
Scrubber
DDD
(gmAr)
4.56x 10"4
1.45xlO~4
2.26x 10"4
3.8x 10'3
9.42x 10"4
2.04x 10'3
3.57x 10'3
1.47x 10'3
6.36x 10'4
2.95x 10"4
2.25x ID"4
2.50x 10"4
3.18x 10~4
2.50x 10"4
2.10x 10"4
1.59x 10-4
DDE
(gmAr)
2.47x 10"3
1.41 x 10~3
2.63xlO'3
6.94x 10"3
2.33x 10'3
4.72x 10~3
6.82x 10~3
1.83
1.82x 10-3
2.73x 10'3
1.92x 10"3
2.96 x 10'3
2.87x 10'3
2.86x 10"3
2.78x 10'3
2.48x 10'3
Notes:
a. Analytical methods described in Appendix B.
b. Test conditions described in Section 4.1, pp. 9 and 10.
* Product Emission Rate = Product DDT Concentration x Product Production Rate.
Air Stream Emission Rate = Air Stream DDT Concentration x Air Stream Flow Rate.
Scrubber Emission Rate = Scrubber DDT Concentration x Scrubber Flow Rate.
-------
Table 15
DDT & COMBUSTION PRODUCTS - TOTAL EFFLUENT STREAMS EMISSION RATES
DDT & DDD & DDE
Prototype Experiments
DDT Feed Rate
(gm/hr)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Notes:
908
908
908
908
2270
2270
2270
2270
181.6
181.6
181.6
181.6
454
454
454
454
(Solid)
(Solid)
(Solid)
(Solid)
(Solid)
(Solid)
(Solid)
(Solid)
(Solution)
(Solution)
(Solution)
(Solution)
(Solution)
(Solution)
(Solution)
(Solution)
1.86x 10'2
6.27x 10"2
1.06x 10~2
0.34
6.5x 10"2
1.48x 10'2
2.92x TO'2
0.949
0.112
2.4x 10'2
8.84x 10;3
5.6x 10"3
rt
1.83x 10'2
1.16x 10'2
0.48x 10~2
DDT Emission Rate DDD Emission Rate
(gmAr)
4.126x 10~2
2.53x 10'3
1.31 x ID'2
1.41 x 1CT2
1.32x 10~2
l.OSx 10'2
5.8x 10~3
0.380
\— I
l.OSx 10"
7.98x 10
1.33x 10
5.84x 10
-3
-3
-3
-2
1.11 x 10
4.94x 10~3
DDE Emission Rate
(gm/hr)
1.84x 10
4.52 x 10
-2
-3
2.186 x ID'2
1.51 x 10~2
1.99x 10'2
4.28x 10~2
9.39x 10
1.99
1.71 x 10
1.06x 10
7.13x 10
-3
-2
-2
-3
1.414x 10
-2
2.56 x 10
8.94x 10'
-2
a. Analytical methods described in Appendix B.
b. Test conditions described in Section 4.1, pp. 9 and 10.
c. DDT feed rate is reported on an active ingredient basis, rather than the total formulation.
44
-------
Test
No.
I
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
DDT Feed
Rate
(gm/hr)
908
908
908
908
2270
2270
2270
2270
181.6
181,
181,
181.
454
454
454
454
Table 16
SUMMARY DDT COMBUSTION EXPERIMENTS
Prototype Experiments
Emission Rate for
Feed Total Effluents
Form (DDT& ODD & DDE)
igm/nr)
0.0783
0.0698
0.115
0.369
0.098
0.068
0.044
7.76
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solution
Solution
Solution
Solution
Solution
Solution
Solution
Solution
0.388
0.027
0.0141
0.033
0.086
0.0273
Eff. of
Destruction* %
99.981
99.983
99.980
99/96
99.995
99.997
99.998
99.66
99.79
99.986
99.993
99.993
99.982
99.994
Average 99.949%
Summary of test conditions displayed in Figure 3 which follows.
Notes:
a. Analytical methods described in Appendix B.
b. Test conditions described in Section 4.1, pp. 9 and 10.
c. DDT feed rate is reported on an active ingredient basis, rather than the total formulation.
* Efficiency of Destruction = DDT Feed Rate - (DDT + DDD + DDE) Emission Rate
DDT Feed Rate
45
-------
SLUDGE +
SOLID DDT
k.
FED ON FIRST
HEARTH (100%)
SLUDOE +
SOLUTION DDT
FED ON THIRD
HEARTH (100%)
FURNACE
1
PRODUCT
[ .0002%]
FURNACE
1
PRODUCT
[ .002%]
AIR _
' STREAM
/ 4
/ SCRUBBER
f [.0007%]
k 4 AB 76O°C fc f OO3%"
^ STREAM ^
* SCRUBBER
^ [.0003%]
V AIR p.
STREAM U
SCRUBBER
[.067 % ]
_ AD optRBr .. fc, r ooT^sT
/ STREAM U
/ 1
/ |
' SCRUBBER
XX [.002%]
fe. U . AB 760°C fc T ffQ7%
'" STREAM *•
v SCRUBBER
^ [.002%]
\ ADorr AIR *roo3%-
STREAM w
SCRUBBER
[.002%]
FIGURE 3
MASS BALANCE DDT COMBUSTION EXPERIMENTS
SHOWING EFFECT OF VARIOUS AFTERBURNER (AB) TEMPERATURES
FOR PROTOTYPE EXPERIMENTS
46
-------
On consideration of Column 5 of Table 16 in light of the above, the significantly
lower efficiency associated with tests 4 and 8 is striking. On the other hand,
the variations among tests 1, 2, 3, 5, 6 and 7 are much smaller and show
no definite trend. Clearly when solid DDT is mixed with sludge and fed on the
top hearth, the afterburner is essential (See Figure 3).
Ib further verify this conclusion, note that for the solution feed
experiments, the top two hearths of the furnace act as afterburners, since the
feed was on the third hearth. In these experiments, the effect of the afterburner
should be conspiciausly less than in the solid feed experiments. Comparison of
the efficiency factors in Column 5 of Table 16 for tests 9-16 with tests 1-3
and test 5-7 shews that, indeed, the presence or absence of the afterburner is
of markedly less significance in those experiments where the third hearth feed
was used.
4.6 Analytical Results on 2,4,5-T Experiments
The analysis of the 2,4,5-T content of the various samples taken
in tests 17-24 was accomplished by standard methods, as discussed in Appendix C.
Essentially, the active ingredient was extracted, cleaned up to remove inter-
fering substances, concentrated and subsequently analyzed by electron capture
detection with a gas chromatograph. The results of these analyses are displayed
in Table 17.
Again using the data from Table 7, Figure 1 and Table 17, we may
compute the discharge rates for 2,4,5-T in each of the emergent streams. The
results of these calculations are shown in Table 18 (carried out exactly as
for the prototype experiments).
4.7 Results of 2,4,5-T Experiments
If we again assume that the efficiency of destruction is given by
the expression:.
Feed rate - emission rate X 100
% Efficiency of destruction =
Feed rate
47
-------
Table
No.
17
18
19
20
21
22
23
24
EFFLUENT STREAMS - 2,4,5-T CONCENTRATIONS (gm/gm x 109= ppb)*
*»
00
Prototype Experiments
Water
(ppb)
4.9
0.32
0.071
0.124
0.131
0.388
0.206
0.132
Scrubber
Particulate
0.315
3.52
1.97
0.30
0.03
1.16
5.9
2.39
Total
5.22
3.84
2.04
0.42
0.16
1.55
6.11
2.52
Impinger
(Ppb)
0.268
0.034
0.23
0.009
0.038
0.322
0.225
sample
lost
Air Stream
Particulate
(Ppb)
0.73
0.126
0.44
0.28
0.015
0.29
0.252
0.04
Total
(ppb)
1.0
0.16
0.67
0.29
0.05
0.01
0.48
---
Product
(Ash)
(ppb)
0.432
19.54
49.50
35.80
15.93
65.0
44.8
8.2
*Tetrachlorodioxin not found in any sample.
-------
where the feed and emission rates are measured on the basis of the active
ingredient, 2,4,5-T, then we may compute the destruction efficiencies for
each test in Table 18. The results of these calculations are displayed
in Table 19 and Figure 4.
The results in Column 5 of Table 19 show a remarkable lack of
variation especially when it is noted that three different sets of
afterburner conditions are included as before. Recalling that in
tests 17-24, the injection of the active ingredient was through the
third hearth, it is again found that the first and second hearth serve
as afterburners, thus alleviating the need for the additional afterburner.
There was some concern about the possibility of producing tetra-
chlorcdioxin as a by-product of the co-incineration of 2,4,5-T with sewage
sludge. In no case in the present work has this compound been found even
at trace levels.
4.8 Summary of Prototype Experiments
The results of the prototype experiments are best summarized in
the following table.
DPP DESTRUCTION EFFICIENCY
Prototype Experiments
Preparation
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solid
Solution
Solution
Solution
Solution
Solution
Solution
Solution
Solution
*AB - Afterburner
NOTE: The feed ratios for the solid EOT experiments were actually .026
and .066 rather than .02 and .05.
49
Feed
Hearth
1st
1st
1st
1st
1st
1st
1st
1st
3rd
3rd
3rd
3rd
3rd
3rd
3rd
3rd
Feed
Ratio
(gm/gm)
0.02
0.02
0.02
0.02
0.05
0.05
0.05
0.05
0.02
0.02
0.02
0.02
0.05
0.05
0.05
0.05
Avg.
Hearth
Temp
(C°)
764
754
715
738
759
795
780
782
841
827
837
842
838
841
810
802
AB*
Temp
7c°T
733
738
900
182
733
716
800
221
672
716
983
204
705
727
830
182
%
Dest.
Eff.
7ir~
99.98
99.98
99.98
99.96
99.995
99.997
99.998
99.66
99.79
99.99
99.99
99.99
99.98
99.99
-------
2,4,5-T DESTRJCTION EFFICIENCY
Prototype Experiments
Feed Feed Hearth
Preparation Hearth Ratio Temp
(gm/gm) fC°)
Solution 3rd 0.02 792
Solution 3rd 0.02 809
Solution 3rd 0.02 781
Solution 3rd 0.02 749
Solution 3rd 0.05 774
Solution 3rd 0.05 793
Solution 3rd 0.05 780
Solution 3rd 0.05 784
*AB - Afterburner
AB*
Tenp
^/>i"OA
711
711
1005
216
694
727
1010
227
Dest.
Eff.
99.98
99.99
99.99
99.98
99.99
99.99
99.99
50
-------
Table 18
MASS BALANCE 2,4,5-T EXPERIMENTS*
Test
No.
17
18
19
20
21
22
23
24
Emission Rate
Air Stream
(gm/hr)
0.0026
0.00041
0.0017
0.0074
0.00013
0.0016
0.0012
Prototype Experiments
Emission Rate
Scrubber
(gm/hr)
0.024
0.017
0.009
0.019
0.001
0.007
0.028
0.014
Emission Rate
Product
(gm/hr)
5.8x 10"7
2.7x ID'5
6.7x 10-5
4.9x 10'3
2.1 x ID'5
8.8x ID'5
6.1 x ID'5
1.1 x 10-4
Total
Emission Rate
(gm/hr)
0.027
0.017
.0108
.0313
0.0011
0.0086
0.029
2,4,5-T
Feed Rate
(gm/hQ
183.0
183.0
183.0
183.0
454.0
454.0
454.0
454.0
* Air Stream Emission Rate = Air Stream Concentration x Air Stream Flow Rate.
Scrubber Emission Rate = Scrubber Concentration x Scrubber Flow Rate.
Product Emission Rate = Product Concentration x Product Production Rate.
2,4,5-T feed rate is reported on an acl-ive ingredient basis, rather than the total formulation.
51
-------
Test Feed Rate Feed Emission Rate Eff. of
No. (gm/hr) Form (gm/M Destruction*
Table 19
SUMMARY 2,4,5-T COMBUSTION EXPERIMENTS
2,4,5-T
Feed Rate
(gm/hr)
183.0
183.0
183.0
183.0
454.0
454.0
454.0
454.0
Prototype
Feed
Form
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Experiments
2,4,5-T
Emission Rate
(gm/hr)
0.027
0.017
.0108
.0313
0.0011
0.0086
0.029
—
17 183.0 Liquid 0.027 99.98
18 183.0 Liquid 0.017 99.99
19 183.0 Liquid .0108 99.99
20 183.0 Liquid -0313 99.93
21 454.0 Liquid 0.0011 99.99
22 454.0 Liquid 0.0086 99.99
23 454.0 Liquid 0.029 99.99
24
* Efficiency of Destruction = 2,4, 5-T Feed Rate - 2,4, 5-T Emission Rate
2,4, 5-T Feed Rate
Operating conditions summarized in diagramatic form in Figure 4.
2,4,5-T feed rate is reported on an active ingredient basis, rather than the total formulation.
52
-------
SLUDOE+
2, 4,6 -T SOLUTION
FED ON THIRD
HEARTH (100%)
FURNACE
PRODUCT
Q<.OOOI%]
[.001%]
\ SCRUBBER
\ [.008%]
\
\_
AB OFF
AIR fc r ooi^i
STREAM L J
SCRUBBER
[ .01 %]
FIGURE 4
MASS BALANCE 2,4,5-T COMBUSTION EXPERIMENTS
SHOWING EFFECT OF VARIOUS AFTERBURNER (AB) TEMPERATURES
FOR PROTOTYPE EXPERIMENTS
53
-------
4.9 Chloride Ion Measurements
The combustion products of a chlorinated hydrocarbon should
be water, carbon dioxide and hydrogen chloride if the combustion
is complete. Since DDT contains approximately 50 per cent chlorine,
one should expect the production of significant amounts of HC1
in these experiments. It was anticipated that using a closed
scrubber water system would make it possible to follow the com-
bustion process simply by observing the continuous increase in
chloride ion in the scrubber system. With this purpose in mind
additional scrubber samples were taken hourly during the two solid
DDT experiments for subsequent chloride ion analysis.
The results of these measurements were uniformly disappointing
in that though an increasing chloride ion concentration was
observed with time, there was no disoemable relationship between
the increase in chloride concentration and the amount of DDT
combusted. Several factors apparently enter into this result:
the nature of the scrubber system; the mechanics of evaporation
within the scrubber; the presence of contaminants in the scrubber
water; and the nature of chloride ion determination.
The chloride ion content of a closed system scrubber could be
expected to increase even without a source of HCl since it is
constantly necessary to make up the water lost due to evaporation.
In the actual scrubber system at Brisbane, there is apparently an
additional source of water loss probably associated with the
entrainment of water droplets in the emergent gas stream. This is
illustrated by comparing the make up rate to the loss rate
associated with the increase in absolute humidity of the emergent
54
-------
air. The observed rates of these quantities was found to vary
quite erratically during a typical furnace run. Since no provision
was made to determine the chloride ion content of these emergent
water droplets, no correction could be made for this loss.
An additional complication turned up in the form of a large
residue of iron within the scrubber solution — iron resulting
from corrosion of the reservoir and probably of the interior
structure of the scrubber. No attempt was made to clean the
scrubber system prior to the test burns. The effect of ferric
ions on the accuracy of electrochemical chloride ion measure-
ments is well known. In addition, the use of hydrosqrcjuinone as
a reducing agent in such cases is well documented. Unfortunately,
in the case in point, the addition of the hydro^quinone to the
scrubber samples resulted in the formation of a gel- like mass
(even in samples taken from the scrubber system prior to the pesti-
cide bums) which severely interfered with chloride ion measure-
ments.
In an attempt to analyze the chloride ion measurements in
the following manner by defining the several quantities as below:
't) = chloride ion concentration at time t in gm/gm
Co = chloride ion concentration at time t = o (gm/gm)
C. = chloride ion concentration of make up feed (gm/gm)
tyn = make up rate in (gm/min)
Mt = total mass of scrubber water in gm
t^ = initial fire up time
ti = time at which DDT feed began
Q = rate of injection of Cl~ ions due to DDT combustion
55
-------
then,
serves to relate the total chloride ion mass in the scrubber
system at time t to the various inputs. The actual values
of Cl~ concentration ranged from 500 ppm to over 1000 ppm.
Using the actual data taken on chloride ion concentration
along with the appropriate times, rates and masses, one can
assemble a set of three simultaneous equations, the solution
of which can presumable be found by conventional methods.
In point of fact, using the chloride ion concentrations
found, one can show that the equation set is indeterminate.
That is to say, only by adjusting the chloride concentration
by what appears to be a set of arbitrary constants can one
arrive at a solution to these equations. For this reason one
must conclude that the results are not especially useful for a
complex closed system such as that used at Brisbane.
56
-------
5.0 FULL SCALE EXPERIMENTS
As a result of the excellent results obtained in the prototype experi-
ments, it was agreed that it would be both safe and appropriate to attempt
a full-scale experiment in a typical municipal incinerator in order to
verify the prototype results. By the kind permission of Mr. Ronald N. Doty
and the City Council of Palo Alto, California, the Palo Alto incinerator
was made available for these experiments. The overall flow diagram of the
sewage sludge treatment plant is illustrated in Figure 5.
5.1 Furnace Operating Conditions
The configuration of the furnace used is similar to that shown
in Figure 1 (which will serve as reference in the following discussion) ex-
cept for its much larger size and capacity. Additionally, the scrubber is
a high energy venturi rather than the impingement type installed on the pi-
lot scale unit. The furnace interior is diagrammed in Figure 6. In order
to facilitate the extrapolation of the results of these experiments to other
such multiple hearth incinerators, it was decided to operate the furnace in
its normal mode using the permanent operational crew with minimal interfer-
ence in the regular operations. A summary of the actual furnace conditions
during the coincineration experiments is given in Tables 20 and 21 with the
same information in English units displayed in Tables 20-A and 21-A. Note
also that the oxygen content of the stack gases is given in Tables 20 and
21. As before, the existence of approximately 7-10 per cent residual oxygen
indicates that the system was operating with something in excess of 100 per
cent excess air. Tables 20 and 21 (20-A and 21-A) also indicate a delay of
1 hour after initiation of pesticide feed before sampling in order to allow
equilibrium to be established on the assumption of a residence time in the
furnace of 45 minutes.
57
-------
5.1.1 Pesticides and Feed Methods
Feeding DDT in both solid and solution preparations as well as
2,4,5-T in solution had been planned in order to verify all of the indi-
vidual tests conducted during the prototype experiments. As before, the
DDT was obtained from Sierra Base, but the drum of what purported to be
20 per cent DDT in kerosene was so questionable that it was feared that
*
it would be excessively dangerous to attempt to burn. Thus, only solid
DDT experiments were attempted. As before, the 2,4,5-T was in the form
•TV*
of the commercial weed control preparation Weedon .
* The contents of the drum were under pressure, produced HC1 fumes and
appeared red in color.
58
-------
FLOW DIAGRAM OF
PALO ALTO SEWAGE TREATMENT PLANT
AE3WTION 7XJKS
01
vo
o
tn
in
r'.i- Tit
Ash To
Refuse
Disposal
Area
i ?
I 3-
i i-™-- 1 3
I?-' sera
<'jj:rE r-=_ -, riai
~;i _ , K'JLDL i
1 ODS1TC (^
V ' T.f-s^ — {
? v 'f1 -'. '
r - il"
1 /C^,
t ^':i~ 1
it
PI^EC LTGTT)
Sludge
Scu-n
Air
F U T U R r
a—
1 ^"^
I1 — — —
5OJU LEX
r
1 !
^t
T
It
-)-+
\\
\ J
t!
I
^--^r
:T*
w:G
{SfXC'JS '
:."> 4
Cdoruie
FUtftL CLARIFISSS
-------
0
33
m
i'A'JST
i=FWJ
JUUl
JUJL
Liuuu
JUUL
lJUUL
LIUUU
UUUL
1
JUUL
UUUL
UUUL
UUUL
UUUL
'* s ** ' s"?r-?
\
.
T-
I1
-2.^;3T
J
\f
t
F^.. ]
VIA
-FCCOOLLR /
7
1 1 rs
u
C
•
I-
J rn
r
JL
; C3J3^-
~~W^
jsT ^
* f
•v^rj?AL C\S
t.
FIGURE . SCK. ATIC PMC ALTO L'NICIPAL
«M.TIPLE HEATTH *VfCffCE
-------
Time
Table 20
FURNACE OPERATING CONDITIONS
Municipal Sewage MHF Incinerator - Palo Alto, Calif.
Solid DDT Peed
Hearth Temperatures
I1
649
658
636
638
602
597
599
638
649
649
649
644
663
649
636
622
I2
705
713
705
705
682
649
644
677
711
711
705
705
705
719
711
711
I3
566
638
622
591
616
591
563
566
608
608
566
544
427
627
588
594
I4
811
844
797
786
791
791
791
788
802
794
794
794
794
802
794
794
!5
800
794
761
772
791
794
791
775
761
766
772
775
805
775
775
775
I6
288
274
269
288
330
344
346
327
274
211
310
310
371
383
344
349
Stack
91
91
88
93
121
93
93
93
88
88
93
99
99
93
88
88
7.5
6.5
9.0
9.0
8.0
9.0
6.5
10.0
10.0
10.0
Notes
Initial feed begun
Sample #1
Sample #2
Increase feed
\2100
Sample #3 /2138
Sample #4
Stop feed
There is no afterburner temperature indicated since the top hearth, region serves as afterburner.
Addenda
Sludge feed - 635 #/hr/dry
DDT feed rates
Feed ratios
1400 - 1800
1800 - 2300
6.92 x
1.64 x
10. gms/hr
10 gms/hr
1400 -
1800 -
1800
2300
/DDT feed rate \
\Solids feed rate/
2 per cent
4.8 per cent
-------
Table 20-A
FURNACE OPERATING CONDITIONS
Municipal Sewage MHF Incinerator - Palo Alto, Calif.
Solid DDT Feed
a\
Time
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
T
(°c)
1200
1215
1175
1180
1115
1105
1110
1180
1200
1200
1200
1190
1225
1200
1175
1150
T
o
(°c)
1300
1315
1300
1300
1260
1200
1190
1250
1310
1310
1300
1300
1300
1325
1310
1310
T
(°c)
1050
1180
1150
1095
1140
1095
1045
1050
1125
1125
1050
1010
800
1160
1090
1100
T
(°C)
1490
1550
1465
1445
1455
1455
1455
1450
1475
1460
1460
1460
1460
1475
1460
1460
T
(°C)
1470
1460
1400
1420
1455
1460
1455
1425
1400
1410
1420
1425
1480
1425
1425
1425
T
(°O
550
525
515
550
625
650
655
620
525
530
590
590
700
720
650
660
T
Stack
(°c)
195
195
190
200
250
200
200
200
190
190
200
210
210
200
190
190
UlXAlrfJN.
Gas
%02
7.5
6.75
9.5
7.5
6.5
9.0
9.0
8.0
9.0
6.5
10.0
10.0
10.0
Notes
Initial feed begun
@
Sample il
Sample #2
Increase feed
Sample #3
Sample #4
Stop feed
Addenda
Sludge feed - 635 #/hr/dry
DDT feed rates
1400 - 1800
1800 - 2300
6.92 x 10^ gms/hr
1.64 x 10 gns/hr
/ DDT feed rate \
Feed ratios \Solids feed rate/
1400 - 1800 2 per cent
1800 - 2300 4.8 per cent
-------
Time
U)
Table 21
FURNACE OPERATING CONDITIONS
Municipal Sewage MHF Incinerator - Palo Alto, Calif.
2,4,5-T Liquid Injection
Hearth Temperatures
I1
616
677
733
677
655
730
666
644
663
644
672
655
655
663
!2
649
705
727
755
674
730
761
755
761
761
766
772
761
775
I3
572
733
716
636
602
927
905
738
733
775
802
811
811
844
T4
858
900
827
905
894
872
905
914
942
942
955
916
914
905
!5
838
827
761
872
866
866
844
844
850
844
844
838
838
838
>
358
368
266
352
368
458
277
249
238
246
238
249
249
249
1800
1900
2000
2100
2200
2300
2400
Refer to Figure 1 for identification of temperatures/hearth.
Addenda
Sludge feed - II hr (dry)
2,4,5-T feed rates
1300 - 1700
1700 - 2100
1.108 x 107 gm/hr
3.45 x 10J grn/hr
Stack
88
88
88
88
88
232
82
82
82
82
82
82
82
82
10.0
Notes
Feed begun on 3rd hearth
Sairple #9
Sample #10
Feed changed to 5/100g
sludge
Sample #11
Sample #12
Feed stopped
Feed ratios /2,4,5-T feed rate\
Feed ratios ^sludge feed rate )
1300 - 1700
1700 - 2100
0.3 per cent
1.1 per cent
-------
Table 21-A
FURNACE OPERATING C30NDITIONS
Municipal Sewage MHF Incinerator - Palo Alto, Calif.
2,4,5-T Liquid Injection
Hearth Temperatures
T
T
Tims
T
Stack
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
1140
1250
1350
1250
1210
1345
1230
1190
1225
1190
1240
1210
1210
1225
1200
1300
1340
1390
1245
1345
1400
1390
1400
1400
1410
1420
1400
1425
1060
1350
1320
1175
1115
1700
1660
1360
1350
1425
1475
1490
1490
1550
1575
1650
1520
1660
1640
1600
1660
1675
1725
1725
1750
1680
1675
1660
1540
1520
1400
1600
1590
1590
1550
1550
1560
1550
1550
1540
1540
1540
675
695
510
665
695
855
530
480
460
475
460
480
480
480
190
190
190
190
190
450
180
180
180
180
180
180
180
180
9.5
12
6.0
8.8
10
6.0
8.0
8.0
7.5
9.5
8.0
8.5
9.5
10.0
Notes
Feed begun on 3rd hearth
Sample #9
Sample #10
Peed changed to 5/100g
sludge
Sample #11
Sample #12
Peed stopped
Addenda
Sludge feed - #1 hr (dry)
2,4,5-T feed rates
1300 - 1700
1700 - 2100
1.108 x 10, gm/hr
3.45 x 10 gm/hr
Feed ratios
1300 - 1700
1700 - 2100
/2,4,
\Slud
5-T feed ratej
LSludge feed rate /
0.3 per cent
1.1 per cent
-------
The DDT feed was accotplished by a hopper arrangement placed
over the screw-feed mechanism used to conduct the de-watered
sludge from the centrifuge to the top hearth of the furnace.
The mechanical properties of the powdered DDT preparation used
were such that the simple gravity feed device was not particu-
larly satisfactory; one might elect to go to a more'elaborate
vibratory feed system in practice. The feed device used did not
effect a constant feed rate, which was less serious than might
be supposed. The sludge feed was found to vary from a low on
the order of 430 kg/hr (950 Ib/hr) to a high on the order of
488 kg/hr (1075 Ib/hr) on a dry basis with a 24 hour average of
454 kg/hr (1000 Ib/hr). This variation seems to be due to
variations in the wet sludge feed to the centrifugal pump and
to variations in the water content of the sludge fed to the
furnace. The DDT preparation was fed at an average rate of
9.2 kg/hr (20.2 Ib/hr) over the initial period (1400 to 1900 -
see Table 20) cotputed on the basis that a total of 50 kg (109 Ibs)
of the preparation was fed during the second 5 hour interval.
These feed rat yield a pesticide preparation to sludge ratio of .02
during the initial period and .05 during the final period. The air
sampling procedure used was such that sampling was accomplished over
elapsed times ranging from a minimum of 24 minutes to a maximum of 44
minutes.
The Palo Alto furnace is equipped with a scum line feeding the
third hearth. The injection of 2,4,5-T solution was accomplished by
feeding the metered solution by gravity feed into the scum flew outside
the furnace. Variations in sludge fed to the top
65
-------
hearth occurred in addition to the variation in the scum feed (not actually
measured, but averaged out to about 20 kg/hr. (44 lb/hr.). Thus, the 2,4,5-T
feed ratio is an average over the test period. The 2,4,5-T preparation was fed
at an average rate of 5.5 kg/hr (12.1 lb/hr) over the initial period [1300 to
1700 - See Table 21] and 17.2 kg/hr (38 lb/hr) over the final period [1700 - 2100 -
See Table 21]. These feed rates yield a pesticide preparation to sludge ratio
of .012 during the initial period and .038 during the final period. The lack of
precision in the feeding mechanism prevented matching exactly the feed ratios used
during the pilot experiments (.02 and .05).
5.2 Gas Stream Sampling
The emergent (stack) gas stream was sampled by methods
exactly similar to those described in Section 4.2 using a seven point
traverse. The impinger solution was hexane for the DDT experiments
and ethylene glycol for the 2,4,5-T experiments. The instrumental
data (after being converted to MRS units) is displayed in Table 22
and the calculated data (see Appendix A) is displayed in Table 22. Appendix
E describes the sampling procedures in detail.
At the end of each gas sampling run, a 1-liter sample of the
scrubber water and 100 gram samples of the product were taken from
the sixth hearth. In addition, composite sludge samples were made
up during each experimental series.
5.3 Analytical Methods and Results of DDT and Products
The collected samples were analyzed for DDT as well as for DDD
and DDE by the methods outlined in Section 4.4 and Appendix B. The
results of these analyses are displayed in Tables 23 through 31 and
summarized in Table 32.
66
-------
5.4 Results of DDT Combustion Experiments
Using the results for the total rate of emission of DDT and its
two principal combustion products from Table 32, the percentage of
destruction may be computed as before. The results of such a calculation
are displayed in Table 33.
Note that, in general, the largest portion of the effluent DDT
and its products is found in the scrubber stream. A realistic analysis
of the plant situation would show that this stream, the scrubber outflow,
is reintroduced into the plant to be recycled. Thus, the combustion
efficiencies shown in Table 33 are somewhat conservative.
The major exception to the above is found in the relatively higher
concentrations of DDE found in the emergent air stream in experiments
3 and 4 (Table 32). Although not immediately obvious, there was a
marked reduction in the temperature of the third hearth during the
sampling interval when sample 3 was taken. From Table 20 we note
that the average temperature of the third hearth was perhaps 590 C
during the period of samples 1 and 2, but fell to less than 430 C
during sampling period 3 (specifically at 2100 hours).
67
-------
Ol
00
Table 22
GAS SAMPLING DATA*
Palo Alto Experiments
Collect Meter Vstnd
Time Vol. TStack Ap P Stack AH Vs Sample Qs
Sample (sec) (m^) (°C) (mrnh^O) (cm Hg) (mmH2O) (m/min) (m^) (nrP/hr)
1
2
3
4
9
10
11
12
2160
2640
2280
1860
1620
1440
2400
2440
0.586
0.535
0.554
0.575
0.703
0.498
0.950
0.799
93.4
93.4
93.4
93.4
93.4
93.4
93.4
93.4
15.2
11.94
16.5
19.56
33.0
30.2
37.3
36.8
75.98
75.98
75.98
75.98
75.95
75.95
75.95
75.95
28.4
22.1
31.0
37.8
60.96
52.58
66.8
67.3
685.8
609.1
704.1
777.2
1067
1013.5
1167.4
1150.6
0.551
0.493
0.513
0.527
0.661
0.459
0.868
0.728
2999.7
2666.4
3079.7
3399.4
4667.1
4433.0
5106.2
5032.7
*See Appendix A where these parameters are defined as are the appropriate calculations. For Samples
1-4 the solid DDT preparation was fed on 1st hearth and for samples 9-12 the 2,4,5-T solution was
fed on 3rd hearth.
-------
Table 23
DDT CONCENTRATIONS/PRODUCTION IN STACK GASES
SAMPLE
Test
No.
1
2
3
4
IMPINGFR
DDT DDT
o-p1 p-p1
(gm) (gm)
5.62xlO"7 1.77X10"6 2.
5.4xlO"7 1.32x10"° 1.
2.8x10"° 5.2 xlO"6 8.
7.2 xlO"7 9.4xlO"7 1.
Notes: a. Analytical
Palo Alto Experiments
PARTICUIATF
DDT
Total
(gm)
3 x 10'6
86 x 10"6
0 x 10"6
66 x 10"°
DDT
o-p1
(gm)
5.8x 10"8
2.2x 10"7
5.6x 10"°
7.5x 10"7
DDT
P-P1
3 x 10"7
8.5 x 10"7
6.0 x 10"°
9.7x 10"7
DDT
Total
(gm)
3.6x 10"7
1.07x10"°
11.6x10-°
1.72x 10'°
DDT
TOTAL
(gm)
2.7x 10"°
2.9x 10"°
19.6x10"°
3.4x10"°
Stack
Sample
(m3)
0.533
0.495
0.515
0.529
DDT
Cone.
gm/m
5.07x ID'6
5.8x10"°
38.1 x 10"°
6.4 x 10"6
Stack
Flow
(m3/hr)
2979
2649
3058
3377
Emission
Rate
(DDT)
(gm/hr)
0.015
0.0154
0.116
0.022
methods described in Appendix C.
b. Test conditions described in Section
a\
\o
5.2, pp 48, 53.
Table 24
DDD CONCENTRATIONS/PRODUCTION IN STACK GASES
Polo Alto Experiments
Test
No.
1
2
3
4
IMPINGER
DDD DDD
o-p1 p-p1
(gm) (gm)
6.2 xlO"8 1.8xlO"7 2
3xlO-10 9xlO"10 1
l.lxlO"7 1. 03x10-° 1
9.1xlO"8 8.7 xlO'8 1
SAMPLE
DDD
Total
.4x 10"7
.2x 10"9
.14x 10"6
.8x ID'7
DDD
o-p1
(gm)
4.14x 10"7
2.3x 10'7
3.9x 10'8
1.95x 10'°
PARTICULATE
DDD
P-P1
(gm)
1.7x 10"8
4 x 10"9
5.2x 10'8
1.34x 10~°
DDD
Total
(gm)
5.9x 10"8
2.3x 10"7
9. 1 x 10'8
3.29x10"°
DDD
TOTAL
(gm)
2.99x 10"7
2.3 x 10"7
1.24xlO"7
3.47xlO"7
Stack
Sample
(rn3)
0.533
0.495
0.515
0.529
DDD
Cone.
gm/m'*
.56x 10"6
.46 x 10"°
.24x 1Q-6
.66x10-°
Stack
Flow
(m3/hr)
2979
2649
3058
3377
Emission
Rate
(DDD)
(gm/hr)
0.0017
0.0012
0.0007
0.002
Notes: a. Analytical methods described in Appendix C.
b. Test conditions described in Section 5.2, pp 48, 53.
-------
Table 25
DDE CONCENTRATIONS/PRODUCTION IN STACK GASES
SAMPLE
Test
No.
o
1
2
3
4
DDE
o-p1
(gm)
7. Ox 10"6
13. 8 x 10"6
74. 7 x 10"6
42 x ID"6
Notes:
IMPINGER
DDE
P-P'
(gm)
16. 6 x 10"6
43 7 x 10"6
90 x 10"6
105 x 10'6
a. Analytical
Palo Alto Experiments
PARTICULATE
DDE
Total
(gm)
23. 6 x 10~°
57. 5 x 10'6
164 x 10-°
147 x 10'6
methods described
DDE
o-p1
(gm)
2.5x 10"7
1 26 x 10"6
173 x 10~6
6 3 x 10'6
in Appendix C .
DDE
P-P'
(gm)
4.42x 10"7
4.63x 10"6
61 x 10~6
34 x 10'°
DDE
Total
(gm)
6.9x 10"7
5.9x 10"6
235 x 10"6
40. 3 x 10~°
DDE
TOTAL
(gm)
24. 3 x 10'6
63. 4 x 10"6
399 x 10"6
187 x 10'6
Stack
Sample
(m3)
0.533
0.495
0.515
0.529
DDE
Cone
gm/m^
45. 6 x 10'6
128xlO~*
773 x 10~6
353 x 10"6
Stack
Flaw
(m3/hr)
2979
2649
3058
3377
Emission
Rate
(DDE)
(gm/hr)
0.14
0.339
2 360
1.192
b. Test conditions described in Section 5.2, pp 48, 53.
-------
Table 26
DDT CONCENTRATIONS/EMISSION RATE IN PRODUCT
Palo Alto Experiments
Test
No.
1
2
3
4
o-p'
DDT
(gm/gm)
5.1 x 10"9
3.3x 10'9
1.38x 1(T8
5.3 x 10~9
P-P1
DDT
(gm/gm)
1.01 x 1(T8
7.4x 10-9
4. Ox ID'8
1.14x ID'8
Total
DDT
(gm/gm)
1.5x 10~8
1.07x TO'8
5.38x ID'8
1.67x 10'8
Product (Ash)
Production Rate
(gm/hr)
8.9x 104
8.9x 104
8.9x 104
8.9x 104
DDT*
Emission Rate
(gm/hr)
1.34x 10"3
0.98x 10~3
4.81 x ID"3
1.51 x 10'3
DDT
Feed Rate
(gm/hr)
6.92x 103
6.92x 103
1.635x 104
1.635 x 104
* DDT Emission Rate in Product = DDT Concentration in Product x P roduct P reduction Rate.
DDT feed rate- is scpoirc-d on un active inyietiisnJ !.>-jib, I'jfiici |-|,an i!ic :orci f
-------
10
1
2
3
4
o-p'
DDD
(gm/gm)
1.8x 10~9
1.2 x 10'8
1.07xlO'8
2.7x ID'9
Table 27
DDD CONCENTRATIONS/EMISSION RATE IN PRODUCT
p-p1
DDD
(gm/gm)
0.8x ID'9
1.9x ID'9
2.3x ID'9
3.1 x 10-9
Palo Alto Experiments
Total Product (Ash)
DDD Production
(gm/gm) (gm/hr)
2.6xlO"9 8.9xl04
1.39X10'8 8.9xl04
l.SOxlO-8 8.9xl04
5.8x10-9 8.9xl04
DDD
Emission Rate
(gm/hr)
0.27x 10'3
1.25x ID'3
1.16x 10'3
0.52x 10"3
DDT Fuec! ioro is .eported on an active ingredient basis, lathe,- than the total foimulal
DDT
Feed Rate
(gm/hr)
6.92x 103
6.92x 103
1.64x 104
1.64x TO4
ion.
-------
-j
u>
1
2
3
4
o-p
DDE
(gm/gm)
5 x 10"9
3 x 10'9
5 x 10'°
1 x 10"9
Table 28
DDE CONCENTRATIONS/EMISSION RATE IN PRODUCT (ASH)
p-p1
DDE
(gm/gm)
7 x 10'9
1.99x 10~6
2.55x 1(T7
1 x TO'9
Palo Alto
Total
DDE
(gm/gm)
1.2x 10"8
1.99x 10~6
3. Ox 10~7
2 x 10~9
Experiments
Product (Ash)
Production
(gmAr)
8.9x 104
8.9x 104
8.9x 104
8.9x 104
DDT
Emission Rate
(gmAr)
1.07x 10'3
1.77x 10'3
26. 7 x ID'3
0.18x ID'3
DDT
Feed Rate
gm/hr
6.92x 103
6.92x 103
1.64x 104
1.64x 104
a. DDT feed rate ib reported on an active ingredient basis, lather than t!ic total formulation.
-------
Table 29
DDT CONCENTRATIONS/PRODUCTION IN SCRUBBER
Test
No.
1
2
3
4
o-p'
(gm/l)
2.6x 10"6
1.2x IO"7
8x IO"9
4.8x IO"9
Notes:
SOLUTION
P-P'
(gm/l)
6.1 xlO"7
3 x 10"7
5.7 x^O-7
1.03x 10"7
SAMPLE
Total
(gm/l)
1.16x IO"6
4.2x IO"7
6.5x IO"7
1 . 1 x IO"7
Palo Alto Experiments
o-p'
(gm/l)
2.7x IO"8
7.6x 10'8
1.3x IO"7
1.28x 10"*
PARTICULATE
P-P'
(gm/l)
7. 1 x IO"8
4.2x ID'7
1 3x 10"7
4.9x IO"6
Total
(gm/l)
1 2 x IO"7
5 x 10"7
2.2xlO"7
6.2x IO"6
TOTAL
1.27x 10~°
9.1 x
2.9x
6.3 x
lO"7
10"7
10"6
Scrubber
Flow
(l/hr)
7.5 x
7.5 x
7.5 x
7 5x
IO4
IO4
IO4
IO4
Emission Rate
DDT
(gmAr)
0.105
0.068
0 022
0 47
b. Test conditions described in Section 5.2, pp. 53.
Table 30
ODD CONCENTRATIONS/PRODUCTION IN SCRUBBER
Test
No.
1
2
3
4
o-p1
(gm/l)
7.1 x IO"7
6.1xlO'7
3 x 10"7
1.9xlO'7
Notes:
SOLUTION
P-P'
(gm/l)
1.02x 10"6
1.1 x 10'7
2.7xlO"8
9 x 10"9
SAMPLE
Total
(gm/l)
1.7x 10'6
7.2x IO"7
3.3xlO"7
2 x IO"7
Palo Alto Experiments
3.
2.
5.
2.
o-p1
(gm/l)
5 x 10"8
2 x IO"7
9 x 10'8
9 x 10"8
PARTICULATE
P-P'
(gm/l)
3.5x IO-8
2.3x 10"7
1.2x IO"7
3.3x IO"7
Total
(gm/l)
7.0 x IO"8
4.5xlO"7
1.8xlO"7
3.6xlO"7
TOTAL
(gm/l)
1.79x 10"6
1.17x IO"6
5.05xlO"7
5.6x IO"7
Scrubber
Flow
(l/hr)
7.5 x
7.5 x
7.5 x
7.5x
IO4
IO4
IO4
IO4
Emission Rate
DDD
(gm/hr)
0.134
0.087
0.038
0 042
a. Analytical methods described in Appendix C..
b. Test conditions described in Section 5.2, pp. 53.
-------
m
Table 31
DDE CONCENTRATIONS/PRODUCTION IN SCRUBBER
Test
No.
1
2
3
4
o-p'
WO
3.8x 10"7
8.6x 10"7
4.4 x 10'7
5.4 x 10"7
Notes:
SOLUTION
P-P1
(gm/i)
8.1 x 10'6
1.01 x 10"6
4.8x 10"7
5.6 x 10"7
SAMPLE
Total
(gm/l)
8.4 x 10"6
1.87x 10"6
9.2x 10"7
6 x 1
-------
Test
No.
1
2
3
4
DDT
Feed
qm/hr
6.92x10;
6.92x 10
1.64xl0
1.64xl0
Table 33
EFFICIENCY OF DESTRUCTION (DDT)
Palo Alto Experiments
Emission Rate
Total Effluent
(DDT + ODD + DDE)
am/hr
1.63
1.71
3.78
2.83
Efficiency
of
Destruction*
99.970
99.975
99.977
99.983
*% Efficiency of Destruction =
Feed Rate - (DDT + ODD + DDE) Emission Rate x 100
DDT Feed Rate
- DDT feed rote is iepo:tod on on active ingrec'.e,,, basis, rather than the ratal Formulation.
76
-------
One further observation can be made from the data in the last column
of Table 32. In spite of the excessive excursion in the third hearth temperature
mentioned above, we note that the average value for the total effluents as given
for test numbers 3 and 4 is less than twice that for the average of that for
test numbers 1 and 2. This result suggests that the factors responsible for the
incomplete reduction of the input DDT are not seriously affected by the feed ratio
at least up to a ratio of 5 grams of DDT per 100 grams of sludge.
5.5 Analytical Results of 2,4,5-T Experiments
As indicated above, 2,4,5-T solution injection was accomplished by
mixing the pesticide solution into the scum feed line outside of the furnace. As
before, samples were taken of the scrubber water, the exhaust air stream, the
ash and the mixed scum/2,4,5-T solution. Analysis was accomplished by the
methods outlined in Appendix C with results that are displayed in Tables 34 and
35. Here, as before, spot checks made to determine the presence of dioxin yielded
negative results. In addition to the data in Tables 34 and 35, several typical
chronatograms are included in Appendix C.
5.6 Results of 2,4,5-T Experiments
Using the results of the analyses, the efficiency of destruction
shewn in these experiments can be computed. Using the feed data as well as the
summarized analytical results, 99.99 + destruction percentages were found as
displayed in the last column of Table 36.
As for the DDT results, the principal source of throughput of
2,4,5-T seems to be in the scrubber. Since, in practice the scrubber effluent
is returned to the plant for recycling, there is every reason to believe that
the efficiency values shown in Table 36 are conservative. It is also reassuring
to note that the efficiency of destruction does not seem to be affected by the
observed feed rate.
77
-------
Table 34
2,4,5-T CONCENTRATIONS VARIOUS EFFLUENT STREAMS
Palo Alto Experiments
Test No.
9
10
11
12
Particulate
(g/i)
1.28x 10"8
6.5 x 10-9
2.9x 10
1 . 1 1 x lO'7
SCRUBBER
Solution
(g/i)
1.31 x 10"6
1.47x 10"6
1.6x 10~6
4.74x 10-°
AIR STREAM
Total
(g/0
1.33x 10-j?
1.47x 10~6
1.63 x 10'°
4.85 x 10-°
Particulate
(g/t)
1.5x 10"9
9.8x ID'9
7. Ox 10'10
3.56x 10~7
Solution
(g/i)
1.88x 10~7
9. 11 x ID'8
5.89x 10~7
4.74x 10-7
Total
(g/i)
1.89x 10"7
l.Ox 1Q-7
5.9x 10~7
8.30x 10~7
Product (Ash)
(g/l)
6. Ox ID'10
3.5x TO'9
1.1 x ID'9
7.0 x 10'10
•J
oo
-------
Test
No.
9
10
11
12
•sj
VO
Table 35
MASS BALANCE 2f 4, 5-T EXPERIMENTS*
Palo Alto Experiments
Emission Rate
2,4,5-T in
Air Stream
(gm/hr)
1.33x 10~3
9.66x 10"4
3.47x 10'3
5.74x 10"3
Emission Rate
2,4,5-T in
Scrubber
(gm/hr)
9.98x 10"2
l.lOx 10"1
1.22x TO'1
3.6x 10"1
Emission Rate
2,4,5-T in
Product
(gm/hr)
5.34x 10~5
3.1 x 10'4
9.8x 10~5
6.2x 10~5
Total
Emission Rate
All Effluents
(gm/hr)
0.102
0.111
0.126
0.366
Input
2,4,5-T
Feed Rate
(gm/hr)
1.108x 103 gm/hr
1.108x 103 gm/hr
3.450x 103grr/hr
3.450x 103 gm/hr
*Tetrachlordioxin was not found in any sample.
2,4,5-T feed rate is reported on an active ingredient basis, rather than the total formulation.
-------
00
o
Table 36
SUMMARY 2, 4, 5-T EXPERIMENTS
Palo Alto Experiments
Total
Emission Rate
2, 4, 5-T 2, 4, 5-T in
Test Feed Rate Feed Exhaust Streams Efficiency
No. (gm/hr) Form (gm/hr) of Destruction* (%)
9 1.108xl03 Solution 0.102 99.991
10 l.lOSxlO3 Solution 0.111 99.990
11 3.45xl03 Solution 0.126 99.996
12 3.45xl03 Solution 0.366 99.990
Average 99.992%
*Efficiency of Destruction = 1, 4, 5-T Feed Rate- 1, 4, 5-T Emission Rate ^
2, 4, 5-T Feed Rate
2/4,5-T feed rate is reported on on active ingredient basis, rather than the total formulation.
-------
5.7 Suntnary of Full Scale Experiments
DDT DESTRUCTION EFFICIENCY
Full Scale Experiments
Preparation
Solid
Solid
Solid
Solid
Feed
Hearth
1st
1st
1st
1st
.Reed
Ifetio
(gm/gm)
0.02
0.02
0.05
0.05
Avg.
Hearth
Temp
629
634
628
659
AB*
Temp
638
649
663
649
Dest.
Eff.
(%)
99.97
99.98
99.98
99.98
*AB - Afterburner
2,4,5-T DESTRUCTION EFFICIENCY
Full Scale Experiments
Preparation
Solution
Solution
Solution
Solution
*AB - Afterburner
Feed
Hearth
3rd
3rd
3rd
3rd
Avg.
Hearth AB*
Temp Temp
700 677
677 655
691 644
698 663
81
-------
5.8 References
(1) "Mechanical Engineer's Handbook", T. Baumeister, Ed.,
McGraw Hill, 1958 pp. 4-69.
(2) "Handbook of Chemistry and Physics", Chem. Rubber Pub.
Co., 13th Edition pp 1396 ff., 1947.
82
-------
6.0 POSSIBIE APPLICATION OF MULTIPLE HEARTH OOPJCINERaTICN OF PESTICIDES
6.1 Furnace and Feed Conditions Required
In order to put the work reported above into the proper context
it is important to demonstrate the probable utility of this method of the
destruction of refractory organic compounds by coincineration with sewage sludge.
The results reported above suggest that such compounds as DDT and 2,4,5-T are
effectively destroyed, and that the total of toxic effluents from the process is
well below tolerance levels,provided that the appropriate furnace conditions are
met. To briefly review the conditions under which such effects have been ob-
tained, the following range of furnace operational parameters appear to offer
effective destruction:
1. Afterburner should be operated at a temperature not below 650 C
(1200 F) with the normal dwell time on the order of a few
hundred milliseconds. When the feed is introduced into the scum
port on the third hearth, the upper two hearths adequately serve
as afterburner and thus obviate the necessity of an auxiliary
afterburner. There is no evidence from this work suggesting that
afterburner temperatures higher than the normal range will serve
a useful purpose.
2• Individual mid^hearth temperatures- should not be allowed to drop
below 500 C (930 F), since there is some evidence to suggest the
formation of significant amounts of intermediate products such as
DDE from DDT under lower temperature conditions.
3. There is apparently no effect due to the ratio of pesticide feed
to sludge feed at least up to a maximum of 5 per cent by dry
weight.
4. An efficient scrubber system is mandatory, since there is evidence
of relatively large amounts of the pesticide and its intermediate
products being entrained in/or on the fly ash particles which are
effectively removed by the scrubber.
83
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5. There seems to be no significant differences noted between
the several options for the pesticide feed — either as
solution feed on the third hearth or as solid feed on the
first hearth. In spite of the observed fact that the destru-
ction ratio is the same for solid powder as for liquid prepara-
tion feed, there are practical considerations which strongly
suggest the latter as the most useful and least complicated feed
method. This topic will be discussed in some detail below.
6.2 Applicability of MHF Coincineration to Other Refractory Organic
Compounds
Although the detailed chemistry of the processes that evidently occur
in the furnace is by no means clear, it seems evident that the high efficiency
of destruction for DDT and for 2,4,5-T by this method allows the cautious extra-
polation that the method should be equally applicable to a wide variety of compounds
having similar structure to the test compounds. Thus, it would appear that similar
destruction ratios should be available for such compounds as:
a. The chlorinated (halogenated) biphenyls and related compounds,
which would include:
DDT Orthotian
DDD Tedion
DDE Tetradiphon
TDE DFDT (fluorine analog of DDT)
DFDT chlorobenside
Perthane chlorobenzilate
Rhothane Dilan
Mitox DCPC
Methoxychlor DJC
Ovotian Kelthane
Ovotox
Prolan
Balan
84
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b. Chlorinated cyclopentadienes, which would include:
Chlordane
Heptachlor
Aldrin
Dieldrin
Endrin
Endosulfor
Heptachlor epoxide
Lindane
c. Phenoxy and benzoic acid derivatives:
2,4,5-T
Amiben
2,4-D
4-(2,4-DB)
MCPA
Methoxone
Agrosone
Methoxone B
MCPP
polychlorcbenzoic acid
Silvex
trichlorobenzoic acid
In the absence of a detailed understanding of the chemical processes
involved in multiple hearth furnace coincineration of refractory organic compounds,
of course, it would be absolutely necessary to conduct tests quite similar to
those reported here in order to apply these conclusions to compounds other than
those actually studied. We can only say that a good probability appears to exist
for effective destruction of the above materials.
Unfortunately, the studies reported herein allow no reasonable extra-
polation as to the probability of a safe and effective destruction of the phosphorus
and the carbamate pesticides. Only appropriate studies similar to those reported
herein would allow such an extrapolation.
85
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6.3 Availability of Multiple Hearth Sewage Sludge Incineration
There are at present a large nuntoer of operating multiple hearth
furnaces widely distributed throughout the United States as is shown in Appendix D,
which is a partial listing of such installations.
6.4 Feed Arrangements for Large Scale Destruction of Tbxic Conpounds
As has been pointed out above (Section 5.2) considerable physical and
mechanical difficulty was experienced in feeding the powder preparation directly
into the sludge at the top hearth. It appears that the final centrifugal de-
watering is most conveniently accomplished in very close proximity of the actual
sludge feed line to the upper hearth so that the only available site for powder
injection would seem to be following the centrifuge. Necessity for control of
the finer particulates of the preparation, coupled with the inconvenience of the
process of transferring a solid preparation from its container to an appropriate
feed system, suggest that solid preparation injection is less practical than a
liquid feed method.
On the other hand, the use of a solvent increases disposal costs and
probably would require petroleum products. However, the accessibility of the
scum feed line and the ease with which provisions can be made for liquid (solution)
injection into the scum line suggests that this method of injection of hazardous
compounds is certainly the most reasonable from an operational viewpoint. For
those materials not already in solution, it would be necessary to prepare a
slurry or, if possible, a solution prior to their being injected into the furnace.
Control of the rate of injection should be reasonably simple for such solution or
slurries.
6.5 Safety Precautions
The required safety precautions for coincineration of hazardous materials
involve the protection of operating personnel, the protection of the facility it-
self and finally the control and monitoring of the various effluent streams to be
assured that the emissions are well within regulations.
Personnel protection can best be accomplished by utilizing an essentially
closed system. The incoming containers of hazardous materials would be handled by
normal industrial procedures for such materials as they are opened and connected
to the feed pump/metering system whereby the material is pumped into the scum line.
85
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Protection of the facility is best accorplished by the procedures of
handling the incoming material and by careful control of the operating conditions
within the furnace and its associated equipment. Even though HC1 is produced by
the combustion of chlorinated organic compounds, the rate of production is suffi-
ciently low, for the feed ratios studied herein, that no significant corrosion
problem should be encountered.
As has been demonstrated by this work, the feed ratios and the
furnace conditions reported result in emission of toxic or hazardous compounds
below acceptable levels. On the other hand, there is no absolute guarantee
that the furnace operations will always be controlled within the limits set by
these experiments. Under these conditions it would seem desirable to provide
for at least periodic sampling of the emergent streams from the furnace (especially
the stack gases) to be assured that the emissions are in fact within the required
limits.
The essential difficulty with the analysis of stack gases for trace
quantities of such compounds as the chlorinated pesticides or their possible de-
composition products lies in the fact that rather elaborate measures most be
taken in order to unambiguously determine the levels of such compounds. In view
of this requirement there seems to be no reasonable method of obtaining real
time control of the pesticide feed using the effluent level as input data.
As an alternative, we suggest that a feedback control system using
the hearth temperature of the upper four (4) hearths, the 02 content of the stack
gas and perhaps the afterburner temperature could be used to control pesticide feed.
In such a system, if any of the measured variables were to fall outside of pre-
determined limits, the system would automatically shut down the pesticide feed.
In order to implement such a system it would be necessary to conduct a study of
the effect of extreme excursions in hearth temperature and excess air in order
to determine the critical levels of such parameters. Although it was the original
intention of this study to carry out such an experiment, it was decided that the
dangers inherent in such an experiment were such as to require a great deal more
information prior to attempting such a parametric variation.
The previously mentioned increase in DDE production which correlates
to a dramatic downward excursion in third hearth temperature at Palo Alto, suggests
that DDE production might offer a safe and meaningful label for a study of extreme
conditions.
87
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7.0 DISCUSSION AND KEOM4ENDATIONS
The experimental results reported here seem to bear out the original
premise that the presence of burning sludge containing significant quantities
of metallic ions (iron) in an atmosphere containing excess oxygen should
cause the destruction of refractory organic compounds at temperatures con-
siderably lower than those required for simple burning of the organic compound
in oxygen. Further, the procedure can be implemented for the routine destruction
of large quantities of such pesticides as DDT with only minimal modifications being
required in the typical municipal plant. The state of the pesticide (solid or
solution) appears to make little difference in the effectiveness of multiple
hearth coincineration. A nuttber of incidental observations suggest, however,
that the solution feed is nore practical than the solid feed.
In order to feed a dry (solid) preparation into the furnace the preparation
must be pre-mixed into the sludge — a requirement which introduces a number of
practical problems. Sludge feed is ordinarily accomplished at the top hearth
of the furnace through a screw or belt feed which carries the dewatered sludge
from the centrifugal separators. Mixing the pesticide powder would probably have
to be accomplished in the physical space between the centrifuge and the furnace
input. This requires that the container be lifted to the furnace top and the
contents transferred to a suitable metering device in the somewhat restricted area
at the furnace top. This procedure was followed during the Palo Alto experiments
with results that were less than satisfactory, primarily because of the physical
properties of the DDT powder preparation. There seemed no reasonable way to
open the containers and transfer their contents to the metering device with-
out the escape of at least some of the finer dust.
Although DDT is not acutely toxic on inhalation, the exposure to DDT
dust over a period of some ten hours seemed to produce an irritation resembling
an upper respiratory infection — the irritation lasted some 24 to 36 hours.
This problem could, of course, be handled by providing the operational personnel
with suitable dust protection equipment, but such an approach can only
88
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aggravate the emotional problems of the operating personnel associated with
handling "dangerous materials". In this context, the reaction at Palo Alto of
the regular operating personnel is probably typical. It was necessary to
spend a considerable amount of tine explaining the nature of the experiment
and in a candid and quite detailed discussion of the potential hazards involved
in handling the DDT. In spite of what appeared to be an entirely satisfactory
response to this briefing, the presence of an inevitable white film in the
furnace top area due to the escaping dust caused considerable alarm. Thus for
a variety of reasons, both practical and psychological, it seems that the best
results will be obtained by using solution feed in the ooincineration of
pesticides.
Apparently it is quite routine for multiple hearth sewage sludge incin-
eration to be equipped with a scun injection system feeding the second or third
hearth. It is a simple matter to arrange to pump the solution to be destructed
from the furnace floor into the scum line to effect injection of the pesticide.
In this way, the handling of the material, the control of contamination and
the metering of the feed rate should be easily controlled and greatly simplified.
89
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8.0 CONCLUSIONS AND OBSERVATIONS
As a result of the experimental study on both prototype and full scale
multiple hearth sewage sludge furnaces, several results have been obtained.
1. Solid DDT mixed with sludge and subsequently fed on the top hearth
(normal sludge feed) shows destruction efficiencies in excess of
99 per cent in the absence of an afterburner. This result appears
to be independent of feed ratio up to 5 per cent of DDT preparation
per dry weight of sludge.
2. Solid DDT mixed with sludge and subsequently fed on the top hearth
shows destruction efficiencies in excess of 99.9 per cent, essentially
independent of the afterburner temperature provided the latter is at
least 760 C (1400 F) (these results obtained with afterburner residence
hold times on the order of 1 to 4 milliseconds) and independent of
feed ratio up to 5 per cent of preparation, per dry weight of sludge.
3. DDT solutions mixed with sludge and subsequently ted on the third
hearth through the scum feed line show destruction efficiencies in
excess of 99.9 per cent independent of feed ratio up to 5 per cent of
the preparation in sludge (dry) and independent of the afterburner
tenperature or afterburner holding time.
4. 2,4,5-T solutions mixed with sludge and subsequently fed on the third
hearth through the scum feed line show destruction efficiencies in
excess of 99.99 per cent independent of the feed ratio up to 5 per cent
of the preparation in sludge (dry) and independent of the afterburner
holding time and temperature.
5. The results quoted above are found to be conservative since the
destruction efficiencies have been found to be an order of magnitude
better in the full scale experiments than was the case for the
prototype scale experiments. This fact may well be attributed to the
artifacts introduced by the use of a partially recycled scrubber water
system in the prototype experiments.
90
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6. The observation that a significant fraction of the pesticide
(and its immediate derivatives in the case of DDT), appears in the
scrubber water (which, in practice, is returned to the plant
for recycling), indicates that the destruction efficiencies
reported here are quite conservative.
7. In general, the results obtained in the prototype experiments
at Brisbane adequately predicted the results obtained in the
full scale experiments at the Palo Alto municipal incinerator.
8. There is sane evidence (tests 3 and 4 at Palo Alto) that it is
important to maintain the internal hearth temperatures in
excess of 550-600 C (1000-1100 F) in order to minimize the
release of such products as DDE.
9. The results of this study indicate that under the proper
conditions DDT and 2,4,5-T can be safely destroyed by coincineration
with sewage sludge in a multiple hearth incinerator.
91
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APPENDIX A
DETERMPBCTICM OF PARTICULftTE EMISSIONS FEOM STATIONARY SOURCES
(Fran Standards of Performance for New Stationary
Sources, Federal Register vol. 36, no. 247)
93
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i. PRINCIPLE: AND APPLICABILITY.
1.1 Principle. Particulate matter is with-drawn isokinetically
from the source and its weight is determined gravimetrically after
removal of uncombined water.
1.2 Applicability. This method is applicable for the.determina-
tion of particulate emissions from stationary souces only when
specified by the test procedures for determining compliance with
New Source Performance Standards.
2. APPARATUS.
2.1 Sampling train. The design specifications of the particulate
sampling train used by EPA are described in APTD-0581. Commercial
models of this train are available.
2.1.1. Nozzle - Stainless steel with sharp, tapered leading edge.
2.1.2 Probe - Pyrex glass with a heating system capable of main-
taining a minimum gas temperature of 250°P. at the exit end during
sampling to prevent condensation from occuring. When length limit-
ations (greater than about 8 ft.) are encountered at temperatures
less than 600°F., Incoloy 825, or equivalent, may be used. Probes
for sampling gas streams at temperatures in excess of 600 F, must
have been approved by the Administrator.
2.1.3 Pitot tube - Type S, or equivalent, attached to probe to
monitor stack gas velocity.
2.1.4 Filter Holder - Pyrex glass with heating system capable of
maintaining minimum temperature of 225°F.
2.1.5 Impingers/Condenser - Four impingers connected in series
95
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with glass ball joint fittings. The first, third, and fourth im-
pingers are of the Greenburg-Smith design, modified by replacing
the tip with a .1/2 inch ID glass tube extending to one-half inch
from the bottom of the flask. The second impinger is of the
Greenburg-Smith design with the standard .tip* A condenser may be
used in place of the impingers provided that the moisture content
of the stack gas can still be determined.
2.1.6 Metering system - Vacuum gauge, leak-free pump, thermometers
capable of measuring temperature to within 5°P., dry gas meter
with 2% accuracy, and related equipment, or equivalent, as required
to maintain an isokinetic sampling rate and to determine sample
volume.
2.1.7 Barometer - To measure atmospheric pressure to _+ 0.1 inches
Hg.
2.2 Sample recovery.
'2.2.1 Probe brush - At least as long as probe.
2.2.2 Glass wash bottles - Two.
2.2.3 Glass sample storage containers.
2.2.4 Graduated cylinder - 250 ml.
2.3 Analysis
2.3.1 Glass weighing dishes.
2.3.2 Desiccator.
2.3.3 Analytical balance - To measure to _+ 0.1 mg.
2.3.4 Trip balance - 300 g. capacity to measure to _+ 0.05 g.
3. REAGENTS
3.1 Sampling.
3.1.1 Filters - Glass fiber or equivalent, numbered for identifi-
cation and preweighed.
96
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3.1.2 Silica gel - Indicating type, 6-16 mesh, dried at 175°C.
(350°P) for 2 hours.
3.1.3 Water.
3.1.4 Crushed ice.
3.2 Sample recovery.
3.2.1 Acetone - Reagent grade.
3.3. Analysis.
3.3.1 Water.
3.3.2 Desiccant - Drierite indicating.
4. PROCEDURE
4.1. Sampling.
4.1.1 After selo-cting the sampling site and the minimum number
of sampling points, determine the stack pressure, temperature,
moisture, and range of velocity head.
4.1.2 Preparation of collection train. Weigh to the nearest gram
approximately 200 g. of silica gel. Label a filter of proper dir.-
meter, disiccate for at lopst 24 hours and weigh to the nearesL
0.5 mg. in a room where the relative humidity is less than 50%.
Place 100 ml. of water in each of the first two impingers, leave
the third impinger empty, and place approximately 200 g. of pre-
wcighed silica gel in the fourth impinger. Set up the train with-
out the probe. Leak check the sampling train at the sampling site
by plugging \ p the inlet to the filter holder and pulling a 15 in.
Hg vacuum. A leakage rate not in excess of 0.02 c.f.m. at vacuum
of 15 in. Hg is acceptable. Attach the: probe and adjust the heater
to provioe a gas tenperature of tibout 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 temperature 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 dar.-
age to the cry gas meter from either moisture condensation or ex-
cessive heat.
4.1.3 Particulate train operation. For each run, record the date
required on the example sheet shown in Figure 5-2. Take readings
97
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at each sampling point, at least every 5 minutes, and when signifi-
cant changes in stack conditions necessitate additional adjustments
in flow rate. To begin sampling, position the nozzle at the first
traverse point with the tip pointing directly into the gas stream.
Immediately start the pump and adjust the flow to isokinetic con-
ditions. Sample for at least 5 minutes at .each traverse point;
sampling time must be the same for each point. Maintain isokine-
tic sampling throughout the sampling period. Nomographs are avail-
able which aid in the rapid adjustment of the sampling rate with-
out 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 sample recovery process
described in section 4.2
4.2 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. Measure the volume of water from the first
three impinaers,then discard. Place the samples in containers as
follows:
Container No. 1. Remove the filter from its holder, place in
this container, and seal.
Container Mo. 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 pol-
iceman to lose adhering particles.
Container No. 3. Transfer the silica gel from the fourth im-
pinger to the original container and seal. Use a rubber policeman
as an aid in removing silica gel from the impinger.
4.3 Analysis. Record the data required on the example sheet shown
98
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in Figure 5-3. Handle each sample container as follows:
Container No. 1. Transfer the filter and any loose particu-
late 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.
Container No. 2. Transfer the acetone washings to a tared
beaker and evaporate to dryness at ambient temperature and press-
ure. Desiccate and dry to a constant weight. Report results to
the nearest 0.5 mg.
Container No. 3. Weigh the spent silica gel and report to
the nearest gram.
5. CALIBRATION
Use methods and equipment which have been approved by the Admin-
istrator to calibrate the orifice meter, pitot tube, dry gas meter
and probe heater. Recalibrate after each test series.
6. CALCULATIONS
6.1 Average dry gas meter temperature and average orifice pres-
sure drop. See data sheet (Figure 5-2).
6.2 Dry gas volume. Correct the sample volume measured by the
dry gas meter to standard conditions (70°F. 29.92 inches Hg) by
using Equation 5-1
Vmstd - Vm
99
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LOCATION
OPERATOR^
DATE
RUN NO.
SAMPLE BOX N0._
METER BOX N0._
METER ^ H$
SCHEMATIC OF STACK CROSS SECTION
C FACTOR
AMBIENT TEMPERATURE
'BAROMETRIC PRESSORE_
ASSUMED MOISTURE, ?„
HEATER BOX SETTING_
PROBE LENGTH, m.
NOZZLE DIAMETER, in._
PROBE HEATER SETTING
o
o
TRAVERSE
POINT
NUMBER
JTOTAL
AVER/..'~E
SAMPLING
TIME'
(e) tnin.
STATIC
PRESSURE
(Ps)iaHg
STACK
TEMP.
.:'}.6 date.
-------
where:
Vm . . o Volume of gas sample through the dry gas meter
(standard conditions), cu. ft.
V *> Volume of gas sample through the dry gas meter
m (meter conditions), cu. ft.
T . , «= Absolute temperature at standard conditions, 530 R.
T c Average dry gas meter temperature, R.
P. = Barometric pressure at the orifice meter, inches Hg.
H «= Average pressure drop across the orifice meter,
inches H-O.
13.6 = Specific gravity of mercury.
P . . = Absolute pressure at standard conditions, 29.92
sca inches Hg.
6.3 Volume of water vapor.
wstd
RTstd
( 0.0474 cu. ftV,
\ ml. j c
equation 5-2
where:
Vw B volume of water vapor in the gas sample (standard
std conditions), cu. ft.
v
1 = Total volume of liquid collected in impingers and
silica gel (see Figure 5-3), ml.
pH~0 = Density of water, 1 g./ml.
MH 0 = Molecular weight of water, 18 Ib./lb. - mole.
R es Ideal gas constant, 21.83 inches Hg - cu.ft./lb.
mole- R.
*p o
std = Absolute temperature at standard conditions, 530 R.
Pstd " Absolute pressure at standard conditions, 29.92 inches Hg,
101
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6.4 Moisture content.
wo
« ,,
mstd wstd
equation 5-3
where:
B = Proportion by volume of water vapor in the gas stream,
dimensionless.
w , , = Volume of water in the gas sample (standard conditions),
sta cu. ft.
m
= Volume of gas sample through the dry gas meter (standard
std conditions), cu. ft.
6.5 Total particulate weight. Determine the total particulate
catch from the sum of the weights on the analysis data sheet
(Figure 5-3)
6.6 Concentration.
6.6.1 Concentration in gr./s.c.f.
C's =
equation 5-4
where:
c1 = Concentration of particulate matter in stack gas,
gr./s.c.f., dry basis.
M= = Total amount of particulate matter collected, mg.
a.
Volume of gas sample through dry gas meter (stand-
m
std ard conditions), cu. ft.
102
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6.6.2 Concentration in Ib/.cu.ft.
cs
equation 5-5
where :
s
Concentration of particulate matter in stack gas,
Ib./s.c.f., dry basis
453,600 = Mg/lb.
Mn c Sa*"al amount of particulate matter collected,
V »> Volume of gas sample through dry gas meter
m
std (standard conditions), cu. ft
6.7 Isokinetic variation.
rv.
xc (pH20)R+ Vm
T
s
I »
'bar +
m
X 100
=T fl.667 min. ^ | /0.00267 in. Hg-cu.ft^ lc + Vm (Pbar + ^ n
s\ sec. / [_S ml.- gR"/ TT" \ 13.6/
6 VsAn
Equation 5-6
where:
I B Percent of isolcinetic sampling.
V. = Total volume of liquid collected in impingers and
c silica gel {See Fig. 5-3), ml.
O = Density of water, 1 g./ml.
R a Ideal gas constant, 21.83 inches Hg-cu.ft./lb.
mole-°R
103
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Ho° • Molecular weight of water, 18 Ib./lb-mole.
m
Volume of gas sample through the dry gas meter
(meter conditions), cu. ft.
T B Absolute average dry gas meter temperature (see Figure
m 5-2), °R.
Pbar » Barometric pressure at sampling site, inches Hg.
AH a Average pressure drop across the orifice (see Figure
5-2), inches HpO.
T a Absolute average stack gas temperature (see Figure 5-2),
s °R.
0 B Total sampling time, min.
V * St.acJc gas velocity calculated by Method 2, Equation
s 2-2, ft./sec.
Pg =» Absolute stack gas pressure, inches Hg.
A_ B Cross-sectional area of nozzle, sq. ft.
n i -»
6.8 Acceptable results. The follwing range sets the limit on
acceptable isokinetic sampling results:
If 9095^1 <110%, the results are acceptable; otherwise, reject
the results and repeat the test.
104
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7. OPERATING NOMOGRAPH FOR ISOKINETIC SAMPLING
The correction factor nomograph and the operating nomograph
have been designed for use with the sampling train as aids for rapid
isokinetic sampling rate adjustments and for selection of a convenient
nozzle size. To determine the correction factor, C, on the nomograph,
the following information is first required:
1. Percent moisture,\% H?0.) This may be determined from a
previous test or presurvey, or before the sample run.
2. Orifice calibration factor, AK@. This is determined from
the calibration sheet. Use the AH@ corresponding to 2".
If a "C" value cannot be obtained, use a higher or lower
AH@ corresponding to higher or lower manometer reading
from the calibration sheet until "C" is obtained.
3. Meter temperature, T . Temperature at the meter rises
above ambient temperature because of the pump and can
easily be estimated with experience. An estimate with-
in 10 F (approximately _+ 1 percent error) is all that
is necessary (an initiaT estimate "of about 25 F above
ambient temperature has been used).
4. Stack pressure, P . This is measured before the sample
run; or if the sampling site is near the exit of the
stack, atmospheric pressure is used.
5. Meter pressure, P . Same as atmospheric pressure.
To obtain correction factor, C
1. Draw line from AH@> to T to obtain point "A" on reference
line 1 (REF 1). m
2. Draw line from point "A" to % H~0 to obtain point "B" on
reference line 2 (REF 2).
3. Draw line from point "B" to the calculated value P /P
to obtain correction factor, C. m
105
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To select the nozzle size and to set the K- fact or on the oper-
ating nomograph, the following information is first required:
1. C factor. This is obtained from the correct ion- factor
nomograph (Figure 9).
2. Stack temperature, T . This is determined in °P by a
rough temperature traverse to within _+ 25 F before the
sample run. "~
3. Average velocity pressure, AP. This is determined by a
rough preliminary pitot traverse, using the average of
minimum and maxiumu AP's in inches of water.
4. Available nozzle sizes, 0.
To select the nozzle size and to set the K- factor pivot point,
use the following procedure (Figure 8):
1. Set correction factor, C, on sliding scale to the refer-
ence mark, "A".
2. Align T with average AP, note probe tip diameter on D
scale, and select exact nozzle closest to it.
3. Align T with exact nozzle size selected and obtain a
value on the AP scale.
4. Align the P value with reference mark, "B" on ^H Scale,
and set the K-f actor pivot point.
To obtain the orifice meter setting, AH, for isokinetic con-
ditions after the K- factor pivot point has been set, use the follow
ing procedure (Figure 8):
1. Position the pitobe nozzle at the sampling point.
2. Read the pitot tube A P.
3. Align the AP through the K-f actor pivot point.
106
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4. Obtain AH and adjust metering valves.
The nomograph assumes the following once the K-factor pivot
is set:
1. T does not change more than 25° for T <1000°P or 50°
far T >1000°F.
o
2. D is not changed during the test.
3. T was estimated correctly and does not vary more than 10°.
4. Percent H-O remains constant, within +^ 1.0%.
5. P and P remain constant, within + 1.0%.
s m —
107
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ORIFICE READING
AH
a!
-f
6J
*
3
5-f
1
~
«
3-1
=
-
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g ""
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• -
-
:
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n.9_lf
0.8-3=
0.7-3
-1
0.6-1
_£
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-|
0.4— |
-£
0.3-£
Jj
0.2-^
-
—
:
0.1 —
Ref.
—Ref.
— 2.0
"
: c
— 1.5
I CORRECHON
FACTOR
1 0
— O.o
— o.a
— 0.7
— 0.6
STACK
— 0.5 TEMPERA Tlffif
2SOO
2000
1500
1000
800
600
500
400
300
200
100
0
—
5 *i
i^-~
-
^—
~~
—
^~
^~
sr
lr
3-
f-
=_
=-
=—
Sliding
Scale
» cut along lines *
3.001 1
1C FA
:fOR HTOT READING =
0.00?—=
o.ms-l
0.004 -|
0.005 -I
b.nop— =
PROBE —
TIP DIAMETER ^-nn8^
D o.oi-=
AH » In. H20
C • dlmenslonlcss
T, • °F
K • dlmenslonless
D > In.
&P * In. H20
e— 1.0 I
=—0.9 -r
=-O.B 0.02-=
H — —
E— 0.7 0.03—1
I 0.04-|
r~°'6 0.05-1
|~ . 0.06 -f
L 0'*S
=-0.4 £
~ -3
r" o j =
"" «s:
f-°-3 0.3-f
^ 0.4-|
0.5-fj
- 0.6 — "
— 0.2 0.8-=
- 1.0-==
;
— 2_|
=
~
3-=
_ d ,-*"
— 0.1 5-|
-=
10
Operating nomograph.
108
-------
APPENDIX B
METHOD FCR ORGANDOnDRINE PESTICIDES IN INDUSTRIAL EFFLUENTS
(from National Pollutant Discharge Elimination
System, Appendix A, Federal Register vol. 38, no. 75, pt. II)
109
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1. Scope and Application
1.1 This method covers the determination of various organochlorine
pesticides, including some pesticidal degradation products and related
compounds in industrial effluents. Such compounds are composed of
carbon, hydrogen, and chlorine, but may also contain oxygen, sulfur,
phosphorus, nitrogen or other halogens.
1.2 The following compounds may be determined individually by this method
with a sensitivity of 1 pg/liter: BHC, lindane, heptachlor, aldrin,
heptachlor epoxide, dieldrin, endrin, Captan, DDE, ODD, DDT, methoxy-
chlor, endosulfan, dichloran, mirex, pentachloronitrobenzene and tri-
fluralin. Under favorable circumstances, Strobane, toxaphene,
chlordane (tech.) and others may also be determined. The usefulness
of the method for other specific pesticides must be demonstrated by
the analyst before any attempt is made to apply it to sample analysis.
1.3 When organochlorine pesticides exist as complex mixtures, the
individual compounds may be difficult to distinguish. High, low, or
otherwise unreliable results may be obtained through misidentifica-
tion and/or one compound obscuring another of lesser concentration.
Provisions incorporated in this method are intended to minimize the
occurrence of such interferences.
2. Summary
2.1 The method offers several analytical alternatives, dependent on the
analyst's assessment of the nature and extent of interferences and/or
the complexity of the pesticide mixtures found. Specifically, the
procedure describes the use of an effective co-solvent for efficient
sample extraction; provides, through use of column chromatography
111
-------
and liquid-liquid partition, methods for elimination of non-pesticide
interferences and the pre-separation of pesticide mixtures. Identifi-
cation is made by selective gas chromatographic separations and may
be corroborated through the use of two or more unlike columns.
Detection and measurement is accomplished by electron capture, micro-
coulometric or electrolytic conductivity gas chromatography. Results
are reported in micrograms per liter.
2.2 This method is recommended for use only by experienced pesticide
analysts or under the close supervision of such qualified persons.
3. Interferences
3.1 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing
misinterpretation of gas chromatograms. All of these materials must
be demonstrated to be free from interferences under the conditions
of the analysis. Specific selection of reagents and purification of
solvents by distillation in all-glass systems may be required.
Refer to Part I, Sections 1.4 and 1.5, (1).
3.2 The interferences in industrial effluents are high and varied and
often pose great difficulty in obtaining accurate and precise
measurement of organochlorine pesticides. Sample clean-up procedures
are generally required and may result in the loss of certain organo-
chlorine pesticides. Therefore, great care should be exercised in
the selection and use of methods for eliminating or minimizing
interferences. It is not possible to describe procedures for over-
coming all of the interferences that may be encountered in industrial
effluents.
112
-------
.s.3 Pol/chlorinated Biphenyls (PCB's) - Special attention is called
to industrial plasticizers and hydraulic fluids such as the PCB's
which are a potential source of interference in pesticide analysis.
The presence of PCB's is indicated by a large number of partially
resolved or unresolved peaks which may occur throughout the entire
chromatogram. Particularly severe PCB interference will require
special separation procedures (2,3).
3.4 I'hthalate Esters - These compounds, widely used as plasticizers,
respond to the electron capture detector and are a source of inter-
ference in the determination of organochlorine pesticides using
this detector. Water leaches these materials from plastics, such
as polyethylene bottles and tygon tubing. The presence of phthalate
esters is implicated in samples that respond to electron capture but
not to the microcoulometric or electrolytic conductivity halogen
detectors or to the flame photometric detector.
3.5 Organophosphorus Pesticides - A number of organophosphorus pesticides,
such as those containing a nitro group, eg, parathion, also respond
to the electron capture detector and may interfere with the determina-
tion of the organochlorine pesticides. Such compounds can be
identified by their response to the flame photometric detector (4).
Apparatus and Materials
4.1 Gas Chromatograph - Equipped with glass lined injection port.
4.2 Detector Options:
4.2.1 Electron Capture - Radioactive (tritium or nickel 63)
4.2.2 Microcoulometric Titration
4.2.3 Klectrolytic Conductivity
113
-------
4 5 KcLorder - Potent lometric strip cha*-;: (10 in.) compatible with
the detector.
4.4 Gas Chromatographic Column Materials:
4.4.1 Tubing - Pyrcx (180 cm long x 4 mm ID)
4.4.2 Glass Wool - Silanized
4.4.3 Solid Support - Gas-Chrom Q (100-120 mesh)
4.4.4 Liquid Phases - Expressed as weight percent coated on
solid support.
4.4.4.1 OV-1, 3%
4.4.4.2 OV-210, 5%
4.4.4.3 OV-17, 1.5% plus QI--1, 1.95%
4.4.4.4 QF-1, 6% plus SL-30, 4%
4.5 Kuderna-Danish (K-D) Glassware (Kontes)
4.5.1 Snyder Column - three ball (macro) and two ball (micro)
4.5.2 Evaporative Flasks - 500 ml
4.5.3 Receiver Ampuls - 10 ml,graduated
4.5.4 Ampul Stoppers
4.6 Chromatographic Column - Chromaflex (400 mm long x 19 mm ID) with
coarse fritted plate on bottom and Teflon stopcock; 250 ml reservoir
bulb at top of column with flared out funnel shape at ton of bulb - a
special order (Kontes K-420540-9011).
4.7 Chromatographic Column - pyrex (approximately 400 mm long x 20 mm ID)
with coarse fritted plate on bottom.
4 8 Micro Syringes - 10, 25, 50 and 100 ul
•1.9 Separatory Funnels - 125 ml, 1000 ml and 2000 ml with Teflon stopcock.
4.10 Blender - High speed, glass or stainless steel cup.
114
-------
4.11 Graduated cylinders - 100, 250 and 1000 ml.
4.12 Florisil - PR Grade ',.60-100 mesh); purchase activated at 1250 F
and store in the dark in glass containers with glass stoppers or
foil-lined screw caps. Before use, activate each batch overnight
at 130 C in foil-covered glass container. Determine lauric-acid
value (See Appendix I).
5. Reagents, Solvents, and Standards
5.1 Ferrous Sulfate - (ACS) 30% solution in distilled water.
5.2 Potassium Iodide - (ACS) 10% solution in distilled water.
5.3 Sodium Chloride - (ACS) Saturated solution in distilled water
(pre-rinse NaCl with hexane).
5.4 -Sodium Hydroxide - (ACS) 10 N in distilled water.
5.5 Sodium Sulfate - (ACS) Granular, anhydrous(conditioned @ 400 C for 4 hrs)
5.6 Sulfuric Acid - (ACS) Mix equal volumes of cone. H-SO. with
distilled water.
5.7 Diethyl Ether --Nanograde, redistilled in glass, if necessary.
5.7.1 Must contain 2% alcohol and be free of peroxides by
following test: To 10 ml of ether in glass-stoppered
cylinder previously rinsed with ether, add one ml of
freshly prepared 10% KI solution. Shake and let stand
one minute. No yellow color should be observed in either layer.
5.7.2 Decompose ether peroxides by adding 40 g of 30% ferrous sulfate
solution to each liter of solvent. CAUTION: Reaction may be
vigorous if the solvent contains a high concentration of
peroxides.
5.7.3 Distill deperoxidized ether in glass and add 2% ethanol.
115
-------
5.8 Acetonitrilc, tlexane, Methanol, Methylene Chloride, Petroleum
Ether (boiling range 30-60 C) - nanograde, redistill in glass
if necessary
3.9 Pesticide Standards - Reference grade.
6. Calibration
6.1 Gas chromatographic operating conditions are considered acceptable
if the response to dicapthon is at least 50% of full scale when
< 0.06 ng is injected for electron capture detection and < 100 ng is
injected for microcoulometric or electrolytic conductivity detection.
For all quantitative measurements, the detector must be operated
within its linear response range and the detector noise level should
be less than 2% of full scale.
6.2 Standards are injected frequently as a check on the stability of
operating conditions. Gas chromatograms of several standard
pesticides are shown in Figures 1, 2, 3 and 4 and provide reference
operating conditions for the four recommended columns.
6.3 The elution order and retention ratios of various organochlorine
pesticides are provided in Table 1, as a guide.
7. Quality Control
7.1 Duplicate and spiked sample analyses are recommended as quality control
checks. When the routine occurrence of a pesticide is being observed,
the use of quality control charts is recommended (5).
7.2 Each time a set of samples is extracted, a method blank is determined
on a volume of distilled water equivalent to that used to dilute the
sample.
116
-------
8. Sample Preparation
8.1 Blend the sample if suspended matter is present and adjust pH to
near neutral (pH 6.5-7.5) with 50% sulfuric acid or 10 N sodium
hydroxide.
8.2 For a sensitivity requirement of 1 pg/1, when using microcoulometric
or electrolytic conductivity methods for detection, 100 ml or more
of sample will be required for analysis. If interferences pose no
problem, the sensitivity of the electron capture detector should
permit as little as 50 ml of sample to be used. Background informa-
tion on the extent and nature of interferences will assist the analyst
in choosing the required sample size and preferred detector.
8.3 Quantitatively transfer the proper aliquot into a two-liter separatory
funnel and dilute to one liter.
9. Extraction
9.1 Add 60 ml of 15% methylene chloride in hexane GV:V) to the sample
in the separatory funnel and shake vigorously for two minutes.
9.2 Allow the mixed solvent to separate from the sample, then draw the
water into a one-liter Erlenmeyer flask. Pour the organic layer into
a 100 ml beaker and then pass it through a column containing 3-4 inches
of anhydrous sodium sulfate, and collect it in a 500 ml K-D flask
equipped with a 10 ml ampul. Return the water phase to the separatory
funnel. Rinse the Erlenmeyer flask with a second 60 ml volume of
solvent; add the solvent to the separatory funnel and complete the
extraction procedure a second time. Perform a third extraction in
the same manner.
9.3 Concentrate the extract in the K-D evaporator on a hot water hath.
117
-------
9.4 Analyze by gas chromatography unless a need for cleanup is indicated.
(See Section 10).
10. Clean-up and Separation Procedures
10.1 Interferences in the form of distinct peaks and/or high background
in the initial gas chromatographic analysis, as well as the physical
characteristics of the extract (color, cloudiness, viscosity) and
background knowledge of the sample will indicate whether clean-up
is required. When these interfere with measurement of the pesticides,
or affect column life or detector sensitivity, proceed as directed
below.
10.2 Acetonitrile Partition - This procedure is used to isolate fats and
oils from the sample extracts. It should be noted that not all
pesticides are quantitatively recovered by this procedure. The
analyst must be aware of this and demonstrate the efficiency of
the partitioning for specific pesticides. Of the pesticides listed
in Scope (1.2) only mirex is not efficiently recovered.
10.2.1 Quantitatively transfer the previously concentrated extract
to a 125 ml separatory funnel with enough hexane to bring
the final volume to 15 ml. Extract the sample four times
by shaking vigorously for one minute with 30 ml portions
of hexane-saturated acetonitrile.
10.2.2 Combine and transfer the acetonitrile phases to a one-liter
separatory funnel and add 650 ml of distilled water and
40 ml of saturated sodium chloride solution. Mix thoroughly
for 30-45 seconds. Extract with two 100 ml portions of
118
-------
hexane by vigorously shaking about 15 seconds.
10.2.3 Combine the hexane extracts in a one-liter separatory funnel
and wash with two 100 ml portions of distilled water. Dis-
card the water layer and pour the hexane layer through a
3-4 inch anhydrous sodium sulfate column into a 500 ml K-D
flask equipped with a 10 ml ampul. Rinse the separatory
funnel and column with three 10 ml portions of hexane.
10.2.4 Concentrate the extracts to 6-10 ml Ln the K-D evaporator
in a hot water bath.
10.2.5 Analyze by gas chrcmatography unless a need for further
cleanup is indicated.
10.3 Florisil Column Adsorption Chromatography
10.3.1 Adjust the sample extract volume to 10 ml.
10.3.2 Place a charge of activated Florisil (weight determined by
lauric-acid value, sec Appendix I) in a Chromaflex column.
After settling the Florisil by tapping the column, add about
one-half inch layer of anhydrous granular sodium sulfate to
the top.
10.3.3 Pre-elutc the column, after cooling, with 50-60 ml of
petroleum ether. Discard the eluate and just prior to
exposure of the sulfate layer to air, quantitatively transfer
the sample extract into the column by decantation and subse-
quent petroleum ether washings. Adjust the elution rate to
about 5 ml per minute and, separately, collect up to three
eluates in 500 ml K-D flasks equipped with 10 ml ampuls.
(See Eluate Composition 10.4).
119
-------
Perform the first ulution hith 200 ml of (A ethyl ether in
petroleum ether, and the second elution with 200 ml of 15%
ethyl ether in petroleum ether. Perform the third elution
with 200 ml of 50% ethyl ether - petroleum ether and the
fourth elution with 200 ml of 100% ethyl ether.
10.3.4 Concentrate the eluates to 6-10 ml in the K-D evaporator
in a hot water bath.
10.3.5 Analyze by gas chromatography.
10.4 Eluate Composition - By using an equivalent quantity of any batch of
Florisil as determined by its lauric acid value, the pesticides will
be separated into the eluates indicated below:
6% Eluate
Aldrin DDT Pentachloro-
BHC Heptachlor nitrobenzene
Chlordane Heptachlor Epoxide Strobane
DDL) Lindane Toxaphene
DDE Methoxychlor Trifluralin
Mirex PCB's
15% Eluate 50% Eluate
Endosulfan I Endosulfan II
Endrin Captan
Dieldrin
Dichloran
Phthalate esters
Certain thiophosphate pesticides will occur in each of the above
fractions as well as the 100% fraction. For additional information
regarding cluatc composition, refer to the FDA Pesticide An.il> tical
M.niual (6).
120
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11. Calculation of Results
11.1 Determine the pesticide concentration by using the absolute calibra-
tion procedure described below or the relative calibration procedure
described in Part I, Section 3.4.2. (1).
(1) Micrograms/liter = (A) (B) (V)
A = ng standard
Standard area
B = Sample aliquot area
V. = Volume of extract injected
V = Volume of total extract (pi)
V = Volume of water extracted (ml)
12. Reporting Results
12.1 Report results in micrograms per liter without correction for
recovery data. When duplicate and spiked samples are analyzed,all
data obtained should be reported.
121
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1. "Method for Organic Pesticides in Water and Wastewater," Environmental
Protection Agency, National Environmental Research Center, Cincinnati, Ohio
45268, 1971.
2. Monsanto Methodology for Aroclors - Analysis of Environmental Materials for
Biphenyls, Analytical Chemistry Method 71-35, Monsanto Company, St. Louis,
Missouri 63166, 1970.
3. "Method for Polychlorinated Biphenyls in Industrial Effluents," Environmental
Protection Agency, National Environmental Research Center, Cincinnati, Ohio
45268, 1973.
4. "Method for Organophosphorus Pesticides in Industrial Effluents," Environ-
mental Protection Agency, National Environmental Research Center, Cincinnati
Ohio 45268, 1973.
5. "Handbook for Analytical Quality Control in Water and Wastewater Laboratories,"
Chapter 6, Section 6.4, U.S. Environmental Protection Agency, National Environ-
mental Research Center, Analytical Quality Control Laboratory, Cincinnati,
Ohio 45268, 1973.
6. "Pesticide Analytical Manual," U.S. Dept. of Health, Education and Welfare,
Food and Drug Administration, Washington, D.C.
7. "Analysis of Pesticide Residues in Human and Environmental Samples," U.S.
Environmental Protection Agency, Perrine Primate Research Laboratories,
Perrine, Florida 33157, 1971.
8. Mills, P.\., "Variation of Florisil Activity: Simple Method for Measuring
Adsorbent Capacity and its Use in Standardizing Florisil Columns," Journal
of the Association of Official Analytical Chemists, 5J_, 29 (1968).
9. Goerlitz, D.F. and Brown, E., "Methods for Analysis of Organic Substances
in Water," Techniques of Water Resources Investigations of the United States
Geological Survey, Book 5, Chapter A3, U.S. Department of the Interior,
Geological Survey, Washington, D.C. 20402, 1972, pp. 24-40.
10. Stccrc, N.V., editor, "Handbook of Laboratory Safety," Chemical Rubber
Company, 18901 Cranwood Parkway, Cleveland, Ohio 44128, 1971, pp. 250-254.
122
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APPENDIX I
13. Standardization of Florisil Column by Weight Adjustment Based on Adsorption
of Laurie Acid.
13.1 A rapid method for determining adsorptive capacity of Florisil is
based on adsorption of lauric acid from hexane solution (6) (8).
An excess of lauric acid is used and amount not adsorbed is measured
by alkali titration. Weight of lauric acid adsorbed is used to
calculate, by simple proportion, equivalent quantities of Florisil
for batches having different adsorptive capacities.
13.2 Apparatus
13.2.1 Buret. -- 25 ml with 1/10 ml graduations.
13.2.2 Erlenmeyer flasks. -- 125 ml narrow mouth and 25 ml, glass
stoppered.
13.2.3 Pipet. -- 10 and 20 ml transfer.
13.2.4 Volumetric flasks. -- 500 ml.
13.3 Reagents and Solvents
13.3.1 Alcohol, ethyl. -- USP or absolute, neutralized to
phenolphthalein.
13.3.2 Hexane. -- Distilled from -all glass apparatus.
13.3.3 Lauric acid. --Purified, CP.
13.3.4 Lauric acid solution. -- Transfer 10.000 g lauric acid to
500 ml volumetric flask, dissolve in hexane, and dilute to
500 ml (1 mi = 20 mg).
13.3.5 Phenolphthalein Indicator. -- Dissolve 1 g in alcohol and
dilute to 100 ml.
123
-------
13.3.6 Sodium hydroxide. -- Dissolve ?0 g NaOH (pellets, reagent
grade) in water and dilute to 500 ml (IN). Dilute 25 ml
1N_ NaOH to 500 ml with water (0.05N). Standardize as follows:
Weigh 100-200 mg lauric acid into 125 ml Erlenmeyer flask.
Add 50 ml neutralized ethyl alcohol and 3 drops phenol-
phthalein indicator; titrate to permanent end point. Calculate
mg lauric acid/ml 0.05 N_ NaOH (about 10 mg/ml).
13.4 Procedure
13.4.1 Transfer 2.000 g Flonsil to 25 ml glass stoppered Erlenmeyer
flasks. Cover loosely with aluminum foil and heat overnight
at 130°C. Stopper, cool to room temperature, add 20.0 ml
lauric acid solution (400 mg), stopper, and shake occasionally
for 15 nun. Let adsorbent settle and pipet 10.0 ml of
supernatant into 125 ml Erlenmeyer flask. Avoid inclusion
of any Flonsil.
13.4.2 Add 50 ml neutral alcohol and 3 drops indicator solution;
titrate with 0.05N_ to a permanent end point.
13.5 Calculation of Lauric Acid Value and Adjustment of Column Weight
13.5.1 Calculate amount of lauric acid adsorbed on Florisil as
follows:
I,auric Acid value = mg lauric acid/g Ilorisil = 200 - (ml
required for titration X mg lauric acid/ml 0.05N_ NaOII).
13.5.2 To obtain an equivalent quantity of any batch of Flonsil,
divide 110 by lauric acid value for that batch and multiply
by 20 g. Verify proper elution of pesticides by 13.6.
124
-------
15,6 Test for Proper Elution Pattern and Recovery of Pesticides.
Prepare a test mixture containing aldrin, heptachlor epoxide,
pjp'-DDE, dieldrin, Parathion and malathion. Dieldrin and
Parathion should elute in the 15% eluate; all but a trace of
malathion in the 50% eluate and the others in the 6% eluate
125
-------
(15 gm)
SOLID
<
SAMPLES.
ASH
AIR STREAM
PARTICULATES
SCRUBBER WATER
PARTICULATES
SEWAGE SLUDGE
EXTRACT c HEXANE
24 HOURS
DDT
( 100 mis)
LIQUID (WATER)
( ALL RECEIVED)
LIQUID SOLVENT
I SAMPLE'
FILTERED SCRUBBER WATER
NEUTRALIZE
pH 6.5-7.5
1
SOLVENT EXTRACT
1
DRY
SAMPLE
FILTERED AIR
EVAPORATE
• FOR ASH, AIR STREAM PARTICULATE,
SCRUBBER WATER PARTICULATE,
SEWAGE SLUDGE, SCRUBBER WATER
FILTRATE, AND SOLVENT EXTRACTED
AIR STREAM SAMPLES.
1
FLORISIL CLEANUP
I
LG CONCENTRATION
1
CONCENTRATION
IN 10 ML TO 4-6 ml
I
REMOVE I ML
FOR 6.C.
1
6LC
SEWAGE SLUDGE TREATED AS A SOLID, OVEN DRIED
FIGURE B-l
ANALYTICAL FLOW SCHEME
FOR DDT AND ITS DEGRADATION PRODUCTS •
126
-------
Figxire B-2. Chronatogram of Typical Non-Particulate Stack Gas Sample
(Full scale DDT burn)
NOte: Figures B-2 through B-7 show that o-p1 - DDE and p-p' -
DDE were the prominent degradation products of the full
scale DDT burn.
127
-------
PeflF.Tp'
qv_Q».b
pP'Doe:
'.ODD:
ejo'.DDT.1
•.pp-^-0
pf" DOT-.'
: 2-V 3
/7V. ? 4;
fc/- ? ;/>i/vj
_JJ
Lj.i
«_
, I * ~~T -"' '
Figure B-3. Chromatogram of Typical Stack Gas Particulate Sanple
(Full scale DDT bum)
128
-------
Figure B-4. Oircttiatogram of Typical Scrubber Water Filtrate Sample
(Full scale DDT burn)
129
-------
Figure B-5. Chronatcxgram of Typical Scrutber Water Particulate Sanple
(Full scale DDT burn)
130
-------
Figure B-6. Chronatngram of Typical Product Sample
(Full scale DDT burn)
131
-------
7, . -, — .. -_.
; ! - t
v? ' ! !
8L.
^7/^i : :
•i i '
'''it
t '• '
MM
i i
; \ 1 ;
— J7J4-
r~T ; ! '• r ; ~ i
Figrire B-7. Chronatogram of Product Sanple
(Full Scale DDT Burn)
In conparison to Figure B-6, this tracing
illustrates some of the degradation pro-
duct variation encountered.
132
-------
Figure B-8. Oiramatogram of Typical Non-Particulate Stack Gas Sample
(Pilot scale DDT bum)
Note: Figures B-8 through B-16 show that o-p1 and p-p1 -
DDE were not consistently the major combustion pro-
ducts of the pilot scale test burn, p-p1 - DDT was
equally prominent.
133
-------
•f i
Figure B-9. Chrcmatogram of Typical Stack Gas Particulate Sanple
(Pilot scale DDT burn)
134
-------
Figure B-10. Chromatogram of Typical Scrubber Water Filtrate Sanple
(Pilot srnle DDT burn)
135
-------
Figure B-ll. Chrcmatcgram of Scrubber Water Filtrate Sample
(Pilot scale DDT burn)
136
-------
Figure B-12. Chratatogrem of Typical Scrubber Water Particulate Sanple
(Pilot scale DDT bum)
137
-------
Figure B-13. Chronatogram of Scrubber Water Particulate Sarrple
(Pilot scale EOT burn)
138
-------
OP' Doe- : /3i.5
Figure B-14. Qirotatogram of Typical Product Sample
(Pilot scale DOT burn)
139
-------
///jeered '• /•
' ' X t
Figure B-15. Chrcmatogram of Product Sanple
(Pilot scale EOT burn)
140
-------
Figure B-16. Typical Chranatogram of Sewage Sludge Sanple
(Pilot scale EOT burn)
141
-------
Figure B-17. Typical Chronatogram of Laboratory Blank
Note: A laboratory blank was analyzed with every four
sairples processed. The raw data was then
corrected for these residual levels.
142
-------
Figure B-18. Chronatogram of Typical Pesticide Conposite Standaxd
143
-------
Figure B-19. Chiotiatogram of DDT Standard
144
-------
iPP'PDET S
. - COA/CCA/rwh c /v •. /oo p i <: og R A rt s
f i r ": r
Figure B-20. Chrxaratogram of p-p1 - DDE Standard
145
-------
Fig\ore B-21. Qiromatogram of o-p1 - DDE Standard
146
-------
Figure B-22. Ghronatogram of o-p1 - EDO Stardard
147
-------
— 9-,
-J—
-t-r -
T
1+'-:-
-—9—-
_Q
L7.
U_U_ i ; J_
5—
j'IPP'POpST
_ CoA/ccA/rtorr/cw •
I .Ml
loo p
'""_. IN3XC7 e^_; ._9_j
p!
r *.«!
<_4 .fmeN. XS
iDRTE OF fi.C.
PP1 PeflK HE^KT :
Figure B-23. Chrctnatogram of p-p1 - ODD Standard
148
-------
APPENDIX C
METHOD FOR CHLORINATED PHENOXY ACID HERBICIDES IN
INDUSTRIAL EFFLUENTS
(from rational Pollutant Discharge Elimination
System, Appendix A, Federal Register vol. 38, no. 75, pt. II)
149
-------
1. Scope and Application
1.1 This method covers the determination of chlorinated phenoxy acid
herbicides in industrial effluents. The compounds 2,4-dichloro-
phenoxyacetic acid (2,4-D), 2-(2,4,5-trichlorophenoxy) propionic
acid (silvex), 2,3-dichloro-o-anisic acid (dicamba) and 2,4,5-
trichlorophenoxyacetic acid (2,4,5-T) may be determined by this
procedure.
1.2 Since these compounds may occur in water in various forms (i.e., acid,
salt, ester, etc.) a hydrolysis step is included to permit the deter-
mination of the active part of the herbicide. The method may be
applied to additional phenoxy acids and certain phenols. However,
the analyst must demonstrate the usefulness of the method for each
specific compound before applying it to sample analysis.
2. Summary
2.1 Chlorinated phenoxy acids and their esters are extracted from the
acidified water sample with ethyl ether. The esters are hydrolyzed
to acids and extraneous organic material is removed by a solvent wash.
The acids are converted to methyl esters which are extracted from
the aqueous phase. The extract is cleaned up by passing it through
a micro-adsorption column. Identification of the esters is made by
selective gas chromatographic separations and may be corroborated
through the use of two or more unlike columns. Detection and measure-
ment is accomplished by electron capture, microcoulometric or
electrolytic conductivity gas chromatography (1). Results are
reported in micrograms per liter.
2.2 This method is recommended for use only by experienced pesticide
analysts or under the close supervision of such qualified persons.
151
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:•. Interferences
5.1 Solvents, reagent, glasbwarc, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing
misinterpretation of gas chromatograms. All of these materials must
be demonstrated to be free from interference under the conditions of
the analysis. Specific selection of reagents and purification of
solvents by distillation in all-glass systems may be required.
Refer to Part 1, Sections 1.4 and 1.5, (2).
3.2 The interferences in industrial effluents are high and varied and
often pose great difficulty in obtaining accurate and precise
measurement of chlorinated phenoxy acid herbicides. Sample clean-up
procedures are generally required and may result in loss of certain
of these herbicides. It is not possible to describe procedures for
overcoming all of the interferences that may be encountered in
industrial effluents.
3.3 Organic acids, especially chlorinated acids, cause the most direct
interference with the determination. Phenols including chlorophenols
will also interfere with this procedure.
3.4 Alkaline hydrolysis and subsequent extraction eliminates many of
the predominant chlorinated insecticides which might otherwise
interfere with the test.
3.5 The herbicides, being strong organic acids, react readily with
alkaline substances and may be lost during analysis. Glassware and
glass wool should be aciu-rinsed and sodium sulfate should be acidi-
fied with sulfuric acid to avoid this possibility.
152
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4. Apparatus and Materials
4.1 Gas Chromatograph - Equipped with glass lined injection port.
4.2 Detector Options:
4.2.1 Electron Capture - Radioactive (tritium or nickel-63)
4.2.2 Microcoulometric Titration
4.2.3 Electrolytic Conductivity
4.3 Recorder - Potentiometric strip chart [10 in.) compatible with
the detector.
4.4 Gas Chromatographic Column Materials:
4.4.1 Tubing - Pyrex (180 cm long X 4 mm ID)
4.4.2 Glass Wool - Silanized
4.4.3 Solid Support - Gas-Chrom-Q (100-120 mesh)
4.4.4 Liquid Phases - Expressed as weight percent coated on
solid support.
4.4.4.1 OV-210, 5%
4.4.4.2 OV-17, 1.5% plus QF-1, 1.95%
4.5 Kuderna-Danish (K-D) Glassware (Kontes)
4.5.1 Snyder Column - three ball (macro) and two ball (micro)
4.5.2 Evaporative Flasks - 250 ml
4.5.3 Receiver Ampuls - 10 ml, graduated
4.5.4 Ampul Stoppers
4.6 Blender - High speed, glass or stainless steel cup.
4.7 Graduated cylinders - 100 and 250 ml.
4.8 Erlenmeyer flasks - 125 ml, 250 ml ground glass J 24/40
4.9 Microsyringes - 10, 25, 50 and 100 pi.
4.10 Pipets - Pasteur, glass disposable (140 mm long X 5 mm 10).
4.11 Separately Funnels - 60 ...i and 2000 ml with Teflon stopcock.
153
-------
!.12 Gias-- -vool - F-ltoriii; ^rade, .i^'d
4.13 [hainld Kit - recon.raended for the generation of diazomethane
(available from Aldrich Chemical Co., Cat. P210,025-2)
4. 14 ilorib'l - VV grjc'e (60-100 mesh) purchased activated at 1250F
and stored at 1 >0 C
5. Reagents, Solvents and standards
5.1 Boron Tnf luor Lde-Methanol-estenfication-reagent, 14 percent
boron trifluoridc b> weight.
5.2 N-methyl-N-nitroso-p-toluenesulfonamide (Diazald) - High purity,
melting point range 60-62 C Precursor for the generation of
diazomethane (see Appendix I).
5.3 Ferrous Sulfate - (ACS) 30% solution in distilled water.
5.4 Potassium Hydroxide Solution - A 37 percent aqueous solution
prepared from reagent grade potassium hydroxide pellets and reagent
water.
5.5 Potassjum Iodide - (ACS) 10* solution in distilled water.
5.6 Sodium Chloride - (ACS) Saturated solution (pre-rinse NaCl with
hexanc) in distilled water.
5.7 Sodium Hydroxide - (ACS) 10 N in distilled water.
5.8 Sodium Sulfate, Acidjfied. -- (ACS) granular sodium
bult.ite, treated as follows. AJd 0.1 ml of cone, sulfunc aciil to
1 (JO y of sodium sulfalt slurncd with enough ethyl ether to just
cover the solid. Remove the ctlier with the vacuum. Mix 1 g ol" the
resulting solid with 5 ml of rejgcnt water and ensure the mixture
to have a pll belo% ; Ston at 150 C
5 9 Sulfurii. acid -- |\CSj content rated, Sp. Cr. 1.84.
5.9.a. Carbitol (dietliylone glyt-ul monoethyl ether).
154
-------
5.10 Diethyl Ether - \anograde, redistilled in glass, if necessary.
5.10.1 Must contain 2% alcohol and be free of peroxides by
following test: To 10 ml of ether in glass-stoppered
cylinder previously rinsed with ether, add one ml of
freshly prepared 10% KI solution. Shake and let stand one
minute. No yellow color should be observed in either layer.
5.10.2 Decompose ether peroxides by adding 40 g of 30% ferrous
sulfate solution to each liter of solvent. CAUTION: Reaction
may be vigorous if the solvent contains a high concentration
of peroxides.
5 10.3 Distill dcpcroxidizcd ether in glass and add 2% ethanol.
5.11 Benzene Hexane - Nanograde, redistilled in glass, if necessary.
5.12 Pesticide Standards - Acids and Methyl Esters, reference grade.
5.12.1 Stock standard solutions - Dissolve 100 mg of each herbicide
in 60 ml ethyl ether, then make to 100 ml with redistilled
hcxane. Solution contains 1 rag/ml.
5.12.2 Working standard - Pipet 1.0 ml of each stock soln into a
single 100 ml volumetric flask. Make to volume with a
mixture of ethyl ether and hexanc (1:1). Solution contains
10 tig/ml of each standard.
5.12.3 Standard for Chromatography - (Diazomethane Procedure) Pipet
1.0 ml of the working standard into a glass stoppered test
tube and evaporate off the solvent using steam bath. Add
2 ml diazomethane to the residue. Let stand 10 minutes with
occasional shaking, then allow the solvent to evaporate
spontaneously. Dissolve the residue in 200 ul of hexane for
gas chromatography.
155
-------
5.12.4 Standard for Chro.natography -CBoron Trifluoride Procedure)
Pipet 1.0 ml of the uorking standard into a glass stoppered
test tube. Add 0.5 ml of Benzene and evaporate to 0.4 ml
using a two-ball Snyder microcolumn and a steam bath.
Proceed as in 11.3.1. 1sters are then ready for gas
chromatography.
6. Calibration
6.1 Gas chromatographic operating conditions are considered acceptable
if the response to dicapthon is at least 50% of full scale when < 0.06
ng is injected for electron capture detection and < 100 ng is injected
for microcoulometric or electrolytic conductivity detection. For all
quantitative measurements, the detector must "be operated within its
linear response range and the detector noise level should be less
than 2% of full scale.
6.2 Standards, prepared from methyl esters of phenoxy acid herbicides
calculated as the acid equivalent, are injected frequently as a check
on the stability of operating conditions.
6.3 The elution order and retention ratios of methyl esters of chlorinated
phenoxy acid herbicides are provided in Table 1, as a guide.
7. Quality Control
7.1 Duplicate and spiked sample analyses are recommended as quality control
checks. Mien the routine occurrence of a pesticide is being observed
the use of quality control charts is recommended (3).
7.2 l.acli tune a set of samples is extracted, a method blank is determined
on a volume of distilled satcr equivalent to that used to dilute the
sample.
156
-------
8. Sample Preparation
H.I Blond the sample, if suspended matter is present.
8.2 For a sensitivity requirement of 1 ug/1, when using electron
capture for detection, take 100 ml of sample for analysis.
For microcoulometric or electrolytic conductivity detection, take
1-liter of sample. Background information on the extent and nature
of interferences will assist the analyst in selecting the proppr
sample size and detector.
8.3 Quantitatively transfer the proper aliquot of sample into a two-liter
scparatory funnel, dilute to one liter and acidify to approximately
pll 2 with concentrated sulfuric acid. Check pH with indicator paper.
9. Lxtraction
9.1 Add 150 ml of ether to the sample in the separatory funnel and shake
vigorously for one minute.
9.2 Allow the contents to separate for at least ten minutes. After the
layers have separated, drain the water phase into a one-liter
hrlcnmeyer flask. Then collect the extract in a 250 ml ground-glass
Lrlenmeyer flask containing 2 ml of 37 percent aqueous potassium
hydroxide.
9.3 Lxtract the sample two more times using 50 ml of ether each time, and
combine the extracts :n the Erlenmeyer flask. (Rinse the one-liter
flask with each additional aliquot of extracting solvent.)
10. Hydrolysis
10.1 Add 15 ml of distilled water and a small boiling stone to the flask
containing the ether extract, and fit the flask with a 3-ball Snydcr
column. Ivaporatc the ether on a steam bath and continue hcatinj;
for a total of 60 minute;..
157
-------
10.2 Transfer the concentrate to a 60 ml separator/ funnel. Extract
the D.'.Sic solution tv> tune:-, iv-ith 20 ml of ether and discard
the ether layers. The herbicides remain in the aqueous phase.
10.3 Acidify the contents of the scparatory funnel by adding 2 ml of
cold (4 C) 25 percent sulfuric acid (5.9). Extract the herbicides
once with 20 ml of ether and twice with 10 ml of ether. Collect
the extracts in a 125 ml Erlenmeyer flask containing about 0.5 g
of acidified anhydrous sodium sulfate (5.8). Allow the extract
to remain in contact with the sodium sulfate for approximately
two hours.
11. Esterification (4,5)
11.1 Transfer the ether extract, through a funnel plugged with glass wool,
into a Kuderna-Danish flask equipped with a 10 ml graduated ampul.
Use liberal washings of ether. Using a glass rod, crush any caked
sodium sulfate during the transfer.
11.1.1 If esterification is to be done with diazomethane, evaporate
to approximately 4 ml on a steam bath (do not immerse the
ampul in water) and proceed as directed in Section 11.2.
11.1.2 If esterification is to be done with boron trifluoride, add
0.5 ml benzene and evaporate to about 5 ml on a steam bath.
Remove the ampul from the flask and further concentrate
the extract to 0.4 ml using a two-ball Snyder microcol-jmn
anil proceed ab in 11.3.
11.2 Diazomethane Esterification
11.2.1 Disconnect the ampul I rom the K-D flask and place i r, a hood
away from steam bath. Adjust volume to -i ml i»ith ether, add
2 nil diazomethane, arn. lot stand 10 minutes with
occasional swirling.
158
-------
11.2.2 Rinse inside wall of ampul with several hundred microliters
of ethyl ether. Take sample to approximately 2 ml to
remove excess diazomethane by allowing solvent to evaporate
spontaneously (room temperature).
11.2.3 Dissolve residue in 5 ml of hexane. Analyze by gas
chromatography.
11.2.4 If further clean-up of the sample is required, proceed as
in 11.3.4 substituting hexane for benzene.
11.3 Boron Trifluoride Esterification
11.3.1 After the benzene solution in the ampul has cooled, add
0.5 ml of borontrifluoride-methanol reagent. Use the
two-ball Snyder micro column as an air-cooled condenser
and hold the contents of the ampul at 50 C for 30 minutes
on the steam bath.
11.3.2 Cool and add about 4.5 ml of a neutral 5 percent aqueous
sodium sulfate solution so that the benzene-water interface
is in the neck of the Kuderna-Danish ampul. Seal the flask
with a ground glass stopper and shake vigorously for about one
minute. Allow to stand for three minutes for phase separation.
11.3.1 Pipet the solvent layer from the ampul to the top of a small
column prepared by plugging a disposable Pasteur pipet with
glass wool and packing with 2.0 cm of sodium sulfate over
1.5 cm of Florisil adsorbent. Collect the eluate in a
graduated ampul. Complete the transfer by repeatedly rinsing
the ampul with small quantities of benzene and passing the
rinses through the column until a final volume of 5.0 ml of
eluate is obtained. Analyze by gas chromatography.
159
-------
12 Cjlcii^ation of Results
12.1 Determine the methyl ester concentration by using the absolute
calibration procedure described below or the relative calibration
procedure described in Part 1, Section 3.4.2 (2).
(1) Micrograms/liter = (A) (B) (V )
(V ) (V )
A = ng standard
Standard area
B = Sample aliquot area
V = Volume of extract injected (yl)
V = Volume of total extract (ul)
V = Volume of water extracted (ml)
12.2 Molecular weights for the calculation of the methyl esters as the
acid equivalents.
2,4-U 222.0 Dicamba 221.0
2,4-D Methyl ester 236.0 Dicamba methyl ester 236.1
Silvex 269.5 2,4,5-T 255.5
Silvex methyl ester 283.5 2,4,5-T methyl ester 269 5
13. Reporting Results
13.1 Report results in micrograms per liter as the acid equivalent without
correction for recovery data. When duplicate and spiked samples are
analyzed all data obtained should be reported.
160
-------
REFERENCES
(1) Goerlitz, D. G., and Lamar, W. L., "Determination of Phenoxy
and Herbicides in Water by Electron-Capture and Microcoulometric
Gas Chromatography", U. S. Geol. Survey Water-Supply Paper
1817-C (1967).
(2) "Methods for Organic Pesticides in Water and Wastewater", (1971)
U. S. Environmental Protection Agency, National Environmental
Research Center, Cincinnati, Ohio.
(3) "Handbook for Analytical Quality Control in Water and Wastewater
Laboratories" (1972), U. S. Environmental Protection Agency,
National Environmental Research Center, Analytical Quality Control
Laboratory, Cincinnati, Ohio 45268.
(4) Metcalf, L. D., and Schmitz, A. A., "The Rapid Preparation of
Fatty Acid Esters for Gas Chromatographic Analysis", Analytical
Chemistry. 33, 363 (1961).
(5) Schlenk, H. and Gellerman, J. L., "Esterification of Fatty Acids
with Diazomethane on a Small Scale", Analytical Chemistry, 32,
1412 (1960). ~~
(6) "Pesticide Analytical Manual", U. S. Department of Health, Education,
and Welfare, Food and Drug Administration, Washington, D.C.
(7) Steere, N. V., editor, "Handbook of Laboratory Safety," Chemical
Rubber Company, 18901 Cranwood Parkway, Cleveland, Ohio 44128,
1971, pp. 250-254.
161
-------
APPENDIX I
Diazomethane in ether (6).
1. CAUTIONS. Diazomethane is very toxic. It can explode under certain
conditions. The following precautions should be observed.
Avoid breathing vapors.
Use only in well-ventilated hood.
Use safety screen.
Do not pipette solution of diazomethane by mouth.
For pouring solutions of diazomethane, use of gloves is optional.
Do not heat solutions to 100 C (EXPLOSIONS).
Store solutions of gas at low temperatures (Freezer compartment of explosion
proof refrigerators).
Avoid ground glass apparatus, glass stirrers and sleeve bearings where
grinding may occur (EXPLOSIONS).
Keep solutions away from alkali metals (EXPLOSIONS).
Solutions of diazomethane decompose rapidly in presence of solid material
such as copper powder, calcium chloride, boiling stones, etc. These solid
materials cause solid polymethylene and nitrogen gas to form.
2. PREPARATION.
Use a well-ventilated hood and cork stoppers for all connections.
Fit a 125 ml long-neck distilling flask with a dropping funnel and an
efficient condenser set downward for distillation. Connect the condenser
to two receiving flasks in scrius - a 500 ml Erlcnmcycr followed by ;i
12S ml l.rlcnmeyer containing 30 ml ether. The inlet to the 125 ml lirlenmeyer
should dip below the ether. Cool both receivers to 0 C.
As water bath for the distilling flask, set up a 2-liter beaker on a
stirplate (hot plate and stirrer), maintaining temperature at 70 C.
162
-------
Dissolve 0 g KOH in 10 m! water in the chstilling flask (no heat).
Add 35 ml Carbitol (diethylene glycol monoethyl ether), stirring bar, and
another 10 ml ether. Connect the distilling flask to the condenser and
immerse distilling flask in water bath. By means of the dropping funnel,
add a solution of 21.5 g Diazald in 140 ml ether over a period of 20 minutes.
After distillation is apparently complete, add another 20 ml ether and
continue distilling until distillate is colorless. Combine the contents of
the two receivers in a glass bottle (WITHOUT ground glass neck), stopper
with cork, and freeze overnight. Decant the diazomethane from the ice
crystals into a glass bottle, stopper with cork, and store in freezer until
ready for use. The final solution may be stored up to six months without
marked deterioration.
The 21.5 g of Diazald reacted in this manner produce about 3 g of
[Kazomethane.
163
-------
SAil
190 •!• dUttql
tar 4 ban
nka bole to pa
0 1 •! portion eDl.09 I UOH
•IxonAilly
lomfuUy
(thzotf out •thei)
mpmm lq«r otactlnn
•eUliy topHJl
•Knet e )
«HkiMll
^
ato*
* tailing OMp
ntxtf
tK i at
«WKr
*r-
IrkB't ttav OK tttvl
•H a •! aunwkm
•it 10
e 1/2 plfK» (ttar
eo S •!• c hum
Agr • elMnv 0110141 oolun
SfaM reputedly (J-SO
c houno
oaioentrau in
In 10 •!
tat-to*
(art.a
1
Figure C-l
164
-------
1.0
•IDOnlMsOH
+ 10 ml »K»
«• Stirling rod
Stir 1 hour
»100 ml hexane
> 200 ml dlst. HjO
Ihour
Nillifoxe
transfer filleiate into
i fumel
Stand
hoanc layer
* IMnlMeOH
+ 10B1 SNK»
ina tep. funnel
20 Bin.
200 ml dlst. Hj
* 100 ml hexane
aqueous layer c 100 ml hexane
discard aqueous layer
i layers
wash with
2X100 ml indaCH
2X 100 ml inHd
X 100 ml dist. H20
Seaazatory funnel
I choke c BjS04 till acid is
clear after standing 10 Bins.
i extract c 2 x 100 ml dist. HjO
diseerd aqueous layer
Dry extract over
•**<•< down to 10 mis
throu^i
- KaHOOj eolinn
pnerinsed
IS 9* A^'i colum
elutewith
(1) 100 ml pet ether
(2) SO ml of 5» diethyl ether
in pet ether
discard
100 Ell of SOt diethylether in pet ether
thzou^i oolum
* collect
•ail dan to about S ml
Cvaponte to diyness
•djuet «alun to 1 nl with hexane
etc
Figure C-2
165
-------
fiTi
Figure C-3. Chranatxigrain of Typical Non-Particulate Stack Gas Sanple
(Full scale 2,4,5-T burn)
Full scale tracings are also typical of pilot scale
tracings.
166
-------
; i • !_;
pftvpTc '/So.'."a- .HV/j- fiHP~
finr. iNJEcTEd .l.^^J.,_
l^TTcM JnT10^ '• Xc^ii
-L : i ^
L_L_i _i_!_J ' ! I . : _L 1
Figure C-4. Chronatogram of Typical Stack Gas Particulate Sample
(Full scale 2,4,5-T burn)
167
-------
Figure C-5. Oircmatogram of Typical Scrubber Water Filtrate Sample
(Full Scale 2,4,5-T burn)
168
-------
Figure C-6. Chromatogram of Typical Scrubber Water Particulate Samples
(Full scale 2,4,5-T burn)
169
-------
Figure C-7. Chromatogram of Typical Product Sample
(Full scale 2,4,5-T burn)
170
-------
44-1.4- :-H-.-f ~ -u-
Figure C-8. Laboratory Blank - 2f4,5-T
Note: A laboratory blank was analyzed with every four samples
processed. The raw data was then corrected for these
residual levels.
171
-------
-I0r
U /?/**•
: <3- / A
-8-
OF
IT
i i
Figure C-9. Chroretogram of 2,4,5-T Standard
172
-------
APPENDIX D
PARTIAL LIST OF OPERATING MUNICIPAL INCINERATORS
IN THE CONTINENTAL UNITED STATES
NOTE: In general, all of the following facilities have
installed scrubber systems which allow them to
comply with current emission standards. Most fa-
cilities constructed previous to 1972 have im-
pingement type scrubbers. High energy venturi
scrubbers have normally been installed in the fa-
cilities constructed after 1972.
173
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BSP DIVISION, ENVIROTECH SYSTEMS
MUNICIPAL WASTE SLUDGE DISPOSAL INSTALLATIONS SINCE 1963
01
Location
1963 Cleveland, Ohio
1963 East Rochester, N.Y.
1963 Oakland, California
1964 New Orleans, La.
1964 Holyoke, Mass.
1964 Ann Arbor, Michigan
1964 East Lansing, Mich.
1965 Cinnaminson, N.J.
1965 Minn.-St. Paul, Minn.
1966 Battle Creek, Mich.
1966 Mattabasset, Conn.
1966 Washington, D.C.
1966 Orangetown, N.Y.
1967 So. Tahoe, Ca.
1967 So. Tahoe, Ca.
1967 Lake Charles, La.
1967 San Lorenzo, Ca.
1967 Middleburg Hts., 0.
1967 Chicqpee, Mass.
1968 Johnston County, Kan.
1968 San Mateo, Ca.
1968 Colorado Springs, Col.
Furnace Dia.
22'3" O.D.- 9H
10'9" O.D.- 5H
10'9" O.D.- 6H
18'9" O.D.- 9H
7'0" x 40' Ig.
16'9" O.D.- 6H
16'9" O.D.- 6H
10'9" O.D.- 6H
22'3" O.D.-llH
18'9" O.D.- 6H
22'3" O.D.- 7H
39" I.D.- 6H
16'9" O.D.- 6H
14'3" O.D.- 6H
14'3" O.D.- 6H
14'3" O.D.- 6H
22'3" O.D.- 6H
10'9" O.D.- 6H
14'3" O.D.- 5H
18'9" O.D.- 5H
18'9" O.D.- 5H
4500 GPH
Design Dry
Solids
(Ibs/hr) Each
5400
600
900
3600
2030
1700
1700
500
6600
2200
4000
25
1750
900
1500
1500
3250
450
1000
1800
2000
2100
Design
Solids
Content
20-28%
25%
25-60%
30%
30%
20-22%
19-22%
20-22%
23-25%
23-25%
25-30%
20-30%
20-22%
20%
40%
22%
22%
20%
28%
22%
25%
5.6%
Sludge Source
Dig.P./Act.
Pri./Humus
Grease Skimmings
Pri./Grit/Scum/Screening
Primary
Pri./Act.
Pri./Act.
Pri./Act.
Pri./Act.
Pri./Humus/Act.
Pri./Chem. Precip.
Pri./Act./Lime Sludge
Pri./Humus
Pri./Act.
Loire Sludge
Dig. Act.
Pri./Act./Dig.
Dig. Act.
Primary
Pri./Act./Dig.
Primary
Pri./Humus
-------
Location
1969 Monterey, Calif.
1969 Atlanta, Ga.
1969 Lake Arrowhead, Ca.
1969 Sunset Valley, Ore.
1969 Concord, Calif.
1969 San Clemente, Ca.
1969 Palo Alto, Ca.
1969 Trenton, Mich.
1969 Colorado Springs, Col.
1969 Colorado Springs, Col.
1969 BEB, Minn.
1970 Enfield, Conn.
1970 Middletown, 0.
1970 Monroe County, N.Y.
1970 Monroe County, N.Y.
1970 Glastonbury, Conn.
1971 New Bedford, Mass.
1971 Stafford Springs, Conn.
1971 Cincinnati, O.
(Muddy Creek Plant)
1971 Cincinnati, 0.
(Muddy Creek Plant)
1971 Little Rock, Ark.
1971 Muskogee, Okla.
1971 Muskogee, Okla.
1971 Stratford, Conn.
1971 Bristol, Term.
1971 Rutherford Heights
(Swatara) Perm.
1971 Canton, Ohio
1971 . Colorado Springs, Col.
1971 Albany, N.Y.
1971 Anchorage, Alaska
Furnace Dia.
Design
Solids
Clbs/hr) Each
14'3" O.D.- 6H
22 '3" O.D.-10H
10'9" O.D.- 5H
1000 GPH
16 '9" O.D.- 6H
14'3" O.D.- 7H
18'9" O.D.- 6H
16'9" O.D.- 8H
6'0" O.D.- 6H
4'0" O.D.- 6H
22 '3" O.D.- 7H
22 '3" O.D.- 6H
18'9" O.D.- 6H
22 '3" O.D.- 6H
22'3" O.D.- 6H
16'9" O.D.- 6H
16'9" O.D.- 5H
10'9" O.D.- 6H
4000 GPH
900
5000
500
420
1200
1100
1200
1200
250
83
3300
2400
1900
3600
2000
1200
1500
390
1830
16'9" O.D.- 6H 2300
22'3" O.D.- 7H 2300
3000 GPH 1375
10'9" O.D.- 6H 1500
16'9" O.D.- 8H 1750
18'9" O.D.- 6H 1350
10'9" O.D.- 6H 390
18'9" O.D.- 6H 2400
5000 GPH 2330
22'3" O.D.-10H 5000
14'3" O.D.- 6H 1100
Design
Solids
Content
20%
20-30%
22%
5%
20-25%
22-28%
15%
20%
60%
50%
22%
20%
25%
40%
20%
22%
30%
20%
4-6 %
35%
35%
5.5%
35%
22%
20%
20%
30%
5.6%
20%
25%
Sludge Source
Pri./Act.
Dig.Pri./ftct.
Pri./Act.
Pri./Act.
Pri./Humus
Pri./Act.
Pri./Act.
Pri./Act.
Lime Sludge
Act. Carbon
Pri./Act.
Pri./Act.
Pri./Act.
Lime Sludge
Pri/Act.
Pri./Act.
'Primary
Pri./Act.
Pri./Act.
Pri.Act.
Pri./ftct.
Pri./Humus
Pri./Humus
Pri./Act.
Pri./Act.
Pri./Act.
Pri./Dig.
Pri./Humus/Dig. Act.
Pri./Act.
Primary
-------
Year
Sold
1971
1971
1971
1971
1971
1972
1972
1972
1972
1972
1972
1972
1972
Location
Auburn, N.Y.
Columbia, S.C.
San Jose, Ca.
Vancouver, Wash.
Erie, Pa.
Portland, Ore.
Groton, Conn.
Groton, Conn.
Savannah, Ga.
Grand Haven, Mich.
Canp-Hill, Lemyone, Pa
Wyoming, Mich.
East Lansing, Mich.
Furnace Dia.
22'3" O.D.- 6H
16'9" O.D.- 7H
22'3" O.D.- 4H
4000 GPH
22'3" O.D.-10H
5000 GPH
2000 GPH
10'9" O.D.- 7H
16'9" O.D.- 8H
16'9" O.D.- 6H
10'9" O.D.- 7H
18'9" O.D.- 6H
16'9" O.D.- 6H
Design
Solids
(Ibs/hr) Each
3000
1695
5000
1675
4500
1875
835
1000
5200
1675
670
1950
1750
Design
Solids
Content
22%
50%
40%
3-8 %
20%
4.5%
5%
35%
50%
30%
30-35%
18-26%
25-30%
Sludge Source
Pri./Act.
Pri./Act.
Grease/Grit/Screen
Pri./Act.
Pri./Act.
Waste Activated
Pri./Act.
Pri./Act.
Pri./Act.
Pri./Act.
Pri./Act.
Pri./Act.
Pri./Act.
-------
NICHOLS ENGINEERING & RESEARCH CORPORATION
SEWAGE SLUDGE INSTALLATION LIST
00
City
Dearborn
Auburn, N.Y.
New Britain, Conn.
Cleveland-Wes t
Minneapolis-St. Paul
Cleveland-South
Barberton, Ohio
Columbus, Ohio
Wayne County, Mich.
Detroit, Mich.
New Haven, Blvd.
New Haven, East
Dayton, Ohio
Cranston, R.I.
Dearborn, Mich.
Fall River, Mass.
Akron, Ohio
Ann Arbor, Mich.
Providence, R.I.
Bridgeport-West
Bridgeport-East
Cincinnati-Little Miami
Minneapolis-St. Paul
1934
1936
1936
1937
No. of
Units
1
1
Capac.
Tons/
24 Hrs.
50
28
48
96
Type of Sludge
Raw primary
Digested activated
Chem. -aerated
Digested
1938
1938
1938
1938
1939
1939
1939
1939
1939
1941
1945
1948
1949
1949
1949
1949
1949
1950
1950
3
4
1
1
1
4
1
1
1
1
1
1
4
1
1
1
1
2
1
22 '3"
18'9"
10'9"
16'9"
16'9
22 '3"
14 '3"
14 '3"
14 '3"
14 '3"
16 '9"
16 '9"
18'9"
14 '3"
22 '3"
18'9"
18'9"
14 '3"
22 '3"
8
8
6
6
8
11
6
6
6
6
7
6
5
6
8
5
5
5
8
540
400
24
60
75
1100
40
40
48
48
75
65
300
45
165
90
75
90
170
Raw primary
Digested
Raw primary
Digested activated
Raw primary
Raw primary
Digested primary
Raw primary
Digested
Digested
Raw primary
Digested
Digested
Digested activated
Raw primary
Raw primary
Raw primary
Digested
Raw primary
-------
10
City
Bay City, Mich.
Arlington, Va.
Campbell-Kenton, Ky.
Vfest New York, N.J.
Milwaukee, Wis.
Williamsport, Pa. (Vfest)
Williamsport, Pa. (Cent.)
Steubenville, Ohio
Marietta, Ohio
Coluntius, Chio
Indianapolis, Ind.
Cincinnati, Mill Creek
Columbus, Chio
Nashville, Tenn.
Grand Rapids, Mich.
Rochester, N.Y.
Euclid, Chio
Bradford, Pa.
Milwaukee, Wis.
Warren, Ohio
McKeesport, Pa.
Battle Creek, Mich.
Johnstown, Pa.
Cuyahoga Co., Ohio
Boston, Mass.
Pontiac, Mich.
Fairbanks, Alaska
Year
Built
1952
1952
1952
1952
1952
1953
1953
1954
1954
1954
1955
1955
1956
1956
1956
No. of
Units
1
1
1
1
1
1
1
1
1
1
4
4
1
1
1
Size
O.D.
14 '3"
18'9"
18'9"
12 '10"
16 '9"
14 '3"
14 '3"
12 '10"
9 '3"
22 13-
22 13"
22 '3"
22 '3"
18'9"
16'9"
Hearths
6
6
5
4
5
6
6
6
6
7
8
9
7
7
7
Capac.
fans/
24 Hrs.
45
80
55
25
48
45
45
36
18
150
675
600
150
108
80
Type of Sludge
Raw primary
Digested
Raw primary
Raw primary
G & SC only
Raw primary
Digested
Digested
Digested
Digested activated
Raw primary
Digested
Digested activated
Raw primary
Digested
1957
1958
1958
1959
1959
1959
1960
1960
1961
1961
1961
1961
1
1
1
2
1
1
1
1
1
1
1
22'3"
14'3"
16'9"
16'9"
16'9"
16'9"
18'9"
14'3"
18'9"
12'10"
22'3"
12'10"
6
7
5
5
7
5
5
5
6
7
5
288
48
74
48
100
70
78
39
75
36
144
27
Digested, G & SC
Digested
Liquid
G & SC only
Raw primary
Raw primary
Digested
Raw primary
Digested
G & SC only
Digested
Raw primary
-------
00
o
City
Detroit, Mich.
Flint, Mich.
Huntington, W. Va.
Wayne County, Mich.
Wyoming, Mich.
Youngstcwn, Ohio
Saginaw, Mich.
Rock Falls, 111.
Detroit, Mich.
Kansas City, Mo.
Canajoharie, N.Y.
Providence, R.I.
Burlington Twsp., N.J.
Bridgeport, Pa.
Jersey City, N.J.
St. Charles, Mo.
New Haven, Conn.
St. Louis (Lemay Plant)
St. Louis (Bissell Point)
Hatfield, Pa.
Nashville, Term.
Colunbus, Ohio
Indianapolis, Ind.
Wyoming Valley, Pa.
Tbnawanda, N.Y.
Fairfax County, Va.
Richmond, Calif.
Up. Moreland-Hatboro, Pa.
Plymouth, E. Norriton, Pa.
Year
Built
1962
1962
1962
1962
1962
1962
1963
1963
1963
1963
1963
1963
1964
1964
1964
1964
1964
1965
1965
1965
1965
No. of
Units
1
2
1
1
1
2
1
1
1
3
1
1
1
1
1
1
1
3
5
1
1
O.D.
22 '3"
18'9"
18 '9"
22 '3"
16'9"
22 '3"
16'9"
10 '9"
22 13-
22 '3"
14'3"
22 '3"
6'0"
6'0"
22 '3"
12 '10"
22 '3"
22 '3"
22 '3"
10 '9"
18'9"
Hearths
11
6
6
6
6
7
6
5
11
8
5
9
6
6
10
5
9
11
11
6
7
1966
1967
1967
1967
1968
1968
1968
1968
4
1
1
2
1
1
1
22'3"
22'3"
18'9"
22'3"
18'9"
16'9"
16'9"
18'9"
8
8
5
7
7
5
8
Capac.
Tons/
24 Hrs.
294
209
108
135
69
319
70
22
294
550
39
240
5
8
246
34
246
750
1,250
22
104
360
672
159
132
252
84
60
123
Type of Sludge
Raw primary, G & Sk
Digested
Raw primary, G, SC&GS
Raw primary
Digested
Raw primary
Raw primary
Raw primary
Raw primary, G & GS
Raw primary & GS
Raw primary
Raw primary
Raw primary TF
Raw primary, TF
Raw primary, SC & G
Raw primary
Raw primary GS & S
Raw primary & G
Raw primary, GS & G
Raw primary & A
Raw primary & A
Raw primary, digested & GS
Digested primary & A
Raw primary & A
Raw primary, digested & G
Raw primary & GS
Digested primary & A
Raw primary & A
Raw primary & sec.
-------
Size
00
City
Greensboro, N.C.
Charleston, S.C.
Oswego, N.Y.
Hartford, Conn.
Newark, Ohio
Upper Gwynedd, Pa.
Kalamazoo, Mich.
Saginaw, Mich.
Minneapolis-St. Paul
RDchester, N.Y.
Rochester, N.Y.
Portage, Indiana
Delta Township, Mich.
Beacon, N.Y.
Detroit, Mich.
Elizabethton, Term.
Warren, Mich.
Brookfield, Wise.
Clarksburg, W. Va.
Paw Paw Lake, Mich.
Passaic Valley, N.J.
Clark County, Nev.
Waterbury, Conn.
Oxnard, Calif.
Naugatuck, Conn.
Dunkirk, N.Y.
Carson City, Nev.
Nashville, Term.
1969
1969
1969
1969
1969
1969
1969
1970
1970
1970
1970
1970
1970
1970
1971
1971
1971
1971
1971
1971
1971
1971
1971
1971
1971
1972
1972
1972
No. of
Units
1
1
2
3
1
1
1
1
1
1
2
1
1
1
6
1
1
1
1
1
2
1
1
1
2
2
1
2
P.P.
18'9"
22'3"
16'9"
22'3"
18'9"
9'3"
22'3"
22'3"
22'3"
22'3"
22'3"
10'9"
16'9"
14'3"
25'9"
12'10"
25'9"
12'10"
14'3"
12'10"
25'9"
18'9"
22'3"
22'3"
2213"
18'9"
10'9"
22'3"
Hearths
5
5
6
11
5
5
7
6
11
6
11
5
5
6
12
5
10
5
6
5
6
7
7
6
6
5
6
11
Capac.
Tons/
24 Hrs.
72
132
125
800
73
13
187
156
300
143
537
12
58
43
2,622
24
326
32
44
31
125
104
136
35
250
44
128
480
Type of Sludge
Raw primary, TF & A
Raw primary
Raw primary
Raw primary, activated
Digested primary & A
Raw primary, TF
Raw primary & A
Low oxidation
Raw primary & A
Raw primary & A
Raw primary & A
Raw primary & A
Raw primary & A
Raw primary & A
Raw primary & digested waste
activated
Raw primary & A
Raw primary & A
Raw primary & A
Raw primary & A
Raw primary & A
Raw primary & TF
G, SC & SK
Heat treated primary & TF
Primary waste activated & SK
Raw primary & SK
Primary & secondary & SK
Primary, secondary
Raw primary, TF, scum
Primary, waste activated scum
-------
00
PO
Monroe Co., N.Y.
Monroe Co., N.Y.
Louisville, Ky.
Orange Co., Calif.
Orange Co., Calif.
St. Charles, Mo.
St. Charles, Mo.
New Orleans, La.
Utoy Creek, Ga.
Detroit, Mich.
Fitchburg, Mass.
Lower Lackawanna, Penna.
Fairfax, Va.
Genesee Co., Michigan
Fitchburg E., Mass.
Middletown, Conn.
Killingby, Conn.
Size
Year
Built
1972
1972
1972
1972
1972
1972
1972
1972
1973
1973
1973
1973
1973
1973
1973
1973
1973
No. of
Units
1
1
3
1
1
1
1
1
1
2
1
1
2
3
1
1
1
O.D.
18'9"
18'9"
22 '3"
9 '3"
22 '3"
9-3»
16'9"
16'9"
22 '3"
25'9"
10 '9"
16 '9"
25 '9"
18'9"
22 ' 3"
12 '10"
22 '3"
Hearths
6
8
8
6
6
6
5
5
6
12
6
7
6
7
9
6
7
Capac.
Tons/
24 Hrs.
84
72
1,200
12
106
12
55
52
114
437
108
68
356
306
14
32
168
Type of Sludge
Primary digested
Line
Prinary, scum
waste activated
Carbon
Line
Carbon
Primary, waste activated
Primary, trickling filter
Raw primary digested
Primary, secondary
S., G., waste activated
Primary
Raw, primary & waste activated
Primary, secondary, scum
Carbon
Raw primary, waste activated
Primary, secondary
Designed to also handle grit (G), screenings (SC), skimmings (SK), scum (S), grease (GS), and ground
refuse (GR). Also trickling filter (TF), activated (A), and activated press cake (APC).
-------
APPENDIX E
STACK SAMPLING PROCEDURES
183
-------
STACK SAMPLING PROCEDURES
The following section has been included in this report to
explain the stack sampling procedures used in this study. Standard
EPA methods were followed to the degree practically feasible.
However, the reader should be aware that the sampling procedures
were modified slightly to accomodate the physical characteristics
of the pilot and full-scale systems. Consequently the data may not
be rigorously quantitative. However, the potential for error is
minimal and the results are considered substantially accurate.
In neither furnace used in this study did there exist a point in
the exhaust duct that was completely suitable for applying the standard
techniques. There was no accessible point that was sufficiently
removed from any flow obstruction to insure a uniform velocity distri-
bution across the duct. The velocity profile measured across each of
the two stacks deviated slightly from a fully established, uniform
velocity profile in the specific sense that the maximum velocity was
found to be slightly closer to one wall of the duct than to the center.
Under these conditions, perfectly isokinetic sampling is difficult,
but was approximated insofar as was possible. The procedures used
are described below.
A single four-point traverse was used in the pilot-scale
tests. The stack of the pilot-scale incinerator was only
eight inches in diameter and had only one sampling port available
at the best sampling position. Therefore, it was impossible
to conduct perpendicular traverses without installing a second
sampling port, which was beyond the means of the contract. On
the basis of the small size of the stack, it was concluded that
a four-point traverse would be adequate to collect a representative
sample.
In the full-scale tests, a seven point single traverse
was used. As in the pilot-scale test, only one sampling port
was available at the best position. A perpendicular traverse
would have required another sample port which the city would
not provide and for which there was not available funding. The
circular stack was 18 inches in diameter. Under these conditions,
it was decided that a seven-point single traverse would be
adequate to collect a representative sample.
185
-------
Since the above procedures are not precisely standard, it
cannot be guaranteed that the samples collected were perfectly
representative. However, the potential for error is very small:
1. Only particulates ranging in size from 2 to 3 microns
could have been misrepresented. Gases and particles
less than 2 microns have uniform concentrations and
can be sampled representatively at any point inside
a stack. Furthermore, it is an established fact that
high energy venturi scrubbers such as used in this
project can remove particulates greater than 3 microns
with 95 percent efficiency. Thus, the potential for
error with this sampling methodology would apply only
to a small fraction of the particulates.
2. Given the sampling conditions used, the maximum potential
error can be illustrated in the following worst-case
example:
If the total amount of pesticide-bearing
particulate matter that was not collected
was of the same amount as that actually
collected (an assumption that obviously
greatly overestimates the actual situation
since at least half of the collected pesti-
cide was included with particulates that
passed through a 0.45 micron filter) the
effect on the results of the experiment would
amount to a decrease of less than 0.01
percent in the destruction ratio. This point
can best be demonstrated by considering the
experimental data in Tables 23, 24, and 25. If
one were to double the quantity of each of the
pesticide residues in the columns headed
"Particulates" on these three tables, sum all
the contributions as is shown in Table 33, one
would find, for the worst-case (Experiment 3),
that the total emitted pesticide would be at
the rate of 5.24 gm/hr rather than the figure
of 3.78 quoted in Table 33. The destruction
ratio would, under these conditions, be 99.968
rather than the quoted 99.977.
From the above it is clear that, under the special circumstances
of the reported experiments, the error in the quoted results that
could have been associated with the selection of the sampling point is
below that associated with normal analytical errors. Thus, the
emission data is considered substantially correct.
M01238
186
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