U.S. DEPARTMENT OF COMMERCE
                                     National Technical Information Service
                                     PB-265 541
DESTROYING CHEMICAL WASTES IN  COMMERCIAL
SCALE INCINERATORS FACILITY REPORT  NO.  1  -
THE  MARQUARDT  COMPANY
TRW  Defense  and Space  Systems  Group
Redondo  Beach,  California
Prepared  for

Environmental  Protection Agency,  Washington,  D. C,
1977

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BIBLIOGRAPHIC DATA
SHEET
                   1. Report No.
                                                  2.
PB   265   541
4. Tide and Subtitle
  DESTROYING CHEMICAL WASTES IN COMMERCIAL  SCALE INCINERATORS
  Facility Report No. 1 - The Marquardt  Company
                                                                  5. Report Date

                                                                    April  1977
7. Authors)
           J.  F.  Clausen, R. J. Johnson,  C.  A.  Zee
                                                                  8. Performing Organization Kept.
                                                                    No.
9. Performing Organization Name and Address
  TRW Defense and Space Systems Group
  One Space Park, Redondo Beach, California  90278
                                                                  10. Project/Task/Work Unit No.
                                                                  II. Contract/Grant No.

                                                                     68-01-2966
12. Sponsoring Organization Name and Address
  U.S.  Environmental  Protection Agency
  Office of Solid Waste
  Washington, D. C. 20460
                                                                  13. Type of Report Si Period
                                                                    Covered

                                                                     Facility  test  report
                                                                  14.
15. Supplementary Notes
16. Abstracts
  Incineration tests were conducted at The  Marquardt Company, Van Nuys,  California, to
  determine the effectiveness of thermally  destroying two selected industrial  liquid
  wastes:   ethylene manufacturing waste and nexachlorocylopentadiene  (C-5,6).   Each
  waste was burned at three different test  conditions to determine the effects of
  normal operating and equipment variables.   Analysis of combustion gas  samples indi-
  cated destruction efficiencies of over  99.999 percent for each waste constituent.
  Standard EPA Method 5 tests were performed on stack emissions to determine particulate
  loading and composition.  Analysis of scrubber water samples indicated no  increase in
  organic content compared to fresh scrubber water.   Burner head residue formed during
  incineration of each waste contained no chlorinated organics.  Results of  these tests
  indicated that either waste can be effectively destructed in a liquid  injection
  incinerator; however, because of tarry  residual,  the C-5,6 waste may be  better
  matched to rotary kiln incineration.  Estimated cost of destroying  an  assumed annual
                            17o. Descriptors
17. Key Words and Document Analysis.
 Waste  Disposal
  Industrial  Wastes
 Ethylene
  Incinerators
  Field  Tests
 Gas  Sampling
 Chemical  Analysis
 Cost Analysis
17b. Identifieis/Open-Ended Terms
  The Marquardt Company
  Liquid Injection Incinerator
  Hexachlorocylopentadi ene
17c. COSATI Field/Group  07-01, 14-02, 14-01
                                         production of 15 million kilograms  of ethylene
                                         waste was $1.8 million capital  investment and
                                         $1.0 million annual operating costs ($69/metric
                                         ton).  Cost of incinerating 4.5 million kilogram
                                         of  C-5,6 per year was estimated to  be $1.6
                                         million capital investment and  $2.2 million
                                         annual  operating costs ($488/metric ton).
18. Availability Statement
19. Security Class (This
Report)
UNCLASSIFIED
20. Security Class (This
"^CLASSIFIED
21. N> -'•>-*•
22. Price pcfiota
FORM NTIS-BB (REV. 1O-73)  ENDORSED BY ANSI AND UNESCO.
                                                 THIS FORM MAY BE REPRODUCED
                                                                            USCOMM-DC B2B3-P74

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            DESTROYING CHEMICAL WASTES IN
            COMMERCIAL-SCALE INCINERATORS

                Facility Report No.  1
This final  report (SW-122c) describes work performed
   for the Federal solid waste management program
           under contract no. 68-01-2966
  and is reproduced as received from the contractor
        U.S. ENVIRONMENTAL PROTECTION AGENCY

                        1977

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This report has been reviewed  by  the U.S. Environmental Protection
Agency and approved for publication.   Publication does not signify
that the contents necessarily  reflect  the views and policies of the
Environmental Protection Agencyt  nor does mention of commercial
products constitute endorsement or  recommendation by the U.S. Government.

An environmental protection  publication  (SW-122c) in the solid waste
management series.


                                  ii

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                                  PREFACE
      The purpose of this study is to evaluate the environmental, technical,
 and economic feasibility of disposing of industrial  wastes  via incinera-
 tion.  This objective is being pursued through a  series  of  test burns con-
 ducted at commercial  incinerators and with real-world  industrial wastes.
 Approximately eight incineration facilities and seventeen different indus-
 trial wastes will be tested under this program.   The incineration facil-
 ities were selected to represent the various design  categories which
 appear most promising for industrial waste disposal.   The wastes were
 selected on the basis of their suitability for disposal  by  incineration
 and their environmental  priority.

      This report describes the test conducted at  the Marquardt Company,
 which was the first facility of the series.  Marquardt manufactures incin-
 eration equipment and has a liquid injection test unit which  was used for
 this project.  Wastes resulting from the manufacture of  ethylene and from
 hexachlorocyclopentadiene were tested and found to be  successfully
 destroyed by the Marquardt incinerator.

      The content of this report is primarily of an objective  nature pre-
 senting the equipment description, waste analysis, operational procedures,
 sampling techniques,  analytical methods, emission data and  cost informa-
 tion.  Facility reports  similar to this  one will  be  published as soon as
 possible after the testing has been completed at  a facility so that the
 raw data and basic results will be available to the  public  quickly.

      This report and the other Facility  Reports will contain  a few subjec-
 tive conclusions.  However, the detailed subjective  analysis  will be
 reserved for the Final Report, which will  be prepared  after all  testing is
 complete.
                            ACKNOWLEDGEMENTS


     TRW wishes to express its sincere gratitude to the Marquardt Company
personnel, particularly Messrs. Joel Hudson, Robert Babbitt and Kenneth
Scheurn, for their cooperation in conducting these facility tests.  Thanks
are also due to Dr. Philip Levins and Mr.  Jeffrey Adams of Arthur D. Little,
Inc., for their advice in modifying the combustion gas sampling probe to
improve cooling capability.  The project is deeply indebted to Messrs.
Alfred Lindsey and John Schaum of the Office of Solid Waste Management
Programs, U.S. Environmental Protection Agency, for their advice and tech-
nical direction.
                                    iii

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                                 CONTENTS
                                                                     Page
1.   Summary                                                           ]
2.   Introduction                                                      6
3.   Process  Description                                              8
     3.1   Facility Process                                            8
           3.1.1   Incinerator and Reaction  Tailpipe                     8
           3.1.2  Air Supply System                                   14
           3.1.3  Waste Fuel  System                                   14
           3.1.4  Auxiliary Fuel  System                               14
     3.2   Instrumentation                                             14
           3.2.1  Process Parameters                                   14
           3.2.2  Gas Analysis                                        17
     3.3   Emission  Controls                                           17
           3.3.1  Venturi Scrubber and  Separator Tank                  17
           3.3.2  Caustic Solution and  Water Supply System             17
           3.3.3  Scrubber  Liquid  Collection System                    19
4.   Test  Description                                                 20
     4.1   Wastes Tested
           4.1.1  Ethylene  Manufacturing Waste                         20
           4.1.2  Hexachlorocyclopentadiene Manufacturing Waste        22
     4.2   Operational  Procedures                                      24
          4.2.1  Test  Procedures                                      25
          4.2.2  Safety  Procedures                                    26
          4.2.3  Test  Commentary                                      27
          4.2.4  Disposal  of  Waste Residues                           36
     4.3  Sampling Methods                                            36
          4.3.1  On-Line Gas  Monitoring                               36
          4.3.2  Sampling  of  Combustion Products                      43
          4.3.3  Sampling  Emissions and Waste Products                48
                                    iv

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                          CONTENTS (CONTINUED)
                                                                     Page
     4.4  Analysis Techniques                                         50
          4.4.1   Extractions and Sample Preparation                   50
          4.4.2   Analytical  Methods                                   52
     4.5  Problems Encountered                                        54
          4.5.1   Field Test Problems                                  55
          4.5.2   Laboratory Analysis Problems                         56
5.   Test Results                                                     59
     5.1  Combustion Gas Data Summary                                 59
     5.2  Waste  Destruction Analysis Summary                          59
          5.2.1   Organic Composition                                  61
          5.2.2   Inorganic Characterization                           66
     5.3  Final  Emissions                                             69
          5.3.1   Stack Gases                                          69
          5.3.2   Scrubber Waters                                      71
          5.3.3   Solid Residues                                       76
6.   Waste Incineration Cost                                          81
     6.1  Capital Investment                                          81
     6.2  Annual Operating Costs                                      84
Appendices
     Appendix A - Assessment of Environmental Impact                  87
                  of Destructlng Chemical Wastes at
                  the Marquardt Company
     Appendix B - Sample Volume Data                                  91
     Appendix C - Calculation of Incinerator                          97
                  Performance
     Appendix D - Analytical Chemistry Details                        101

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                                 FIGURES
                                                                      Page
 3-1     TMC Test Facility Process Flow Diagram                          9
 3-2     Overall  Test Installation                                      10
 3-3     Incineration Unit                                              11
 3-4     Waste Fuel  Supply System                                       12
 3-5     Basic Burner System Geometry                                   13
 3-6     Process  Controls and Instrumentation                            16
 3-7     TMC On-Line Gas Analysis Equipment                             18
 4-1     MA-II Clinker                                                  30
 4-2     MA-III Clinker                                                 32
 4-3     MA-IV Clinker                                                  33
 4-4     MA-V Clinker                                                   34
 4-5     MA-VI Clinker                                                  35
 4-6     MA-VII Clinker                                                 37
 4-7     Sampling System For On-Line Monitors                            3.8
 4-8     Gas  Conditioning and Analysis  System For On-Line Instruments    39
 4-9     Instrument  Racks                                               41
 4-10    Calibration  Gases and Gas  Conditioner                           42
 4-11    Work Area Behind Instrument Racks                               42
 4-12    Combustion Zone Sampling Train Schematic                        44
 4-13    Combustion Zone Sampling Train                                 45
4-14    Water Cooled  Probe Schematic                                   46
4-15    Sampling System For Combustion Zone                             47
4-16    Sampling System For Stack                                       49
4-17    Sorbent Trap  Extractor                                         58
                                   vi

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                           FIGURES (CONTINUED)

                                                                       Page

5-]    Filters From Combustion Zone Gas Sampling After Solvent          67
       Extraction

5-6    Toxic Trace Metals at Level of Interest (mg/m3) by AAS           68

5-2    Filters From Stack Gas Sampling                                  70
                                    vii

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                                  TABLES
                                                                      Page
 1-1     Results Summary                                                 4
 3-1     Instrumentation for Waste Destruction Testing  - Marquardt       15
 4-1     Composition of Ethylene Manufacturing Waste  Representative      21
        Sample
 4-2     Trace Metals in the Ethylene Representative  Waste Sample        22
 4-3     Composition of Hexachlorocyclopentadiene Waste Survey           23
        Sample
 4-4     Composition of C-5,6 Waste Representative Sample                24
 4-5     Trace Metals in the C-5,6 Waste                                25
 4-6     Incinerator System Parameters Data  Summary                     28
 4-7     Description of On-Line Instruments                              40
 4-8     Summary of Analytical  Methods                                  53
 5-1     Total  Gas  Composition  in  the Combustion  Zone by Volume          60
 5-2     Results of Gas Chromatographic Analysis                         62
 5-3     Organic Material  Extracted From Combustion Zone Filters         63
 5-4     Organic Material  Extracted From Sorbent  Traps, Survey           64
        Analysis
 5-5     Analysis of Organics in Grab Gas Samples                        65
 5-6     Toxic  Trace Metals at  Level  of Interest  (mg/m3) by AAS          68
 5-7     Particulate Mass  Loadings                                       71
 5-8     Percent Sodium Salts as Nad  on  Stack  Filters                   72
 5-9     Gastec^Tube  Results                                           72
 5-10    Results of Gas Chromatographic Analysis  of Scrubber             73
       Water  Samples
5-11     Results of Analysis  of Concentrated Organic Extracts of         74
       Scrubber Water Samples
5-12    Elemental  Analysis of  Scrubber Water by AAS (ppm)                75
                                    vi ii

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                           TABLES (CONTINUED)
                                                                     Page
5-13   C and H Analysis of Clinkers                                    76
5-14   Results of Analysis of Clinker Extracts by Gas                  78
       Chromatography
5-15   Residue Extracted From Clinker                                  78
5-16   Inorganic Composition of Clinkers (ppm)                         80
5-17   OES Detection Limits                                            80
6-1    Capital Investment - 15 Million kg./Yr. Ethylene Manu-          82
       facturing Waste Incineration Plant
6-2    Capital Investment - 4.5 Million kg./Yr. Hexachlorocyclo-       83
       pentadiene Waste Incineration Plant
6-3    Annual Operating Cost - 15 Million kg./Yr. Ethylene             85
       Manufacturing Waste Incineration Plant
6-4    Annual Operating Cost - 4.5 Million kg./Yr. Hexachloro-         86
       cyclopentadiene Waste Incineration Plant
B-1    Gas Volume Data                                                 93
B-2    Final Corrected Gas Volumes                                     94
B-3    Liquid Impinger Volume Data                                     95
D-l    Extracted Material From Control Samples                         103
D-2    Filter Weights Through Analyses (mg)                            112
D-3    Particulate Mass Loadings                                       113
D-4    Elemental Survey of Selected Samples  (mg/m3)                    115
D-5    Caustic Impinger Analyses                                       116
                                    ix

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                               1.  SUMMARY


     Numerous organic wastes from industrial operations are generated in
 liquid form.  From a physical point of view, they are often suited for dis-
 posal in commercial liquid injection incinerators.  If a given liquid waste
 possesses a significant heating value, it may be a candidate for heat re-
 covery by utilizing it as a supplementary fuel or by combustion-for example-
 in a water wall incinerator.  Ideally, such a high heating value waste
 would have a relatively low toxicity level, little ash content, minimal
 suspended solids, be pumpable at ambient temperatures, and annually generated
 in significant volumes.  At the other end of the spectrum are those liquid
 wastes which are quite hazardous and have low heating values.  Organochlorine
 wastes represent an excellent example of this class of waste.  Annual waste
 quantities generated tend to be large, hence the disposal problem is signi-
 ficant.  Solids loadings and ashing characteristics will vary.  Because of
 the hazardous nature of these liquid wastes, however, thermal destruction
 appears to be a desirable disposal method relative to other alternatives.

     Two representatives of liquid organic industrial wastes were selected
 for incineration at The Marquardt Company facility.  In great measure, they
 exemplify extremes of this generic waste form.  The two wastes selected for
 incineration were those resulting from the manufacture of ethylene and hexa-
 chlorocyclopentadiene (C-5,6).   On the one hand, ethyl ene manufacturing
 waste is a relatively nonhazardous. high heating value waste.  It is gen-
 erated at a rate of approximately 15 million kilograms per year

     This waste was a clear light brown solution with no apparent sediment
 or particulate at room temperature.  Indeed, it possessed physical  and chem-
 ical properties not unlike distillate oil.  For example, this waste had  a
 specific gravity of about 0.9 and a heating value of around 10,000 kcal/kg.
 Its chemical composition was approximatelv 89 percent carbon and 9 percent
 hydrogen.  Halogens-as chlorine-were about 0.004 percent.  Sulfur and nitrogen
 contents were relatively low; namely 1.32 and 0.13 percent, respectively.
Ash content (nonvolatile inorganics) in this waste was less than 0.01 per-
 cent.  A viscosity of 1.28 centistokes (at 22°C) allowed this material  to be
 pumped and injected into the incinerator without preheating or other condi-
 tioning.  In reality,  this waste appears to be a good candidate for use  as
 a supplementary fuel.

     Conversely,  hexachlorocyclopentadiene manufacturing waste (4.5 million
 kilograms  annually)  was significantly different in comparison with the
ethylene waste.   This highly chlorinated waste would not sustain combustion
without auxiliary fuel.   Its heating value was only 2,400 kcal/kg.   Physi-
cally, the C-5,6  waste was a dark brown dense and viscous liquid with sus-
pended, wax-like  particulate matter.   Specific gravity of the C-5,6 was  in
excess of 1.7,  while  its viscosity at room temperature  was 11.3 centistokes.
Fortunately, this waste was miscible in No.  2 fuel  oil  which facilitated
 injection and combustion in a liquid incinerator.

     Selection  of hexachlorocyclopentadiene waste is  important since it
represents a class of heavily chlorinated wastes.   Safe destruction of
this hazardous  material  is indicative of what may be  anticipated by

                                     1

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Incinerating similar organochlorine wastes.  Further* C-5,6 is the princi-
intermediate for synthesis of important polychlorocyclodiene pesticides,
including chlordane, haptachlor, aldrin, dieldrln, isodrin. endrin. mirex
and kepone.  In this regard, prolonged storage of such pesticides can re-
sult in product degradation in which C-5,6 may be formed.  Further, incin-
eration of chlorinated pesticides may result in the formation of C-5,6 as
an intermediate reaction product.  Therefore, adequate thermal destruction
of C-5,6 waste suggests that similar wastes as well as unused C-5,6 based
pesticide formulations could be safely incinerated with a significant
degree of confidence.

     Incineration tests with these two wastes were conducted at The
Marquardt Company facility. Van Nuys, California.  The purpose of the tests
were to determine the effectiveness of thermally destroying these two dif-
ferent wastes from a combustion standpoint! and to insure that incineration
could be accomplished in an environmentally safe manner.  Marquardt1s
incineration facility was chosen for a number of reasons.  Basically, it
is a liquid injection system and thus compatible with the waste farm,
Further, the incinerator was capable of combustion temperatures in the
800°C to 1400°C (1500°F to 2500°F) temperature range desired for adequate
waste destruction.  In addition, a caustic venturi scrubber was available
to neutralize HC1 formation derived from combustion of the heavily
chlorinated C-5,6 waste.

     Marquardt's liquid injection incinerator consisted of a SUE® (for
SUdden Expansion) burner; air, waste, and auxiliary fuel feed systems; and
aThigh energy venturi scrubber.  The incinerator was a well-instrumented
test unit but similar in operation to their commercial configuration.
Marquardt has numerous commercial incinerator installations of this basic
system in field operation.  The incinerator is scaled up to process larger
waste throughputs by simply adding more basic units with proper manifolding,
controls and an appropriately sized scrubber.  In this regard, the test
incinerator was very representative of typical Marquardt commercial instal-
lations.  Further, the incinerator is setup to use No. 2 fuel oil as an
auxiliary fuel; a necessity with low heating value fuels such as C-5,6
waste.

     Each waste was burned at three different conditions to ascertain the
effects of normal operating and equipment variables as well as attempting
to define minimum destruction requirements where feasible.  Ethylene waste
incineration proved relatively straightforward and trouble free.  In
reality, its combustion characteristics were quite similar to No. 2 oil,
although some solid residue formation was apparent following long duration
runs.

     The C-5,6 waste presented obvious problems associated with a liquid
injection and feed system.  Waste suspended solids tended to clog filters
rapidly.  Smaller particulate passing through a filtration system will,
after prolonged operation, abrasively erode injection orifices.  This can
be minimized by premixing the C-5,6 with fuel oil in holding tanks and
allowing the particulate to settle.  In any event, a steam or electrically
heated and insulated waste feed system would be necessary where premixing,
settling or other processing takes place at ambient temperatures less
than 20°C.
                                     2

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     Elemental chemical analysis of the C-5,6 showed the following composi-
tion: 20.76 percent carbon, 0.67 percent hydrogen, 0.37 percent N, 0.02
percent S, and 76.47 percent halogens as chlorine.  The chlorinated species
were predominantly C5C16 (hexachlorocyclopentadiene) and C5C18 (octachloro-
cyclopentane).  As a result, incineration of this waste necessitates use of
a caustic wet scrubber to remove the large quantities of the HC1  combustion
product.

     As indicated previously, the test program was conducted using three
operating conditions for each waste.  The ethylene wastes were burned at
three different combustion temperatures to evaluate the impact on destruc-
tion efficiency.  The combustion of C-5,6 however, required a different
approach due to the fact it would not support combustion without  the pres-
sence of an auxiliary fuel.  Because of this, there was concern that
chlorinated species (principally CsCle or CsCls) would be emitted to the
atmosphere as a result of incomplete destruction at lowered combustion tem-
peratures.  For this reason, it was arbitrarily decided that the  fuel/air
ratio would be held approximately constant at the highest combustion tem-
perature attainable.  Thus to evaluate destruction of C-5,6 under different
operating conditions, this waste was burned using three blends of fuel oil
and waste.

     A summary of the test results is presented in Table 1-1, beginning
with the range of test conditions for each waste, including combustion tem-
perature, residence time, and waste feed rate.   Standard EPA Method 5 tests
were performed on the stack emissions to determine particulate loading and
the nature of the particulate.  Grain loadings  of 20-25 mg/mg3 were obtained
for the No. 2 oil and ethylene waste tests.  Particulate loadings of 36 to 113
mg/m3 were obtained for the C-5,6 tests, but 90 percent of the particulate
matter from these tests was found to be sodium  salts generated by the
reaction of the caustic scrubber with HC1  and 0)3.  The particulate was
analyzed for toxic metals and none were found to exist above 0.1  mg/m3 in
the stack gases.

     The stack gases were sampled for hydrocarbons and SOX on all tests,
and for HC1, Cl2» and phosgene on the C-5,6 tests.  The only specie
detected was SOX at levels consistent with the  fact that the ethylene waste
contained more than 1 percent sulfur.  The limits of detection for the
other species are discussed in Section 4.4.

     Benzene and mesityl  oxide were found  in the test filter and  sorbent
trap samples at levels which ranged from <0.2 to 2.4 mg/m3.  These levels
are about the same as those obtained for the appropriate control  samples.
Nothing of the less volatile materials, e.g., heavily chlorinated organics,
POM, etc., were seen for any of the tests  above the lower limits  of detection
for the analyses.  These detection limits  were  estimated to be 0.1 mg/m3.

     Samples of scrubber water were also analyzed for organic content.
Organic material was found in the scrubber water but at the same  approxi-
mate levels as in the control samples of fresh  scrubber water. Gas
chromatographic retention data indicates that the same compounds  are pre-
sent in all samples.

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                           TABLE 1-1.   Results  Summary
Combustion Temperature (°C)
Residence Time (sec)
Feed Rate ( kg/ml n)
Quality of Stack Emissions:
Parti art ate (mg/m )
Trace Metals (mg/m )
Quality of Combustion Gas:
2
Total Organlcs (mg/m }
2
Waste Content (mg/m )
Trace Metals (mg/m )
Quality of Scrubber Water:
Total Organlcs (mg/1)
Trace Metals (mg/1)
Quality of Solid Residue (Clinker):
Waste Content (mg/g)
Destruction Efficiency:
Total Organics (percent)
Waste Constituents (percent)
Capital Cost ($)
Operating Cost ( I/metric ton)
Plant Size (Kg/yr)
Ethyl ene Waste
1349-1752
0.14-0.19
1.4-2.0
20-25
0.001-0.003 Pb
13-22
Not Detected
(<0.02)
0.002-0.003 Pb
Not Significant^3^
0.02 Pb
1.8-2.4
99.96-99.98
>99.999
1 ,318,000
69.31
15 million
C-5,6 Waste
1348-1378
0.17-0.18
2.0-2.9*15
36-113<2>
0.003-0.006 Pb
0.034-0.065 Hn
21-27
Not Detected
(<0.02)
0.55-1,40 Pb
0.077-0.19 Mn
0.090-0.33 Co
Not Sign if leant (3)
0.21-0.54 Pb
Not Detected
(<.026)
99.97
> 99. 999
1,630,000
487.59
4.5 million
(^Mixture of C-5,6 and No. 2 oil; feed rate of C-5,6 alone is 0.66-1.5

(2'85-90 percent of stack particulate content was calculated (based  upon
   sodium analysis) to be NaCl produced by the reaction of the caustic
   scrubber solution with HC1 and C02.

^ 'Levels not significantly higher than background water samples.
                                      4

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     A burner head residue was found to form during  incineration  of both
waste materials.   These residues were typically 95 to  99  percent  carbon
and had some remnants of the fuel feed contained in  them  at <0.5  percent.
Constituents of ethylene waste were easily detectable  in  the  clinker from
those runs, but the organics found in the C-5,6 test clinker  were not
chlorinated.

     The waste destruction performance is also summarized in  Table 1-1  for
both total organics and the specific waste constituents.   Emissions and
efficiencies are measured at the combustion zone exit  prior to the scrubber
system.  A sample destruction efficiency calculation is presented in
Appendix C.


     The results of these tests indicate that the C-5,6 waste can be
effectively destructed in a liquid injection incinerator.  No evidence  of
C-5,6 or any other chlorinated organic was found in  any of the samples
including the "coke like" burner head residue referred to as  clinker.  How-
ever, because of the tarry residual in the waste, the  C-5,6 may be better
matched to rotary kiln incineration, which can accommodate tars and sludges,

     Chemical composition, combustion characteristics, and emissions of the
ethylene waste are so nearly identical to No. 2 oil  that  the  use of this
waste as a primary or secondary boiler fuel should be  seriously considered.
With the possible exception of the formation of clinker,  which appears  to
have small impact, the incineration of this type of  ethylene  waste is
clean and efficient.

     Both capital investment and annual operating costs were  estimated  for
SUE®incineration systems to handle the annual source  plant productions  of
the ethylene and C-5,6 wastes.  Annual waste production of the ethylene
waste was assumed to be 15 million kilograms (33 million  pounds), result-
ing in an estimated total capital investment of $1,818,000 and annual oper-
ating costs of $1,037,500 ($69.31/metric ton).  An annual waste production
of 4.5 million kilograms (10 million pounds) was used  to  estimate the
C-5,6 waste incineration costs.  Total capital investment was estimated to
be $1,630,000 with annual operating costs of $2,211,700 ($487.59/metric
ton).

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                              2.   INTRODUCTION


     The  objective  of this facility test program was  to evaluate the ef-
fectiveness of thermally destructing specific  industrial chemical wastes
In an existing commercial  scale  processing facility.  These facility tests
are part  of an overall  U.S.  Environmental  Protection  Agency sponsored
program involved  with selective  testing of seventeen  different wastes at
eight generic  types of thermal destructing facilities.  The purpose of
this test program is to acquire  useful  disposal  technology as well as
economic  information.   This  report describes test  operations and results
of incinerating two different liquid wastes in a commercially available
liquid injection  incinerator operated by The Marquardt Company (TMC),
Van Nuys, California.   TMC is a  manufacturer of  incinerators, not a waste
disposal  company,and operates a  test facility  for  evaluation of their
incinerator with  different wastes.

     TMC  has been involved in combustion research  and production of com-
bustion devices for over 30  years, including ramjets, rocket-ramjet hybrids,
and rocket engines.   Concurrent  with the evolution of this advanced tech-
nology, TMC developed a burner for in-house use  to generate high pressure,
high temperature  gases  for the testfng of supersonic  ramjets and materials~
as well as related  aerodynamic testing.   The TMC burner is called the SUE®
(for SUdden Expansion burner) and was ultimately integrated into a full-
scale, commercially available incineration system.

     The  TMC incinerator was selected for use  on this program for several
reasons.   It utilizes a unique liquid injection  configuration which has
good air/fuel  mixing properties.   Development  and  application of the TMC
incinerator system  has  been  ongoing for over 12  years, it is commercially
available and  currently in use at various industrial  facilities.  As a
result, this incinerator concept has been found  to be effective in de-
stroying  waste propel!ants and solvents as well  as chlorinated hydrocarbons
including herbicides and pesticides.   TMC's incinerator is a well-instru-
mented installation equipped with a high energy  venturi scrubber for control
of atmospheric emissions.

     The  two materials  tested at TMC, ethylene waste  and hexachlorocyclo-
pentadiene (C-5,6)  waste,  were selected based  upon physical compatibility
with the  incinerator,  annual  waste generation  quantities and the hazardous
nature of the  wastes.   Both  wastes are  liquid  and  thus suitable for a
liquid injection  system.   Similarly,  both wastes are  generated in relatively
large quantities.   Further,  they are representative of even larger classes
of similar Industrial wastes. The ethylene waste  has a high heating value
and is therefore  ultimately  a candidate for heat recovery although the
present TMC incinerator did  not  utilize a water  wall  combustion chamber.
Conversely, the C-5,6 material has a very low  heating value (requiring
auxiliary fuel  to sustain  combustion),  but is  heavily chlorinated and quite
hazardous.  For these reasons, the two  wastes were burned in the TMC
facility  to demonstrate incineration as a viable alternative to landfill
disposal.

-------
     Although the TMC incinerator tested on this program had a maximum
input feed rate of 3.5 liters/min (55 GPH), it is truly representative
of commercial scale applications.  This is because applications requiring
greater feed rates are achieved simply by using multiples of the existing
design.  A 12.6 liters/min system, therefore, would only necessitate
manifolding four TMC incinerators onto a common foundation.   Controls and
safety devices would be essentially the same as with a single incinerator.
In most applications, exhaust gases would be manifolded to a single ade-
quately sized wet scrubber.  For these reasons, data generated at the
Marquardt test facility are deemed representative of larger systems.  In
addition, the single TMC unit was both convenient and economic insofar as
the EPA program objective of demonstrating waste destruction efficiency.
The fact that TMC's facility was very well instrumented facilitated the
conduct of a well controlled and environmentally sound test program.

     The following report sections describe in detail  the incinerator
process equipment (Section 3), and the waste destroyed and test and
sampling procedures followed (Section 4).  Test results are presented and
discussed (Section 5), including effectiveness of destruction of the wastes.
An estimate of the capital investment and operating costs of disposing of
wastes using this type of incinerator equipment is also included in the
report (Section 6).

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                         3.  PROCESS DESCRIPTION
3.1  FACILITY PROCESS
     The Marquardt liquid incineration test facility process is  shown
schematically in Figure 3-1.  Basic system components, shown in  Fig-
ures 3-2 through 3-4, include:

       t  Bidden .Expansion (SUE®) incinerator

       •  Radiation cooled reaction tailpipe

       •  Air supply system

       •  Waste fuel system

       t  Auxiliary fuel system

       •  Instrumentation

       •  Emission control system

     Following is a description of the incinerator and feed system.  Facil-
ity instrumentation and emission controls are discussed in subsequent
report Sections 3.2 and 3.3,  respectively.

3.1.1  Incinerator and Reaction Tailpipe

     The configuration of the SUE® incinerator and radiation cooled  reac-
tion tailpipe is shown in Figure 3-5.  The burner consists of an inlet
pipe connected to a large diameter combustion chamber by means of a  flat
plate.  Fuel nozzles protruding through the plate spray the fuel radially
into the inlet oxidizer stream.  Burning occurs in the recirculation zone
formed by the flat plate and  the combustion chamber wall.  An overall view
of the combustion chamber and tailpipe is presented in Figure 3-3.

     The combustion chamber wall is constructed of 310 stainless steel  and
is actively cooled by process air prior to its entry into the combustion
zone, thus preheating the air to between 150° to 370°C.  The reaction
tailpipe, also of 310 stainless steel, is cooled by radiation to the envi-
ronment and provides a hot walled chamber for completion of the  incinera-
tion process.  The mating flanges of the reaction tailpipe are internally
water cooled to prevent warping or leakage and are sealed with high-
temperature asbestos fiber material.  Ports were provided as shown on Fig-
ure 3-5 for instrumentation and gas sampling.  This unit operates at
velocities of 30 to 45 m/sec, depending on mass flow and temperatures,
with resulting "stay time" to the end of the reaction tailpipe (and  gas
sampling ports) of approximately 0.12 to 0.2 seconds.  The incinerator
was designed for a continuous feed rate of 190 to 230 liters per hour and
a maximum wall temperature of 1650°C, and has successfully destructed
chlorinated wastes such as herbicides and pesticides.
                                    8

-------
     _^_  -.  ©
       g>  YY
                                                                                              ^*—
                                                                                               43b—
                                                                                 S^i.-j€  "^IT^  IIMMI
Figure 3-1.  TMC Test Facility  Process  Flow Diagram (Figure Courtesy of TMC,  Van  Nuys,  California)

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      STACK SAMPLING
   ''  PLATFORM
   ,V
                   EXHAUST
                   STACK
                  SEPARATOR
                  TANK
                     I
                             VENTURI
                             SCRUBBER
                 CONTROL
                 ROOM
                                                    REACTION
                                                    TAILPIPE
                                          SUE     INCINERATOR
                                         - COMBUSTION CHAMBER
                       AUXILIARY
                      . FUEL INLET
                WASTE SUPPLY
                INLET
'igure 3-2.   Overall Test Installation (Courtesy of The Marquardt Company)
                                10

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                           SPENT SCRUBBER WATER CATCH TANKS
                  .REACTION TAILPIPE
CHAMBER EXIT
THERMOCOUPLES
                                                        SUE* INCINERATOR
                                                        COMBUSTION CHAMBER.!
S AIR SUPPLY SYSTEM
                                                               PREHEAT
                                                               THERMOCOUPLf

  Figure 3-3.  Incineration Unit (Courtesy of The Marquardt Company)

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r •
                                                                 WASTE FUEL FEED TANK
                                                                            RECIRCULATION PUMP
DRUM TRANSFER
STATION
                                                      TRANSFER PUMP
                      Figure 3-4.  Waste Fuel  Supply System (Courtesy of The Marquardt Company)

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                                                TM MMMIUMT CMFOtATMM
                                                                                                  Mn   /*-**- y v
8MS/C
                                            rzsr  sysre^t
     7C4.
wttrf
                     _Lf
      /A/
    i.zsjr.o.
                                 .-r_tf
r
                                                                                                 ^_ 4-
                                                                                      LL
                                                                          _/x«7 rt>
                                                                                                       **
                                                                                    f*## SfOfJ
                                                                               US. 01TKMr "O. 3,074-. 44,9
                                   Figure 3-5.   Baste Burner System  Geometry

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3.1.2  Air Supply System

     Combustion air was supplied from the 4,140-kilopascal  (600 psi)  facil-
ity storage tanks.   The Marquardt facility normally maintains a high  pres-
sure air supply for ramjet engine testing.  Combustion air  flow rate  is
regulated by a remotely controlled valve and metered with a sonic venturi.
Air feed lines to the combustion chamber are shown in Figure 3-3.  This
system is used by TMC due to its availability.   Commercial  installations
utilize conventional forced draft fans for combustion air.

3.1.3  Waste Fuel System

     Waste fuel was transferred from 208-liter (55 gallon)  drums into a
1,140-liter, 3,450-kilopascel  (500 psi) feed tank (Figure 3-4).  The  tank
was pressurized with nitrogen, and fuel was fed to the incinerator through
either of two parallel 5 micron filters, a remote control valve, and  a
turbine flowmeter.   The fuel line was purged with N2 after  use.  A recir-
culation system was used to mix the tank contents.  In commercial practice,
the waste feed would be pumped from a run tank into the incinerator.

3.1.4  Auxiliary Fuel System

     The auxiliary fuel inlet to the incinerator is shown in Figure 3-2.
Propane gas was used to preheat the incinerator system to an equilibrium
temperature of approximately 815°C before introduction of the waste liquid.
Once combustion was established with the waste fuel, the propane was
turned off and a small air flow introduced into the propane system for
burner nozzle cooling.  For controlled test purposes, a gaseous nitrogen
(GN2) purge was included to clean the system during shutdowns.  All flows
were controlled remotely and metered with sonic venturi.

3.2  INSTRUMENTATION

     Instrumentation capability provided at the Marquardt facility for this
test program is shown on the Figure 3-1 schematic.  All instrumentation was
calibrated and certified by the Marquardt Standards Laboratory prior to
initiation of testing.  Measurements were made of all process parameters,
including pressures, temperatures, and mass flow rates.  In addition, on-
line gas analysis of combustion products was conducted.

3.2.1  Process Parameters

     Continuous measurements were made of all pressures, temperatures, and
mass flow rates required to control and monitor the incineration process,
including the scrubbing and sampling systems.  Process instrumentation is
listed in Table 3-1.  Figure 3-6 shows the process control  panel and
instrumentation readouts.  Direct pressure gauges were located outside of
the viewing windows.  Temperatures were recorded on 8 or 16 point recorders.
Turbine flowmeter readouts were read directly in Ibs/sec.  Estimated waste
flow measurement accuracy was ±2 to 4 percent, depending on whether the
flow rate was in the mid range of the calibration or not.
                                    14

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     Table 3-1.   Instrumentation for  Waste Destruction Testing - Marquardt
                                 (Refer  to Figure 3-1)
System
Air


Natural
Gas or
Nozzle
Cooling
A1r/GN2


Waste
Fuel






SUE
Burner


Scrubber
Systems






Sampling
Systems


Symbol
d*
PT1
TC-1
d*
n
T2
£
Ps2
TC-2
PT5
Wf
TC-3
PT3
pTg
Py

Li
TC-8
PT3
*P1
TC-4
TC-5,6,7
Wr
c
Ww
TC-12

TC-10

TC-9

PT6
"T7
Tc-n
Function 1 Note
I
Air flow Venturl
Upstream total pressure
Inlet total temperature
Gas flow Venturl

Upstream total pressure

Throat static pressure
Inlet total temperature
Manifold pressure
Turbine flowmeter
Inlet fuel temperature
Manifold pressure
Supply tank pressure
Supply pressure downstream
filters
Fuel tank liquid level
Fuel tank temperature
Burner Inlet pressure
Burner pressure drop
Burner air Inlet temperature
Exhaust gas temperature
Caustic Solution
Water flowmeter
Scrubbed effluent gas tem-
perature
Scrubber water exit tem-
perature
Caustic solution Inlet tem-
perature
Beckman probe cooling air
TRW probe purge air
Beckman sample gas temperature
N/A
2
1
N/A

2

2
1
2
2
1
2
2
2

3
2
2
2
1
1,2
2
2
2

1

1

2
2
2
Size or Range
0.80" d1a.
0-200 psig
0-100°F
0.227" dia.

0-50 psig

0-50 psig
0-100°F
0-50 psig
.05-. 20 pps
0-200°F
0-500 psig
0-500 psig
0-500 psig

Sight Gauge
0-200° F
0-10 psig
0-25" H20
0-1000°F
0-2400° F
0.5-1.6 pps
0.5 - 3 pps
0-200°F

0-200°F

0-100°F

0-100 psig
0-100 psig
0-300°F
NOTES
1.   Continuously measured and recorded  parameters.
2.   Continuously measured but manually  read/recorded every 30 minutes or
    whenever deemed necessary by operational changes.
3.   Manually measured/checked and recorded whenever deemed necessary.
                                           15

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o
                                   DIRECT PRESSURE
                                   INSTRUMENTS
                                                                      r PW-
                                                              REMOTE PRESSURE!
                                                              INSTRUMENTS
                                                 Irrmtrm
                                                      mt •
'''.'//.•' .-••'"•'*'
                                                                                           FLOW
                                                                                           READOUTS;
                      »•••••
                TEMPERATURE
                RECORDERS
                           SYSTEM CONTROLS
                        •w. ,'^..,-

                            ,
                                 •
                        t  '
                Figure 3-6.  Process Controls and Instrumentation (Courtesy of The Marquardt Company)

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3.2.2  Gas Analysis

     On-line continuous monitoring of combustion gas products  was performed
for all tests using the following instruments (shown in  Figure 3-7).

       CO  - Beckman 315A (Infrared), Span 0-5000 ppm

       NO  - Beckman 315A (Infrared), Span 0-200 ppm

       CHX - Beckman 109A (Flame lonization), Span 0-30,000 ppm (Variable)

     Valves were provided to allow sampling from either  the combustion
zone or the stack exit, as shown in Figure 3-1.   Data from the combustion
zone gas analysis was used to indicate relative  system combustion effici-
ency and to verify attainment of steady state operating  conditions prior
to initiating gas sampling runs.

3.3  EMISSION CONTROLS

     Atmospheric emissions from the combustion of liquid wastes during the
Marquardt incineration tests were controlled by  a high energy  venturi
scrubber system.  The major components of the scrubber system, shown  in
Figures 3-2 and 3-3, are described in the following paragraphs.  Disposal
of spent scrubber liquids is also discussed.

3.3.1  Venturi  Scrubber and Separator Tank

     Combustion gases leaving the reaction tailpipe passed through the
high energy venturi scrubber into the separator  tank (Figure 3-2).  Quench-
ing and scrubbing water with caustic solution (10-12% NaOH/water) were
injected at the venturi inlet and mixed with the combustion gas at veloci-
ties up to 125 m/sec in the venturi throat.  The separator tank is equipped
with a metex screen demistor.  Spent scrubber water was  collected in  the
separator tank and transferred to holding tanks  (Figure  3-3) by a cyclic
pumping system.  The water saturated, scrubbed effluent  gases  were dis-
charged up the stack.

3.3.2  Caustic Solution and Water Supply System

     Fresh water to the venturi scrubber was supplied from the
965-kilopascal (140 psi) facility water system at the rate required to
quench the gases and scrub at a rate of approximately 19 liters/min per
28 actual cubic meters per minute.  When burning the C-5,6 waste, caustic
solution was also injected to neutralize the HC1 and Clg in the combustion
products .  Caustic flow (approximately 12 percent NaOH  in water) was
injected at a rate about three times the amount  required to neutralize the
theoretically expected amounts of HC1.  Both flows were  regulated by
remote control valves and metered by turbine flowmeters.
                                    17

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                                                SAMPLE FLOW  «
                                                CONTROLS
                                    HYDROCARBON
                                    ANALYZER
Figure 3-7.
TMC On-Line Gas Analysis Equipment  (Courtsey of
The Marquardt Company)
                         18

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3.3.3  Scrubber Liquid Collection  System

     Spent scrubber water was  collected in  any of three  21-kiloliter
(5,500-gallon) catch tanks  (Figure 3-3).  The pump cycle was monitored to
allow taking of samples during actual  separator  tank  pumpout.  The  col-
lected liquid was discharged to the facility's 5.3 megaliter reservoir.
Reservoir water is analyzed and neutralized, if  required,  before  release
to the municipal sewer system.
                                    19

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                          4.  TEST DESCRIPTION


     This section presents the manner  in which the tests were carried out.
It is divided into the following  subsections, listed in order of
discussion:

         •   Physical and chemical description of the wastes that were
             tested

         •   Operational procedures used and a test-by-test commentary

         •   Sampling methods

         •   Analysis techniques

         •   Description of  the problems encountered related to the facility
             and sampling.

4.1  WASTES TESTED

     The two wastes  selected for  testing at TMC were from the manufacture
of ethylene and hexachlorocyclopentadiene  (C-5,6).  Survey samples were
received as early as possible before the tests and representative samples
were obtained by compositing another sample at the time the waste material
to be burned was drummed.  These  samples were then analyzed for both organic
and inorganic composition to determine the expected compounds of interest
in the test burn samples.

4.1,1  Ethylene Manufacturing Waste

     The ethylene waste was  a clear light  brown solution with no apparent
sediment or particulate at room temperature.  It had a strong pungent odor
but did not fume when exposed to  the atmosphere.  The loss on ignition at
800°C (LOI) for this material was greater  than 99.99 percent, indicating a
very low concentration of non-volatile inorganics.  Other physical charac-
teristics of the waste sample were:

         •   Heat content of 10,050 kcal/Kg (18,100 Btu/lb)

         9   Specific gravity of  0.91

         •   Kinematic viscosity  of 1.28 centistokes at 22°C

     Elemental analyses performed on the ethylene waste showed the composi-
tion to be:
                     carbon               - 88.7  percent
                     hydrogen             -  8.6  percent
                     nitrogen             -  0.13 percent
                     sulfur               -  1.3  percent
                     halogens  as  chlorine - 40 ppm
                                     20

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4.1.1.1   Organic Composition

     Analytical  techniques used to determine the organic composition
included infrared spectrophotometry (IR),  low resolution mass spectroscopy
(LRMS),  and combined gas chromatography/mass spectroscopy (GC/MS).   The IR
spectrum revealed the presence of aromatic and aliphatic hydrocarbon struc-
tures.  All significant peaks correlated to major constituents found in
the GC/MS analysis discussed below.  No evidence of -OH, -NH, -COOH, -C=0,
or any other peaks indicating the presence of other functional groups were
observed.  Analysis by LRMS indicated alkyl substituted benzenes, indenes,
and napthalenes as the primary species.  The spectra indicated a rather
complex mixture of species, but no appreciable signal  was detected for
compounds of molecular weight over 170.

     The combined GC/MS analysis of the survey sample found eleven species
whose chromatographic response was 0.1 percent or more of the total nor-
malized area.  The results, summarized in Table 4-1, showed the waste to
consist primarily of unsaturated cyclic and aromatic compounds.  No organic
sulfur compound could be identified which would relate to the 1.32 percent
S found by elemental analysis.  Thus, the sulfur is most likely present
in an inorganic form.  These compositional values are based on equal
response of all these hydrocarbons to the flame ionization detector (FID).
This assumption is adequate for the purpose of identifying major compounds
and/or partial decomposition products in the combustion test samples.  The
representative sample of the ethylene wastes fed to the incinerator was
analyzed by GC under the same conditions used to analyze the survey sample.
The chromatograms were compared and the results indicated that the two
materials were identical except for small  differences in the relative peak
areas of a few of the smaller peaks.  The relative concentrations of the
major constituents of the waste remain essentially the same as shown in
Table 4-1.
            Table 4-1.  Composition of Ethylene Manufacturing
                        Waste Representative Sample
            Compound
Approximate Concentration
        (percent)
    Cyclopentadiene
    1,3, 5-Hexatriene
    Methylcyclopentadi ene
    Benzene
    Cyclohexadiene
    Toluene
    Xylene
    Styrene
    Methyl Styrene
    Indene
    Molecular Weight 131 or 132
    Methylindene and Divinyl Benzene
    Naphthalene
    Ethyl Naphthalene
           30.
           20.
           20.
            3.
           20.
            0.8
            5.0
           <0.1
            1.
            3.
            0.2
                                    21

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4.1.1.2  Trace Elements

     Trace elemental analysis was  performed by spark source mass spectro-
scopy (SSMS).  This analysis showed  no metals present at greater than 1  ppm
levels.  A few potentially  toxic metals  were found at low ppb levels.
These elements and their  predicted combustion concentrations from the SSMS
data, using  Run  IV as  an  example for waste feed rate and other operating
conditions,  are  shown  in  Table  4-2.  Of  these elements, only Pb and As  are
susceptible  to loss during  the  dry ashing sample preparation step for SSMS
and may  be somewhat low.  The mercury determination was performed by a
hignly quantitative atomic  fluorescence  technique  in order to be sure of
an accurate  measurement.  The extremely  low concentrations of these ele-
ments in the ethylene  waste indicate an  expectation of correspondingly low
emissions.
                 Table 4-2.   Trace Metals in the  Ethylene
                             Representative Waste Sample
Element
Cr
Cu
Mn
Pb
As
Hg
Ba
Measured
Concentration
in Waste (ppb)
14
41
2
16
8
70*
1
Predicted
Concentration Produced
by Combustion (yq/m3)
1.0
3.0
0.2
1.2
0.6
4.9
0.1
 *Determined by atomic fluorescence
 4.1.2  Hexachlorocyclopentadiene Manufacturing Waste

      The C-5,6 waste was a dark brown liquid with darker,  suspended, semi-
 solid,  wax-like particulate matter.  The material had a slight odor but did
 not fume when exposed to the atmosphere.  The material  lost 99.96  percent
 of its  mass upon ignition at 800°C, indicating a low inorganic content.
 Heat content for the survey sample was determined to be 2,400 Kcal/Kg
 (4,300  Btu/lb).  Its specific gravity was 1.74, and its viscosity  at 22°C
 was 11.34 centistokes.
                                     22

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     Elemental  analyses  performed  on  the  C-5,6 waste showed  the composition
to be:
                     carbon
                     hydrogen
                     nitrogen
                     sulfur
                     halogens as  chlorine
20.8   percent
 0.67  percent
 0.37  percent
 0.016 percent
76.5   percent
4.1.2.1  Organic Composition

     Analytical  techniques used to determine the organic composition in-
cluded IR, LRMS, and GC/MS.  The infrared spectrophotometric analysis did
not reveal the presence of -CH, -OH, -NH, -C=0, -COOH,  or any other func-
tional groups other than those attributable to halogenated organics.  Most
of the major peaks in the spectrum matched those of hexachlorocyclopenta-
diene, Cede-  Other peaks matched that of its eight chlorine analogue,
octachlorocyclopentene, CsClg.  Low resolution mass spectrometry confirmed
the two major species to be €5015 and CsClg-  Heating the waste sample and
pumping removed the most volatile compounds of the mixture.   The residue
yielded a mass spectral pattern of higher molecular weight analogues of
CcCls including the dimer of pentachlorocyclopentadiene.  Analogues with
molecular weights as high as 470 were noted.

     Combined gas chromatographic-mass spectrometric analysis of the survey
sample found five compounds whose chromatographic response was 0.1 percent
or more of the total normalized area.  The results of this analysis are
presented in Table 4-3.  As mentioned previously, these values are based
on assuming an equal response to all hydrocarbons by the FID.
          Table 4-3.  Composition of Hexachlorocyclopentadiene
                      Waste Survey Sample
           Compound
 Approximate Concentration
         (percent)
          hexachlorocyclopentadiene

    C5HCl7 heptachlorocyclopentene

    Chromatogram had doublet peak but
    mass spectrum shows only
    octachlorocyclopentene, C5Clg

    MW 308, chlorinated organic

    MM 281, chlorinated organic

    MW 376, C5HC19 or C8C18
           50.

            5.

           30.
           15.


            0.2

            0.1
                                    23

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     The representative sample of  the C-5,6 waste was analyzed by GC using
an OV-225 column and compared to the chromatogram of the survey sample
obtained under the same conditions.  The chromatograms were very similar
including even the minor  constituents.  There was, however, a change in the
relative composition of the major  constituents.  The areas were computed
and normalized under the  assumption of equal response to equal weights of
the major constituents.   The composition of the C-5,6 representative sample
is shown in Table 4-4.  The remaining minor constituents shown in Table 4-2,
did not appear to significantly change relative to each other.  However
these minor constituents  increased in the normalization to account for the
drop in the level of 05^7 and CsClg from those measured in the survey
sample.  These changes do not impact the conduct of the test or the analyt-
ical methods for the test samples.

4.1.2.2  Trace Elements

     Elemental inorganics were determined by SSMS on the representative
sample.  The highest ppm  concentrations found were for innocuous metals,
such as Fe @ 82, Si @ 27, Al @ 38, Na @ 34, and Ca @ 25 ppm.  Lower and
trace ppb levels were found for numerous other non-hazardous elements.
The potentially toxic elements, their concentrations in the waste and their
predicted combustion concentrations using Run VI for operating condition
data (including the dilution with  No. 2 oil) are shown in Table 4-5.  Of
these elements, all have  some tendancy to volatilize as chloride salts due
to the conditions (high Cl concentration, dry ashing) of their preparation
for SSMS analysis.  Thus, all of the predicted combustion values could be
low, with the exception of mercury which was determined by a highly quanti-
tative atomic fluorescence technique in order to be sure of an accurate
measurement.

4.2  OPERATIONAL PROCEDURES

     Detailed operating procedures, including both a test plan and a safety
plan, were reviewed and approved prior to arrival of the TRW sampling team
on site.  Procedures and  operating conditions were also recorded during the
field tests.  Following are brief  summaries of both plans, a test-by-test
commentary on events that took place in the field, and information on the
disposal of waste residues.


                  Table 4-4.  Composition of C-5,6 Waste
                              Representative Sample
               Compound
Approximate Concentration
        (percent)
          Hexachlorocyclopentadiene

           Heptachlorocyclopentene

    CeClg Octachlorocyclopentene

    Other Minor Constituents
           66

            3

           29

            2
                                    24

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             Table 4-5.  Trace Metals in the C-5,6 Waste
Element
Cr
Cu
Mn
Pb
As
Hg
Ba
Co
Se
V
Measured
Concentration
In Waste (ppb)
12,000
1,900
330
7
1
10*
36
42
3
4
Predicted
Cone. Produced by
Combustion (wg/rn^)
400
64
11
0.2
0.03
0.3
1.2
1.4
0.1
0.1
*Determined by atomic fluorescence


4.2.1  Test Procedures

     Tests at TMC were run with two wastes,  ethylene manufacturing wastes
and C-5,6, as previously described in Section 4.1.   The basic procedure for
each waste test was:

         e   Fill waste tank, measure specific gravity

         •   Verify instrumentation and sampling systems ready

         •   Ignite on auxiliary fuel (propane) and stabilize
             temperatures

         •   Activate on-line analyzer system

         •   Transfer to waste fuel combustion and observe effluent

         •   Stabilize system thermally

         •   Extended burn duration

             -  Process data acquisition
             -  Combustion gas composition data acquisition

             -  Combustion zone and stack gas sampling

             -  Scrubber liquid sampling
                                    25

-------
         •   Transfer  to  auxiliary fuel  combustion

         •   Shutdown  and secure,  inspect  for  and collect samples of
             deposits  in  combustion chamber.

     The test series for  each  waste consisted  of three  burn periods during
which a three hour  combustion  gas  sample was acquired at steady state oper-
ating conditions.   A three hour sample run with No.  2 oil was also required
to obtain background data prior to the C-5,6/No. 2 oil  mixture runs.

     Target  test  conditions for the ethylene waste were:

         •   Air  flow  rate  -   680 g/sec

         •   Fuel flow rate -  27 to 41 g/sec

         •   Theoretical  combustion temperature  -   1430° to 1815°C

     Initial test conditions for the C-5,6 wastes were:

         •   Air  flow  rate  -   680 g/sec

         •   Fuel flow rate -  39 to 66 g/sec

         •   Theoretical  combustion temperatures  -   1430° to 1870°C

         •   C-5,6/No. 2  oil mixture ratio  -   1/1 and  1/2 by weight

4.2.2  Safety Procedures

     TMC standard safety  procedures for handling and incinerating industrial
chemicals were  observed during this test program, including the following:

         •   Only authorized personnel with prior approval were permitted
             in the test  area  during operations.

         •   Chemicals were handled only by personnel wearing suitable
             protective clothing and trained  in  handling such materials.

         •   Safety shower and eyewash was available in immediate area.

         •   All  leaks or spills were to be flushed  with JP4 and incinerated
             in the same  manner as test wastes.

         •   Visual observation of the test system was  maintained at all
             times  during operation.

         •   Safety ropes were used to isolate the test area during actual
             operation.
                                     26

-------
         o   Canister gas masks were available to all  personnel

             -  Masks were placed in easy access in control  room

             -  Personnel outside control room carried masks

         •   Emergency medical  treatment was available both onsite and
             at defined outside medical  facilities.

4.2.3  Test Commentary

     All recorded data for the test burn incinerator operating conditions
were provided by TMC and are summarized in Table 4-6.   Each test was num-
bered consecutively by TMC Run Nos. 1 through 15.  TRW Run Nos.  I through
VII were assigned only to runs during which combustion zone and stack gas
samples were acquired.  The ratios shown in Column 3 for the C-5,6/No. 2
oil are by weight.  Certain of the thermocouples (i.e., TCs and TCe, TCy
and TC-|3) are redundant and are meant to provide an average temperature
at the same point.

     After checkout and background data tests with No. 2 oil were accom-
plished, three test conditions were evaluated with both ethylene and C-5,6
wastes.  Initial test conditions included calculated combustion temperature
variations from 1315° to 1760°C.  Corresponding measured temperatures at
the end of the reaction tailpipe where combustion gas  samples were taken
were 982° to 1150°C.

4.2.3.1  Checkout and Background Tests

     A series of tests were conducted with No. 2 oil as fuel to checkout
the incineration and sampling systems.  A full duration sampling run was
then performed to obtain background emission data burning No. 2 fuel oil
only.

     TMC Run No. 1:  An initial checkout run with No.  2 oil  was made to
     verify operation of the TRW trailer on-line instrumentation as well
     as to check out the incinerator and scrubber systems.  Sampling
     trains were operated at the combustion zone and exhaust stack, but
     no actual acquisition of samples was intended.  This run was 70 min-
     utes in duration at a reaction tailpipe temperature of 1132°C.  Com-
     bustion sample qas temperatures were 105° to 110°C at the filter
     inlet. All'systems  operated satisfactorily, and preparations were made
     for full duration sample tests.

     TMC Run No. 2:  This test was conducted to measure stack gas velocities
     after a second stack sampling train monorail system was added.  Capa-
     bility was thus provided to make sampling traverses 90 degrees apart.
     Stack velocity measurements were utilized to select a probe nozzle
     diameter for isokinetic sampling.

     TMC Run No. 3;  A baseline sampling test with No. 2 oil was begun at
     the same operating conditions as TMC Tests 1 and 2.  This test,
     intended as a 3-hour sample run, was terminated after one hour when
                                    27

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                                Table 4-6 Incinerator System Parameters Data Summary
1



TMC
Test
NO
1
2
3
4-1
4-2
4-3
4-4
5
6-1
6-2
6-3
6-4
7
6
9
2



TRW
Run
No
-
-
-
-
-
-
-
3


Fuel
and Waste
To Fuel Oil
Ratio
No. 2 oil
No 2 oil
No 2 oil
No 2 Oil



1 , No 2 oil
~

-
II
-
ill
IV
Ethyl ene
Waste


Ethyl ene
Waste
Ethyl ene
waste
Ethyl ene
Waste
in i No 2 Oil
10 ~ (Rinse)
11-1 1- CcC!,/oil
56
11-2 1 2

1?

13
14
15
V !CcjCl6/oil

VI
VII
-
i i
C5C1 6/oil
C.C It/oil
11
JP-7
4
5
6
7
Process Flow Rates


Air
Avg.
Kg/Sec
0 694
0 689
0.689
0 694
0 694
0 694
0 694
0 694
0 694
0.694
0 694
OE94
0 572
0 567
0 558
0 685
0 572
0 572

0.567

0 572
0 572
0 504


Fuel
Avg
Kg/Sec
0 0324
0.0312
0.0315
0.0182
0.0227
0.0285
0 0317
0 0301
0.0227
0.0273
0 0349
0.0330
0.0316
0 0229
0.0317
0 0295
0 0356
0 0295

0 0340

0 0393
0 0490
0 0322

Scrub.
H20
Avg.
Kg/ Sec
1.42
1 37
1.36
1 39
1.39
1 41
1.41
1 37
1 36
1.36
! 36
1 37
1 20
1 19
1.23
1 39
1 13
1 07

1 13

1 07
0 88
1 31
Scrub.
NAOH
Sol.
Avg
Kg/Sec
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
0 34
0 34

0 27

0 37
0 57
0 33
8

lhamb
Press
"3
Kilo-
Pascals
9 65
9.65
8 96
9 31
9 31
8.96
8.96
10 0
10.34
8.96
11.03
9 65
8.96
8 96
8 96
11 03
12.41
11 72

11 38

11 38
13 44
12 41
9
10
11
12
13
14
15
Temperatures

Fuel
TC3
Hvg.
°C
23
27
19
14
13
13
13
13
14
14
14
16
21
26
19
22
14
14

24

18
14
10
Pre-
Heat
TC^
Avg

216
216
210
99
143
182
202
202
135
182
254
246
321
238
381
199
257
232

271

25b
266
230
Chamb
Exit
TC5
Avg

1235
1249
1218
860
1029
1174
1229
1198
893
1054
1166
1137
1241
1031
1229
1168
1166
1060

1185

1219
1244
1204
Chamb
Exit
TCg
Avg

-
1254
1252
849
1029
-
-
1184
918
1049
1216
1169
1256
1052
1244
1168
1181
1088

1183

1184
-
1196
Smpl.
Point
TC?
Avg.

1132
1121
1132
860
971
1089
1138
1119
885
993
1143
1114
1151
960
Smpl.
Point
TC]3
Avg

-
1088
1104
843
949
1060
Stack
Exit
TC,2
Avg

80
79
79
69
74
78
1113 80
1073 ( 79
857
960
1093
1048
1046
968
- ,1144
-
-
-

1117

1108
1142
1110
1099
1077
933

1102

1121
1154
1107
71
75
79
79
79
74
79
79
79
79

78

79
81
78
16
17
18
19
20
21
22 23
24
Calculated Process Parameters

Fuel/
Air
Ratio
Kg/Kg
0.0470
0.0450
0 OlbO
0 0262
0 0327
0 0411
0.0456
0.0433
0 0327
0 0393
0 0503
0 0476
0 0553
0 0404
0 0566
0 0430
0 0622
0 0515

0 0596

0 0687
0 0861
0 0540


TC
Theo
°C
-
-
-
-
-
-
-
1646
1131
1318
1602
1535
1726
1349
1752
-
1393
1201

1348

1370
1378
-


TC
Avg
°C
-
-
-
-
-
-
-
1371
1001
1147
1360
1308
1412
1156
1448
-
1235
1097

1228

1242
1263
-


Chamb
Vel
m/Sec
-

-
-
-
-
-
44 1
32 9
36 9
42.7
41 7
36 9
30 8
36 9
-


Stay
Time
sec
-
-
-
-
-
-
-
0 131
0.176
0 157
0 135
0 139
0 157
0 188
0 157

NAOH
Applied
Avg
kg/Sec
-
-
-
-
-
-
-
-

NAOH/
NA04 Excess
Theo • Air
Avg
- ; -
- ' -
- ' -
-
- ; -
- ' -
; -
- 56 8
130
-
- ' 91 3
49 3
- ' - ' 58 0
Stoic
Fuel/
Air
Ratio
Kg/ Kg
-
-
-
-
-
-
-
0 0679
0 0752
0.0752
0 0752
0 0752
35 5 ,0 0752
- ;- lto.i
0 0752
- 1 - 32.9 |00752
, 1
33 1 '0 1741 0 040 38 54 7 ;0 0962
29 7 0 195


32 5 0 178
0 040 4 6 86 8

0 033 33 61 4

33 2
33 G
-
0 174 | 0 044 ;3 1 54 3
0 172
-
0 068 3 2 41 1
0 0962

0 0962

0106
0 122
" j " , i "
25
26 !
Sectarian


Stack
HC
'PHCHj
3 5
-
-
18
7
7
12
8
-
9
-
1.5
2
2 5
2
-
4
5

5

! * 5
O 0
-1 0

Snip' •
Point
HC
PPIICH^
3 5
""
\ * '
20
7
! 9
14
9
;
-
-
1 5 ,
3 ,
i
2 5
1 5 !
1 _
1
~ t
1

1
—
\
1 -
rs>
CO

-------
     combustion  zone  gas  temperatures at the filter inlet suddenly rose
     from the  normal  110°  to  177°C.  This higher temperature would have
     been detrimental  to  the  filter  seals,  so the  test was terminated.
     Cooling of  the combustion  gases by an  air stream around the quartz
     probe liner had  been  satisfactory in prior tests, but appeared  to be
     marginal  in cooling  capability.  Water as well as air was added to
     the  liner coolant flow (Figure 4-14) for subsequent tests.

     TMC  Run No. 4:   This  test  was conducted to verify the effectiveness
     of the modified  combustion gas  cooling system prior to repeating the
     sampling  run.  A temperature excursion from 860° to 1140°C as meas-
     ured at the reaction  tailpipe was made by varying the fuel/air  ratio
     of the incinerator.   The water/air combustion gas cooling system
     enabled filter inlet  temperatures of 80° to 95°C to be maintained,
     allowing  a  considerable  safety  margin  in assuring temperatures  of less
     than 115°C  at the filter inlet.  Preparations were again made for a
     full duration sample  run.

     TMC  Run No. 5. TRW Run  I:   A background run with No. 2 oil for  a full
     3 hour combustion zone  sample time was completed.  Stack sampling was
     conducted for two hours.  Temperature  at the  reaction tailpipe  aver-
     aged 1095°C, and calculated theoretical combustion temperature  was
     1645°C (Table 4-6).   Residence  time  in the reaction tailpipe was
     0.131 seconds.

4.2.3.2  Ethylene Waste Tests

     After completion of the  baseline sample tests, No. 2 oil was drained
from the feed  tank and ethylene waste was  loaded.

     TMC  Run  No. 6. TRW Run  II: The first  test with ethylene waste  was
     performed.   Prior to sampling,  a 3 point traverse of reaction tailpipe
     temperatures was made at nominally 870°, 980°, and 1150°C, with cor-
     responding  combustion temperatures of  1130°,  1320°, and  1600°C. A  3-
     hour sample test was  made  at  1090°C  reaction  tailpipe  temperature and
     1535°C calculated combustion temperature.  Residence time was 0.139
     seconds.   Deposits in>the  combustion chamber  after the test were
     photographed (Figure 4-1)  and clinker  samples were taken.

     TMC  Run  No. 7;   This run was  intended  as the  second ethylene  sample
     test at an  increased reaction  tailpipe temperature of  1150°C  (combus-
     tion temperature of 1725°C), and residence time of 0.157  seconds.
     After one hour of sampling, filter  inlet temperature on  the  combustion
     zone sample train suddenly dropped  from a normal 88° to  93°C,  to 16°C
     and the  quartz  probe liner was  observed to have moved,  probably re-
     tracting  the probe tip  through  the  seal.  The test was  discontinued,
     as combustion  gases were not  being  acquired  by  the sampling  system.
     The probe liner  was safety-wired  to  prevent  axial movement  in  sub-
     sequent tests,  thus precluding  repetition of  this  leak.

     TMC Run  No. 8. TRW Run  III;  The  second ethylene  run was  successfully
     completed.   Three hours  of combustion  zone  sampling were conducted at
     a reaction  tailpipe temperature of  970°C and  a  calculated  combustion


                                    29

-------

LO
O
                              Figure 4-1 MA-II Clinker  (Courtesy of the Marquardt  Company)

-------
     temperature of 1350°C.   Residence  time was  0.188  seconds.   Deposits
     in the combustion  chamber  were  again  photographed (Figure  4-2)  and
     samples taken.

     TMC Run No.  9. TRW Run  IV:   The third ethylene  test was  conducted  at
     increased operating temperatures.   Reaction tailpipe  temperature was
     nominally 1150°C and calculated combustion  temperature was 1750°C.
     Residence time was 0.157 seconds.   A  3-hour sample run was completed,
     although accumulation of deposits  in  the  combustion zone resulted  in
     some excursions in system  temperatures during  the run.   Deposits were
     photographed (Figure 4-3),  sampled, and removed prior to the next  run.

     TMC Run No.  10: This run  was made to flush the system prior to C-5,6
     runs by rinsing the fuel tank with No. 2  oil and  operating the  in-
     cinerator on No. 2 oil  for over one hour.

4.2.3.3  Hexachlorocyclopentadiene Tests

     The heating value  of the C-5,6  waste  was  not sufficient  to maintain
combustion, and therefore was mixed  with No. 2 oil  for these  tests.   Dif-
ferent mixture ratios of C-5,6  to No. 2 oil were incinerated, as noted  in
Table 4-6 and mentioned in the  following test  descriptions.

     TMC Run No.  11: A checkout run was made  with  C-5,6 waste.  A 15-
     minute sample was  taken with a  TMC benzene  train  for  analysis before
     full duration testina.   Laboratory analysis of the samole indiratpri
     less than 0.22 ppm of C-5,6 in  stack  exhaust.   A TRW  gas chromatograpn
     read hydrocarbon values of 20 ppm, indicative  of satisfactory com-
     bustion efficiency.

     TMC Run No.  12, TRW Run V:   The first sample run  with C-5,6 was made
     at a reaction tailpipe  temperature of 1107°C and calculated combustion
     temperature of 1363°C.   Residence time was  0.178 seconds.   The  C-5,6
     waste was mixed with No. 2 oil  at a weight  ratio of 1:2  (1 kg C5.6
     to 2 kg No.  2 oil).  The test was terminated at 2 hours  15 minutes
     when caustic solution in the large impinger in the combustion zone
     sample train appeared to be neutralized by  HC1; however, a sufficient
     sample had been obtai-ned for analyses.  Deposits  were photographed,
     (Figure 4-4) sampled, "and  removed. TMC changed the fuel manifold  dia-
     meter from 23  to 20 cm  to  improve combustion in an attempt to reduce
     deposits.  A decision was  made  to maintain  high combustion tempera-
     tures of nominally 1370°C, and  vary the ratio  of C-5,6  to No. 2 oil
     for subsequent tests.

     TMC Run No. 13. TRW Run VI:   The second C-5,6  sample  run was made  at
     a 2:3 weight ratio of C-5,6 to  No. 2  oil.   Reaction tailpipe nominal
     temperature again  was 1107°C, and calculated combustion  temperature
     was 1370°C.  Residence  time was 0.174 seconds.   Some  fluctuation in
     system pressures and temperatures occurred  due to deposit formations.
     A full 3-hour sample duration was attained. Deposits were photo-
     graphed (Figure 4-5) and removed from combustion chamber.
                                   31

-------

                                                                                 -'A
                                                                                 •


Figure 4-2 MA-III Clinker (Courtesy of the Marquardt Company)

-------

Figure 4-3 MA-IV Clinker  (Courtesy of  the Marquardt  Company)

-------
• .
                              Figure 4-4 MA-V Clinker CCourtesy of the Marquardt Company)

-------
00
en

                               Figure 4-5 MA-VI  Clinker (Courtesy of the Marquardt Company)

-------
     TMC Run No. 14. TRW Run VII:  The third C-5,6 run was made at a
     1150°C reaction tailpipe temperature, and a 1378°C calculated com-
     bustion temperature.  Residence time was 0.172 seconds.  Equal weights
     of C-5,6 and No. 2 oil were mixed for this test.  Deposit formations
     again caused some system fluctuations.  Shutdown was premature at
     about 2-1/2 hours due to depletion of waste fuel in tank.  Deposits
     were photographed (Figure 4-6) and samples taken.

     TMC Run No. 15:  The fuel tank was rinsed with JP-7, which was then
     burned for over 1-1/2 hours to flush the system.

4.2.4  Disposal of Waste Residues

     The residual ethylene and C-5,6 waste materials along with the empty
drums left from the test burns were disposed of by a contract disposal
firm in accordance with all applicable regulations.

4.3  SAMPLING METHODS

     Sampling methods used in the  tests at TMC were chosen to cover three
basic areas.  These were:

         1)  Continuous, on-line monitoring of gas composition to deter-
             mine and follow steady state conditions.

         2)  Collection and concentration of hot zone combustion products
             to identify and quantify the trace organic and inorganic
             species formed.

         3)  Collection of final emission and waste products to evaluate
             the environmental safety of the tests.

     Following is a brief summary  of the methods for each of these areas.
More detailed discussions can be found in the Marquardt Analytical Plan.*

4.3.1  On-Line Gas Monitoring

     Gases were drawn continuously from the hot zone through a ceramic
probe and then through a heated Teflon sample line to the trailer.  The
location of this probe at the Marquardt test stand is shown in Figure 4-7.
The gas then entered the system shown in Figure 4-8.  The gas conditioner
supplied a cool, dry, particulate  free sample to all of the analyzers with
the exception of the hydrocarbon (HC) monitor which uses an untreated sam-
ple.  A heated Teflon line carries the HC gas sample from a tee in the
unconditioned sample line to the HC analyzer.  Because it uses an untreated
gas sample, the HC monitor is the  only instrument exposed to the moist acid
(HC1 coming from the C-5,6 waste burns) stream and is thus the most
*TRW Document #27033-6001-RU-00,  "Analytical Plan for Facility No. 1 Tests
 to be Conducted at Marquardt  Corporation", by J. F. Clausen and C. A. Zee.
                              36

-------
• •
•

                            Figure 4-6 MA-VII Clinker (Courtesy of the Marquardt Company)

-------
!0
00
              CONTROL BOX
              FOR STACK
              TRAIN
      CONTROL BOX
      FORCOMBUSTION._
      ZONE TRAIN
HEAT
SHIELD
                                                                     FOIL WRAPPED
                                                                     MULLITE PROBE
                                                                     FORON-LI&JE
                                                                     INSTRUMENTS
                                                                                   HEATED SAMPLE LIN
                                                                                   O TRAILER
               WATER-COOLED
               PROBE FOR
               SAMPLING TRAIN
                Figure 4-7 Sampling System For On-Line Monitors (Courtesy of the Marquardt  Company)

-------
to
to
                2B,
                rl-3

                HCF
                '1-2
                      COMPRESSED
                      AIR SOURCE
                                                                                                                                         VENT
2 WAY BALL VALVE
WHITEY SS-4234
3 WAY BALL VALVE
WHITEY SS-43XS4
      SS-45X38

5 WAY BALL VALVE
WHITEY SS-432

FLOWMETER WITH INTEGRAL
CONTROL/SHUTOFF VALVE

HYDROCARBON REMOVAL
FILTER
PRESSURE REGULATOR WITH
GAGE (2 STAGE)
DRYER/FILTER

CONDENSATE TRAP
                     	1/4" TUBE
                     	 I/S" TUBE
                               Figure  4-8 Gas Conditioning  and Analysis System For  On-Line  Instruments-

-------
susceptible to corrosion.  To avoid potential problems,  a Perkin-Elmer 881
gas chromatograph with an open tubular column and a flame ionization detec-
tor was substituted as a total hydrocarbon analyzer during tests with the
C-5,6 waste.

     The monitoring instruments used are listed with their operating ranges
in Table 4-7.  Data was recorded on Hewlett-Packard 680M strip  chart rec-
orders.  Figure 4-9 shows the instrument racks mounted in the sampling
trailer.  The analyzers, recorders, and manifold valves  were all located
in racks to provide ease of operation and accessibility.  The location of
calibration gases and gas conditioning system across from the racks is
shown in Figure 4-10, and the work area behind the racks is shown  in
Figure 4-11.
             Table 4-7.  Description of On-Line Instruments
        Species Analyzed
Manufacturer
 and Model
       Range*
    Total  hydrocarbons (HC)
    Carbon monoxide (CO)
    Carbon dioxide (C02)


    Oxygen (02)
    Oxides of nitrogen (NO  )
                          A
 Beckman
 model 402

 Beckman
 model 865

 Beckman
 model 864

 Taylor
 OA 273
 Thermo
 Electron
 model 10-A
0.05 ppm - 10% with
eight ranges

2-200 ppm
10-100 ppm

0.05 -5%
0.02 - 20%

0.05 - 5%
0.25 -25%
  1  - 100*

0.05 - 10,000 ppm
with eight ranges
 *A11  of these manufacturers report an accuracy  of  ±1 percent of full scale
  for their instruments.
                                     40

-------
Hgure 4-9 Instrument  Racks
             -

-------
                                                        i
                                                       .
                     CALIBRATION GAS CYLINDERS
Figure 4-10 Calibration Gases  and Gas Conditioner


                                        ^
  Figure 4-11  Work Area Behind Instrument  Racks
                        42

-------
4.3.2  Sampling of Combustion  Products

     The sampling train used to  collect  hot  zone  gases,  vapors,  and  parti-
culate is shown schematically  in Figure  4-12 and  as set  up  for a test  run
in Figure 4-13.  It consisted  of a  standard  EPA Method 5 train with  the
following important modifications.

         •   There was  a stainless  steel jacketed, water-cooled  probe
             (shown schematically in  Figure  4-14} with a quartz  liner.
             The liner  provides  an  inert surface  for the sample  gas  and
             the cooled, stainless  steel jacket shields  this gas from
             extreme hot zone  temperatures in order to quench any further
             reactions  of the  sample  constitutents.  Further cooling of
             the gas can be  modulated by aspirating an air/water mixture
             into the space  between the  steel jacket and quartz  liner.

         •   Special  fittings  were  fabricated to  allow a back purge  of the
             probe with purified compressed  air while the sampling train
             was not in operation.  This eliminated the  possibility  of con-
             tamination from the relatively  high  amounts of organic, partial
             combustion products produced during  start-up and shut-down of
             the incinerator.  The  back  purge connection was made at the
             point where the dogleg from the probe liner mates to the  filter.

         •   A chromel/alumel  thermocouple was potted into  the dogleg  going
             from the quartz probe  liner to  the filter housing to check
             the temperature of  the gas  stream at that point.

         •   An ultra high-purity glass  fiber filter was used, Gelman Spec-
             troquality Type A.   The  filters were muffled to remove organ-
             ics and have extremely low  background levels of inorganics.
             They were  tared by  desiccating  and weighing on consecutive
             days to a  constant  weight { ±0.1 mg), and were then  stored and
             handled throughout  the tests and analyses   in glass  petri
             dishes.

         •   A solid sorbent trap,  designed  to adsorb the organic consti-
             tuents  in  the sample gas stream, is  located downstream of the
             heated  filter and upstream of the first impinger.   The  sorbent
             trap, with overall  dimensions of 170 x 45 mm, contained ^40 g
             of XAD-2,  an Amberlite resin of the type commonly used as a
             chromatographic support.

         •   A Teflon valve  was  added to the glass connector between the
             sorbent trap and  the first  impinger through which glass bulbs
             were filled with  the sample gas  to be analyzed for  any  volatile
             or gaseous components  not collected by the  sorbent  trap.  This
             valve is also shown in Figure 4-13.

         •   For the C-5,6 test  burns where  large quantities of  HC1 were
             produced by combustion,  a large, two-liter  impinger (shown in
             Figure  4-13) was  added between  the solid sorbent trap and the
             first modified  Greenburg-Smith  (G-S) impinger.  One  liter of
                                    43

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                              4 INCH
                               FILTER
                              HOLDER
   INCINERATOR
   WALL
  WATER
 COOLED
  PROBE
                                    SOLID
                                    SORBENT
                                    TRAP
GAS
SAMPLE
VALVE
QUARTZ
LINER
               HEATED AREA-
              THERMOMETERS


              ORIFICE
                                                     THERMOMETER
                                                         CHECK
                                                         VALVE
                            BVALVES     IMPINGERS   VACUUM
                                     (MAXIMUM SIX)  GAUGE
                                                               7
                                                          VACUUM LINE
                                                       MAIN
                                                       VALVE
                                              AIR-TIGHT
                                                PUMP
                 DRY TEST METER


Figure  4-12 Combustion Zone Sampling  Train Schematic

-------
:
                                                                                 P ARTICULATE
                                                                                    FILTER
                                                                                        £1
SOLID SORBENT
    TRAP
        NTT*
                                                                                           ATER-COOLED
                                                                                             PROBE
                      SAMPLE VALVE
                LARGE CAUSTIC
                IMPINGFR FOR
                TESTS V THRU VII
                             BACK-PURGE
                             LINE
                                             ASPIRATED AIR/WATER
                                             COOLANT LINES
                    Figure 4-13  Combustion Zone Sampling Train (Courtesy of  the Marquardt Company)

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                PROBE
                LIIIER
               AIR/WATER COOLANT
               FOR SAMPLE GAS
               INLET
                  Figure 4-14 Water  Cooled  Probe  Schematic

             15 to 20 percent NaOH was  placed  in  this  large  impinger in
             addition to 100 ml  of 5 percent NaOH in each of the first
             two G-S impingers.   The third  impinger was empty and the fourth
             held silica gel.   For the  background No.  2 oil  and ethylene
             waste tests,  only  distilled water was used in the first two
             G-S impingers.

     This hot zone train was operated at a  flow  rate of approximately
30 liters/min for 3 hours  during each test, thereby sampling an average of
4 to 5 cubic meters.  Gas  volumes were measured  to 0.03 liter, with a leak
rate of less than 0.6 liter/min. Operating parameters for the train and
sample volume data are  tabulated in  Appendix  B.

     The following hot  zone samples  were obtained from each  test:

         •   Solvent probe wash

         •   10 cm diameter particulate filter

         •   Solid sorbent trap

         e   Grab gas

         •   Combined impinger  solutions

         •   Acidified  split of combined liquid  impingers

         •   Spent silica  gel

The location of the combustion  zone  sampling  train at  the test site is
shown in Figure 4-15.

                                     46

-------
 UMBILICAL TO
 CONTROL BOX
;» •
 SAMPLING TRAIN
 CONTROL BOXES
                                                            VENTURI SCRUBBER
                          :,'
                           ,  itti^#4M
                          WATER-COO LEDfES
                          PROBE
COMBUSTION GAS
SAMPLING TRAIN
                                  HEAT SHIELD
Figure 4-15 Sampling System For Combustion Zone (Courtesy of the Marquardt Company)

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4.3.3  Sampling Emissions and Waste Products

     Samples of the stack effluent, spent scrubber water, and solid com-
bustor residue (clinker), were taken during and after each test to evaluate
the environmental safety of the final emissions.  An EPA Method 5 test was
performed at the stack for particulate mass loading and composition deter-
minations.  Location of the sampling train at the test site is shown in
Figure 4-16.  The standard train was used and two right angle, six-point
traverses of the one-meter diameter stack were made, sampling for one hour
at approximately 20 liters/min.  It was decided at the start of the Mar-
quardt tests that owing to the low velocity in the stack (6 to 8 ft/sec),
the sample would be drawn superisokinetically in order to have an adequate
particulate sample for compositional analyses.  Gas volumes were measured
to 0.03 liter, with a leak rate of less than 0.6 liter/min.  Operating
parameters for the train and sample volume data are tabulated in Appen-
dix B.

     The following samples were obtained for each test from the stack sam-
pling train:

         •   Aqueous probe wash

         •   10-cm diameter particulate filter

         •   Impinger solutions

         *   Acidified split of impinger solutions

         •   Spent silica gel

     Gaseous stack effluents were determined by the use of Gastec®
indicating absorbtion tubes.  Toxic gases in ppm levels such as NO , S02,
CL2, HC1, and COC12 were looked for at the stack.

     All of the spent scrubber water samples were obtained from a tap down-
stream of the tank which holds the water after it has passed through the
venturi scrubber.  Periodically during the test, as this water level rises,
a pump removes the scrubber water from the tank and transfers it to a stor-
age tank.  It was during these pumping periods that composite samples were
taken which make up the entire sample.  The city water control sample was
taken from a line which supplies water to the venturi scrubber,  whenver
caustic scrubbing solutions are required in the scrubber, the caustic con-
centrate is blended with city water in a line leading to the venturi scrub-
ber.  No tap or sampling point was available in the line between the blend-
ing point and the venturi scrubber, hence, it was necessary to prepare the
fresh caustic scrubber water control sample by blending the correct portions
of concentrated caustic with city water.  The mixing was performed within
the one-gallon sample jug.  Aliquots of these scrubber samples were acid-
ified for subsequent metal analyses.

     Samples of solid residue (or clinker) which accumulated in the combus-
tor samples were collected when the burner assembly was removed after each
test burn.  The residue was then scraped out from the burner as completely
as possible and wrapped in aluminum foil.

                                     48

-------
                           TRAVERSE
                           MONORAILS
     EFFLUENT GAS METHODS
     SAMPLING TRAIN
SCRUBBED EFFLUENT
EXHAUST STACK
UMBILICAL TO
CONTROL BOX
                         Figure 4-16 Sampling System For

                     Stack (Courtesy of the Marquardt Company)
                                       49

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4.4  ANALYSIS TECHNIQUES

     Samples taken as described  In  Section  4.3, were analyzed for both
organic and inorganic constituents.   When necessary, extractions were per-
formed first to concentrate  the  sample  in a suitable form for analysis.
Techniques used for these  extractions and analyses will be briefly summa-
rized here.  For more detailed discussions, see the Marquardt Analytical
Plan.

4.4.1  Extractions and  Sample Preparation

     Both solvents and  acids were used  to extract organics and inorganics
respectively, from the  appropriate  samples. These procedures and the basic
sample preparation steps are listed by  sample  type:

         •   Probe Mashes

             Combustion Zone.. The  methylene chloride rinse was added
             directly to the filters after  they were folded and placed in
             the Soxhlets  for organic extraction  (see filters below).

             Stack.  The acetone probe  rinse was evaporated and the residue
             weighed.   This  weight  was  added to the weight of the particu-
             late on the filter  for total mass loading calculations, in
             accordance with EPA Method 5 procedures.

         •   Filters

             Combustion Zone. The  tared sample filters plus two controls
             were desiccated and weighed on consecutive days to a con-
             stant weight  ±0.1 mg,  and  then extracted in a Soxhlet appa-
             ratus for  24  hours  with methylene chloride.  Solvent extracts
             were evaporated to  10  ml for analysis.  Filters were then
             cut in half and one of the halves was weighed, low tempera-
             ture plasma ashed,  reweighed,  and extracted with constant
             boiling aqua  regia  for two hours. This acid extract was
             reduced to 50 ml for analysis.

                     The tared sample filters  were weighed and cut in
                    One of the halves was weighed, low temperature plasma
                    reweighed, and  extracted with constant boiling aqua
             regia for  two hours.  The  acid extracts were reduced to
             50 ml for  analysis.

             Solid Sorbent Traps

             Combustion Zone.  The  XAD-2 resin was transferred from the
             traps to pre-extracted paper  thimbles and then extracted  in
             a Soxhlet  apparatus with pentane  and methanol for 24 hours
             with each  solvent.   These  extracts were evaporated to
             10 ml for  analysis. Two unused traps were also extracted
             for background  values  and  a blank (empty thimble) control
             was also run.


                                     50

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    The original  analysis plan had called for extraction of the
    sorbent traps with only one solvent, pentane.   However, as
    discussed in Section 4.5.2, a second extraction with meth-
    anol was found to be necessary to remove the majority of
    material adsorped on the resin.  In addition,  the first set
    of traps to be extracted had even a third extraction with
    benzene.  The benzene removed very little additional material
    and this third extraction was not continued through the
    remainder of the traps.

    Stack.  No solid sorbent traps were used in the stack sampling
    train.

•   Grab Gas

    Combustion Zone,.  No special preparation was required.

    Stack.  No gas.samples were taken at the stack.

t   Impingers

    Combustion 7nnp and Stack.  The volume of liquid in the
    impingers was measured and the spent silica gel was weighed
    in the field after each test burn to determine the amount
    of water collected.  The impinger liquids from the com-
    bustion zone were also combined and a 100 to 250 ml aliquot
    acidified in the field to stabilize the metals for anal-
    ysis.  No extractions or other special preparation steps
    were performed on any of the impinger samples.

•   Scrubber Waters

    500 to 1000 ml aliquots of the scrubber water samples were
    extracted for organics according to the procedure for the
    separatory funnel extraction with Freon for oil and
    grease from water recommended by the EPA Handbook on
    Methods for Chemical Analyses of Water and Wastes (National
    Environmental Research Center, Cincinnati, Ohio, 45268,
    EPA-626-/6-74-003).  However, instead of evaporating the
    material to the dried residue, the Freon extracts were
    concentrated to a 10 milliliter sample by use of a Kuderna-
    Danish concentrating evaporator.  Aliquots of this 10 mil-
    liliter sample were then used for the survey analysis
    (IR and LRMS) and for gravimetric determination of residual
    material after evaporation at ambient conditions and im-
    mediate weighing.

0   Solid Combustion Residues

    The solid residues (clinkers) were first weighed, then
    ground and blended to provide a homogeneous sample. Ten
    to 20 g portions were extracted in a Soxhlet apparatus
    for 24 hours with methylene chloride.  The solvent ex-
    tracts were then evaporated to 10 ml for analysis.
                             51

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4.4.2  Analytical Methods

     After extraction of the samples for organic material and other
preparation for inorganic material, the concentrated extracts, and aqueous
solutions were analyzed by several methods which are summarized in
Table 4-8.  A general treatment of the sample preparation and analytical
procedures is discussed below.

4.4.2.1  Organic Analyses
     With the exception of the gas grab samples in glass bulbs, all  of  the
samples for organic analysis were in 10 ml solvent extracts.   Gas samples
were analyzed on the Hitachi-Perkin-Elmer mass spectrometer.   The samples
were contained in double ended glass sampling vessels which have a septum
through which syringe samples can be drawn.  A gas tight syringe was used
to remove part of the sample from the sample vessel and inject it into  a
heated stainless steel inlet system.  The pressure of the sample in  a con-
stant volume portion of the inlet system was measured with a quartz  man-
ometer.  Known pressures of helium and a 10.6 ppm propane standard were also
introduced to the mass spectrometer (MS) for the purpose of background  and
calibration of instrument response.  Tests samples were introduced to the
MS with interspersed background samples to ensure that the instrument was
not slowly accumulating a "memory" in the m/e peaks of interest.

     The concentrated solvent extracts of the filters, sorbent traps,
scrubber waters, and sand bed samples were analyzed by gravimetry,  IR,  LRMS
and GC techniques.  An aliquot of each extract was evaporated at ambient
conditions to remove the solvent.  The residue was weighed and analyzed
by IR and LRMS.

     The IR and LRMS analyses yield qualitative information about  the
classes or types of compounds  (e.g., hydrocarbons, phenols, ROMs,  etc.)
present as well as an idea of the complexity of the concentrated sample.
Knowledge of the classes of compounds present provides a measure of the
toxicity, if any, of the residue.  The detection limits  for these  analytical
techniques vary somewhat with  the type of compound (see  Table 4-8).

     Two gas chromatograph systems were employed to cover the boiling point
range of compounds which were expected in the samples if less than  complete
combustion were  to occur.  The first system described is for what  are being
called low boilers.  This  includes  the very volatile solvents including
methylene chloride, pentane and  includes  all of the compounds found in  the
ethylene waste with boiling points increasing up to but  not including
napthalene and ethylnaphthalene.  These two compounds do in fact elute
from this column system but with  such long retention times that they are
better analyzed with the second  column system.  The column system used  for
low boilers  is as  follows:

     Column          Chromasorb  102,80/100 mesh, 6 ft x  1/8 inch
     Temperature     200°C  isothermal
     Carrier Gas     helium at  30 cc/min
     Detector        FID
                                     52

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                                                 Table 4-8 Summary of Analytical  Methods
en
CO
                             Method
Organic Analyses

   Gravimetry

   Infrared
   Spectrophotometry
   (IR)

   Low Resolution Mass
   Spectrometry
   (LRMS)

   Gas
   Chroma tography
   (GC)

   Combined Gas
   Chromatography/Mass
   Spectrometry
   (GC/MS)
                     Inorganic Analyses

                        Inductively Coupled
                        Plasma Optical Emission
                        Spectrophotometry (ICPOES)

                        Atomic Absorption
                        Spectrophotometry
                        (AAS)

                        Spark Source
                        Mass Spectrophotography
                        (SSMS)
                                    Instrument Manufacturer
                                           and Model
                                                        Mettler, microbalance

                                                        Perkin Elmer, 521
                                                         Hitachi-Perkin Elmer,
                                                         RMU-6 Mass
                                                         Spec tome ter

                                                         Varian, 1860 dual
                                                         FID
Varian, 1860 GC and
Hitachi-Perkin Elmer,
RMU-6 MS

        or

Finnigan, 9500 GC and
Finnigan, 3100D Quadrapole
Mass Spectrometer
                                     Applied Research
                                     Laboratories,  QA-137
                                     Jarrell  Ash,  810
                                     AEI Scientific
                                     Apparatus Ltd.,  MS 702R
                                 Detectability for a  Compound  or Element
                                           Being Searched  For
                                        1 jig

                                        - 3-5% of the sample being
                                        examined
                                         -10 jig
                                        (IX of a 1 mg sample)
                                               per jjl of sample
~1 jig per jil of sample
                                                                                                  -100 ng per jil  of sample
                                         -0.5-2000 ppb
                                         -1-0.001 ppm
                                         -50-100 ppb

-------
     The second column system used in the GC analysis was for what are
called high boilers.  These materials are defined as those which have the
higher boiling points which begin around 200°C and increase from there.
Napthalene is one of the first eluting compounds this system and the larger,
higher boiling materials, such as POM, hydrocarbon oils etc., elute after
napthalene.  The operating parameters used for the GC separation of the
high boilers follows.  These two column systems combined were able to elute
all the constituents found in both the wastes tested at TMC as well as
possible incomplete combustion products or species formed in combustion.

     Column          OV-225
     Temperature     1800C isothermal
     Carrier Gas     helium at 30 cc/min
     Detector        FID

4.4.2.2  Inorganic Analyses

     Inorganic analyses were performed using atomic absorption spectros-
copy (AAS), optical emission spectroscopy  (OES), and inductively coupled
plasma optical emission spectroscopy (ICPOES).  Selected samples of the
acid extractions of the particulate  filters and the acidified splits of
the scrubber waters and the impingers were surveyed for trace metals by
ICPOES.

     The ICPOES analysis determines  32 elements, including most of the  toxic
elements of interest to the program, down  to ppb levels with an accuracy
of 100  to  200 percent.  The purpose  of this survey is primarily to check
that the metals in  these test  samples are  in approximately the same amounts
relative to each other as  they were  in  the waste material.   Those elements
which from the results either  of the ICPOES survey or of the analysis of
the waste  material  seemed  to  be  present  at potentially toxic levels, were
determined quantitatively  by AAS.   The sensitivity of this method  varies
from approximately  1.0  to  0.001  ppm for  the elements which were determined,
with an accuracy between 10  to  50 percent.

     In addition  to  the AAS and  ICPOES  analyses performed on the test
samples, spark source mass spectrophotography  (SSMS) was used to analyze
the waste  material  for  trace elements.

     Some  wet chemical  methods were also performed on the combustion zone
impinger solutions.   Total  available chlorine  was  determined by a  ferrous
ammonium sulfate  titration,  chloride by a modified  Volhard tritration, and
carbonate  by  evolution  and gravimetry.

4.5  PROBLEMS ENCOUNTERED

     Problems which occurred during either the field  testing or  laboratory
analysis phases  of the  Marquardt test program are  described  in  the following
sections.   Corrective actions taken and final  disposition, when  applicable,
are  also  discussed.
                                     54

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4.5.1  Field Test Problems

     In spite of careful  selection of equipment and checkout at actual  or
simulated test conditions, a few incidents  occurred during field testing
that had not been anticipated.   Corrective  actions were  immediately taken
in each case, and testing was completed as  scheduled.  All necessary
samples were acquired.

4.5.1.1  Inadequate Cooling of Combustion  Gas Sample

     Combustion gases at 1090°C or higher  had to be cooled to 115°C or
less at the entrance to the sampling train  to avoid damage to the filter
seals.  A thermocouple in the gas stream at the entrance to the filter was
used to monitor this temperature.  Cooling  of the sample gas was accomplished
both by radiation from the quartz probe liner to the water-cooled probe
(Figure 4-14) and by convective cooling with a stream  of compressed air
directed around the probe liner.  Checkouts of this cooling method both in
a boiler at TRW and during initial tests at TMC (TMC Run #1) were successful
in maintaining a sample gas temperature of  220-230°F at  the filter inlet.
However, during the first sampling test (TMC Run #3),  the sample gas
temperature suddenly rose to 1770C at the  filter inlet even after over an
hour of steady-state operation had been completed with the temperature at
this point well controlled at 105 to 11QOC.

     This problem was corrected by adding water as well  as compressed air
to cool the combustion gas.  Facility air and water flow, controlled by
metering valves, were mixed in a tee fitting and fed into a tube exiting
along the quartz probe liner (Figure 4-14).   Both air  and water flows could
then be precisely metered to control the sample gas temperature.  Using
this cooling method, sample gas temperature was maintained at safe levels
of 80 to 105°C at the filter inlet for the  remainder of  the tests.
4.5.1.2  RAC^ Train Modifications

     The standard EPA Method 5 sampling trains  ordered from Research
Appliance Corporation required certain modifications before they could be
used on this program.  These modifications  were completed before the start
of actual sampling tests,  so no schedule delays were involved.

     First, the heated oven box enclosing the particulate filter was poorly
insulated and sealed, making control  of the internal temperature erratic.
Next, the oven box fan took in cold outside air instead of recirculating the
warm air within the box.   This resulted in  large thermal  fluctuations and
gradients.

     Modifications to the  sample train included re-insulating the heater
box by removing the loose  filter fiber glass matting and installing fire
resistant 1.3-cm thick acoustic tiles to the interior of the box.  Although
the oven box blower motor  had to remain outside of the heater box (because it
could not withstand the internal temperature of nominally 120°C), the
squirrel-cage blower itself was re-installed inside the box to  recirculate
only the heated air.  These modifications greatly improved the  control of
oven box temperature by reducing thermal gradients and eliminating most of
the heat losses.

                                     55

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4.5.1.3  HC1 Corrosion of Hydrocarbon Analyzer

     Examination of the analyzer components prior to testing made it
apparent that the HC analyzer could not withstand continuous, long-duration
exposures to moist, hot, HC1 gas streams without significant damage to its
brass and copper plumbing.  The choice was then made to substitute a Perkin-
Elmer 881 gas chromatograph with an open tubular column and FID for the
Beckman instrument for monitoring hydrocarbon levels during the C-5,6 waste
burns.  The chromatograph's primarily stainless steel plumbing was less
susceptible to HC1 attack and could be operated intermittenly to further
minimize its exposure to the corrosive sample stream.

4.5.1.4  Caustic Scrubbing of Acid Gases

     The acid gas stream produced in the C-5,6 runs would also corrode the
pump and gas meter in the sampling train control box.  To protect these
components and also to measure quantitatively the volume of HC1 produced,
a large, 2-liter impinger (shown in Figure 4-13) was added to the train.
This impinger was filled with 100 to 1200 ml of 13 to 22 percent sodium
hydroxide solution.  A small amount of phenolphthalein was added to this
impinger before each test run in order to visually be able to observe
neutralization of the caustic solution.

     Early neutralization did occur on the first test burn (TRW Run #V),
causing sampling to be stopped after 2-1/4 hours.  The premature exhaustion
of the caustic solution was attributed to underestimating the effect of (XL
being scrubbed out as sodium carbonate.  On subsequent test runs, allowance
was made for this factor and no further problems with the caustic impingers
were encountered.

4.5.2  Laboratory Analysis Problems

4.5.2.1  Trace Metal Losses from Chlorinated Organic wastes

     It is not totally unexpected that it is proving difficult to obtain
accurate and precise determinations, with a minimum detectability of
1 ppm, of the trace metals in the chlorinated, organic matrix of our waste
materials.  Of the techniques which can be performed on the neat sample,
the detection limits of X-ray fluorescence range from 5 to 500 ppm; and
chlorine is a major interferent with neutron activation analysis.  Other
techniques with good accuracy and sensitivity, such as SSHS, AAS, and
ICPOES, require an ashed sample.  During ashing, volatile metals and metal
halides are lost which negates the quantitative capability of the analysis.

     A set of comparative experiments is planned in order to evaluate
special ashing and oxidizing procedures for trace metal retention.  A
commercially prepared standard containing 20 elements in fuel oil will
be mixed with chlorinated organics to obtain an appropriate matrix.  Tech-
niques for analyzing the ash will in turn be compared using the optimum
ashing and preparation methods selected.
                                    56

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4.5.2.2  Extraction of the Solid Sorbent Traps

     Extraction of the collected samples from the solid  sorbent traps was
complicated by problems with the designed extractors.  The  extractor, shown
in Figure 4-17 was fabricated so that the sorbent trap would fit between
the upper and lower portions and distilled solvent would be continuously
passed through the resin bed.  The only difficulty was in obtaining a leak-
free seal around the ball and socket joints.   The best solution has turned
out to be Teflon sleeves.  Some were ordered, but were not  received until
late in the analysis schedule.  With the Teflon sleeves, the designed
extractors work well, and will be used for future test samples.

     In the meantime, it was decided to use a standard Soxhlet apparatus.
This technique involved pre-extracting paper thimbles, transfering the
XAD-2 resin to the thimble, and then extracting the resin in the Soxhlet.
The principle behind the two methods is the same.  However, the Soxhlet
method presents the question of background organic contributions from the
thimbles.

4.5.2.3  Use of Multiple Solvents for Extractions

     After completion of the initial pentane extraction  of the first set
of sorbent traps, the resin was observed to have remained considerably dis-
colored.  This discoloration was assumed to represent organic compounds
still absorbed on the resin.  Subsequent extraction of the traps with a
polar solvent, methanol, removed five to six times more  material by weight.
These results showed that a single solvent extraction, even over a 24-hour
period, would not remove those compounds which are only  slightly soluble in
the solvent.  Proceeding with this new information, a third extraction was
performed using benzene since this would be the best solvent for aromatics,
chlorinated aromatics, and ROMs.  However these extracts contained insigni-
ficant amounts of material, showed no trace of any of the above compounds,
and had  high backgrounds due to the resin not having been precleaned with
benzene.  Consequently, the benzene extractions were not continued, and
only pentane and methanol extracts were made of the remaining sorbent traps,
                                     57

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                         H20
                      -CONDENSER
                    24/40 JOINTS
                            --FLEXIBLE TEFLON
                         -I    COUPLING
                    FRIT  "
                    24/40 JOINTS
                        250 ml FLASK
Figure 4-17.   Sorbent Trap  Extractor

                 58

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                            5.    TEST  RESULTS


     Test burns at The Marquardt Company (TMC)  consisted  of  a  background
test with No.  2 fuel  oil  (MA-I), three tests with ethylene waste (MA-II,
III, IV)  and three tests  with C-5,6/fuel oil blends (MA-V. VI. VII).   This
section presents results  of analyses performed  on these test samples.   The
section is divided into results  for: 1) on-line combustion gas analysis,
2) waste destruction analysis,  and 3)  final  emissions  analysis which  in-
clude stack gases, scrubber waters and burner  head residues.  Methods  and
procedures for the preparation and analysis  of  test samples  can be found
in Section 4.4.

5.1  COMBUSTION GAS DATA SUMMARY
     Gas concentrations (by volume) as measured primarily by the on-line
instruments are presented in Table 5-1.  Other  methods were  used to quantify
those species which were not measured by continuous monitors.   Percent water*
was calculated according to EPA Method 4 using  the volume of water col-
lected in the combustion zone sampling train.   To determine  the mole
percent of HC1 and Cl2 gases, chlorides and  total available  chlorine  were
titrated in the combustion zone sampling train  caustic impinger solutions.
In addition, SO  gases were determined by Gastec® indicating tubes.
               X
     The data generally follow the operating parameters of the respective
tests.  The ethylene tests consisted of varying the waste and air feeds to
achieve different combustion temperatures and  therefore the  C02i H20,  and
NOx values rise along with increasing feed/temperature conditions.  Due to
the high sulfur content of the ethylene waste  (1.32%)  the resulting SOx
emissions could only be.«roughly estimated.  SOX levels were  difficult to
measure with the Gastec® tubes because the tubes were calibrated for 1 to
100 ppm.


     The C-5,6 tests consisted of holding nominally constant feed rates
while increasing the waste/auxiliary fuel ratio.  This produced corres-
ponding increases in the levels of HC1 and Cl2 while C02. NOX, and SOX
levels remained essentially the same.  The fairly constant level of CO
throughout all seven tests indicates that good combustion was achieved at
all tested conditions.  The HC values are not  believed to indicate signif-
icant differences betwen tests since: 1) readings were at the low range
of the Beckman analyzer where its accuracy is  somewhat poor, and 2) mea-
surements were made non-redundantly with two different analyzers (Tests I to
IV with the Beckman 402, and Tests V to VII  with the gas  chromatograph)
so that the two sets of values cannot be directly compared.

5.2  WASTE DESTRUCTION ANALYSIS SUMMARY
     Sampling of the combustion zone from the  SUE®burner reaction tail-
pipe was accomplished just upstream of the venturi scrubber  with the
sampling train described in Section 4.3.2.  The samples from the train
consisted of a probe wash, filter, sorbent trap, grab gas sample and
impinger liquids.  These samples were then separated into their organic
and inorganic constituents and analyzed by appropriate techniques, as
described in Section 4.4.  Analysis of the combustion products is aimed


                                    59

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Table 5-1.  Total  Gas Composition In the Combustion Zone by Volume
Run No. and
Fuel Description
Fuel 011 Background
I
Ethyl ene Waste
II
III
IV
C-5,6 Fuel Oil
V
VI
VII
o2 (x)

6.3

7.2
9.4
4.9

8.1
5.6
5.5
co2 (%)

9.8

10.3
9.3
11.5

8.4
9.7
9.5
N2 (5)

73.0

74.0
73.4
74.2

69.6
68.8
67.9
H20 (5)

10.9

8.5
7.9
9.4

12.7
14.2
14.7
HC1 (%)

-

.
-
-

1.15
1.64
2.35
C12 (ppm)

-

-
-
-

<0.05
15
56
CO (ppm)

12

17
17
22

20
17
17
NOX (ppm)

170

200
150
520

145
140
120
HC (ppm)

10

5-10
5-15
5

10-25
35-65
30-35
S02 (ppm)

15-20

100-200
100-200
100-200

5
6
5

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mainly at identifying and quantifying any unburned waste or hazardous
partial combustion products.   The production of potentially toxic levels
of trace metals from burning  these wastes is also examined.  Where
quantified species are calculated in mg/nP in the sample gas stream, the
gas volume data used to make  these calculations are summarized in Appendix
B.  The level of interest for this program is defined as 0.1 mg/m3 of sam-
ple gas, which represents the threshold level of the bulk of the most
toxic species as defined by OSHA and other health and safety organizations.

5.2.1  Organic Composition
     The organic analyses were divided into: 1) quantitative searches by
gas chromatography for uncombusted constituents from the waste material or
other specific compounds that could be expected to be present, and 2)
qualitative surveys to identify unexpected compounds.

5.2.1.1  Results of Quantitative Analyses
     The results of the gas chromatographic analyses on the extracts of the
combustion zone filter and sorbent trap samples are presented in Table 5-2.
The table shows that benzene, known to be present in the ethylene waste,
and mesityl oxide (identified subsequently by GC/MS) were found in the
combustion zone filter extracts.  Mesityl oxide (4-methyl-3-pentene-2-one),
an industrial solvent and rust remover, was found in MA-IV.  It is likely an
artifact of contamination during sampling or sample preparation.

     Results of the analysis  of the sorbent trap extracts by gas chroma-
tography indicated that a total of five compounds are present in the seven
sorbent trap extracts.  Chromatograph retention times for these compounds
did not coincide with retention times for the waste constituents thus no
identification could be made on that basis.  These compounds were arbi-
trarily identified as Compounds A through E based on chromatographic
retention time.  Their concentration levels, based on equal detector
response, are presented in Table 5-2.  Each sample had at  least one of
these  compounds and six samples had two or more.  Combined GC/MS was used
to help resolve the composition of the extracts and identify the five un-
known  compounds.  Four samples were selected for GC/MS in  such a way that
all five unknowns were contained in at least one of the selected samples.

     Results of the GC/MS analysis indicated the presence  of compounds pre-
dominantly silicones and oxygenated organics.  None of the  representative
waste  constituents were found in these sorbent trap extracts.  No further
analyses were performed on these samples  since: 1) they are not part of the
original composition waste, 2) they represent low ppm levels in the sample
gases, and 3} there is no evidence of toxic characteristics in what is
known  of the compounds.

5.2.1.2  Qualitative Survey Analysis
     Samples were surveyed by gravimetric,  infrared spectrometry  (IR), and
low resolution mass spectrometry  (LRMS)  techniques.  Since the qualitative
results correlate more to sample  type than  to waste burn,  the data  are dis-
cussed in  the following order:
                                     61

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                                   Table 5-2.  Results of Gas  Chromatographlc Analysis

Run Number and
Fuel Description
Fuel Oil Background
MA-I

Ethyl ene Waste
MA-I I

MA-III


MA- IV



C-5,6/Fuel Oil
MA-V


MA- VI
MA-VI1



Sample Gas.
Volume (mj)

5.28


5.20

4.80


5.07




4.15


5.53
4.54



Compound

Benzene


{Note 1)

(Note 1)


Mesityl
Oxide



(Note 1)


Benzene
Benzene


Amount
Found (mg)

1


None Detected
Above Back-
ground
ii n


12




None Detected
Above Back-
ground
3
3


Concentration of
Detected Compounds
(mg/m3)

0.2



-------
     a.  Combined particulate filter and probe wash extracts

     b.  Sorbent trap extracts

     c.  Grab gas samples

a.   Combined Probe Wash and Parti oil ate Filter Extracts

     The combustion zone filters were extracted with methylene chloride
using the procedures described in Section 4.  Table 5-3 presents the
amount of residues found In the combustion zone filter extracts and the
resulting concentrations in the sampled gas.  The values  have been cor-
rected for the amount of material extracted from the control, an unused
filter.  The amount of material found after extraction of the control
filter was only somewhat less than that found on each of  the sample
filters and its qualitative nature was also similar.  This is Indicative
of low level contamination which often plagues trace organic analysis,
even though these filters were fired in a muffle furnace  carefully pre-
conditioned, handled in clean glassware, and extracted with  chromatographic
grade solvent.

     The extractable organic material from the combustion zone filters
analyzed by IR and LRMS consisted of alkyl hydrocarbons and  alkyl  esters
of phthalic acid which are not considered toxic.  No evidence of any of
the starting toxic materials was seen.  No additional  effort was made  to
fully identify the esters and/or hydrocarbons present. A detailed dis-
cussion of observations made during preparation of the filters is found in
Appendix D.
   Table 5-3.  Organic Material  Extracted From Combustion Zone Filters
Run No.
Fuel Oil
Background
I
Ethyl ene Waste
II
III
IV
C-5,6 Fuel Oil
V
VI
VII
Amount of Material
Extracted (mg)
0.80
0.55
0.65
4.40
1.50
1.55
1.35
Sample Gas Volume,
Met Basis (m3)
at 1 atm and 21°C
5.28
5.20
4.80
5.07
4.15
5.53
4.54
Concentration
Level in Gas
(mg/m3)
0.15
0.11
0.14
0.87
0.36
0.28
0.30
                                    63

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b.  Sorbent Traps

     This section presents  the  results of the survey analyses performed on
the extracts of the sorbent traps from the combustion zone sampling train.
The amounts of organic materials found by extraction and gravimetry in the
samples are presented in Table  5-4.

     Examination of the IR  and  LRMS data leads to the conclusion that cer-
tain classes of compounds commonly used as processing aids and found in
many industrial products and  processes are present.  There is evidence to
believe these compounds are indeed present in the combustion gases, but
were also found in the control  and blank samples which were never exposed
to combustion gases.  Details of control  and blank analyses are provided
in Appendix D.

     Table 5-4 shows that significant amounts of extractable materials were
found and at levels considerably higher in the sample traps than the un-
used sorbent trap which was used as a control.  The IR and LRMS data indi-
cated hydrocarbon oils or greases, fatty acid compounds and phthalic acid
esters.  The amounts of these materials found in the sample traps are so
much greater than the amounts found in the several control experiments
that either or both of the  following conclusions must be reached:  1) these
species were actually present in the combustion gases, or 2) they were
originally in the sorbent trap  resins despite prior clean up, and the
exposure to conditions inherent during sampling somehow aids in their
release from the resin matrix and subsequent solvent extraction.
 Table 5-4.  Organic Material  Extracted  From Sorbent Traps, Survey Analysis
Sampl e
MA-I-CG-ST
MA-II-CG-ST
MA-III-CG-ST
MA-IV-CG-ST
MA-V-CG-ST
MA-VI-CG-ST
MA-VII-CG-ST
Control (Unused
Sorbent Trap)
Amount of Material
Extracted
(Corrected for
Control) (mq)
60.67
49.49
70.32
100.86
92.60
133.58
119.76
7.36
b ample Gas
Volume, Wet
Basis
(m3 @ 1 atm
and 21 °C)
5.28
5.20
4.80
5.07
4.15
5.53
4.54
4.00
Assigned
Concentration
Level in Sample
Gas (mg/m3)
11.5
9.5
14.6
19.9
22.3
24.2
26.4
1.8
                                     64

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c.  Grab Gas Samples
     Grab gas samples were taken from the combustion  zone sampling train
downstream of the sorbent trap during train operation.   Analysis of these
grab gas samples for possible organic species passing through the solid
sorbent traps was performed by LRMS.   Inspection of the mass  spectra indi-
cates that only propane and butane were present in the samples at rather
constant levels which never exceeded  10 pom.  No other organic materials
were present in the sample.  The calculated lower limit of detection for
other compounds of similar organic composition under  the same analytical
conditions is 2 ppm.  Table 5-5 summarizes the results of the analysis.
The levels are reported as ppm propane since a propane standard was used
to determine mass spectrometer response factors.
            Table 5-5.   Analysis of Organics in Grab Gas  Samples
                     Sample


                  MA-I-CG-GG

                  MA-II-CG-GG

                  MA-III-CG-GG

                  MA-IV-CG-GG

                  MA-V-CG-GG

                  MA-V-HA-GG

                  MA-VI-CG-GG

                  MA-VI-HA-GG

                  MA-VII-CG-GG

                  MA-VII-HA-GG
Organic Content
(ppm as Propane)


       9

       9

       9

       9

       9

       8

       9

       9

       9

       8
                  Those samples with the designation "CG"
                  in their labels were taken from the
                  sampling valve downstream of the sorbent
                  trap in the combustion zone sampling
                  train.  Those with a "HA" were taken
                  downstream of the gas chromatograph
                  which was being used as a total hydro-
                  carbon analyzer during the last three
                  runs with the chlorinated waste.
                                    65

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5.2.2   Inorganic  Characterization

     Inorganic elemental  concentrations were determined by analysis of the
particulate filters and aqueous  impinger samples.  The filters were first
weighed to determine  total  participate loading.  The loadings obtained are
reported  in Appendix  D, Section  D.7, along with other weights taken at
subsequent steps  of filter  preparation for analysis.

     After total  participate weights were measured, the combustion zone
filters were solvent  extracted for  organic species and the filters were
then photographed.  Figure  5-1 shows a photograph of the particulate fil-
ters obtained from sampling the  combustion gases from Tests I through VII,
in order  going from left  to right and top to bottom.  The sooty nature of
the filters from  the  C-5,6  tests agrees with observations made during these
three tests that  relatively larger  amounts of burner residue (clinker) were
being formed.  The clinker  itself is described in Section 5.3.3.  The
irregular dark and light  markings on the filters shown in the photograph
are the result of prior folding  of  the filters for solvent extraction.

     Trace metals on  the  particulate filters were put into solution by
acid digestion of the filters.   The liquid collected in the impingers was
combined  into one sample  and an  aliquot of that was acidified for trace
metal analyses.  The  filter digests and acidified impinger solutions from
Tests I (No. 2 background), IV (ethylene waste), and VI (C-5,6 waste) were
surveyed  semi-quantitatively by  inductively coupled argon plasma optical
emission  spectrometry (ICPOES).

     Quantitative analysis  for selected elements were then performed by
atomic absorption spectrometry (AAS) on all samples.  The elements to be
analyzed were selected by the following criteria:

     1.   Potentially  toxic  (e.g., Pb, Cd, Sb, and Hg)

     2.   Present  at significant  levels as determined by
          the: survey  analysis of the wastes (Section 4.1),
          and/or survey analysis  of  the filter acid digests
          and impinger solutions.

     Using these  criteria,  four  elements were selected for AAS analysis,
Cr, Pb, Co, and Sb.   Although not among the most toxic of metals,  Cu, Zn
and Mn were also  analyzed for an additional comparison of the ICPOES and
AAS results.  The ICPOES  analysis indicated only very low levels of any
toxic elements (see Appendix D,  Section D.8), which is confirmed by the
AAS results shown in  Table  5-6,  with the exception of the element Pb.
Results from analysis of  the stack  samples are also included in this table
for purposes of comparison.

     In those cases where elements  were either not detected or were mea-
sured at  levels less  than or equal  to background levels, a less than
value is given.  As expected, metal concentrations are fairly constant for
Runs II,  III, and IV  in which the ethyl ene waste was fed at approximately
the same  rate for each test.  On the other hand, for Runs V, VI, and VII,
in which  the C-5, 6 was was fed  at  increasingly higher concentrations, a

                                     66

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                                                                                       -
                                                                                       '
Figure 5-1.    Filters From Combustion Zone Gas Sampling After Solvent Extraction

-------
               Table 5-6.   Toxic Trace Metals at Level of  Interest  {mg/m ) by  MS

Run I
Stack
Combustion
zone
Run II
Stack
Combustion
zone
Run III
Stack
Combustion
zone
Run IV
Stack
Combustion
zone
Run V
Stack
Combustion
zone
Run VI
Stack
Combustion
| zone
Run VII
Stack
Combustion
zone
Copper
Impingers Filter
NGTB
<0.003
NGTB
0.022 <0.001
NGTB
<0.001
0.022 0.002
NGTB
<0.001
O.Ull 0.002
NGTB
<0.005
0.021 0.002
0.014
0.071 u.015
0.008
O.OB6 0.008
0.022
0.059 0.013
Chromium
mplngers Filter
ND
<0.001
ND ND
<0.001 <0.001
NO
<0.001
ND
<0.001 0.003
ND
<0.001
ND NGTB
<0.001 <0.001
ND
<0.001
ND
<0.001 0.001
0.008
0.002 0.030
0.014
0.001 0.045
0.037
0.001 0.14
Lead
mplngers Filter
0.001
0.002 0.002
0.001
0.003 0.003
0.001
ND
<0.001 0.002
0.003
0.002 0.002
0.01 0.003
0.55 0.010
0.01 0.005
0.95 0.006
0.05 0.006
1.40 0.008
Zinc
mplngers Filter
NGTB
<0.2
NGTB
0.005 <0.008
NGTB
<0.05
NGTB
0.009 <0.06
NGTB
<0.1
NGTB
0.010 <0.007
NGTB
<0.07
NGTB
o.on 
-------
corresponding rise in the level  of metals emitted can be  seen.   Of the
metals analyzed by AAS, only chromium is trapped predominently  on the
filter, which substantiates the  need for careful metal  analysis of the
impinger solutions.

     In addition to the trace metal analyses,  the impinger solutions from
the C-5,6 tests were also analyzed by wet chemical  methods for  the HC1,
Cl2, and C02 scrubbed from the combustion gases by the caustic  in the
impingers.  The volumes of HC1 and C02 were needed in order to  correct the
gas sample volumes as measured by the dry gas  meter.   The levels of free
chlorine, a potentially toxic specie, were determined to  be <0.005, 15,
and 56 ppm for Tests V, VI, and  VII, respectively.   Complete results of
these wet chemical analyses are  described in Appendix D,  Section D-8.

5.3  Final Emissions
     The stack gas, scrubber water and burner head residue (clinker)  that
make up the final emissions from the SUW^burner incineration system were
sampled during each test and analyzed to determine the  environmental  safety
of the tests at TMC.

5.3.1  Stack Gases

     Stack effluents were sampled during the tests with both a standard EPA
Method 5 train and Gastec® detection tubes.  The Method 5 train was  used
to obtain samples for the determination of parti oilate>  loading and ele-
mental composition of the particulate, and the Gastec© tubes were used to
measure potentially hazardous gaseous species such as hydrocarbons, HC1,
C12> and COClp.

5.3.1.1  Samples Obtained From the Method 5 Train

     The particulate filters obtained from sampling the stack gas are shown
in Figure 5-2.  The filters from Tests I through VII are presented in order
going from left to right and top to bottom.

     Particulate mass loading was determined by adding  the weight of partic-
ulate found on the filter to the weight of the residue  obtained by evap-
orating the probe washes to dryness.  This gross weight is then corrected
for the appropriate blank or control values and divided by the total  gas
sample volume.  The resulting values, in both metric and English units,
for the particulate emitted from the stack are presented in Table 5-7.

     After weighing, the filters were acid digested and selected samples
were surveyed for trace metals by inductively coupled argon plasma optical
emission spectroscopy (ICPOES).   The ICPOES results (presented in Appendix
D, Section D.8) indicated very low levels of all toxic  elements as did the
quantitative analyses by atomic absorption spectrometry (AAS) presented in
Table 5-6.  Because of the relatively high level of lead and its pre-
dominante collection in the impingers from the combustion gas, lead was
also determined in the stack impingers and found to be  quite low.
                                     69

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•vj
o

                                       Figure  5-2.    Filters  From  Stack Gas Sampling

-------
                Table 5-7.  Participate Mass Loadings
Test No.
I
II
III
IV
V
VI
VII
parti GUI ate Loading
Mg/m3
21.2
20.9
25.0
20.4
36.2
43.8
113.5
Grains/Std. Ft3
0.0092
0.0091
0.0109
0.0089
0.0158
0.0192
0.0494
     In addition to the seven elements discussed in Table 5-6, the element
sodium was also determined by MS in the digests of the stack filters from
the C-5,6 runs since it was suspected that the relatively high weights on
these samples were due to NaCl produced by the caustic scrubber.   Indeed,
if all the Na measured (after correction for the background of the control
filters) is assumed to be present as NaCl, the weight of NaCl accounts for
85 to 90 percent of the stack particulate, as shown in Table 5-8.   This
calculation is probably a good average since the values for the weight of
sodium salts would be higher for any sodium carbonate present and  lower
for any sodium hydroxide present.
                (ft
5.3.1.2  GastecwTube Measurements
     Gastec^detection tubes were used to analyze for low concentration
gases that could be present.   Sulfur oxides were measured in this way
and these results reported in Table 5-1.  Other gases  which were checked
using Gastec
-------
    Table 5-8.   Percent Sodium Salts as NaCl  on Stack  Filters


Run
No.
V
VI
VII

Total Wt. of
Material
on Filter (mg)
38.1
93.9
139.4
Wt. of Na
Recovery by
Acid Digestion
(mg)
13.0
33.5
46.50

Wt. Sodium
Salts
as NaCl (mg)
33.04
85.14
118.18
Percent NaCl
of Parti cul ate
on Filter
(mg)
87
91
85
                  Table 5-9.  Gastec^Tube Results
Sampling Location
Stack
Stack
Gas Chromatograph
Outl et
Run No.
All
V. VI
and VII
V, VI
and VII
Detector Tube
Gasoline (aliphatic)
HC1
Cl2
COC12
CoCl2
Limits of
Detecti on
<0.005
percent
<0.2 ppm
<0.33 ppm
<0.1 ppm
<0.1 ppm
The only practical  opportunity  for testing the combustion zone gases
with Gas tec® tubes  to  check  for  any production of phosgene was at the
outlet of the GC  sample bypass  line.  The GC, as previously mentioned,
was substituted for the Beckman HC monitor during the C-5,6 runs.
                                  72

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5.3.2.1  Organic Characterization

     Quantitative
     The various scrubber water samples were extracted with Freon to remove
and analyze the organic materials in them.  The concentrated extracts were
then analyzed by gas chromatography.  The results are summarized in Table
5-10.
           Table 5-10.
Results of Gas Chromatographic Analysis
of Scrubber Water Samples
Run Number
Fuel Oil
Background
I
Ethyl ene
Waste
II
III
IV
C-5,6/Fuel
on
V
VI
VII
City Water
Control
Fresh
Caustic
Water
Control
Scrubber Water
Volume of
Scrubber Water
Extracted
(Liters)
1.00
1.00
0.50
1.00
0.50
1.00
1.00
1.00
1.00
Low Boiling
Material in
Scrubber Water
Extract
(mg)a
26
73
30
28
60
20
26
53
12
Higher Boiling
Material in
Scrubber Water
Extract
(mg)a
0.7
0.8
0.4
0.5
<0.1
<0.1
<0.1
<0.1
<0.1
Concentration
of Extracted
Material in
Scrubber Water
(mg/1)
27
74
61
28
120
20
26
53
12
a See Section 4.4.2 for definition  of low boiling  and  higher  boiling
  materials.   Instrument response (calibration)  for low  and higher
  boilers was determined with standard injections  of benzene  and
  naphthalene respectively.
                                     73

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     No evidence of the  ethylene waste or C-5,6 waste constituents were
found in the chromatographic data.  The levels reported in Table 5-10
represent three artifacts that  are present in the control samples and the
fuel oil background samples as  well as the test samples.  It can be rea-
sonably concluded that these materials are not generated as a result of
burning waste.

     Qualitative Survey
     An aliquot of the concentrated organic extract from the scrubber water
samples was also subjected to the survey analysis for unexpected combustion
by-products etc.  The results of the  gravimetric determination of the
residue is presented in  Table 5-11.   A trend of changing organic content in
the scrubber water than  the No. 2 oil  baseline burn or the ethylene waste
burns.  The premature shutdown  of Test VII test is not believed to have
caused the higher value  for the scrubber water extract sample.  Instead
the low values associated with  Runs V and VI, are considered to be in-
consistently low.
         Table  5-11.
Results of Analysis of Concentrated Organic
Extracts of Scrubber Water Samples
Sampl e
City Water9
Fuel Oil
Background
MA-I-SW
Ethylene Waste
MA-II-SW
MA-III-SW
MA-IV-SW
Control
MA-V-FSWb
C-5.6/Fuel Oil
MA-V-SW
MA-VI-SW
MA-VII-SW
Volume of
Scrubber
Water
Extracted
(liters)
1.00
1.00
1.00
0.50
1.00
1.00
0.50
1.00
1.00
Amount of Extracted
Material by
Gravimetry
(mi Hi grams)
0.53
84.42
70.0
62.0
77.1
16.3
0.9
0.7
33.2
Concentration
in Scrubber Water,
mg/ liter
0.5
84.4
70.0
124.0
77.1
16.3
1.8
0.7
33.2
 a  City water was used as the wet scrubber feed for Tests  MA-I  through MA-IV.
   This sample is therefore the control sample for the first four  tests.

 b  A control  sample of fresh caustic scrubber solution was prepared by blend-
   ing concentrated caustic with city water according to the blending propor-
   tions used for Test MA-V.  Therefore, this sample is the control for tests
   MA-V through MA-VII.

-------
     Survey analyses by infrared spectrophotometry (IR)  and  low resolution
mass spectrometry (LRMS) were performed on the residues  obtained from the
evaporation of the Freon solvent in which the residues were  dissolved.   The
IR data for all the scrubber water extract samples were  all  extremely simi-
lar, and while no evidence of the waste constituents were seen, the spectro
indicated hydrocarbon oils, greases, fatty acid esters.   The LRMS data
supported the IR findings but also detected minor amounts of phthalate
esters.

5.3.2.2  Inorganic Characterization

     The scrubber water samples, aliquots of which had been  acidified in the
field, were analyzed by AAS for several elements of interest.   Identified
for analysis as a result of being detected in the representative waste
samples were Cu, Cr, Pb, Zn, Mn.  Cobalt (Co) an antimony (Sb)  were found
in the combustion test samples and were added to the test matrix.  The  re-
sults of those analyses, corrected for appropriate background are presented
in Table 5-12.

     The Los Angeles County Sanitation District Phase I  concentration limits
for point source discharge to a sewer were consulted. These heavy metal
concentrations are all at least a factor of ten below the most stringent
maximum allowable concentration for these listed metals  which is 10 mg/liter
(ppm).  It is concluded that these scrubber waster were  sewered in accor-
dance with local regulations.
      Table 5-12.   Elemental Analysis of Scrubber Water by AAS (ppm)
Run No.
I
II
III
IV
V
VI
VII
Cu
0.10
0.11
0.07
0.13
0.15
0.14
0.23
Cr
0.21
0.29
0.01
0.38
0.18
0.18
0.35
Pb
0.08
0.02
0.02
0.02
0.21
0.31
0.54
	 -
Zn
0.37
0.82
0.12
0.74
0.23
0.21
0.17
Mn
0.48
0.42
0.06
0.59
0.19
0.12
0.23
Co
—
—
—
—
0.051
0.074
0.12
Sb
—
— — -
— — —
— — -
0.18
0.22
0.24
                                     75

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5.3.3  Solid Residues
     The solid residue  (clinker)  samples were obtained when the burner head
was opened after each test burn.  The clinker was then scraped off the bur-
ner head as completely  as possible  and wrapped in aluminum foil.  The
quantities obtained were as  follows:
                Fuel Oil

                Run  I

                Ethylene Waste

                Run  II
                Run  III
                Run  IV

                C-5.6/Fue1  Oil

                Run  V
                Run  VI
                Run  VII
None (probably <50g)
295g
245g
533g
662g
2327g
1480g
     It must be  noted,  however,  that  these weights in no way represent the
total weight of  clinker produced in each  burn.  There was evidence from both
feed pressure  readings  and  acoustic observations that the clinker tended to
build up,  break  off,  and travel  down  the  tail pipe through the scrubber.
In fact, on the  last  run (VII),  the tip of the mullite probe at the end of
the tailpipe for the  on-line instruments  was believed to be broken by
clinker hitting  it.

     The clinkers were  analyzed  in duplicate by a micro-analytical com-
bustion technique for their carbon and hydrogen content.  The black, powdery,
coke-like  appearance  of the clinkers  indicated that they would probably be
95 to 99 percent elemental  carbon. The micro analysis results, shown in
Table 5-13, supported this  conclusions.
                  Table 5-13.   C and H Analysis  of Clinkers
Element
Percent
Carbon
Percent
Hydrogen
Total
Run II
98.46
0.61
99.07
Run III
97.07
0.79
97.86
Run IV
99.30
0.52
99.82
Run V
88.90
1.19
90.09
Run VI
97.27
0.40
97.67
Run VII
98.02
0.40
98.42
                                     76

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5.3.3.1  Organic Analysis
     Portions of the clinker from each test were extracted for orgam'cs
with methylene chloride solvent in a Soxhlet extractor.   The extract was
further prepared for analysis using the procedures in Section 4.4.   The
concentrated extracts were analyzed by GC for waste constituents as
well as other unexpected by-products.  The survey analysis, gravimetry,
IR, LRMS were also applied to the extracts.

     Quantitative
     The results of the GC analysis of the clinker extracts for the runs
with ethylene wastes are presented in Table 5-14.  It shows that detectable
amounts of extractable material were present in the clinker from MA-II,
MA-III and MA-IV.  Furthermore, the retention times on the gas chromatograms
for the sample extracts are the same as those of the ethylene waste repre-
sentative sample.  It is concluded that uncombusted ethylene waste  is pre-
sent in the clinker at the levels shown in Table 5-14.  This is borne out
by the IR and LRMS survey analysis on the same extracts  which also  indicated
residuals of the original waste.  Two compounds were found by GC to be
present in the clinker extracts from the C-5,6 tests (Table 5-14).   The
retention times for the two peaks do not coincide with retention times for
any of the compounds in the representative sample of C-5,6 which was
chromatographed under the same conditions.  Further work to identify these
two peaks present at these relatively low levels was not carried out since
LRMS and IR of, the clinker from these tests (discussed next) did not indi-
cate the presence of any chlorinated hydrocarbon species.

     Survey
     Aliquots of the concentrated clinker extracts were mildly evaporated
and the residues subjected to gravimetry, IR and LRMS.  The amount  of
residue obtained after mild evaporation of the clinker extracts are pre-
sented in Table 5-15.  The ethylene test clinkers clearly have more
extractables than the C-5,6 clinker.

     Inspection of the IR spectra of the clinker extracts from the  tests
with the ethylene manufacturing wastes (Runs II, III and IV) revealed that
all three samples contain aliphatic and aromatic hydrocarbons.  Comparison
of these spectra with that of the waste feed indicates that uncombusted or
incompletely combusted waste feed is present in the clinker.  The clinker
has a strong odor characteristics of dicyclopentadiene,  a constituent of
the waste.

     The LRMS data for the clinker extracts from the ethylene waste tests
Runs II, III and IV also indicate the presence of alkyl  substituted
naphthalenes and cyclohexadiene.  There is no evidence of any polynuclear
aromatic hydrocarbons larger than naphthalene.

     The IR and LRMS survey analyses of the clinker extracts from the C-5,6
tests (Runs V, VI and VII) showed that the three samples have essentially
the same composition.  The IR spectra indicate that these extracts  were all
aliphatic hydrocarbons, the source of which was likely the auxiliary fuel
that was mixed with the C-5,6 waste prior to burning.  The clinker  extract


                                     77

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 Table 5-14.  Results of Analysis of Clinker Extracts by Gas  Chromatography
Run Number
and Fuel
Description
Fuel Oil
Background
I
Ethyl ene
Waste
II
III
IV




C-5.6/
Fuel Oil
V
VI
VII



Weight
of Clinker
Sample
Extracted
(g)


Low Boiling
Material in
Clinker
Extract
(mg)a


Higher Boiling
Material in
Clinker
Extract
(mg)a


Concentration
of Extracted
Material in
Clinker (mg/g
Clinker)


NOT APPLICABLE NO CLINKER RECOVERED


10.360
9.102
15.654






13.166
15.160
14.110





25
16
27






11
8
14





0.5
0.8
0.8






<0.1
<0.1
<0.1





2.4
1.9
1.8






0.8
0.5
1.0



Comments





Extracted
materi al s
were iden-
tified as
ethyl ene
waste con-
stituents


Extracted
materi al s
not iden-
tTTied as
C-5,6 waste
constituents
a See Section 4.4.2 for definition of low boiling and higher boiling materials.
  Instrument response  (calibration) for low and high boilers was determined
  with standard injections of  benzene and maphthalene respectively.
              Table 5-15.  Residue Extracted from Clinker

mg extracted
g clinker
I
Ethyl ene
Run II
4.73
Run III
21.12
Run IV
3.71
C-5,6
Run V
0.52
Run VI
0.28
Run VII
0.15
                                     78

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from MA-VII also contained  eitheraldehydes,  ketones, esters, or  possibly
a mixture of them as  shown  by  IR.   Neither the  IR  nor the LRMS data  show
any trace of C-5,6 similar  chlorinated species, or POM.  The level of
detection of the IR for these  materials was  experimentally  determined to
be about 5 percent in the extractables.

     Samples of this  solid  clinkers themselves were also directly  examined
by LRMS (no extraction) before and after  they were solvent  extracted.  The
following observations were made:

     •   The ethylene waste test clinkers contained the waste  con-
         stituents confirming  the GC analysis.  Examination of the
         solvent extracted  clinker by the same  LRMS technique  showed
         only a trace organic  content.  The  extraction of the  clinker
         was thus estimated to be more than  95  percent complete
         based upon mass spectrometer instrument response.

     •   The unextracted clinker from the C-5,6 tests contained
         benzene and/or toluene, aliphatic hydrocarbons, and
         monatomic and diatomic chlorine  combustion products.
         Hexachlorocyclopentadiene (C-5,6) and  other chlorinated
         orgam'cs were specifically searched for,  but no trace
         of any chlorinated compounds were detected in the  un-
         extracted clinker. Levels of detection are estimated
         at 0.1 and 1 percent  of the clinker.  In  addition, the
         typical 149 AMU peak  for phthalate  esters was found in
         all of these C-5,6 clinker samples. This is significant
         because  these clinker samples were not extracted  or
         otherwise processed except for grinding,  and the prob-
         ability of contamination during  grinding  is very small
         indeed.  Thus, the presence of phthalates in the
         clinker is strong  evidence for the  presence of phthalates
         in C-5,6 waste/fuel oil feed used in the  tests.  This
         can exaplain the presence of at  least  part, if not all,
         of these phthalates in the samples  from C-5,6 testing.
         Examination of the extracted clinker showed only traces
         of hydrocarbon pickets and methylene chloride, indi-
         cating an extraction  efficiency  similar to that found
         for the ethylene test clinkers.

5.3.3.2  Inorganic Analysis
     Samples of the clinkers were also analyzed by optical  emission
spectroscopy (OES) for elemental inorganic composition.  The results of
this analysts are presented in Table 5-16.

     Certain other elements whose presence was  indicated in the  represen-
tative samples by analysis  (see Section 4) were, in turn not detected by
OES.  Table 5-17 presents these elements  of  interest and their limits of
detection below which they  would not be seen by OES when present in  a
carbon matrix similar to the clinker.
                                   79

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            Table 5-16.  Inorganic Composition of Clinkers  (ppm)
Element
Al
B
Ca
Cr
Cu
Fe
Pb
Mg
Mn
Ni
Si
Na
Run II
30
10
10
300
5
1000
20
50
10
200
50
ND***
Run III
100
100
20
10
100
200
30
800
10
NO**
500
ND***
Run IV
100
50
50
100
50
3000
30
800
20
1000
500
ND***
Run V
30
10
20
10
5
70
50
30
ND*
ND**
10
2000
Run VI
30
30
10
30
10
30
10
30
10
ND**
20
ND***
Run VII
30
30
10
30
5
100
10
' 30
10
ND**
20
ND***
<5 ppm
**<10 ppm
**
<100 ppm







Table 5-17.
Element
As
Ba
Co*
Hg
Sb*
V*
Zn


OES Detection Limits
Estimated Detection
Limit (ppm)
100
500
5
1000
50
30
200
* Would only be likely to be present in C-5,6 test samples (Runs V,  VI
  and VII).
                                    80

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                        6.   WASTE INCINERATION COST


     Individual economic analyses were performed to determine the costs of
incinerating, on an industrial basis, the annual source plant productions
of the two waste materials  tested at The Marquardt Company (TMC).  The
economic analyses were divided into capital  investment and annual operating
costs.  The economic analysis for each disposal  facility,  for the SUE(Jy
incinerator and scrubbing system portion, was based on equipment prices,
estimates of manpower requirements, and fuel  and power consumptions obtained
from TMC.  The costs of other portions of the disposal facilities and
associated labor were estimated using the Happel Method,  data from Guthrie
("Capital Cost Estimating", Chemical Engineering, March 24, 1969) and
standard engineering reference methods.  Equipment costs  were adjusted to
January 1976 prices using the Marshall Steven Cost Indexes.  Land prices
and transportation costs are not included in  the two disposal plant cost
estimates.  Both incineration plants are assumed to be at the manufacturing
plant generating the waste  to be disposed.

6.1  CAPITAL INVESTMENT

     The capital investment for the facility  to  incinerate 15 million
kilograms per year of ethylene manufacturing  wastes shown  in Table 6-1 is
based upon a design concept which employs in  parallel  one  1500 liters/hour
(400 GPH) and one 760 liters/hour (200 GPH) SUE® burner-incinerator-scrubber
system, fed by a common automatic feed system.   The facility costs include,
as common use items, an ethylene manufacturing waste storage tank (16 hour
storage capacity), a scrubbing water supply system (24-hour storage capacity),
and a settling pond with a  24-hour retention  capacity.   It was assumed that
the only fuel needed for the incinerators was the ethylene manufacturing
wastes.

     The size of the facility was based on a  ninety percent plant operating
factor and 15 million kilograms per year of ethylene wastes with a density
of 910 g/liter.  The 2270 liters/hr, ethylene wastes incineration plant has
a nominal capacity of 10 percent over the required capacity of 2070 liters/
hr.

     The total capital  investment for the ethylene manufacturing waste
incineration facility is estimated at $1,818,000.   It should be noted that
over one-third of this  capital investment is  directly  due  to scrubbing
equipment and scrubbing related facilities which may not  be required for
incinerating a fuel as  "clean" as the ethylene manufacturing wastes tested.

     The capital investment for the plant required to  incinerate 4.5 million
kilograms per year of the hexachlorocyclopentadiene wastes mixture shown in
Table 6-2 is based on sizing the incinerator  conservatively on the heat of
combustion resulting from feeding a 1:2 weight ratio of Cede waste and
No. £-/uel oil.  This is equivalent in size to a 1500  liters/hr (400 GPH)
SUE U5  burner incinerator.   The plant design concept  includes the associated
scrubber system, an automated feed system, a  CcClg waste storage tank (with
24-hour storage), a No.  2 fuel oil  storage tank  (z4-hour storage), and the
caustic soda solution storage tank (24-hour capacity).  Auxiliary equipment


                                    81

-------
                                     Table 6-1.   Capital Investment
                 15 Million kg./Yr. Ethylene Manufacturing  Waste  Incineration Plant
Equipment
fo\ ^
1-SUE w Basic incinerator, with scrubbing system
1-Ethylene Manufacturing Waste Storage Tank system
1 -Scrubbing Water Supply System - Tank
- Pumps
1 -Automated feed system, waste
1 -Scrubber Wastes Collection Settling Pond
Piping (at 45%)
Foundations (4%)
Buildings (4%)
Structures (4%)
Fire Protection (0.75%)
Electrical (4.5%)
Painting & Cleanup (0.75%)
Material & Labor
Overhead (30%)
Total Erected Cost (130%)
Engineering Fee (10% erected)
Contingency Fee (10% Erected)
Total Capital Investment
Size
2,270 LPH
33,300 liters
2,650,000 liters
8,950-17,900 watts
2,650,000 liters
$1,165,175
350,000
1,515,000
151,500
151,500
$1,818,000
Estimated
Eouioment
272,750
11,500
100,000
50,000
20,000
454,250
225,000
20,000
20,000
20,000
3,750
22,500
3,750
769,250
Costs
Labor

45,425
225,000
30,000
14,000
4,000
22,500
32,500
22,500
395,925
* Includes burner, incinerator, reaction tailpipe, Venturi  scrubber, scrubber tank,
  pump, air supply system, waste pump.

-------
00
CO
                                     Table 6-2.  Capital  Investment
                 4.5 Million kg./Yr.  Hexachlorocyclopentadiene Waste Incineration Plant
Eau lament
1-SUE ^ Basic incinerator, with scrubbing system*
1-CgClg Waste Storage Tank, Heated, SS
1-No. 2 Fuel Oil Storage Tank (& Pump)
1 -Scrubbing Water Supply System-Tank
-Pump
1-50% Caustic Soda Storage Tank & Pump
1- Automated. feed system, waste & oil
1-20% HC1** Storage tank & pump, rubberlined
1-pH Control System, scrubber pond
1-Scrubber Wastes Collection & Settling Pond

Piping (45%)
Foundations (4%)
Buildings (4%)
Structures (4%)
Fire Protection (0.75%)
Electrical (4.5%)
Painting & Cleanup (0.75%)

Material & Labor
Overheat (30%)
Total Erected Cost (130%)
Engineering Fee (10%)
Contingency (10%)
Total Capital Investment
Size
1 ,500 LPH
7,950 liters
31 ,400 gal
1,890,000 liters)
17,900 watts }
22,710 liters

16,870 liters

1,890,000 liters









$1,044,400
313,300
1,358,000
136,000
136,000
$1,630,000
Estimated
Eauioment
171,250
22,500
10,000
80 000
UW ) WWW
8,300
100,000
12,200
10,000
15,000
429,500
193,300
17,200
17,200
17,200
3,200
19,300
3,200
700,100






Costs
Labor










43,000
193,300
25,800
12,000
3,500
19,500
28,000
19,200
344,300






      * Includes burner, incinerator, reaction tailpipe, Venturi scrubber, scrubber tank,
        pump, air supply system, waste pump.
        From plant waste HC1.
**

-------
also includes  the scrubbing water supply  system tank  (24-hour capacity)
and pump, the  scrubber wastes  collection/settling pond (24-hour storage),
the pH control system, and the storage  tank  (24-hour  capacity) for the
plant waste HC1  used  to adjust pH.

     The estimated capital investment for the CsClg waste mixture is
$1,630,000.  This estimate, as noted  above,  is conservative since the tests
at TMC showed  that only a 1:1  feed ratio  between waste and No. 2 fuel oil
was required to  achieve satisfactory  incineration.

6.2  ANNUAL OPERATING COSTS

     The annual  operating costs consist of annual labor, chemical and
utility costs  plus cost of capital, equipment depreciation, maintenance,
taxes and insurance.  The labor costs have been calculated on the number of
personnel assigned to operate  the incinerator and the automatic waste
loading equipment at  rates prevalent  in the  chemical  industry.  The costs
for supervision, supplies and  payroll-related expense are also included.

     The utility costs include electricity and scrubber water; solid waste
disposal costs are shown separately.  In  the plant for hexachlorocyclopenta-
diene waste incineration, the  costs shown also include the annual require-
ments for No.  2  fuel  oil and sodium hydroxide.  The amount of No. 2 fuel
oil consumed was based on a 1:1 weight  ratio with Cede wastes (shown to
have proper incineration characteristics  by  tests at Tftc). Annual electric-
ity usage was  based on estimates from TMC.   Scrubber water and caustic
soda requirements were calculated from  plant test data.

     The annual operating costs for the plant to incinerate 15 million
kilograms per year of ethylene manufacturing wastes are summarized in
Table 6-3.  The estimated annual operating expense for this plant is
$1,037,500 or  $69.31/metric ton.   As noted  earlier for "Capital Investment",
approximately one-third of this annual  cost  for the disposal of ethylene
wastes is due  to scrubber-associated  systems which may not be mandatory in
this case.

     The annual operating costs for the plant to incinerate 4.5 million
kilograms per year of hexachlorocyclopentadiene wastes are summarized in
Table 6-4.  The estimated annual expense  based on hexachlorocyclopentadiene
wastes is $2,211,700  or $487.59/metric  ton.

     Both disposal plant annual cost  estimates were premised on 24-hour per
day operation, 330 days per year.   The  "cost of capital" shown is based on
the assumption that private debt financing is used for each disposal plant.
                                     84

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                                      Table  6-3.   Annual Operating Cost
                     15 Million kg./Yr.  Ethylene Manufacturing Waste Incineration Plant
                       Item               	                              Cost - $/Yr.

    Depreciation (15% of plant investment)                                           272,700
    Cost of Capital (10% of plant investment)                                        181,800
    Maintenance (8% of plant investment)                                             145,400
    Utilities                                                                        86,400
        Electric power 290KW(7920) ($0.015)                           =  34,500
        Scrubber water 787 x 107 liters/yr @ $0.066/1000 liters       =  51,900

    Solid Waste disposal @ 6.50/metric  ton  for
                           n wt. processed  =  15 x 10°  (.02)  ($6.50)  =  2,000           2,000
                                               1000

»   Labor                                                         x                 312,800
         Incinerator Operator                 1  x 24 x 365  x
         Incinerator Operator Helper          1  x 24 x 365  x $6.50  /=  184,000
         Automatic Feed System Operator       1  x 24 x 365  x
$7.50^
$6.50 > =
$7.00j
         Supervision (15% Operating Labor)                            =   27,600
         Supplies (20% Operating Labor)                               =   36,800
         Payroll Related Expense (35% Labor)                          =   64,400

    Taxes & Insurance @ 2% Plant Investment                                          .36.400
                                                             Total               $1,037,500
    Cost per metric ton of ethylene manufacturing waste        =  $69.31

-------
                                         Table 6-4.  Annual Operating Cost
                 4.5 Million kg./Yr. Hexachlorocyclopentadiene Waste Incineration Plant
                     Item                            	Cost - $/Yr.

    Depreciation (15% of plant investment)                                           244,500
    Cost of Capital (10% of plant investment)                                        163,000
    Maintenance (8% of plant investment)                                             130,400
    Utilities                                                                         60,400
         Electric power 190KW{7920) ($0.015)                   = 22,600

         Scrubber water 572 x 107liters/yr @ $0.066/1000liters= 37,800

    Supplies, Chemical            g                                                1,266,000
         Fuel Oil, No. 2,  4.5 x 10° kg = 32,530 bbl<3 $13.00/bbl= 423,000

         NaOH (5035 solution) 5.35 x 106 kg 6 $158 metric ton   = 843,000
c»        HC1 - Plant waste at zero value, 10.2 x 106 kg

    Solid Waste Disposal & 5.90/ton for 2% of waste processed                          2,000
    Labor                                                                            312,800
         Incinerator Operator   1 x 24 x 365 x
         Incinerator Operator Helper 1 x 24 x 365 x $6.50    } =184,000
         Automatic Feed System Operator 1 x 24
 $7.50        1
365 x $6.50    >
 x 365 x $7.00J
Supervision (152 labor)
Supplies (20% labor)
Payroll Related Expense (35% labor)
Taxes & Insurance @ 2% of Plant Investment
= 27,600
= 36,800
= 64,400
Total
32,600
$2,211,700
    Cost per metric ton of C,-C1, waste                         =$487.59
                            o  6

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          APPENDIX  A

  ASSESSMENT OF ENVIRONMENTAL
IMPACT OF DESTRUCTING CHEMICAL
WASTES AT THE MARQUARDT COMPANY
               87

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      ASSESSMENT OF ENVIRONMENTAL  IMPACT OF DESTRUCTING CHEMICAL WASTES


                                     AT
                            THE MARQUARDT COMPANY
                            16555  SATICOY STREET
                            VAN NUYS, CALIFORNIA


     The Marquardt liquid injection incinerator, located in Van Nuys,
California, is adjacent to the Van Nuys Municipal Airport.   This incinerator
will be used for the destruction and evaluation of the following wastes:

     1)  Ethylene manufacturing waste

     2)  Hexachlorocylcopentadiene (C-5,6)

     The Los Angeles Air Pollution Control District has been notified  of
the intent to thermally destruct these wastes at the Marquardt facility.
The incinerator is operated under  L.A. APCO Permit No. P55506.

     The SUE® (SJJdden .Expension)  burner, derived from aerospace engine
technology, has demonstrated high  effectiveness in incinerating waste
propellents and solvents as well as chlorinated hydrocarbon herbicides
and pesticides.  The burner was designed for a continuous feed rate of 50
to 60 gallons per hour of liquid wastes, and a maximum wall temperature of
3000°F.  TMC's incinerator facility is a well-instrumented research type
installation equipped with a high  energy venturi scrubber for control  of
atmospheric emissions.  Scrubber water is analyzed by TMC personnel before
discharge to the municipal water treatment system.  Solid residue is dis-
posed of in an approved landfill after analysis by TMC.

     The area surrounding the incinerator facility includes other Marquardt
test areas, the Van Nuys airport,  and residential areas.  The nearest
residential area is a trailer court approximately 400 yards from the incin-
erator.  Prevailing winds are from the west (toward the airport runways)  at
usually moderate velocity.  The parking lot and nearby residential streets
are lined with trees.  No wildlife was observed in the immediate area.

     Local vehicular traffic is not affected by this program, since drums
are delivered only at the start of the test series.  Operation of the
incinerator is not noisy compared  to other equipment, such as ramjets,
tested at TMC.  Only a white steam plume from the wet scrubber can be
observed when the incinerator is operating.  The incinerator facility  oper-
ates 8 hours per pay only when tests are scheduled.  A test crew consists
of four to five persons.

     The potential detrimental environmental effects are expected to result
from:  1) storage and handling of  wastes prior to destruction, 2) emissions
occurring during tests, and 3; disposal of liquid and solid residue remain-
ing after combustion.  The most significant hazard would result from contact
with waste liquid and/or fumes during a spill.  The polymeric oil waste  from
ethylene manufacture has physical  characteristics (viscosity, density, color)
and elemental composition (88.7% C, 8.61% H, 1.32% S) similar to the No.  2

                                     88

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oil.  The principal  hazard of this waste is its  flammability.   The CgClg
waste contains approximately 56 percent CrCle,  33 percent octachlorocycTo-
pentene (C5C18), and a number of other chlorinated cyclic compounds.   CsClg
is known to be moderately toxic by ingestion,  inhalation or through skin
contact.  The 1973 Toxic Substances List provides the following data on
C5C16:

     Oral Toxicity (rat):  LD5Q - 505 mg/kg

     Dermal Toxicity (rabbit):  lowest lethal  dose -  430 mg/kg

     Inhalation Toxicity:

         LC5Q (rat)  - 3.1 ppm (3hr)

         Lowest lethal dose (mouse) - 1.4 ppm (3 hr)

         Lowest lethal dose (rabbit) - 1.4 ppm (3 hr)

         LCgo (guinea pig) - 3.2 ppm (7 hr)

Toxicity data on CgClg are not available.   The  toxicity of CgClg is probably
in the same range as CgClg.

Storage and Handling

     TMC has established  safety procedures for handling hazardous materials,
including propellents and explosive materials.   A detailed safety plan
has been prepared for this program, including waste handling procedures.
Wastes will be received by truck in 55-gallon drums,  which will be inspected
for leaks and stored in a bonded area until transferred into the run tank.
All transfer operations will be conducted within a diked, electrically
grounded area by trained personnel using appropriate  equipment and protec-
tive clothing.  Any leaks or spills will be flushed and incinerated.

Incineration Tests

     Operating temperature and residence time of the  liquid injection incin-
erator should provide essentially complete combustion of the wastes,  result-
ing in harmless exhaust emissions.  On-line monitoring of gases from the
combustion zone will be utilized as an indication of combustion efficiency.
In addition, stack emissions (downstream of scrubber) will  be checked for
hazardous gaseous species using Gastec®  analyzer tubes for specific gases
and vapors.  Caustic scrubbing solution will be used for chlorine removal.

Disposal of Residue

     Residue material from the incineration process will consist of scrubber
water and ash.  Liquid residue from the scrubber will be analyzed before
discharge to the municipal water treatment plant by TMC personnel.  Solid
residues (ash) will  also be tested by the TMC personnel prior to approved
landfill.  Wastes remaining in the storage/run tanks  and wash down liquids
from any spills will be incinerated at the conclusion of the test program.


                                    89

-------
       APPENDIX  B

SAMPLE TRAIN OPERATION AND
    SAMPLE VOLUME DATA
                Preceding page blank
             91

-------
                                APPENDIX B

                        SAMPLE TRAIN OPERATION AND
                            SAMPLE VOLUME DATA


     For each test, data was collected on the operation  of the  two sampling
trains.  This information is presented in Table B-l.   The  percent of
isokinetic at which the gas samples were drawn from both the  stack and
combustion zone sampling sites was calculated from the following equation
given in EPA Method 5:

                                                  • •
         /i C77 "i1n\  f/n no267 in. Hg-cu ft\ v  + _m /p     +    H  \] T
         V-677IeTJ  ^°-OOZ67    ml - OR  ) vw * Tm Tbar   13.6 j) 's

     1 =                       ^TP   /'7854 DnZ\
                                 5 s  V  144    /
     The terms of this equation are defined, and values measured for each
test burn are summarized in Table B-l.  It was assumed for the purpose of
these calculations that Ps at the stack was nearly ambient or slightly
positive, and that the 0.5-inch diameter combustion zone probe would behave
roughly like a 0.5-inch nozzle.

     Tables B-2 and  B-3 summarize the  sample gas and collected water volume
data.
                                     92

-------
                                            TABLE  B-l.     GAS VOLUME DATA

Weights/Conditions
Volumes at Standard
Conditions (ft3)
V .
meter
V
water
u ,
C12
w ,
VHC1
u
CO 2 scrubbed
Mole Fractions
B ,.
water

Cl
U2
BHC1
Gas Molecular
Weight (Ib/lb-mole)
M..
dry
•w
Run I
SG


62.71

46.93







.452






30.05

24.63
CG


70.81

15.6'







.109






30.0

28.7
Run II
ST


64.68

30.62







.347






30.11

25.91
CG


72.57

11.00







.085






30.11

29.08
Run III
SG


47.72

24. 6'i







.366






30.02

25.62
CG


160.22

9.K







.079






30.02

29.0
Run IV
SG


46.84

33.75







.444






30.25

24.81
CG


66.65

12.23







.093






30.25

29.11
R'in V
SG


46.76

30.15







.417






29.94

24.96
CG


129.72

14.98

o.oot

1.68(

	 *

.127

.000

.012


Run \I
SG


82.99

39.72







.349






30.02 30.09

28.57

25.87
CG


169.04

22.75

0.00

3.20

0.27

.142

.000

.016


30.19

28.56
tur VII
ST


45.75

31.19







.430






30.10

24.90
CG


136.29

19.55

0.00

3.75

0.57

.147

.000

.024


30.25

28.60
\o
to
           insufficient sample to analyze.

-------
TABLE  B-2.    FINAL CORRECTED GAS VOLUMES

Run

Run I
Stack
Combustion Zone
Run II
Stack
Combustion Zone
Run III
Stack
Combustion Zone
Run VI
Stack
Combustion Zone
Run V
Stack
Combustion Zone
Run VI
Stack
Combustion Zone
Run VII
Stack
Combustion Zone
Dry
	 T~
fr

62.71
170.87

64.68
172.57

47.72
160.22

46.84
166.65

46.76
131.41

82.99
172.52

45.75
140.63
3


1.78
4.84

1.83
4.89

1.35
4.54

1.33
4.72

1.32
3.72

2.35
4.89

1.30
3.98
Met
. 3
ft

109.64
186.51

95.30
183.57

72.37
169.32

80.59
178.88

76.91
146.39

122.71
195.27

76.94
160.18
3
m

3.11
5.28

2.70
5.20

2.05
4.80

2.28
5.07

2.18
4.15

3.48
5.53

2.18
4.54

-------
TABLE  B-3.     LIQUID IMPINGER VOLUME DATA
c . Starting Volume Volume Final
bample Before Test (ml) After Test (ml) Sample
Volume (ml)
MA-I-SR-CI
MA-I-CG-CI
MA-I-CG-C1-A
Mft-II-SO-Cl
MA-II-C6-C1
•W-II-CG-CI-A
.'1A-III-SG-C1
r'A-III-CG-CI
'1A-III-CG-CI-A
MA-IV-SG-C1
-A-iv-cr.-ci
'1A-IV-CG-C1-A
flA-V-SG-Cl
'4A-V-CG-LI
MA-V-CG-L1-A
MA-V-CG-CI
W-V-CG-CI-A
MA-VI-SG-CI
I1A-VI-CG-LI
MA-VI-C6-I.I-A
MA-VI-CG-CI
f1A-VI-CG-CI-A
F1A-VII-SG-CI
MA-VII-CG-LI
'1A-VII-CG-LI-A
MA-VII-CG-CI
MA-VII-CG-CI-A
ZOO
200

ZOO
200

200
200

200
200

200
500

200

200
1200

200

200
1000

200

1171
471

826
387

702
348

883
422

819
730

250

1019
1543

300

R34
1293

290

1171
221
250
826
117
250
702
98
250
883
172
250
819
500
500
150
100
1019
1293
250
200
100
834
1000
son
190
100
Volume of Water
Collected (ml)
971
271

626
187

502
148

683
222

619
230

50

819
343

100

634
293

90

                    95

-------
              APPENDIX  C
CALCULATION OF INCINERATOR PERFORMANCE
           Preceding page blank
                    97

-------
                                 APPENDIX  C

                   CALCULATION OF INCINERATOR  PERFORMANCE

     The destruction  efficiencies  presented in Table  1-1 were calculated for

each of the tests  where  the  appropriate on-line and hot zone samples were
taken.  The data used in these  calculations can be found in Tables 4-6,
5-2,  5-3,  and 5-4.

     The waste destruction efficiency (DEwaste) is based upon comparing the

waste  input rate to the  waste  emitted rate.


           DEwaste  = waste Input^ waste emitted x , QQ%                 ((M }



Equation C-l  restated in another form, is


           DEwastfi  = ^aste - j^V Ewaste]   x 1QO%                   (C-2)
                                waste


where:
           I    «. - input rate of the waste =  fuel feed  rate x weight
           waste    fraction  of waste in fuel.  Units  are milligrams
                    per second.   Table 4-6.
              VFR = volumetric  flow rate of combustion gases from the
                    burner.   Approximately equal to  input rate Table
                    4-6.   Units are cubic  meters per second.
           Ewaste = concentration of organic waste constituents  in
                    the combustion gas as  determined by  G.  C.  It is
                    the sum of the waste constituents  found in the
                    probe wash, filter and sorbent trap  samples  from
                    the combustion zone (Table 5-2).   Units are  milli-
                    grams per cubic meter.
      Similarly the destruction efficiency for total  organics
      .   )  compares the input rate of combined waste and auxiliary  fuel to
organics
the  emitted rate of all organic material found in the combustion zone samples,
                             '               E
           DEtotal organic =  fue1 "          tOta1 Or
-------
where:

     *fue1 = Input rate of combined waste and fuel oil (when used).
             Units are milligrams per second.  Table 4-6.

      total organics = sum of the concentrations of all  organics
             found in the combustion zone samples.  (Tables 5-2,

             5-3,5-4)  Units are milligrams per cubic meter.

     The waste destruction efficiency calculation for Test MA-V is presented

below as an example.  Initially Iwaste is calculated, then VFR   , and
finally Ewastg is taken from 5-2, added to the equation to calculate


           ^aste = 0.0341 kg/sec x 1 x 10  mg/kg
                                   3
                 = 11,400 mg/sec


where:
          0.0341 kg/sec = total fuel feed rate Table 4-6


          1/3 = C-5,6 weight fraction in fuel

Volumetric Flow Rate of Gas


        VFRr,ac = °-568 JSSL * mole  x lOOOg/kg x 0.024 m3 x 294° K
           gas         sec   28.8g                mole     273° K

               =0.51 m /sec
 where:  0.568 kg  = air feed rate Table 4-6
               sec

 where:  0.568 kg    = air feed rate Table 4-6
               sec

         mole air    = estimated molecular weight of combustion gas
          28.8g

         0.024  itr   = approximate molar volume of gas at 21°C
               mole
                                    99

-------
          294° K = volume correction based on temperature.
          273° K

Waste Destruction Efficiency


          DEwaste = 11.400 - [0.51 x <0.2]  1(m                       (c_2)
                          11,400          x  u

                  = >99.9991%

          The destruction efficiencies for total organics.  DEtQtal  Organ1c

are calculated in a similar manner using equation C-3 and inputing  the com-
bined waste and auxiliary fuel feed and the concentration total  organic found

(Tables 5-2, 5-3 and  5-4).
                                    100

-------
        APPENDIX  D





ANALYTICAL CHEMISTRY DETAILS
             101

-------
                                APPENDIX D
                       ANALYTICAL  CHEMISTRY DETAILS


     The elements of this  appendix consist of the interpretation of the
instrumental data that led to  the  results discussed in Section 5.  As
part of the on-going effort to thoroughly characterize hardware and sample
behavior in this relatively new analysis technology, extra effort was  made
to characterize certain  control samples and monitor filter weights during
their preparation.  Details of this effort are also documented in this
appendix.

D-l.  Survey Analysis on Combustion Zone Filter Extracts

     The material found  in the solvent  (methylene chloride) extracts of
the combustion zone filters was surveyed for its qualitative nature by
infrared spectrophotometry (IR) and low resolution mass spectrometry
(LRMS).  The IR data indicates that two main classes of compounds are
present.  The first is alkyl esters of phthalic acid.  This commonly used
placticiser and lubricant  may  have been in the waste feeds or may be a
contaminant from the system.   Whether one compound or several members of
the family of these compounds  is  present cannot be determined from the IR
scans alone.  The second group of  compounds is esters of fatty acids such
as adipic and sebacic acids.   The  evidence for this is that the 2800 to
2900cm~' IR region is more intense than that usually found on commonly
occurring phthalate esters.  Further evidence is shown by the LRMS data.

     The LRMS data support these  conclusions drawn from the IR data.  The
m/e 149 peak is quite evident, but is not the strongest peak in any of the
mass spectra.  For all phthalate esters in the available literature, this
149 peak,which is caused by the stable  "anhydride plus 1 hydrogen" ion, is
the strongest peak.  Other m/e peaks in the sample such as 27, 29, 41, 43,
55, 57, 69, 71, etc., are  stronger and  this indicates that alkyl hydro-
carbon groups, classically represented by this peak pattern, predominate.
The presence of a peak at  167  atomic mass units (AMU) is indicative of
di-n-octyl phthalate and dimthyl  phthalate being present.  A peak at 185
AMU is strong evidence for adipate and sebacate (fatty acid) esters.

     It is important to  note that  the samples show no evidence of any of
the hazardous constituents of  the  original waste feeds.  That is to say,
none of the constituents of the ethyl ene waste nor C-5,6 and its chlori-
nated homologues can be  seen in the filter extract samples from their
respective tests.

D-2.  Survey Analysis of Control  Sorbent Trap Extracts

     This section presents the results of the analysis of solvent and
sorbent traps that were  examined as part of the analysis of the traps
actually used in the sample trains during testing.  This discussion is
important from an analytical view  point because significant amounts of
background material were found in  these control traps.  As discussed later,
the materials found in both the samples and controls are quite similar and


                                     102

-------
the discussion here is a prelude to the discussion of the materials ex-
tracted from the test burn samples.  Furthermore, results gathered here
impact on the preparation and use of these traps in the future in order to
lower their background contribution.

     Two solid sorbent trap control samples were analyzed.  The require-
ment for two samples resulted from the fact that two lots of pre-cleaned
resin were used in the tests.  The first control sample, MA-ST-C1, was
extracted using a standard soxhlet extractor with pre-extracted thimbles
into which the resin was placed after removal from the trap.  The second
control, MA-ST-C2, was extracted using the special apparatus which performs
a Soxhlet-type extraction of the resin without its removal from the trap.
The survey analysis results of these control samples show some weight
differences depending on the extraction method used.  The soxhlet extracted
resin yields more weighable residue (Table D-l).  The table also shows that
the combined thimble and solvent blank also yielded a residue in spite of
the prior extraction of the thimble, and the use of the highly pure sol-
vents.

     The first control trap, extract residue MA-ST-C1, contained esters of
phthalic acid, perhaps an amide, and substituted benzene compounds.  This
material is present in spite of the extensive sorbent trap resin cleanup
and pre-extraction of the Soxhlet thimbles and apparatus.
          Table D-l.  Extracted Material from Control Samples
Sample
MA-ST-C1
Control Sorbent Trap
MA-ST-C2
Control Sorbent Trap
MA-ST-BLANK
Soxhlet Thimble
Solvent Blank
Material Extracted
by Pentane (mg)
1.370

0.430

0.810


Material Extracted
by Methanol (mg)
12.3501

4.490

1.635


   1
The soxhlet thimble used for the C-l  control was not pre-extracted
with methanol prior to extracting the sorbent resin with methanol.
The reported value is believed to be higher than would have been
achieved with a methanol pre-extracted thimble.
                                    103

-------
     The  Infrared  spectra of the, MA-ST-C1 residues were quite similar for
both pentane and methanol  extracts.  The qualitative information is as
follows:
     Spectral
      Region

     3025

     3000-2800

     1740

     1450

     1680

     1260
     Assignment
vC-H
C-H bending
vOO
vC-N, 6-N-H or vC-O-C
Possible Compounds

 aromatic,  possibly phthalates

 alkyl hydrocarbon

 ester
 alkyl hydrocarbon
 amide
 ester or amide
The LRMS data  from  the  MA-ST-C1  sample displayed the following pattern.

               AMU                                   Assignment
     27, 29, 41, 43,  55,  57,  etc.

     77, 91, 105



    149
                          Alkyl hydrocarbon

                          Alkyl substituted benzene
                          compounds such as toluene,
                          ethyl benzene and xylene

                          Phthalate esters
     The second control  sorbent  trap, sample MA-ST-C2, yielded consider-
ably less residue than the  first control resin.  The reason is believed to
be the elimination of the thimble as contributor of some of the contami-
nating materials, however the weight of residue obtained from resin itself
also indicates a source  of  potential contaminants.  The IR spectrum of
the pentane extract residue was  very weak and of little use.  At the
most favorable sensitivity, only the 3000 to 2800cm-' region (alkyl hydro-
carbons) was discernable. The methanol extract residue showed only traces
of the methanol solvent  and one  peak at 1610 to 1520cm'1 (-NHg scissoring)
which suggests, but which does not confirm an amine.

     The material extracted from the second resin control  sample by
pentane had a LRMS peak  pattern  that was rather typical of the types of
compounds seen in the Cl control sorbent trap and in many other sorbent
trap extracts.  Later discussion of other samples will refer to this
pattern.  The significant aspects of the low resolution mass spectra are
as follows:
          Mass Spectra  Peak  Pattern

    A dense peak pattern  commonly called
    "pickets" containing  stronger peak
    pairs at 27, 29, 41,  43,  55, 57, 69,
    71, etc., increasing  in  14 AMU Incre-
    ments (CHo).  These peaks usually
    extend up'through the 111, 113 AMU
    peak pair befor they  become no more
    intense than surrounding  peaks.

                                    104
                                   Assignment

                              Alkyl,  normal and
                              branched hydrocarbons
                              either  as a  class of
                              compounds or as  sub-
                              stituents on other
                              classes of compounds.

-------
     Mass Spectra Peak Pattern                     Assignment
           91, 105                           Alkyl  substituted
                                             benzene compounds, e.g.,
                                             toluene, ethyl  benzene
                                             styrene (benzoates are
                                             also possible).
         Ill, 129, 185                       Adi pate, sebecate esters
                                             (fatty acid esters)
             149                             Phthalate esters
             241                             Di-butyl sebecate
     The methanol extract of the MA-ST-C2 resin trap contained not only
the same "picket" pattern, the substituted benzene pattern,  and phthalate
peaks described immediately above; but also contained a 279  AMU peak
which, while not found in the TRW base of mass spectrometric data, has
been identified as characteristic of dodecanoic (lauryl) sulfonates com-
monly found in detergents and surfactants.
D-3.  Survey Analysis of Thimble and Solvent Blanks
     The background sample characterization for sorbent traps was completed
with an analysis of a third control  sample obtained by extracting an
empty thimble with pentane and methanol after it had already been pre-
extracted with these solvents as per the standard resin extraction procedure.
The amounts of recovered material are small in relation to the other
samples but the LRMS data indicate the same basic types of compounds:
              AMU                               Assignment
         Dense "pickets"                 Alkyl hydrocarbons
         149                             Phthalates
         111, 129, 185                   Adi pate, sebecate esters
         167                             Di-methyl  phthalate
         256, 73                         Palmitic acid esters
There was insufficient sample in the extract aliquot to obtain a useful
IR spectra.
D-4.  Survey Analysis of Test Sorbent Trap Extracts.
     This section presents the results of the survey analysis on the
extracted material from the sorbent  traps used in the sample  trains.  The
procedures for the extracting these  traps is discussed in Section 4.4,  and
                                   105

-------
the weight of extracted material is summarized in Table 5-4.  in general,
the composition of these materials from tests with the same waste are quite
similar, and for ease of presentation the results are given in two groups:
(1) MA-I, V, VI, VII, relating to the tests with C-5,6/fuel oil, and
(2) MA-II, III, IV, relating to the tests with ethylene manufacturing
waste.

     MA-I, V, VI, VII

     The IR spectra for pentane and methanol (and benzene 1n the three
samples where it was used) extracts are very similar.  However, there are
some differences from which inferences can be made with respect to the
overall composition.  These differences are discussed below.  The peaks
found in the pentane extract residues and which are useful in determining
the structure of these materials follow.

     The pentane extracts of the solid sorbent traps yielded the IR
spectra and assignments below.  The methanol extract residues display the
same pattern except that there is a trace of aromatic C-H absorption above
3000cm-l and the carbonyl (C=0) peak in the 1750 cm-1 is somewhat
stronger indicating that the methanol may be more effective in extracting
the ester material.  There is no evidence in the IR spectra that indicates
the presence of any uncombusted C-5,6.  The levels of sensitivity at which
C-5,6 would be seen in this sample matrix were discussed in Section 4.4.2
and are on the order of less than 5 percent of the residue from each
extract as shown in Table 5-4.


     Spectral Region cm"1                    Assignment

       2950                      vas CH3

       2920                      vas CH2

       2850                      vs CH3, CH2
       1750 - 1730               VC=0   ester
       1700                      VC=0

       1650 - 1500,  weak         phenyl  nucleus or weak amide

       1460 - 1450               6asCH3,  CH2 scissoring

       1380 - 1350,  weak         6s  CH3  bending of methyl  group
                                        from alkyls,  esters
       1300 - 1250               asym C-O-C  stretch;  esters,  ethers

       1100 - 1050               sym C-O-C stretch;  esters,  ethers

     The LRMS data of the sorbent trap pentane extracts confirm the general
features of  the IR spectra.  The typical  hydrocarbon fragment  "picket"
pattern is evident in all samples.  Alkyl substituted benzene compounds
                                    106

-------
are indicated (77,  78,  79,  91,  105,  133 AMU).   Phthalate esters  are  also
present but not as  the  predominant class of compounds.  The  presence of
esters of fatty acids  (adipic,  sebacic) are shown by the 111,  129,  185
peaks in several of these samples.

     The methanol extracts  of the sorbent traps contained  the  same  com-
pounds.  The 149 AMU phthalate  peak was stronger in these  extracts.   A
45, 60, 74 AMU pattern  was  indicative of alkyl, monocarboxylic acids.
Some of the fatty acid  compounds  produce these peaks.   As  a  matter  of
routine examination of  all  LRMS data from all  samples,  mass  spectral
evidence of hexachlorocyclopentadiene (C-5,6)  and any other  cholorinated
hydrocarbons were specifically  and carefully searched for.   None were
detected.  The sensitivity  of the mass spectrometer solids probe analysis
technique for searching for particular compounds in a sample is  discussed
in Section 4.4.2.  The  detectable level for a compound  under the worst
circumstance was 10 percent (w/w) of the sample residue being  examined.

     MA-II-. Ill, IV

     The MA-II, III and IV  sorbent trap extracts display differences in
the compositional nature of the extracted material  especially  between that
extracted by pentane and that extracted by methanol.  The  IR spectra for
the pentane extract residues of MA-II, III, and IV are  essentially  the
same as the pattern discussed earlier for MA-I-C6-ST.   The MA-III
spectrum is weaker than the others, but the major peaks are  apparent.
The aromatic composition of the MA-II, III, IV pentane  extracts  is
greater than that for the MA-I  baseline run.  This is consistent with the
high aromatic content of the ethylene waste.  The spectrum of  the MA-II
methanol extract residues show the strong alkyl and carbonyl patterns
discussed above with respect to the C-5,6 tests, but the MA-III  and IV
spectra show extremely  small amounts of absorption in these  areas.   The
esters and hydrocarbons previously mentioned are present at  very low
levels in these two samples.  The only peaks in these spectra  valuable
for identification purposes are caused by small amounts of residual
methanol in the sample  after evaporation.

     The LRMS data confirms the observation that the esters, etc.,  are
present in these samples at lower levels relative to the others  sorbent
trap extracts.  The LRMS data from the sorbent trap pentane  extracts for
Runs II, III, and IV again show distinct similarity to  each  other and
with the patterns earlier described for the sorbent trap control samples:

              AMU                              Assignment

     hydrocarbon pickets            alkyl hydrocarbons  or  hydrocarbon
     41, 43, 55, 57, etc.           substituents on other  compounds

     73 (strong peak)                C-O-R esters, ethers,  etc.,  sub-
     77, 78, 79, 91, 105            stituted benzene compounds

     133                            phenyl  compounds, substituted
                                    benzenes,  benzoates, phthalates
                                   107

-------
              AMU                             Assignment
     149                            phthalates

     167                            dimethyl phthalate

     185                            ad1pate and sebacate esters

     p+14 (-CH9) pattern            hydrocarbon oils and greases
     from ^2077 221, etc.,
     out to AMU 600 and
     higher

     The LRMS data from the methanol extract residues of the sorbent  traps
for Runs II, III, and IV show the same pattern discussed above, but the
patterns are less Intense and indicate that the esters and automatic
compounds are likely present at lower levels.  This trend agrees  with the
IR data discussed above.  Different patterns are evident in the methanol
extracts but examination of the literature provided a multitude of com-
pounds which ionize into some of the fragments listed above but there is
not a sufficiently good fit of the literature data with the sample
spectra in other areas of the spectrum to arrive at even a tentative  con-
clusion as to what types of compounds are presents.  It is stressed how-
ever that this spectra bears little or no resemblance with that of the
original waste.

     AMU                                     Assignment

     31                         primary alcohols, esters, or ethers
     32
     48
     64
     65
     80
     81
     82
     95
    110
    113                         possible furyl or similar ring ethers

     Mass Spectrometer Analysis of Sorbent Trap Resins By Direct  Probe

     Additional LRMS direct probe analysis of the sorbent trap resins from
selected tests was carried out to 1) determine the nature of the  material,
if any, which might still be absorbed on the resin after solvent  extrac-
tion, and (2) gather additional information as to the source of the  fatty
acid esters and phthalic acid esters which are found in many of the
samples.
                                   108

-------
     Four samples  were  selected  for  analysis:

        •  MA-ST-C1           pre-cleaned,  unused  resin

        •  MA-I-CG-ST        base-line  test  with  No.  2 oil

        o  MA-III-CG-ST      second  test with  ethylene waste

        o  MA-V-CG-ST        first test with C-5,6  waste/fuel  oil

Resin samples from MA-III  and MA-V were selected  because  the amounts  of
materials extracted from the sorbent traps for these  tests  were signifi-
cantly lower than the recoveries obtained  from the  other  tests with  the
same waste, leading one to suspect that there  might be unextracted mate-
rial still on the resin.  A portion  of  the resin  was  placed in the solids
probe of the mass spectrometer.  The probe block  was  heated from 50°  to
350°C at 100°C increments  and the  thermally  desorbed  constituents  were
then analyzed.  This analysis provides  no  quantitative estimate of what
might be present on the resin, it  only  provides qualitative information.

     The results of the mass spectra of desorbed  materials  are summarized
as follows:
           Sample

     MA-ST-C1
     MA-I-CG-ST
     MA-III-CG-ST
     MA-V-CG-ST
            Observations

Only residual benzene (the third and
final  extraction  solvent) and the
149 AMU phthalate fragment were noted
at all temperatures.

Benzene is the only compound seen at lower
temperatures.  A pattern at 60 to 64 AMU is
apparent at 150°C and 250°C probe tempera-
tures.  At higher temperatures after
benzene is driven off, a 91,105 pattern of
substitued benzene can be seen.  Phthalate
ester peak at 149 is seen.

Alky! substituted benzene compounds
were detected along with benzene, fatty
acid esters and phthalate esters.

Benzene and alkyl substituted benzenes,
fatty acid and phthalic acid esters,
dimethyl phthalate.  Chlorinated species
were specifically looked for and none were
found.
                                    109

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     The results of the analysis on the extracted resins from selected
runs show that no new classes of compounds were thermally desorbed  from
the resins which had not already been determined as part of the solvent
extracted material.  The fact that traces of phthalate esters were  found
on the MA-ST-C1 control resin is evidence which supports the belief that
the resins retained these compounds in low levels in spite of the resin
cleanup procedures which were performed prior to the test program.   The
presence of these materials  does not reduce the effectiveness of searching
for toxic species; their presence only makes the task more difficult.

D-5.  Survey Analysis of Scrubber Water Sample Extracts

     The LRMS data from the  carefully evaporated residues of the scrubber
water extracts for tests MA-I through MA-IV were quite similar.  They
displayed a pattern shown by a mixture of alkyl hydrocarbons.  The  m/e  27
and 29 peaks are strongly present.  These peaks are caused by the C2Ha
and C2H5 fragments, respectively.  This two-peak pattern is repeated every
14 atomic mass units  (AMUs), i.e., 41 and 43, 55 and 57 (propyl, butyl,
etc.).  The 14 AMUs correspond to the -CH2 fragment which is added  to  the
molecular weight with increasing carbon number in a homologous series.
There is evidence of constituents with molecular weights greater than  350.
This is not uncommon with hydrocarbon oils.  A compound with a molecular
weight around 350 would contain about 25 carbon atoms.  Evidence of the
minor presence of phthalates is provided by the characteristic m/e  149
peak.  The presence of substituted benzene compounds such as toluene,
xylene, ethyl benzene, etc., at trace levels is also indicated.

     Three additional peaks  are present and are not in the 14 AMU peak
pattern discussed above.  These peaks occur at 247, 303, and 340.  The
compound(s) causing these peaks could not be identified using the
available literature.  Substituted benzenes and naphthalenes at low
levels are also  indicated,  but xylene and toluene are not among those  present.

     The LRMS data had weak  spectral patterns since only very small amounts
of extract residue  were  found in the city water control sample, the fresh
caustic scrubber control  sample and the spent scrubber waters from MA-V -
MA-VI as very little  sample  residue available for transfer to the mass
spectrometer sampling system.  The only signal shown by these extracts is
the hydrocarbon cracking  pattern discussed above.  The highest detectable
molecular weights are 139/141 although it is believed that higher
molecular weight materials  are likely to be present at undetected levels.

     The LRMS spectrum of the MA-VII scrubber water extract  residue is quite
similar to the MA-I through  MA-IV spectra discussed above, except that the
m/e 247, 303, 340 pattern is absent.  There is no evidence of any C-5,6 in
the residue.  The estimated  levels at which these materials  are seen in the
mass spectrometer have been  discussed in Section 4.4 and apply here.

D-6.  Survey of  the Ground  Clinker by LRMS Direct Probe.

     The LRMS data for the  ground clinker form the tests with  C-5,6/fuel
oil display the  hydrocarbon  pickets at m/e 27, 29, 41, 43, etc., up to 69,
                                     110

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71.  Traces of benzene and/or toluene were noted.   Peaks  at  35  and 70
were observed that can be described to monotomic and diatomic chlorine.
These material are expected as combustion products.   Hexachlorocyclopen-
tadiene (C-5,6) and other chlorinated compounds  organics  were specifically
searched for, but no trace of any chlorinated compounds were detected in
the unextracted clinker.   In addition, the typical  149 AMU peak for
phthalate esters was found in all of these C-5,6 clinker  samples.   This
is significant because these clinker samples were not extracted or other-
wise processed except for grinding, and the probability of contamination
during grinding is very small indeed.  Thus, the presence of phthalates  in
the clinker is strong evidence for the presence  of these  materials in C-5,6
waste/fuel oil feed used in the tests.  This can explain  the presence of
at least part, if not all, of these materials in the samples related to
C-5,6 testing.  Examination of the extracted clinker showed  only traces  of
hydrocarbon pickets and methylene chloride, indication an extraction
efficiency similar to that found for the ethylene test clinkers.

D-7.  Weight Behavior of Combustion Filters During Analytical  Preparation.

     Weights were obtained on both the stack and combustion  zone filters
with their trapped particulate at several stages of their preparation as
part of the on-going effort to understand the behavior of these samples
during preparation and final analysis.  They were first tared  before
their use and then weighed after the tests to determine the  amount of
particulate trapped.  The weight of material extractable  with  solvent
was then determined as well as the weight loss upon a low temperature
plasma ashing.  These weights are summarized in Table D-2.   The data show
that the amount removed by solvent extraction of the combustion zone
filters ranges from 1 to 37 percent  (13 percent average)  of  the total
lost by solvent extraction and plasma ashing combined.  Since  the
majority of the material removed by ashing is carbon in the  form of soot,
this result is not surprising.  However, there are certain data which
indicate that the solvent extraction process needs further study.

     •  Sample MA-II lost 66.3 percent of the original weight  from
        plasma ashing and yet the visible nature of the filter does not
        indicate carbonaceous soot (Figure 5-1).

     •  All of the hot zone filters from tests I, II, III,  and IV have
        consistently larger losses (relative to tests V,  VI, and VIII)
        from ashing although the filters showed little or no visible
        soot.  These losses may represent organic materials  that are
        not being recovered by the solvent extraction.  The  amount of
        material lost by plasma ashing, averaged for all  seven tests,
        represents 4 mg/m3 of sample gas.  This value would  be the maxi-
        mum amount of unextracted organics if more of the particulate were
        carbonaceous.
                                    Ill

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                            Table D-2,  Filter Heights Through Analyses (mg)
Sample
Run I
Stack
Combustion Zone
Run II
Stack
Combustion Zone
Run III
Stack
Combustion Zone
Run IV
Stack
Combustion Zone
Run V
Stack
Combustion Zone
Run VI
Stack
Combustion Zone
Run VII
Stack
Combustion Zone
Tare Weight
Before Test
605.6
617.1
609.9
606.6
647.2
656.8
652.8
653.6
643.8
655.7
658.8
658.7
658.2
655.6
Weight
After Test
627.9
653.1
641.6
709.7
668.0
697.0
679.4
690.1
681.9
684.0
752.7
700.4
797.6
711.9
Gain Due to
Parti cul ate
21.4
35.1
30.8
102.2
19.9
39.3
25.7
35.6
37.2
27.4
93.0
40.8
138.5
55.4
Loss on
Solvent
Extraction
0.8
0.6
0.6
4.1
1.5
1.6
1.4
Loss on
Plasma
Ashing
2.1
19.3
13.7
67.2
5.7
18.4
5.8
6.9
0.6
9.9
-2.8a
6.4
1.2
11.2
Remaining
Weight
on Filters
19.3
15.0
17.1
34.4
14.2
20.3
19.9
24.6
36.6
16.0
95. 8a
32.8
137.3
42.8
% Loss
9.8
57.3
44.5
66.3
28.6
48.4
22.6
30.9
1.6
30.7
-3.0a
19.6
0.9
22.7
a - Weight Gain

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D-8.  Measurement of Particulate Loadings  In the  Combustion  Zone vs Stack

     Comparison of the measured participate  loadings,  shown  in  Table D-3,
between the combustion zone and stack values, also yields  valuable in-
formation on the performance of the  process  and the ability  of  the
sampling and analytical techniques to accurately  measure that performance.
               Table D-3.   Particulate Mass Loadings
Run No.
I
II
III
IV
V
VI
VII
Combustion Zone
mg/m
7.3
20.9
8.7
7.5
7.4
8.4
13.9
grains/std. ft3
0.0032
0.0091
0. 0038
0.0033
0.0032
0.0037
0.0060
Stack
mg/m
21.2
20.9
25.0
20.4
36.2
43.8
113.5
grains/std. ft3
0.0092
0.0091
0.0109
0.0089
0.0158
0.0192
0.0494
     The fact that the concentration of particulate measured  in  the stack
(downstream of a participate scrubber)  is higher than  the  level  measured
in the combustion zone is considered to be the result  of a combination of
four factors.

     1.  The stack was sampled superisokinetically. Rates at the
         stack ranged from 125 to 200 percent of isokinetic.   At
         the hot zone, the rates were approximately 30 to  50
         percent of isokinetic even though the hot  zone train was
         operated at its maximum flow rate since it was not pos-
         sible to put a nozzle on the hot zone probe.   Superiso-
         kinetic sampling results in a  bias toward  a higher than
         actual small particulate/large particulate ratio.
         Sampling at lower than the isokinetic rate yields a
         bias in the opposite direction.

     2.  There was no nozzle on the hot zone probe.  The use  of
         a nozzle at Marquardt was ruled  out as being  impossible
         to protect and/or cool in the  hot, corrosive  combustion
         zone.  It does appear possible,  however, that the absence
         of a nozzle could also have resulted in substantially
         reduced collection of the large  particulates  at the
         combustion zone.
                                   113

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     3.   The combustion zone probe rinsings were not  evaporated
         to dryness and weighed as were the stack probe rinses.
         The hot zone probe rinses were not evaporated  because
         of the likelihood of losing or altering any  organics
         which might be present.  The significance of this
         factor can be estimated from the fact that the probe
         rinse weights from the stack were on the average equal
         to 30 percent of the filter particulate weight.

     4.   Salts generated by the HC1 1n the C-5,6 runs from  the
         caustic in the scrubbing process were entrained in the
         scrubber mists and were carried to the stack filter,
         where they evaporated leaving a solid residue  which was
         weighed as part of the particulate.  A more  efficient
         demister would likely reduce the salt emissions.


D-9.  Inorganic Survey Analyses by  ICPOES

     To determine  the inorganic composition  of the particulate from the
combustion and stack gases,  selected  filter  acid digests and impinger
solutions were first surveyed  for 32  elements by ICPOES.  These results
are shown in Table D-4.1   Normally the ICPOES method  is,  in itself, highly
accurate.  However, solutions  with  high  solids contents  such as the
samples from caustic impingers and  acid  digested filters, create Inter-
ferences in the method which reduce its  accuracy.  Thus  the ICPOES data
does not agree with the MS  analyses  as  well as would  generally be
expected.

     In addition to the elements  shown in  Table D-4, the following ele-
ments are determined by ICPOES but  were  not  detected in the submitted
samples:  Au, As,  Be, Eu, Pb,  P,  Se,  Te, W,  and U.


D-10.  Wet Chemical Analyses for HC1.  CU. and C0g

     The caustic impinger solutions were analyzed for chloride, free
chlorine, and carbonate to determine  the amounts of  each which were
scrubbed from the  combustion gases  of the  C-5, 6 tests.  The results are
listed in Table D-5.  The large, 2-liter impinger (described in Section
4.3.2) was analyzed separately from the  standard Greenburg-Smith Impingers
to determine the relative scrubbing efficiencies for each specie.  No
free chlorine was  found in the Impingers from test V,  thus a less than
value representing the detection  limit of  the technique  is reported.
                                   114

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           Table D-4.  Elemental Survey of Selected Samples  (mg/m3)

ELEMENT
Ag
Al
Ba
Ca
Cd
Co
Cr
Cu
Fe
K
Kg
Mn
Mo
Na
N1
Si
Sr
T1
V
Zn
RUN I
COMBUSTION ZONE
IMPINGERS
ND
0.006
ND
0.025
ND
ND
ND
0.018
0.007
1.6
0.006
ND
ND
ND
ND
1.4
ND
ND
ND
0.004
FILTER
NGTB
<0.001
NGTB
<0.004
NGTB
<0.004
NGTB
<0.032
<0.001
ND
<0.001
<0.001
0.001
ND
NGTB
< 0.009
<0.001
ND
NGTB
<0.22
NGTB
<0.002
...
NGTB
<0.001
<0.001
ND
NGTB
<0.002

STACK
FILTER
NGTB
<0.001
NGTB
<0.11
NGTB
<0.14
NGTB
<0.53
<0.002
ND
0.001
< 0.001
0.002
ND
NGTB
<0.14
< 0.001
ND
NGTB
<1.7
NGTB
<0.002
...
NGTB
<0.007
<0.001
ND
NGTB
< 0.079
RUN IV
COMBUSTION ZONE
IMPINGERS
ND
0.052
ND
0.024
ND
ND
ND
0.019
0.039
1.5
0.008
ND
ND
ND
ND
1.6
0.0003
0.004
0.0004
0.009
FILTER
NGTB
<0.001
NGTB
<0.005
NGTB
<0.001
NtfB
<0.028
<0.001
ND
0.001
0.001
0.021
ND
NGTB
<0.007
0.001
ND
NGTB
<0.34
O.,002
—
NGTB
<0.001
ND
ND
NGTB
< 0.003
STACK
FILTER
NGTB
<0.001
NGTB
<0.030
NGTB
<0.035
NGfB
<0.33
0.002
ND
0.001
0.001
0.011
ND
NGTB
< 0.085
0.001
ND
NGTB
<1.5
NGTB
< 0.007
...
NGTB
<0.002
NO
ND
NGTB
< 0.020
RUN VI
COMBUSTION ZONE
IMPINGERS
0.010
ND
ND
0.056
0.0004
0.028
0.009
0.099
0.016
a
0.009
ND
0.076
a
0.002
1.2
0.017
ND
0.002
0.020
FILTER
NGTB
<0.001
NGTB
<0.009
NGTB
<0.001
NGTB
<0.048
<0.001
0.001
0.019
0.003
0.38
ND
NGTB
<0.013
0.022
ND
NGTB
<0.42
0.055
...
NGTB
<0.001
<0.001
NO
NGTB
0.005
STACK
FILTER
NGTB
<0.001
NGTB
<0.094
NGTB
<0.11
NGtB
<0.23
0.001
ND
0.008
0.003 ;
0.24
ND
NGTB
« 0.071
0.022
ND
6.2
1
0.056 •
...
NGTB
'0.004
-0.001
ND
NGTB
0.15
N6TB -  Not greater than backoround

a - The caustic implnger solution had very
   high backgrounds of Na and K
                                      ND -  Not detected

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                                     Table D-5.   Caustic  Impinger Analyses
Sample
Run V
Large Impinger
G.-S? Impingers
Total
Run VI
Large Impinger
G.-S. Impingers
Total
Run VIII
Large Impinger
G.-S. Impingers
Total
Chloride
g Cl

66.900
3.175
70.075
130.075
3.120
133.195
151.800
4.350
156.150
liters HC1

47.74
90.76
106.41
Chlorine
mg Cl

<0.5
<0.5
<1
18.5
203.4
221.9
471.0
322.5
793.5
HterSCl2

<0.003
<0.076
0.269
Carbonate
g C02


6.635
7.680
14.315
22.950
6.989
29.939
liters C02


7.82
16.31
•e
Q
I
* Greenburg - Smith

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