United States
      Environmental Protection
      Agency
Office of Solid Waste and
Emergency Response
Washington, DC 20460
Center for Environmental
Research Information
Cincinnati, OH 45268
       Technology Transfer
June 1989
EPA/625/6-89/021
EPA  Handbook
       Hazardous Waste
       Incineration
       Measurement Guidance
       Manual

       Volume  III of the
       Hazardous Waste
       Incineration Guidance
       Series

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                                        ERA/625/6-89/021
                                          June 1989
          Handbook


      Hazardous Waste
Incineration Measurement
      Guidance Manual

Volume 111 of the Hazardous Waste
   Incineration Guidance Series
  Office of Solid Waste and Emergency Response
     US. Environmental Protection Agency
         Washington, DC 20460
 Air and Energy Engineering Research Laboratory
      Research Triangle Park, NC 27711
               and
  Center for Environmental Research Information
     Office of Research and Development
     US. Environmental Protection Agency
          Cincinnati, OH 45268
                                Printed on Recycled Paper

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                                               Notice
This document has been reviewed in accordance with the U.S. Environmental Protection Agency's peer and administra-
tive review policies and approved for publication. Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.

The guidance document is intended to provide information on how regulatory requirements in 40 CFR Subpart O may
be satisfied in a wide variety of situations. This guidance document is not, in and of itself, a regulatory requirement and
should not be regarded as such. Therefore, although compliance with regulatory requirements is mandatory, compli-
ance with this guidance manual (although useful as a means of satisfying regulatory obligations) is not.

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                                              Abstract
This document provides general guidance to permit writers in reviewing the measurement aspects of incineration
permit applications and trial burn plans. It is oriented to how measurements are made, not what measurements to make.
The guidance deals specifically with commonly required measurement parameters and measurement methods for
process monitoring,  sampling and analysis aspects of trial burns and subsequent operation of the incinerator, and
quality assurance/quality control (QA/QC) associated with these activities. As a guidance tool, this document intro-
duces the major  elements of incineration measurements  via sample checklists, general discussion, and technical
references.                                                                  -

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                                     Acknowledgements
This guidance document was prepared for the U.S. Environmental Protection Agency's Office of Solid Waste (OSW) and
the Office of Research and Development (ORD) under the direction of Sonya M. Stelmack and Robin M. Anderson of
OSWfe Permits and State Programs Division and Larry D. Johnson of ORD's Air and Energy Engineering Research
Laboratory (now with Atmospheric Research and Exposure Assessment Laboratory). The document was prepared by
Midwest Research Institute (MRI) under subcontract to AT. Kearny,  Inc.  The principal investigator was Andrew
Trenholm. Major MRI contributors included Gary Kelso, Mitchell Erickson, Scott Klamm, and Dennis Hooten. Additional
contributions and technical review were provided by Clarence Haile, John Coates, Roy Neulicht, Gary Hinshaw, Paul
Gorman, and Bruce Boomer. Drafts of the document were reviewed by the U.S. EPA Incinerator Permit Writers Work
Group.
                                                 iv

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                                             Contents
                                                                                                Page

Abstract	 Hi

Acknowledgements  :........			. . . . iv

Contents			v

Tables			vi

Figures	 vii

1. Introduction .....	1

2. Specific Recommendations for Permit Reviewers	3
       2.1 Trial burn runs	 3
       2.2 Trial burn schedule			3
       2.3 Monitoring ,	3
       2.4 Sampling and analysis	3
       2.5 Reporting of results	 .	6
       2.6 Continuing analysis and monitoring	8

3. Measurement Methods	,	..9
       3.1 Specification of method options			.9
       3.2 Process monitoring	 9
       3.3 Sample collection	 11
       3.4 Chemical analysis	15

4. Quality Assurance/Quality Control			25
       4.1 Data quality objectives	.-..	25
       4.2 General discussion of QA project plan	25
       4.3 Guidance for precision  and accuracy objectives		...>...	29

5. References	 31

Appendices
  A. Analysis methods for Appendix VIII hazardous constituents given in EPA-600/8-84-002 and SW-846	33
  B. Measurement checklists	41

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                                              Tables
Number                                                                                       Page
 1  Example of a trial burn schedule	3
 2  Example calculation to determine whether VOST sample size is sufficient to measure 99.99% ORE for
       carbon tetrachloride	•	6
 3  Example reporting of volatile POHC emissions	•	7
 4  Sampling methods for stack gases in RCRA trial burns	13
 5  EPA reference methods used to test RCRA hazardous waste incinerators	13
 6  VOST audit compounds	 14
 7  Selected problem POHCs	 17
 8  Sample preparation methods given in EPA-600/8-84-002	18
 9  Sample preparation and introduction techniques given in SW-846	 18
10  Analytical methods for characteristics of RCRA hazardous waste feed samples	 19
11  Analytical methods for principal organic hazardous constituents (POHCs) given in EPA-600/8-84-002	19
12  Analytical methods for principal organic hazardous constituents (POHCs) given in SW-846	 .*.	20
13  Analytical methods for inorganics	•	21
14  Analytical methods for stack gas samples	22
15  Essential elements of a QA project plan	25
16  Summary of precision and accuracy objectives	 • •'•••'• • • -29
                                                 VI

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                                        Figures
Number
1  Example daily schedule.
 Page
	4
                                           VII

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                                              Section 1
                                            Introduction
 Subtitle C of the Resource Conservation and Recovery
 Act (RCRA) requires the US. Environmental Protection
 Agency (EPA) to develop, promulgate,  and implement
 regulations which control the generation, transportation,
 treatment, storage,  and disposal  (TSD) of hazardous
 wastes. An integral  part of these activities is reviewing
 and issuing permits to hazardous waste incineration
 facilities.

 Several documents have been or are being prepared as
 a  Hazardous Waste Incineration Guidance Series pre-
 pared by EPA to assist both the applicant and the permit
 writer in the RCRA Part B process leading to a final
 operating permit for hazardous waste incinerators. This
 document on measurement guidance is Volume III of this
 series. Below is a list of additional guidance manuals in
 the series:

 Volume I Guidance Manual of Hazardous Waste Inciner-
         ator Permits, Mitre Corporation, SW-966, NTIS
         PB84-100577, July 1983 (document scheduled
         for revision). This describes  the overall
         incinera tor permitting process, highlights the
         specific guidance pro vided by other manuals,
         and addresses permitting issues not covered
         in the other manuals such as treatment of data
         in lieu of a trial burn. Thus it can be viewed as
         a road map and a good summary of all permit-
         ting issues.

Volume II Guidance on Setting Permit Conditions and
         Reporting Trial Burn Results, Acurex, EPA-625/
         6-89-019,  1989. Includes guidance on select-
         ing key operating parameters,  translating trial
         burn  data into permit operating conditions,
         and reporting trial burn results. Also discusses
         planning a trial burn to achieve workable per-
         mit limits.

Volume IV Guidance on Metals and Hydrogen Chloride for
         Hazardous Waste Incinerators, Versar, 1989
         (draft under EPA  review). Specific guidance
         on limiting metals emissions from incinerators
         is  provided. In particular, a risk assessment
         approach  to setting limits on metal compo-
         nents in the waste is employed. Guidance
         is  also provided on  doing risk-based checks
         on  HCI emissions. (Note: Earlier title  was
          Guidance for Permit Writers for Limiting Metal
          and HCI Emissions from Hazardous Waste
          Incinerators.)

 Volume V Guidance on PIC Controls for Hazardous Waste
          Incineration, Midwest Research Institute, 1989
          (draft under EPA review). Details the specific
          permit  requirements for CO and total hydro-
          carbon (THC) emissions from hazardous
          waste incinerators in the RCRA system.  Emis-
          sion limits for CO and THC and the rationale
          for their selection are discussed. (Note: Earlier
          title was: Guidance on Carbon Monoxide Con-
          trols for Hazardous Waste Incineration.)

 Volume VI Proposed Methods for Measurement of CO, O2,
          THC, HCI,  and Metals at Hazardous Waste
          Incinerators, 1989 (draft under EPA  review).
          Presents a draft mea surement method for the
          above  parameters including performance
          specifications for continuous CO monitors.

 In addition,  a  document has  been prepared to assist
 regulatory personnel  in observing trial burns: Trial Bum
 Observation Guide EPA-530/SW-89-027 March 1989,
 Midwest Research Institute, September 1988. Includes
 general guidance  on  preparation, on-site activities, and
 reporting aspects of observing a trial burn test.

 The Hazardous Waste Incineration Measurement Guid-
 ance Manual provides general guidance to permit writers
 in reviewing the measurement aspects of  incineration
 permit applications and trial burn plans. It is oriented to
 how measurements are made, not what measurements
 to make. The guidance deals specifically with commonly
 required measurement parameters and measurement
 methods for process monitoring, sampling and analysis
 aspects of trial burns and subsequent operation of the
 incinerator,  and quality assurance/quality control  (QA/
 QC) associated with these activities.

 As a guidance tool, this document introduces the major
 elements of incineration measurements via general dis-
 cussion and technical references.  It  is not  intended to
specify a complete list of measurements that should be
 required  in every  case,  nor does it provide  complete
descriptions of all pertinent methods.  The references
cited provide additional  descriptions of measurement

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methods, and at times, measurement experts may need
to be consulted for judgments in unusual situations. Test-
ing, operating, and permitting hazardous waste incinera-
tors typically involves best engineering and scientific
judgment on a case-by-case basis. No single publication
can answer all of the possible technical and regulatory
questions related to incineration measurements.

The following sections of the report cover recommenda-
tions to permit reviewers, methods, and QA/QC. Sec-
tion 2 provides some specific recommendations to permit
reviewers on various aspects of the trial burn plan and
permit application. Section 3 gives  commonly  used
methods for measuring the monitoring, sampling, and
analysis parameters. Section 4 discusses the QA/QC
procedures which should be addressed for the measure-
ment methods in the quality assurance plan. Section 5
gives  the  references  used in the report. Appendix A
reproduces guidance for analyses methods given in EPA-
600/8-84-002 and in SW-846. Appendix B provides
checklists to be used by permit writers to help assess the
completeness of measurement information in trial burn
plans and incinerator permit applications. The checklists
include process monitoring parameters,  sampling
parameters, analysis of samples, and QA/QC for the pro-
cess monitoring and sampling and analysis parameters.

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                                              Section 2
                    Specific Recommendations for Permit Reviewers
 Many aspects of RCRA incinerator trial burns are not
 specifically addressed in the regulations (40 CFR Parts
 264 and 270). This can result in different judgments or
 decisions made by RCRA permit  reviewers as  they
 review permit applications. Case-by-case judgments are
 appropriate at times; however, a more uniform decision-
 making process among reviewers is needed. This sec-
 tion provides  specific recommendations  for some
 aspects of the trial burn and the reporting of the results to
 promote this uniformity.

 2.1 Trial Burn Runs
 Three replicate runs are recommended for each specific
 set of incinerator operating conditions. Sufficient waste
 feed must be stockpiled or readily available in order that
 the same waste characteristics are used for replicate
 runs. All three  replicate runs should comply with  the
 RCRA  requirements for destruction and removal effi-
 ciency (ORE), particulate emissions, and hydrogen chlo-
 ride (HCI) emissions. This provides added  assurance
 that the incinerator can repeatedly meet the standards. If
 the incinerator fails only some of the standards (e.g., only
 particulate), measurement of only those standards that
 failed can be considered for a retest, provided that the
 key operating conditions remain the same and that any
 modification to the incinerator would not negatively affect
 the unit's ability to comply with  the  other performance
 standards.

 2.2 Trial Burn Schedule
 • Generally, one run per day should be scheduled. This
  can vary depending upon the complexity of the spe-
  cific trial burn.

 • A trial burn schedule indicating the overall test sched-
  ule and an anticipated  daily schedule, similar to the
  examples shown in Table 1 and Figure 1, should be
  included in the trial burn plan. The daily schedule in
  Figure 1  assumes 2 h of actual sample time for the
  semivolatile organic sampling train (semi-VOST) and
  three volatile organic sampling train (VOST) trap pairs
  at a 40-min sampling time per pair, as an example.
2.3 Monitoring
• The regulations call for continuous monitoring of com-
  bustion temperature, waste feed rate, the indication of
  combustion gas velocity, and CO in the stack gas [40
   CFR 264-347(a)(1)]. Monitoring of key process param-
   eters should be as continuous as feasible. A recom-
   mended  minimum  requirement for  selected key
   parameters is reading a measurement value at least
   every 15 s and recording a value at least every minute.
   Strip charts and/or data loggers can be used to record
   data. If these minimum requirements cannot be met,
   then justification for why less frequent measurement/
   recording times are acceptable should be provided by
   the  applicant. Continuous monitoring with alarms or
   automatic shutdown at specified set points, without
   permanent  data recording,  may be appropriate  for
   some parameters.  Volume VI of the Guidance Series
   (referenced in Section 1) contains draft performance
   specifications for CO monitors.
Table 1.  Example of a Trial Burn Schedule
Prior to     • Incinerator shakedown/site modifications
test       • "Miniburns"
          • Monitors) calibration/evaluation
          • Preparation of special wastes
          • Pretest meeting(s)
Day 1        Arrive on-site                  :
            Set-up
            Sample solid wastes .
Day 2        Complete set-up
            Sample solid wastes
            Preliminary measurements
Day 3        Run 1
Day 4        Run 2, audits
Day 5        Run 3
Day 6        Pack equipment/leave site
Day 4-8       Samples arrive at lab
Day 35-50     Sample analysis complete
Day 35-60     Preliminary results reported
Day 95       Test report submitted


2.4 Sampling and Analysis

• Waste feed samples should be collected every 15 min
  over the entire period of stack sampling and then  be
  composited into one sample per test run for  each
  waste feed. The applicant may justify less frequent
  sampling if data are provided  to  show that the

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Figure 1. Example dally schedule.
                                                 Daily Schedule
Activity
Incinerator Operation
at Test Conditions
Daily Test Equipment
Preparations
Start Test
Method 5, Sample
Semi VOST Sample
Method 3 ORSAT Sample
VOST S/
Waste Feed Samples ^/
(Each Waste Stream)
Solid Waste Samples"/
Scrubber Water Samples
Ash Residue
Auxiliary Fuel
End Test
Lunch
Recover Samples/ORSAT Analysis
Traeeability/Sample Storage
Contingency
Time (hr)
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     J2/Traverse 1      -£/Three Trap Pairs
     jy Traverse 2      A/Grab Samples,  Composite
                        and Individual  VOA Vials (If necessary)
 -S/May be necessary to Sample
    Previous Day
   homogeneity and composition of the waste feed do
   not vary.

   Each  drum burned during the trial burn should be
   sampled, unless the applicant can  justify why this is
   not necessary. Grab samples should be composited
   for each waste type.

   All other process samples (e.g., scrubber water,  ash,
   etc.) should be taken every 30  min over the entire
stack sampling period, and then be composited into
one of each sample type per test run. In some cases it
may not be feasible to comply with this recommenda-1
tion for ash sampling.
Sampling should not begin until the incinerator opera-1
tion has reached steady-state on waste feed. A mini-
mum of 30  min of  operation  feeding waste is
recommended, or for a rotary kiln, the greater of 301
min or the solids residence time.

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 •  Sampling should continue through incinerator operat-
   ing abnormalities unless the waste feed cutoff system
   shuts the incinerator down. If sampling is stopped
   during a trial burn, the test may be completed using
   the same sampling trains if the burn is completed on
   the same day it was started.

 •  Minimum stack sampling time for each run (actual
   sampling time not including time for port changes,
   changing VOSTtrap pairs, etc.) should be 1 h for EPA
   Method 5 (M5), semi-VOST, and VOST. Data from less
   than  1 h of sample collection would be an invalid test
   run.  Two hours ,of stack sampling time is recom-
   mended as optimal. In some cases more than 2 h of
   sampling may be required,  eg., to achieve required
   detection limits. A minimum of three VOST trap pairs
   per run is also recommended. A .fourth pair is often
   taken in case one pair is broken or lost due to analysis
   problems.

 •  All sampling required for a test run in  the trial burn
   should, whenever possible, be  conducted concur-
   rently, with only the normal minor differences associ-
   ated with different sampling methods (e.g., MM5 and
   VOST schedules in Figure 1). However, differences in
   sampling period start and finish due to sampling prob-
   lems  are allowable. Examples are a particulate train
   that fails a leak check at port change and sampling
   must  be restarted with a new train, a VOST trap that
   breaks  at the end of the sampling period so that
   another  pair  must be run, or sequential  sampling
   required due to limitations in available sampling ports.
   However, all waste feed sampling must be continued
   for the entire period, and possibly any water effluent or
   ash sampling. Also, the incinerator must continue at
   the same process operating conditions with collection
   of the operating data for the entire period.
 •  Separate semi-VOST (SW-846 Method  0010), com-
   monly called Modified Method 5 (MM5), and Method 5
   (M5) should be used  for semivolatile and nonvolatile
   POHCs and particulates, respectively. This is neces-
   sary since drying the  particulates collected and probe
   rinse  prior to weighing may result in loss of semivo-
   latile POHCs.
 •  Semi-VOST sampling trains with XAD resin traps
   should not be used to  collect samples for HCI analysis.
   XAD resins may be contaminated with chlorides prior
   to sampling or HCI may be retained in the XAD during
   sampling.
 •  Condensate collected in impingers after the XAD resin
   module in a semi-VOST sampling train should always
   be considered part of a semivolatile POHC sample.
   The condensate should be extracted and the extract
   combined with the extracts from other portions of the
   sampling train.
• The final leak check  for VOST should be run at the
   highest vacuum used during the sampling run but not
   less than 1 in of mercury vacuum.
• A sampling train which develops problems during a
  trial burn may be validated on a case-by-case basis if it
   can be shown that the results were not significantly
   biased. For example, if an M5 train passed the leak
   check after sampling in the first port but failed the
   confirming leak check before beginning sampling in
   the second port due to a probe liner being broken
   during port change, the test could be allowed to con-
   tinue after replacement of the probe liner and including
   rinsing  of  the broken liner for particulate  recovery.
   However, if the train failed the leak check after removal
   from the first port, the sample would be invalid, even if
   it were believed that the probe liner was broken as the
   probe was  removed from the port (i.e., it is not possible
   to know if  the probe liner was already broken before
   removal from the port).

•  POHCs which have a boiling point between  100° and
   140°C may break through the XAD-2 resin in a semi-
   VOST if the sampling time is too long or may be diffi-
   cult to purge from a VOST trap. The  validity of the
   method chosen  for these POHCs  should be deter-
   mined prior to testing (see Section 3.4.5.4). Experts in
   analytical  chemistry  may need to be consulted to
   determine the appropriate sampling method for these
   POHCs.

•  Volatile  POHCs should be sampled with the VOST
   (SW-846 Method 0030),  if possible. Samples may be
   collected in bags if VOST samples cannot be per-
   formed. The bag sample procedure is  less desirable
   due to potential problems with adsorption in the bag
   and loss of sample. Stability of the POHC to be sam-
   pled in the  bag should be checked prior to sampling, if
   this method is used.  Field blanks are  essential with
   bag sampling.
•  VOST field  blanks are required, and VOST trip blanks
   and laboratory blanks are highly recommended.
•  It is recommended that both the front (Tenax) and back
   (Tenax/charcoal) trap of all pairs of traps from each run
   be analyzed separately. The results of these separate
   analyses allow determination of the percent distribu-
   tion of the  volatile POHCs collected on the front and
   back traps. The samples are considered valid (no
   breakthrough) if the back trap contains no more than
   30% of the quantity collected on the front trap. This
   criteria does not apply when the quantity of sample
   collected is low (i.e., less than 75 ng on the back trap).
   Some latitude in judging the validity of a sample versus
   this criteria can be considered based on how closely
   the DRE standard was met and how closely the trap
   distribution criteria was met. For example, if the DRE
   was 99.999% and the distribution was slightly higher
   than 30% on the back trap, one could still have confi-
   dence a 99.99% DRE was achieved.  Use of three
   traps in series (Tenax-Tenax-Tenax/charcoal) can be
   considered to  provide further indication  of sample
   validity,  however, use of thi§; approach should be
   reviewed by an expert experieheeclin VOST sampling
   and analysis.

• The VOST protocol allows multiple pairs of traps from
   the same run to be combined for analysis, if increased
   analytical sensitivity is required. In  rare cases where

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  this increased sensitivity  is needed,  a reasonable
  approach is to combine all front traps from a test run
  for one analysis and all back traps for a second analy-
  sis. This procedure retains information on distribution
  of POHCs between the front and  back traps while
  allowing the  greater sensitivity.  The  same criteria
  described above is used to judge the  validity of the
  samples.
• The trial burn plan should show that a sufficient quan-
  tity of POHCs is in the waste feed  to demonstrate a
  destruction and removal efficiency (ORE) of 99.99%,
  given the VOST or semi-VOST sample size and lower
  detection limits of the analytical instrumentation. An
  example calculation  based on VOST sampling  is
  shown in Table  2. Generally, a concentration  of 100
  ppm in the waste is considered a minimum detectable
  level for POHCs.
• Traceability procedures must be used for handling all
  samples. Full chain-of-custody procedures  are typi-
  cally much more labor-intensive but may be used at the
  applicants option.
2.5 Reporting of Results
The results should be reported in a format which includes
all  information  and  data necessary  to calculate final
results,  presented in as clear and  succinct format as
possible. This will include a description of the operating
system;  the operating conditions during the  test; the
measured quantities of POHCs, HCI,  and paniculate in
all samples; and the calculated results. Example formats
for presentation of these data are presented in the Guid-
ance  on Setting Permit Conditions and Reporting Trial
Bum Results.

The results of the analyses for particulate emissions, HCI
emissions  and  removal efficiency, and ORE should be
reported separately for each run and should not be aver-
aged for the trial runs. This does not preclude averaging
multiple samples taken during each run.

• VOST analytical results should be reported as individ-
  ual values for each trap as well as an average value for
  each run (as total  ng/L of sample).  The average
  amounts to dividing the total quantity (ng) on all traps
  by the total sample volume (L) for all traps. An illustra-
  tive example is provided in Table 3. In this example, in
  run 3, a sample was lost, but the total sampling period
  was still > 60 min, so the results are usable. Ordinar-
  ily,  120-min sampling is  the goal. Note that samples
  were collected with four pairs of VOST traps so that the
  minimum recommendation of three pairs of traps per
  run is still met when data for one pair are lost in run 3.
• The permit reviewer should consult the Guidance on
  Setting Permit Conditions and Reporting Trial Burn
  Results for further guidance on how results should be
  reported and the Practical Guide —  Trial Burn for Haz-
  ardous Waste Incinerators1 and other  references on
  how sampling and analytical data should be converted
  into final results. A portion of the Practical Guide is
  repeated below to provide practical suggestions
  regarding blank correction, significant figures, round-
  ing,  and handling "less than"  and "greater  than"
  values.
Table 2.  Example Calculation to Determine Whether VOST
        Sample Size Is Sufficient to Measure 99.99% ORE for
        Carbon Tetrachloride

Basis   •

Waste feed flow rate: 15.2 kg/min (2,000 Ib/h)
POHC: Carbon tetrachloride
Waste feed concentration: 500 ppm (0.50 g/kg feed)
Stack gas flow rate: 4,500 scfm (127.4 rrf'/min)
Lower detection limit: 2 ng per trap

Proposed sampling

VOST: 3 trap pairs at 500 mL/rriin flow rate; 20 L sample/pair

1. POHC input rate
  15.2 kg/min x 0.50 g/kg = 7.6 g/min    .

2. POHC stack output rate at 99.99% ORE
  7.6 g/min (1 — 0.9999) = 0.00076 g/min

3. POHC concentration in stack gas at 99.99% ORE
  0.00076 g/min _ o.0000060g/m3x109ng/gx lO^mVL = 6.0 ng/L
  127.4 mVmin                  !
4. Sample amount collected on one pair of traps
  20 Lx 6.0 ng/L = 120 ng

Since the VOST lower detection limit for carbon tetrachloride is 2 ng,
the sample is sufficient to detect carbon tetrachloride to determine a
ORE of 99.99% or lower. A margin of safety above the detection limit
is desirable.                    :,  •  - .

This calculation assumes both traps in a pair are combined for
analysis. If they are analyzed separately, the distribution of mass on
each trap must be considered.
2.5.1  Blank Correction
Because achievement of 99.99% ORE often  results  in
stack concentrations  that are at or  below ambient or
laboratory levels for POHCs, contamination of samples
can be a significant problem. The purpose of blank cor-
rection procedures is to account for  any portion of the
sample results that represent contamination,  or some-
thing other than the value intended to  be measured (e.g.,
stack emissions).

The underlying philosophy of the procedure is based on a
paper prepared by the American Chemical Society Com-
mittee on Environmental Improvement2 and on experi-
ence in conducting and interpreting trial burn data. The
ACS paper assumes that blank values are random sam-
ples that vary because of preparation,  handling,  and
analysis activities. Under this assumption, blank values
can be treated statistically. The "best estimate" for the
blank for any particular sample is the mean of the avail-
able blanks. The ACS procedure also enables determina-
tion of whether a sample is "different from" the blank. If
the sample value is not significantly different from the
blank value,  a  sample cannot be  blank-corrected.
Even  so, the measured sample  value does provide an
upper bound for the emission value and may still provide
sufficient information for determining if the required ORE
of 99.99% was met.

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Table 3.  Example Reporting of Volatile POHC Emissions
Run no.
1

2

3

Trap pair
1
2
3
4
Total/average"
1
2
3
4
Total/average0 "
1
2?
3
4
Total/average"
Sample
period
(mln)
30
30
30
30
120
30
31
30
30
121
30
29
30
89
Sample
volume*
(L)
20.1
19.8
21.3
19.5
80.7
19.7
22.1
20.8
21.0
83.6
20.4
20.2
19.9
60.5
Average blank value1 (ng)
Standard deviation1 (ng)
POHC concentration0 Stack gas Emission rate*
POHC collected" (ng) (ng/L = ng/Nm») flow rate" (ug/mln)
CCI4
16
19
30 (24)
25 (19)
78
37(31)
21 (15)
28 (22)
31 (25)
93
14
8.6
12
35
5.8
6.9
CCI2CHCI CCI4
71 (60)
180 (170)
45 (34)
105 (94)
360 0.97
220 (210)
180(170)
270 (260)
210(200)
840 1.1
56 (45)
37 (26)
48 (37)
108 0.58
11
2.7
CCI,CHCI (NmVmln) CCI, CCI,CHCI

4.5 181 180 810

10.0 173 190 1700

1.8 190 110 340


Note: Slow VOST results are shown; a similar format would be used for fast VOST or integrated bag sampling for volatiles.
• Sample volume is dry standard liters of stack gas.
" If blank corrected, that value shown in parentheses.
c Blank corrected as applicable.

' Stack gas flow rate is dry normal (standard) cubic meters per minute.
•Totals for sample period, volume, and amount collected; averages for concentration, flow rate, and emission rate.

1 All blanks (both field blanks and trip blanks) were used for average and standard deviation.
8 Sample lost.
The blank correction procedure applies mainly to stack
emission samples and consists of the following:

a. Assemble data for each POHC from all of the field and
  trip blanks. An example of such data for VOST might
  be:
                        Run 1       Run 2      Run 3
  POHC A  Field blank    0.008 ug  < 0.002 ug    0.004 ug
          Trip blank     0.005 u,g   0.004 ng    0.003 pig

b. Determine whether or not the field blanks are statisti-
  cally differ ent from the trip blanks by using the paired
  t-test (consult a statistics text).

  If the field blanks are significantly higher than the trip
  blanks, use the field blank data only. If the blanks are
  not significantly different, use all of the blank values.
  Higher field blanks indi cate background due to field
  exposure, which trip blanks do not measure.

c. Calculate the average and standard deviation of the
  blanks (many calculators have statistics  functions
  which allow you to do this easily).

d. Determine whether or not each measured  sample
  value is "different from" the blank value by  using the
  following test for each sample:

  s = sample value (ug)
  b = (blank average)  + 3  (standard deviation  of
  blanks)
  If s is greater than b, then the sample is "different"
  from the blanks.

e. If the measured sample value is different from the
  blank value, then the blank correction procedure is
  applied:

  Blank-corrected emission value (ug) =
  measured sample value (ug) - average  blank value
f. If measured sample value is not different from blank
  value, then the measured sample value is used as an
  upper bound emission value, and the emission rate is
  considered less than or equal to the measured value.
  This results in the reporting of emission concentration
  and mass emission rate with a "< " sign. As a conse-
  quence, DRE would be reported with a " > " sign.

2.5.2 Significant Figures and DRE
DRE is  usually reported with one or two significant fig-
ures depending on the accuracy of the measured values
which go into the calculation of DRE. It is important to
note that a reported DRE of 99.99% or 99.999% has only
one significant figure. The reason for this is that what is
actually being measured is the penetration, which is the
amount of a compound which is not destroyed. That is:

-------
ORE = 100% — Penetration

For a ORE of 99.99%, the penetration is 0.01 % (one
significant figure). For a ORE of 99.9916%, the penetra-
tion is 0.0084% (two significant figures).

The ORE is reported with the same number of significant
figures as the least accurately measured value used in
the calculations. The controlling measurement that deter-
mines the number of significant figures is usually the
stack concentration. GC/MS methods can normally only
report concentrations with one or two significant figures.
This will result in a ORE with the same number of signifi-
cant figures as reported concentrations, unless another
measured value (waste feed concentration, waste feed
flow rate, or stack gas flow rate) has fewer significant
figures.

2.5.3 Rounding Off ORE Results
The rules on this are stated in the Guidance Manual for
Hazardous Waste Incineration Permits:3 "... if the ORE
was 99.988%, it could not be rounded off to 99.99%." In
other words, your calculated value, after rounding to the
proper number of significant figures,  must  equal or
exceed 99.99% to be acceptable. (Note: This same rule
applies to rounding HCI results to 99%.)

2.5.4 Reporting ORE with a " < " or" > " Sign
As mentioned in the section on blank corrections, if the
sample is not  "different" from the blank (greater than the
average blank plus  three standard  deviations),  then it
cannot be blank-corrected. As a consequence, the ORE
will be reported with, a ">" sign. This reported ">"
value will also occur when the POHC in the sample is
undetected (below  detection limit of the  analysis
method). But as long as the ORE is > 99.99%, this is not
a problem.

In cases where both the blanks and samples have high
values, a ORE below 99.99% may be preceded by a " > "
sign (i.e., > 99.96%). Such a number is useless in evalu-
ating achievement of 99.99%. Experience in using the
recommended sampling methods and avoiding contami-
nation is the only way to minimize this possibility.
Occasionally, a sample may saturate the GC/MS with the
POHC in question. This will result in an emission rate
with a ">" sign and a ORE with a "<" sign.  If such a
ORE is below 99.99%, the incinerator clearly fails. If it is
above 99.99% (i.e., <99.9964%), the number is use-
less. To avoid such problems, the test protocol should be
chosen based on estimated concentrations. Several fac-
tors to consider include (1) collecting less sample on the
VOST (2) using a sample splitter during analysis so that
only a portion of the sample is directed  to the GC/MS, or
(3) using alternative sampling methods (e.g., integrated
bag).  If these techniques are being  considered, the
Source Methods  Standardization Branch, AREAL, EPA
or OSW, EPA should be consulted.

The conclusion of this section is always design  the sam-
pling and analysis so that passage/failure of the 99.99%
criterion is determinable. This can best be done by pre-
liminary estimates of POHC concentrations in the stack
(assuming 99.99% ORE) and with selection of sampling
and analysis methods  having  appropriate  upper and
lower limits  of detection.  Experience  in use  of these
methods to avoid  contamination is also  a key factor.

2.6 Continuing Analysis and Monitoring
After the trial burn test is completed and after the permit
is obtained, analysis and monitoring must continue. Each
type of waste feed material must be analyzed at least on
an annual basis  according to  recent EPA policy. More
frequent analysis is necessary if composition  of the
waste feed is highly variable or is expected to change
(e.g., different source, process change, etc.).

The permit will establish the monitoring requirements for
process parameters, air pollution control devices, and
stack gas emissions. The exact parameters to  be moni-
tored  are  established  on a case-by-case basis, as
described  in the Guidance on Setting Permit Conditions
and Reporting Trial Burn Results. The permit monitoring
requirements and continuing waste feed analyses are
intended to verify continued satisfactory operation of the
incinerator.

-------
                                              Sections
                                      Measurement Methods
 Many methods can be used for process monitoring, sam-
 pling, and analysis of samples during a trial burn and
 subsequent operation of the incinerator. This review
 focuses on the most commonly used and recommended
 methods for measurement.

 3.1 Specification of Method Options
 The trial burn plan must present the sampling and analyt-
 ical methods in sufficient detail for both review and field
 and laboratory implementation.  Many of the referenced
 methods give several options which may be employed by
 the sampler or analyst. The trial burn plan should specify
 which options will  be  used.  If selection of an option
 depends on the sampling conditions or sample charac-
 teristics and cannot be made at the time the plan  is
 submitted, the decision criteria for subsequent selection
 of  the  options must be  presented. Some  referenced
 methods,  especially those presented in the Arthur D.
 Little report, Sampling and Analysis Methods for Hazard-
 ous Waste Combustion,4 are general  descriptions of the
 methods and may not provide sufficient detail to specify
 the methods. In such cases, the trial burn plan should
 give a detailed step-by-step procedure. Often the sam-
 pling crew and analytical laboratory will have sets of
 standard operating procedures (SOPs) for the common
 analyses encountered in hazardous waste incineration.
 These SOPs can be appended to the trial burn plan and
 cited in the text.

 For many trial burns, sampling and analysis of different
 analytes will be performed by more than one laboratory.
 Few laboratories have the capabilities to do all of the
 analyses required. In these cases the applicant should
 specifically identify the laboratory who will be doing the
 work for each method  and should specify the methods
 employed in the same level of detail for all laboratories.
 The trial burn plan  may  include this information  or  it
 should specify a time, sufficiently before the trial burn to
 allow EPA review, that it will be provided. The laboratory
 that conducts the sampling and analysis  may not have
 been selected when the trial burn plan is submitted.

 3.2 Process Monitoring
Two important parameters which must be continuously
 monitored during operation of the incinerator are the
 waste feed  rate and the combustion temperature.
 Another important parameter is the combustion chamber
 pressure, which is often used as a method of monitoring
 fugitive emissions. Methods used to measure these three
 parameters are discussed below. CO monitoring will be
 covered in Volume VI of the Guidance Series (see Sec-
 tion 1.0) being prepared by EPA. Other parameters, e.g.,
 combustion gas velocity, are not covered at this time. The
 EPA, Office of Solid Waste, may be  consulted for addi-
 tional guidance.

 3.2.1 Waste Feed Rate

 The waste feed rate to an incinerator can be monitored in
 a variety of ways, depending upon the types of feeds
 encountered. The feeds may be solids or sludges, free-
 flowing liquids, or gases.

 3.2.1.1 Solid-Sludge Feeds
 Volumetric  methods — These include calibrated
 augers and pumps, rotary feeders, and belt conveyors.
 These systems are not generally available precalibrated
 but must be calibrated by the user for each  particular
 feed material. The accuracy of the method depends upon
 steady operation at a given speed and assumes appro-
 priate feeders are used to ensure the cavities are always
 filled to capacity. Most of these  methods can provide
 some kind of tachometer signal to indicate speed, which
 must be related to feed  rate by performing calibration
 tests. These methods are generally more appropriate as
 secondary indicators of feed rate.

 Level indicators — These include methods based upon
 mechanical, ultrasonic, nuclear,  and radio  frequency
 principles of operation. Nearly all tank level indicators will
 perform better with somewhat uniform (free-flowing) par-
 ticles. This will  aid in distributing the level of material
 evenly within the vessel, allowing for more accuracy in
 whatever monitoring  system  is  used. Typically, these
 methods can monitor tank levels to within ± 1 %.

 Since level indicators cannot provide physical character-
 istics for the feed material (i.e., density,  moisture), care
 must be taken  when using any  of these systems  to
account for cross-sectional area of the tank and changes
in composition of the feed.

-------
 Stationary weight indicators—These methods, which
 include weigh hoppers/bins and platform scales, deter-
 mine the dead weight of material loaded into a hopper,
 bin, or container. After weighing, the contents are then
 fed as batches into the process. All of these weigh sys-
 tems give fairly accurate monitoring of weight (within
 *1%), but one must consider the batch feeding system
 operations before a true appraisal of the feed rate moni-
 toring can be made.

 Conveyor weighing systems—These methods include
 belt weighers, weigh belts/augers, and  loss-in-weight
 feeders. All conveyor weighing systems are fairly similar
 in operation, mainly differing because of placement loca-
 tions of the weighing device. In general, the accuracy of
 these systems is around ±2% but tends to decrease as
 particles become larger and less uniform in size. Sludges
 can be monitored with the systems, provided  that wet
 material does not drain off the conveyor belt.  Screw
 augers,  however, can often be used in such cases to
 replace the conventional conveyor belt.

 Momentum flowmeters—Two types of these solid flow-
 meters are available, based upon either impact or torque.
 These devices work fairly well with dry, f lowable materials
 but are  less accurate if feed particles  are very large,
 nonuniform, or viscous. Typical accuracies are  within
 *2%. Sludges are not recommended because of their
 viscosity and splashing effects.

 Nuclear absorption — Methods based upon absorption
 of gamma radiation include nuclear level meters, nuclear
 belt or auger scales, and a combination of nuclear den-
 sity meters and ultrasonic flowmeters. Nuclear absorp-
 tion only measures density; therefore, another instrument
 must also be used to measure volume, speed, or another
 parameter to  obtain feed rate. Nuclear instruments can
 be used on nearly any material including sludges.  Radia-
 tion absorption is proportional to the mass present, so
 particle  size  and configuration will  not  greatly  hinder
 accuracy. Sludge operations will work best with a nuclear
 density detector/ultrasonic flowmeter combination, ena-
 bling the process material to be fed through conventional
 piping. Accuracies of nuclear devices may not be as high
. as gravimetric systems but may be sufficient on a practi-
 cal basis.

 3.2.1.2 Liquid Feeds
 Typical flowmeters used to monitor the liquid waste feed
 rate to incinerators are detailed below.

 Rotameter — This type of flowmeter is available for a
 wide  range of liquid viscosities including some light-
 weight slurries. It is calibrated through  using a fluid of
 known density. Reported accuracies are within ±5% of
 full-scale.

 Orifice meter—This instrument is used with gases and
 low viscosity fluids. Typical accuracies  are ±1% full-
 scale,  which is the  accuracy of the differential
pressure measuring device used on a clean fluid. When
used with dirty or viscous fluids, both accuracy and life of
the instrument are sacrificed. An accuracy of ±5% may
be more realistic in these cases.

Vortex shedding meter — This device is applicable to
low-viscosity fluids and gases under turbulent flow condi-
tions. The accuracy is ±2% under normal operations.

Positive displacement meter — This type of flowmeter
is more applicable than other types for use with higher
viscosity fluids. However, accuracy is highest when used
with a clean, moderately viscous fluid. It cannot be used
with  multiphase liquids, gases, or slurries of  varying
density.

Mass flowmeter — This instrument, also known as a
Coriolis flowmeter,  applies to liquids of widely varying
viscosity and density and most slurries. It has been
advertised for use with gases, but that application may be
rare. The reported accuracy is within ± 1 %.

3.2.1.3 Gaseous Feeds
The  best types of flowmeters for gases are the orifice
meter and the Vortex shedding meter, discussed above
under liquid feeds.

3.2.2 Combustion Temperature
Combustion temperature is usually monitored  through
the use of thermocouples, optical pyrometers, or both.

3.2.2.1 Thermocouples
Thermocouples are available in a variety of types, with
each type constructed of specific metals or alloys. The-
temperature ranges and reported accuracy vary by type.
The environment the thermocouple is suited for also var-
ies. A summary of thermocouple types  and limitations is
given below.
Type Materials
                       Upper Thermocouple
                       Temp.   Accuracy
                                         Environment
J

E
K
S

R

B

Iron/constantan

Chromel/constantan
Chromel/Alumel
Pt 10% rhodium/pure Pt

Pt 13% rhodium/pure Pt

Pt 30% rhodium/pure Pt
6% rhodium
1400

1650 !
2300
2650

2650

3100

0.75

0.50
0.75
0.25

0.25

0.50

Reducing, vac-
uum, or inert
Oxidizing or inert
Oxidizing or inert
Oxidizing or inert
(no metal tubes)
Oxidizing or inert
(no metal tubes)
Oxidizing or inert
(no metal tubes)
 Source: Complete Temperature Measurement Handbook and Encyclopedia,
 Omega Engineering Inc., 1986.5

 The accuracies given above do not consider environ-
 mental effects. Thermocouple location in the combustion
 chamber, for example, greatly affects the accuracy of
 temperature readings. Typically,  thermocouples  are
 located at the gas exit from  the combustion chamber.
 This is generally believed to give the best overall average
                                                     10

-------
combustion chamber temperature. Other factors to con-
sider when examining thermocouple locations are:

• Temperature readings will be affected by radiant
  pickup or loss if the thermocouple is located close to
  and within a direct line of sight of either the flame or
  the cold quench chamber.
• To improve accuracy and limit wall effects, the thermo-
  well should extend 3 to 6 in. beyond the refractory and
  should be located where the gas velocity is high and
  not in a stagnant corner of the chamber.
The use of two thermocouples in separate wells is recom-
mended to provide a check on continued proper opera-
tion.  The  difference in the readings between the two
thermocouples should be noted during initial operation;
e.g., one thermocouple will likely give a reading higher
than the other one. The difference between the two read-
ings should then be checked periodically as an indicator
of problems with one of the thermocouples. If the differ-
ence changes  by more than  50 °F, both thermocouples
should be checked for proper operation.

Following the above guidelines allows for some degree of
consistency in measuring combustion temperature in an
incinerator. Changes in either the thermocouple type or
location should prompt reconsideration of the accuracy
and representativeness of the measurement.

3.2.2.2 Optical Pyrometers
Optical pyrometers are typically used to measure the
temperature of the furnace wall or an object within the
furnace but can be used to measure the combustion gas
temperature. In cases  where the  gas temperature  is
desired, the pyrometer is normally  equipped with a
closed end tube much like a thermocouple well but larger,
and the pyrometer is sighted on the end of this tube. In
this situation, emissivity corrections are not needed, This
configuration is normally used for high temperatures
when contamination or breakage of thermocouples is a
problem and the cost or difficulty of replacement is high.
The  pyrometer will normally require  calibration but
should, when calibrated, be approximately as accurate
as a thermocouple.

3.2.3 Combustion Chamber Pressure
Monitoring of the combustion chamber pressure is often
used to ensure correct operation of the incinerator and to
prevent fugitive emissions. Many combustion chambers
are operated under  draft (less than atmospheric pres-
sure)  conditions,  which ensures that  combustion off
gases do not exit the chamber before passing on to the
scrubber or other air pollution control equipment.

Instruments used to  monitor combustion chamber pres-
sure  are known as differential pressure  gauges, AP
transducers, or draft  gauges. Such instruments are com-
posed of a bellows or diaphragm enclosed within a stain-
less steel casing. Deflection  of the diaphragm due to
 combustion chamber pressure is then measured by mag-
 netic pickup coils also mounted within the casing. The
 instruments are located on the combustion chamber and
 typically measure pressures on the order of several
 inches of water.

 Accuracy of a differential pressure gauge is within ± 1 %
 full-scale, although the combustion chamber environ-
 ment severely hinders this performance. Particulate clog-
 ging, moisture, corrosion,  and other contaminants are
 typical problems. A precise measure  of combustion
 chamber pressure is difficult, but these instruments can
 be used to indicate whether the pressure within the com-
 bustion  chamber is positive or negative. Calibration
 against  an inclined manometer at least annually  is
 recommended.

 3.3 Sample Collection

 Sampling methods for the waste feed, stack gases, auxil-
 iary fuel, quench and scrubber water, and ash are given
 primarily in four sources: (1) Tesf Methods for Evaluating
 Solid Waste — Physical/Chemical Methods, SW-8466; (2)
 Sampling and Analysis Methods for Hazardous Waste
 Combustion*; (3) Code of Federal Regulations, 40 CFR
 Part 60, Appendix A7; and  (4) The American Society for
 Testing and Materials, Annual Book of ASTM Standards.*
 EPA-600/8-84-002 should be consulted first as it provides
 cross-references to more fully documented sources of
 methods (i.e., SW-846  or ASTM). These other sources
 should then be consulted.  If there is a conflict between
 these documents, SW-846 has precedence. The discus-
 sion which follows addresses the most commonly used
 methods available for sampling these parameters.

 3.3.1 Waste Feed
 The objective of waste feed sampling is to obtain a repre-
 sentative sample of the waste feed. It is important that the
 sampling plan be explicit  and that it explain the logic
 behind the selection of the sample  collection scheme.
 For many waste feeds, representative sampling is
•difficult.

 The waste feed for incinerators may be a free-flowing
 liquid, slurry, sludge, or a powdered, granular, or large-
 grained solid. Various methods are available for sampling
 these waste feeds and are described in SW-846,6 EPA-
 600/8-84-0024 and the  ASTM Standards.8 These meth-
 ods are discussed in further detail in the  following
 subsections.

 3.3.1.1 Free-Flowing Liquids
 The most  common  method  used for sampling free-
 flowing, low-viscosity liquids is tap  sampling from the
 waste feed line or tank.  Other methods that may be used
 for sampling from drums, tanks, or ponds include a col-
 iwasa (composite liquid waste sampler), weighted bottle,
 or dipper. Each of these methods and types of equipment
 used are described in the following sources:
                                                  11

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               SW-846
Sampling Method  Chapter 9,
EPA-600/
8-84-002
Method
  Old      New
  ASTM     ASTM
Standards  Standards
Tip sampling
Cottwasa
Dipper
Weighted bottla
TMof
p. 49-51
p. 50.53
p. 50,52
p. 50,54
S004
S001
S002
S003
S005
                                D-270-75
                                D-270-75
                                E-300-73
                                        D-4057-9.3
                                        D-4057-9.6
                                        D-4057-9.5
                                        D-4057-9.7
Sampling a free-flowing liquid waste feed can be per-
formed by obtaining tap samples from the storage tank or
process feed line(s). The liquid in a storage tank should
be thoroughly agitated and mixed to obtain representa-
tive samples. If the feed contains two immiscible liquid
phases or solids which could stratify in the feed line, a
mixer may need to be inserted in the feed line prior to the
tap to obtain representative samples.

3.3.7.2 Viscous Liquids, Slurries, Sludges, and Solid
       Waste Samples
Sampling methods and the equipment required for vis-
cous liquids, slurries, sludges, and solid waste feeds are
described in SW-846, EPA-600/8-84-002, and the ASTM
Standards. These methods are described in SW-846 and
EPA-600/8-84-002 as follows:
   Method Name
                     Type of Waste
Thiol (grain sampler) Dry powder or granules
Trior(corof)       Sludge or moist solids
Trowel (scoop)     Moist or dry solids
Auger           Packed solids
               SW-846   ADL
              Chapters Method

               p. 50,54   S005
               p. 50,55   S006
               p. 50     S007
               p. 50      —
The sampling protocols given in the ASTM Standards for
the different types of waste feeds are:
Extremely viscous liquids
Crushed or powdered materials
Soil or rock-lite material
SoiWika material
Fly ash-like material
   ASTM Standard D140-70
   ASTM Standard D346-75
   ASTM Standard D420-69
  • ASTM Standard D1452-65
   ASTM Standard D2234-76
Samples  of extremely viscous liquids,  slurries, and
sludges are usually obtained from their containers by the
methods described above. Samples of solid waste are
usually obtained from the containers, waste piles, or from
the process feed system, such as a conveyor belt or
auger system.

3.3.2 Auxiliary Fuel
Sampling of liquid auxiliary fuel may be appropriate so
that the samples may be analyzed for the POHCs and
higher heating value (for total heat input), although this
measurement is not required by RCRA. The methods for
sampling the fuel are the same as those  used for free-
flowing liquid wastes. Tap sampling (S004) is the most
common method used for liquid fuels.

3.3.3 Stack Gases
Stack gases must be sampled for the following parame-
ters during the trial burn; particulates, hydrogen chloride
(HCI),  H2O, CO2, CO, and principal organic hazardous
constituent (POHC) emissions. Stack gas flow rate, vol-
ume, and temperature must be measured during the
sample collection. Analyses of these  samples are
required by 40 CFR Part 264 (Subpart O) and 40 CFR
Parts 270.19 and 270.62.7 Table 4 summarizes the sam-
pling methods used for stack gases for RCRA trial burns.
Many of these parameters can be sampled using the
standard EPA reference methods shown in Table  5.
Methods for  both  volatile and nonvolatile  metals are
included in Table 4 for completeness, since sampling may
be requested. Additional information on methods for CO,
oxygen, total hydrocarbon  (THC), HCI, and metals,
including draft performance specifications for CO and
oxygen, can  be found in Volume  VI of the Guidance
Series (see Section 1).

An important aspect of obtaining a valid stack gas sam-
ple is the experience and performance of the sampling
personnel. The sampling personnel, especially the
supervisor,  must be adequately trained, as evidenced by
either previous experience or documented training.

3.3.3.7 HCI
Hydrochloric  acid  (HCI) emissions are currently mea-
sured using a CEM or manual methods consisting of a
collection train and/or analytical procedure. Manual col-
lection methods normally extract a gas sample from the
stack and absorb the HCI in an absorbent. The sampling
train consists of a  particulate filter,  the absorption solu-
tion, and a provision for measuring the  sampled gas
volume. The EPA Method 5 train, an EPA Method 5 train
modified for metals, or a specific impinger train have all
been employed. The M5 trains are  normally used when
HCI is to be collected in addition to sampling for particu-
lates or metals. If sampling is to be performed for only
HCI, then a specific impinger train is employed. For sam-
pling HCI using the M5 as described in the Federal Regis-
ter, the M5 procedures are followed except that the water
in the impingers is replaced with an absorbing solution. A
draft method for HCI sampling,  Determination of HCI
Emissions from Municipal and Hazardous Waste Inciner-
ators, is being prepared by EPA, AREAL, Source  Meth-
ods Standardization Branch. This method is undergoing
further revision, e.g.,  a  better filter arrangement than
shown in the current draft will be recommended.

A solution of sodium  of  potassium hydroxide has fre-
quently been used to absorb the HCI. This approach has
been satisfactory except that the solution also absorbs
the other acid gases contained in the sample including
carbon dioxide (CO.,). The use of the hydroxide solution
therefore may require that a correction be applied  to the
sample volume for  the gases that were removed before
the gas volume meter in the sampling stream. This cor-
rection may be avoided by substituting other solutions for
                                                    12

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Table 4.  Sampling Methods for Stack Gases in RCRA Trial Burns
               Sampling parameter
                        Sampling method
Particulates, C\; H2O, nonvola-
tile metals (if present in feed)
Semivolatile and nonvolatile
POHCs

Volatile POHCs

C02,02

CO


Volatile metals (if present in
feed)
M5 train with appropriate solutions in one
or more of the impingers

Semi-VOST (SW-846 Method 0010)


VOST (SW-846 Method 0030)                         ,

EPA Method 3 Orsat analysis of integrated bag sample

Continuous monitor, proposed performance specifications are being prepared by
EPA3  .                      .

M5 train with appropriate solutions in the
second impinger
NOTE: POHCs = Principal organic hazardous constituents.
      VOST = Volatile organics sampling train.
Table 5.  EPA Reference Methods Used to Test RCRA Hazardous Waste Incinerators
                  Method description
EPA Method 1:       Sample and velocity traverses for stationary sources

EPA Method 2:       Determination of stack gas velocity and volumetric flow rate (type S pilot tube)
EPA Method 2A:      Direct measurement of gas volume through pipes and small ducts  ,  ..

EPA Method 3:       Gas analysis for carbon dioxide (CO2), oxygen (O2), excess air, and dry molecular weight (Orsat)

EPA Method 4:       Determination of moisture content in stack gases

EPA Method 5:       Determination of particulate emissions from stationary sources

NOTE: All of these EPA methods are fully described in 40 CFR Part 60, Appendix A, revised as of July 1,19857
the hydroxide. There  is a  lack of consensus  on the
impinger reagent most appropriate for collection of HCI.
A sodium carbonate solution has  been recommended,
since this reagent will not absorb CO2. There is evidence
to suggest that caustic reagent is not necessary and that
HCI is efficiently trapped in any aqueous medium. If this
is true, then distilled water (e.g., ASTM Type II reagent
water) may be the reagent of choice for collection of HCI.
The draft method being prepared by EPA recommends
dilute acid solutions.

3.3.3.2 Volatile Organics
The  methods used to sample the POHCs and other
organics depend upon their volatility. Volatile POHCs
(generally those with a boiling point between 30°  and
100°C, see Section 3.4.5.4.1) are sampled using a VOST
The VOST and  its  operation are fully described in the
Protocol for the Collection and Analysis of Volatile POHCs
Using VOST,a the two-volume study Validation of the Vola-
tile Organic Sampling  Train (VOST) Protocol,10 the EPA-
600/8-84-002" as Method S012, and Part 111, Chapter 10
of SW-846 as Method 0030.

Several variations on the basic VOST design are avail-
able from vendors or may be constructed by the sampling
organization. The sampling plan should show a sche-
matic of the train actually used and also describe the
exact apparatus and operation. Critical aspects include
          the train setup, probe position in the actual stack geome-
          try to be tested, leak check procedures, and sample
          handling. The latter is particularly important, since the
          volatile organics in ambient air as well as other sources of
          contamination can affect the accuracy of results. There-
          fore, care must be taken to prevent contamination of the
          sorbent cartridges before and after the collection of the
          stack gas sample.

          In planning the VOST sample collection, the sample vol-
          ume required to demonstrate the 99.99% ORE should be
          calculated as described in Section 2.4 and Table 2. The
          volume of  the VOST collection  can  then  be  scaled
          accordingly. If numeric values for  POHCs at concentra-
          tions much  higher than the value needed for the 99.99%
          ORE must be reported, a second VOST collection with a
          smaller sample volume may be required to prevent satu-
          ration of the GC/MS system.

          As noted in the documents describing VOST, a variety of
          methods are available for generating standards for cali-
          bration of the GC/MS. The VOST protocol10 specifies the
          injection of a methanolic standard solution onto the car-
          tridge followed by flash evaporation of the methanol. This
          is workable but presents several practical problems. Very
          volatile compounds can evaporate from the  methanolic
          solution. The residual methanol prevents scanning the
          mass spectrometer below about mass 34 (M + 2 of meth-
                                                     13

-------
anol). There is also a possibility that some POHCs may
react with the methanol. Other alternatives listed in the
validation documents10 are gas cylinder standards, per-
meation devices, and static gas bottle standards.

Gas cylinder  standards are  prepared from outside
sources and certified  by the supplier. These cylinders
can be purchased to contain various POHCs at various
gas concentrations.

Permeation tubes and other devices can generate a reli-
able, accurate gas mixture. They are commercially avail-
able or can be prepared for most POHCs. However,
setting up, maintaining, and monitoring a permeation
system is expensive and time-consuming. In addition,
the concentrations of the POHCs in the gas stream are
governed by their permeation  rate, so the flexibility to
generate different concentrations is limited.

Static gas bottle standards are generated by evaporating
a known amount of the POHCs in a gas bottle to give a
known gaseous concentration. This is a simple standard
preparation method; however, accuracy can be a prob-
lem if evaporation is incomplete or the POHC adsorbs to
the wall of the vessel.

The EPA also operates a program to develop organic gas
audit materials and provide these audit gas cylinders for
use in VOST performance audits during trial burns. Four
different  audit  cylinders are available that contain the
volatile organic compounds shown in Table 6. Any fed-
eral, state, or local agency or its contractor planning haz-
ardous waste trial burn tests may request a performance
audit by contacting Mr. Robert Lampe, USEPA, Environ-
mental Monitoring Systems Laboratory,  Quality
Assurance Division, Research Triangle Park, North Caro-
lina 27711.

Collection of stack gas samples in Tedlar bags is listed as
an option for sampling volatile organics in Method S011
 in EPA-600/8-84-002; however, several problems with the
 analysis of bag samples severely limit the utility of this
 option. Samples are collected in 30-L Tedlar gas bags
 using an integrated gas sampling train. The bags are
 then transported to the analytical laboratory, and if the
 VOST traps are saturated, a small volume of gas from the
 bag is transferred to a clean VOST trap for analysis. This
 approach presents some practical problems. Tedlar bag
 samples have a relatively short holding time of 1 to 2 days
 for some specified compounds according to EPA Method
 23.12 Therefore, the use of Tedlar bags is practically lim-
 ited to tests where the VOST analysis is being conducted
 on-site or within a very  short holding time. The bag sam-
 ple procedure is less desirable than VOST due to poten-
 tial  problems with adsorption  in  the  bag and loss  of
 sample. Stability of the POHC to be sampled in the bag
 should be checked prior to sampling,  if this method is
 used. Field blanks are essential with bag sampling.

 3.3.3.3 Semivolatile Organics


 Semivolatile  POHCs and other organics with  boiling
 points above 100°C are sampled with a semi-VOST
 (sometimes referred to as a Modified  Method 5 [MM5]
 train). Those organic  compounds with boiling  points
 between 100° and 140°C may also be suitable for sam-
 pling with VOST However, experts in analytical chemistry
 should be consulted for sampling of compounds in this
 boiling point range.

 The semi-VOST is an  EPA Method 5 train which has
 been modified by placing a sorbant module (usually con-
 taining XAD-2 resin) before the first impinger. This train is
 identified in Part III, Chapter 10 of SW-846  as Method
 0010,6 and in EPA-600/8-84-002 as Method S008.4 The
 sampling train is fully  described in Modified Method 5
 and Source Assessment Sampling System  Operations
 Manual,™ and in the two-volume report, Laboratory and
 Field Evaluation of the  Semi-VOST (Semivolatile organic
 sampling train) Method." Sampling trains with XAD resin
 traps should not be used to collect HCI.
Tables.  VOST Audit Compounds*
Group I compounds            Group II compounds
Group III compounds
Group IV compounds
Carbon tetrachloride
Chloroform
Perchtoroethylene
Vinyl chloride
Benzene
Group 1 ranges
7to90ppb
90to430ppb
430 to 10.000 ppb
Trichloroethylene
1,2-Dichloroethane
1 ,2-Dibromoethane
Acetonitrile
Trichlorofluoromethane
(F-11)
Dichlorodifluoro-
methane (F-12)
Bromomethane
Methyl ethyl ketone
1,1,1-Trichloroethane
Group II ranges
7 to 90 ppb
90 to 430 ppb
Vinylidene chloride
1,1,2-Trichloro-1,2,2-
trifluoroethane
(F-113)
1,2-Dichloro-1,1,2,2-
tetrafluoroethane
(F-114)
Acetone
1-4 Dioxane
Chlorobenzene
Group III ranges
7 to 90 ppb
90 to 430 ppb
Acrylonitrile
1,3-Butadiene
Ethylene oxide
Methylene chloride
Propylene oxide
Ortho-xylene
Group IV ranges
7 to 90 ppb
430 to 10,000 ppb
Source: "Performance Audit Results for Volatile POHC Measurements," JAPCA, Vol. 38, No. 6, June 1988."
• All gas standards are in a balance gas of nitrogen.
                                                   14

-------
 Each stack-testing organization uses a slightly different
 variation on the basic semi-VOST The sampling  plan
 should show a schematic of the train actually to be used
 and briefly describe the semivolatile collection appa-
 ratus, as well as cite the protocol to be followed. Critical
 aspects include the train setup and position of the XAD
 cartridge. Contamination from grease in the glassware
 fittings in the train has caused problems with the subse-
 quent analysis. Therefore, most guidance (see, for exam-
 ple, Referenced) states that no grease (either
 hydrocarbon or silicone) is to be used in the train. This
 lack of grease may cause problems with demonstrating a
 satisfactory leak check but ensures against gross sample
 contamination which can render the samples
 unanalyzable.

 In recovering the sample from the sampling train  and
 subsequent analysis, it must be emphasized that all inte-
 rior portions of the train prior to and including impingers
 that contain cpndensate after the XAD-2 sorbent module
 must be considered as part of the semivolatile organics
 sample. This includes nozzle and probe rinses, impinger
 contents, the filter, the XAD-2, and all glassware rinses. In
 addition, it should be noted that the filter from this sample
 collection should not be used for the paniculate measure-
 ment. Upon heating to  constant weight to measure the
 paniculate, the filter may lose some or all of the semivo-
 latile organic analytes. The contents of the impingers
 after the XAD-2 sorbent module should be analyzed for
 all POHCs,  but is particularly important for very water-
 soluble compounds.

 3.3.3.4 Metals

 When specific metals can be identified as potential emis-
 sions,  sampling will probably be best addressed  by
 selecting a specific sampling and analytical approach.
 Specific methods which have been  developed include
 EPA Method 12 for lead, Method 101A for mercury, Meth-
 ods 103 and 104 for beryllium, and Method 108 for arse-
 nic. In most cases, however, sampling will be required for
 multiple metals. For this, the draft metals protocol Meth-
 odology for the Determination of Trace Metal Emissions in
 Exhaust Gases From Stationary Source Combustion Pro-
 cesses (prepared by the EPA, AREAL, Source Methods
 Standardization Branch) describes the only system that
 has been proposed to collect both the volatile and non-
 volatile fraction of the stack gases. This draft protocol will
 be incorporated into a methods document under prepa-
 ration by EPA, OSW as background for proposed amend-
 ments to the RCRA incinerator regulations.9 Sampling for
 hexavalent chromium presents several problems. These
 problems are the stability of the  sample and recovery
efficiencies when separating low level samples. Both oxi-
dizing and reducing materials may affect the stability Of
the samples and produce errors in the determination.
 EPA  is currently working on a suitable procedure to col-
lect chromium(VI) stack samples. A separate sampling
*rain used  only for collection  of  chromium(VI)  is
recommended.
 3.3.4 Quench and Scrubber Waters

 Samples of quench and scrubber waters (both input and
 output) are usually taken by the tap sampling method
 (S004) or by dipper (S002). Weighted bottles (S003) can
 also be used. The corresponding ASTM and SW-846
 methods are listed in Section 3.3.1.

 3.3.5 Incinerator Ash (Residue)

 The method most commonly used for sampling ash is the
 trowel method (S007). The protocols given in the ASTM
 Standards or SW-846 methods manual for sampling solid
 materials given previously in Section 3.3.1 provide addi-
 tional information.

 3.3.6 Documentation

 The trial burn plan should address documentation of all
 sample collection activities. Sample collection times and
 conditions must be recorded when the samples are col-
 lected. For the VOST and semi-VOST, defined periodic
 readings of temperature and flow  parameters  must be
 recorded. Generally, example  data recording  forms
 should  be provided in  the trial  burn plan.  Often com-
 puters or programmable calculators are used for calcula-
 tion of  the sampling  parameters.  These should  be
 addressed in the plan with sufficient information to docu-
 ment how calculations were made.

 3.4 Chemical Analysis

 The recommended methods for analyzing samples taken
 during the trial  burn or routine  operation of an  RCRA
 hazardous waste incinerator are found primarily in SW-
 846,6 EPA-600/8-84-002,4 40 CFR Part 60, Appendix A,7
 and in the ASTM Standards.8 EPA-600/8-84-002 should
 be consulted first as it provides cross-references to more
 fully documented sources of methods (i.e., SW-846 or
 ASTM), These other sources should then be consulted. If
 there is a conflict between these documents, SW-846 has
 precedence.

 The following sections discuss sample shipping, receipt,
 and documentation; planning the analysis; general ana-
 lytical considerations; analysis of waste feed; analysis of
 stack samples; and analysis of other effluent streams.

 3.4.1 Sample Shipping, Receipt, Documentation,
     and Storage
The trial burn plan must contain provisions for orderly
 and welldocumented transfer of the  samples from the
 incinerator to the laboratory including documentation of
how samples were handled.

The trial burn plan should address:

a. Sample storage requirements on-site and during stor-
  age at the labo ratory prior to analysis.

b. Holding times prior to analysis.
                                                  15

-------
c. Sample labeling.

d. Documentation procedures for handling and transfer
  of samples.

Sample storage conditions and times should be speci-
fied. Holding times and storage conditions prior to extrac-
tion can be particularly important depending on the type
of sample. Between analysis steps, appropriate storage
conditions must also apply. The holding time and archiv-
ing conditions for samples and extracts after the analysis
also should be specified. If possible, they should be held
long enough to permit reanalysis if requested.

The sample labeling procedures and logging (notebook,
forms, barcode) of the samples should be addressed.

Documentation of sample shipping, receipt, and transfer
must  be addressed in the plan.  Generally, traceability
forms accompany the samples and are signed and dated
at each event. If formal chain-of-custody is to be used,
additional documentation certifying the  unbroken chain
and security of the samples is required.

3.4.2 Planning the Analysis
The analysis must be carefully planned in order to pre-
vent costly mistakes or schedule slippage. The trial burn
plan should address how samples will be transferred to
the appropriate laboratory personnel and how the per-
sonnel will be instructed on the  analytical  objectives.
Written instructions to the analysts should address the
following: sample numbers, storage location, the analyti-
cal methods to be used, the  analysis objective and limit
of detection required if not implicit in the method, analy-
sis sequence,  QC requirements (duplicates, spikes,
blanks, etc.), other special instructions, and due date.
The plan should indicate  the presence of or have
attached SOPs.

The first step in planning the analysis is to identify the
target analytes. The process for selection of the organic
hazardous constituents to be determined in  the waste
feed is described in Section III.B of the EPA-600/8-84-
002* and in Part III, Chapter  13 of SW-846.6 The general
characteristics of the waste feed are determined first by
proximate analysis, then survey analysis, and finally by
directed analysis. Based on these results, a limited num-
ber of organics are selected for recommendation as prin-
cipal  organic  hazardous  constituents  (POHCs). This
selection  procedure is  not discussed  in  detail in  this
report.

One important consideration  in selecting the POHCs is to
avoid those which are difficult to analyze. Table 7 shows
a select list of "problem" POHCs, the cause of the prob-
lem, and some possible solutions to the problem.
3.4.3 General Analytical Considerations

3.4.3.7 Glassware Cleaning and Tracking
All glassware used for the analyses must be  properly
cleaned. Each laboratory must develop adequate stan-
dard operating procedures for glassware cleaning. Sepa-
rate cleaning procedures are generally  required for
organic and inorganic analysis, since different interfer-
ences are of concern.

It is highly advisable to have a glassware tracking system
in place to prevent cross-contamination of  glassware.
The analyses described  in this document address both
high level (e.g., feed samples at 30% POHC concentra-
tion) and trace analysis (e.g., the same POHC in the
stack gas sample at the nanogram-per-gram level). Thus,
the potential for cross-contamination is great.

A glassware screening system is also advisable to verify
the adequacy of the glassware cleaning.

3.4.3.2 Standards, Reagents, and Solvents
Standards, reagents, and solvents must be of the appro-
priate purity. New lots should be checked for purity. New
standards should also be checked for chemical identity
and their concentration verified.

3.4.3.3 Physical Sample Preparation
Some  samples may require homogenization, blending,
aliquoting,  or compositing.  Basic guidance  is given  in
Methods P001, P002, and  POOS of the EPA-600/8-84-
0024 and in Part III, Chapter 9 of SW-846.6 Specific proce-
dures should  be detailed in the trial burn plan.

3.4.4  Analysis of Waste Feed
The waste feed  must  be  sampled  and analyzed  in
accordance with 40  CFR  Parts 270.19, 270.62,  and
264.13.7 Specifically, the waste feed must be analyzed for
higher heating value, viscosity (if liquid), and the hazard-
ous organic  constituents listed in 40  CFR Part  261,
Appendix VIII.7 Analysis  is required for any of the ~ 300
constituents in Appendix VIII, which may be reasonably
expected to be present for waste characterization or for
selected constituents  from the list for trial burns. Many
other parameters may be determined to fully characterize
the waste. Various methods and techniques are available
to prepare the field samples for analysis. Table 8 lists the
sample preparation methods described in the EPA-600/
8-84-002. Table 9 lists the sample preparation and intro-
duction techniques described in SW-846.6  Table  10
shows the recommended analytical methods that may be
used to characterize the waste feed.

Physical analyses give information on the physical char-
acteristics and  general chemical  composition of the
waste including the following:
                                                    16

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Table 7.  Selected Problem POHCs
Compound
Cause of problem
Possible solution
Acetonitrile
Acetyl chloride
Aflatoxins
Aniline
Benzenearsonic acid
Benzidine
Bis(chloromethyl)ether
2-Butanone peroxide
2-sec-Butyl-4,6-dinitrophenyl
Carbon oxyfluoride
Chloral
Coal tars
Creosote
Cyanogen
Cyanogen bromide
Cyanogen chloride
Cycasin
A/,W-Diethylhydrazine
1,1-Dimethyl.nydrazine
1,2-Dimethylhydrazine
1,4-Dioxane
1,2-Diphenylhydrazine
Diphenylamine
Formaldehyde
Formic acid
Hydrazine
Hydroxydimethylarsine oxide
Iron dextran
Maleic anhydride
Maleic hydrazide
Mustard gas
Nitroglycerin
Phenylmercury acetate
Phosgene
Pyridine
Selenourea
Toluene diisocyanate
Water soluble
Decomposition
High toxicity
Water soluble
Low volatility
Decomposition?
Decomposition
Reactive
Acidic, extracts poorly
Decomposition?
Water soluble
Complex mixture
Complex mixture
Gas
Gas
Gas
Low volatility
Unstable
Unstable
Unstable
Water soluble
Unstable
Basic, extracts poorly
Water soluble
Water soluble
Unstable
Low volatility
High molecular weight
Unstable
Unstable
Highly toxic
Explosive
Low volatility
Highly toxic
Water soluble
Low volatility
Water soluble
Derivatize with HI
Sample with Semi-VOST train
Derivatize to sample
DerivatizewithHI
GPC
Derivatize with HI


Special HPLC column
•  Heating value
•  Viscosity (if liquid)
•  Ash content
•  Total organic chlorine
«  Moisture content
•  Solid content
•  Elemental composition (optional)
The heating value and viscosity (for liquids) are required
by RCRA. The ash  content is generally required as an
indicator  of inorganic loading and  other factors which
may affect the amount of paniculate generated. Total
organic chloride is needed to determine the HCI removal
efficiency. The other analyses are not required but may
be of value to the incinerator operator in characterizing
the waste feed and in operating the incinerator.

A method for analysis of total organic chloride in waste is
under development by EPA, AREAL. In certain situations
measurement of total chloride in the waste may be substi-
tuted for  total organic chloride. The Source Methods
Standardization Branch, AREAL or OSW, should be con-
sulted on this topic.
                     3.4.4.7 Analysis of Waste Feed for POHCs

                     A major objective of the trial burn is to measure the ORE
                     of selected POHCs. To do this, the sampling and analysis
                     program must measure both the input and output rates of
                     the POHCs. Only those organics selected for measure-
                     ment (i.e., the POHCs) need to be measured in the waste
                     feed during a trial burn.

                     The RCRA hazardous compounds are given in 40 CFR
                     Part 261, Appendix VIII.7 The methods for analyzing vari-
                     ous matrices for the POHCs are given in EPA-600/8-84-
                     0024 as  Methods A101 to A190 and  in SW-8466  as
                     Methods 8010 and 8310. Table 11 lists the methods given
                     in  EPA-600/8-84-002, and Table 12 lists the methods
                     given in SW-846.

                     Specific  methods for the Appendix  VIII compounds
                     (including inorganic compounds) given in EPA-600/8-84-
                     002 and SW-846 are shown in the appendix.

                     3.4.4.2 Analysis for Inorganics

                     Inorganic analysis is not addressed in detail in this man-
                     ual. The applicable analytical methods are cited for com-
                     pleteness in Table 13. For further information, the reader
                     is referred to EPA-600/8-84-0024 and SW-846.6
                                                      17

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 3.4.5 Analysis of Stack Samples
 Stack samples are analyzed for POHCs to determine
 ORE, hydrogen chloride, and participate as required in 40
 CFR 264.34S.7  In addition, other analyses may be
 required for specific demonstrations. The recommended
 methods for analysis of stack samples are listed in Table
 14. This section describes the methods generally used
 and discusses some potential problems and solutions.

 3.4.5.1 Hydrogen Chloride Analysis
 The hydrogen chloride in the stack gas must be mea-
 sured to demonstrate an emission rate of less than 4 Ib/hr
 or 99%  removal before discharge to the atmosphere (40
 CFR 264.345). (It may be possible to use data from
 analysis of chlorine in the waste to determine compliance
 with an  uncontrolled HCI emission rate or to determine
 control device inlet HCI rates for calculation of efficiency.)
 A number of analytical methods have been employed to
 analyze the  impinger catch  for HCI.  These methods
 include the automated ferricyanide colorimetric Methods
 9250 and 9251 and the titrimetric Method 9252 from.SW-
 846, ion chromatography ASTM Method D-4327-84 and
 Method 300.0  from Chemical Analysis of Water and
 Wastes. Ion chromatography is  the preferred method.
 Because  of  the greater detail provided, the ASTM
Table 8.  Sample Preparation Methods Given in
         EPA-600/8-84-002

Sample preparation method
Method
number
Representative aliquots (composites) of field samples
  Liquids (aqueous and organic)                       P001
  Sludges                                         POQ2
  Solids                       "                   P003
Surrogate addition to sample aliquots for organic analysis
  Volatile organics                                  P011
  Basic extractable organics                          P012
  Acidic extractabla organics              •            P013
  Neutral extractable organics                         P014
Extraction of organic compounds
  Aqueous liquids                            *      P021
    SemivoIatHes                                  P02la
    Vbtatiles                                       P02ib
  Sludges (including gels and slurries)                   P022
    Somivolatiles                                  P022a
    Volatiles                                       P022b
  Organic liquids                                   P023
  SolWs                                   .       P024
    Semh/olatiles by homogenization                   P024a
    Semivolatiles by Soxhiet extraction                  P024b
    Volatiles                                       P024c
Drying and concentrating solvent extracts                P031
Digestion procedures for metals                        P032
Sample cleanup procedures
  Ftorfsif column chromatography                      P041
  BioBeadsSX-3                                   R042
  Silica gel chromatography                          P043
  Alumina column chromatography                     P044
  Liquid/liquid extraction                             P045

Source: Arthur D. Little, Inc., "Sampling and Analysis Methods for
       Hazardous Waste Combustion," EPA-600/8-84-002,
       PB84-155845; February 1984.4
           D-4327-84  procedure  is  recommended over  Method
           300.0. The other methods mentioned above may be suit-
           able in some circumstances.  The draft  EPA  method
           referred to in Section 3.3.3.1 specifies ion chromatogra-
           phy and provides details.

           3.4.5.2 Particulate Analysis
           Particulate must be measured in the stack gas to demon-
           strate a maximum particulate emission concentration of
           no greater than 180 mg/Nm3, corrected to 7% O2 (50%
           excess air) (40 CFR 264.345). The particulate  is mea-
           sured gravimetrically according to the procedures estab-
           lished in EPA Reference Method 5 (40 CFR 60).

           Two procedures are available. In the first procedure, the
           filter is desiccated and then  weighed  to a constant
           weight. In the alternate procedure, the filter is oven-dried
           for 2 to 3 h at  105°C (220°F) and cooled in a desiccator
           Table 9.  Sample Preparation and Introduction Techniques
                   Given in SW-846'
           Sample preparation and introduction techniques
                                                Method
                                                number
Sample workup techniques           '
  Inorganics
    Acid digestion of waters for total recoverable           3005
      or dissolved metals for analysis by FLAA" or ICPC
    Acid digestion of aqueous samples and extracts         3010
      for total metals analysis by FLAA or ICP
    Acid digestion for aqueous samples and extracts        3020
      for total metals analysis by GFAA"
    Dissolution procedure for oils, greases, or waxes        3040
    Acid digestion of sediments, sludges, or waxes          3050
  Organics
    Organic extraction and sample preparation             3500
    Separatory funnel liquid-liquid extraction              3510
    Continuous liquid-liquid extraction                    3520
    Soxhiet extraction                                3540
    Sonication extraction                              3550
    Waste dilution                                   3580
Sample introduction techniques
  Purge and trap method                              5030
  Protocol for analysis of sorbent cartridcjes from           5040
    VOST"
Sample cleanup
  Cleanup                                          3600
  Alumina column cleanup                             3610
  Alumina column cleanup and separation of               3611
    petroleum wastes
  Florisil column cleanup                              3620
  Silica gel cleanup                                  3630
  Gel-permeation cleanup             .                3640
  Acid-base partition cleanup        ,                  3650
  Sulfur cleanup                                     3660

• Source: U.S. Environmental Protection Agency/Office of Solid
       Waste, Washington, DC, "Test Methods for Evaluating Solid
       Waste: Physical/Chemical Methods," SW-846, Third
       Edition, November 1986.6

" FLAA = flame atomic absorption spectroscopy.

c ICP = inductively coupled  plasma spectroscopy.

0 GFAA = graphite furnace atomic absorption spectroscopy.

•VOST = volatile organic sampling train.
                                                        18

-------
 before the filter is weighed to a constant weight. Note that
 the filter used for participate analysis should not also be
 used as part of the semivolatile organic analysis, since
 the drying-to-constant-weight procedure may lose some
 of the semivolatile organics.

 The probe rinse is checked for any leakage during trans-
 port. The liquid is measured volumetrically or grayimetri-
 cally to the nearest  ±1 ml_ (±1  g).  The  contents are
 transferred to a tared 250-mL beaker. The probe rinse is
 evaporated to dryness at ambient temperature and pres-
 sure. The beaker is weighed to a constant weight, and the
 results are reported to the nearest 0.1 mg.
Table 10.  Analytical Methods for Characteristics of RCRA
          Hazardous Waste Feed Samples
Characteristics of hazardous wastes
Analysis
method
Source"
Ignitability: Pensky-Martens closed-cup
method


Ignitability: Setaflash closed-cup method


Corrosivity toward steel

pH electrometric measurement

Reactivity

Extraction procedure "(EP) toxicity

•Appendix VIII hazardous constituents
Ultimate analysis (elemental composition)
"Viscosity '•" '

'Higher heating value


Chlorides
Ash: Sample drying and ignition

Ash: Thermogravirhetric analysis

Total organic carbon (TOC)

Total organic halides (TOX)b

Total and amenable cyanide
Sulfides

1010
D-93-80
C001
1020
D-3278-78
C001
1110
C002
9040
C002
8.3
COOS
1310
C004
See Appendix
A003
A005 -
D-445-79
A006
D-2015-77
D-3286-77
D-808-81
A001a,b
D-1888-78
A002
D-1888-78
9060
A004
9020
A004
9010
9030

SW-846
ASTM
ADL
SW-846
ASTM
ADL
SW-846
ADL
SW-846
ADL
SW-846
ADL
SW-846
ADL

ADL
ADL
ASTM
ADL
ASTM
ASTM
ASTM
ADL
ASTM
ADL
ASTM
SW-846
ADL
SW-846
ADL
SW-846
SW-846
Note: * Required under RCRA,
• Sources:
 ADL  = Arthur D. Little, Inc., "Sampling and Analysis Methods for
 Hazardous Waste Combustion," EPA-600/8-84-002, PB84-155845,
 February 1984.'
 SW-846 = U.S. Environmental Protection Agency/Office of Solid
 Waste, Washington, DC, "Test Methods for Evaluating Solid Waste:
 Physical/Chemical Methods," SW-846, Third Edition, November
 1986.6
 ASTM = American Society for Testing and Materials, "Annual Book
 of ASTM Standards," Philadelphia, Pennsylvania.8
0 The methods listed were developed for wastewater and are not
 applicable to organic waste. If this analysis is necessary, the Source
 Methods Standardization Branch, AREAL, EPA or OSW, EPA
 should be consulted.
Weights are  reported separately as filter weight and
probe rinse.

3.4.5.3 Oxygen and Carbon Dioxide
Oxygen and carbon dioxide are collected in sample bags
(e.g., Mylar, Tedlar) and  analyzed  by EPA  Reference
Method 3 (see Table 5).  The method uses the Orsat
apparatus to  measure the volumetric change  in liquid
volume with selective absorption of oxygen or CO2. Sam-
ples must be analyzed within 3 h, so  the analysis is
almost always conducted on-site.

Integrated bag  samples, if required, must be collected
over the entire test period.

3.4.5.4 Analysis for POHCs
The POHCs are divided into two general groups for anal-
ysis — volatile  and semivolatile organics. Methods for
these groups are discussed below.  Analysis for metals
may also be required and is presented briefly below.

Volatile POHCs — The volatile POHCs are collected
either on the VOST or in Tedlar gas bags (S011) for the
high  concentration volatiles which saturate the
                        Table 11.  Analytical Methods for Principal Organic Hazardous
                                 Constituents (POHCs) Given in EPA-600/8-84-002

                                                                       Analysis
                        Description of analysis methods                    method

                        Volatiles                                         A101
                          Purging procedure for the analysis of aqueous liquids    A101 a
                          Purging procedure for the analysis of sludges          A101b
                          Purging procedure for the analysis of solids           A101c
                        Extractables                                      A121
                        HPLC/UV generalized procedure                      A122
                        HPLC/UV generalized procedure   .       '           A123
                        Aldehydes — derivatization procedures                A131
                        Aldehydes — HPLC analysis                         A132
                        Carboxylic acids              ,                    A133
                        Alcohols      •                                   A134
                        Phosphine                                       A136
                        Fluorine                                         A137
                        Gases — cyanogens and phosgene                   A138
                        Gases — mustards                                A139
                        Gases                                          A141
                        Acid chlorides                                     A144
                        Aflatoxins                                        A145
                        Brucine                                         A148
                        Citrus red No. 2                                   A149
                        Cycasin                                         A150
                        Ethylene oxide                                    A156
                        2-Fluoroacetamide                                A157
                        Lasiocarpine                          ,            A160
                        Phenacetin                                      A174
                        Strychnine                                       A180
                        Oximes                                         A183
                        Tris(1-aziridinyl)phosphinesulfide                      A190

                        Source: Arthur D. Little, Inc., "Sampling and Analysis Methods for
                              Hazardous Waste Combustion," EPA-600/8-84-002,
                              PB84-155845, February 1984.4
                                                        19

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VOST, as described in Section 3.3.3.2. The sorbent
tubes from  the VOST are  analyzed by thermal
desorption/gas chromatography/mass spectrometry as
described in the VOST Method 5040 in SW-846.6 Several
variations on the basic thermal desorption unit design
are available from vendors or may be constructed by the
analytical laboratory.  The desorption  unit  must be
leakand contamination-free, as  demonstrated by QC
sample performance. The laboratory must also have the
capability and experience to generate reliable standards
for quantitation.

VOST analyses require not only adequate facilities, but
also experience and good technique. A major potential
problem is the presence of background  compounds in
the samples as evidenced by the blank samples.  Back-
ground contamination can generally be traced to prob-
lems with  the trap cleanup, sample collection, or sample
handling (see Section 3.3.3.3). In addition, care must be
taken that the analysis step does not introduce contami-
nation. Cross contamination  from previous high-level
samples can be a problem. Contamination from ambient
air can also be a problem.

The VOST method  (5040  in SW-8466) indicates that
VOST is valid for compounds with a boiling point of less
than 100°C (and generally higher than 30°C) and should
be validated  prior to use outside this range. There is
Table 12.  Analytical Methods for Principal Organic Hazardous
         Constituents (POHCs) Given in SW-846
Description of analytical methods
                                            Analysis
                                             method
Gas chromatographlc methods (GC)
  Hatogenated volatile organics                        8010
  Nonhalogenated volatile organics                     8015
  Aromatic volatile organics ,                          8020
  Acrolein, acrylonitrile, acetbnitrile                     8030
  Phenols                                       8040
  Phthalate esters                                 8060
  Organochtorine pesticides and PCBs1                  8080
  Nilroaromatlcs and cyclic ketones                     8090
  Polynuclear aromatic hydrocarbons                   8100
  Chlorinated hydrocarbonsd                         8120
  Organophosphorus pesticides                       8140
  Chlorinated herbicides                             8150
Gas chromatographlc/mass spectroscopy methods (GC/MS)
  GC/MS method for volatile organics                   8240
  GC/MS method for semivolatile organics:
    Packed column technique                        8250
    Capillary column technique                       8270
  GC/MS method for PCDD/PCDP                     8280
H/p/i performance liquid chromatography (HPLC)
  HPLC — polynuclear aromatic hydrocarbons            8310

Source: US. Environmental Protection Agency/Office of Solid Waste,
      Washington, DC, "Test Methods for Evaluating Solid Waste:
      PhysicalfChemical Methods," SW-846, Third Edition,
      November 1986.«
• PCBs = polychforinated biphenyls
• PCDD = polychlorinated dibenzo-p-dioxins
 PCDF = polychlorinated dibenzofurans
occasionally a need to consider use of VOST for com-
pounds with boiling points in the 100° to 130° range. A
compound with a boiling point in this range may be diffi-
cult to purge from the VOST trap. The  validity of the
method for these POHCs should be determined prior to
testing; this can be done by using previous test data or by
validating the method using QA samples. For example,
the VOST protocol provides a QA procedure whereby the
sample traps are spiked with the compound  of interest
and analyzed to determine percent sample recovery.

One operational problem with VOST is sample overload
during the analysis. The objective of the VOST analysis is
to demonstrate a ORE of 99.99% or greater. The amount
of a POHC collected on the VOST  is dependent on both
the ORE and the amount fed into the incinerator. The
amount of POHC fed should be scaled to yield the POHC
at a concentration near the middle of the  GC/MS range,
assuming 99.99% ORE. Thus very low quantities from
the VOST trap indicate far greater than the required ORE,
and very high quantities indicate far  less than the
required ORE. High VOST analysis results may be above
the cutoff for the  ORE requirement. Depending on the
data-reporting requirements, precise quantitation of high
values may not be necessary if the 99.99% ORE require-
ment  is not met. In this case the VOST sample volume
and the calibration range of the analysis can be scaled to
demonstrate the 99.99% ORE with less concern about
quantitation  of values much greater or lower than the
regulatory target. The best approach for most  trial burns
is to scale the POHC feed rate to match the needed
collection on the  VOST.  If this is not possible, use a
second sampling method (i.e., bag sample) as a backup
in case the VOST samples saturate the GC/MS.

An option listed in EPA-600/8-84-0024 by which a sample
of stack gas is collected in a Tedlar bag (Method S011)
presents several problems with respect to the short hold-
ing times of  these  samples, as discussed  in Sec-
tion 3.3.2.3. If Tedlar bag samples are used to quantitate
high-level samples, a known volume of gas is pulled
through a clean VOST trap. The gas volume to be col-
lected on the trap is determined from an estimation of the
concentration  of the  POHC from the saturated peak
obtained in the analysis of the first VOST trap. The trial
burn plan must include appropriate QA measures to dem-
onstrate that field samples are valid for the holding times
and gas matrix actually encountered from  the test.

Semivolatile POHCs — The semivolatile POHCs are
sampled using a semi-VOST with an XAD-2 sorbent
module,  as  described in  Section 3.3.3.3. Nonvolatile
POHCs (boiling points above 300 °C) are also collected
by the semiVOST sampling train.

The semivolatile and nonvolatile  POHCs are generally
analyzed by extraction followed by GC/MS analysis. The
appropriate standard methods are cited in Tables 8,9,11,
and 12, and Appendix A. Tables 8  and 9  list the sample
preparation and introduction techniques.  Tables 11 and
                                                    20

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Table 13.  Analytical Methods for Inorganics
                    ADL              SW-846
                  method  Analysis   method  Analysis
Inorganics         number  method*   number  method*
Aluminum

Antimony


Arsenic


Barium


Beryllium


Boron
Cadmium


Calcium

Cobalt


Chromium

Hexavalent chromium1



Copper

Iron

Lead

!
Magnesium

Manganese

Mercury

Molybdenum


Nickel


Osmium


Phosphorus
Potassium

Selenium


Silicon
Silver


Sodium
.
Strontium


A021

A221


A222


A021
A223

A021
A224

A021
A021
A225

A021

A021


A021
A226
_
—
—
—
AQ21

A021

A021
A227

A021

A021

A228

A021


A021
A229

A021
A230

A021
A021

A231


A021
A021
A232

A021

A021
A233

ICAP

AAS, DAM
AAS, GFM

AAS, GFM
AAS, GH

ICAP
AAS, DAM
AAS, GFM
ICAP
AAS, DAM
AAS, GFM
ICAP
ICAP
AAS, DAM
AAS, GFM
ICAP

ICAP


ICAP
AAS, DAM
AAS, GFM
—
—
—
ICAP

ICAP

ICAP
AAS, DAM
AAS, GFM
ICAP

ICAP

'CV.AAS

ICAP


ICAP
AAS, DAM
AAS, GFM
ICAP
AAS, DAM
AAS, GFM
ICAP
ICAP

AAS, GFM
AAS, GH

ICAP
ICAP
AAS, DAM
AAS, GFM
ICAP

ICAP
AAS, DAM
AAS, GFM
6010
7020
6010
7040
7041
6010
7060
7061
6010
7080

6010
. 7090
7091
6010
6010
7130
7131
6010
7140
6010
7200
7201
6010
7190
7191
7195
7196
7197
7198
6010
7210
6010
7380
6010
7420
7421
6010
. 7450
6010
7460
7470
7471
6010
7480
7481
6010
7520

7550


V1U .
6010
7610
6010
7740
7741
6010
6010
7760
7761
6010
7770



ICAP
AAS, DAM
ICAP
AAS, DAM
AAS, GFM
ICAP
AAS, DAM
AAS.GH
ICAP
AAS, DAM

ICAP
AAS, DAM
AAS, GFM
ICAP
ICAP
AAS, DAM
AAS, GFM
ICAP
AAS, DAM
ICAP
AAS, DAM
AAS, GFM
ICAP
AAS, DAM
AAS, GFM
COPRTN
C
C/E
DPP
ICAP
AAS, DAM
ICAP
AAS, DAM
ICAP
AAS, DAM
AAS, GFM
ICAP
AAS, DAM
ICAP
AAS, DAM
CV.AAS.L
CV,AAS,S
ICAP
AAS, DAM
AAS, GFM
ICAP
AAS, DAM

AAS, DAM


_
ICAP
AAS, DAM
ICAP
AAS, GFM
AAS.GH
ICAP
ICAP
AAS, DAM
AAS, GFM
ICAP
AAS, DAM



     Table 13.  (continued)

                         ADL              SW-846
                       method  Analysis   method  Analysis
     Inorganics         number  method*   number  method*
Thallium


Thorium
Titanium
Vanadium


Zinc
A021
A234

A021
A021
A021
A235

A021
ICAP
AAS, DAM
AAS, GFM
ICAP
ICAP
ICAP
AAS, DAM
AAS, GFM
ICAP
6010
7840
7841
	
	
6010
7910
7911
6010
ICAP
AAS, DAM
AAS, GFM

' 	 , '
ICAP
AAS, DAM
AAS, GFM
ICAP
     Zirconium
     Anions
     Total cyanides

     Phosphides
     Sulfides
                                                                               A021
                                                                               A251
                                                                               A252
ICAP
 1C
TC
                                                                               A253   GC/FPD     —
                                                                                —       —      9030
                                           7950   AAS, DAM
                                                                                                 9010
                                                                                                 9012
     * ICAP      = inductively coupled argon plasma emission
                  spectroscopy
      AAS, DAM  = atomic absorption spectroscopy, direct aspiration
                  method
      AAS, GFM  = atomic absorption spectroscopy, graphite furnace
                  method
      AAS.GH   = atomic absorption spectroscopy, gaseous hydride
                  method
      COPRTN   = coprecipitation method
      CV, AAS   = cold vapor/atomic absorption spectroscopy
      CV, AAS, L  = cold vapor/atomic absorption spectroscopy, for
                  liquids.
      CV, AAS, S  = cold vapor/atomic absorption spectroscopy, for
                  solids
      C         = colorimetric method
      C/E       = chelation/extraction method
      T         = titration method
      1C        = ion chromatography               .
      GC/FPD   = gas chromatography/flame photometric detector
      DPP       = differential pulse polarography

    Sources: Arthur D. Little, Inc., "Sampling and Analysis Methods for
            Hazardous Waste Combustion," EPA-600/8-84-002,
            PB84-155845, February 1984."

            US.  Environmental Protection Agency/Office of Solid
            Waste, Washington, DC, "Test Methods for Evaluating Solid
            Waste: Physical/Chemical Methods," SW-846, Third
            Edition, November 1986.6
    • The methods listed for hexavalent chromium were developed for
    water samples.


    12 list applicable instrumental analysis methods. Appen-
    dix A lists  all of the  analysis  methods for the Appen-
    dix VIII hazardous constituents by compound or element
    in alphabetical order.

    Each semi-VOST sample returns to the laboratory in
    several  fractions which must be treated and ultimately
    combined to yield a full sample. Typically the fractions are
    (1) filter,  (2)  sorbent trap, (3) front-half organic rinse, (4)
    back-half organic rinse,  and (5) cqndensate from and
    rinses of impingers. The fractions are spiked with surro-
    gates,  extracted,  combined,  cleaned  up,  and then
    analyzed.

    Surrogate compounds are generally isotopically labeled
    (e.g., deuterated) analogs of the POHCs or similar com-
21

-------
pounds not found in the waste feed which can be spiked
into  the  samples to monitor recovery of the native
POHCs. Since several fractions must be extracted using
different techniques, surrogates may be split into groups
to monitor recovery of each extraction.


Table 14.  Analytical Methods for Stack Gas Samples
Sample
Analysis
parameter Analysis method
MS train
Filter, probe rinse
Water impingers
Caustic impinger
Multiple metals train
Seml-VOST
Filter, probe rinse
XAD-2
Condensate
VOST
Mylar gas bag
Tedlargasbag
Particulate
CI-(HCI)
CI-(HCI)
Metals
SV-POHCs
SV-POHCs
SV-POHCs
V-POHCs
C02,O2
V-POHCs
EPA Method 5"
Ion chromatography
or EPA 352.2=
Ion chromatography
or EPA 352.2=
See Table 13
See Appendix A
GC/MS
GC/MSperSW-846,
Method 5040
EPA Method 3b
Transfer to Tenax
trap and GC/MS
perSW-846,
Method 5040
 1 SV-POHCs = semivolatile and nonvolatile principal organic
             hazardous constituents
   V-POHCs = volatile principal organic hazardous constituents
 • Source: 40 CFR Part 60, Appendix A.7
 «Reference:" Methods for Chemical Analysis of Water and Wastes,"
          EPA-600/4-79-020, March 1979."


 The  filter and sorbent traps are generally Soxhlet-
 extracted  with dichloromethane (Method 3540), ben-
 zene, hexane, or other organic solvent. The organic rinse
 fractions are combined with the filter and sorbent trap
 extracts. The aqueous  fractions are extracted using
 liquid-liquid  partition in a separatory funnel (e.g., EPA
 Method 3510 using dichloromethane) or by continuous
 liquid-liquid extraction (e.g.,  EPA Method 3520 with dich-
 loromethane). A second extraction of aqueous fractions
 with methyl-t-butyl ether may be necessary when the
 POHC is a water-soluble compound (e.g., pyridine).

 The sample extracts are then evaporatively concentrated
 to the desired volume. Kuderna-Danish  evaporation and
 other techniques are described in the appropriate SW-
 846 extraction methods.

 A variety of adsorbent column and other cleanup meth-
 ods are available for cleanup of organic extracts prior to
 analysis. Several are listed in SW-846 (Section 4.2.2) and
 EPA-600/8-84-002 (P041-P045). The selection  of the
 sample cleanup technique is dependent on the type and
 concentration of the interferences. Prior experience with
the matrix or screening of the samples can help charac-
terize the interferences. For many trial burns with rela-
tively clean stack gases, no cleanup may be required. If
the POHC levels are low enough to require special mass
spectral  techniques,  such as selected ion monitoring,
cleanup is more likely to be required.

Implementation  of the extraction, concentration,  and
cleanup  methods requires not only the detailed written
methods and  appropriate reagents and materials, but
also qualified  personnel.  Effective  execution of these
methods, as measured by surrogate compound recover-
ies and the amount  of interferences,  comes only after
extensive training in general trace organic laboratory
methods and experience in the specific methods.

Although not  specifically required,  most laboratories
choose to analyze the extracts for POHCs by GC/MS.
The ability of this technique to  quantitate the POHCs
reliably makes it cost-effective relative to the additional
laboratory cleanup required for GC with other detectors.
In addition, there is a much greater chance of obtaining
higher than true values due to interferences with other
detectors, which can result in a reported ORE that is
lower than actual.

The GC/MS data must be interpreted both qualitatively
and quantitatively. Methods 8240,8250,8270, and other
applicable methods give general guidance on data inter-
pretation. Qualitative data interpretation entails matching
the retention  time and spectral characteristics of the
sample with the standards. The QA plan must specify
criteria on the retention time and spectral characteristics
(e.g., presence  of ions,  ion intensity ratios, etc.). The
 POHCs are quantitated by the internal standard method.
Specifically, the area of the unknown is ratioed to that of
the internal standard, multiplied by the amount of the
 internal  standard, and also multiplied by the response
factor for that compound relative to the internal standard.
The details of the quantitation must be specified in the
 trial burn plan including number  and levels of standards,
 analysis sequence, blanks, and repeat injections. In addi-
 tion, the trial burn plan should address contingencies for
 interferences, high level samples, samples  outside the
 standard curve, and other anticipated problems.

 For many high-efficiency incinerators, the  POHCs in the
 stack gas will be below the lower limit of  quantitation
 (LOQ) or even below the limit of detection (LOD). The trial
 burn plan should give the criteria for LOQ and LOD and
 should also state how samples in these ranges will be
 reported. Reporting  of low-level  numbers  can affect the
 calculation of the ORE and can  also cause confusion in
 the trial burn report review process.

 Data interpretation not only requires qualified and experi-
 enced personnel, but also time. Sufficient time must be
 allowed in the  analysis and reporting schedule for the
 data reduction.
                                                      22

-------
 Metals.— Analysis of stack gas samples for metals may
 be conducted during some trial burns and the applicable
 methods are listed in Table 13. The draft protocol for the
 multiple metals train discussed in Section 3.3.3.4 con-
 tains additional  information on analysis.  It employs a
 hydrofluoric acid/nitric  acid  digestion in microwave
 bombs for the probe rinse and filter samples resulting
 from stack sampling. It also offers an option of either a
 hydrofluoric acid/nitric  acid  digestion in microwave
 bombs or a nitric acid/hydrogen peroxide digestion on a
 hot plate for the impinger contents except the potassium
 permanganate impinger, which is analyzed for mercury
 only. An aliquot  of the other (combined) impinger con-
 tents is also reserved for  mercury analysis.

 3.4.6 Analysis of Other Effluent Streams
 In addition to the stack samples, samples from the other
 effluent streams  must be analyzed. Although not calcu-
 lated in the ORE, a quantitative analysis of the scrubber
water, ash residues, and other  residues is required by 40
 CFR, Part 270.62 for the purpose of estimating the fate of
 POHCs. This section addresses analysis of quench and
scrubber water  samples and ash  samples. Analysis
 methods for other effluent streams should be adaptable
from  similar waste  matrices, as described in  Sec-
tion 3.4.4.

General characterization (e.g., proximate analysis) and
inorganic analysis of the  water and ash samples can be
conducted using  the same methods used for waste feed
samples, as discussed in Section 3.4.4 and summarized
in Table 10.

3.4.6.1 Quench and Scrubber Water
For semivolatile analysis, water samples are  extracted
using liquidliquid  partition in a separatory funnel (Method
 3510 in SW-846 using dichloromethane) or continuous
 liquid-liquid  extraction (Method 3520 in SW-846 using
 dichloromethane). The sample extracts are then evapo-
 ratively concentrated to the desired volume. Kuderna-
 Danish evaporation and other techniques are described
 in the appropriate SW-846 extraction methods. If needed,
 a variety of adsorbent column and other cleanups are
 available for cleanup of organic extracts prior to analysis.
 Several are listed in SW-846 (Section 4.2.2) and EPA-
 600/8-84-002 (P041-P045). For many trial burns with rela-
 tively clean stack gas and thus clean scrubber water, no
 cleanup will be  required. Most laboratories choose to
 analyze the quench and scrubber water extracts by GC/
 MS. Methods 8250, 8270, and other applicable methods
 give general guidance on analysis of semivolatiles and
 data interpretation. For volatile POHCs, the samples are
 prepared for and analyzed by purge and trap using the A.
 D. Little A101 series methods or  the SW-846 Methods
 5030 (preparation) and 8240 (analysis). Section 3.4.5.4.2
 addresses the GC/MS analysis in more detail.

 3.4.6.2 Ash Samples
 To determine semivolatile POHCs in ash samples, the
 samples  are Soxhletextracted using dichloromethane
 (Method 3540  in SW-846),  benzene, hexane, or other
 organic solvent. The sample extracts are then evapora-
 tively concentrated to the desired volume, cleaned up,
 and analyzed by GC/MS as described for the water sam-
 ples in the  preceding section. To determine volatile
 POHCs in ash  samples, the samples are prepared in a
tetraglyme dispersion (Method 5030 in SW-846, A101C
 in EPA-600/8-84-002) and then analyzed by purge and
trap.
                                                  23

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                                                Section 4
                               Quality Assurance/Quality Control
 4.1 Data Quality Objectives

 The  subject of  data quality objectives (DQOs) has
 recently been addressed by the Quality Assurance Man-
 agement Staff (QAMS) of EPA in a publication entitled
 Development of Data Quality Objectives: Description of
 Stages I and /A16 This document describes an approach
 to designing environmental data collection programs
 based on the development of DQOs which is intended to
 define  the quality  of the data  needed to achieve an
 acceptable  level of confidence and provide adequate
 information to make regulatory decisions and recommen-
 dations. The DQO process provides a logical, objective,
 and quantitative  framework for finding an appropriate
 balance between the time and resources  that will be
 used to collect data and the quality of the data needed to
 make the decision.

 Data quality objectives are statements of  the level  of
 uncertainty that a decision maker is willing  to accept in
 results derived  from environmental data, when the
 results  are going to be used in a regulatory or program-
 matic decision.  These quantitative DQOs must  be
 accompanied by clear statements of:

 •  The decision to be made.
 •  Why  environmental data are needed and how they will
   be used.

 •  Time and resource constraints on data collection.
 *  Descriptions  of the environmental  data to be
   collected.

 •  Specifications regarding the domain of the decision.
 •  The calculations,  statistical or otherwise,  that will be
   performed on the  data in order to. arrive at a result.
 Once DQOs have been  developed and a design for the
 data collection activity expected to achieve these objec-
tives has been selected,  DQOs are used to define quality
assurance (QA) and quality control (QC) programs that
are specifically tailored  to the data collection program
being initiated. A QA Project Plan is prepared document-
ing all of the activities needed to ensure that the data
collection  program  will produce  environmental data, of
the type and quality required to satisfy the DQOs. With-
out first developing  DQOs, a QA program can only be
used to document the quality of data obtained, rather
 than to ensure that the quality of data obtained will be
 sufficient to support an Agency decision. This approach
 to DQOs is recommended when planning QA for an
 RCRA trial burn.

 4.2 General Discussion of QA Project Plan

 The quality assurance/quality  control  (QA/QC) proce-
 dures for the process monitoring, sampling, and analyti-
 cal activities for a trial burn and the continuing operation
 of a hazardous waste incinerator must be included in a
 quality assurance (QA) project plan which accompanies
 the permit application. The QA plan should be based on
 the guidelines document issued by the Office of Monitor-
 ing Systems  and Quality Assurance  of  EPA  entitled
 Interim Guidelines and Specifications for Preparing Qual-
 ity Assurance Project P/ans.1? The document has identi-
 fied 16 essential elements of a QA plan, which are shown
 in Table 15.


 Table 15.  Essential Elements of a QA Project Plan
 1. Title Page
 2. Table of Contents
 3. Project Description
 4. Project Organization and Responsibility
 5. QA Objectives
 6. Sampling Procedures
 7. Sample Custody
 8. Calibration Procedures and Frequency
 9. Analytical Procedures
 10. Data Reduction, Validation, and Reporting
 11. Internal Quality Control Checks
 12. Performance and Systems Audits
 13. Preventative Maintenance
 14. Specific Routine Procedures Used to Assess Data Precision,
   Accuracy, and Completeness
 15. Corrective Action
 16. Quality Assurance Reports to Management

Source: U.S. Environmental Protection Agency/Office of Monitoring
      Systems and Quality Assurance, Office of Research and
      Development, Washington, D.C., "Interim Guidelines and
      Specifications for Preparing Quality Assurance Project  -
      Plans," QAMS-005/80 (December 29,1980)."
                                                    25

-------
A QA plan prepared for a trial burn must contain specific
QA/QC procedures for the process monitoring, sampling,
and analytical activities identified in the trial burn plan
and permit application. The plan should contain suffic-
ient detail to allow the permit writer to assess the ade-
quacy of the QA/QC procedures that will be used.

The discussion that follows first presents a general dis-
cussion of the 16 elements required in a QA plan and
then discusses specific guidance for assessing precision
and accuracy for individual  measurement methods.

4.2.1 Title Page
The title page of the QA plan must be signed by approv-
ing personnel. The plan must be approved by the project
leaders immediate supervisor and the quality assurance
manager (QAM). If the QA plan is prepared by a subcon-
tractor to the permit applicant, the title page should also
contain the approving signatures of the subcontractor's
program manager and QAM.

4.2.2 Table of Contents
The table of contents should list the introduction, the 16
essential elements of the QA plan,  and any appendices
attached to the plan (such  as standard operating proce-
dures, etc.).

4.2.3 Project Description
The project description is presented in detail in  the per-
mit application. In the QA plan, a brief summary of the
project description should  be provided and reference to
the applicable section(s) of the permit application should
be made. The summary should, however, provide suffic-
ient detail so that the reviewer of the QA plan can under-
stand the important elements of the  project plan.

4.2.4 Project Organization and Responsibility
The project organization responsible for all QA/QC activ-
ities should be provided in  an organization chart that
gives the names, titles, and line authority of the individ-
uals. The resumes and QA/QC  responsibilities for each
individual in the organization should  be provided. This
organization should include the following:

•  Project leader
•  Quality assurance manager (QAM)

•  Field sampling task leader
•  Field sampling quality control coordinator
•  Analytical task leader
•  Analytical quality control coordinator
•  Quality control and data manager
•  Data analysis task leader
4.2.5 QA Objectives
The primary QA objective for any project is to ensure that
the measurement data collected are precise, accurate,
complete, and representative. This section of the QA plan
should give specific precision, accuracy, and complete-
ness objectives for each process measurement and anal-
ysis performance. Guidance for precision, accuracy, and
completeness objectives for specific measurement
parameters is given in Section 4.3.

The terms precision, accuracy, completeness, and repre-
sentativeness may be defined as follows:

•  Precision  is the degree of agreement between
   repeated measurements of one property using the
   same method or technique and  is usually expressed
   as a range percent  (R%) for a small number of data
   points (2 < n  < 8) or as percent relative standard
   deviation (%RSD) for a large (n  > 8) number of data
   points.
•  Accuracy is the degree of agreement of a measure-
   ment (or average of measurements of the same thing),
   X, with an accepted reference or true value, T, usually
   expressed  as percent accuracy  (%A) defined as X/T
   (X100).
•  Completeness is a measure of the amount of valid data
   obtained from a measurement  system  compared to
   the amount of data collected that was expected, usu-
   ally expressed as a percent.   |
•  Representativeness  expresses the degree to which
   measurement data and samples precisely, accurately,
   and completely characterize the  process conditions.
4.2.6 Sampling Procedures
The sampling procedures to be used in the trial burn and
continuing operation of the  incinerator should be speci-
fied in the trial burn plan and permit application. Sam-
pling procedures should include the sampling methods,
sampling  locations, sampling  frequencies,  sampling
equipment, and datarecording methods.  All forms for
recording sampling data should be given.

The QA plan should present  any  details  necessary to
describe the sampling procedures that are not given in
the trial burn plan and  permit application. Particular
attention should be given to any anticipated deviations
from referenced sampling methods.

4.2.7 Sample Custody
Two procedures can be used to document sample cus-
tody  for a trial burn:  traceability  and chain-of-custody.
Traceability procedures are  acceptable to EPA and
should be used unless litigation is anticipated, in which
.case the applicant may select the more rigorous chain-of-
custody procedures.

The QA plan should describe all of the elements of sam-
ple traceability including  sample labeling, preservation,
packing, shipping, and laboratory  receiving and storage
procedures. All documentation and record-keeping forms
such as field sampling traceability forms,  field logbook,
sample analysis request sheet, laboratory  traceability
forms, and laboratory logbook should be described. Stor-
                                                    26

-------
 age of samples after analysis must also be addressed.

 If the chain-of-custody procedure will  be used, then a
 complete description of the procedure  must be given in
 the QA plan. Chain-of-custody procedures acceptable to
 EPA are fully described in SW-846, Section 1.3.6

 4.2.8 Calibration Procedures and Frequency
 The calibration procedures for all monitoring and sam-
 pling equipment to be calibrated should be specifically
 defined. For each piece of equipment,  the calibration
 technique, reference standard(s), acceptance limits, and
 frequency of calibration should be specified.

 Calibration of analytical instruments is  usually specified
 in the reference methods. If the analytical methods do not
 specify calibration  procedures or deviations  from  the
 methods are anticipated, the calibration  procedures must
 be fully described. The calibration standards, calibration
 curves, average response factors,  and/or  relative
 response factors to be used for each  instrument and
 analysis should be specified. The methods for recording
 and storing calibration data should be given.

 4.2.9 Analytical Procedures

 The analytical procedures to be used to analyze samples
 collected  should be specified in the trial burn plan and
 permit application. Analytical  procedures should include
 the analytical methods, instrumentation and equipment,
 and data-recording methods. All forms to be  used for
 recording analytical data should be given.

 The QA plan should provide any details necessary to
 describe the analytical procedures that are not given in
 the trial burn plan and permit application. Particular
 attention should be given to any anticipated deviations
 from referenced procedures and methods.

 4.2.10 Data Reduction, Validation, and Reporting
 All procedures for the reduction of monitoring, sampling,
 and analytical data collected should be  specified. Equa-
 tions, calculations,  and conversion factors should  be
 given for determining specific results to be reported, such
 as stack  emissions, waste feed concentrations, etc.
 Methods used to obtain and reduce analytical data, such
 as method internal standards, recovery internal stan-
 dards, relative  response factors, and  qualitative and
 quantitative peak identification, should be given.

 Procedures to validate the integrity and quality of the
data acquired through readings, interpretations, and cal-
culations should be specified. Some examples of data
validation  procedures are:

a. Verification by the analytical task leader that all raw
   data gen erated have been properly stored.

b. Examination of at least 5% of the raw data (e.g., chro-
   matograms) by the analytical task leader and analyti-
   cal QCC to verify adequacy of documentation, confirm
   peak shape  and resolution, ensure computer was
   sensing peaks appropriately, etc.

 c. Confirmation that raw areas for internal standards and
   calibration standards and raw and relative areas for
   surrogate compounds  are within  acceptable limits
   around the expected value.

 d. Verification that all  associated  blank, standard, and
   QC data are reported along with  analytical results.

 e. Examination of all field data forms by the field sam-
   pling task leader and field sampling QCC.

 f. Verification  of all calculations for one test run by a
   second reviewer.

 The test results and operating parameters to be reported
 should be specified in a table including the units (e.g., Ib/
 h) for each parameter. All documentation (e.g., field data
 sheets, calculations, GC/MS printouts, etc.) that  will be
 delivered with the reported results should be identified*

 4.2.11 Internal Quality Control Checks
 All internal quality control methods should be described
 for monitoring, sampling, and analysis activities. Internal
 quality controls serve to document the validity of the data
 obtained and to control the quality of the data as it is
 being generated.

 Items which should be included in the QA plan as internal
 quality control checks include the following:

 • Calibration standards and devices
 • Zero/span gases
 • Audit gas cylinders
 • Blank samples
   — Field trip blanks
   — Field equipment blanks
   — Method blanks       ^
   — Reagent and solvent blanks
 « Method internal standards
 • Recovery internal standards
 • Spiked blanks
 • Spiked samples
 •  Replicate analyses
 •  Matrix/spike duplicate analyses
 • Surrogates
 • Calibration checks

4.2.12 Performance and Systems  Audits
The QA plan should describe the types of performance
and  systems audits that  will occur  and  identify the
responsible individuals. Performance of equipment and
personnel should be audited periodically by the project
leader, field sampling leader, analytical task leader, the
                                                    27

-------
quality assurance officer, and the quality control coordi-
nators. Systems audits should also be performed periodi-
cally on monitoring systems, sampling, and analytical
systems.

4.2.13 Preventive Maintenance
The frequency and types of scheduled preventive main-
tenance procedures used for process monitoring equip-
ment, sampling  equipment,  and analytical equipment
and instrumentation should be given in the QA plan. In
addition, any  nonscheduled maintenance procedures
which may occur when troubleshooting should be pro-
vided.  It is desirable that the  preventive maintenance
procedures be described in  standard operating  proce-
dure (SOP) manuals for the various types of equipment
used.

Logbooks for maintenance performed by field sampling
and laboratory personnel should  be maintained.  Equip-
ment logbooks should also be kept for maintenance per-
fowned by internal service  departments and outside
service departments.

4.2.14 Specific Routine Procedures Used to Assess
       Data Precision, Accuracy, and Completeness
The specific procedures that will  be used to assess the
precision and  accuracy of measurement data on a rou-
tine basis must be given. The procedures should include
equations to calculate precision and accuracy. Examples
are given below.

4.2.14.1 Precision
For data sets with a small number of points (2 < n < 8),
the estimate  of precision can be expressed as range
percent (R%):
                               n-1
For large data sets (n > 8), the estimate of precision can
be expressed as percent relative  standard  deviation
(%RSD):
Standard deviation (SD) =


0/oRDg - 100°/o_x SD
               C
The methods for determining how precision will be deter-
mined for each measurement parameter should  be
given.

4.2.14.2 Accuracy
Accuracy can be determined for process monitors and
analyses from performance and audit samples (i.e., stan-
dards supplied as blind audits by the QCC to determine
percent accuracy [A°/o]); for analyses as percent recov-
ery (R%)  of native analytes from  blanks spiked with
native analytes prior to sample preparation; and for anal-
yses as percent recovery of internal standards (RS%)
spiked prior to sample preparation. Example  equations
for accuracy calculations are given below.

For performance samples:

AO/O _ Amount found  x 100
        True value

For samples spiked with native analyte:
_„,   n Amount calculated-native amount prior to spiking   100
H°/0 = y _	.	•	•	  X 	
    ._            Amount spiked             in
                                                       Rs% =
where: C, = highest value determined

       C2 = lowest value determined

       C = mean value of the set

and

_   n  C
C=Z   n1
    i = 1

where: C, = ith determination
      *
       n = number of determinations
      n Amount calculated - amounk of internal standard spiked   100
     ._       Amount of internal standard spiked        i   n
4.2.15 Corrective Action
Corrective action procedures thsit will be taken if prob-
lems are  detected during system audits, performance
audits, and data collection; if data are lost; or if significant
QA problems develop which must be described in the QA
plan. The individuals responsible for initiating corrective
action procedures should be identified and the methods
for reporting corrective actions should be described.

4.2,16 Quality Assurance Reports to Management
The quality control coordinators, in cooperation with the
project leader, analytical task leader, field sampling task
leader, and data analysis task leader should inspect criti-
cal areas of the project requiring QA/QC activities. The
inspections should include a review, where applicable, of
the following:
                                                    28

-------
 •  Staff qualifications
 •  Equipment calibration and maintenance records
 •  Instrument performance
 •  Protocol adherence
 •  Sample custody
 •  Document control
 •  Data entry including error handling, correction, and
   additions
 •  Data traceability and completeness
 •  Data calculation and validation
 •  Internal QC data
 •  External QA data
 •  Data accuracy, precision, and completeness
 The results of inspections/audits should be reported by
 the QAM to the project leader and corporate manage-
 ment; summaries should be included in the final report.

 The QCCs should independently maintain a QA file  for
 the project. At the end of the project, the QA project file
 should be turned over to the QA manager.
        •                                     ••
 4.3 Guidance for Precision and Accuracy
     Objectives
 The quality assurance objective of any project is to pro-
 vide reliable data for documenting the performance of the
 incinerator.

 Specific precision and accuracy objectives for general
 analytical procedures are given in Table 16. Objectives
 for semivolatile POHCs are goals recommended by EPA
 in  the  publication Sampling  and Analysis Methods for
Hazardous Waste Combustion.4 Objectives for chlorine
and hydrogen chloride are estimated from past analysis
of similar types of samples.
Quality assurance objectives for completeness and rep-
resentativeness should be determined  from the data
quality objectives (DQOs)  and should reflect specific
requirements of the project.

Table 16.  Summary of Precision and Accuracy Objectives
                                          Accuracy"
Parameter
Semivolatile POHC











Volatile POHC







Chlorine




Hydrogen chloride
Matrix
Stack emissions
XAD-2
Filter
Water
Front-half rinse
Back-half rinse
Aqueous waste
Sludge
Solid waste
Scrubber water
Ash/residual
Organic liquid
VOST traps
(stack emissions)
Aqueous waste
Sludge
Solid waste
Scrubber water
Organic liquid
waste
Aqueous waste
Sludge
Solid waste
Organic liquid
waste
KOH solution
Precision*
(range %
or % RSD)
<30





<30
<30
< 30
<30
< 30
< 30
<50

<30
<30
<30
< 30

<30
< 10
< 10
<10

< 10
15
mean
recovery
(%)
>50





>70
>50
>50
>70
>50
' > 70
50-150%''

NAC
NA
NA
NA

NA
NA
NA
NA

NA
100 * 15
• Procedures for assessing precision are presented in Section 4.2.14.
' Procedures for assessing accuracy are presented in Section 4.2.14.
c Not available.
                                                   29

-------

-------
                                            Section 5
                                          References
 1. Midwest Research Institute, Practical Guide — Trial
   Burns for Hazardous Waste Incinerators, EPA-600/2-
   86/050, NTIS PB86-190246, April 1986.

 2. "Guidelines for Data Acquisition and Data Quality
   Evaluation in Environmental Chemistry," Analytical
   Chemistry, 52(14):2242-2249, December 1980.

 3. US.  Environmental  Protection  Agency, Guidance
   Manual for Hazardous Waste Incinerator Permits, SW-
   966, NTIS PB84-100577,  Office of Solid Waste,
   Washington, D.C., 1983.

 4. Arthur D. Little, Inc., Sampling and Analysis Methods
   for Hazardous Waste Combustion, EPA-600/8-84-
   002, NTIS PB84-155845, February 1984 (new edition
   expected in 1989).

 5. Complete Temperature Measurement Handbook and
   Encyclopedia, Omega Engineering, Inc., 1986.

 6. U.S. Environmental Protection Agency, Test Methods
   for Evaluating Solid  Waste — Physical/Chemical
   Methods, SW-846, Third Edition,  Office of Solid
   Waste and Emergency Response, Washington, D.C.,
   November 1986.

 7.  Code of Federal Regulations, Revised as of July 1,
   1985.

8. American Society for Testing Materials, Annual Book
  of ASTM Standards,  Philadelphia, Pennsylvania,
  Annual Series.

9. U.S. Environmental Protection  Agency, Protocol for
  the Collection and Analysis of Volatile POHCs Using
   VOST, EPA-600/8-84-007, NTIS  PB84-170042, March
   1984.
10. US. Environmental Protection Agency, Validation of
    the Volatile Organic Sampling Train (VOST) Protocol,
    EPA-600/4-86-014,  NTIS  PB86-145547 (Vol. 1),
    PB86-145554(Vol. 2), Environmental Monitoring Sys-
    tems Laboratory, 2 Volumes, January 1986.

11. "Performance Audit Results for Volatile POHC Mea-
    surements," JAPCA, Vol. 38, No. 6, June 1988.

12. Federal Register, Volume 45, No. 114, Wednesday,
    June 11,1980.

13. US. Environmental  Protection  Agency, Modified
    Method 5 Train and Source Assessment Sampling
    System Operator's Manual, EPA-600/8-85-003, NTIS
    PB85-169878, February 1985.

14. Radian Corporation, Laboratory and Field Evaluation
    of the Semi-VOST (Semi-Volatile  Organic Sampling
    Train) Method, EPA-600/4-85-075,  NTIS  PB86-
    123551, Environmental Monitoring Systems Labora-
    tory, 2 Volumes, November 1985.

15. US. Environmental Protection Agency, Methods for
    Chemical Analysis of Water and Wastes, EPA-600/4-
    79-020, NTIS PB297686, March 1979.

16. US. Environmental Protection Agency, Development
   of Data  Quality Objectives:  Description of Stages I
   and II, Quality Assurance Management Staff, July 16,
    1986.

17. US. Environmental Protection Agency, Interim Guide-
   lines and Specifications  for Preparing  Quality
   Assurance Project Plans, Office of Monitoring Sys-
   tems and Quality Assurance, QAMS-005/80, Decem-
   ber 29,1980.
                                                31

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-------
                  Appendix A
   Analysis Methods for Appendix Vill Hazardous
Constituents Given in EPA-600/8-84-002 and SW-846
Analysis Methods for Appendix Vill Hazardous Constitutents
EPA-600/8-84-002 SW-846
Compound Method No.* Method No."
Acetonitrile
Acetophenone
3-(a-Acetonylbenzyl)-4-hydroxy-coumarin and salts (Warfarin)
2-Acetylaminofluorene
Acetyl chloride
1-Acetyl-2-thiourea
Arcolein
Acrylamide
Acrylonitrile
Aflatoxins
Aldrin
Allyl alcohol
Aluminum phosphide
4-Aminobiphenyl
6-Amino-l,la,2,8,8a,8b-hexahydro-8-(hydroxymethyl)-8a-
methoxy-5-methylcarbamate azirino[2 ' ,3 ' : 3,4]pyrrolo
[1,2-a]indole-4,7-dione(ester) (Mitomycin C)
5-(Aminomethyl)-3-isoxazolol
Amitrole
Aniline '
Antimony and compounds, N.O.S.
Aramite
Arsenic and compounds, N.O.S.
Arsenic acid
Arsenic pentoxide
Arsenic trioxide
Auramine
Azaserine
Barium and compounds, N.O.S.
Barium cyanide

Benz(c)acridine
Benz(c)anthracene
Benzene
Benzene, 2-amino-1-methyl
Benzene, 4-amino-1-methyl
Benzenearsonio acid
Benzene, dichloromethyl-
Benzenethiol
Benzidine
Benzo(b)fluoranthene
Benzo(j)fluoranthene
Benzo(a)pyrene
p-Benzoquinone
Benzotrichloride
Benzyl chloride
Beryllium and compounds, N.O.S.
A101
A121
A122
A121
A144
A123
A101
A101
A101
A145
A121
A134
A253
A121
A122


A121
A121
A121
A221
A121
A222
A222
A222
A222
A121
A123
A223
A223
A252
A121
A121
A101

	
A222
A121
A121
A121
A121
A121
A121
A121
A121
A121
A224
8030, 8240
8250
8250
8250
*
8250
8030, 8240
8015, 8240
8030, 8240
8250
8080, 8250
8240

8250



8250
8250
8250
7040, 7041
8250
7060, 7061
7060, 7061
7060, 7061
7060,7061
8250
*
7080, 7081
7080
9010
8250
8100, 8250, 8310
8020, 8240
*
*
7060,7061
8120,8250
8250
8250
8100, 8250, 8310
8100, 8250, 8310
8100, 8250, 8310
8250
8120, 8250
8010, 8120, 8250
Compound
Type'
V
sv
sv
sv;
V
sv
V
V
V
* .
. sv
v
s
sv
sv


sv -
sv
sv
M
sv
M
M
M
M
SV
SV
M
M
CN
SV
SV
V


M
SV
SV
sv
sv
sv
sv
sv
sv
sv
'~M
Analysis
Method"
GC, GC/MS
GC/MS
HPLC, GC/MS
GC/MS
GC/MS
HPLC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
HPLC, GC/MS
GC, GC/MS
GC/MS
GC/FPD
GC/MS
HPLC


GC/MS
GC/MS
GC/MS
AAS
GC/MS
AAS
AAS
AAS
AAS
GC/MS
HPLC
ICAPAAS
ICAP.AAS
T, C
GC/MS
GC, GC/MS
GC, GC/MS


AAS
GC, GC/MS
GC/MS
GC/MS
GC, GC/MS
GC, GC/MS
GC, GG/MS
GC/MS
GC, GC/MS
GC, GC/MS
ICAPAAS
                     33

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Analysis Methods for Appendix VIII Hazardous Constltutents (continued)
EPA-600/8-84-002 SW-846 Compound Analysis
Compound Method No.' Method No." Type' Method"
Bis{2-ch!oroethoxy)methane
Bis(2-chtoroethyl)ether
N,N-Bis{2-chloroethyl)-2-naphthyl-amine
Bis(2-chloroisopropyl) ether
Bis{chtoromethyl) ether
Bis(2-othylhexyl) phthalate
Bromoacetone
Bromomethane
4-Bromophenyl phonyl ether
Bfucine
2-Butanono peroxide
Butyl benzyl phthallde
2-sec-Bulyl-4,6-dlnitrophenol (DNBP)
Cadmium and compounds, N.O.S.
Calcium chromate
Calcium cyanide
Carbon disulfide

Carbon oxylluorlde
Chloral (as hydrate)
Chtorambucil
Chlordane (a and Y isomers)
Chlorinated benzenes, N.O.S.
Chlorinated ethane, N.O.S.
Chlorinated (luorocarbons, N.O.S.
Chlorinated naphthalene, N.O.S.
Chlorinated phenol, N.O.S.
Chloroacetaldehyde
Chloroalkyl ethers, N.O.S.
p-Chloroaniline
Chlorobenzene
Chtorobenzilate
p-Chtoro-m-cresol

1-Chtoro-2,3-epoxypropane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
Chloromethyl methyl ether
2-Chloronaphlhalene
2-Chlorophenol

Chloropreno
1-{c-Crilorophenyl)thiourea
3-Chtoropropene
3-Chloroproptonitnle
Chromium and compounds, N.O.S.

Chrysene
Citrus Red No. 2
Coal tars
Copper cyanide
Creosote
Cresols
Crotonatdehyde

Cyanides (soluble salts and complexes), N.O.S.
Cyanogen
Cyanogen bromide
Cyanogen chloride
Cycasin
2-Cyclohexyl-4,6-dinitrophenol
Cyclophosphamide
Oaunomycin
ODD
DDE
DDT
Diallate
A121
A121
A121
A121
A121
A121
A101
A101
A121
A148
A121
A121
A121
A225
A226
A252
A101
A141
A101
A131
A122
A121
A101
A121
A101
A101
A121
A121
A131
A101
A121
A101
A121
A121
A122
A101
A101
A101
A101
A101
A121
A121
A122
—
A123
—
A121
-A226

A121
A149
A121
A252
A121
A121
A123
A131
A252
A138
A138
A138
A150
A121
—
A122
A121
A121
A121
A121
8010, 8240, 8250
8010, 8240, 8250
A
8010, 8240, 8250
8010, 8250
8060, 8250

8010, 8240
8250
8250
8250
8060, 8250
8040, 8250
7130, 7131
7190, 7191
9010
8015, 8240

It
8010,8240
*
8080, 8250
8010, 8240
8020,8250
8010,8240
*
8120, 8250
8040, 8250
8010, 8240
*
* '
8020, 8240
*
8040, 8250

*
8010, 8240
8010, 8240
8010, 8240
8010
8120, 8250
8040, 8250

*
*
*
8250
7190, 7191, 7195,
7196, 7197
8100, 8250, 8310
*
#
9010
8100, 8250
8040, 8250
*

9010
9010
9010
9010

8040, 8250
—
*
8080, 8250
8080, 8250
8080, 8250
*
to co co co co co •
V
V
iSV
SV
SV
SV
SV
M
M
CN
V
G
V
V
SV
SV
V
SV
V
V
SV
SV
V
V
SV
V
SV
sv
sv
V
V
V
V
V
sv
sv
sv

sv

sv
M

sv
sv
sv
CN
sv
sv
sv
sv
CN
G
G
G

SV

SV
SV
sv
sv
sv
GC, GC/MS
GC, GC/MS
GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
S>/^/k JO
GC/MS
GC, GC/MS
GC/MS
GC/FID, HPLC
GC/MS
GC, GC/MS
GC, GC/MS
ICAPAAS
ICAP.AAS
ICART, C
GC/MS
GC/TCD
GC/MS
GC, GC/MS,
HPLC
HPLC
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS,
HPLC
GC/MS
GC/MS
GC, GC/MS
GC/MS
GC, GC/MS
HPLC
GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
HPLC

HPLC

GC/MS
ICAPAAS

GC, GC/MS
HPLC
GC/MS
T,C
GC, GC/MS
GC, GC/MS
HPLC
GC/MS
. • T,C
GC/TCD, T-C
GC/TCD, T, C
GC/TCD, T, C

GC, GC/MS

HPLC
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC/MS
34

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Analysis Methods for Appendix VIII Hazardous Constitutents (continued)
EPA-600/8-84-002 SW-846
Compound Method No.' Method No."
Dibenz(a,h)acridine
Dibenz(a,j)acridine
Dibenz(a,h)anthracene
7H-Dibenzo(c,g)carbazole
Dibenzo(a,e)pyrene
Dibenzo(a,h)pyrene
Dibenzo(a,i)pyrene
1,2-Dibromo-3-chloropropane
1,2-Dibromoethane
Dibromomethane
Di-n-butyl phthalate
Dichlorobenzene (meta, ortho and para isomers)

Dichlorobenzene, N.O.S.

3,3 ' -Dichlorobenzidine
1 ,4-Dichloro-2-butene
Dichlorodifluoromethane
1,1-Dichloroethane
1,2-Dichloroethane
trans-1,2-Dichloroethene
Dichloroethylene, N.O.S.
1 ,1-Dichloroethylene
Dichloromethane
2,4-Dichlorophenol :.

2,6-Dichlorophenol

2,4-Dichlorophenoxyacetic acid


Dichlorophenylarsine
Dichloropropane, N.O.S.
1 ,2-Dichloropropane
Dichloropropanol, N.O.S.
Dichlpropropene, N.O.S.
1 ,3-Dichloropropene
Dieldrin
1 ,2:3,4-Diepoxybutane
Diethylarsine
N,N-Diethylhydrazine
0,0-Diethyl S-methyl ester of phosphorodithioic acid
0,0-Diethylphosphoric acid, 0-p-nitrophenyl ester
Diethyl phthalate
0,0-Diethyl 0-2-pyrazinyl phosphorothioate
Diethylstilbestrol
Dihydrosafrole
3,4-Dihydroxy-a-(rnethylamino)methyl
benzyl alcohol [Epinephrine]
Diisopropylfluorophosphate (DFP)
Dimethoate
3-,3 ' -Dimethoxybenzidine
p-Dimethylaminoazobenzene
7,12-Dimethylbenz(a)anthracene.
3,3 ' -Dimethylbenzidine
Dimethylcarbamoyl chloride
1,1-Dimethylhydrazine
1,2-Dimethylhydrazine
3,3-Dimethyl-1-(methylthio)-2-butanone,0-((methylamirio)
carbonyljoxime [Thiofanox]
a.a-Dimethylphenetriylamine
2,4-Dimethylphenol - -
Dimethyl phthalate
Dimethyl sulfate
Dinitrobenzene, N.O.S.
4,6-Dinitro-o-cres'ol (and salts)

2,4-Dinitrophenol • •

2,4-Dinitrotoluene
2,6-Dinitrotoluene
A121
A121
A121
A121
A121
A121
A121
A101
A101
A101
A121
A101
A121
A101
A121
A121
A101
A101
A101
A101
A101
A101
A101
A101
A121
A122
A121
A122
A122

A133
A222
A101
A101
A121
A101
A101
A121
A121
A222
A121
A121
A121
A121
A121
A123
A121
A123

A121
A121
A121
A121
A121
A121
A144
A121
A121
A183

A121
A121
A121
A121
A121
A121
A122
A121
A122
A121
A121
8100
8100
8100, 8310, 8250
8100
8100
8100
8100
8010, 8240
8010, 8240
8010, 8240
8060, 8250
8010,8120
8250
8010, 8120
8250
8250
8010, 8240
8010
8010, 8240
8010, 8240
8010, 8240
8010
8010
8010, 8240
8040, 8250

8040, 8250

8150, 8250


7060, 7061
8010, 8240
8010, 8240
8120, 8250
8240
8240
8080
* ' ,
7060/7061
*
8250
8250
8060, 8250
8250

*
*

*
8140
*
*
*
*
*
*
*
*

»
8040, 8250
8060, 8250
8250
8090, 8250
8040, 8250

8040, 8250

8090, 8250
8090, 8250
Compound Analysis
Type0 Method"
SV
sv
SV
sv
sv
sv
sv
V
V
V
sv
V
sv
V
sv
sv
V
V
V
V
V
V
V
V
sv
sv
sv
sv
sv

sv
M
V
V
sv
V
V
sv
sv
M
sv
sv
sv
sv
sv
sv
sv
sv

sv
sv
sv
sv
sv
sv

sv
sv


sv
sv
sv
sv
sv
sv
sv
sv
sv
sv
sv
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC.GC/MS
GC/MS -
GC, GC/MS
GC/MS
GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
HPLC
GC, GC/MS
HPLC
GC, GC/MS,
HPLC
GC/MS
AAS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC/MS
GC/MS
GC, GC/MS
GC/MS
AAS
GC/MS
GC/MS
GC/MS
GC, GC/MS •
GC/MS
HPLC
GC/MS
HPLC

GC/MS
GC, GC/MS
GC/MS
GC/MS
GC/MS
' GC/MS

GC/MS
. GC/MS
GC/FPD

GC/MS
GC, GC/MS
GC, GC/MS
GC/MS
GC, GC/MS
GC, GC/MS
HPLC
GC, GC/MS
HPLC '
GC, GC/MS
GC, GC/MS
35

-------
Analysis Methods for Appendix VIII Hazardous Constitutents (continued)
Compound
Dl-n-octyl phthalate
1,4-Dioxane
Diphenylamine
1,2-Diphenylhydrazine
Di-n-propylnitrosamine
Disulfoton
2,4-Dithiobiuret
Endosulfan
Endrin (and metabolites)
Ethyl carbamate
Ethyl cyanide
Ethyleneblsdithiocarbamic acid (salts and esters)
Ethylenelmine
Ethyfene oxide
Ethyfene thiourea
Ethyl methacrylate
Ethyl methanesulfonate
Fluoranthene
Fluorine
2-Fluoroacetamide
Fltioroacatic acid, sodium salt
Formaldehyde
Formic acid


Qlycldylatdehyde
Hatomethane, N.O.S.
Heptachlor
Heptachlor epoxlde (a, p, and y isomers)
Hexachtorobenzcno
Hexachlorobutadiene
Hexachtorocyclohexane (all isomers)
Hexachtorocyclopenladiene
Hexachlorodibenzo-p-dioxins
Hexachlorodibenzofurans
Hcxachtoroethane

1,2,3,4l10,10-Hexachloro-1,4,4a,5,8,8a-hexahydro-
1,4:5l8-endo,endo-d!methanonaphthalene
Hexachtorophene
Hexachloropropene
Hexaethyl tetraphosphate
Hydrazlne

Hydrocyanic acid
Hydronuorlcacid
Hydrogen sulfide
Hydroxydimethylarslne oxide
lndono(1,2,3-c,d)pyrene
lodomethane
Iron dextran (complex)
Isocyanic acid, methyl ester
Isobutyl alcohol
isosafrole
Kepone
Lasiocarplne
Lead and compounds, N.O.S.
Lead acetate
Lead phosphate
Lead subacetate
Maleic anhydride
Maleic hydrazlde
Malononitrile
Melphalan
Mercury fulminate
Mercury and compounds, N.O.S.
Methacrylonitrile
Methanethiol
Methapyriline
EPA-600/8-84-002 SW-846 Compound Analysis
Method No.' Method No." Type' Method"
A121
A101
A121
A121
A121
A121
A121
A121
A121
A121
A252
A121
A156
A123
A121
A121
A121
A137
A157
A121
A131
A101
A121
A133
A131
A101
A121
A121
A121
A121
A121
A121
A101
A121
A121
A121
A101
A121
A101
"A141
A141
A251
A251
A141
A222
A121
A101
—
A101
A134
A121
A121
A160
A227
A227
A227
A227
A121
A121
A121
A122
A228
A228
A121
A101
A121
8060, 8250
*
*
*
*
8140
*
8080, 8250
8080, 8250
*
9010
*
*
*
8100,8250,8310
—
*
*
8015, 8240
*
8250
*
*
*
8080, 8250
8080, 8250
8120, 8250
8120, 8250
8120
8120, 8250
8280
8280
8010, 8240
8120, 8250
*
*
*
*
*

* '
*
*
7060, 7061
8100, 8250, 8310

*

.
8080
*
7420, 7421
7420, 7421
7420, 7421
7420, 7421
8250
*
*
*
7470, 7471
7470, 7471
*
*
SV
V
SV
SV
SV
SV
SV
SV
SV
SV
CN
SV
V
SV
I sv
' SV
SV
G
*
SV
V
V
SV
SV
SV
V
SV
SV
SV
SV
SV
SV
SV
SV
V
SV
SV
SV
V
SV
V
G
G
AN
AN
G
M
SV
V

V
V
SV
SV

M
M
M
M
SV
SV
SV
SV
M
M
SV
V
SV
GC, GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC, GC/MS
GC/MS
GC, GC/MS
GC, GC/MS
GC/MS
T,C
GC/MS
GC/FID
HPLC
GC/MS
GC/MS
GC, GC/MS
*
GC/FID
GC/MS
GC, GC/MS,
HPLC
GC/MS
GC/MS
GC/MS
GC/MS, HPLC
GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC/MS
GC/MS
GC, GC/MS
GC, GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/TCD
GC/TCD
1C
1C
GC/TCD
AAS
GC, GC/MS
GC/MS
'
GC/MS
GC/MS
GC/MS
GC, GC/MS

ICAPAAS
ICAPAAS
ICAPAAS
ICAPAAS
GC/MS
GC/MS
GC/MS
HPLC
CV/AAS
CV/AAS
GC/MS
GC/MS
GC/MS
                                                          36

-------
Analysis Methods for Appendix VIII Hazardous Constitutents (continued)
EPA-600/8-84-002 SW-846
Compound Method No.* Method No.6
Metholmyl

Methoxychlor
2-Methylaziridine
3-Methylcholanthrene
Methylchlorocarbonate
4,4 ' -Methylenebis(2-chloroaniline)
Methyl ethyl ketone (MEK)

Methyl hydrazine

2-Methyllactonitrile
Methyl methacrylate
Methyl methanesulfonate
2-Methyl-2-(methylthio)propionaldehyde-0-
(methylcarbonyl)oxime
N-Methyl-N ' -nitro-N-nitroso-guanidine
Methyl parathion
Methylthiouracil
Mustard gas
Naphthalene
1 ,4-Naphthoqui none
1-Naphthylamine
2-Naphthylamine
1-Naphthyl-2-thiourea
Nickel and compounds, N.O.S.
Nickel carbonyl
Nickel cyanide

Nicotine (and salts)
Nitric oxide
p-Nitroaniline
Nitrobenzene
Nitrogen dioxide
Nitrogen mustard (and hydrochloride salt)
Nitrogen mustard N-Oxide (and hydrochloride salt)
Nitroglycerine
4-Nitrophenol

4-Nitroquinoline-1-oxide
Nitrosamine, N.O.S.
N-Nitrosodi-n-butylamine
N-Nitrosodiethanolamine
N-Nitrosodiethylamine
N-Nitrosodimethylamine
N-Nitroso-N-ethylurea
N-Nitrosomethylethylamine
N-Nitroso-N-methylurea
N-Nitroso-N-methylurethane
N-Nitrosomethylvinylamine
N-Nitrosomorpholine
N-Nitrosonornicotine
N-Nitrosopiperid i ne
N-Nitrosopyrrolidine
N-Nitrososarcosine
5-Nitro-o-toluidine
Octamethylpyrophosphoramide
Osmium tetroxide
7-Oxabicyclo[2.2.1 ]heptane-2,3-dicarboxylic acid
Paraldehyde

Parathion
Pentachlorobenzene
Pentachlorodibenzo-p-dioxins
Pentachlorodibenzofurans
Pentachloroethane
Pentachloronitrobenzene (PCNB)
Pentachlorophenol
Phenacetin
A122

A121
A121
A121
—
•'•• A121
A101
A121
A101
A121
A121
A121
A121
. A183

A121
A121
A121
A139
A121
A121
A121
A121
A123
A229
A229
A229
A252
A121
A141
A121
A121
A141
A139
A139
A121
A121
A122
—
A121
A121
A121
A121
A121
A121
A121
A121
A121
A121
A121
A121
A121
A121
A121
A122
A121
A230
A133
: A131

A121
A121
—
—
A121
A121
A121
A174
8250

8080
* -
8100
*
*
8015, 8240
*
. *
*
*
*
*
*

*
8140
_ *
*
8100, 8250, 8310
8090, 8250
*
*
*
7520, 7521
7520, 7521
7520, 7521
9010
*
*
*
8090, 8250
*
*"
*

8040, 8240
8250
*
8250
8250
8250
8250
8250
8250
8250
8250
8250
8250
8250
8250
8250
8250
8250
*
* -
*
*
8015, 8240

8140
*
8280
8280
*
*
8040, 8250
*
Compound Analysis
Type' Method"
SV

sv
SV
sv

sv
V
sv
V
sv
sv
sv
sv
*

sv
sv
sv
V
sv
sv
sv
sv
sv
M
M
M
CN
SV
G
SV
SV
G
V
V
SV
SV
sv

sv
sv
sv
sv
sv
sv
sv
sv
sv
sv
sv
sv
sv
sv
sv
sv
sv
M
sv
V

sv
sv
sv
sv
sv
sv
sv
sv
GC, GC/MS,
HPLC
GC, GC/MS
GC/MS
GC, GC/MS

GC/MS
GC, GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/FPD

GC/MS
GC, GC/MS
GC/MS
GC/FPD
GC, GC/MS
GC, GC/MS
GC/MS
GC/MS
HPLC
ICAP.AAS
ICARAAS
ICAP.AAS
T,C
GC/MS
GC/TCD
GC/MS
GC, GC/MS
GC/TCD
GC/FPD
GC/FPD
GC/MS
GC, GC/MS
GC/MS, HPLC

GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
HPLC
GC/MS
ICARAAS
GC/MS
GC, GC/MS,
HPLC
GC, GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC/MS
GC, GC/MS
HPLC
37

-------
Analysis Methods for Appendix VIII Hazardous Constltutents (continued)
EPA-600/8-84-002
Compound Method No.'
Phenol

Phenylenediamine
Phenylmercury acetate
N-Phenylthiourea
Phosgene
Phosphine
Phosphorodithloic acid, 0,0-dlethyl
Sn((ethylthio)methyl) ester [Phorate]
Phosphorothioic acid, 0,0-dimethyl 0-(p-((dimethylamino)sulfonyl)
phony!) ester [Famphur]
Phthalicacid esters, N.O.S.
Phthalic anhydride
2-PicoHne
Polychlorinated biphenyl, N.O.S.
Potassium cyanide
Potassium silver cyanide

Pronamtde
1,3-Propane suifone
n-Propylamine
Propylthiouracil
2-Propyn-1-ol
Pyridine
Reserplne
Resorcinol
Saccharin (and salts)
Safrole
Selenious acid
Selenium and compounds, N.O.S.
Selenium sulfide
Selenourea
Silver and compounds, N.O.S.
Silver cyanide

Sodium cyanide
Streptozotocin
Strontium sulfide
Strychnine (and salts)
1,2,4,5-Tetrachlorobenzene
2,3,7,8-Tetrach!orodibenzc~p-dioxin(TCDD)
Tetrachtorodibenzo-p-dioxins
Tetrachlorodibenzofurans
Tetrachtoroethane, N.O.S.
1,1,1,2-Tetrachloroethane
1,1,2,2-Telrachloroethano
Tetrachloroethylene
Tetrachloromethane
2,3,4,6-Tetrachlorophenol

TetraBthyldithiopyrophosphate
Tetraethyl lead
Tetraethylpyrophosphate
Totranltromethane
Thallium and compounds, N.O.S.
Thalllc oxide
Thallium(l) acetate
Thallium(l) carbonate
Thallium(l) chloride
Thallium(l) nitrate
Thallium selenite
Thallium(l) sulfate
Thioacetamide
Thiosemlcarbazide
Thiourea
Thiuram
Tbluene
Toluenediamine, N.O.S.
2,4-Toluencdiamine
2,6-Toluenediamine
A121
A122
A121
A228
A123
A138
A136
A121
A121
A121
A121
A121
A121
A252
A232
A252
A121
A121
A121
A121
A134
A121
A122
A134
A121
A123
A121
A231
A231
A231
A231
A232
A232
A252
A252
A122
A233
A180
A121
A121
—
A101
A101
A101
A101
A101
A121
A122
A121
A227
A121
A101
A234
A234
A234
A234
A234
A234
A234
A234
A123
A123
A123
A122
A101
A121
A121
A121
SW-846
Method No."
8040, 8250

*
7470, 7471
*
*
8140
'8140
8060
8090, 8250
8090, 8250
8080,8250
9010
7760, 7761
9010
*
*
8090, 8250
*
*
*
*
7740, 7741
7740, 7741
7740, 7741
7740, 7741
7760, 7761
7760, 7761
9010
9010
*
*
8120, 8250
8280
8280
8280
8010, 8240
8010, 8240
8010, 8240
8010, 8240
8010, 8240
8040 8250

*
7420, 7421


—
—
—
—
*
*
*
*
8020, 8240
8250
8250
8250
Compound
Type0
SV
SV
SV
M
SV
G
V
SV
sv
SV
SV
SV
SV
CN
i M
CN
SV
SV
SV
SV
V
SV
SV
SV
SV
SV
SV
M
M
M
M
M
•M - :
; CN
CN
SV
M
SV
SV
SV
SV
SV
V
V
V
V
V
SV
SV
SV
M
SV
V
M
M
M
M
M
M
M
M
SV
SV
, sv
SV
V
SV
SV
SV
Analysis
Method"
GC, GC/MS
HPLC
GC/MS
CV/AAS
LJDI /"*
HrLO
GC/TCD
GC/FPD
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
TC
ICAPAAS
l^ C
GC/MS
GC/MS
GC/MS:
GC/MS
GC/FID, GC/MS
GC, GC/MS
HPLC
GC/FID, GC/MS
GC/MS
HPLC
GC/MS
AAS
AAS
AAS
AAS
ICAPAAS
ICAPAAS •
TC
T C
LJDI O'
HrL(_>
ICAPAAS
HPLC
GC, GC/MS
GC/MS
GC/MS
GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
GC, GC/MS
HPLC
GC/MS
ICAPAAS
GC/MS
GC/MS
ICAPAAS
ICAPAAS
ICAPAAS
ICAPAAS
ICAPAAS
ICAPAAS
ICAPAAS
ICAPAAS
HPLC
HPLC
HPLC
HPLC
GC, GC/MS
GC/MS
GC/MS
GC/MS
38

-------
 Analysis Methods for Appendix VIII Hazardous Constitutents (continued)
                                                             EPA-600/8-84-002
                         Compound                            Method No.'
                 SW-846
               Method No."
               Compound
                 Type'
            Analysis
            Method"
 3,4-Toluenediamine
 o-Toluidine hydroohloride
 Tolylene diisocyanate
 Toxaphene
 Tribromomethane
 1,2,4-Trichlorobenzene
 1,1,1-Trichloroethane
 1,1,2-Trichloroethane
 Trichloroethene
 Trichloromethanethiol
 Trichloromonofluoromethane
 2,4,5-Trichlorophenol

 2,4,6-Trichlorophenol

 2,4,5-Trichlorophenoxyacetic acid (2,4,5-T)

 2,4,5-Trichlorophenoxypropionic acid (2,4,5-TP) (Silvex)

 Trichloropropane, N.QS.
 1,2,3-Trichloropropane
 0,0,0-Triethyl phosphorolhioate
 sym-Trinitrobenzene
 Tris-(1-azridinyl)phosphinesulfide
 Tris(2,3-dibromopropyl) phosphate
 Trypan blue
 Uracil mustard
 Vanadic acid, ammonium salt
 Vanadium pentoxide
 Vinyl chloride
 Zinc cyanide
 Zinc phosphide
 A121

 A121
 A121
 A101
 A121
 A101
 A101
 A101
 A121
 A101
 A121
 A122
 A121
 A122
 A122
 A133
 A122
 A133
 A101
 A101
 A121
 A121
 A190
 A121
 A123

A235
A235
A101
A252
A253
   8250
     *

   8250
 8080, 8250
 8010, 8240
 8120,8250
 8010, 8240
 8010,8240
 8010, 8240
     *

 8010, 8240
 8040,8250

 8040,8250

 8150,8250

 8150,8250

 8010, 8240
 8010,8240
8010, 8240
   9010
 SV

 SV
 SV
 V
 SV
 V
 V
 V
 SV
 V
 SV
 SV
 SV
 SV
 SV
 SV
 SV
 SV
 V
 V
 SV
 SV
 V
 SV
 SV

 M
 M
 V
CN
 S
   GC/MS

   GC/MS
 GC, GC/MS
 GC, GC/MS
 GC, GC/MS
 GC, GC/MS
 GC, GC/MS
 GC, GC/MS
   GC/MS
 GC, GC/MS
 GC, GC/MS
   HPLC
 GC, GC/MS
   HPLC
 GC, GC/MS
  GC/MS
 GC, GC/MS
  GC/MS
 GC, GC/MS
 GC, GC/MS
  GC/MS
  GC/MS
  GC/FPD
  GC/MS
   HPLC

 ICAP.AAS
 ICAP.AAS
GC, GC/MS
    1C
  GC/FPD
• Source: Arthur D. Little, Inc., "Sampling and Analysis Methods for Hazardous Waste Combustion," EPA-600/8-84-002 PB84-155845
          February 1984.
  — = No method given.
" Sources: (1) "Test Methods for Evaluating Solid Waste — Physical/Chemical Methods," EPA/OSW, Third Edition, SW-846  November 1986
         (2) 40 CFR Part 261, Appendix III.                  -   .                                           '
         (3) All VOST tube, analysis must be by Method 5040. Other methods are applicable to other matrices
   = Method not specified for the substance in SW-846, but SW-846 methods may apply
  — = No method given.        -                                                                             ,    '
c V  = Volatile substance
  SV = Semivolatile substance
  M  =• Metal
  CN = Cyanide
  S  = Solid
  AN = Anion
  G  = Gas
  *   = Not found
"  GC      = Gas chromatography
  GC/MS   = Gas chromatography/mass spectromeJry
  GC/FID   = Gas chromatography with flame lonization detector                 ;
  GC/TCD = Gas chromatography with thermal conductivity detector
  GC/FPD = Gas chromatography with flame photometric detector
  HPLC   = High performance liquid chromatography
  AAS    SB Atomic absorption spectroscopy
  CV/AAS = Cold vapor/atomic absorption spectroscopy
  ICAP    = Inductively coupled argon plasma emission spectroscopy
  1C      = Ion chromatography
  C      = Colorimetry
 T  •     = Titration
 —      = No method found
  *       = No method available
                                                           39

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                                             Appendix B
                                     Measurement Checklists
 B.1 Introduction

 Checklists have been prepared to assist the permit writer
 in determining the completeness of a trial burn plan and
 permit application relative to process monitoring, sam-
 pling,  and analysis of samples. These checklists show
 the parameters required by regulation or typically recom-
 mended for measurement during a trial burn and the
 essential information which should be given in the trial
 burn plan for the measurement, sampling, or analysis of
 each parameter. Table B-1 is the checklist for the monitor-
 ing parameters, Table B-2 is for the sampling parameters,
 and Table B-3 is for the analysis of samples.

 One important aspect of any trial burn  plan or permit
 application is the description of the QA/QC procedures.
 A checklist  of the QA/QC  items which  should be
 addressed in the project Quality Assurance (QA) plan for
 each of the monitoring, sampling, and analysis parame-
 ters is given in Table B-4.

 The checklists should be filled in by the permit writer as
 the trial burn plan and permit application are reviewed. In
 each column indicate Y for yes, N for no, I  for incomplete,
 or NA for not applicable. The blanks which have an N or I
 result in an incomplete,trial burn plan and permit applica-
 tion and should be subsequently addressed to complete
 the documents. The checklists address only information
 related to measurements; they do not include other infor-
 mation required for complete applications and trial burn
 plans.

 The following discussion provides a description of each
 checklist, followed by the checklists.
B.2 Process Monitoring
The process monitoring checklist (Table B-1) contains
both parameters that must be monitored continuously
during the trial burn and subsequent operation of the
incinerator, as provided in the Code of Federal Regula-
tions, 40 CFR Parts 264.345 and 264.347, and others
typically  recommended  for measurement  during trial
burns. Parameters on the checklist are (1) waste feed
rate, (2) combustion temperature, (3) a measure of com-
bustion gas velocity, (4) combustion chamber pressure,
(5)  carbon monoxide concentration (CO) in the stack
gases, (6) oxygen concentration in the stack-gases, (7)
the waste feed pressure, (8) auxiliary fuel flow rate and
pressure, (9) waste atomization airflow rate and pressure,
 (10) input quench water flow rate, (11) input and output
 scrubber water flow rates and output pH, (12) other air
 pollution control device(s) parameters, (13) waste feed
 cutoff system parameters, and (14) other parameters as
 appropriate.

 The essential information which should be included in the
 trial burn plan and permit application for each selected
 process monitoring parameter is shown in the columns in
 Table B-1. This information includes (1) whether ornot the
 parameter will be monitored, (2) the monitoring method,
 (3) monitoring equipment,  (4) monitoring  location, (5)
 monitoring frequency, and (6) method of data recording.
 These subjects should be addressed in the trial burn plan
 and permit application.  Other information such as meth-
 ods of data reduction and storage, calibration of equip-
 ment, and inspection and maintenance of the equipment
 should be given in the project QA plan.

 B.3 Sampling

 The sampling checklist (Table B-2) contains a list of sam-
 ples which may be taken during the trial burn and ana-
 lyzed  in accordance  with 40 CFR  Parts 264.341
 264.342, 264.343, 264.345, 270.19, and 270.62.7 The
 samples required by regulation are (1) waste feed, (2)
 stack gases,  (3)  scrubber water, (4) ash, and (5) other
 samples, as appropriate. Collection of auxiliary fuel and
 scrubber inlet samples are optional. None of these sam-
 ples are required during the subsequent operation of the
 incinerator unless specified in the permit.

 The essential information which should be included in the
 trial burn plan for each sampling parameter is shown in
 the columns of Table B-2. This information  includes (1)
 whether or not the sample(s) will be taken, (2) the sam-
 pling method, (3) sampling equipment, (4) sampling loca-
 tion, (5) sampling frequency,  and (6) method of  data
 recording. These subjects should be addressed in the
trial burn plan. Other information such as calibration and
 maintenance of the equipment, data reduction, and data
storage should be given  in the project QA plan.

B.4 Analysis

The checklist for analysis of the samples  (Table B-3)
contains parameters which may be evaluated for the trial
burn,  in accordance with  40 CFR Parts 270.19 and
                                                  41

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270.627 Some of the analyses including the principal
organic hazardous constituents (POHCs) in the auxiliary
fuel and metals may be appropriate only in some cases.

Essential information which should be included in the
trial burn plan for each analytical parameter is shown in
the columns in Table B-3. This information includes (1)
whether or not the sample(s) will be analyzed, (2) analyti-
cal procedure, (3) analytical equipment, (4) sample trace-
ability, and (5) data recording. These subjects should be
addressed in the trial burn plan. Other information such
as  calibration and maintenance of equipment, data
reduction and validation, data reporting, and data storage
should be given in the project QA plan.

B.5 Quality Assurance/Quality Control
Each permit application and trial burn plan must have a
quality assurance (QA) plan. The QA plan must address
all data-gathering  activities (e.g., process monitors  as
well as sampling  and analytical activities).  This  plan
should conform to the  specifications established  in
SW-846,  Test Methods for  Evaluating Solid Waste —
Physical/Chemical Methods,6 and Interim Guidelines and
Specifications for Preparing Quality Assurance Project
Plans," and must address all measurement parameters.

The purpose of the QA plan is to establish a specific
program  to  (1)  help ensure that the monitoring  data,
sampling, and analytical activities meet specific quality
objectives;  and (b)  routinely assess the quality of the
data. The QA/QC checklist (Table  B-4) includes all of the
monitoring, sampling, and analytical parameters given in
the previous three  checklists  and  shows the  QA/QC
items required for each parameter in the Interim Guide-
lines and Specifications for Preparing Quality Assurance
Project Plans." Each of the QA/QC items is discussed in
Section 4.0.                  i

It should be noted that there is redundancy among the
information required in Tables EM to B-4. This informa-
tion may be provided in either the trial burn plan and
permit application or the QA plan, or both. QA/QC infor-
mation provided in  the trial bum plan should be  refer-
enced in the Q A plan.
                                                    42

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 Table B-1.   Checklist for Process Monitoring Parameters for RCRA Incinerators
 Monitoring                                            To be     Monitoring              Monitoring  Monitoring     Data
 parameter                                           monitored*   method    Equipment   location   frequency   recording

 Waste feed rate"
   Stream No. 1                                         			      	      	       '  '  •
   Stream No. 2	      		      	      	      	
   Stream No. 3                                         	      		      	      	      	
 Combustion temperature(s)"                              	      	      		      	      	
 Combustion gas velocity indicator                         	   .   	      	     f	      	      	
 Combustion chamber pressure
   Primary                                              	      	      	      	      	      _____
   Secondary                                           	      	      	      	      	         '

 CO in stack gases"                                      	      	      ..	      		      	
 Oxygen in stack gases		      	      	     •	
 Waste feed pressure(s)                                   	      	      	      	        "
 Auxiliary fuel
   Feed rate                                            		      	      	      	         " .
   Pressure                 '                            	      	      	      	      	      	
 Waste atomization                                                                                                   ,  ,
   Airflow                                               	      	        -          _i	      	      	
   Pressure                                             	      	      	      J	      		
 Quench water
   Input flow rate                                        	      	      	     	      		
 Scrubber water
   Input flow rate                                        	      	         •        	      		
   Output flow rate                                       		      	        ,          	      	
   Output pH                                           	      		     _____      		

 Air pollution control device(s) parameters
Waste feed cutoff system
Other
* Indicate Y = Yes; N = No; I  = Incomplete; NA = Not applicable.
a Continuous monitoring specifically required by RCRA regulations.
                                                            43

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Table B-2.  Checklist for Sampling Parameters for RCRA Incinerators
Sampling                                            Tobe     Sampling
parameter
sampled*
_...r....a               Sampling   Sampling      Data
method   Equipment   location    frequency   recording
Waste feed
  Stream No. 1
  Stream No. 2
  Stream No. 3
Stack gases
  Particulates
  HCI
  H,O
  POHCs
  O,
  CO,
  Stack gas flow rate
  Stack gas temperature
Auxiliary fuel
Quench water
  Inlet
Scrubber water
  Inlet
  Outlet
Ash
Other
  Indicate Y = Yes;N = No; I = Incomplete; NA = Not applicable.
                                                           44

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 Table B-3.  Checklist for Analysis of Samples for RCRA Incinerators
 Analytical                                  To be
 parameter                                analyzed*        Procedure
Equipment
  Sample
traceability
  Data
recording
 Waste feed analysis
   High heating value
   Chlorine
   POHCs
   Ash
   Viscosity
   H2O
   Metals
   Volatile matter
 Stack samples
   Particulates
   HCI
   POHCs
   02
   CO2
   Metals
 Auxiliary fuel
   POHCs
   HHV
   Chlorine
   Ash
 Quench water input
   POHCs
   PH
 Scrubber water input
   POHCs
   PH
 Scrubber water output
   POHCs
   PH
Ash residue
   POHCs
   Heavy metals
  TCLP
Other
  Indicate Y = Yes;N = No; I = Incomplete; NA = Not applicable.
                                                        45

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Table B-4.  Quality Assurance/Quality Control Checklist for Monitoring, Sampling, and Analysis Parameters for Incinerators
  Mnnltnrlno. «amn1ina                                    Quality assurance/quality control Items*	:
      -sa?       SSL  ±ax  aag.ass.  Ja,  j±. JJSL.'JS?
Monitoring
  Waste faod rate           	      N/A
  Combustion temperature    	      N/A
  Combustion gas velocity    	      N/A
  CO In stack gas           	      N/A
  Auxiliary fuel             	      N/A
  Atomlzation pressure      	      N/A
  Combustion chamber
    pressure              	      N/A
  Quench water            	      N/A
  Scrubber water           	      N/A
  Air pollution control
    devices              	      N/A
  Waste feed cutoff system    	      N/A
  Other                 	      N/A

Sampling
  Waste feed sampling      	     	—
  Stack gas sampling       	     	
  Auxiliary fuel            	     	
  Scrubber water           	     	
  Ash sampling            	     	
  Other                 	     	
   Waste feed analysis
     High heating value       	
     Chlorides              	
     POHCs               	
     Ash                  	
     Viscosity              	
   Stack samples
     Particulars           	
     HCI                  	
     0,                   	
     CO,                  	
     POHCs               	
   Auxiliary fuel POHCs       	
   Scrubber water
     POHCs               	
     pH                  	
   Ash residue
     POHCs               	
     Heavy metals          	
   Other                  	

 GeneralQA/QC
   Project description

   Project organization and responsibility
     Organization chart
     Resumes of key Individuals
     Description of individual responsibilities

   Performance and system audits
     Internal performance audits
     Internal systems audits
     External performance audits
     External systems audits

   Corrective action

   OA reports to management
     Types of reports
     Individual^) responsible
     Frequency
  * Indicate Y » Yes;N = No; I = Incomplete; NA = Not applicable.
                                                                     &U.S. GOVERNMENT PRINTING OFFICE:
                                                                                                   1992 - «48-003/4183I

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