United States
                    Environmental Protection
                    Agency
Environmental Monitoring and
Support Laboratory
Cincinnati OH 45268
                    Research and Development
EPA/600/S4-88/006   Mar. 1988
&EPA          Project  Summary
                    Validation of SW-846  Methods
                    8010, 8015,  and  8020
                    J.E. Gebhart, S.V.Lucas, SJ. Naber, A.M. Berry, T.H. Danison,
                    and H.M. Burkholder
                      A hierarchical approach is being
                    implemented for the  development
                    and validation of analytical methods
                    for the determination of the over 400
                    RCRA Appendix VIII  and Michigan
                    List compounds in wastes. Th'e first
                    phase of this  approach  involved
                    testing GC/MS methods for  the
                    detection and measurement of these
                    compounds. Next,  semivolatile
                    compounds determined to  be
                    amenable to GC/MS  were used to
                    evaluate the performance  of SW-846
                    Method 3510. In the study described
                    in  the full report,  volatile organic
                    compounds determined to  be
                    amenable to GC/MS  were used to
                    evaluate the performance  of SW-846
                    Method 5030.
                      The performance of Method 5030
                    was evaluated in conjunction with
                    SW-846 Methods  8010,  8015, and
                    8020. In these studies, purge-trap-
                    desorb   sample   introduction
                    techniques were used for synthetic
                    aqueous and solid samples, and
                    direct liquid injection was used  for
                    synthetic nonaqueous liquid wastes.
                    The results of these studies  are
                    presented,  including  purging
                    efficiencies  and estimated method
                    detection  limits for compounds in
                    aqueous  samples  and  method
                    detection  limits for compounds in
                    nonaqueous liquid wastes.
                      This  Project Summary  was
                    developed by  EPA's Environmental
                    Monitoring and Support Laboratory,
                    Cincinnati,  OH, to  announce  key
                    findings of the research project  that
                    is fully documented in a separate
                    report of the same title (see Project
                    Report ordering information at back).
 Introduction

   The Resource Conservation  and
 Recovery  Act specifies over 300 toxic
 organic compounds in its Appendix  VIII
 to 40 CFR 261 listing that may be used
 to identify hazardous wastes. In response
 to a petition by the State of Michigan, the
 U. S.  Environmental  Protection Agency
 (EPA)  has proposed the amendment of
 RCRA Appendix VIII1 by adding over  100
 other organic compounds to give a total
 of over 400 organic constituents. Various
 gas chromatographic (GC) methods for
 determining Appendix VIII compounds in
 wastes are given in  SW-846, Test
 Methods for Evaluating Solid Wastes2. In
 many  cases, these  methods   are
 modifications of procedures cited under
 the Clean Water  Act for determining
 some, but not all,  of Appendix VIII  and
 Michigan  List compounds in wastewater.
 The EPA is  currently attempting  to
 validate  the  appropriate  SW-846
 analytical  methods for as many of  the
 400 plus target compounds as possible.
 A hierarchical  approach  to  these
 validation  efforts is being pursued.
   A schematic   illustration  of   the
 hierarchical approach to the development
 and validation of  analytical methods for
 the determination of over 400 organic
 compounds in wastes is  presented in
 Figure 1. The first phase of this approach
 was conducted under Work Assignment
 4 of  EPA Contract  Number  68-03-
 32243 and involved identifying volatile
 and semivolatile  compounds that  are
 amenable  to GC  separation  and mass
 spectrometric  (MS) detection.  Next,  the
 semivolatile compounds determined to
 be amenable to GC/MS were then used
 to evaluate the performance of SW-846
 Method 35104. This  work focussed on
 the recovery from water and aqueous
 stability of the semivolatile compounds

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                                                    Analyte
                                                                     Fail
                                       1. HPLC
                                       2. Derivatization
                                       3. Non-chromatographic
    1. Add to list

    2. Test in
      non-MS
      methods
                               Fail
                            Evaluate other options:

                            1. Heated PTD
                            2. Direct injection
                            3. Micro extraction
                            4. Distillation
                            5. Non-GC methods
                                                        1. Add to list

                                                        2. Test in
                                                          non-MS
                                                          methods
                                1. Modified extraction
                                  conditions (SPE. other
                                  solvents, etc.)

                                2. Develop/improve
                                  cleanup procedures
 Figure 1.    Hierarchical approach for analytical method development for organic RCRA analytes.
using  standardized  storage  and
extraction  procedures.   These
experiments were conducted under Work
Assignment 8 of EPA Contract  Number
68-03-3224. In the study described  in
the full  report, volatile  compounds
determined  to  be  amenable to GC
separation were used to evaluate  SW-
846  Method  8010,  8015, and 8020.
Evaluating these methods was one of the
major  objectives of   this  Work
Assignment.  These  experiments which
comprised these  evaluations and  the
results obtained  are presented in the full
report. Recommendations for further
effort in the evaluation of methods for the
determination  of  volatile  organic
compounds (VOCs) in waste samples are
also  provided in the report.  The other
major objective of this Work Assignment
was to use the results of Methods 8010,
8015,  and 8020  testing to  formulate
recommendations  for including specific
compounds is the scope of  Method  5030
for the validation of Method 8240. These
recommendations  are made  based  on
the recovery  and  precision of  the
determination of  these analytes  using
procedures specified  in Methods  8010,
8015, and 8020.
   Methods 8010,  8015,  and  8020
provide  packed-column GC conditions
for the determination of certain VOCs.
Waste samples are analyzed using these
Methods in conjunction with purge-
trap-desorb (PTD), Method 5030;  direct
liquid injection  (DLI); or  headspace
sampling,  Method  5020,   sample
introduction techniques.  Temperature
programs are used in the GC to separate
organic  compounds.  Detection  is
achieved by halogen specific detector for
Method 8010, a flame ionization detector
for Method 8015, and a photoionization
detector for Method 8020.
   These Methods were evaluated using
procedures  described in  the Single
Laboratory Method Validation  Protocol
(SLMVP)5 which was  developed  under
Work Assignment 1  of EPA  Contract
Number  68-03-3224.  While  the
SLMVP  specifies six  steps for  full
method validation,  only  the first  tv
steps,  Instrumentation  Range Determi
ation and Preliminary Method Evaluatic
were used in these evaluations. Th
approach was taken  because EF
anticipated that many laboratories wou
soon have the capability to conduct PI
analysis  using capillary  column  G'
Consequently, full validation  of packe
column methods  was  not  consider*
necessary or  appropriate.  Resear(
results  provided in  the  full  report a
intended to define the scope  of the thre
packed-column  methods  and establi:
a  basis  for  testing   of   capillai
columnbased  methods  for  th
determination of VOCs in waste sample

Experimental Approach
   Compounds initially  considered  fi
inclusion  in the Methods 8010, 8015, ar
8020 testing are listed in Table 1. Bast
on preliminary evaluations, a number
these analytes were excluded from the*
experiments  because of  poor  purgir
efficiency,  poor  chromatograph

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                                      Determine
                                Analyte Concentration
                                  to Give S/NofS
                               Prepare Standards Contain-
                               ing Method Analytes at S/N
                                 5-5000 Concentrations
                                 Determine Interference
                                   Concentration Limit
                                  Analyze 4 Replicates
                                    of Each Standard
 Analyze
  New
Standards
                      Fail
                                Test Instrument Responses
                                       for Outliers
           Pass
                         Pass]
                 Test for
             Response Factor
             Calibration Model
                              Fail
                         Test for
                         Linear
                        Calibration
                         Model
                                  Pass
  Eliminate
 High or Low
   Analyte
Concentration
    Level
                                                        (or)
                                                Test for
                                               Quadratic
                                           Calibration Model
                                                (or)
                                  Modify Method Writeup
                                   to Include Appropriate
                                     Calibration Model
                                                   TJ
                                         Define
                                 Instrumentation Range
                                     as High to Low
                                    Concentration of
                                Validated Calibration Model
                  Fail
                                                    Test Alternative
                                                   Calibration Model
                                                                        Fail
Figure 2.
                        Preliminary Method Evaluation

     Instrumentation range determination.

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behavior,  or lack of  pure standard
material. These compounds are  listed in
Table  2 along  with  the reason  for
elimination from testing.
   The first phase of method evaluation
was  the   Instrumentation  Range
Determination step of the SLMVP. These
experiments involved  replicate  analysis
of aqueous calibration standards  using
the PTD sample introduction technique
and  of  nonaqueous  liquid  calibration
standards  using the  DLI   sample
introduction method. In these studies, at
least four  replicate standards  were
analyzed at each of seven concentration
levels. The  concentrations were  selected
to cover a three-orders-of-magnitude
range. Results obtained in this validation
step establish a basis for determining the
test  concentrations and  the calibration
function to be used in later steps of the
validation.   A  flow  diagram illustrating
specific activities of the  Instrumentation
Range Determination  step  is shown in
Figure 2.
   The second  phase  of  the  method
testing  was  the  Preliminary  Method
Evaluation  step  of  the  SLMVP. These
studies  involved  the  analysis  of eight
replicates of synthetic aqueous and solid
samples that  had been fortified  with the
known  amounts of the  compounds of
interest. In  these experiments,  only  the
PTD sample introduction technique  was
used. The  synthetic aqueous  samples
consisted of  reagent  water  which  was
spiked as a 500  mL batch, divided  into
40  ml  aliquots,  and  stored in Teflon-
lined septum screw cap vials overnight at
4°C. The  synthetic solid sample  was
composed of equal parts of Celite  503
and  Kaolin. Two gram  aliquots of  this
sample  were  spiked,  mixed thoroughly,
and stored overnight at 4°C. This step of
the validation  is conducted to determine
if the method performs  adequately for
specified  analytes  before  actual
validation  begins.  This  preliminary
evaluation  ensures  that  no major
technical difficulties are  inherent in  the
method, that  reasonable results can be
obtained for method analytes,  and  that
the time, effort,  and cost of a validation
study  will  not  be  spent  on   an
unsatisfactory method. A flow  diagram
illustrating  specific  activities of  the
Preliminary Method  Evaluation  step is
shown in Figure 3.
   Analyses of all standards and  samples
in these studies were conducted exactly
according to the procedures presented in
Method 5030.  The  chromatographic
columns and conditions used for  the
analyses  were  those  described in
Method 8010, 8015, and 8020.
Results and Discussion

   A summary of the results obtained
from the evaluations  of  Methods 8010,
8015, and 8020 is provided in Table 3
which presents the compounds for which
each of these Methods was found to be
suitable.  These results  are  discussed
below.
Method 8010

   A total  of 53 compounds  were
originally considered for inclusion  in the
evaluations  of Method 8010. Preliminary
experiments were  conducted to evaluate
purging efficiencies and chromatographic
behavior of these compounds.  Based on
these experiments a number of analytes
were excluded from  the PTD and/or the
DLI portions  of Method  8010 testing.
Chloroacetaldehyde was excluded from
all testing because a commercial source
could  not  be  identified.  Bis  (2-
chloroisopropyl) ether was excluded from
all experiments because the  standard
material  obtained was  not  pure  and
another  batch could not be obtained  in
time for  use  in these  studies.  Of the
remaining 51  compounds, seven  were
excluded from the PTD  portion of the
experiments because of  poor purging
efficiencies. These compounds including
bis (2-chloroethoxy)  methane; bromo-
acetone;  2-chloroethanol;  2-chloro-
ethyl vinyl  ether;  chloromethyl  methyl
ether;  1,3-dichloro-2-propanol;  and
epichlorohydrin  were used in the DLI
portion  of the method  performance
testing.  Four  analytes  including  bis(2-
chloroethyl) sulfide;  chloral,  3-
chloropropionitrile;  and  pentachloro-
ethane were excluded from both the PTD
and  the  DLI  portions of  these studies
because  of  poor  chromatographic
behavior  under  the  Method  8010
conditions.  Chloroprene was  excluded
from the DLI experiments because  of
apparent decomposition  in the injector.
This analyte  was  included in the PTD
portion of these  studies  in which this
effect was  not observed.  Based on the
results of these preliminary experiments,
a  total of 40 compounds, including 26
priority  pollutant  compounds,  was
included  in the PTD portions of  these
studies.  Forty-six  compounds, including
27 priority  pollutants were used  in the
DLI  portion  of  the  Method  8010
evaluations.
   Based  on  the  results  of  the
Instrumentation Range  Determination
and  the  Preliminary  Method  Evaluation
experiments,  Method 8010  was
determined  to be  suitable for the
determination of  36 of  the 40  ti
compounds used in the  PTD portion
these studies. The compounds for wh
the performance  of this  Method  w
considered unacceptable  included metl
iodide, benzyl chloride,  4-chlorotoluei
and  dichlorodifluoro-methane. For  t
determination of  these  analytes
aqueous and  solid  matrices, Meth
8010  did not achieve  the  criteria
recovery and precision  that  we
established with  the priority pollutai
which  were  used  as   referen
compounds throughout these  studies.
   Based  on  the  results of  t
Instrumentation Range  Determinati
experiments, the performance of Meth
810 was considered to be acceptable
all 46  of the analytes used  in  the  [
portion of these studies.
Method 8015

   A total  of  21  compounds  we
originally considered for inclusion in t
evaluations  of  Method 8015. Due to t
results of preliminary  experiments, t\
compounds including acrylamide and
hydroxypropionitrile were excluded  frc
both the PTD  and the  DLI portions
these   studies  because  of  po
chromatographic  behavior  under  tl
Method 8015  conditions. A number
compounds were excluded from  the PI
experiments because  of poor  purgii
efficiencies. These analytes includf
acetonitrile;  allyl chloride;  carbt
disulfide; 1,2,3,4-diepoxybutane;  1,
dioxane; ethylene  oxide; isobutanc
malononitrile; methyl  mercapta
paraldehyde;  propargyl  alcohol;
propiolactone;  and propionitnle. The;
compounds  were included  in  the  D
experiments  of Method 8015  testin
Based  on the results of these prelimina
experiments,  six analytes  were  used
the PTD portion of Method 8015 testir
and 19 compounds were used in the D
experiments. None of  these compoun<
were priority pollutants.
   Based on  the  Instrumentation Rant
Determination and  the  Preliminai
Method Evaluation experiments, Methc
8015  was  considered  to  perfor
acceptably  for five of the six compounc
used in the PTD portions of the testin
Methyl isobutyl ketone  was eliminate
from   these  experiments when  tf"
performance of the  Method  for th
compound  was  not  found  to b
sufficiently reproducible  for  reliab
instrument calibration.  Based  on  th
Instrumentation Range  Determinatic
experiments, Method  8015  wa

-------
                                                  Spike 8 Samples of Standard
                                                  Matrix with Method Analytes
                                                   at S/N 100 Concentration
                                                  Calibrate Instrumentation
                                                    According to Method
                            Analyze
                             New
                            Samples
                                        Fail
                                                   Process 8 Spiked Samples
                                                       Through Method
         Test Concentrations Found
               for Outliers
                                                               Pass
                                    Calculate Percent
                                   Recovery Statistics;
                                      Compare to
                                       Recovery
                                      Performance
                                     Requirements
                                 Pass
                                                           (and)
              Fail
                        Fail
      Calculate Percent
      Relative Standard
     Deviation Statistics;
        Compare to
    Precision Performance
       Requirements
                                               Eliminate
                                                Method
                                               Analyte(s)
                    (or)
Terminate
Validation
                                               ^ Ruggedness Testing

                     Figure 3.    Preliminary method evaluation.
                                                                                        Pass
considered to be suitable for 16 of the 19
compounds used in the DLI portions of
these studies. The  performance of this
Method appeared to be unsuitable for the
determination  of  carbon disulfide,
malononitrile,  and  p-propiolactone in
nonaqueous  liquid  matrices primarily
because of the very low response of the
flame ionization  detector  used  in  this
Method for these analytes.


Method  8020

   A total  of 14 analytes  were  initially
considered for inclusion in the evaluation
of Method 8020. Based on the results of
preliminary experiments,  pyridine  and
thiophenol were eliminated from both the
PTD  and the  DLI portions  of  these
studies  due  to  poor chromatographic
behavior under the conditions specified
by Method 8020. In addition,  2-picoline
was  eliminated  from  the  PTD
experiments because of  poor purging
efficiency. This compound was included
in the DLI studies. Data obtained during
these preliminary experiments resulted in
the  use of 11 compounds in the PTD
portion of Method 8020 testing and 12
analytes in the DLI studies. In each case,
seven  of  the compounds used were
priority pollutants.
               Based  on  the  results  of  the
            Instrumentation Range Determination and
            the Preliminary Method  Evaluation steps
            of method testing, Method  testing was
            considered  to be suitable  for the
            determination  of  all 11  compounds  in
            aqueous  and solid  matrices.  These
            experiments involved the use of the PTD
            sample introduction  technique  and the
            criteria  for  acceptable  method
            performance  was based  on  results
            obtained for the seven  priority pollutant
            compounds.  Method  8020  was
            considered  to be suitable  for the
            determination  of all  12  of the analytes

-------
used  in  the DLI  portion  of these
experiments.


Conclusions and
Recommendations

  Based  on the studies described and
the  results presented  in the  full report,
the following conclusions are drawn:
• Using  the PTD sample introduction
  technique, Method 8015 was found to
  be  suitable for the determination  of
  five of the 21  test compounds  in
  aqueous and  solid samples.  This
  Method, in  combination  with DLI
  sample introduction,  was  demon-
  strated to be  successful for the
  determination of 19 of the 21 analytes
  in nonaqueous liquid samples.
• Method 8020  was  determined to  be
  suitable for the determination of 11  of
  the 14 test compounds in  aqueous
  and solid samples using PTD sample
  introduction.  Using  DLI  sample
  introduction,  this  Method  was
  demonstrated  to be successful in the
  determination  of  12 of  the  14
  compounds  in nonaqueous  liquid
  samples.
• Poor  purging  efficiency  and  poor
  chromatographic  behavior for  a
  number of test compounds prevented
  Methods 8010, 8015, and  8020 fro*
  performing successfully  for  these
  analytes.
  Table 1 lists the compounds for which
these  Methods were  determined to  be
suitable  based  on  the  experiments
conducted during these studies. Table 4
lists  the  compounds for  which the
performance of  these Methods was
found  to be unacceptable.  This table also
provides a brief comment  of the
difficulties encountered  with  each  of
these  compounds.
  Based  on the experiments described
and the  results presented  in the full
report, the following  recommendations
are  made.
• Pending further method  suitability
  testing, the compounds listed in Table
  1 should be included in the scopes of
  Methods 8010,  8015,  and  8020  as
  indicated.
• A total of 51  compounds was used to
  evaluate Method 8010. This Method
  was determined to  be suitable for the
  determination of 36 of  these analytes
  in aqueous and solid samples using
  the PTD  sample   introduction
  technique. When  the  DLI sample
  introduction  technique was  used,
  Method 8010 was found to be suitable
  for the determination of 46 of the test
  compounds in nonaqueous  liquid
  samples.
• At  this time,  compounds listed in
  Table 4 should be excluded from the
  scopes of Methods 8010, 8015, and
  8020.
• Further method suitability  testing
  should involve the use  of capillary
  columns  and should include those
  analytes excluded from this study on
  the basis  of poor chromatographic
  behavior.
• Further evaluations of these Methods
  should  include analysis of actual
  waste samples, rigorous determination
  of  method  detection limits  for  all
  analytes,  and the conduct  of the
  referee validation step of the SLMVP.
• Compounds listed in Table  5  have
  been  determined  to  purge  with
  acceptable efficiency and precision
  from  aqueous samples.  These
  compounds should  be  included in
  performance  testing  of SW-846
  Method 8240.
• For future studies involving these and
  other methods for the determination of
  volatile  compounds, more  reliable
  procedures  for the preparation of
  spiked aqueous  and solid samples
  should   be  developed   and
  implemented.  Emphasis  should  be
  placed on minimizing analyte  losses
  during the  preparation  of replicate
  samples.

References
1. Federal  Register, 49, No.  247,
  December  21,  1984,   pp  49784-
  49793.
2. Test Methods  for Evaluating  Solid
  Waste, U.S. Environmental Protection
  Agency,  Office of Solid Waste and
  Emergency Response,  SW-846,
  Third Edition, November,  1986.
3. GC-MS  Suitability Testing,  U.S.
  Environmental  Protection  Agency,
  Environmental Monitoring and Support
  Laboratory -  Cincinnati,  EPA
  Contract Number 68-03-3224,  Work
  Assignment 1-04.
4. Screening of Sent/volatile Organic
  Compounds for  Extractability and
  Aqueous  Stability  by SW-846
  Method  3510,  U.S.  Environmental
  Protection Agency,  Environmental
  Monitoring and Support  Laboratory  -
  Cincinnati,  EPA  Contract  Number
  68-03-3224, Work  Assignment 2-
  08.
5. Development of a Single Laboratory
  Method Validation Protocol, U.S.
  Environmental  Protection Agency,
  Environmental Monitoring and  Support
  Laboratory -  Cincinnati,  EPA
Contract  Number  68-03-3224, Wi
Assignment  1-01.

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Table 1. Compounds Considered for Inclusion in the Suitability Testing of Methods 8010, 8015, and 8020
            Compound              CAS Number    Listf*)                 Source
Method 8010
Allyl chloride
Benzyl chloride
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl)sulfide
Bis(2-chloroisopropyl)ether
Bromoacetone
Bromobenzene
Bromodichloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlomacetaldehyde
Chloral
Chlorobenzene
Chloroethane
2-Chloroethanol
Chloroform
1-Chlorohexane
2-Chloroethyl vinyl ether
Chloromethane
Chloromethyl methyl ether
Chloroprene
3-Chloropropionitrile
4-Chlorotoluene
Dibromochloromethane
1 ,2-Dibromo-3-chloropropane
Dibromomethane
1 ,2-Dichlorobenzene
1 ,3-Dichlorobenzene
1 ,4-Dichlorobenzene
l,4-Dichloro-2-butene
Dichlorodifluoromethane
1 ,1 -Dichloroethane
1 ,2-Dichloroethane
1 , 1 -Dichloroethylene
Trans-l,2-dichloroethylene
Dichloromethane
1 ,2-Dichloropropane
1 ,3-Dichloro-2-propanol
Cis-1 ,3-dichloropropylene
Epichlorohydrin
Ethylene dibromide
Methyl iodide
Pentachloroethane
i, i ,2,2-Tetrachloroethane
i, 1, 1,2-Tetrachloroethane
Tetrachloroethylene
i, i, 1 -Trichloroetfiane
i, i ,2-Trichloroethane
Trichloroethylene

107-05-1
100-44-7
111-91-1
505-60-2
108-60-1
598-31-2
108-86-1
75-27-4
75-25-2
74-83-9
56-23-5
107-20-0
75-87-6
106-90-7
75-00-3
107-07-3
67-66-3
544-10-5
100-75-8
74-87-3
107-30-2
126-99-8
542-76-7
106-43-4
124-48-1
96-12-8
74-95-3
95-50-1
541-73-1
106-46-7
764-41-0
75-71-8
75-34-3
107-06-2
75-35-4
156-60-5
75-09-2
78-87-5
96-23-1
10061-01-5
106-89-8
106-93-4
74-88-4
76-01-7
79-34-5
630-20-6
127-18-4
71-55-6
79-00-5
79-01-6

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8
8,9
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PP, 8, 9
PP, 8, 9
PP, 8, 9
8
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PP, 8, 9
PP, 9
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PP, 8, 9
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PP, a
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Chem Services, Inc.
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Analabs
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Matheson Gas Products
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Burdick and Jackson Laboratories
Fluka AG Chemical Company
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Aldrich Chemical Company
Aldrich Chemical Company
Fisher Scientific Company
Aldrich Chemical Company
Aldrich Chemical Company
                                                                                 (Continued)

-------
Table 1. (Continued)
Compound
Method 8010 (Continued)
Trichlorofluoromethane
1 ,2,3-Trichloropropane
Vinyl chloride
Method 801 5
Acetonitrile
Allyl alcohol
Acrylamide
Carbon disulfide
1 ,2,3,4-Diepoxybutane
Diethyl ether
1,4-Dioxane
Ethylene oxide
Ethyl methacrylate
2-Hydroxypropionitrile
Isobutanol
Malononitrile
Methacrylonitrile
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl mercaptan
Methyl methacrylate
Paraldehyde
Propargyl alcohol
(l-propiolactone
Propionitrile
Method 8020
Benzene
Chlorobenzene
1 ,2-Dichlorobenzene
1 ,3-Dichlorobenzene
1 ,4-Dichlorobenzene
Ethyl benzene
2-Picoline
Pyridine
Styrene
Thiophenol
Toluene
o-Xylene
m-Xylene
p-Xylene
CAS Number

75-69-4
96-18-4
75-01-4

75-05-8
107-18-6
79-06-1
75-15-0
1464-53-5
60-29-7
123 -91-1
75-21-8
97-63-2
78-97-7
78-83-1
109-77-3
126-98-7
78-93-3
108-10-1
74-93-1
80-62-6
123-63-7
107-19-7
57-57-8
107-12-0

71-43-2
106-90-7
95-50-1
541-73-1
106-46-7
100-41-4
109-06-8
1 10-86-1
100-42-5
108-98-5
108-88-3
95-47-6
1477-55-0
106-42-3
Listfa)

PP, 8, 9
8,9
PP, 8, 9

8
8
8
8,9
8
--
a
8
8,9
M
8
8
8
8,9
-
8
8,9
a
8
M
8

PP, 8, 9
PP, 8, 9
PP, 8, 9
PP, 8, 9
PP.8, 9
PP, 9
8,9
8,9
9,M
8
PP, 8, 9
9
9
9
Source

Aldrich Chemical Company
AJdrich Chemical Company
Matheson Gas Products

Burdick and Jackson Laboratories
Aldrich Chemical Company
Aldrich Chemical Company
Matheson, Coleman, and Bell
Sigma Chemical Company
Burdick and Jackson Laboratories
Burdick and Jackson Laboratories
Matheson Gas Products
Aldrich Chemical Company
Aldrich Chemical Company
Aldrich Chemical Company
Aldrich Chemical Company
Aldrich Chemical Company
Burdick and Jackson Laboratories
Aldrich Chemical Company
Matheson Gas Products
Matheson Gas Products
Sigma Chemical Company
Aldrich Chemical Company
Sigma Chemical Company
Aldrich Chemical Company

Burdick and Jackson Laboratories
Matheson, Coleman, and Bell
Aldrich Chemical Company
Aldrich Chemical Coompany
Aldrich Chemical Company
Poly Science Corporation
Aldrich Chemical Company
Aldrich Chemical Company
Chem Services, Inc.
Aldrich Chemical Company
Burdick and Jackson Laboratories
Burdick and Jackson Laboratories
Chem Services, Inc.
Matheson, Coleman, and Bell
(a) PP = Priority Pollutant; 8 ~ Appendix VIII; 9 = Appendix IX; M = Michigan List; -- = not on any list.

-------
Table 2.  Compounds Not Included in Evaluations of Methods 8010, 80f 5, and 8020
                                                                      Portion of Study From Which
                                                                         Compound Excluded
                                         Reasons for Exclusion
Compound
PTD
DLI
Method 8010
    8/s(2-ch/oroetf?oxy>neihane
    Bis(2-ch/orae(ny))su/fide
    Bis(2-chloroisopropyl)ether
    Bromoacetone
    Chloroacetaldehyde
    Chloral
    2-Chloroethanol
    Chloroethyl vinyl ether
    Chloromethyl methyl ether
    Chloroprene
    3-Chloropropionitrile
    1,3-Dichloropropanol
    Epichlomhydrin
    Pentachloroethane
Method 8015
    Acetonitrile
    My} alcohol
    Aery/amide
    Carbon disulfide
    1,4-Dioxane
    Ethyl oxide
    2-Hydroxypropionitrile
    Isobutanol
    Matononitrile
    Methyl mercaptan
    Paraldehyde
    Propargyl alcohol
    fl-Propiolactone
    Propionitrile
Method 8020
    2-PiCOline
    Pyridine
    Thiophenol	
                      Poor purging efficiency
                      Poor chromatographic behavior
                      Standard impure
                      Poor purging efficiency
                      Standard not available
                      Poor chromatographic behavior
                      Poor purging efficiency
                      Poor purging efficiency
                      Poor purging efficiency
                      Poor chromatographic behavior
                      Poor chromatographic behavior
                      Poor purging efficiency
                      Poor purging efficiency
                      Poor chromatographic behavior

                      Poor purging efficiency
                      Poor purging efficiency
                      Poor chromatographic behavior
                      Poor purging efficiency
                      Poor purging efficiency
                      Poor purging efficiency
                      Poor chromatographic behavior
                      Poor purging efficiency
                      Poor purging efficiency
                      Poor purging efficiency
                      Poor purging efficiency
                      Poor purging efficiency
                      Poor purging efficiency
                      Poor purging efficiency

                      Poor purging efficiency
                      Poor chromatographic behavior
                      Poor chromatographic behavior
 X
 X
 X
 X
 X
 X
 X
 X
 X

 X
 X
 X
 X

 X
 X
 X
 X
 X
 X
 X
 X
 X
 X
 X
 X
 X
 X

 X
 X
 X
 X
 X

 X
 X
 X
 X
 X
 X

-------
Table 3. Compounds Recommended for Inclusion in the Scopes of Methods 8010, 8015, and 8020

                                                        Sample Matrix for Which Method
                                                           Was Found to Be Suitable
Compound
Method 8010
Allyl chloride
Benzyl chloride
Bis(2-chloroethoxy)methane
Bromoacetone
Bromobenzene
Bromodichloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethanol
Chloroform
1 -Chlorohexane
2-Chloroethyl vinyl ether
Chloromethane
Chloromethyl methyl ether
Chloroprene
4-Chlorotaluene
Dibromochloromethane
1 ,2-Dibromo-3-chloropropane
Dibromomethane
1 ,2-Dichlorobenzene
1 ,3-Dichlorobenzene
1 ,4-Dichlorobenzene
l,4-Oichloro-2-butene
Dichlorodifluoromethane
1,1-Dichloroethane
1 ,2-Dichloroethane
1 , 1 -Die h/oroelfty/ene
Trans -1,2 -dichloroethylene
Dichloromethane
1 ,2-Dichloropropane
l,3-Dichloro-2-propanol
Cis-1 ,3-dichloropropylene
Epichlorhydrin
Ethylene dibromide
Methyl iodide
1, 1 ,2,2-Tetrachloroethane
1, 1, 1 ,2-Tetrachloroethane
List

X
(d)
(e)
(e)
X
X
X
X
X
X
X
(e)
X
X
(e)
X
(e)
X
(d)
X
X
X
X
X
X
X
(d)
X
X
X
X
X
X
(e)
X
(e)
X
(e)
X
X
Nonaqueous
Sample Matrices^)

X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X

-------
Table3.  (Continued)
                                                            Sample Matrix for Which Method
                                                               Was Found to Be Suitable
                                                           Aqueous/Solids      Nonaqueous
Compound
Method 8010 (Continued)
Tetrachloroethylene
1,1,1 -Trichloroethane
1, 1 ,2-Trichloroethane
Trichloroethylene
Trichloroftuoromethane
1 ,2,3-Trichloropropane
Vinyl chloride
Method 8015
Acetonitrile
Allyl alcohol
1 ,2,3,4-Diepoxybutane
Diethyl ether
1,4-Dioxane
Ethylene oxide
Ethyl methacrylate
Isobutanol
Metfracryfonrtri/e
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl mercaptan
Methyl methacrylate
Paraldehyde
$-Propiolactone
Propionitrile
Method 8020
Benzene
Chlorobenzene
1 ,2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 , 4 -Dichlorobenzene
Ethyl benzene
2-Picoline
Styrene
Toluene
o-Xylene
m-Xylene
p-Xylene
Ustf*)

PP,8.9
PP
PP.8,9
PP,8,9
PP,8,9
8,9
PP.8,9

8
8
8
—
8
8
8,9
8
8
8,9
-
8
8,9
8
M
8

PP,8,9
PP,8,9
PP.8,9
PP,8,9
PP,8,9
PP,9
8,9
9,M
PP,8,9
9
9
9
Sample Matrices

X
X
X
X
X
X
X

(e)
(e)
(e)
X
(e)
(e)
X
(o)
X
X
(d)
(e)
X
(e)
(e)
(e)

X
X
X
X
X
X
(d)
X
X
X
X
X
Sample Matrices^)

X
X
X
X
X
X
X

X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X

X
X
X
X
X
X
X
X
X
X
X
X
(a)  pp = priority Pollutant; 8 = Appendix VIII; 9 = Appendix IX; M = Michigan List; -- = not on any
    list.
(b)  Method testing with aqueous and solid samples involved the use of PTD sample introduction.
(c)  Method testing with nonaqueous liquid samples involved the use of DLI sample introduction.
(d)  Method determined to be unsuitable for determination of this compound in the sample matrix
    indicated.
(e)  Compound not included in this portion of testing due to poor purging efficiency.
(f)  Chloroprene not included in this portion of testing due to poor chromatographic behavior with DLI
    sample introduction under conditions specified in method.  See text for discussion.
                                             11

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Table 4. Compounds Recommended for Exclusion from the Scopes of Methods 8010, 8015, and 8020
                                            Sample Matrix for
                                          Method was Found to
                                             be Unsuitable
                                          Aqueous  Nonaqueous

Compound
List<*)
Solid
-------
Table 5. Compounds Recommended for Inclusion in Method 8240 Performance Testing
Compound
Allyl chloride
Benzene
Bromobenzene
Bromodichloromethane
Bromoform
Bromomethane
Carbon Tetrachloride
Chlorobenzene
Chloroethane
Chloroform
1 -Chlorohexane
Chloromethane
Chloroprene
Oibromochloromethane
1 ,2-Dibromo-3-
chloropropane
Dibromomethane
1 ,2-Dichlorobenzene
1 ,3-Dichlorobenzene
1 ,4-Dichlorobenzene
1 , 4 -Dich /oro-2 -butene
1,1-Dichloroethane
1 ,2-Dichloroethane
1 , 1 -Dichloroethylene
Trans-i ,2-Dichloroethylene
Dichloromethane
1 ,2-Dichloropropane
Cis-i,3-Dichloropropylene
Diethyl ether
Ethyl benzene
Ethyl methacrylate
Ethylene dibromide
Methacrylonitnle
Methyl ethyl ketone
Methyl methacrylate
Styrene
1 , 1 ,2,2-Tetrachloroethane
1,1,1,2-Tetrachloroethane
Tetrachloroethylene
1,1,1- Trichloroethane
1 , 1 ,2-Trichloroethane
Trichloroethylene
Trichlorofluoromethane
1,2,3-Trichloropropane
Toluene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
CAS Number
107-05-1
73-41-2
108-86-1
75-27-4
75-25-2
74-83-9
56-23-5
706-90-7
75-00-3
67-66-3
544-10-5
74-87-3
t26-99-8
724-48-7
96-72-8

74-95-3
95-50-7
547-73-7
706-46-7
764-47-0
75-34-3
707-06-2
75-35-4
756-60-5
75-09-2
78-87-5
70067-07-5
60-29-7
700-47-4
97-63-2
706-93-4
726-98-7
78-93-7
80-62-6
700-42-5
79-34-5
630-20-6
727-78-4
77-55-6
79-00-5
79-07-6
75-69-4
96-78-4
708-88-3
75-07-4
95-47-6
7477-55-0
706-42-3
Retention Time
(minutes)
10.17
2.59
29.05
75.44
27.72
2.90
74.58
2549
5.78
72.62
26.26
7.40
75.60
78.22
2809

73.83
37.96
36.88
38.64
23.45
77 27
73 74
70.04
77.97
7.56
76.69
77.00
77 24
872
2398
79.59
73.09
72.93
20.22
77.60
23.72
27.70
23.05
74.48
78.27
77.40
9.26
22.95
5.74
3.25
70.54
9.77
9.78
Purging
Efficiency
(percent)
88
77
87
707
65
77
87
57
85
88
76
73
90
709
74

78
83
82
80
30
86
703
78
707
86
90
700
90
94
55
77
37
74
55
86
702
85
57
97
83
85
82
50
99
81
92
99
98
Estimated
Detection Limit
(Itgll-)
0.272
0.0554
0.278
0.738
0.957
0.850
0.777
0707
0755
0.723
0.283
0.258
2.50
0.488
7.66

0.900
7.59
0.274
0.362
0.488
0.764
0.729
0.780
0897
293
0.300
0377
0.073
0.0957
0.389
0.645
2.53
0.789
0.064
0.778
0.740
0.777
0.402
0.082
0.049
0.724
0797
0.346
0.0867
0.733
0.0326
0.725
0.0759
                                       13

-------
  J. E.  Gebhart, S.V. Lucas,  S.J. Naber, AM Berry, T.H.  Danison, and  H.M.
        Burkholder are with Battelle  Columbus Division,  Columbus, OH 43201-
        2693.
  James E. Longbottom is the EPA Project Officer (see below).
  The complete report, entitled 'Validation of SW-846 Methods 8010, 8015, and
  8020," (Order No. PB88-161 567/AS; Cost: $14.95, subject to change) will be
  available only from:
           National Technical Information Service
           5285 Port Royal Road
           Springfield, VA 22161
           Telephone:  703-487-4650
  The EPA Project Officer can be contacted at:
           Environmental Monitoring and Support Laboratory
           U.S. Environmental Protection Agency
           Cincinnati, OH 45268
                                                      OulO ,/ >> B METEfll
                                                     vUl-MU/  62501091
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
     BULK RATE
POSTAGE & FEES PAID
         EPA
  PERMIT No. G-35
Official Business
Penalty for Private Use $300

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