United States
                    Environmental Protection
                    Agency
Atmospheric Research and
Exposure Assessment Laboratory
Research Triangle Park, NC 27711
                    Research and Development
EPA/600/SR-93/101   September 1993
vyEPA      Project  Summary
                    Field Test of Generic  Method for
                    Halogenated  Hydrocarbons
                    J.F. McGaughey, J.T. Bursey, R.G. Merrill, Jr.
                      Validation of a method for a particu-
                    lar analyte or group of analytes means
                    that the performance of the sampling
                    and analytical methodology for these
                    analytes has been established and dem-
                    onstrated through field tests at the type
                    of source category of interest:  that is,
                    the precision and bias  of the method
                    have been established experimentally.
                    In examination of the available method
                    validation data for organic compounds
                    listed in Title III of the Clean Air Act
                    Amendments (CAAA) of 1990, the lack
                    of overall method validation data is
                    readily apparent. In  some cases, ana-
                    lytical methods have been validated for
                    a number of analytes, but there is no
                    validation information for the sampling
                    methodology. Full validation for sam-
                    pling and analytical methods, for both
                    field and laboratory operations, is avail-
                    able for fewer than 10 % of the analytes
                    listed in Title III of  the CAAA at  any
                    source category. Field validation may
                    be performed by side-by-side compari-
                    son of a candidate  method to a vali-
                    dated method to establish comparable
                    performance for the same analytes in
                    the same matrix (same  source  cat-
                    egory). Another  procedure for valida-
                    tion of a method is to perform spiking
                    operations in the field so that the  pre-
                    cision and bias of the method can be
                    demonstrated from  sample collection
                    through analysis. Both  dynamic  and
                    static procedures for the validation of
                    a method are permitted in EPA's Vali-
                    dation Protocol in Method 301.
                      This Project Summary was developed
                    by EPA's Atmospheric Research  and
                    Exposure Assessment Laboratory, Re-
search Triangle Park, NC, 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 United States Environmental Pro-
tection Agency (EPA), under the authority
of Title III of the Clean Air Act Amend-
ments (CAAA) of 1990, requires the iden-
tification and/or validation of sampling and
analytical  methods  for  the halogenated
volatile and  semivolatile organic  com-
pounds which are listed (Table 1 and Table
2). The candidate methods for testing the
volatile organic compounds are VOST
(SW-846 Sampling Method 0030 and SW-
846 Analytical Methods 5040 or 5041),
and for testing the semivolatile organic
compounds, SemiVOST (SW-846  Sam-
pling Method 0010 and SW-846  Analytical
Method 8270) is used. The VOST and
SemiVOST methods were first  evaluated
in a laboratory environment, and dynamic
spiking procedures were also developed
and evaluated. The  results of the labora-
tory study were reported in an earlier docu-
ment.
  After the laboratory evaluation, the next
step was  to attempt to validate the two
candidate  test methods at  a  coal-fired
power plant that does not routinely emit
high levels of these hazardous  air pollut-
ants (HAPs).  The absence of high levels
of the  HAPs was determined by analyzing
samples collected during a  pretest sur-
vey. A field test was planned  to further
verify  the  analyte spiking methodology in
a non-laboratory environment and to as-
sess the added effect of sampling a com-

          1^ A) Printed on Recycled Paoer

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bustion matrix (stack gas). Minimizing the
source contribution of  the HAPs in  the
sample matrix simplified the evaluation of
the results for the effectiveness of  the
spiking procedures. A source with signifi-
cant levels of all the HAPs  shown in Tables
1 and 2 could not be located.

Results and Discussion
  Validation of VOST and  SemiVOST was
accomplished by performing sampling and
analysis following the EPA methods  ex-
cept for the use of a quadruple (QUAD)
probe system required by EPA Method
301. Validation procedures for a method
include protocols for determining and docu-
menting the quality of data generated  by
that method.  The bias  (systematic error)
and precision (reproducibility of measure-
ment) are determined in a  statistically valid
manner. The  procedures  for validating a
method for a  given analyte  or set  of
analytes  require introducing known con-
centrations of the analyte(s) into the sam-
pling  train  or comparing  the  candidate
method against a validated test  method.
The bias  of the method can be evaluated
by determining the recovery of the known
quantity of analyte which has been spiked
into the sampling train  or  by comparison
of the results obtained by the candidate
method to the results obtained by the vali-
dated method.  In order to determine  the
precision  of the test method,  multiple or
collocated simultaneous samples are taken
and analyzed.  If dynamic spiking tech-
niques are used, it is  essential  that  the
analyte be introduced  into the  sampling
train as near  to the end of the  probe  as
possible,  and  that the  analyte  be intro-
duced continuously for the duration of the
sampling  operation.
  Bias may result from  analytical interfer-
ences, errors in calibration, or inefficien-
cies in the collection of the analyte. When
the bias of the method is determined for a
given  analyte,  a correction for the bias
may be made.  The EPA  Method 301  al-
lows for this correction  within  a range of
70 to  130%. Bias values outside this range
may require the rejection of the candidate
method.
  Precision is the variability in the data
that is obtained from the entire measure-
ment system (both sampling and analysis)
as determined from the multiple or collo-
cated  sampling trains. Following the EPA
Method 301 procedures, two paired sam-
pling  trains were used to determine  the
precision  of the entire system. Use  of
QUAD trains with four collocated sam-
pling probes allows operation of two spiked
trains  and two unspiked trains. EPA
Method 301  requires  that the  precision
not be greater  than 50 % relative stan-
dard deviation for the method to be valid.
To  determine bias  and precision in the
field,  a total  of  24 samples  using  qua-
druple collocated sampling trains was col-
lected. For quadruple trains, six complete
sampling  runs constitute the minimum
Method 301 requirement.
  The halogenated compounds listed in
the CAAA of  1990 for which method vali-
dation  is required and for which labora-
tory testing has been performed are shown
in Tables  1 and  2. Pesticides, polychlori-
nated  biphenyls,  2,3,7,8-tetrachlorodi-
benzo-p-dioxin, and dibenzofurans were
excluded from this  study, since  special-
ized  methods  are available  for these
analytes Not  all of the candidate analytes
for the VOST and SemiVOST performed
successfully in those methods. Four com-
pounds could not  be  analyzed by  the
VOST of  SemiVOST  methods either in
the laboratory or in the field:
  • Bis(chloromethyl) ether, chloromethyl
    methyl  ether, and epichlorohydrin
    could not be analyzed by the VOST
    analytical method.  Since  these com-
    pounds  are  water-soluble and react
    with  water, the failure of the VOST
    analytical  methodology   was antici-
    pated.
  • Chloroacetic acid  could  not  be ana-
    lyzed in the  SemiVOST analytical
    method  because of its  unstable and
    reactive nature.

  The  laboratory evaluation included  the
following  components:


  • Determination of chromatographic re-
    tention  times  for  both  volatile and
    semivolatile  compounds using gas
    chromatography/mass  spectrometry
    (GC/MS);
  • Determination of recoveries from sor-
    bents for both volatile and  semivolatile
    compounds;
  • Determination of analytical method de-
    tection  limits  for   both volatile and
    semivolatile halogenated organic com-
    pounds; and
  • Design,  construction, and evaluation
    of  dynamic  spiking equipment and
    techniques for use  in the field spiking
    of  volatile and semivolatile  haloge-
    nated organic compounds.
  The  fied  validation  of the  VOST and
SemiVOST was accomplished by  dynami-
cally spiking the trains  with  the  specific
halogenated organic compounds while si-
multaneously sampling  emissions from  a
combustion  source. During each QUAD
sampling run,  only two of the four sam-
pling trains were dynamically spiked;  the
other two unspiked trains were  used to
establish the background  level of any tar-
get compounds in the stack gas. A sam-
pling scheme to meet the requirements of
method validation was designed statisti-
cally to ensure the collection of appropri-
ate numbers of samples for each method.
Samples were  analyzed according to SW-
846 Method 5041  and  SW-846 Meth-
od 8270, with statistical evaluation of data.
Results are  summarized in Tables 3  and
4.
  Based on the work performed in the
laboratory and the field evaluation of the
VOST and SemiVOST methods, the fol-
lowing conclusions  may  be  drawn  from
the results shown in Tables 3  and 4:


  • Using the  criteria  for  acceptable per-
    formance of recovery  between 50 and
    150 %,  with a percent standard de-
    viation of 50 or less, the VOST meth-
    odology performed successfully in  a
    coal-fired  boiler emission  matrix at  a
    nominal concentration of 12  ng/liter
    for the following compounds: cis-1,3-
    dichloropropene,  trans-1,3-dichloro-
    propene, trichloroethene, methyl chlo-
    roform (1,1,1-trichloroethane), carbon
    tetrachloride,  vinyl chloride, 1,1,2-tri-
    chloroethane, tetrachloroethene, chlo-
    robenzene, vinylidene chloride  (1,1-
    dichloroethene), chloroform, methyl-
    ene chloride, ethylene dichloride (1,2-
    dichloroethane), ethylidene dichloride
    (1,1-dichloroethane),  methyl iodide
    (iodomethane),  propylene dichloride
    (1,2-dichloropropane), vinyl bromide,
    methyl bromide (bromomethane), and
    ethyl chloride (chloroethane).
  • Using the  criteria  for  acceptable per-
    formance of recovery  between 50 and
    150 %  with a percent relative stan-
    dard  deviation of 50 or less,  the
    SemiVOST  methodology performed
    successfully in a coal-fired  boiler emis-
    sions matrix at a  nominal concentra-
    tion of 6 |ig/ft3 for the following com-
    pounds:   hexachloroethane,  benzyl
    chloride, hexachlorobutadiene, 1,1,2-
    trichloroethane, 2,4,5-trichlorophenol,
    chlorobenzene, dichloroethyl ether,
    benzotrichloride, bromoform, 1,2,4-tri-
    chlorobenzene, ethylene dibromide
    (1,2-dibromoethane), 1,1,2,2-tetra-
    chloroethane, 1,4-dichlorobenzene, 2-
    chloroacetophenone, tetrachloro-
    ethene,  and trans-1,3-dichloro-
    propene.

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   The VOST methodology did not per-
   form  acceptably .under the field  con-
   ditions  for methyl chloride (chloro-
   methane), chloroprene, ethylene di-
   bromide (1,2-dibromoethane), and al-
   lyl chloride (3-chloropropene).
   The SemiVOST methodology did not
   perform acceptably  under the  field
   conditions  for 2,4,6-trichlorophenol,
   cis-1,3-dichloropropene, 1,2-dibromo-
   3-chloropropane, hexachlorobenzene,
  pentachloronitrobenzene,  pentachlo-
  rophenol, hexachlorocyclopentadiene,
  chlorobenzilate, epichlorohydrin, 3,3'-
  dichlorobenzidine,  and  bis(chloro-
  methyl) ether.
  Some compounds were tested in both
  methodologies because they  exhib-
  ited volatility (boiling points) appropri-
  ate for inclusion in either method. The
  following compounds  performed  ac-
  ceptably  in  both  VOST and  Semi-
           VOST:  tetrachloroethene, trans-1,3-
           dichloropropene, 1,1,2-trichloroethane,
           and chlorobenzene. Ethylene dibro-
           mide (1,2-dibromoethane) performed
           acceptably in  the  SemiVOST meth-
           odology, but did not meet recovery
           criteria  for the  VOST methodology.
           cis-1,3-Dichloropropene performed ac-
           ceptably using the VOST methodol-
           ogy but did not meet the criteria for
           successful  performance  in  the
           SemiVOST methodology.
Table 1.  Halogenated Compounds for Which Laboratory Testing Has Determined the Applicability of the VOST Method.
            Compound
Boiling point fC)
                                                                                          Comments
Allyl chloride
bis(chloromethyl) ether
Carbon tetrachloride
Chlorobenzene
Chloroform
Chloromethyl methyl ether
Chloroprene
1 , 3-Dichloropropylene
Epichlorohydrin
Ethyl chloride
Ethylene dibromide
Ethylene dichloride
Ethylidene dichloride
Methyl bromide
Methyl chloride
Methyl chloroform
Methylene chloride
Methyl iodide
Propylene dichloride
Tetrachloroethylene
1, 1,2-Trichloroethane
Trichloroethylene
Vinyl chloride
Vinyl bromide
Vinylidene chloride
44-46
106 '
77
132'
60.5-61.5
55-57
59.4
1 05-106 2
115-177'
123
131-132 '
83
57
43
-24.2 3
74-76
39.8-40
41-43
95-96
121 '
110-115'
86.9
-13.43
164
30-32
Acceptable performance in laboratory
Decomposes in water; cannot be analyzed
Recovery too high in laboratory study
Acceptable performance in laboratory
Acceptable performance in laboratory
Decomposes in water; cannot be analyzed
Acceptable performance in laboratory
Acceptable performance in laboratory
Decomposes in water; cannot be analyzed
Acceptable performance in laboratory
Acceptable performance in laboratory
Acceptable performance in laboratory
Acceptable performance in laboratory
Recovery unacceptable high in laboratory
Erratic and unacceptable n laboratory
Recovery too high in laboratory study
Recovery too high in laboratory study
Acceptable performance in laboratory
Acceptable performance in laboratory
Acceptable performance in laboratory
Acceptable performance in laboratory
Acceptable performance in laboratory
Acceptable performance in laboratory
Acceptable performance in laboratory
Acceptable performance in laboratory
 Above the maximum VOST boiling point of 100°C; Included in the testing because compounds in the range of 100-132°C are frequently tested by the VOST method.
 Boiling temperature at 730 mm Hg.
 Below the common lower temperature limit of 30°C usually used for VOST.
 Boiling temperature at 750 mm Hg.
 Table 2.  Halogenated Compounds for which Laboratory Testing has Determined the Applicability of the SemiVOST Method.
            Compound
Boiling po
                                                                                           Comments
  Benzotrichloride
  Benzyl chloride
  bis(Chloromethyl) ether4
  Bromoform
  Chloroacetic acid
  Chlorobenzene4
  2-Chloroacetophenone
  Chlorobenzilate
  1,2-Dibromo-3-chloropropane
    219-223
    177-181
      106
    150-151
      189
      132
    244-245
      147
      196
Acceptable performance in laboratory
Acceptable performance in laboratory
Unacceptably low recovery in laboratory
Acceptable performance in laboratory
Cannot be analyzed by SemiVOST method
Acceptable performance in laboratory
Acceptable performance in laboratory
Unacceptably low recovery in laboratory
Acceptable performance in laboratory

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Table 2.   Halogenated Compounds for which Laboratory Testing has Determined the Applicability of the SemiVOST Method (continued).
              Compound
Boiling point (°C)
 Also tested in VOST methodology.
 Boiling temperature at 740 mm Hg.
 Boiling temperature at 730 mm Hg.
 Boiling temperature at 15 mm Hg.
Table  3.   Results of VOST Field Validation
Comments
1 ,4-Dichlorobenzene
3,3'-Dichlorobenzidine
Dichloroethyl ether
1 , 3-Dichloropropene
Epichlorohydrin '
Ethylene dibromide '
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclopentadiene
Hexachloroethane
Pentachloronitrobenzene
Pentachlorophenol
1, 1,2,2-Tetrachloroethane
Tetrachloroethylene '
7, 2, 4- Trichlorobenzene
1,1,2-Trichloroethane '
2,4, 5- Trichlorophenol
2, 4, 6- Trichlorophenol
173
MP=165
6567"
105 106 3
115-117
131-132
323-326
210-220
239
186
328
3095
147
121
214
110-115
248 2
246
Acceptable performance in laboratory
Erratic performance in laboratory
Acceptable performance in laboratory
Unacceptably low recovery in laboratory
Acceptable performance in laboratory
Acceptable performance in laboratory
Unacceptably low recovery in laboratory
Acceptable performance in laboratory
Erratic performance in laboratory
Acceptable performance in laboratory
Unacceptably low recovery in laboratory
Unacceptably low recovery in laboratory
Acceptable performance in laboratory
Unacceptably low recovery in laboratory
Acceptable performance in laboratory
Acceptable performance in laboratory
Erratic performance in laboratory
Unacceptably low recovery in laboratory
                   Compound
                  Percent recovery
        Percent RSD
Methyl chloride (chloromethane)
Ethylidene dichloride (1, 1 -dichloroethane)
Chlorobenzene
Vinyl chloride
Vinylidene chloride (1, 1-dichloroethylene)
Chloroform
Propylene dichloride (1,2-dichloropropane)
Methyl bromide (bromomethane)
Ethyl chloride (chloroethane)
Methylene chloride
Methyl chloroform (1, 1, 1-trichloroethane)
Carbon tetrachloride
Ethylene dichloride (1,2-dichloroethane)
Trichloroethylene
cis- 1, 3-Dichloropropene
trans - 1 , 3-Dichloropropene
1, 1,2-Trichloroethane
Tetrachloroethene
Methyl iodide (iodomethane)
Allyl chloride (3-chloropropene)
Ethylene dichloride (1,2-dibromoethane)
Chloroprene
Vinyl bromide
937.0
75.7
88.2
110.4
88.0
81.8
67.2
53.7
50.3
77.7
109.6
106.7
76.6
125.5
136.8
134.9
98.0
97.7
72.8
29.9
34.9
40.1
60.7
53.8
13.7*
22. 02
27.32
31.32
14.82
9.6?
20.22
28. T2
27.1*
43. S2
47.2s
33.02
15.62
26. 02
38. 12
22. 12
21.92
37.6
19.5
31.6
22.4
34.32
1  Chloromethyl methyl ether, bis(chloromethyl) ether, and epichlorohydrin could not be analyzed by the VOST methodology.
2  Acceptable performance by the analyte in the VOST method, using acceptability criteria of 50-150% recovery, with Percent Relative Standard Deviation of 50 or less.

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Table 4.   Results of SemiVOST Field Validation
                 Compound	                               Percent recovery                        Percent RSD
bis(Chloromethyl) ether
Epichlorohydrin
cis- 1, 3-Dichloropropene
trans- 1 , 3-Dichloropropene
1, 1,2-Trichloroethane
1 ,2-Dibromoethane
Tetrachloroethene
Chlorobenzene
Bromoform
1, 1,2,2-Tetrachloroethane
Dichloroethyl ether
1 ,4-dichlorobenzene
Benzyl chloride
Hexachloroethane
1 , 2-Dibromo-3-chloropropane
1,2,4- Trichlorobenzene
Hexachlorobutadiene
Benzotrichloride
2- Chloroace tophenone
Hexachlorocyclopentadiene
2,4, 6- Trichlorophenol
2,4, 5- Trichlorophenol
Hexachlorobenzene
Pentachlorophenol
Pentachloronitrobenzene
Chlorobenzilate
3, 3 '-Dichlorobenzidine
0.0
6.0
49.1
52.0
56.4
58.9
53.2
63.3
59.8
64.1
60.9
56.1
60.1
74.0
44.8
59.5
65.4
60.1
56.0
42.3
49.8
62.7
44.6
42.4
43.4
40.7
4.4

128 1
37.5
352s
37 T2
369*
372*
35 12
37 62
35. 32
34.7s
352s
36 S2
369s
360
35 T2
43. 12
36 S2
40 T2
61 8
470
432*
339
41 5
379
506
1649
 Chloroacetic acid could not be analyzed by the SemiVOST methodology.
 Acceptable performance by the analyte in the SemiVOST method, using acceptability criteria of 50-150% recovery, with Percent Relative Standard Deviation of 50 or less.
                                                                                         . GOVERNMENT PRINTING OFFICE: 1993 - 750-071/80076

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  J.F. McGaughey, J.T. Bursey, and R.G. Merrill, Jr., are with Radian Corporation,
    Research Triangle Park, NC 27709.
  Merrill D. Jackson is the EPA Project Officer (see below).
  The complete report, entitled "Field Test of a Generic Method for Halogenated
    Hydrocarbons," (Order No. PB93-212181AS; Cost:  $36.50, 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:
          Atmospheric Research and Exposure Assessment Laboratory
          U.S. Environmental Protection Agency
          Research Triangle Park, NC 27711
United States
Environmental Protection Agency
Center for Environmental Research Information
Cincinnati, OH 45268
Official Business
Penalty for Private Use $300
      BULK RATE
POSTAGE & FEES PAID
         EPA
   PERMIT NO. G-35
EPA/600/SR-93/101

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