Gc-ms Suitability Testing Of RCRA Appendix Viii and Michigan List Analytes


                    United States
                    Environmental Protection
                    Agency
Environmental Monitoring and
Support Laboratory
Cincinnati OH 45268
                    Research and Development
EPA/600/S4-87/024 Jan. 1988
<>EPA         Project  Summary
                    GC-MS Suitability Testing of RCRA
                    Appendix  VIII and  Michigan List
                    Analytes
                    S. V. Lucas and R. A. Kornfeld
                      As a first step in a hierarchical scheme
                    to demonstrate the suitability of present
                    U.S. Environmental Protection Agency
                    (EPA) analysis methods and/or develop
                    new methodology, the gas chromato-
                    graphic (GC) separation  and  mass
                    spectrometric (MS)  detection  char-
                    acteristics of 328 toxic and/or hazard-
                    ous organic materials ware investigated.
                    The analytes in question are the non-
                    priority pollutant organic substances in
                    the RCRA Appendix VIII listing plus
                    those on the "Michigan List."
                      Volatile and semivolatile analytes were
                    tested using  the GC-MS  conditions
                    specified in EPA Methods 8240 and
                    8270, respectively, as modified by the
                    Contractor Laboratory Program  (CLP)
                    protocol. Standard mixtures of analytes
                    in organic solvent were analyzed by
                    septum  injection onto  the analytical
                    column without any  prior  sample
                    workup procedures.
                      For analytes that proved suitable for
                    GC-MS analysis by Methods 8240 and
                    8270, the relevant characteristics for
                    GC retention and for MS detection are
                    reported. For analytes not detected by
                    GC-MS or omitted a priori from testing,
                    recommendations for future work are
                    made.
                      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 Re-
covery Act (RCRA) specifies over 300
toxic organic compounds in its Appendix
VIII listing which may be used to identify
hazardous wastes. In response to a peti-
tion by the state of Michigan, the U.S.
Environmental Protection Agency (EPA)
has proposed the amendment of  RCRA
Appendix VIII by the addition of over 100
other organic compounds. EPA is cur-
rently attempting to validate analytical
methods for as many of these 400 plus
compounds as possible. A  hierarchical
approach to these validation efforts  is
being pursued.
  An example of a hierarchical approach
to the development and validation of
analytical methods for the determination
of organic compounds  in wastes is pre-
sented in Figure 1. The final report com-
pletely describes the  procedures and
presents fully the results obtained from
implementation of this first phase of the
hierarchical approach. The compounds
were classified  as candidates for the
application of either EPA Method 8240 or
Method 8270 to test for volatile or semi-
volatile organic compounds, respectively.
Some compounds were not tested be-
cause they fell into one of the following
categories:
  • Priority pollutants — The chromato-
    graphic behavior of these compounds
    has already been thoroughly char-
    acterized.
  • Unstable — Compounds known  to
    degrade rapidly in aqueous sample
    matrices.

-------
  • Not amenable to gas chromatography
    (GC) — Compounds known to be too
    polar and/or too thermally labile to
    elute using Method 8240 or Method
    8270 conditions.
  • Not available  — Compounds for
    which standards were not available
    from  the EPA  repository  or  from
    commercial sources.
For compounds determined to be amen-
able to the two  methods, the following
data were obtained:
  • GC  Performance  —  retention
    characteristics.
  • Mass Spectral (MS) Performance —
    response factors, key ions for detec-
    tion and quantification  using ex-
    tracted ion current profiles (EICP).
  Figure 1 shows the context in which
the results of this  project lead to sub-
sequent method development activities.
Implementation of the hierarchical
method development approach is ex-
pected to contribute to the development
of a suite of analytical methods with a
limited number of analytic procedures for
determining  a  large proportion of the
more than 400 organic compounds in the
amended  RCRA Appendix VIII. Covering
extraction, cleanup, and  determinative
steps,  this limited number of analytical
procedures would  form  the  core of  a
generic approach to the selection of ap-
propriate analytical methods for hazardous
wastes. The proposed system is generic
in the  sense that the specifications of
type of analyte, type of matrix, and type of
sensitivity and required specificity would
generate, from the limited suite of com-
ponent analytical procedures, the  most
appropriate set of analysis conditions.
  This type of generic approach would
permit  reduction  in the number and
variety of methods required to characterize
wastes and should provide cost benefits
both to the government and to the regu-
latory community. Also, the generic ap-
proach would facilitate periodic updates
of the  method, as new information be-
comes available about specific analytes
in specific matrices. Further, areas re-
quiring method  modification  or method
development could  be clearly identified
and easily prioritized for research resource
allocation.


Experimental Approach
  The initial set of analytes consisted of
organic compounds  included  in RCRA
Appendix VIII (Federal Register, October
1, 1984)  plus  those included  in the
Michigan  petition  (Federal Register,
December, 1984) minus the EPA priority
                                     Analyte
                                                      1. HPLC
                                                      2. Derivatization
                                                      3. Non-chromatographic
 1. Add to list
 2. Test in
   non-MS
   methods
                         1.  Add to list
                         2.  Test in
                            non-MS
                            methods
                  Evaluate other options.

                  1  Heated PTD
                  2. Direct injection
                  3. Micro extraction
                  4. Distillation
                  5. Non-GC methods
    1. Modified extraction
      conditions (SPE, other
      solvents, etc.)

    2. Develop/improve
      cleanup procedures

   	I
Figure 1,   Hierarchical  approach for  analytical  method development  for organic RCRt
           analytes.
pollutants. After eliminating redundancies
in the two lists, the remaining compounds
were classified by their predicted suit-
ability for SW 846 Method 8240 (volatiles),
Method 8270 (semi-volatiles), or for their
predicted inability to be determined by
either method.
  Sources for the selected analytes were
identified in the following order of priority:
1) the EPA repositories  of  reference
compounds  and pesticides (EMSL - Las
Vegas and RTP), 2) the EPA repository of
certified  solutions (EMSL  - Cincinnati),
and  3)  commercial  suppliers. GC-MS
suitability studies utilized analyte mix-
tures prepared  after consideration of
chemical reactivity.
  For most  of the  analytes,  individual
analyte  concentrations  in  the volatile
mixtures were 200  /ig/mL,  for  a  few
analytes  predicted to exhibit lower  re-
sponse factors; concentrations were 400
/jg/mL.   Injections of volatile analytes
provided  a minimum of 300 ng of analyte
on column. The  concentrations  of  in-
dividual semivolatile analytes in the in-
jection standards were 40 /ug/mL For
analytes not detected on the first attempt
higher concentrations were  employed
ranging from 50-400 /ig/mL. Injections
of semivolatile analytes provided a mini
mum of 80 /ug of analyte to the splitless
injection evaporator  cavity. The usua
packed GC column, 1 percent SP1000/
Carbopack  B (Supelco),  was  used  fo
volatile  compounds, and a 30 meter ;
0.25 mm ID fused silica coated with 0.2C
micron  immobilized  methyl phenyl  sili
cone (J&W DB-5) was used for semi
volatile compounds.
  Internal standards specified in the CLF
for both volatile and semivolatile analyse:
were used to provide  measures for both
GC relative retention indices and  MS
detection  response  factors.  Surrogate
standards specified in the CLP were in-
cluded in volatile  analyte mixtures bu
not in the semivolatile mixtures. In the
latter case, data interpretation would be
more difficult with little increase in use-
fulness  of results. In  all cases, the  CLF
GC and MS analysis conditions and ME
quality  control  checks on ion  source
tuning were used.

-------
 Results and Discussion

Selection and Procurement of
Analytes to be Tested
  After elimination of redundancies, the
combined Appendix  VIII and  Michigan
analyte sets contain 440 compounds, 112
of which  are already  thoroughly char-
acterized  EPA priority  pollutants. Thus,
328 substances qualified for the present
study.  Each  substance  was  classified
according to its amenability to analysis by
Method 8240 (volatile analytes), Method
8270 (semivolatile analytes), or by neither
method.  Eight  of  the  compounds are
classified as both volatile and semivolatile
since, after failing to elute in the volatile
compound testing, they were carried into
the semivolatile compound testing.
  Table 1 lists 58 analytes that are omitted
a priori from GC-MS suitability testing.
Reasons for a priori omission and sug-
gestions for future method development
can be classified as follows:

  • Acids — 14 Compounds. Typically,
     these acids are carboxylic acids (or
     of comparable strength) and require
     derivatization to achieve acceptable
     GC performance.

  • Nonvolatile — 12 compounds. These
     analytes are so polar and/or of such
     high molecular weight that there is
     essentially no possibility of their elu-
     tion  from a GC column.  Typical of
     these compounds  are macrolytic
     antibiotics  and dye molecules  for
     which HPLC, rather than  a derivati-
     zation-GC  approach  is  ap-
     propriate for most cases.

  • Hydrolytically or otherwise unstable
     — 9 compounds. Since groundwater
     and wet soils and sludges are sample
     matrices of  interest, there  is no need
     to demonstrate analysis  capability
     for  compounds which decompose
     rapidly in these sample types.


  • Aldehydes — 6 compounds. Special
     GC conditions have been  used suc-
     cessfully  for  a  number  of these
     analytes but, generally, the associ-
     ated sample workup procedures are
     not fully  successful in preserving
     these reactive analytes prior to their
     detection. Hence  derivatization fol-
     lowed by HPLC with UV  detection,
     which has been shown to be sensi-
     tive and reproducible for  formalde-
     hyde, is clearly the favored analytical
TaWe 1.    Analytes Omitted A Priori From GC-MS Suitability Testing
No.
1
2
3
4
5
6
7
a
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
Substance
Acetaldehydefb)
Acetyl chloride
Actinomycin D
Aflatoxins(b)
Aniline hydrochloride
0-Anisidine hydrochloride
Azaserine
Benzal chloride
Benzenearsonic acid
Benzidine sulfate
Benzotrichloride
Chlorambucil
Chloroacetaldehyde(b)
Coal tars
Creosote
Crotonaldehyde(b)
Cycasin
2.4-D
Daunomycin
Dimethylcarbamoyl chloride
Diphenylamine(c)
5,5-Diphenylhydantoin monosodium salt
2,4-Dithiobuiret
Endothal
Epinephrine
Ethylene bis-dithiocarbamates
Fluoroacetic acid, sodium salt
Formaldehyde(bl
Formic acid
Glycidaldehyde (b)
Hydrazine
Ketene
Lasiocarpine
Malachite green
Melphalan
Methyl chlorocarbonate
Mitomycin C
Monocrotaline
Nitrogen mustard N-oxide
N-Nitrososarcosine
Paraldehyde{b)
Peroxyacetic acid
Phenesterin
Phenyl dichloroarsine
Polybrominated biphenyls(b)
Polychlorinated biphenylsfb)
Reserpme
Semicarbazide
Silvex
Streptozotocin
2.4.5-T
2.3.7.8-TCDD(bJ
Thiosemicarbazide
Thiourea
Thiram(d)
Tnchloromethanesulfenyl chloride
Trypan blue
Ziram
ListfaJ
a
8
M
8
M
M
8
8
8
M
8
8
8
8
8
8
8
8
8
8
8
M
a
8
8
8
8
8
8
8
8
M
8
M
8
8
8
M
a
8
8
M
M
8
M
8
8
M
8
8
8
8
8
8
a
8
8
M
CAS No.
75-07-0
75-36-5
50-76-0
98-05-5
142-04-1
134-29-2
1 15-02-6
98-87-3
98-05-5
531-86-2
98-07-7
305-03-3
107-20-0
20830-81-3
8001-58-9
123-73-9
14901-08-7
94-75-7
20830-81-3
79-44-7
62-74-8
630-93-3
541-53-7
129-67-9
51-43-4
142-59-6
62-74-8
50-00-0
64-18-6
765-34-4
302-01-2
463-51-4
303-34-4
569-64-2
148-82-3
79-22-1
50-07-7
315-22-0
302-70-5
13256-22-9
123-63-7
79-21-0
3546-10-9
696-28-6
59536-65-1
1336-36-3
50-55-5
57-56-7
93-72-1
18883-66-4
93-76-5
1746-01-6
79-19-6
62-56-6
137-26-8
594-42-3
72-57-1
137-30-4
la) 8 = Appendix VIII; M = Michigan List.
(b) Partially or fully demonstrated method for selected matrices already exists.
(c) Diphenylamine  has  been well characterized by  GC-MS since  the priority pollutant
   N-nitrodiphenyl-amine has been thoroughly demonstrated to quantitatively decompose to
   diphenylamine upon GC injection.
(d) This family of analytes have  been successfully determined in aqueous media  by GC-
   Hall/Sulfur analysis of carbon disulfide decomposition product.

-------
    approach for these compounds. Thus,
    there was no need to include them
    in GC method testing.
    Redundancies  —  5 compounds.
    Typically, these compounds are salts
    of a free base also listed as an
    analyte. Diphenylamine was con-
    sidered redundant  with the priority
    pollutant,  N-nitrosodiphenylamine
    since the latter is known to decom-
    pose quantitatively to the former in
    GC injectors.

    Inappropriate for inclusion in  the
    present scope  for  miscellaneous
    reasons —  12 substances. Some
    analytes were considered  inappro-
    priate because  they  can hardly be
    considered organic  analytes.  Ex-
    amples of this category  include
    hydrazine, thiosemicarbizide, semi-
    carbizide, thiourea and dithiobiuret.
    Others are currently, or expected to
    be addressed by other specialized
    methods. Examples of this category
    include tetrachlorodibenzodioxin and
    polychlorinated and polybrominated
    biphenyls. Two substances, coal tars
    and creosote, are too heterogeneous
    for  inclusion in  Method  8270.
    Epinephrine had to be omitted since
    it could not be dissolved at suffici-
    ently high concentration in any rea-
    sonable GC injection solvent.

  Some 32 analytes could not be obtained
in time  to be included in this work and
are listed in Table 2. One of these, chloral,
is available as the hydrate  which was
included in the  volatile analyte testing.
Thus, the  summary  listings show 31
analytes as "unavailable."


Results of Volatile Analyte Testing
  Table  3 lists 54 volatile analytes tested
with Method 8240 GC conditions. The
status of each analyte is indicated: satis-
factorily detected  (S);  detected  with  a
response factor versus benzene-D6 below
Table 2.    Volatile and Semivolatile Analytes Not Obtainable in Time for Inclusion
No.  Substance
                 List(a)
                                                                     CAS No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
1 -Amino-2-methylanthraquinone
5-(Aminomethyl)-3-isoxazolol
Azinophos-ethyl
Benz(c)acridine
7,8-Benzfluoranthene
4-(Butylnitrosoamino)- 1 -butanol
Chloral(b)
Chloronaphazine
1 -<2-Chlorophenyl)thiourea
Citrus Red No. 2
1 ,2:5.6-Dibenzacridine
3.4:5.6-Dibenzocarbazole
Dibenzofa. i)pyrene(c)
Dibenzo(a.h)pyrene
Diethylarsine
1 ,2-Diethylhydrazine
Diisopropyl fluorophosphate
3.3-Dimethyl- 1 -(p-chlorophenyl)triazene
O, O-Dimethyl-S-methyl phosphorodithioate
Furathiazole
Hexaethyl tetraphosphate
4.4'-Methylenebis(2-methylaniline)
2-Methyl- 1 -nitroanthraquinone
Nifurthiazol
Niridazole
Nithiazide
N-Nitrosomethylvinylamine
N-Nitrosonornicotine
Phosacetim
4,4'- Thiodianiline
Trisfl -azridinyl)phosphine sulfide
Uracil mustard
M
8
M
8
8
M
8
8
8
8
8
8
8
8
8
8
8
M
8
M
8
M
M
M
M
M
8
8
M
M
8
8
82-28-0
2763-96-4
2642-71-9
225-51-4
205-82-3
3817-11-6
75-87-6
494-03-1
5344-82-1
6358-53-8
226-36-8
194-59-2
189-55-9
129-67-9
692-42-2
1615-80-1
55-91-4
7203-90-9
3288-58-2
531-82-8
757-58-4
838-88-0
129-15-7
3570-75-0
61-57-4
139-94-6
4549-40-0
16543-55-8
4104-14-7
139-65-1

66-75-1
(a) 8 = Appendix VIII; M = Michigan list.
(b) Chloral hydrate was substituted for chloral.
(c) Judged cost prohibitive for this program.
0.02 (LR), or not detected (ND). Thirty
three analytes were satisfactorily detecte
and six were detected with low responsi
factors.  The very low  response factor
will probably result in unacceptably higl
minimum detection  limit  (MDL) value:
for Method 8240.
  Table  3 also lists 15 volatile  analyte:
that  were  not detected under Metho<
8240 conditions. All of these  analyte!
were analyzed at least twice, with thi
repeat analysis  usually at 2- to 5-fok
higher levels than the original 300 nc
level. Three of these 15 analytes, hexa
chloropropene,  tetranitromethane, am
thiophenol, were thought  to have faile<
to elute due to boiling points and/o
polarities that  were too  high for th<
SP1000/Carbopack B column, and thesi
compounds  were  retested  using th<
Method 8270  (semivolatile  analyte
conditions.
   Non-detection of the hydrazines anc
aziridines (6 analytes) was probably due
to extreme  GC peak tailing on tru
SP1000/Carbopack  B  column.  Five  o
these nitrogen bases were also  testec
with the semivolatile analytes. The sixth
N(2-hydroxyethyl)ethyleneimine, was not
tested due to its extreme polarity.
   In  the injector, 2-Butanone  peroxide
apparently quantitatively decomposed  tc
2-butanone. Methyl mercaptan apparently
coelutes with methanol on the SP1000/
Carbopack B column and would be sub-
stantially lost at  the jet separator due  tc
the presence of the methanol vapor dis-
placement  of the helium carrier.  The
remaining four undetected volatile com-
pounds, two  haloethers,  methyl  iso-
cyanate, and 2-methyllactonitrile,  were
not repeated in the semivolatile set since
they were both too volatile to be recovered
in a  Kuderna-Danish (KD) distillation  of
extraction solvent and were also known
to be chemically and/or  hydrolytically
labile.

Results of Semivolatile
Analyte Testing

   Table  4 lists the 185 semivolatile
analytes and the eight volatile analytes to
be retested with Method 8270 conditions.
The  status of each  analyte is indicated;
satisfactorily detected (S),  expected to be
satisfactory for GC-MS  determination
based on other information (ES), detected
with  a  response factor less than 0.02
versus  phenanthrene-D10 (LR), or not
detected (ND). One hundred and twenty
eight analytes were detected with satis-
factory response  factors and nine analytes
were detected with low response factors.

-------
Table 3.    GC-MS Suitability Testing Results for Volatile Analytes
No.
1
2
3
4
5
6
7
a
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
Substance
Acetonitrile
Ally/ alcohol
Allyl chloride
Benzyl chloride
Bis-(2-chloroethyl) sulfide
Bis(chloromethyl) ether
Bromoacetone
2-Butanone peroxide
2-Butanone
Carbon disulfide
Chloral hydrate
2-Chloroethanol
Chloromethyl methyl ether
Chloroprene
3 - Chloropropionitrile
1 . 2 -Dibromo -3 -chloropropane
Dibromomethane
1 ,4-Dichloro-2-butene
Dichlorodifluoromethane
1 . 3 -Dichloro-2-propan ol
1 ,2,3.4-Diepoxybutane
1 , 1 -Dimethylhydrazine
1 ,2-Dimethylhydrazine
1 ,4-Dioxane
Epichlorohydrm
Ethylene dibromide
Ethylene oxide
Ethylenimine
Ethyl methacrylate
Hexachloropropene
N-(2-Hydroxyethyl)ethyleneimine
2-Hydroxypropionitrile
Isobutyl alcohol
Malononitrile
Methacrylonitrile
2-Methylaziridine
Methylhydrazine
Methyl iodide
Methyl isocyanate
2-Methyl/actonitnle
Methyl mercaptan
Methyl methacrylate
Pentachloroethane
2-Picoline
Propargyl alcohol
(i-Propiolactone
Propionitrile
N-Propylamine
Pyndine
Styrene
1, 1 , 1 ,2-Tetrachloroethane
Tetranitromethane
Thiophenol
1 ,2.3- Trichloropropane
List(a)
8
8
8 M
8
8 M
8
8
8
8
8
8
M
a
8 M
8
8
8
8
8
8
8
8
8
8
8
8
a
8
8
8
M
M
8
8
8
8
8
8
8
8
8
8
8
8
8
M
8
8
8
M
8
8
8
8
RCRA
CAS No. Number
75-05-8
107-18-6
107-05-1
100-44-7
505-60-2
542-88-1
598-31-2
1338-23-4
78-93-3
75-15-0
75-87-6
107-07-3
107-30-2
126-99-8
542-76-7
96-12-8
74-95-3
764-41-0
75-71-8
96-23-1
1464-53-5
57-14-7
540-73-8
123-91-1
106-89-8
106-93-4
75-21-8
151-56-4
97-63-2
1888-71-7
1072-52-2
78-97-7
78-83-1
109-77-3
126-98-7
75-55-8
60-34-4
74-88-4
624-83-9
75-86-5
74-93-1
80-62-6
76-01-7
109-06-8
107-19-7
57-57-8
107-12-0
107-10-8
110-86-1
100-42-5
630-20-6
509-14-8
108-98-5
96-18-4
U003
POOS
U317
P028
P158

P017
U160


U034
P133
U046
U276
P027


U074


U085
U098
U099
U108


U115
P054
U118
U243
U289


U149
U152
P067
P068
U138
P064
P069

U162

U191
P102
U302
P101
U194
U196
U323

P112
P104

Status
Code(b)
S
S
S
S
LR
ND
S
ND
S
S
LR
LR
ND
S
S
S
S
S

S
S
ND
ND
S
S
S
S
ND
S
ND
ND
LR
S
S
S
ND
ND
S
ND
ND
ND
S
S
S
LR
S
S
LR
S
S
S
ND
ND
S
 (a) 8 - Appendix VIII: M - Michigan list.
 (b) LR- low response factor
    S: suitable for GC-MS analysis
   ND not detected in GC-MS data.
All of these latter nine analytes are highly
polar and are expected to be sensitive to
thermal decomposition in the injection
port.
  Table 4 contains 11 analytes with the
status "ES." All 11 of these analytes are
suitably analyzed in Work Assignment 2-
08 which extracts analytes from spiked
aqueous  standards, concentrated and
analyzed by fused silica capillary GC-FID.
Thus, although MS data was not obtained
in the WA 2-08 work, their non-detection
in the present work is anomalous. Except
for the two organophosphates, these "ES"
analytes  in Table  4 are strongly  basic
molecules; a possible explanation for their
non-detection is that the GC column used
was somewhat acidic, precluding satis-
factory elution.
   Also listed in  Table 4,  are the  45
analytes  for which non-detection in the
GC-MS  data cannot  be  classified  as
anomalous. Generally, these analytes are
highly  polar, or  labile  to decomposition
before or during chromatography.  Four
of these  45  analytes are  aromatic dia-
mines, 1,2- and 1,3-phenylenediamine,
2,4-diaminoanisole, and 1,5-naphthalen-
diamine. These  four analytes probably
can be analyzed by fused silica GC if
special precautions are taken to ensure
good performance for  basic materials.
Ethylene thiourea (ETU) has been shown
in previous work at Battelle to be amen-
able to GC analysis using special condi-
tions. For another six analytes (acrylamide,
cycloheximide, 2-fluoroacetamide, niclo-
samide, oxydemeton-methyl, and thioace-
tamide)  polarity,  volatility and  lability
considerations apparently do not account
for the non-detection, and, therefore, a
more thorough attempt to develop GC-
based  methods might be successful.  For
the remaining 34 analytes, the causes of
non-detection can be classified as one or
more of the following: exceptionally high
polarity,  thermal or chemical lability, or
insufficient volatility. Recommendations
for further method development for these
analytes focus  on  HPLC techniques,
especially  ion chromatography or post
column derivatization methods.

Conclusions and
Recommendations
   After the elimination of redundancies,
the Appendix VIII and Michigan list com-
pounds include 440 organic compounds.
The classification of these  compounds
and results of testing them for suitability
for  inclusion in  present  volatile and
semivolatile analysis methods are  sum-
marized as follows:

-------
Analytes Considered
Tested for GC-MS Suitability 239*
Omitted Priority Pollutant 1 1 2
Omitted A Priori 58
Not obtainable 31
Total considered 440
Volatile Analyte Testing
Suitably Detected 33
Detected with Low
Response Factor 6
Nnt DptprtpH 1 ^
IWl LXOIOV*IOU 1 *J
Sub Total 33 + 21 = 54*

Semivolatile Analyte Testing

Suitably Detected 1 28
Expected to be
Suitable 1 1
Detected with Low
Response Factor 9
Not Detected 45
Sub Total 139 + 54 =193*

Total Suitable 1 72


Total Not Suitable 75


Total Tested 247*

* Eight of the analytes that failed volatile
testing were carried into the semi-
volatile testing. Two of these eight
analytes were suitably detected in
semivolatile testing.


For the 39 volatile and 1 37 semivolatile
compounds which were detected by GC-
MS analyses, key GC performance and
mass spectral data were obtained.
The general recommendation arising
from the data and results generated in
the studies presented in this report is to
continue implementation of the hier-
archical research strategy. The following
specific recommendations are made:
• The 39 volatile compounds detected
using the GC conditions of Method
8240 should be included in an evalu-
ation of the Method 5030 PTD
sample introduction.
• Extractability studies of the 137
semivolatile compounds detected
using the GC conditions of Method
8270 should be conducted.
• The 1 1 compounds which were
anomalously not detected should
receive more detailed examination.
• Twelve additional analytes that were
not detected should also receive
further direct GC investigation.
Table 4. GC-MS Suitability Testing Results for Semivolatile Analytes
RCRA
No. Substance List(a) CAS No. Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
Ojf
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
Acetophenone
2-Acetylaminofluorene
1 -Acetyl-2-thiourea
Acrylamide
Aldicarb
2-Aminoanthraquinone
Aminoazobenzene
4-Aminobiphenyl
3-Amino-9-ethylcarbazole
Amitrole
Anilazine
Aniline
o-Anisidine
Aramite
Aura mine
Azinphos-methyl
Barban
Benomyl
p-Benzoquinone
Bromoxynil
Brucine
Captafol
Captan
Carbaryl
Carbofuran
Carbophenothion
Chlorfen vinphos
4-Chloroaniline
Chlorobenzilate
5-Chloro-2-methylaniline
3-(Chloromethyl)pyridine hydrochloride
4-Chloro- 1 ,3-phenylenediamine
4-Chloro- 1 ,2-phenylenediamine
Coumaphos
p-Cresidine
Crotoxyphos
Cupferron
Cycloheximide
2-Cyclohexyl-4.6-dinitrophenol
Cyclophosphamide
Demeton
Dial/ate
2,4-Diaminoanisole sulfate
2.4-Diaminotoluene
Diazinon
1, 2:7,8 -Dibenzacridine
1, 2:4,5 -Dibenzopyrene
Dichlone
2,6-Dichlorophenol
Dichlorovos
Dicrotophos
Diethylstilbestrol
Diethyl sulfate
Dihydrosafrole
Dimethoate
3.3'-Dimethoxybenzidine
1 , 4 -Dimethylaminoazobenzene
7, 1 2-Dimethylbenzfa)anthracene
3, 3 '-Dimeth ylbenzidine
1, 1 -Dimethylhydrazine
1 ,2-Dimethylhydrazine
aa-Dimethylphenethylamine
1 . 2 -Dinitrobenzene
1 ,3-Dinitrobenzene
1,4-Dinitrobenzene
Dinocap
8
8
8
a
8
8
8

8

8
8



8






8
8








8
8

8

8
8
8
8


8

a
8
8
8
8
8
8
8
8
8
8
8



M
M
M
M

M

M
M

M
M
M

M
M
M
mjj
M
M
M
M


M
M
M
M
M
M
M
M
M


M

M
M
M
M

M
M

M







M
98-86-2
53-96-3
591-08-2
79-06-1
116-06-3
117-79-3
60-09-3
92-67-1
132-32-1
61-82-5
101-05-3
62-53-3
90-04-0
140-57-8
492-80-8
86-50-0
101-27-9
17804-35-2
106-51-4
1689-84-5
OK~7 C~7 "3
JO/-O/-3
2425-06-1
133-06-2
CO OK O
OO-2D-Z
1563-66-2
786-19-6
470-90-6
106-47-8
510-15-6
95-79-4
6959-48-4
5131-60-2
95-83-0
56-72-4
120-71-8
7700-17-6
135-20-6
66-81-9
131-89-5
50-18-0
8065-48-3
2303-16-4
39156-41-7
95-80-7
333-41-5
224-42-0
192-65-4
117-80-6
87-65-0
62-73-7
141-66-2
56-53-1
64-67-5
56312-13-1
60-51-5
1 19-90-4
60-11-7
57-97-6
119-93-7
57-14-7
540-73-8
122-09-8
99-65-0
528-29-0
100-25-4
39300-45-3
U004
U005
P002
U264
U257
U274
U253
U011
U333

U260
U326
U014
P151
U280
U271
U197
U272
nf\i O
PO18
U285
U266
1 IO7Q
uz/y
U127
U148
P143

U038
U329
U319
U305
U306
P130
U262
U238
U290
P134
P034
U058
P155
U062
U307
U327
U313
U299

P144
P146
U086
U325
U090
U091
U093
U094
U095
U098
U099
P046

U284
Status
Code(b)
S
S
LR
ND
ND
S
S
S
ES
ND
S
ES
S
S
ND
S
LR
ND
S
S
A/n
Nu
S
S
S
S
S
S
S
S
S
ES
ES
S
S
S
ND
ND
LR
ND
S
S
ND
S
ES
S
S
S
S
S
S
S
LR
ND
S
LR
S
S
S
ND
ND
S
S
S
S
S

-------
• For 33 non-detected analytes, HPLC Table 4. (continued)
(including ion chromatography or 67 Dinoseb
post-column derivatization) should 68 Dioxathion
be investigated. 69 5.5-Diphenylhydantoin
• No recommendations can be made 70 1 ,2-Diphenylhydrazine
at this time for 7 analytes not de- 71 Disulfoton
tected in this study. 72 EPN
73 Ethion
74 Ethyl carbamate
75 Ethylenimine
76 Ethylene thiourea
77 Ethyl methanesulfonate
78 Famphur
79 Fensulfothion
80 Fenthion
81 Fluchloralin
82 2-Fluoroacetamide
83 Hexachlorophene
84 Hexachloropropene
85 Hexamethyl phosphoramide
86 Hydroquinone
87 Isodrin
88 Isonicotinic acid hydrazide
89 Isosafrole
90 Kepone
91 Leptophos
92 Malathion
93 Maleic anhydride
94 Maleic hydrazide
95 Mestranol
96 Methapyrilene
97 Methomyl
98 p,p'-Methoxychlor
99 2-Methylaziridine
100 3-Methylcholanthrene
101 4.4 '-Methylenebisf2-chloroaniline)
102 4,4'-Methylenebis(N,N-dimethylaniline)
103 Methylhydrazine
104 Methyl methanesulfonate
105 N-Methyl-N-nitro-N-nitrosoguanidine
106 Methyl parathion
107 2-Methylphenol
108 3-Methylphenol
109 4-Methylphenol
1 10 Methylthiouracil
1 1 1 Mevinphos
1 12 Mexacarbate
1 13 Mir ex
114 Monocrotophos
1 15 Naled
116 1 ,5-Naphthalenediamine
117 1 ,4-Naphthoquinone
118 1 -Naphthylamine
1 19 2-Naphthylamine
120 1 -Naphthyl-2-thiourea
121 Niclosamide
122 Nicotine
123 5-Nitroacenaphthene
124 4-Nitroaniline
125 5-Nitro-o-anisidine
126 4-Nitrobiphenyl
127 Nitrofen
128 Nitrogen mustard
129 Nitroglycerine
130 5-Nitro-o-toluidine
131 4-Nitroquinoline-l-oxide
132 N-Nitrosodibutylamine
133 N-Nitrosodiethanolamine
134 N-Nitrosodiethylamine
135 p-Nitrosodiphenylamine

8


a
a


8
8
8
8
8



8
8
8


8

8
8


8
8

8
8
8
8
8
8

8
8
8
8
8
8
8
8






8
a
8
8

8

8



8
8
8
8
8
8
8



M
M


M
M





M
M
M



M
M

M


M
M


M






M








M
M
M
M
M
M




M

M

M
M
M
M






M

88-85-7
78-34-2
57-41-0
122-66-7
298-04-4
2104-64-5
563-12-2
51-79-6
151-56-4
96-45-7
62-50-0
52-85-7
115-90-2
55-38-9
33245-39-5
640-19-7
70-30-4
1888-71-7
680-31-9
123-31-9
465-73-6
54-85-3
120-58-1
143-50-0
21609-90-5
121-75-5
108-31-6
123-33-1
72-33-3
91-80-5
16752-77-5
72-43-5
75-55-8
56-49-5
101-14-4
101-61-1
60-34-4

70-25-7
298-00-0
95-48-7
108-39-4
106-44-5
56-04-2
7786-34-7
315-18-4
2385-85-5
6923-22-4
300-76-5
2243-62-1
130-15-4
134-32-7
91-59-8
86-88-4
50-65-7
54-11-5
602-87-9
100-01-6
99-59-2
92-93-3
1836-75-5
51-75-2
55-63-0
99-55-8
56-57-5
924-16-3
1116-54-7
55-18-5
156-10-5


P153

U109

P141
P154
U238
P054

U119
P097
P156

U330
P057
U132
U243
U312

P060

U141

P140
U324
U147

U301
U155
P066

P067
U157
U158
U255
P068

U163




U164
P131
P128
U297
P147
U309
U298
U166
U167
U168
P072
U321
P075
U250

U263
U275
U288
P132
P081
U181


U173

U287

S
S
S
ND
S
S
S
S
ND
ND
S
S
S
S
S
ND
S
S
S
S
S
ND
S
S
S
S
S
ND
S
S
ND
S
ND
S
LK
£S
ND
S
ND
S
S
S
S
ND
S
S
S
S
S
ND
S
S
ES
ND
ND
S
S
S
S
S
S
ND
ND
S
S
S
ND
S
ES

-------
Table 4. (continued)
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188
189
190
191
192
193
N-Nitroso-N-ethylurea
N-Nitrosomethylethylamine
N-Nitroso-N-methylurea
N-Nitroso-N-methylurethane
N-Nitrosomorpholine
N-Nitrosoplperidine
N-Nitrosopyrrolidine
Octamethylpyrophosphoramide
Oxydemeton-methyl
4,4'-Oxydianiline
Parathion ethyl
Pentachlorobenzene
Pentachloronitrobenzene
Phenacetin
Phenazopyridine hydrochloride
Phenobarbital
1 ,2-Phenylenediamine
1 ,3-Phenylenediamine
1 ,4-Phenylenediamine
N-Phenylthiourea
Phorate
Phosalone
Phosmet
Phosphamidon
Phthalic anhydride
Piperonyl suit 'oxide
Pronamide
1,3-Propane sultone
Propylthiouracil
Resorcinol
Rotenone
Saccharin
Safrole
Strychnine
Sulfallate
Terbufos
1,2.4,5- Tetrachlorobenzene
2, 3,4,6- Tetrachlorophenol
Tetrachlorvinphos
Tetraethyl dithiopyrophosphate
Tetraethyl pyrophosphate
Tetranitromethane
Thioacetamide
Thiofanox
Thionazine
Thiophenol
Toluene diisocyanate
o-Toluidine
Trichlorform
2,4,5- Trichlorophenol
0,0,0- Triethyl phosphorothioate
Trifluralin
2,4,5- Trimethylaniline
Trimethyl phosphate
1,3,5- Trinitrobenzene
Tris(2, 3 -dibromopropyl) phosphate
Tri-p-tolyl phosphate(c)
Warfarin
8
8
8
8
8
8
8
8


8
8
8
a


8
8
8
8
8
8


8

8
8
8
8

8
8
8


8
8

8
8
8
8
8
8
8
8
8

8
8



8
8

8








M
M




M
M






M
M

M


M

M



M
M


M








M
M


M
M
M


M

759-73-9
10595-95-6
684-93-5
615-53-2
59-89-2
100-75-4
930-55-2
152-16-9
301-12-2
101-80-4
56-38-2
608-93-5
82-68-8
62-44-2
136-40-3
50-06-6
95-54-5
108-45-2
106-50-3
103-85-5
298-02-2
2310-17-0
732-11-6
13171-21-6
85-44-9
120-62-7
23950-58-5
1120-71-4
51-52-5
108-46-3
83-79-4
81-07-2
94-59-7
57-24-9
95-06-7
13071-79-9
95-94-3
58-90-2
961-11-5
3689-24-5
107-49-3
509-14-8
62-55-5
39196-18-4
297-97-2
108-98-5
584-84-9
95-53-4
52-68-6
95-95-4
126-68-1
1582-09-8
137-17-7
512-56-1
99-35-4
126-72-7
78-32-0
81-81-2
U176

U177
U178

U176

P085
P157
U303



U187
U320
U268



P093



P145
U19Q
U270

U193
U334

U273
U202
U203

U277
P149


U308
P109

P1 12
U128
P04S
P040
P104
U223
U328
P139


U332
U259
U310
U234
U235

P001
ND
S
ND
ND
ES
S
S
LR
ND
S
S
S
S
S
ND
S
ND
ND
S
ND
S
S
S
S
S
S
S
ND
LR
S
ND
ND
S
S
S
S
S
S
S
ES
S
ND
S
ND
S
S
S
S
ND
S
ES
S
S
S
S
LR
S
ND
(a) 8 = Appendix VIII; M = Michigan list.
(b)  S - apparently suitable for GC-MS analysis
   LR - low response; response factor, versus phenanthrene-D10, less than 0.02
  ND - not detected
   ES - expected to be suitable for GC-MS analysis but not detected in this study.
fc) Substituted for the non-specific mixture, tricresyl phosphate.

-------
S. V.  Lucas and R. A.  Kornfeld are with Battelle Columbus Laboratories.
  Columbus, OH 43201-2693.
J. E. Longbottom is the EPA Project Officer (see below).
The complete report, entitled "GC-MS Suitability Testing of RCRA Appendix
  VIII and Michigan L ist A nalytes," (Order No. PB 87'-227674 /A S; Cost: $ 13.95.
  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 Officer can be contacted at:
        Environmental Monitoring and Support Laboratory
        U.S. Environmental Protection Agency
        Cincinnati. OH 45268

-------