EPA/600/A-95/123
APPLICATION OF VOST AND SEMIVOST TO
NONHALOGENATED CAAA COMPOUNDS
Merrill D. Jackson
U. S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
Joan T. Bursey, James F. MeGaughey, and Raymond G. Merrill
Radian Corporation
Research Triangle Park, North Carolina 27709
ABSTRACT
A laboratory study was performed to demonstrate applicability of VOST (SW-846 Methods 0030 and
5041) and SemiVOST (SW-846 Method 0010, Draft Method 3542, and Method 8270) for collection and
analysis of nonhalogenated organic compounds listed in Title III of the Clean Air Act Amendments of
1990. Compounds with boiling points <132':C were selected as candidate VOST analytes, and VOST
analyses (Method 5041) of spiked sorbent tubes were performed to demonstrate successful analysis.
Analytes with recovery > 50% were prepared as a single certified gaseous standard. VOST dynamic
spiking studies were performed in the laboratory. For semivolatile and nonvolatile compounds (boiling
points >100°C), GC/MS analyses (Method 8270) were performed on analytes combined in a single
solution. Several instances of chemical incompatibility and poor solubility were encountered, and
incompatible or insoluble analytes were eliminated from further study. Laboratory SemiVOST dynamic
spiking studies featured acid/neutral analyies in one solution, and base/neutral analytes in a second
solution; two sets of experiments were performed. Five of 19 VOST candidates and 52 of 66
SemiVOST candidates with recoveries > 50°'o will be tested in field dynamic spiking studies at a coal
fired steam plant.
INTRODUCTION
Previous studieshave evaluated the applicability of the VOST' and SemiVOST3 to the volatile and
semivolatile halogenated organic compounds in Title III of the Clean Air Act Amendments of 1990.
Nonhalogenated organic compounds selected for this study were expected to be amenable to analysis by
gas chromatography/mass spectrometry (GC MS).
For candidate VOST analytes, preliminary analysis using Method 5041 (GC/MS) was performed to
demonstrate that the compounds could be analyzed. For candidate SemiVOST analytes, a scheme was
designed to test analyte compatibility in a single spiking solution. However, the ultimate combination
scheme resulted in three solutions: an Acid Solution, a Basic Solution, and a Neutral Solution.
Method performance of the VOST and SemiVOST analytes was evaluated by dynamic spiking of the
trains. For VOST analytes, gaseous dynamic spiking was performed using a certified cylinder of analytes
into VOST trains sampling clean dry air. For SemiVOST analytes, liquid dynamic spiking was
performed using a methylene chloride solution with the SemiVOST trains sampling clean dry air.
Sampling trains and dynamic spiking apparatus and procedures have been described in detail in previous
studies.1,2
EXPERIMENTAL PROCEDURES
A selection of the compounds to be used in dynamic spiking was performed. Those compounds that
could be chromatographed using the standard methods were then evaluated by dynamic spiking of the
sampling trains.
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Selection of Appropriate Analytes
Prior to purchase of a certified gas cylinder for VOST dynamic spiking studies, nineteen candidate
VOST analytes were evaluated to determine the applicability ofVOST sampling and analysis in the field.
Preliminary VOST analyses were performed by spiking candidate analytes onto VOST tubes from liquid
solution by flash evaporation and analyzing the spiked VOST tu&es according to Method 50413.
Candidate compounds were then divided into three groups (Table 1).
A total of 66 semi volatile nonhalogenated organic compounds, listed in Table 2, from Title III of the
CAAA were selected for study. Based on previous laboratory work4, semivolatile organic analytes were
combined into three methylene chloride solutions prepared according to the following guidelines:
Hydroquinone and 1,4-phenyienediamine were insoluble in methylene chloride at the desired level, so
these analytes were eliminated from further testing. The solution was prepared to ultimately arrive at
a single spiking solution containing all of the analytes that could be used for SemiVOST dynamic
spiking. As different solutions were analyzed and combined, several compounds exhibiting chemical
incompatibilities were eliminated from further testing: captan, 1,3-propane sultone, ethylene thiourea,
hexamethylene-l,6-diisocyanate. catechol, and 2.4-toluenediamine. Maleic anhydride, which converts
almost entirely to maleic acid in methylene chloride solution, was excluded from further testing since
the maleic acid decomposition product does not chromatograph under standard SemiVOST analytical
conditions. Because of the likelihood of reaction between acids and bases, stocks were prepared as three
concentrated solutions: Acid, Base, and Neutral. The compounds are listed in Table 3.
Dynamic Spiking Experiments
A VOST train was used with SW-846 Method 0030. except that dynamically-spiked gaseous organic
analytes were introduced according to procedures established in previous laboratory and field tests1-2.
A certified cylinder containing analytes amenable (based on the chromatographic test) to VOST (nominal
concentration of 1 ppm) was obtained to perform laboratory dynamic spiking. Since toluene had
previously been tested successfully in the VOST method3, laboratory tests for toluene were not
performed. Two series of six spiking runs were performed, one at a nominal spiking level of 250 ng,
and one at a nominal spiking level of 500 ng.
Because of chemical incompatibilities and the requirement for stability in solution, the SemiVOST
dynamic spiking experiments were designed with two spiking solutions: One a combined Acid/Neutral
solution, with both components at a low spiking level; and Second, a combined Base/Neutral solution,
with basic components at a high level and neutral components at a low spiking level. To perform
dynamic spiking, a standard SemiVOST train was used following SW-846 Method 0010 with the
dynamic spike introduced immediately behind the heated probe. Two series of six spiking runs were
performed, one each with the Acid/Neutral or the Base/Neutral spiking solution.
RESULTS AND CONCLUSIONS
Five of the VOST compounds could be chromatographed using Method 5041, The others either had
no analytical response or were water soluble, resulting in poor analytical response (Table 1). The results
of the dynamic spiking of the VOST are shown in Table 4. The VOST analytical results show very good
reproducibility, indicating the dynamic spiking is being performed successfully. Recoveries at low
spiking range were low, although still within the acceptable range of 50-150% with 50% or better
relative standard deviation (RSD). All analytes selected for VOST field testing were successful in the
laboratory testing, indicating a high probability of success in field dynamic spiking.
The results of the dynamic spiking of the SemiVOST are shown in Table 3. Recoveries are generally
good with reproducible results. Toluene shows an anomalous high recovery probably due to laboratory
contamination and failure of a carbon filter to remove all of the toluene from the laboratory air that was
being sampled. The compounds with the poorest recoveries show the poorest reproducibility. Using the
criteria for acceptable recovery of 50-150 percent, with relative standard deviation of 50 percent or less,
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Table 5 predicts the results expected when the Semi YOST method is tested at a stationary source with
dynamic spiking.
The four VOST compounds and the SemiVOST compounds in Table 5 that meet the criteria and
those that are marginal will be subjected to dynamic spiking tests at a field site.
REFERENCES
1.	Laboratory Validation of VOST and SemiVOST for Halogenated Hydrocarbons from the Clean Air
Act Amendments List, Volumes 1 and 2, EPA 600/R-93/123a and b. NT IS PB93-227163 and
PB93-227171. July, 1993.
2.	Field Test of a Generic Method for Halogenated Hydrocarbons, EPA 600/R-93/101. NTIS
PB93-212181, June, 1993.
3.	"Test Methods for Evaluating Solid Waste, Physical/Chemical Methods. SW-846 Manual, 3rd ed,"
Document No. 955-001-0000001. Available from Superintendent of Documents, U. S. Government
Printing Office. Washington. D.C. November, 1986.
4.	Handbook of GC/MS Data and Information for Selected Clean Air Act Amendments Compounds,
EPA/600/R-94/021. January. 1994.
5.	Fuerst, Robert F., Thomas J. Logan, M. Rodney Midgett and John Prohaska, Validation Studies of
the Protocol for the Volatile Organic Sampling Train, J. Air & Waste Management 37:388-394
(1987).
ACKNOWLEDGMENTS
We wish to acknowledge contributions of the following individuals to the success of this program:
Mark Owens, Danny Harrison, Tom Buedel, Rohini Kanniganti, Mike Bryant, Sam Foster, and Sarah
Godfrey.
DISCLAIMER
This material has been funded wholly or in part by the Environmental Protection Agency under
contract 68-D1-00I0 to Radian Corporation. It has been subjected to the Agency's review, and it has
been approved for publication as an EPA document. Mention of trade names or commercial products
does not constitute endorsement or recommendation for use.
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Table 1. Candidate CAA Compounds for YOST Evaluation arranged after GC/MS Evaluation
Amenable to VOST
2,2,4-trimethylpentane
carbon disulfide
benzene
toluene
n-hexane

High water solubility; poor VOST analytical response.
Excluded from further VOST
testing.


acrylonitrile
1,4-dioxane
ethyl acrylate
methyl ethyl ketone
methyl isobutyl ketone
methyl methacrylate
methyl tert-butyl ether
vinyl acetate

No VOST analytical response. Excluded from further VOST testing.
acetonitrile
1.1 -dimethylhydrazine
ethylene imine
propylene oxide
1.2-propylene imine
triethylamine
Table 2. Semivolatile Organic Compounds: Candidates for the SemiVOST Methodology
i			————				
4-aminobiphenyl
m-/D-cresol
dichlorvos

aniline
naphthalene
heptachlor

o-anisidine
nitrobenzene
hexamethylphosphoramide

benzidine
4-nitrobiphenyl
lindane

biphenyl
4-nitrophenol
methoxychlor

bis(2-ethylhexyl) phthalate
N-nitrosodimethylamine
parathion

cumene
N-nitrosomorpholine
1,3-propane sultone

dibenzofurari
phenol
propoxur

di-n-butyl phthalate
1,4-phenyienediamine
quinoline

N,N-diethylaniline
toluene
styrene oxide

N,N-dimethylaniline
o-toluidine
1,4-dioxane

dimethylaminoazobenzene
trifluralin
ethyl carbamate

3,3'-dimethoxy benzidine
ethyibenzene
ethylene thiourea

dimethyl phthalate
styrene
hexamethylene-1,6-



diisocyanate

4,6-dinitro-o-cresoI
o-xylene
maleic anhydride

2,4-dinitrophenol
m-/o-xylene
quinone

2,4-dinitrotoluene
2-acetylaminofiuorene
catechol

3,3'-dimethy Ibenzidine
caprolactam
methyl isobutyl ketone

hydroquinone
captan
phthalic anhydride

isophorone
carbaryl
2,4-toluenediamine

4,4'-methy!ene
chlordane


bis(chloroaniline)

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Table 3. SemiVOST Dynamic Spiking Experimenlal Results.

Average1



%
Std,
%
Neutral Analytes
Recovery
Dev.
RSD
1,4-dioxane
91.9
7.0
7.6
methyl isobutyl
103.3
8.9
8.6
ketone



toluene
340.5
154.5
45.4
ethylbenzene
94.0
9.3
9.9
m,p-xylene
104.2
9.3
8.9
styrene
104.3
8.7
8.4
o-xylene
103.3
8.6
8.4
cumene
102.5
8.9
8.7
acetophenonc
131.5
15.6
1 1.9
Basic Analytes
Average2
%
Recovery
Std.
Dev.
%
RSD
96.0
8.8
9.2
69.3
14.5
20.9
28.2
27.2
96.5
67.0
7.4
11.0
85.1
19.9
23.4
79.5
17.1
21.5
97.0
11.4
11.8
67.2
11.5
17.1
104.0
16.5
15.9
Acidic
Analytes
Average1
%
Recovery
Std.
Dev.
%
RSD
96.0
6.7
7.0
100.2
5.4
5.4
104.8
5.1
4.8
105.3
9.5
9.0
5.3
8.3
155.1
38.2
12.7
33.1
43.6
19.1
43.9
118.1
11.8
10.0
109.7
34.5
31.5
N-nilrosodimclhylumine
ethyl carbamate
quinone
aniline
4-nitrosomorpholine
o-toluidine
N,N-dimethylaniline
o-anisidine
N,N-diethylaniline
styrene oxide
49.1
32.6
66.3
caprolactam
90.9
16.6
18.2
nitrobenzene
97.1
9.0
9.3
hexamethylphosphoramide
48.6
36.0
74.2
isophorone
105.7
14.1
13.4
propoxur
97.3
19.3
19.9
naphthalene
107.3
8.1
7.5
triflural in
149.2
15.7
10.5
dichlorvos
67.6
20.5
30.3
4-aminobipheny!
50.2
20,6
41.0
quinoline
98.7
8.0
8.1
carbaryl
93.9
20.8
22.2
phthalic anhydride
2.4
3.3
135.9
benzidine
8.3
6.7
80.6
biphenyl
106.0
9.8
9.3
4,4,-methyIe»edianiline
6.4
4.7
73.3
2,4-dinitrotoIuene
110.0
26.9
24.5
3,3'-dimeihylbenzidine
27.7
14.0
50.7
di ben 7.0 fy rati
110.1
11.8
10.7
dimethyhtminoazobenzene
105.5
16.9
16.0
lindane
106.9
9.3
8.7
2-acetylaminofluorene
106.3
17.8
16.7
4-nitrobiphenyl
103.8
11.9
11.5
3,3'-dimethoxy benzidine
20.0
9.9
49.5
heptachlor
95.3
8.9
9.3
4.4'-methylene bis(o-
cnloroanmne)
75.4
20.0
26.5
parathion
96.3
11.0
11.4




chiordane
92.9
12.6
13.5




DDE
120.4
12.3
10.2




methoxvehlnr
73.3
21.9
29,9




phenol
o-cresol
m/p-cresol
dimethyl
phthalatc
9,4-
3'mitrophenol
4-nitrophenoI
dintro-o-cresol
djbutyl
phthciiate
'Average of 14 runs. 'Average of 6 runs. 'Average of 8 runs.
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Table 4. VOST Analytical Results, Dynamic Spiking Experiments
Percent Recovery

Mean1
Std.
Dev.2
%RSD5
Analytes



Low Level Spike



carbon disulfide
54
11
21
n-hexane
88
11
13
benzene
66
5
7
2,2,4-trimethylpentane
69
9
13
High Level Spike



carbon disulfide
60
9
15
n-hexane
105
9
8
benzene
99
6
6
2.2.4-trimethvlDentane
83
9
11
' Average of Six Runs. 2 Standard deviation. 3 Percent
relative standard deviation: 100 (standard
deviation/mean).
Table 5. SemiVOST Results Expected in Field Dynamic Spiking
Expected to Meet Acceptance Criteria In the Field
acetophenone
biphenyl
bis(2-ethylhexyl) phthalate
. cumene
dibenzofuran
di-n-butyl phthalate
N,N-diethylaniline
N,N-dimelhylaniline
dimethylaminoazobenzene
dimethyl phthalate
2,4-dinitrotoluene
isophorone
o-cresol
rrWc-cresci
naphthalene
nitrobenzene
4-nitrobiphenyl
N-nitrosodimethylamine
N-nitrosomorpholine
phenol
toluene
o-toluidine
trifluralin
ethylbenzene
styrene
o-xylene
nv/j>-xylene
2-acetylaminofluorene
ca pro lactam
carbaryl
chlordane
DDE
heptachlor
lindane
parathion
propoxur
quinoline
1,4-dioxane
methyl isobutyl ketone
Marginal: Will Most Probably Not Meet Acceptance Criteria in the Field
4-aminobiphenyl	dichlorvos	styrene oxide
aniline	4,4'-methylene bis(chloroaniiine)	hexamethylphosphoramide	ethyl carbamate
o-anisidine	4-nitrophenol	methoxychlor	quinone
4,6-dinitro-o-cresol	3,3'-dimethylbenzidine
Will Not Meet Acceptance Criteria With Standard SemiVOST Method
benzidine	4,4'-methylenedianiline
3,3'-dimethoxybenzidine	1,4-phenylenediamine
2,4-dinitrophenol	captan
hydroquinone	1,3-propane sultone
hexamethylene-1,6-diisocyanate catechol
ethylene thiourea	phthaiic anhydride
maleic anhydride	2,4-dinitrotoluene

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TECHNICAL REPORT DATA
1. REPORT NO. 2.
EPA/600/A-95/123
3 .R
4. TITLE AND SUBTITLE
Application of VOST and SemiVOST to Nonhalogenated
CAAA Compounds
5. REPORT DATE
6.PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
M. Jackson, J. Bursey, J. McGaughey, R. Merrill
8.PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Radian Corporation
Box 13 000
Research Triangle Park, NC 27709
10.PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.•
68D1-0010
12. SPONSORING AGENCY NAME AND ADDRESS
US EPA
Research Triangle Park, NC 27711
13.TYPE OF REPORT AND PERIOD COVERED
Conf. Proceedings 7/93-6/94
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
A laboratory study was performed to demonstrate applicability of VOST (SW-846 Methods 0030 and
5041) and SemiVOST (SW-846 Method 0010, Draft Method 3542, and Method 8270) for collection and
analysis of nonhalogenated organic compounds listed in Title III of the Clean Air Act Amendments of
1990. Compounds with boiling points <:132°C were selected as candidate VOST analytes, and VOST
analyses (Method 5041) of spiked sorbent tubes were performed to demonstrate successful analysis.
Analytes with recovery ;> 50% were prepared as a single certified gaseous standard. VOST dynamic
spiking studies were performed in the laboratory. For semivolatile and nonvolatile compounds (boiling
points *100°C), GC/MS analyses (Method 8270) were performed on analytes combined in a single
solution. Several instances of chemical incompatibility and poor solubility were encountered, and these
analytes were eliminated from further study. Laboratory SemiVOST dynamic spiking studies featured
acid/neutral analytes and base/neutral analytes in separate solutions; two sets of experiments were
performed. All compounds with recoveries ^ 50% will be tested in a field dynamic spiking study.
17. KEY WORDS AND DOCUMENT ANALYSIS
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b.IDENTIFIERS/ OPEN ENDED
TERMS
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