EP A/600/A-97/067
An Evaluation of the SemiVOST Method for
non-Halogenated Compounds at a
Agricultural Chemical Manufacturing Facility
Merrill D. Jackson
U. S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
Joan T. Bursey, James F. McGaughey, and Raymond G. Merrill
Eastern Research Group, Inc
Morrisville, North Carolina 27560
ABSTRACT
Laboratory testing and one field evaluation study have been performed to assess the performance
of the SemiVOST method for non-halogenated semivolatile organic analytes listed in Title ID of the
Clean Air Act Amendments of 1990. This paper reports on a second field evaluation study performed at
a different source category to demonstrate that the methodology is not source-specific. An incinerator
that burned chemical waste was selected as the second test site. The field test was designed according to
the guidelines of EPA Method 301, using liquid dynamic spiking with two spiking schemes. The
semivolatile organic compounds were spiked as a liquid spike into two of four quadruple SemiVOST
trains either as a solution of Acid/Neutral compounds or Base/Neutral compounds. These two solutions
were spiked in separate sampling runs to avoid compound losses due to known acid/base chemical
reactions. A minimum of ten quadruple sampling runs each was performed for Acid/Neutral and
Base/Neutral SemiVOST. Statistical analysis of the results was performed according to the guidelines of
EPA Method 301. Of the 55 semivolatile organic compounds tested by the SemiVOST method, 24 met Method
301 acceptance criteria. Bias and precision were good for the Neutrals, but poor for the Acidic and Basic
compounds.
INTRODUCTION
The U. S. Environmental Protection Agency (EPA), under the authority of Title HI of the Clean
Air Act Amendments of 1990, requires the identification and/or validation of sampling and analytical
methods for the analytes that are listed. To determine whether the development of a new sampling and
analytical method is required for a given analyte, it is necessary to determine the effectiveness and range
of applicability of existing methods. For organic compounds, guidance for the application of sampling
methods is very general: the Volatile Organic Sampling Train1 (VOST, SW-846 Method 0030 ) may be
applied to all organic compounds with boiling points between 30°C and 100°C. The Semivolatile
Organic Sampling Train1 (SemiVOST, SW-846 Method 0010) is applicable to all organic compounds
with boiling point above 100°C. Since a boiling point above 100°C would encompass the vast majority
of organic compounds, the VOST and SemiVOST are logical methods for an initial evaluation of
applicability to the approximately 149 organic analytes listed in the Clean Air Act Amendments. Initial
evaluation of the methodology has focussed on halogenated organic compounds that have been
previously reported.2*3
Evaluation of a stationary source test method for a particular analyte or group of analytes means
that the precision and bias of the method have been established experimentally. The evaluation is
performed in the field in order to encompass the entire method, from sampling through analysis. U. S.
EPA Method 3014 has established guidelines for the field validation of methods for measuring emission
concentrations from stationary sources.

-------
The non-halogenated semivolatile organic confounds selected for evaluation of the SemiVOST
method are shown in Table 1. The SemiVOST method has been evaluated for applicability to these
analytes in a laboratory study5 and in an initial field test using dynamic spiking.6
To provide method evaluation data for a different source categoiy, a second method evaluation
field test was scheduled at a site at which moisture levels were high (approximately 55%). At this test
site, a field evaluation of the SemiVOST sampling procedure with dynamic spiking of semivolatile non-
halogenated organic compounds was performed using quadruple collocated probes with four similar
sampling trains. EPA Method 301 was used to provide statistical guidelines for design of the sampling
strategy. Samples were prepared for analysis using Proposed Method 35427, and analysis was performed
using Method 82701. Method 301 statistical techniques were used to evaluate bias and precision for each
of the analytes listed in Table 1.
PROCEDURE
The field evaluation was conducted at a chemical manufacturing facility which operates a
multipurpose incinerator with primary and secondary aqueous sonic scrubbers. The incinerator is used to
burn aqueous waste, with small amounts of chloroacetic acid, trichloroethylene, and toluene. Grab
samples obtained during a presurvey visit at the test site showed no significant background levels for the
compounds of interest. The analvte level selected for dynamic spiking in the field was approximately 500
^g/analyte, spiked into the trains using a solvent volume of approximately 20 mL. Sampling was
performed by withdrawing stack gas from a single port in the stack through a Quad probe, then directing
the sampled gas to four similar sampling trains. No traversing of the stack with the Quad probe was
performed, since the true concentration of any organic components of the stack gas was of no interest to
this program as long as any quantities of the compounds of interest were equal for each train. Two of the
trains for each Quad run were dynamically spiked and two were unspiked.
Sampling followed Method 00101, with the following modifications: (1) A Quad probe was used
instead of the regular single probe; (2) a heated glass elbow equipped with a dynamic spiking injection
port was used to connect the probe to the heated filter; and (3) because of the high moisture levels, a
standard single condenser was not sufficient to cool the stack gas entering the XAD-2® module to the
temperature of 20°C (68 °F). An extra-large condenser with higher capacity than the standard condenser
was designed to cool the stack gas sufficiently.
For dynamic spiking, non-halogenated semivolatile organic compounds were introduced into the
sampling system in liquid form (methylene chloride solution) by means of syringe injection through a
heated glass elbow mounted at the outlet of the probe of the sampling train. Reagent and field blanks
were also collected, with one field blank for every three Quad sampling runs.
Train components were prepared for analysis using the Proposed Method 3542. The parts of the
Method 0010 train yield three 5-mL extracts to be analyzed according to the procedures of Method
8270. The parts are: (1) the particulate matter filter extract, combined with the extract of the front half
rinse, (2) the condensate rinse and condenser rinse fractions, and (3) the combination of the XAD-2®
extract with the rinse of the back half of the filter holder and the rinse of tubing connecting the filter
holder to the condenser. A critical step in the preparation of SemiVOST train samples, especially with
high levels of moisture present during sampling, is the transfer of the wet XAD-2® from the sampling
module to the Soxhlet extractor according to the procedures of Proposed Method 3542.
Analyses were performed according to the protocol of Method 8270, with the following
exceptions: (1) extracts were generated from methylene chloride extraction of SemiVOST sampling train
components; (2) each final extract volume was 5 mL, rather than 1 mL as specified in Method 8270 for
the extraction of water or soil; (3) filters, XAD-2®, and condensate were extracted separately to generate
three extracts for analysis; and (4) impinger contents were archived.
2

-------
RESULTS AND DISCUSSION
Overall recoveries for spiked surrogate compounds (spiked in the laboratory immediately prior to
preparation of samples) were 92.3%, so no correction for surrogate recoveries was made in the statistical
treatment of the data. As anticipated, the most and highest recoveries for the dynamically spiked
compounds are obtained from the XAD-2®.
There were 10 acid/neutral and 11 base/neutral quad sampling trains run. Due to sample
preparation and analytical problems with two of the acid/neutral runs only 8 were used in the statistical
analysis.
The latest version of Method 301 describes the data analysis method necessary to evaluate both
bias and precision of emission concentration data from stationary sources. Once the bias is determined
for each analyte, a two-way test of hypothesis is performed on the bias term to test whether the bias is
different from zero and statistically significant. For those analytes with a calculated bias found to be
significantly different from zero, a correction factor is calculated which may be used to correct the results
to 100% recovery. Compounds that have correction factors outside the 0.70 to 1.30 window show
unacceptable performance in the sampling and analytical method. The test statistic used is the Student's
t-statistic, and the test is conducted at the 0.05 level of confidence. Precision, in terms of relative
standard deviation, is calculated for each compound for both the spiked and the unspiked sampling trains.
Precision estimates less than 50% are considered acceptable. The bias and precision calculated for the
semivoktile non-halogenated organic compounds which were dynamically spiked in the field are shown in
Table 1.
Statistical calculations for the SemiVOST compound recoveries were also performed using the
methods presented in the EPA Handbook for Quality Assurance/Quality Control (QA/QC) Procedures
for Hazardous Waste Incineration8. The results shown in Table 1 were obtained.
CONCLUSIONS AND RECOMMENDATIONS
The following conclusions may be drawn from the results of the second SemiVOST method
evaluation field test for selected Clean Air Act analytes:
•	Using the EPA Method 301 criteria for acceptable performance (correction factor between 0.70
and 1.30, with relative standard deviation of 50% or less), the SemiVOST methodology showed
acceptable performance in a chemical waste incinerator for the following compounds. Acids: di-
n-butyl phthalate, dimethyl phthalate; Bases: carbaryL, N-nitrosodimethylamine, N-
nitrosomorpholine; Neutrals: 1,4-dioxane, 2,4-dinitrotoluene, 4-nitrobiphenyI, acetophenone,
biphenyl, chlordane, cumene, DDE, dibenzofiiran, ethylbenzene, isophorone, lindane, m-/p-)cylene,
methyl isobutyl ketone, naphthalene, nitrobenzene, o-xylene, and toluene.
•	The chemical composition of the background source matrix is a significant factor in the success or
failure of individual compounds in the sampling and analytical methodology. However, because
there were successful compounds at the second source, the method is not source-specific.
•	Application of the SemiVOST to polar reactive semivolatile compounds produces widely variable
results at different sources, depending upon the reactivity of the background matrix. Laboratory
tests will demonstrate that the methodology can in general be applied to a particular analyte and
can predict certain failure of the methodology under field conditions. That is, if an analyte cannot
be quantitatively extracted from the XAD-2® and analyzed reproducibly, failure under field
conditions is very highly probable. However, successful performance under laboratory conditions
does not guarantee that field testing at a given source will be successful. The chemical and
physical characteristics of the particular source must be considered.
3

-------
•	When a source such as the chemical waste incinerator has a high moisture content, it is essential
to monitor the desorption temperature of the VOST tubes to ensure that the tubes become
sufficiently hot for quantitative desorption of the collected analytes. The high level of moisture
collected on the tubes during sampling (up to several mL of collected water) slows the heating of
the tubes when they are being desorbed for analysis. If the temperature does not reach the
desorption temperature specified by Method 5041 for the period of time required by the method,
analyte recoveries will not be quantitative.
•	When polar water-soluble semivolatile organic compounds are sampled by the SemiVOST at a
source with high moisture, the polar compounds tend to wash through the sampling train to be
collected in the condensate. When polar water-soluble semivolatile confounds are dissolved in
the condensate, these compounds are recovered poorly by the pH-adjusted extraction techniques
required by the SemiVOST.
On the basis of the results of this field method evaluation study, the following
recommendations can be made:
•	Careful consideration of the chemical properties of candidate analytes is essential in predicting
success or failure in the application of SemiVOST sampling and analytical methodology.
•	For compounds with marginal or unacceptable performance in the SemiVOST methods, a detailed
study of the chemical properties of these compounds may provide guidance for the modification
of existing methods to optimize the methodology for these compounds.
REFERENCES
1.	"Test Methods for Evaluating Solid Waste, Physical/Chemical Methods, SW-E46 Manual, 3rd ed."
Document No. 955-001-0000001. Available from Superintendent of Documents, U. S. Government
Printing Office, Washington, D.C. November, 1986.
2.	Field Test of a Generic Method for Halogenated Hydrocarbons, U. S. Environmental Protection
Agency. EPA 600/R-93/101. NTIS PB93-212181.
3.	Jackson, Merrill D,, Joan T. Bursey, James F. McGaughey, Raymond G. Merrill, An Evaluation of
the SemiVOST Method for Halogenated Compounds at a Chemical Manufacturing Facility,
Proceedings of 1995 EPA/AWMA Symposium of Toxic and Related Air Pollutants,, pp. 227-232,
Research Triangle Park, NC, May 16 -18,1995.
4.	EPA Method 301. Protocol for the Field Validation of Emission Concentrations from Stationary
Sources. U. S. Environmental Protection Agency. EPA 450/4-90-0015. April 1991.
5.	Jackson, Merrill D., James F. McGaughey, Joan T. Bursey, Raymond G. Merrill, Method Evaluation
Study: Application of SemiVOST to Nonhalogenated Semivolatile Organic Compounds from the
Clean Air Act Amendments, Proceedings of 1996 EPA/AWMA Symposium of Toxic and Related Air
Pollutants, pp.620-625, Research Triangle Park, NC, May 7-9,1996.
4

-------
6.	Jackson, Merrill D., Joan T. Bursey, James F. McGaughey, Raymond G. Merrill, Application of
VOST and SemiVOST to nonHalogenated CAAA Compounds, Proceedings of 1995 EPA/AWMA
Symposium of Toxic and Related Air Pollutants, pp.233-240, Research Triangle Park, NC, May 16 -
18,1995
7.	Proposed Third Update to SW-846 Manual, Published for Public Comment Federal Register July,
1995.
8.	Handbook Quality Assurance/Quality Control (QA/QC) Procedures for Hazardous Waste
Incineration. EPA/625/6-89/023. January, 1990.
DISCLAIMER
The information in this document has been funded wholly by the United States Environmental
Protection Agency under contract 68-D4-0022 to Eastern Research Group, Inc. It has been subjected to
Agency review and approved for publication. Mention of trade names or commercial products does not
constitute endorsement or recommendation for use.
ACKNOWLEDGMENTS
We wish to acknowledge the contributions of the following individuals to the success of this program:
Danny Harrison, Mark Owens, Jim Southerland, Amy Bederka, Jennifer Regan, Donna Tedder, Linh
Nguyen, Tiffany Sorrell, Jenia Doerle, Mike Bryant, Judi McCartney, Rob Martz, and Phyllis OHara.
5

-------
Table 1. Statistical Evaluation of Field Data Obtained from Quadruple SemiVOST
Sampling Runs with Dynamic Spiking of Title III Clean Air Act Analytes
(Eight Acid/Neutral Sampling Runs, Eleven Base/Neutral Sampling Runs)
Semivolatile Organic
Compound
Mean
Recovery
Meets Method 301
Acceptance
Criteria?3
Meets EPA QA/QC
Handbook
Acceptance
Criteria?4
Acids'
di-M-butyl phthalate
107 ± 14%
Yes
Yes
bis(2-ethylhexyl) phthalate
65 ± 93%
No
No
w-//?-cresol7
65 ± 49%
No
Yes
dimethyl phthalate
123 ±7%
Yes
Yes
phenol
56 + 22%
No
Yes
o-cresol
71 ± 34%
Yes
Yes
2,4-dinitrophenol
24 ± 87%
No
No
4-nitrophenol
59 ± 18%
No
Yes
4,6-dinitro-o-cresol
53 ± 34%
No
Yes
Bases1
dimethylaminoazobenzene
17 ± 67%
No
No
3,3' -dimethoxybenzidine
6 ± 129%
No
No
o-anisidine
4 ± 149%
No
No
o-toluidine
24 ± 70%
No
No
benzidine
8 ± 95%
No
No
N,N-dimethylaniline
54 ± 31%
No
Yes
aniline
35 ± 45%
No
No
4,4'-methylene
bis(2-chloroaniline)
25 ± 49%
No
No
3,3' -dimethy lbenzidine
6 ± 129%
No
No
N,N-diethylaniline
54 + 31%
No
Yes
carbaryl
125 + 51%
No
Yes

-------
Semivolatile Organic
Compound
Mean
Recovery
Meets Method 301
Acceptance
Criteria?3
Meets EPA QA/QC
Handbook
Acceptance
Criteria?4
ethyl carbamate
27 ± 33%
No
No
caprolaetam
22 ± 107%
No
No
N-nitrosomorpholine
81 ± 26%
Yes
Yes
N-nitrosodimethylamine
81 ± 27%
Yes
Yes
propoxur
75 ± 61%
No
No
2-acetyIaminofluorene
49 ± 45%
No
No
Neutrals2
methoxychlor
75 ± 51%
No
No
toluene
97 ± 11%
Yes
Yes
rn-fp-x ylene6
79 ± 12%
Yes
Yes
quinoline5
82 + 30%
Yes
Yes
styrene
39 ± 81%
No
No
o-xylene
97 ± 9%
Yes
Yes
1,4-dioxane
79 ± 21%
Yes
Yes
cumene
95 ± 9%
Yes
Yes
ethylbenzene
93 ± 9%
Yes
Yes
parathion
76 ± 28%
Yes
Yes
isophorone
96 ± 13%
Yes
Yes
acetophenone
98 ± 13%
Yes
Yes
naphthalene
94 ± 10%
Yes
Yes
dibenzofuran
103 ± 12%
Yes
Yes
dichlorvos
57 ±27%
No
Yes
DDE
93 ± 24%
Yes
Yes
4-nitrobiphenyl
104 + 10%
Yes
Yes
heptachlor
35 ± 107%
No
No

-------
Semivolatile Organic
Compound
Mean
Recovery
Meets Method 301
Acceptance
Criteria?3
Meets EPA QA/QC
Handbook
Acceptance
Criteria?4
biphenyl
105 ± 12%
Yes
Yes
lindane
104 + 8%
Yes
Yes
nitrobenzene
100 ± 10%
Yes
Yes
2,4-dinitrotoluene
102 ± 21%
Yes
Yes
methyl isobutyl ketone
101 ± 11%
Yes
Yes
chlordane
85 ± 25%
Yes
Yes
'Values represent the mean from eight complete quad sampling runs with dynamic spiking, two spiked
trains and two unspiked trains.
2Values represent the mean from nineteen complete quad sampling runs with dynamic spiking, two
spiked trains and two unspiked trains. Neutral compounds were spiked in combination with both the
Acid and the Bases, and all neutral data are included in the composite values.
3EPA Method 301 acceptance criteria include recovery of 70 - 130%, with a precision < 50 %
relative standard deviation and a correction factor between 0.70 and 1.30.
4EPA QA/QC Handbook acceptance criteria include recovery of 50 - 150%, with a precision < 50 %
relative standard deviation.
5Quinoline was placed in Neutral solution rather than Basic solution because of confusion of name
with quinone.
'Listed together in the table because of chromatographic coelution.
8

-------
TECHNICAL REPORT DATA
1. REPORT NO. 2.
EPA/600/A-97/067
3
i. TITLE AND SUBTITLE
An Evaluation of the SemiVOST Method for non-Halogenated
Compounds at a Agricultural Chemical Manufacturing Facility
5.REPORT DATE
6,PERFORMING ORGANISATION CODE
7. AUTHOR
-------