EPA/600/R-93/004
January 1993
EVALUATION OF POHC AND PIC
SCREENING METHODS
Robert E. Adams
Ruby H. Janes
David S. Weinberg
Southern Research Institute
Birmingham, Alabama 35255-5305
Contract 68-02-4442
Work Assignments 31, 63, and 83
for
Larry D. Johnson, Project Officer
Methods Research and Development Division
Atmospheric Research and Exposure Assessment Laboratory
Research Triangle Park, NC 27711
ATMOSPHERIC RESEARCH AND EXPOSURE ASSESSMENT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
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TECHNICAL REPORT DATA
1. REPORT NO.
EPA/600/R-93/C04
2.
3' PB93-144137
«. TITLE AND SUBTITLE
Evaluation of POHC arid PIC Screening Methods
5.REPORT DATE
January 1993
6.PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
R.E. Adams, R.H. James, D.S. Weinberg
8.PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Southern Research Institute
P.O. Box 55305
Birmingham, Alabama 35255-5305
ID.PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-02-4442
12. SPONSORING AGENCY NAME AND ADDRESS
Atmospheric Research and Exposure Assessment
Laboratory; US EPA, Office of Research and
Development; Research Triangle Park, NC 27711
.13.TYPE OF REPORT AND PERIOD COVETLED
H. SPONSORING AGENCY CODE
IS. SUPPLEMENTARY NOTES
AREAL Project Officer is Larry D. Johnson, MD-77A, (919) 541-7943
16. ABSTRACT
A recurring theme in environmental work is the need to characterize emissions to
the maximum extent at the minimum cost. Unfortunately, many projects have been
carried out in the past with little thought or planning concerning the optimum
application of analytical methods available. Even worse, many of the analysis data
taken have been subjected to only cursory interpretation. This report represents
the latest in a series of projects designed to improve our ability to plan,
execute, and interpret survey analyses or screening characterization of
environmental source samples. The application of a tiered approach to the analysis
of source emission samples was evaluated for the semi-volatile and non-volatile
organic compounds. The analyses supported the proposed applications of a tiered
approach for screening combustion effluents. If it is known that most of the toxic
compounds of interest are present in the 100-300° C boiling range then gas
chromatography coupled with mass spectrometry (GC/MS) analysis will provide
specific details and gravimetric analysis by the GRAV procedure described in the
report will give an indication of the amount of high boiling non-volatile material
present. Alternately screening of the extract by the total chromatographable
organics procedure (TCO) and GRAV may be sufficient for the characterization of
material in the sample, but high performance liquid chromatography with ultraviolet
detection (HPLC/UV) may be needed for the analyses of target principle organic
hazardous constituents (POHCs). When products of incomplete combustion (PICs) are
to be determined, a chromatographic procedure combined with mass spectrometry will
probably be required.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
b. IDENTIFIERS/ OPEN ENDED TERMS
C.COSAlI
IS. DISTRI2UTION STATEMENT
19. SECURITY CLASS (This R»cort)
21.NO. OF PAGES
51
20 SECURITY CLASS [This F»^e)
22. PRICE
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DISCLAIMER
The information in this document has been funded wholly or in part by the
United States Environmental Protection Agency under Contract 68-02-4442 to
Southern Research Institute. It has been subjected to the Agency's peer and
administrative review, and it has been approved for publication a.s an EFA
document. Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
ii
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FOREWORD
This report has been prepared as a part of a source sampling and analysis
nethods development program conducted by the Atmospheric Research and Exposure
Assessment Laboratory in support of the regulatory programs of the U.S.
Environmental Protection Agency.
A recurring theme in environmental work Is the need to characterize
amissions to the maximum extent at the minimum.cost. Unfortunately, many
projects have been carried out in the past with little thought or planning
concerning the optimum application of analytical methods available. Even
worse, many of the analysis data taken have been subjected to only cursory
interpretation.
This report represents the latest in a series of projects designed to
improve our ability to plan, execute, and interpret survey analyses or
screening characterization of environmental source samples.
Gary J. Foley
Director
Atmospheric Research and Exposure Assessment Laboratory
Research Triangle Park, North Carolina 27711
iii
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ABSTRACT
The analysis of incinerator effluents often focuses on the analysis of
one or a few compounds as principal organic hazardous constituents (FOHCs) and
on products of incomplete combustion (PICs) to provide coverage for other
compounds. Comprehensive techniques that allow the analysis of all organic
compounds in an effluent do not exist and would be costly to apply. Recent
studies have proposed a risk-driven tiered-analysis protocol to characterize
combustion effluents. These procedures do not preclude the analyses of
targeted FOHCs to measure destruction and removal efficiency or targeted FICs
such as polychlorinated dibenzo-£-dioxins and dibenzofurans (PCDD/F) but
supplement them- to provide extended coverage to compounds of environmental
interest that may not be detected in a directed analysis protocol.
The testing of screening methods in this project has focused on the
evaluation of procedures to develop information on the semivolatile and
nonvolatile components found in KM-5 samples. Ve have applied Soxhlet
extraction, gravimetric analysis (GRAV), total chromatographable organic (TCO)
analysis, gas chromatography/mass spectrometry (CC/MS), high performance
liquid chromatography/ultraviolet detection (HPLC/UV), and HPLC/MS to the
analysis of MM-5 samples obtained from incinerators and the analysis of
laboratory spiked samples to determine the feasibility and applicability of
screening techniques.
The application of a tiered approach to the analysis of source emission
samples was evaluated for semivolatile and nonvolatile organic compounds. The
analyses supported the proposed applications of a tiered approach for
screening combustion effluents. GC/HS analysis will provide specific details
for many compounds of interest in the 100 *C to 300 *C boiling range and GRAV
will give an indication of the amount of high-boiling-point nonvolatile
material present. Alternately, screening of the extract by TCO and GRAV may
be sufficient for the characterization of material in the sample, but HPLC/UV
may be needed for the analyses of target POHCs. When FICs are to be
determined, a chromatographic procedure combined with mass spectrometry will
probably be required.
This report was submitted in fulfillment of Contract 68-02-4442 by
Southern Research Institute under the sponsorship of the U.S. Environmental
Protection Agency. This report covers a period from March 1988 to September
1969, and work was completed as of September 1989.
iv
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TABLE OF CONTENTS
Page
FOREWORD iii
ABSTRACT iv
FIGURES > . . . vi
TABLES vii
ACKNOWLEDGMENTS viii
SECTION 1 INTRODUCTION 1
SECTION 2 CONCLUSIONS 2
SECTION 3 RECOMMENDATIONS 3
SECTION 4 TECHNICAL APPROACH 4
GENERAL CONSIDERATIONS 4
SAMPLES 4
CHEMICALS AND REAGENTS 5
Solvents 5
Standards 5
Gases 5
EXTRACTIONS 5
SAMPLE ANALYSIS 5
Gravimetric Analysis 5
Total Chromatographable Organic
Material Analysis 6
Gas Chromatography /Mass Spectrometry 6
High-Performance Liquid Chromatography/
Ultraviolet Detection 6
High-Performance Liquid Chromatography/
Mass Spectrometry 6
SECTION 5 RESULTS AND DISCUSSION 7
GENERAL 7
GRAVIMETRIC ANALYSIS 7
TOTAL CHROMATOGRAPHABLE ORGANIC ANALYSIS 7
GAS CHROMATOGRAPHY/MASS SPECTROMETRY 7
HIGH PERFORMANCE LIQUID CHROMATOGRAPHY WITH
ULTRAVIOLET DETECTION 8
HIGH PERFORMANCE LIQUID CHROMATOGRAPHY WITH
MASS SPECTROMETRY 8
SUMMARY 9
SECTION 6 QUALITY ASSURANCE SUMMARY 10
REFERENCES 51
v
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LIST OF FIGURES
Figure Page
1 Total-Ion chromatogran of coabined extracts of condensate,
sorbent nodule, probe rinse, coil rings, and
iapinger rinae 42
2 HPLC/UV chromatogram of 60 pg/aL PAH standard
(acenaphthylene, benzo(k)fluoranthene, pyrane,
indeno(l,2,3-ed)pyrene) 43
3 HPLC/UV chromatogran of MM-5 Run 227 44
4 HPLC/UV (upper trace) and HPLC/KS-moving belt (lower trace)
chxonatograms of PAH standard 45
5 Total-ion chromatograa of a Mixture containing 100 /.ig/mL
each of resorcinol, benzidine, 2,6-dichlorophenol,
pentachlorophenol, 2,4,5-trichlorophenol,
diethylstlbestrol, 1,2-diphenylhydrazine, and resperine. . . 46
6 Mass spectrua of benzidine 47
7 Mass spectrua of 1,2-diphenylhydrazine 48
8 Mass spectrum of diethylstilbestrol 49
9 Mass spectrum of reserpine 50
vi
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LIST OF TABLES
Table Page
1 Cravisetric and Total Chromatographable Organiea Result* ... 11
2 Semivolatlles (Solvent Blank) 12
3 Semivolatlles (Solvent Spike) 14
4 Semivolatlles (Extracts of Condensate, Sorbent Module,
Probe Rinse, Coil Rinse and Xmpinger Rinse) 16
5 Semivolatlles (Extract of Baghouse Ash) 18
6 Semivolatlles (Extract of Cyclone Ash) 20
7 Semivolatlles (Extracts of Condensate, Sorbent Module,
Probe Rinse, Coil Rinse and Impinger Rinse) 22
8 Semivolatlles (Extract of Cyclone Ash) 24
9 Semivolatlles (Extract of Baghouse Ash) 26
10 Semivolatlles (Laboratory Blank) 28
11 Semivolatiles (Field Blank) 30
12 Semivolatiles (HM-5 #1) 32
13 Semivolatiles (MH-5 #2) 34
14 Semivolatiles (MH-5 #3) 36
15 Synthetic Samples Spiked with Appendix V1X1 Compounds 38
16 Recoveries of PAH by GC/MS Analysis 39
17 Analysis of Polychlorodibenzo-£-Dioxins and
Dibenzofurans 40
18 LC/MS Analysis of Representative PICS 41
vii
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ACKNOWLEDGMENTS
The authors are especially graceful for the individual efforts of the
professional staff of the Instrumental Analysis Division and the Analytical
Chemistry Division of Southern Research who participated in the performance of
this vork.
viii
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SECTION 1
INTRODUCTION
S^5=i! £
&**> <£V3
H
The work from references 1 and 2 proposed several standard methods for
screening purposes. Seven screening protocols were proposed:
Gas chromatography/flame ionization detection (GC/FID) screening for
volatile compounds
Gas chromatography/mass spectrometry (GC/MS) screening for volatile
compounds
Soxhlet extraction for sample preparation
Total chromatographable organic (TCO) determination
GC/MS for semivolatile compounds
Gravimetric (GRAV) determination
High performance liquid chromatography/ultraviolet detection (HPLC/UV)
The methods are from EPA SW-846 (3) or from other EPA documents (4). To these
methods we propose to add high performance liquid chromatography/mass
spectrometry (HPLC/MS) as a screening method.
The testing of screening methods in this project has focused on the
evaluation of procedures to develop information on the semivolatile and
nonvolatile components found in modified method 5 (MM-5) samples. We have
applied Soxhlet extraction, GRAV, TCO, GC/MS, HPLC/UV, and HPLC/MS to the
analysis of MM-5 samples obtained from incinerators and the analysis of
laboratory spiked samples to determine the feasibility and applicability of
screening techniques.
¦=.-=-^==E*The analysis of incinerator effluents often focuses on the analysis of
one or a few compounds as principal organic hazardous constituents (POHCs) and
on products of incomplete combustion (PICs) to provide coverage for other
compounds Comprehensive techniques that allow the analysis of all organic
compounds in an^effluent do not exist. Any proposed technique probably would
be costly to applyf^Recent studies (=l-,2)^have proposed a risk-driven, tie.red-
analysis protocol to characterize combustion effluents."^These "procedures do
not preclude the analyses of targeted POHCs to measure destruction and removal
efficiency (DRE) or targeted PICs such as polychlorinated dibenzo-g-dioxins
and dibenzofurans (PCDD/Fs) but supplement them to provide extended coverage
to compounds of environmental interest that may not be detected in a directed
analysis protocol.
1
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SECTION 2
CONCLUSIONS
The application of a tiered approach to the analysis of source emission
samples was evaluated for semivolatile and nonvolatile organic compounds. The
analyses illustrate that in many cases a combined approach will be useful.
GC/MS analysis will provide specific details for many compounds of interest in
the 100 °C to 300 *C boiling range, and GRAV will give an indication of the
amount of high-boiling-point nonvolatile material present. Alternately,
HFLC/UV may be needed for the analysis of a target POHCs of interest, and
screening of the extract by TCO and GRAV may be sufficient for the
characterization of other materials in the sample. When PICs are to be
determined, a chromatographic procedure combined with mass spectrometry will
probably be required.
This task did not address the volatile PICs and POHCs.
2
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SECTION 3
RECOMMENDATIONS
The recommendations for future investigations are as follows:
Investigate the development of standard high-performance liquid
chromatography/mass spectrometry methods for screening POHCs and PICs.
Continue to develop guidelines for the use of screening techniques in
the analysis of source emissions.
3
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SECTION 4
TECHNICAL APPROACH
GENERAL CONSIDERATIONS
The testing of screening protocols for the measurement of organic
emissions from incinerators can be divided into three categories: volatile,
semivolatile, and nonvolatile. Volatile compounds are sampled with bags,
canisters, volatile organic sampling trains (VOST), and other techniques
designed to capture compounds that boil at temperatures lower than about 130
*C. Semivolatile and nonvolatile compounds are usually captured with an MM-5
train. This study has concentrated on the semivolatile and nonvolatile
categories of organic emissions. Samples were obtained from incinerator tests
or were prepared as laboratory spike samples.
SAMPLES
Method evaluations were based on two types of samples. These were
laboratory spiked samples to provide coverage of compounds of interest and
field samples from incinerator tests.
Incinerator samples were obtained from two sources. One group of
samples consisted of two MM-5 samples, two baghouse ash samples, and two
cyclone ash samples. These samples^-were extracted and analyzed by GRAV, TCO,
HPLC/UV, and GC/MS techniques. The other group of samples consisted of three
split MM-5 trains. These were extracted and analyzed by GRAV, TCO, HPLC/UV,
GC/MS, and HPLC/MS techniques.
The coverage of the method evaluation was extended by preparing several
laboratory spike samples. The laboratory spikes were prepared by adding
semivolatile and nonvolatile compounds to XAD-2 resin. The extracts of these
resin samples were analyzed by GRAV, TCO, HPLC/UV, GC/MS, and HPLC/MS
techniques. Laboratory spike A contained 100, 400, or 1000 mg each of
benzidine, 4,4'-DDT, diethylstilbesterol, 2,4-dinitrotoluene, 2,4,5-
trichlorophenol, pentachloronitrobenzene, reserpine, hexachlorobenzene,
1,2,3,4-tetrachlorobenzene, pentachlorophenol, pentachlorobenzene, 4,4'-
methylenedianiline, 2,4-dichlorophenol, 1,2,4-trichlorobenzene, 2-
chlorophenol, 2-dichlorobenezene, and chlorobenzene. Laboratory spike E was a
duplicate of laboratory spike A. A polycyclic aromatic hydrocarbon (PAH)
spike contained acenaphthene (800 Mg), fluoranthene (160 mg), naphthalene (800
Mg), benzo[a]anthracene (80 fig), benzo[a]pyrene (80 Mg), benzo|b]fluoranthene
(160 Mg), benzo[k]fluoranthene (80 Mg), chrysene (75 Mg), acenaphthylene (1600
ng), anthracene (80 Mg), benzo[g,h,ijperylene (160 Mg), fluorene (160 Mg),
phenanthrene (80 Mg) , dibenzo[a,h]anthracene (160 Mg) , lndenoCl.2.3-cd)pvrene
(80 Mg), and pyrene (80 Mg), all from Supelco PAH Mix 610-M, and 200 Mg of
terphenyl -it*.
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CHEMICALS AND REAGENTS
Solvents
High-purity, distilled-in-glass methylene chloride, hexene, toluene, and
methanol (Burdick and Jackson Laboratories, Inc) were used in this study.
Standards
Standards were obtained from Supelco, Aldrich, Chem Service, Cambridge
Isotope Laboratories, and MSD Isotopes. All standards were >95Z purity, and
most were 99X pure.
Gases
Helium and nitrogen were ultra-high-purity or high-purity grades.
EXTRACTIONS
Standard methods were used to extract all samples. Resin samples,
filters, and ash samples were extracted with methylene chloride according to
Method 3540 from SW-846 (Soxhlet extraction). Condensate samples were
extracted by Method 3510 of SW-846 (Separatory Funnel Liquid-Liquid
Extraction). Samples and blanks analyzed for dioxins were spiked with 50 ng
of 13C12-2,3,7,8-TCDD. Samples and blanks for base-neutral-acid (BNA) analysis
were spiked with 100 ng of nitrobenzene-^, terphenyl-^14, 2-fluorobiphenyl
and 200 pg of phenol-d5, 2-fluorophenol, and 2,4,6-tribromophenol. Samples
were concentrated to final extract volumes by Kuderna-Danish concentration and
nitrogen blow-down.
SAMPLE ANALYSIS
All analyses were by standard methods if available. GRAV, TCO, GC/MS
are described in SW-846. HPLC/UV has been evaluated for POHC and PIC analysis
as reported in several publications (5,6). HPLC/MS procedures were based on
the HPLC/UV methods and modified for the LC/MS interfaces. The general
philosophy of the analysis was to apply the tiered approach presented in
reference 1 to evaluate the utility of low cost methods for the characteriza-
tion of samples and then more complex (and more expensive) methods for the
analysis of samples that contain significant levels of unidentified materials.
Gravimetric Analysis
Gravimetric analysis (3) was used for quantification of organic sample
components with boiling points higher than 300 ®C. This analysis was done
after the sample extract had been concentrated. A 1-5-mL aliquot (10X of the
sample) is evaporated to dryness (constant weight) and weighed with a
precision of at least 0.1 mg. GRAV results are reported as one number for the
entire sample.
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Total Chromatopraphable Organic Material Analysis
In this procedure (Method 0010, Appendix B, SU-846) gas chromatography
vas used to determine the quantity of hydrocarbons with lower boiling points
(B.P. between 100 °C and 300 *C) in the concentrates of organic solvent rinses
and extracts of environmental samples. The extent of compound Identification
vas United to classification of materials into boiling point ranges.
Similarly, the analysis was semiquantitative.
The analysis was performed with a Hewlett-Packard 5890 GC/FID. The
following conditions were used - 30-m x 0.32-mm DB-5 (0.25-nm film thickness)
column; 2-nL splitless injection (injector at 290 *C and detector at 325 *C)
performed at 40 °C; column held for 4 min and programmed to 300 ®C at 15
*C/min; and the carrier gas was N2 at 2 mL/min. A calibration standard
containing jj-heptane, jj-decane, jj-dodecane, E-tetradecane, and n-heptadecane
was used.
Gas Chromatography/Mass Spectrometry
GC/MS analysis was based on Method 8270 from SU-846 for semivolatile BNA
compounds and on Method 8280 from SU-846 for dioxins. Method 8270 was
performed on a Hewlett-Packard 5895 or a VG 70S GC/MS equipped with a column
similar to that described above. Samples were injected in a splitless mode at
40 °C, the column was held for 4 min, programmed to 300 *C at 8 *C/min, and
held for a total analysis time of 40 min. A 5-point calibration curve for the
"priority pollutant" or Contract Laboratory Program (CLP) compounds was used
for quantitation. Dioxin analysis was performed on a VG-70S GC/MS with
parameters specified in Method 8280 of SU-846. Limited standards were
available, and only 13C12-2 ,3 , 7 , 8-TCDD and 37Cl4-2 ,3 ,7,8-TCDD were used in the
analysis.
High Performance Liquid Chromatography/Ultraviolet Detection
Measurements with HPLC/UV were done according to the screening procedure
in reference 2. A 10- to 50-mL aliquot of the sample extract was analyzed on
a Hewlett-Packard 1084B HPLC/UV at 254 nm. The column was a jiBondapak C18, 300
mm x 3.9 mm, with gradient elution (15-100% water-acetonitrile).
High-Performance Liquid Chromatographv/Mass Spectrometry
Two different LC/MS interfaces were employed in this study. A moving-
belt interface from VG instruments was used with a VG-70S mass spectrometer to
obtain data on PAH compounds. Vestec Corporation supplied data from a Model
201 Thermospray/electron impact (EI) liquid chromatography/mass spectrometry
(LC/MS) system (particle-beam LC/MS) coupled to a Compaq 386 personal computer
(PC) with Teknivent software. Samples analyzed by LC/MS were prepared in the
laboratory as standards or as spiked resin samples.
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SECTION 5
RESULTS AND DISCUSSION
GENERAL
The experiments conducted in this project were tiered to apply the least
complicated and least expensive techniques to samples first and then to apply
the more specific and thus more complex and costly methods to develop data
that would indicate complete coverage of the organic materials in the samples.
The procedure usually employed TCO analysis and GRAV analysis prior to GC/MS,
HPLC/UV, or HPLC/MS. In this section we discuss the results of all the
analyses performed on the field and laboratory samples.
GRAVIMETRIC ANALYSIS
A portion of each sample was taken for GRAV analysis. Table 1 gives the
GRAV results. The values for the MM-5 and ash samples varied from about 1 mg
to 83 mg. The laboratory spike samples all contained between 1 and 11 mg of
GRAV material. The four laboratory blanks contained from <1 to 6 mg.
TOTAL CHROMATOGRAFHABLE ORGANIC ANALYSIS
Each sample was analyzed for TCO with GC/FID. Table 1 summarizes the
TCO measurements. The MM-5 and ash samples ranged from less than 1 mg to
about 25 mg of TCO. The TCO in the spiked samples was in the 1- to 10-mg
range. The four laboratory blanks contained from <1 to 4 mg.
The data from the TCO and GRAV experiments indicate that usually a more
extensive analysis would be needed to aid in the characterization of emission
sources. However, if a source has already been extensively characterized
these simple analytical procedures may provide enough information to monitor
the emissions of organic compounds into the atmosphere.
GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS)
We analyzed samples by GC/MS with SW 846 Method 8270. The results are
listed in Tables 2-14. A typical total-ion chromatogram is shown in Figure 1.
Mass-spectrometeric analysis can identify compounds in chromatographic peaks
to determine if hazardous substances are present. We also analyzed laboratory
spiked XAD-2 resin for compounds of environmental interest. Table 15 lists
the recoveries of three levels of spikes performed in duplicate. The
recoveries of the spikes were somewhat variable. The more volatile and more
polar compounds tended to exhibit poor recovery (chlorobenzene, benzidine,
4,4-DDT, 4,4'-methylenedianiline). Excluding these compounds, recoveries
7
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exceeded 502 for most (85%) of the spiked compounds in Table 15. The recovery
of chlorobenzene vas low in all spikes and can probably be attributed to
losses during sample concentration. Spikes of several polynuclear aromatic
compounds were also analyzed by GC/MS. Table 16 gives recovery data for the
PAH spike. Recoveries of the PAH spikes were variable. The wide range of
spiking levels may have contributed to the range of recoveries obtained.
A simplified version of SW 846 Method 8280 was employed to determine the
detectability of PCDD/Fs in the MM-5 samples. Two labelled PCDDs were added
to the sample extracts to serve as surrogate (SS) and internal (IS) standards
(13C12-2,3,7,8-tetrachloro(p)dibenzo dioxin was the SS and 37Cl4-2,3,7,8-TCDD
was the IS). The results are sumarized in Table 17. Matrix interferences
make positive identification of PCDD/Fs uncertain. This analysis indicated
that when data for PCDD/Fs are required, then a simple screening procedure is
inadequate. A more complete screen for PCDD/7s requires extensive and complex
sample cleanup and analysis techniques such as those described in Method 8290.
Analysis by GC/MS gives data that can characterize the organic emissions
from a source in the boiling range of 0 °C to about 300 "C. The range of
compounds investigated in this project was from about 90 *C to 300 *C.
Although excellent identification and adequate quantitation of target
compounds can be made by GC/MS, the range of coverage is small. Compounds
with high boiling points or compounds that are thermally labile will not be
detected easily by GC/MS. Further analysis by other techniques is needed to
extend coverage to these compounds.
HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY WITH ULTRAVIOLET DETECTION
The MM-5 and ash samples were analyzed by HPLC/UV to determine if
compounds that were suitable for measurement by HPLC/UV were present. Figure
2 is the chromatogram of a standard and Figure 3 is an example of the
chromatograms obtained from MM5 samples. A few peaks were found in the
samples, but identification and thus quantification were not performed.
These experiments indicate that HPLC/UV is useful for the analysis for
target compounds where standards are available and interferences are not
present. However, screening of high-boiling-point, polar, and thermally
labile compounds from emission sources will require a technique that gives
more specific identification and allows for interferences to be minimized.
HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY WITH MASS SPECTROMETRY
Two approaches were used to examine HPLC/MS analysis. We had a moving
belt interface available in our laboratory and the application of this type of
interface to samples that contain PAHs has been demonstrated. Our efforts
used PAH and other compounds of environmental interest to explore the
applicably of this interface for screening purposes. Figure 4 gives the
HPLC/UV and HPLC/MS traces for the PAH compounds identified in Table 17.
Compounds of molecular weights from 166 to 278 were detected. Interferences
from the belt itself precluded analyzing compounds of lower molecular weight.
8
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Investigations of KM-5 samples and laboratory spike samples did not give
positive results. The measurement of compounds by moving belt LC/MS is not
amenable to quick or easy screening techniques for environmental analysis. In
our second approach, a sample containing eight compounds was submitted to
Vestec Corporation for analysis by a Model 201 dedicated Thermospray/EI LC/MS
coupled to a Compaq 386 computer with Technivent software. This particle-beam
interface was also of limited usefulness for the sample. Table 18 and Figures
5-9 give the results of this analysis. Other particle-beam interfaces or
Thermospray interfaces may provide more usable screening data for the
evaluation of emission sources.
The use of HPLC/MS in the characterization of emission sources offers
the possibility of extending the coverage of analysis to high-boiling-points,
thermally labile, and polar compounds. The techniques are complex, and much
development work is needed to formulate standard methods for routine, general
analysis.
SUMMARY
The compounds identified in the GC/MS analysis of incinerator effluents
accounted for much of the amount indicated by the GRAV and TCO results. Many
of the compounds detected by GC/MS were not on the targeted analyte list and
were estimated from a response factor of 1.0. Also, many of the compounds
detected were not from "Appendix VIII" or from other lists of pollutants.
The results from these samples indicate that for screening purposes
GC/MS will usually be required to characterize samples. If highly toxic
compounds, such as PCDD/F, are expected in samples, other techniques involving
high resolution GC/high resolution MS will be required to provide adequate
selectivity and sensitivity. Specifically targeted analytes and POHCs may
require other specialized techniques such as LC/MS.
9
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SECTION 6
QUALITY ASSURANCE SUMMARY
The work that was completed at Southern Research Institute (SRI) and
presented in this report was performed under an SRI Quality Assurance Plan
entitled "POHC and PIC Screening" for EPA Contract 68-02-4442, Work
Assignments 31, 63, and 83. The QA/QC requirements for a method development
or feasibility study were met.
The major effort of SRI was to evaluate screening protocols for the
analysis of organic compounds in combustion effluents. The work assignments
were directed to testing protocols. In this report, SRI presents the results
of evaluation of the screening of combustion effluents that must be the
initial phase in developing a risk-driven protocol. This task was
accomplished.
Specifically, total chromatographable organics, GC/MS screening for
semivolatile organic compounds, gravimetric analyses of organic compounds, and
HPLC/UV and HPLC/MS screening for organic compounds were performed. The
analyses of the spiked and field extracts were conducted under the Quality
Assurance/Quality Control (QA/QC) general guidelines for developmental
research project. The Quality Control (QC) associated with these methods
included the analysis of method blanks, spiked samples, surrogate spiked
samples, and calibration standards. Also, the GC/MS was tuned with
decafluorotriphenylphosphine (DFTPP) and calibration curves were prepared.
10
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Table 1. Gravimetric, Total Chromatographable Organics,
and Total Gas Chromatography/Mass Spectrometry Results
Sample
GRAV
TCO
GC/KS
be/dscm*
m^/dscm"
Bfc/dSCB
1.
HM-5-227
0.86
2.3
2.8
2.
MM-5-302
8.3
<0.29
3.2
3.
MM-5-Blank
<0.20
<0.29
0.48
4.
MM-5-Run-l
1.1
0.57
0.55
5.
MM-5-Run-2
0.57
0.86
0.51
6.
MM-5-Run-3
1.1
0.29
1.4
mff /pnb
my/pi**
mg/pB*'
7.
Baghouse-Ash-227
0.60
<0.050
0.069
8.
Cyclone-Ash-227
0.30
0.55
0.42
9.
Baghouse-Ash- 302
0.10
0.20
3.2
10.
Cyclone-Ash-302
0.25
1.25
0.39
11.
Lab Spike A (100 pg)
0.20
0.10
0.024
12.
Lab Spike A (400 jig)
0.15
0.10
0.095
17.
Lab Spike A (1000 pg)
0.55
0.30
0.29
18.
Lab Spike B (100 Mg)
0.050
0.050
0.019
19.
Lab Spike B (400 /*g)
0.20
0.15
0.12
20.
Lab Spike B (1000 jig)
0.30
0.35
0.33
21.
PAH Spike
0.15
0.25
0.085
'Calculated based on an assumed sample volume of 3.5 dry standard
cubic meters (dscm).
Calculated based on a 20 gram ash sample for baghouse and cyclone
ash and on a 40 gm XAD-2 resin sample for the Lab spikes and PAH spike.
11
-------
Table 2. Semlvolatlles
(Solvent Blank)
Sponsor SRI Amount
Sample No. Sample No. Compound* (jig)b
Solvent V01072 Phenol 24,9
Blank for bl»(2-Chloroethyl)«ther NDC
Samples 1-6 Aniline ND
of fable 1 2-Chlorophenol ND
(No Surro- 1,3-Dichlorobenzene ND
gates 1,4-Mchlorobenzene ND
Added) Benzyl alcohol 794
1,2-Dichlorobenzene ND
2-Methylphenol ND
bis-(2-Chloroisopropyl)ether ND
4-Methylphenol 13.5
N-Nltroso»di-n-propylaj»lne ND
Hexachloroethane ND
Nitrobenzene ND
Isophorone ND
2-Nitrophenol ND
2,4-Dlnethylphenol ND
Benzoic acid ND
bis(2-Chloroethyoxy)methane ND
2,4-Dichlorophenol ND
1.2.4-Trlchlorobenzene ND
Naphthalene ND
4-Chloroanlllne ND
Hexaehlorobutadiene ND
4-Chloro-3-methylphanol ND
2-Methylnaphthalene ND
Hexaehlorocyclopentadlene ND
2,4,6-Trlehlorophenol ND
2.4.5-Trlchlorophenol ND
2-Chloronaphthalene ND
2-Nltroanillne ND
Dlmethylphthalate ND
Acenaphthylene ND
3-Nitroaniline ND
Acenaphthene ND
2,4-Dinitrophenol ND
4-Nltrophenol ND
Dlbenzofuxan ND
2,4-Dinitrotoluene ND
2,6-Dinitrotoluene ND
Dlethylphthalate ND
4-Chlorophenylphenylathar ND
Fluorene ND
4-Nltroanlllne ND
4,6 -Mnitro- 2-methylphenol ND
N-Nltrosodiphenylamine ND
(continued)
12
-------
Table 2 (Continued)
Sponsor SRI
Amount
Sample No. Sample No.
Compound*
(*g)b
Solvent V01072
Tetrachlorophenol
ND
Blank for
4-Bromophenylphenylether
ND
Samples 1-6
Hexachlorobenzene
ND
of Table 1
Fentachlorophenol
ND
(No Surro-
Phenanthrene
ND
gates
Anthracene
ND
Added)
Di-n-butylphthalate
ND
(cont)
Fluoranthene
ND
Pyrene
ND
Butylbenzylphthalate
ND
3,3'-Dichlorobenzidine
ND
Benzo[a]anthracene
ND
bis(2-Ethylhexyl)phthalate
ND
Chrysene
ND
Di-n-octylphthalate
ND
Benzo{b]fluoranthene
ND
Benzo[k]fluoranthene
ND
Benzo[a]pyrene
ND
Indeno[1,2,3-cd]pyrene
ND
Dibenz[a,h]anthracene
ND
Benzo[g,h,i]perylene
ND
Silane, trichloroeicosyl- (Scan 14)d
17.5
Ethyl cyclohexane (Scan 19)d
51.2
1,2-Dimethyl benzene (Scan 62)d
1,744
1,4-Dimethyl benzene (Scan 76)d
1,385
1,4-Dimethyl benzene (Scan 104)d
229
Benzaldehyde (Scan 213)d
2,559
Urea, (Phenylmethoxy)- (Scan 472)d
1,016
1,2-Diphenyl ethane (Scan 863)d
321
• Surrogate compounds were not spiked.
bDivide by 3.5 to estimate stack concentration based on a 3.5 dry standard
cubic meter sample or by 20 to estimate concentration in a 20-ash sample.
CND - not detected (detection limit - 12.5 (ig).
dTentatively identified compound.
13
-------
Table 3. Semivolatiles
(Laboratory Blank)
Sponsor SRI Amount
Sample No. Sample Mo. Compound (pg)a
Laboratory V01073 Phenol 21.4
Blank for bis(2-Chloroethyl)ether ND*
Samples 1-6 Aniline ND
of Table 1 2-Chlorophenol ND
(Surrogates 1,3-Dichlorobenzene ND
Added) 1,4-Dichlorobenzene ND
Benzyl alcohol® 1,071
1,2-Dichlorobenzene ND
2-Methylphenol ND
bis-(2-Chloroisopropyl)ether ND
4-Methylphenol ND
N-Nitroso-di-n-propylamine ND
Hexachloroethane ND
Nitrobenzene ND
Isophorone ND
2-Nitrophenol ND
2,4-Dimethylphenol ND
Benzoic acid ND
bis(2-Chloroethyoxy)methane ND
2,4-Dichlorophenol ND
1.2.4-Trichlorobenzene ND
Naphthalene ND
4-Chloroaniline ND
Hexachlorobutadiene ND
4-Chloro-3-methylphenol ND
2-Methylnaphthalene ND
Hexachlorocyclopentadiene ND
2,4,6-Trichlorophenol ND
2.4.5-Trichlorophenol ND
2-Chloronaphthalene ND
2-Nitroaniline ND
Dimethylphthalate ND
Acenaphthylene ND
3-Nitroaniline ND
Acenaphthene ND
2,4-Dinitrophenol ND
4-Nitrophenol ND
Dibenzofuran ND
2,4-Dinitrotoluene ND
2,6-Dinitrotoluene ND
Diethylphthalate ND
4-Chlorophenylphenylether ND
Fluorene ND
4-Nitroaniline ND
4,6-Dinitro-2-»ethylphenol ND
N-Nitrosodiphenylamine ND
(continued)
14
-------
Table 3 (Continued)
Sponsor SRI
Amount
Sample Mo. Sample No.
Compound
d
965
1,4-Dimethyl benzene (Scan 108)e
220
Nonane (Scan 115)*
112
Benzaldehyde (Scan 215)C|d
2,535
1-Phenyl-ethanone (Scan 347)c•d
12.5
Thiocyanic acid, phe ny line thy 1 ester
(Scan 384)c
17.5
Benzene, 1,1'-(l,2-ethanediyl)bis-
(Scan 864)e-d
344
Benzene, l-methyl-4-(phenylmethyl)-
(Scan 8B0)e•d
13.8
'Divide by 3.S to estimate stack concentration based on a 3.5 dry standard
cubic meter sample or by 20 to estimate concentration in a 20 g ash
sample.
bND - not detected (detection limit - 12.5 fig).
eTentatively identified compound.
dPeaks in blank at similar retention time and concentration.
•Nonane present as solvent for 13C12-2,3,7,8-TCDD which vas spiked into the
sample.
15
-------
Table 4. Semivolatiles
(Extracts of Condensate, Sorbent Module, Probe Rinse,
Coil Rinse, and Iapinger Rinse)
Sponsor SRI Amount
Sample No. Sample No. Compound (pg/dscs)*
KM-5-227 V01094 Phenol ND*
bis(2-Chloroethyl)ether ND
Aniline ND
2-Chlorophenol KD
1.3-Dichlorobenzene ND
1.4-Dichlorobenzene ND
Benzyl alcohol ND
1,2-Dichlorobenzene RD
2-Methylphenol ND
bis-(2-Chloroisopropyl)ether ND
4-Methylphenol ND
N-Nitroso-di-n-propylanine ND
Hexachloroethane ND
Nitrobenzene ND
Isophorone ND
2-Nitrophenol 12.4
2,4-Dimethylphenol ND
Benzoic acid ND
bis(2-Chloroethyoxy)methane ND
2,4-Dichlorophenol ND
1.2.4-Trichlorobenzene ND
Naphthalene ND
4-Chloroaniline ND
Hexachlorobutadiene ND
4-Chloro-3-n»ethylphenol ND
2-Methylnaphthalene ND
Hexachlorocyclopentadiene ND
2,4,6-Trichlorophenol ND
2.4.5-Trichlorophenol ND
2-Chloronaphthalene ND
2-Nitroaniline ND
Dinethylphthalate ND
Acenaphthylene ND
3-Nitroaniline ND
Acenaphthene ND
2,4-Dinitrophenol ND
4-Nitrophenol ND
Dibenzofuran ND
2,4-Dinitrotoluene ND
2,6-Dinitrotoluene ND
Diethylphthalate 30.9
4-Chlorophenylphenylether ND
Fluorene ND
4-Nitroaniline ND
4,6-Dinitro-2-Bethylphenol ND
N-Nitrosodiphenylamine ND
(continued)
16
-------
Table 4 (Continued)
Sponsor SRI Amount
Sample No. Sample Ho. Compound (pg/dscm)a
MM-5-227 V01094
Tetrachlorophenol
ND
(cont.)
4-Bromophenylphenylether
ND
Hexachlorobenzene
ND
Pentachlorophenol
ND
Phenanthrene
ND
Anthracene
ND
Di-n-butylphthalate
ND
Fluoranthene
ND
Pyrene
ND
Butylbenzylphthalate
ND
3,3'-Dichlorobenzidine
ND
Benzo[a]anthracene
ND
bis(2-Ethylhexyl)phthalate
62.9
Chrysene
ND
Di-n-octylphthalate
120
Benzo[b]fluoranthene
ND
Benzo[k]fluoranthene
ND
Benzo[ajpyrene
ND
Indeno[1,2,3-cd]pyrene
ND
Dibenz[a,h]anthracene
ND
Benzo[g,h,i]perylene
ND
1,3-Propanediol, 2,2-diethyl- (Scan 39)e
134
1,3-Dioxan-5-ol, 4,4,5-trimethyl- (Scan 51)e
172
3,5-Dimethyl-heptane (Scan 63)e
159
2-Propanone, 1-(acetyloxy)- (Scan 113)c
153
2-Cyolohexen-l-one (Scan 174)c
214
2-Butenedioic acid, 2-methyl-,
(E)- (Scan 202)e
154
Silane, trinethyl(tridecyloxy)- (Scan 208)c
70.9
Cyclohexanol, 2-chloro-, trans- (Scan 308)c
351
Cyclohexane, 1,2-dichloro-, trans-
(Scan 344 )e
73.7
Unknown (Scan 439)*
157
A Phthalate (Scan 1,652)*
44.3
A Phthalate (Scan 1,836)E
228
A Phthalate (Scan l,882)e
317
A Phthalate (Scan l,984)c
319
•A 3.5 dscm sample was used to calculate stack concentration (actual volume
collected was unknown).
bND - not detected (detection limit - 3.6/ng/dscm).
cTentatively identified compound.
dPeaks in blank at similar retention time and concentration.
•Unknown compound.
17
-------
Table 5. Semivolatiles
(Extract of Baghouse Ash)
Sponsor SRI Amount
Sample No. Sample No. Compound* (Mg/g»)
Baghouse- V01090 Phenol ND*
Ash-227 bis(2-Chloroethyl)ether RD
Aniline ND
2-Chlorophenol KD
1.3-Dichlorobenzene KD
1.4-Dichlorobenzene RD
Benzyl alcohol ND
1,2-Dichlorobenzene ND
2-Methylphenol ND
bis-(2-Chloroisopropyl)ether ND
4-Methylphenol ND
N-Nitroso-di-n-propylamine RD
Hexachloroethane KD
Nitrobenzene ND
Isophorone ND
2-Nitrophenol ND
2,4-Dime thylphenol ND
Benzoic acid ND
bis(2-Chloroethyoxy)methane ND
2,4-Dichlorophenol ND
1.2.4-Trichlorobenzene ND
Naphthalene ND
4-Chloroaniline ND
Hexachlorobutadiene ND
4-Chloro-3-methylphenol ND
2-Hethylnaphthalene ND
Hexachlorocyclopentadiene ND
2,4,6-Trichlorophenol ND
2.4.5-Trichlorophenol ND
2 -Chloronaphthalene ND
2-Nitroaniline ND
Dimethylphthaiate ND
Acenaphthylene ND
3-Nitroaniline ND
Acenaphthene ND
2,4-Dinitrophenol ND
4-Nitrophenol ND
Dibenzofuran ND
2,4-Dinitrotoluene ND
2,6-Dinitrotoluene ND
Diethylphthalate ND
4-Chlorophenylphenylether ND
Fluorene ND
4-Nitroaniline ND
4,6-Dinitro-2-aethylphenol ND
N-Nitrosodiphenylamine ND
(continued)
18
-------
Table 5 (Continued)
Sponsor SRI Amount
Sample No. Sample Ho. Compound* (pg/gn)
Baghouse V01090
Tetrachlorophenol
ND
Ash-227
4-Bromophenylphenylether
ND
(cont.)
Hexachlorobenzene
ND
Fentachlorophenol
HD
Phenanthrene
ND
Anthracene
HD
Di-n-butylphtha1ate
ND
Fluoranthene
ND
Pyrene
ND
Butylbenzylphthaiate
ND
3,3'-Dichlorobenzidine
ND
Benzo[a]anthracene
ND
b i s(2-Ethylhexy1)phthalate
ND
Chrysene
ND
Di-n-octylphthalate
ND
Benzo[b]fluoranthene
ND
Benzo[k]fluoranthene
ND
Benzo[ajpyrene
ND
Indeno[1,2,3-cd)pyrene
ND
Dibenz[a,h]anthracene
ND
Benzo[g,h,i]perylene
ND
2,4-Dimethyl-2-pentanol (Scan 25)c
21.0
2-Hexenal (Scan 41)e
5.50
2-Cyclohexen•1-ol (Scan 88)e'd
1.81
Nonane (Scan 103)*
22.7
2-Cyclohexen-1-one (Scan 152)e
3.87
4-Chloro-trans-cyclohexanol (scan 282)c
2.19
3-3-Dimethyl-l,4-pentadiene (Scan 337)c
2.13
2-Bromo-trans-cyclohexanol (Scan 387)c
1.19
4-Chloro-cyclohexanone (Scan 422)e
0.750
2,5-Diethyltetrahydro-furan (Scan 515)e
1.56
l-Butyl-2-iodo-cyclopropane (Scan SSB)6-"1
1.19
Cyclohexane, l-bromo-2-chloro-, cis-
(Scan 569)c
5.50
•Surrogate compounds were not spiked.
bND - not detected (detection limit * 0.625 ftg).
eTentatively identified compound.
dPeaks in blank at similar retention time and concentration.
"Nonane present as solvent for 1SCX2"2,3,7,8-TCDD, which was spiked into
the sample.
19
-------
Table 6. Semivolatiles
(Extract of Cyclone Ash)
Sponsor
SRI
Amount
Sample Wo.
Sample Mo.
Compound*
(Mg/g»)
Cyclone-
V010B4
Phenol
ND*
Ash-227
bis(2-Chloroethyl)ether
ND
Aniline
ND
2-Chlorophenol
ND
1,3-Dichlorobenzene
ND
1,4-Dichlorobenzene
ND
Benzyl alcohol"1
30.1
1,2-Dichlorobenzene
ND
2-Methylphenol
ND
bis-(2-Chloroisopropyl)ether
ND
4-Methylphenol
ND
N-Nitroso-di-n-propylamine
ND
Hexachloroethane
ND
Nitrobenzene
ND
Isophorone
ND
2-Nitrophenol
ND
2,4-Dimethylphenol
ND
Benzoic acid
ND
bis(2-Chloroethyoxy)nethane
ND
2,4-Dichlorophenol
ND
1,2,4-Trichlorobenzene
ND
Naphthalene
ND
4-Chloroaniline
ND
Hexachlorobutadiene
ND
4-Chloro-3-methylphenol
ND
2-Methylnaphthalene
ND
Hexachlorocyclopentadiene
ND
2,4,6-Trichlorophenol
ND
2,4,5-Trichlorophenol
ND
2-Chloronaphthalene
ND
2-Nitroaniline
ND
Dimethylphthalate
ND
Acenaphthylene
ND
3-Nitroaniline
ND
Acenaphthene
ND
2,4-Dinitrophenol
ND
4-Nitrophenol
ND
Dibenzofuran
ND
2,4-Dinitrotoluane
ND
2,6-Dinitrotoluene
ND
Diethylphthalate
ND
4-Chlorophenylphenylether
ND
Fluorene
ND
4-Nitroaniline
ND
4,6-Dinitro-2-methylphenol
ND
N-Nitrosodiphenylamine
ND
(continued)
20
-------
Table 6 (Continued)
Sponsor SRI Amount
Sample No. Sample Ho. Compound* (fig/gm)
Cyclone- V01084 Tetrachlorophenol ND
Ash-227 4-Bromophenylphenylether ND
(cont.) Hexachlorobenzene ND
Pentachlorophenol ND
Phenanthrene ND
Anthracene ND
Di-n-butylphthalate ND
Fluoranthene ND
Pyrene ND
Butylbenzylphthalate ND
3,3'-Dichlorobenzidlne ND
Benzo[a]anthracene ND
bis(2-Ethylhexyl)phthalate ND
Chrysene ND
Di-n-octylphthalate ND
Benzo[b]fluoranthene ND
Benzo[k]fluoranthene ND
Benzo[ajpyrene ND
Indeno[l,2,3-cd]pyrene ND
Dibenz[a,h]anthracene ND
Benzo[g,h,i]perylene ND
Ethyl cyclohexane (Scan 15)e,d 3.69
1.3-Dimethyl benzene (Scan 62)e,d 134
1,2-Dimethyl benzene (Scan 75)ed 121
1.4-Dinethyl benzene (Scan 101)e-d 11.0
Benzaldehyde (Scan 206)e
-------
Table 7. Semivolatiles
(Extracts of Condensate, Sorbant Module, Probe Rinse,
Coll Rinse and Impinger Rinse)
Sponsor SRI Amount
Sample No. Sample No. Compound (jig/dscm)*
MM-5-302 V01003 Phenol 71.1
bis(2-Chloroethyl)ether ND*
Aniline KB
2-Chlorophenol ND
1.3-Dichlorobenzene ND
1.4-Dichlorobenzane ND
Benzyl alcohol*1 211
1,2-Dichlorobenzene ND
2-Methylphenol ND
bis-(2-Chloroisopropyl)ether ND
4-Methylphenol ND
N-Nitroso-di-n-propylaaine ND
Hexachloroethane ND
Nitrobenzene ND
Isophorone ND
2-Nitrophenol ND
2,4-Dimethylphenol ND
Benzoic acid ND
bis(2-Chloroethyoxy)methane ND
2,4-Dichlorophenol ND
1.2.4-Trichlorobenzene ND
Naphthalene ND
4-Chloroaniline ND
Hexachlorobutadiene ND
4-Chloro-3-methylphenol ND
2-Methylnaphthalene ND
Hexachlorocyclopentadiene ND
2,4,6-Trichlorophenol ND
2.4.5-Trichlorophenol ND
2*Chloronaphthalene ND
2-Nitroaniline ND
Dimethylphthalate ND
Acenaphthylene ND
3-Nitroaniline ND
Acenaphthene ND
2,4-Dinitrophenol ND
4-Nitrophenol ND
Dibenzofuran ND
2,4-Dinitrotoluene ND
2,6-Dinitrotoluene ND
Diethylphthalate 11.1
4-Chlorophenylphenylether ND
Fluorene ND
4-Nitroaniline ND
4,6-Dinitro-2-aethylphenol ND
N-Nitrosodiphenylamine ND
(continued)
22
-------
Table 7 (Continued)
Sponsor SRI Amount
Sample Ho. Sample No. Compound (j*g/dscin)a
MM-5-302 V01003 Tetrachlorophenol ND
(cont.) 4-Bromophenylphenylether ND
Hexachlorobenzene ND
Fentachlorophenol ND
Phenanthrene ND
Anthracene ND
Di-n-butylphthalate ND
Fluoranthene ND
Pyrene ND
Butylben2ylphthalate ND
3,3'-Dichlorobenzidlne ND
Benzo[a]anthracene ND
bis(2-Ethylhexy1)phthalate 30.7
Chrysene ND
Di-n-octylphthalate 43.1
Benzofb]fluoranthene ND
Benzofkjfluoranthene ND
Benzo[a]pyrene ND
Indeno[1,2,3-cd]pyrene ND
Dibenz[a,h]anthracene ND
Benzo[g,h,ijperylene ND
2-Fentanol, 2,4-dimethyl- (Scan 40)c 95.4
1.3-Dloxan-5-ol, 4,4,5-trimethyl- (Scan 51)c 183
2-Bromo-heptane (Scan 63)e-d 160
2-Fropanone, 1-(acetyloxy)- (Scan 126)c 247
2-Cyclohexen-l-one (Scan 178)e 246
Silane, trimethyl(tridecyloxy)- (Scan 212)e 73.1
Cyclohexanol, 4-chloro-, trans-
(Scan 307)e 528
Cyclohexanol, 4-chloro-, trans-
(Scan 310)c 455
2-Chloro-cyclohexanone (Scan 341)e 194
Unknown (Scan 346)* 131
3-Butyl-2,4-pentanedlone (Scan 436)e 60
3-Butyl-2,4-pentanedione (Scan 443>e 210
1.4-Cyclohexanedlol, dlacetate, trans -
(Scan 622)e 84.3
A Phthalate (Scan l,880)c 144
'A 3,5 dscm sample was used to calculate stack concentration (actual volume
collected was unknown).
bND - not detected (detection limit - 3.6/pg/dscm).
cTentatively identified compound.
dPeaks in blank at similar retention time and concentration.
'Unknown compound.
23
-------
Table B. Semivolatiles
(Extract of Cyclone Ash)
Sponsor
SRI
Amount
Sample No.
Sample No.
Compound*
(fig/m)
Cyclone-
V01086
Phenol
RDl>
Ash-302
bis(2-Chloroethyl)ether
ND
Aniline
ND
2-Chlorophenol
ND
1,3-Dichlorobenzene
ND
1,4-Dichlorobenzene
ND
Benzyl aleohold
10.3
1,2-Dichlorobenzene
ND
2-Hethylphenol
ND
bis-(2-Chloroisopropyl)ether
ND
4-Me thylpheno1
ND
N-Nitroso-di-n-propylaaine
ND
Hexachloroethane
ND
Nitrobenzene
ND
Isophorone
ND
2-Nitrophenol
ND
2,4-Dimethylphenol
ND
Benzoic acid
ND
bis(2 -Chloroethyoxy)methane
ND
2,4-Dichlorophenol
ND
1,2,4-Trichlorobenzene
ND
Naphthalene
ND
4-Chloroaniline
ND
Hexachlorobutadiene
ND
4-Chloro-3-methylphenol
ND
2-Kethylnaphthalene
ND
Hexachlorocyclopentadiene
ND
2,4,6-Trichlorophenol
ND
2,4,5-Trichlorophenol
ND
2-Chloronaphthalene
ND
2-Nitroaniline
ND
Dimethylphthalate
ND
Acenaph thylene
ND
3-Nitroaniline
ND
Acenaphthene
ND
2,4-Dinitrophenol
ND
4-Nitrophenol
ND
Dibenzofuran
ND
2,4-Dinitrotoluene
ND
2,6-Dinitrotoluene
ND
Diethylphthalate
ND
4-Chlorophenylphenylether
ND
Fluorene
ND
4-Nitroaniline
ND
4,6-Dinitro-2-»ethylphenol
ND
N-Nitrosodiphenylaoine
ND
(continued)
24
-------
Table 8 (Continued)
Sponsor SRI Amount
Sample No. Sample No. Compound* (pg/gm)
Cyclone- V01086
Tetrachlorophenol
ND
Ash-302
4-Bromophenylphenylether
ND
(cont.)
Hexachlorobenzene
ND
Pentachlorophenol
ND
Phenanthrene
ND
Anthracene
ND
Di-n-butylphthalate
ND
Fluoranthene
ND
Pyrene
ND
Butylbenzylphthalate
ND
3,3'-Dichlorobenzidine
ND
Betizo [ a ] anthracene
ND
b is(2-Ethylhexyl)phthalate
ND
Chrysene
ND
Di-n-octylphthalate
ND
Benzo[b]fluoranthene
ND
Benzo[k]fluoranthene
ND
Benzo[a]pyrene
ND
Indeno[1,2,3-cd]pyrene
ND
Dlbenz[a,h]anthracene
ND
Benzo[g,h,ijperylene
ND
9-Methyl-1-undecene (Scan 16)e-d
1.25
Ethyl cyclohexane (Scan 21)e-d
5.95
1,2-Dimethyl benzene (Scan 66)c-d
153
l,5-Heptadien-3-yne (Scan 80)e-d
107
1,4-Dimethyl benzene (Scan 106)e,d
15.3
Nonane (Scan 114)*
8.8
Benzaldehyde (Scan 205)ed
41.5
Urea, (phenylmethoxy)- (Scan 463)c-d
3.31
Unknown aromatic (Scan 862)d-f
2.69
Unknown aromatic (Scan 960)*
18.5
Unknown aromatic (Scan 973)'
16.5
Unknown aromatic (Scan 976)*
2.88
Unknown aromatic (Scan 984)f
4.50
* Surrogate compounds vere not spiked.
bND - not detected (detection limit - 0.625 Mg) •
cTentatively identified compound.
* Peaks in blank at similar retention time and concentration.
•Nonane present as solvent for 13C12-2,3,7,8-TCDD, which vas spiked into
the sample.
'Unknown compound.
25
-------
Table 9. Samivolatiles
(Extract of Baghouse Ash)
Sponsor SRI Amount
Sample Ho. Sample Ho. Compound* (Mg/gn)
Baghouse- V01092 Phenol HI^
Ash-302 bis(2-Chloro«thyl)ether ND
Aniline HD
2-Chlorophenol ND
1.3-Dichlorobenzene HD
1.4-Dichlorobenzene HD
Benzyl alcohol11 4.66
1,2-Dichlorobenzene ND
2-Methylphenol HD
bis-(2-Chloroisopropyl)ether HD
4-Me thylphenol HD
N-Nitroso-di-n-propylamine HD
Hexachloroethane HD
Hitrobenzene ND
Isophorone HD
2-Hitrophenol HD
2,4-Dinethylphenol HD
Benzoic acid HD
bis(2-Chloroethyoxy)nethane ND
2,4-Dichlorophenol ND
1.2.4-Trichlorobenzene ND
Naphthalene HD
4-Chloroaniline ND
Hexachlorobutadiene HD
4-Chloro-3-nethylphenol ND
2-Methylnaphthalene HD
Hexachlorocyclopentadiene ND
2,4,6-Irichlorophenol ND
2.4.5-Trichlorophenol HD
2-Chloronaphthalene HD
2-Hitroaniline HD
Dinethylphthalate ND
Acenaphthylene HD
3-Nitroaniline ND
Acenaphthene HD
2,4-Dinitrophenol HD
4-Hitrophenol ND
Dibenzofuran ND
2,4-Dinitrotoluene ND
2,6-Dinitrotoluene ND
Diethylphthalate HD
4-Chlorophenylphenylether KD
Fluorene ND
4-Nitroaniline ND
4,6-Dinitro-2-aethylphenol ND
H-Hitrosodiphenylaisine KD
(continued)
26
-------
Table 9 (Continued)
Sponsor SRI Amount
Sample Ho. Sample No. Compound* (MB/g»)
Baghouse V01092
Tetrachlorophenol
ND
Ash-302
4-Bromophenylphenyle ther
ND
(cont.)
Hexachlorobenzene
KD
Pentachlorophenol
ND
Fhenanthrene
KD
Anthracene
ND
Di-n-butylphthalate
ND
Fluoranthene
ND
Pyrene
ND
Butylbenzylphthalate
ND
3,3'-Dichlorobenzidine
ND
Benzo[a]anthracene
ND
bis(2-Ethylhexyl)phthalate
ND
Chrysene
ND
Di-n-octylphthalate
ND
Benzo[b]fluoranthene
ND
Benzo[k]fluoranthene
ND
Benz o[a]pyrene
ND
Indenofl,2,3-cd]pyrene
ND
Dibenz[ a, h ]anthracene
ND
Benzo[g,h,i]perylene
ND
Ethyl cyclohexane (Scan 20)e'd
2.81
2,4-Dimethyl-l,3-dioxolane-2-methanol
(Scan 37)e
1.81
1,3-Dimethyl benzene (Scan 67)c-d
126
l,5-Heptadien-3-yne (Scan 80)e>d
116
1,4-Dimethyl benzene (Scan 104)e,d
9.25
Nonane (Scan 112)*
4.00
Benz aldehyde (Scan 205)c,d
38.1
Hydrazinecarboxylic acid, phenylmethyl
ester (Scan 273)c-d
0.69
Benzene, 1,1'-(l,2-ethanediyl)bis-
(Scan 862)e'd
3.13
Unknown aromatic (Scan 1,560)*
6.70
•Surrogate compounds were not spiked.
bND - not detected (detection limit - 0.625 fig).
eTentatively identified compound.
dPeaks in blank at similar retention time and concentration.
"Nonane present as solvent for 13C12-2,3,7,8-TCDD, which was spiked into
the sample.
'Unknown compound.
27
-------
Table 10. Semivolatiles
(Laboratory Blank)
Sponsor SRI Anount
Sample No. Sample No. Compound (pg/dscn)*
Solvent 21140 Phenol ND*
Blank bis(2-Chloroethyl)ether ND
for Samples Aniline ND
9-12 of 2-Chlorophenol ND
Table 1 1,3-Dichlorobenzene ND
1,4-Dichlorobenzene NT
Benzyl alcohol KD
1,2-Dichlorobenzene ND
2-Methylphenol ND
bis-(2-Chloroisopropyl)ether ND
4-Methylphenol ND
N-Nitroso-di-n-propylamine ND
Hexachloroethane ND
Nitrobenzene ND
Isophorone ND
2-Nitrophenol ND
2,4-Dine thylpheno1 ND
Benzoic acid ND
bis(2-Chloroethyoxy)methane ND
2,4-Dichlorophenol ND
1.2.4-Trichlorobenzene ND
Naphthalene ND
4-Chloroaniline ND
Hexachlorobutadiene ND
4-Chioro-3-m«thylpheno1 ND
2-Methylnaphthalene ND
Hexachlorocyclopentadiene ND
2,4,6-Trichlorophenol ND
2.4.5-Trichlorophenol ND
2-Chloronaphthalene ND
2-Nitroanillne ND
Dimethylphthaiate ND
Acenaphthylene ND
3-Nitroaniline ND
Acenaphthene ND
2,4-Dinitrophenol ND
4-Nitrophenol ND
Dibenzofuran ND
2,4-Dinitrotoluene ND
2,6-Dinitrotoluene ND
Diethylphthalate ND
4-Chlorophenylphenylether ND
Fluorene ND
4-Nitroanlline ND
4,6-Dinitro-2-methylphenol ND
N-Nitrosodiphenylamine ND
(continued)
26
-------
Table 10 (Continued)
Sponsor SRI
Sample No. Sample No.
Compound
Amount
(jig/dscm)
Solvent 21140
Tetrachlorophenol
NL
Blank
4-Bromophenylpheny1ether
ND
for Samples
Hexachlorobenzene
ND
9-12 of
Fentachlorophenol
NL
Table 1
Fhenanthrene
ND
(cont)
Anthracene
ND
Di-n-butylphthalate
ND
Fluoranthene
ND
Fyrene
ND
Butylbenzylphthalate
ND
3,3'-Dichlorobenzidine
ND
Benzo[a]anthracene
ND
bis(2-Ethylhexyl)phthslate
ND
Chrysene
ND
Di-n-octylphthalate
ND
Benzo[b]fluoranthene
ND
Benzo[kjfluoranthene
ND
Benzo[a]pyrene
ND
Indeno[1,2,3-cd]pyrene
ND
Dibenz[a,h]anthracene
ND
Benzo[g,h,i]perylene
ND
'A 3.5 dscm sample was used to calculate stack concentration.
bND - not detected (detection limit - 3.57 pg/dscm).
29
-------
Table 11. Semivolatiles
(Field Blank)
Sponsor SRI Amount
Sample No. Sample No. Compound (pg/dacm)*
MK-5-Blank 21146 Phenol NDk
bis(2-Chloroethyl)ether KD
Aniline HD
2-Chlorophenol ND
1.3-Dichlorobenzene ND
1.4-Dichlorobenzene ND
Benzyl alcohol NB
1,2-Dichlorobenzene ND
2-Kethylphenol ND
bis-(2-Chloroisopropyl)ether ND
4-Methylphenol ND
N-Nitroso-di-n-propylaaine ND
Hexachloroethane ND
Nitrobenzene ND
Isophorone ND
2-Nitrophenol ND
2,4-Dimethylphenol ND
Benzoic acid ND
bis(2-Chloroethyoxy)methane ND
2,4-Dichlorophenol ND
1.2.4-Trichlorobenzene ND
Naphthalene ND
4-Chloroaniline ND
Hexachlorobutadiene ND
4-Chloro-3-methylphenol ND
2-Methylnaphthalene ND
Hexachlorocyclopentadiene ND
2,4,6-Trichlorophenol ND
2.4.5-Trichlorophenol ND
2-Chloronaphthalene ND
2-Nitroaniline ND
Dimethylphthalate ND
Acenaphthylene ND
3-Nitroaniline ND
Acenaphthene ND
2,4-Dinitrophenol ND
4-Nitrophenol ND
Dibenzofuran ND
2,4-Dinitrotoluene ND
2,6-Dinitrotoluene ND
Diethylphthalate 12.6
4-Chlorophenylphenylether ND
Fluorene ND
4-Nitroaniline ND
4,6-Dinitro-2-methylphenol ND
N-Nitrosodiphenylamine ND
(continued)
30
-------
Table 11 (Continued)
Sponsor SRI Amount
Sample No. Sample No. Compound* (/ig/dscm)*
HM-5-Blank 21146 Tetrachlorophenol ND
(cont) 4-Bromophenylphenylether ND
Hexachlorobenzene ND
Pentachlorophenol ND
Phenanthrene ND
Anthracene ND
Di-n-butylphthalate 5.93
Fluoranthene ND
Pyrene ND
Butylbenzylphthalate ND
3,3'-Dichlorobenzidine ND
Benzo[a]anthracene ND
bis(2-Ethylhexyl)phthalate 4.06
Chrysene ND
Di-n-octylphthalate 59.7
Benzo[b]fluoranthene ND
Benzo[k]fluoranthene ND
Benzo[ajpyrene ND
Indeno[1,2,3-cd]pyrene ND
Dlbenz[a,h]anthracene ND
Benzo[g,h,i]perylene ND
•A 3,5 dscm sample was used to calculate stack concentration.
bND - not detected (detection limit - 3.57 jig/dscm).
31
-------
Table 12. SemivolatileB
(MM-5 #1)
Sponsor SRI Amount
Sample Ho. Sample No. Compound (pg/dsca)a
MM-5-Run 1 21142 Phenol ND*
bis(2-Chloroethyl)ether ND
Aniline ND
2-Chlorophenol 0.570
1.3-Dichlorobenzene ND
1.4-Dichlorobenzene ND
Benzyl alcohol ND
1,2-Dichlorobenzene ND
2-Methylphenol ND
bis-(2-Chloroisopropyl)ether ND
4-Methylphenol ND
N-Nicroso-di-n-propylamine ND
Hexachloroethane ND
Nitrobenzene ND
Isophorone ND
2-Nitrophenol 0.860
2,4-Dimethylphenol ND
Benzoic acid ND
bis(2-Chloroethyoxy)methane ND
2,4-Dichlorophenol ND
1.2.4-Trlchlorobenzene ND
Naphthalene 0.570
4-Chloroaniline ND
Hexachlorobutadiene ND
4-Chloro-3-nethylphenol ND
2-Methylnaphthalene ND
Hexachlorocyclopentadiene ND
2,4,6-Trichlorophenol ND
2.4.5-Trichlorophenol ND
2 -Chloronaphthalene ND
2-Nitroaniline ND
Dinethylphthalate 7.70
Acenaphthylene ND
3-Nitroaniline ND
Acenaphthene ND
2,4-Dinitrophenol ND
4-Nitrophenol ND
Dibenzofuran ND
2,4-Dinitrotoluene ND
2,6-Dinitrotoluene ND
Diethylphthalate ND
4-Chlorophenylphenylether 6.90
Fluorene ND
4-Nitroaniline ND
4,6-Dinitro-2-aethylphenol ND
N-Nitroaodiphenylaaine ND
(continued)
32
-------
Tabic 12 (Continued)
Sponsor SRI Amount
Sample No. Sample No. Compound (pg/dacm)*
MM-5-Run 1 Tetrechlorophenol KD
(cont.) 4-Bromophenylphenyle ther ND
Hexachlorobenzene KB
Pentachlorophenol ND
Phenanthrene KD
Anthracene ND
Bi-n-butylphthalate 3.14
Fluoranthene KD
Fyrene ND
Butylbenzylphthalate 2.26
3,3'-Dichlorobenzidine KD
Benzo[a]anthracene KD
bis(2-Ethylhexyl)phthalate 449
Chrysene KD
Di-n-octylphthalate 82.9
Ben2o[b]fluoranthene KD
Benzo[kjfluoranthene KD
Benzo[a]pyrene KD
Indeno[l,2,3-cd]pyrene KD
Dibenz[a,h j anthracene KD
Benzo[g,h,i]perylene KD
'A 3.5 dscm sample was used to calculate stack concentration.
bND - not detected (detection limit - 3.57 ng/dscm).
33
-------
Table 13. Semivolatiles
(MM-5 #2)
Sponsor SRI Amount
Sample No. Sample No. Compound (pg/dscm)*
MM-5-Run 2 22141 Phenol ND*
bis(2-Chloroechyl)echer ND
Aniline ND
2-Chlorophenol ND
1.3-Dichlorobenzene ND
1.4-Dichlorobenzene ND
Benzyl alcohol ND
1,2-Dichlorobenzene ND
2-Methylphenol ND
bis-(2-Chloroisopropyl)ether ND
4-Methylphenol ND
N-Nitroso-di-n-propylamine ND
Hexachloroethane ND
Nitrobenzene ND
Isophorone ND
2-Nitrophenol ND
2,4-Dimethylphenol ND
Benzoic acid ND
bis(2-Chloroethyoxy)»ethane ND
2,4-Dichlorophenol ND
1.2.4-Trichlorobenzene ND
Naphthalene 2.00
4-Chloroaniline ND
Hexachlorobutadiene ND
4-Chloro-3-methylphenol ND
2-Methylnaphthalene 0.286
Hexachlorocyclopentadiene ND
2,4,6-Trichlorophenol ND
2.4.5-Trichlorophenol ND
2-Chloronaphthalene ND
2-Nitroaniline ND
Dimethylphthalate 6.00
Acenaphthylene ND
3-Nitroaniline ND
Acenaphthene ND
2,4-Dinitrophenol ND
4-Nitrophenol ND
Dibenzofuran ND
2,4-Dinitrotoluene ND
2,6-Dinitrotoluene ND
Diethylphthalate 11.7
4-Chlorophenylphenylether ND
Fluorene 0.571
4-Nitroaniline ND
4,6-Dinitro-2-methylphenol ND
N-Nitrosodiphenylamine ND
(continued)
34
-------
Table 13 (Continued)
Sponsor SRI Amount
Sample No. Sample No. Compound (pg/dscm)*
MM-5-Run 2 21141 TeCrachlorophenol ND
(cont.) 4-Bromophenylphenylether ND
Hexachlorobenzene ND
Pentachlorophenol ND
Phenanthrene ND
Anthracene ND
Di*n-butylphthalate 3.71
Fluoranthene ND
Pyrene ND
Butylbenzylphthalate 2.00
3,3'-Dichlorobenzidine ND
Benzo[a]anthracene ND
bis(2-Ethylhexyl)phthalate 446
Chrysene ND
Di-n-octylphthalate 40.0
Benzofb]fluoranthene ND
Benzofkjfluoranthene ND
Eenzo[a]pyrene ND
Indeno[l,2,3-cd]pyrene ND
Dibenz[a,h]anthracene ND
Benzo[g,h,i]perylene ND
'A 3,5 dscn sample was used to calculate stack concentration.
bND - not detected (detection limit - 3.57 pg/dscm).
35
-------
Table 14. Semivolatiles
(MM-5 #3)
Sponsor SRI Amount
Sample No. Sample Ho. Compound (pg/dscm)*
MM-5-Run 3 21147 Phenol KDb
bls(2-Chloroethyl)ether ND
Aniline HD
2-Chlorophenol HD
1.3-Dlchlorobenzene HD
1.4-Dichlorobenzene HD
Benzyl alcohol HD
1,2-Dlchlorobenzene HD
2-Mechylphenol ND
bis-(2-Chlorolsopropyl)ether HD
4-Methylphenol HD
H-Nlcroso-di-n-propylamine ND
Hexachloroethane ND
Nitrobenzene HD
Isophorone HD
2-Hitrophenol HD
2,4-Dimethylphenol HD
Benzoic acid HD
bis(2-Chloroethyoxy)methane ND
2,4-Dichlorophenol HD
1.2.4-Trichlorobenzene HD
Naphthalene HD
4-Chloroaniline HD
Hexachlorobutadiene HD
4-Chloro-3-methylphenol HD
2-Methylnaphthalene HD
Hexachlorocyclopentadiene ND
2,4,6-Trichlorophenol ND
2.4.5-Trichlorophenol ND
2-Chloronaphthalene HD
2-Hltroanillne HD
Dimethylphthalate 6.29
Acenaphthylene HD
3-Nitroanlline HD
Acenaphthene ND
2,4-Dinitrophenol ND
A-Nitrophenol ND
Dlbenzofuran HD
2,4-Dinitrotoluene ND
2,6-Dinitrotoluene ND
Diethylphthalate 4.57
4-Chlorophenylphenylether ND
Fluorene ND
4-Nitroanillne ND
4,6-Dinitro-2-methylphenol ND
N-Nitrosodlphenylamine ND
(continued)
36
-------
Table 14 (Continued)
Sponsor SRI Amount
Sample No. Sample No. Compound (pg/dscm)*
KM-5-Run 3 21147 Tetrachlorophenol ND
(cont.) 4-Bromophenylphenylether ND
Hexachlorobenzene ND
Pentachlorophenol ND
Phenanthrene ND
Anthracene ND
Di-n-butylphthalate 1.71
Fluoranthene ND
Pyrene ND
Butylbenzylphthalate ND
3,3'-Dichlorobenzidine ND
Benzo[a]anthracene ND
bis(2-Ethylhexyl)phthalate 606
Chrysene ND
Di-n-octylphthalate 74.3
Benzo[b]fluoranthene ND
Benzo[k]fluoranthene ND
Benzo[a]pyrene ND
Indeno[1,2,3-cd]pyrene ND
Dlbenz [a,h]anthracene ND
Benzo[g,h,ijperylene ND
•A 3.5 dscm sample was used to calculate stack concentration.
bND - not detected (detection limit - 3,57 jig/dscm).
37
-------
Tabid IS. Synthetic Sasplea Spiked with Appendix VIII Compounds
100 nR
100 Hg
400 f
-------
Table 16. Recoveries of FAH from XAD-2*
fig spiked
Hg recovered
% recovered
Naphthalene
800
536b
67
Acenaphthylene
1600
117 5b
73
Acenaphthene
800
497b
62
Fluorene
160
210
131
Phenanthrene
80
57.5
72
Anthracene
80
29.2
37
Fluoranthene
160
196
123
Pyrene
80
37.4
48
Benzo[a]anthracene
80
31.4
39
Chrysene
80
22.6
28
Benzo[b)fluoranthene
160
87.9
55
Benzo[k]fluoranthene
80
28.3
35
Benzo[a]pyrene
80
39.8
50
Indeno[1,2,3•cd]pyrene
80
39.3
49
Dibenzo[a,h]anthracene
160
159
99
Benzo[g,h,i]perylene
160
252
158
•Analysis by GC/MS.
bPrimary ion appeared saturated. Results calculated from secondary ions.
39
-------
Tab la 17. Analyala of Polychlorodlbenzo-B-Dioxina and Dlbenzofurana
Run No. (I Recovery [,JClt-2,3,7,8-t®tr«chlorodlbenzo(l,4)dloKln]
or nanograms of eonponent detected)
Solvent blank
Spiked blank
for Sasplei 1-6
for Sanplee 1-6
Cyclone-
Cyclone-
Baghouee-
Baghouae-
Component
of Table 7
of Table 1
A«h-227
Aah-302
Aah-302
Aah-227
MM-3-227
HH-5-302
,JCli,-2,1,1 ,8-Tetiachlorodibenzo(l ,4)dloxln
(¦uzzogate coocwund)
(na)
<84)
(76)
(•0)
(80)
<2.9)
<5.0)
-------
Table 16. LC/HS Analysis of Representative PICS
Component
Kass (ng)
Retention time (nin)
Detected ?
Resorcinol
>200
(2.15)*
No
Benzidine
20
8.06
Yes
2,6-Dichlorophenol
>200
(12.59)
No
Pentachlorophenol
>200
(14.64)
No
2,4,5-Trichlorophenol
>200
(15.96)
No
Diethylstilbestrol
20
15.67
Yes
1,2-Diphenylhydrazine
50
15.33
Yes
Reserpine
200
17.69
Yes
"The quantity in parentheses is the retention tine detemined by using a
UV detector.
41
-------
mm (I-3M 15-JUL-TO 14 25 TBS (CH
ChroMtofrat Identifiers • fl dllC
hit 2 UL [815-21-3 • IS (188 tJL t938-2-n, 1227, M
SysPRIPfll
m
57963
W 785
¦*—,——•—i1 ¦ » i
m 688 en
928 1239 1552
1188 1288
19 85 22 17
1488 1688 1888 2888 2288
25 38 28 43 31 58 35 89 38 22
SDN
m
Figure 1. Total-ion chroraatograa of combined extracts of condensate, sorbent module,
probe rinse, coil rinse, and Impinger rinse. (Refer to Table 4).
-------
•7
l> r
fr
ir
ir o
i*i.
-IPC
¦j r
c
f'..v
(• 0
*-
u»
,J CfN^jr
mm
iWjpTflmt
nswCv r
•mr-rc
THWfi
l^f^ncMWWP
.^tewm-rowr-
*A| I JTTWJ
AjMUAWm^
iWfflffTlrMi
$
£
tr
s
iT
ci
p.
*
Figure 2. HPLC/UV chronatogran of 60 pg/taL PAII standard
(acenaphthylene, benzo[k]fluoranthene, pyrerte,
lndenoj1,2,3-cd]pyrene). Column has a pBondapak-
C19, 20-jiL Injection, 15-100% CH3H/H20 gradient
elutlon.
v»
¦ •.
(V
f
if. Ps c. r
, r . r-:
u.
i
.
•
. , . , ,
a
G
E
PT
•£ r- r. •- n
-------
o:
rf r
jS&SE
Figure 3. HPLC/UV chromatogra* of HM-5 Run 227.
*)
>
s
^ it r o sm! ® a, >j: r». *x o b i
it * & «- 0" << n «f <*¦ * <*>•^ ^ f* "M
ii .< i i i
(i - <•¦
u " " IT a t. o a « « K n rc r. •• « v* ¦* i
ft r If o CC ^ B O. K M p. ^ K ^ p ^ 1 '
I K 4 ^ 4 M' IT - If 5 M' « fN- - '
•X K 0 »" f* *f '
If
oc
IX.
.. I
f" P ,v o: r e if r c-s s c. (T -i f - ^ < r 1 f - •>
n i »- « - r ^ ci ? t r ' f- ? r- o g - t ¦* i
T
-------
V01827 11-1130 &HWHS 17*.3I 70S
mm
Tort: 20 UL SUPOXO Pttf 810 MIX INTO tflC
(E1+)
Shs'LCHS
1001A
IG17
10©
4; 08
8:14
840
12:20
720 .
16127
1080
24540-
1260
20:4€
LOO
8730
Figure 4. HPLC/UV (upper trace) and HPLC/MS-moving belt (lower case)
chromacograras of PAH standard.
-------
\OF\BOSR10
Run started on 6 Aug,1989 at 16:24:26
and consists of 430 scans acquired at a rate of 3.457 seconds/scan.
Thermospray EI; 20 ut Injection of 100 ng/uL MIX Sample E620-14O-4
EM=2400 V SMS INTERG O PRESCALAR
Flow Rate =1.0 «l/min., Mobile Phase: -01M NH40Ac/ACN 90/10-0/100 (30 win.)
T1=60,T2=139,T(spray)=62
Masses were acauired as:
45- 620
TRERHOSPRAV EI TOTAL I0H CHftOtttTOCMH OF 2 Microgram
TIC EACH OF THE STP IN IR1 tAMFLE 1X28-146-4
1200.
1100
900
C00.
200
TIME (Minutes)
Figure 5. Total-ion chromatogram of a mixture containing 100 fig/mL each of
resorcinal, benzidine, 2,6-dichlorophenol, pentachlorophenol,
2,4,5-trichlorophenol, diethylstilbescrol, 1,2-diphenylhydrazine,
and resperine.
46
-------
\DF\80SR6
Run started on 6 Aug,1989 at 13:53:31
and consists of 521 scans acquired at a rate of 3.457 seconds/scan.
Thermospray EI; 20 uL Injection of 1 ng/uL MIX Sample E62B-140-4
EM=2400 V 5MS INTERG 0 PRESCALAR
Flow Rate = 1.0 mL/min., Mobile Phase: .01M NH40Ac/ACN 90/10-0/100 (30 min.)
T1=60, T2 =139,T(spray)=62
Masses were acquired as:
45- 620
k/z 184
<726
5000
4888
3B88,
2008.
1088.
0
THERMOSPRAV EI ION CMRONATOCRAM AND SPECTRUM OF
28 nano?raMS OF BENZIDINE (MM 184> OF SRI
SAMPLE E628-140-4
Scan at 8.06633
6442
5008
4008
3008.
2008
5
TIKE*?mnutes)
1088
8.
I
15
184
rr
28
58 75 188 125 158 175 208 225 250
n/t (nass/chai>9t>
Figure 6. Mass spectrum of benzidine.
47
-------
\DF\B05R7
Run started on 6 Aug.1989 at 14:33:47
and consists of 521 scans acquired at a rate of 3.457 seconds/scan.
Thermosoray EI; 5 uL Injection of 10 ng/uL MIX Sample E62B-140-4
EM = 2400 V 5HS INTERG 0 PRESCALAR
Flow Rate =1.0 ml/min., Mobile Phase: .01M NH40Ac/ACN 90/10-0/100 (30 min.)
T1=60.T2=139,T(spray)=62
Masses were acquired as:
45- 620
THERMOS PRAY EI ION CHROMTOGRAM AND SPECTRUM OF
n/z 184 56 n&nosrr&MS OF 1,2-DIPHEN¥LH¥BRAZ!NE
-------
\DF\80SR6
Run started on 6 Aug,1989 at 13:53:31
and consists of 521 scans acquired at a rate of 3.457 seconds/scan.
Thermospray EI; 20 UL Injection of 1 ng/uL MIX Sample E62B-140-4
EM= 2400 V SMS INTERG 0 PRESCALAR
Flow Rate =1.0 mL/min., Mobile Phase: .OlM NH40Ac/ACN 90/10-0/100 (30 win.)
T1=60,T2=139,T(spray)=62
Masses were acquired as:
45- 620
n/z 268
1188
1888.
888.
688.
488.
288.
THERNOSPRAV El ION CHROttATOCRAM AND SPECTRUK OF
28 nanograms OF DIETHVLSTILBESTROL
-------
\DF\B05R9
Run started on 6 Aug,1989 at 15:47:46
fi watv« ¦
Flow Rate =1.0 mL/min., Mobile Phase: .01M NH40Ac/ACN 90/10-0/100 (30 min )
T1=60,T2-139,T(spray)=62
Masses were acquired as:
4 5- 620
THDWOSPRAV El ION CHROMATOGRAHS ftKD SPECTRUM OF
n/z 608 200 nanograms OF RESERFIHZ
-------
REFERENCES
1. Johnson, L.D.; MldgeCt, M.R.; Janes, R.H.; Thomason, K.M.; Manier, K.L.
Screening Approach for Principal Organic Hazardous Constituents and Products
of Incomplete Combustion. JAPCA 39: 709-713; 1989.
2. Janes, R.H.; Thonason, K.M.; Manier, M.L. POHCs and PICs Screening
Protocol, EPA 600/8-89-080, PB 90-116930/AS. Available fron National
Technical Information Service, Springfield, VA, October 1989.
3. U.S. Environmental Protection Agency, Test Methods for Evaluating Solid
Waste, Physical/Chemical Methods, 3rd ed., SW-846 Manual, Document No. 955-
001-0000001. Available from the Superintendent of Documents, U.S. Government
Printing Office, Washington, DC, January 1987.
4. Lentzen, D.E.; Wagoner, D.E.; Eastes, E.D.; Gutknect, W.F. IERL-RTP
Procedures Manual: Level 1 Environmental Assessment, 2nd ed., EPA-600/7-78-
201, PB 293795. Available from National Technical Information Service,
Springfield, VA, July 1984.
5. James, R.H.; Adams, R.E,; Finkel, J.M.; Miller, H.C.; Johnson, L.D.
Evaluation of analytical methods for the determination of POHC in combustion
products. JAPCA 35: 959-969; 1985.
6. Johnson, L.D.; James, R.H. Sampling and Analysis of Hazardous Haste. In:
Standard Handbook for Hazardous Waste Treatment and Disposal, H.M. Freeman,
Editor, McGrav/Hill, New York, 1988.
51
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