EPA-600/2-76-075
March 1976
Environmental Protection Technology Series
ANALYSIS OF POLYCYCLIC ORGANIC
MATERIAL IN COAL, COAL ASH, FLY ASH, AND
OTHER FUEL AND EMISSION SAMPLES
Industrial Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into five series. These five broad
categories were established to facilitate further development and application of
environmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed to develop and
demonstrate instrumentation, equipment, and methodology to repair or prevent
environmental degradation from point and non-point sources of pollution. This
work provides the new or improved technology required for the control and
treatment of pollution sources to meet environmental quality standards.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental
Protection Ag3ncy, and approved for publication. Approval
does not signify that the contents necessarily reflect the
views and policy of the Agency, nor does mention of trade
names or commercial products constitute endorsement or
recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-76-075
March 1976
ANALYSIS OF POLYCYCLIC ORGANIC MATERIAL
IN COAL, COAL ASH, FLY ASH, AND
OTHER FUEL AND EMISSION SAMPLES
by
A. G. Sharkey, J. L. Schultz,
C. White, and R. Lett
U.S. Energy Research and Development Administration
Pittsburgh Energy Research Center
4800 Forbes Avenue
Pittsburgh, Pennsylvania 15213
Contract No. IAG-D4-0501
ROAP No. 21AXM-012
Program Element No. 1AB015
EPA Project Officer: Larry D. Johnson
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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Analysis of Polycyclic Organic Material in Coal,
Coal Ash, Fly Ash and Other Fuel and Emission Samples
Summary
The purpose of this high resolution mass spectrometric investigation was to
determine the major polynuclear aromatic hydrocarbons (PNA) in samples derived
from various fuel conversion processes and related plant emissions. Particulate
materials and extracts of hydrocarbons in the particulate materials collected
on filters placed in flue gas streams from coking, smelting, and similar
industrial operations were studied. Fourteen highly carcinogenic PNA's, with
nine unique formulas, were considered in the high resolution mass spectrometer
analysis. Additional quantitative data were obtained by low ionizing voltage
techniques for. major aromatic hydrocarbon classes, where possible. The gases
evolved from the particulate samples were also identified.
Possible carcinogens were detected in particulate material from four industrial
sources. Nine formulas, indicating the possible presence of 14 highly carcino-
genic PNA's, were observed in data for particulate matter collected at an
aluminum plant. Eight of the formulas, corresponding to 12 carcinogens, were
detected in the spectra of an extract of particulate material and a filter
from the exhaust gas stream from ferroalloy operations. Data for 3 other
extracts of particulate emissions from ferroalloy processing, CSL 7, 12, and
13, indicated the possibility of 5, 9, and 11 carcinogens, respectively. A
pyridine extract of a filter from a chromium smelter and the tar from a coke
oven vapor showed 1 and 4 possible carcinogens, respectively. No evidence of
carcinogenic PNA's was detected in particulate material collected at the
remaining 8 industrial sources. A.s.0, was found in the particulate material
associated with a copper smelter.
Introduction
Under an interagency agreement between the Environmental Protection Agency
(EPA) and the U. S. Bureau of Mines (now Energy Research and Development
Administration), a minimum of 10 samples, furnished by EPA, from various fuel
emissions, and other processes was to be analyzed by high resolution mass
spectrometry (HRMS) for polynuclear organic material. It was anticipated
that some modification, adaptation, and improvement of existing technology
would be required.
Polynuclear aromatic hydrocarbons (PNA) are associated with particulate
emissions from many commercial processes. It is important to determine the
nature of PNA's as many hydrocarbon mixtures derived from pyrolysis and other
high-temperature operations contain hazardous compounds including carcinogenic
components.
High-resolution mass spectrometry has the capability of determining the
precise masses of the hydrocarbons.from which the chemical formulas can be
derived. While the elemental composition can be determined, the particular
isomeric form cannot be identified from HRMS data alone. High resolution
mass spectrometry can be used for the preliminary screening of complex mixtures
-------
for the possible presence of several hundred hazardous and/or toxic compounds.
Detailed analyses then need be carried out for only those components with
formulas detected by HRMS. Major structural types including alkyl derivatives
are determined quantitatively using low-ionizing voltage mass spectrometry.
In the current investigation, a screening technique has been devised and
incorporated in the computer calculation of high-resolution data. Three
hundred ten (310) compounds with low TLV values are included in addition to
14 carcinogens of specific interest. These 14 PNA's have 2-, 3-, and 4-star
ratings in the NAS 1972 Handbook. Several of the compounds are isomers leaving
9 precise masses for detailed investigation by mass spectrometry.
Experimental Procedure
All data were obtained with,a Dupont Model 21-HOB high resolution mass
spectrometer at 300° C, 10 torr. Mass spectra obtained at low resolution
(1 part in 3,000) and recorded on strip charts were used for low ionizing
voltage data which determines molecular ions for PNA's. The high resolution
(1 part in 15,000) mass spectra were recorded on photographic plates and the
data processed by computer using a program which calculates the precise masses
of the ions present, determines their elemental composition, and screens the
results for specific formulas corresponding to those of 310 toxic and
hazardous compounds. High resolution mass spectral data can be summarized
by plotting H vs. C for each formula occurring in the sample - a form of
schematic representation. The number of hydrogen atoms in each hydrocarbon
formula derived from the high-resolution mass spectral data is indicated by
a point at the corresponding carbon numberJ a sequence of formulas at any one
carbon number results in a continuous line. The position of the upper terminus
of this line is indicative of the class of hydrocarbon compounds present in
the sample. Figure 1 illustrates the limiting values for several compound
classes. A schematic representation whose vertical lines approach line (a)
indicates aliphatic hydrocarbons. Since the molecular ion of olefins and
non-condensed naphthenes contains less hydrogen than the corresponding
paraffins, the presence or absence of these compounds in a paraffinic matrix
cannot be established by this method. Line (b), figure 1, is the limiting
value for perhydroaromatic compounds and condensed naphthenes. The hori-
zontal lines labeled (d) indicate the molecular ions of polynuclear aromatic
hydrocarbons with varying degrees of condensation. Line (c) represents the
terminus of lines for polynuclear aromatic hydrocarbons with a five carbon
alkyl substituent. This line is an approximation since the number of hydrogens
at a specified carbon number is determined by the degree of condensation of
the polynuclear aromatic hydrocarbon. The carbon number distribution and
hydrocarbon class of the sample components can be readily observed from
schematic representations of high resolution mass spectral data.
Results and Discussion
The identification, source, and sample form of the samples investigated
are shown in table 1.
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EPA-1002 and EPA-72-001-159
The samples were first examined by direct vaporization using direct probe
introduction. Components indicated in the gases obtained by direct
vaporization are indicated in table 2. As very little volatile matter
was detected in either sample at 300 C in the mass spectrometer, pyridine
extraction of the samples was attempted. Extraction yields and also the
percent of the extract vaporized in the mass spectrometer are given in
table 2. The organic material obtained from both samples contained aliphatic,
aromatic and oxygenated species. The upper carbon number limits found by
mass spectrometry are shown in table 2. Both samples are complex mixtures
of organic material. Sample 1002 appeared to contain a higher concentra-
tion of organic material which extended to higher carbon numbers than
material from sample 72-001-159.
Both extracts were screened for formulas corresponding to possible hazardous
and toxic components. The list prepared for the screening was derived from
several of the current lists containing compounds with low TLV values. Pre-
liminary screening of the two samples indicated molecular formulas for 12
possible hazardous components in sample 1002 and 6 in sample 72-001-159 as
shown in tables 3 and 4. It should be emphasized that the screening
technique is based upon a matching of molecular formulas and the particular
isomeric form cannot be identified by high-resolution mass spectrometry. The
value of this screening technique is that, within the sensitivity limits of
the mass spectrometer, many highly toxic components can be eliminated from
consideration. The analytical effort can then be concentrated on components
for which molecular formulas corresponding to toxic components are indicated.
Coke oven vapor, run 2, stack 1
This coke oven vapor sample was studied by high-resolution mass spectrometry to
determine if hazardous and toxic compounds are present. A summary of the high-
resolution data is given in figure 2. The top series of lines that indicates
the highest H/C values extends to approximately C»nand is indicative of
highly saturated material. The lower series of lines results from components
with a much lower H/C ratio, indicative of polynuclear aromatic material.
This series of components extends to C__. Trace components containing single
oxygens were detected to C.. ^.
Screening of the high-resolution data gave formulas for the components given
in table 5.
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CSL-11
A sample of material extracted from a ferroalloy plant emission designated
as No. CSL-11 was supplied as a dilute solution in methylene chloride; prior
to analysis it was necessary to remove much of the solvent. The sample
analyzed corresponded to 3.6% of the original solution.
The presence of possible carcinogenic PNA's was of particular interest.
The HRMS data show 8 of the 9 precise masses of interest and a summary of the
results including relative concentrations is given in table 6. The only
formula not detected was C»..H..,N at m/e 279, corresponding to the dibenzacridines.
These HRMS data indicate that more specific follow-up techniques should be used
for the other 12 compounds. The relative concentrations shown are based upon
the best calibration data available. Anthracene/phenanthrene and pyrene/
fluoranthene, m/e 178 and 202, respectively, were detected as major compon-
ents in the sample. Table 7 is a summary of the data for the major struc-
tural types. The values include the alkyl derivatives. These data confirm
that the highest concentrations are for the 3-, 4-, and 5-ring PNA's with
peri-condensed structures such as pyrene and/or fluoranthene. Concentra-
tions of the alkyl derivatives are much lower than for the basic ring
structures; methyl derivatives are only a few percent of the basic ring
structures. The ratio (derived from the mass spectral data) of unsubsti-
tuted to substituted rings is about 2.3:1.
CSL-7;72-003-110
Mass spectrometric analyses were obtained of a filter sample designated
Ferroalloy CSL7:72-003-110. Three different sections of CSL-7:72-003-110
were examined to determine if the filter sample was homogeneous. The
mass spectral data for the three sections from the filter sample indicate
that the filter loading was not uniform, but that the emission particulates
probably contain similar organic material throughout the exhaust stream.
These conclusions are based on the data in table 8.
The 14 highly carcinogenic PNA's of interest were considered in the
screening by high-resolution mass spectrometry. As shown in table 9,
components with formulas corresponding to 8 of the 9 PNA's distinguishable
by molecular formula were detected.
The sample was also examined by low ionizing voltage. The major structural
types and percent of each are shown in table 10. Alkyl derivatives with 4 to
6 alkyl carbons were found for the major aromatic ring systems, with decreased
concentrations as the number of alkyl carbons increased.
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CSL-7, 12, 13 (Methylene chloride extracts)
Survey mass spectra of the three methylene chloride extracts of composited
ferroalloy emission samples received from Battelle, Columbus confirmed their
evidence that the PNA species varied in concentration among the samples
(CSL-13>CSL-12?CSL-7). After removal of most of the solvent, both high-
resolution and low ionizing voltage mass spectra were obtained.
The high-resolution mass spectrometric data from the 14 selected carcinogenic
PNA's of particular interest are shown in table 11. Peak matching techniques
at masses 267 and 279 confirmed the absence of nitrogen heterocycles.
Table 12 is a summary of the data for the major PNA's detected in the low
ionizing voltage mass spectra, including alkyl derivatives. The distribution
of the structural types is similar for all the extracts; the major difference
among the extracts is the degree of substitution on the aromatic ring systems.
The ratio of unsubstituted aromatic ring systems to substituted rings is 0.8:1
for CSL-7, while. CSL-12 and CSL-13 have ratios of 3.64:1 and 2.87:1, respectively.
Series 11593
Mass spectrometric data were obtained for 14 particulate samples supplied by TRW
under contract with the EPA. TRW prepared the samples collected from coking,
smelting, and similar industrial sources, using 3 cyclones in series plus
a backup filter to fractionate the particulates by size. Different particle
sizes from the same source were examined.
Table 13 lists the percent of the particulate sample vaporized and the com-
ponents observed in the mass spectra. Samples 14-4 and 14-5 showed intense
mass peaks identified as As.O,, the dimer of As000. Some As000 may also
HO L j Z J
be present although the intensity at the corresponding mass is much lower than
that of As.O,. The presence of HCN, NO, N0~, and COS in many of the samples
4 o 2
may also be significant.
The distribution of the aromatic hydrocarbons observed in 16-4 is shown in
table 14. Eighty-seven percent of the aromatic hydrocarbon content is con-
centrated in 4- to 6-ring aromatic systems. These data were obtained using
low ionizing voltage techniques.
Pure compound studies of 4-, 5-, and 6-ring aromatic hydrocarbons, representative*
of those found in 16-3 and 16-4, have shown that their rate of vaporization in the
mass spectrometer varies with both the number of aromatic rings in the molecule
and type of condensation (peri or cata). Data shown in table 15 were obtained
I/ Previously identified in Seattle ambient air. Schuetzle, D., A. L. Crittenden,
and R. J. Charlson, J. Air Poll. Cont. Ass'n., vol. 23, August 1973,
pp. 704-709.
-------
from integrated peak height versus time curves for 16-3 and 16-4. Successive
scans of the mass spectra were made over the period of time during which the
sample'continued to yield vaporization products. Ion intensities versus time
were plotted and the area under the curves determined. These data also permitted
corrections for the contribution of C from the aromatic hydrocarbons to the
molecular ions of the nitrogen containing compounds and determinations for
small concentrations of these components not possible by the routine analytical
method.
The computer data for the series 11593 were screened for the 9 precise masses
indicating the possible presence of carcinogenic PNA's; table 16 shows the
results of the screening. The mass spectra of the samples from the aluminum
plant, 16-3 and.16-4, indicate the possibility of all of the carcinogenic PNA's
as well as the typical aromatic hydrocarbons associated with electrode binder
pitches listed in tables 14 and 15. The precise masses indicating possible
carcinogens were not detected in any of the other samples.
CONCLUSIONS
Twenty-two samples of particulate material were analyzed by high resolution
mass spectrometry for polycyclic organic material, including 14 highly
carcinogenic polynuclear aromatic hydrocarbons.
A technique using HRMS to determine molecular formulas was successfully
adapted to screening complex mixtures for carcinogens and other hazardous
compounds. The technique is particularly amenable to the detection of PNA's
because of their high sensitivity under mass spectrometric analysis. A major
advantage of this technique is that the system can be completely automated to
provide formulas for hundreds of compounds in mixtures.
Two limitations that are common to most types of mass spectrometer analysis
are: (1) The_compound must have at least minimal volatility (a few microns
at 300 C, 10 torr) and (2) the compound must be stable under the above
conditions of analysis. Mass spectral analysis of particulate material is
limited by both volatility and stability. However, identification of
gases evolved at 300 C, 10 torr provides some insight into the structure
of the inorganic components of the particulate matter.
-------
APPENDIX I
Tables
1. Identification, source, and form of samples investigated.
2. Mass spectrometric analyses of filter samples.
3. Screening of sample EPA-72-001-159 for possible hazardous compounds.
k. Screening of sample EPA-1002 for possible hazardous compounds.
5. Screening of coke oven vapor sample (Run 2, Stack l) for possible
hazardous compounds.
6. High-resolution mass spectrometric data for selected carcinogenic PNA's
- Sample CSL-11.
7« Mass spectrometric analysis for PNA's in Sample CSL-11.
8. Mass spectral data for samples from CSL-7 72-003-110.
9. High-resolution mass spectrometric data for selected carcinogenic PNA's
- Sample CSL-7= 73-003-110.
10. Mass spectrometric analysis for PNA's in Sample CSL-7 : 73-003-110.
11. High-resolution mass spectrometric data for selected carcinogenic
PNA's in methylene chloride extracts of ferroalloy emission samples
- CSL-7, 12, and 13-
12. Mass spectrometric analyses of PNA's in methylene chloride extracts
of ferroalloy emission samples - CSL-7, 12, and 13.
13. Mass spectral information derived from Sample Series 11593
Ik. Mass spectral analysis of EPA-TRW sample 11593-16-^.
15. Semi-quantitative mass spectral analysis of particulate matter collected
in aluminum plant; integrated peak height versus time curves.
16. Results of mass spectral screening for carcinogenic PNA's - Series
11593: TR₯ Particulate Samples.
Figures
1. Limiting H/C values for several classes of hydrocarbon compounds.
2. High-resolution mass spectrometry data for coke oven vapor, run 2, stack 1.
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Table 1. Identification, Source, and Form of Samples Investigated
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
Identification
EPA-1002
EPA-7 2-001-159
Run 1, stack 2
CSL-11 -1
CSL-7: 72-003-110
CSL-7
CSL-12
CSL-13
11593-3-3 -1
11593-3-4
11593-4-4
11593-7-4
11593-10-5
11593-10-6
11593-14-4
11593-14-5
11593-16-3
11593-16-4
11593-20-2
11593-20-3
11593-22-2
11593-22-3
Source
Chromium smelter
Ferroalloy plant
Coke oven vapor
Ferroalloy plant
Ferroalloy plant
Ferroalloy plant
Ferroalloy plant
Ferroalloy plant
Open hearth
Open hearth
Coke oven stack
Basic oxygen furnace
Iron sintering plant
Iron sintering plant
Copper smelter
Copper smelter
Aluminum plant
Aluminum plant
Ceramics plant
Ceramics plant
Municipal incinerator
Municipal incinerator
Form
Filter + pyridine extrai
Filter + pyridine extrai
Tar
CH-Cl- extract
Filter
CH2C12 extract
CH2C12 extract
CH2C12 extract
Particulates
Particulates
Particulates
Particulates
Particulates
Particulates
Particulates
Particulates
Particulates
Particulates
Particulates
Particulates
Particulates
Particulates
a/ CSL denotes sample received from Battelle, Columbus Laboratories.
b_/ 11593 designates samples received from TRW.
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Table 2. Mass Spectrometric Analyses of Filter Samples
Sample
EPA-72-001-159
EPA-1002
% extracted in pyrldine
% of extract vaporized in
mass spectrometer
Compound type
Aliphatics
Aromatics
Oxygenates
Gases by direct vaporization
from filter
a/
69% 100%
Maximum carbon number detected
14
Possible toxic compounds '
NO
6
18
'8 °16
Gases detected
CO
co2
HC1
so.
HN3
H2C°3
CO
CO,
so2
N02
NO
H2C03
HC1
12
aj Based upon formulas derived by high-resolution mass spectrometry;
particular isomer not identified (see text).
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10
Table 3. Screening of Sample EPA-72-001-159 for
possible hazardous compounds
Possible hazardous or
Precise mass Formula toxic compound
Benzene
Mesityl oxide
Ethyl benzene
Allylglycidyl ether
Naphthalene
Anthracene
78.0468
98.0729
106.0780
114.0678
128.0624
178.0780
C6H6
C6H10°
C8H10
C6H10°2
C10H8
C14H10
a/ Particular isomer not identified (see text).
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11
Table 4. Screening of Sample EPA-1002 for Possible Hazardous Compounds.
Precise mass
Formula
92.0624
106.0789
108.0573
118.0780
120.0936
128.0624
154.0782
170.0729
178.0780
202.0789
228.0936
C7H8
C8H10
W
C9H10
C9H12
C10H8
C12H10
C12H10°
C14H10
C16H10
C18H12
Possible hazardous or
o 7
toxic compounds
Toluene
Ethylbenzene
Cresol
Vinyltoluene
Cumene
Naphthalene
Diphenyl
Phenyl ether
Anthracene/phenanthrene
Pyrene
Chrysene
a/ Particular isomer not identified (see text).
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12
Table 5. Screening of Coke Oven Vapor Sample (Run 2, Stack 1)
for Possible Hazardous Compounds.
Precise mass
78.0463
92.0624
104.0624
106.0780
118.0780
120.0936
128.0624
138.0428
148.1248
178.0780
202.0780
228.0936
252.0936
Formula
C6H6
C7H8
C8H8
C8H10
C9H10
C9H12
C10H8
C6H6N2°2
C11H16
°14H10
C16H10
1812
y
y
2012
Possible hazardous or
toxic compounds
Benzene
Toluene
Styrene
Ethylbenzene
Vinyltoluene
Cumene
Naphthalene
Nitroaniline
P-Tert-butyl toluene
Anthracene/phenanthrene
Pyrene
Chrysene
Benzopyrene
a/ Particular isomer not identified (see text).
b_/ Possible carcinogens.
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13
Table 6. High Resolution Mass Spectrometric Data for Selected
Carcinogenic PNA's - Sample CSL-11
Relative
m/e
228
252
254
256
267
268
278
279
302
178
202
Formula Concentration
C18H12 12
C20H12 17
C20H14 l
C20H16 * 1
C H- N ^0.1
P U / (\ 1
C21H16 < °'1
C22H14 2
C21H13N - S/
C24H14 *
Additional PNA's - major
C14H10 14
C16H10 17
Possible Compounds
Benzo ( c ) phenanthrene
Benzo (b) f luoranthene
Benzo ( j ) f luoranthene
Benzo(a)pyrene
Benz ( j ) aceanthrylene
( cholanthr ene )
7 , 12-Dimethylbenz (a) anthracene
Dibenzo (c , g) carbazole
3-Methy Icho lanthr ene
Dibenz (a, b) anthracene
Dibenz (a , j ) acr idine
Dibenz (a, b)acridine
Dibenzo (a, b)pyr ene
Dibenzo (a, i) pyrene
Dibenzo (b , def ) chry sene
components
Anthracene/phenanthrene
Pyrene/f luoranthene
aj Only relative concentrations determined.
b/ Not detected.
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14
Table 7. Mass Spectrometric Analysis for PNA's in Sample CSL-11.
Structural type, including
Alkyl derivatives
Weight, percent
Naphthalenes
Acenaphthylenes/fluorenes
Acenaphthenes
Anthracenes/phenanthrenes
Phenyl naphthalenes
Methylene phenanthrene
4-rings, peri-condensed
4-rings, cata-condensed
5-rings, peri-condensed
5-rings, cata-condensed
6-rings, peri-condensed
Binaphthyls
Methylene chrysene
6-rings, cata-condensed
7-rings, peri-condensed
Total
a/ Weight percent in solvent as submitted.
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15
Table 8. Mass Spectral Data for Samples from CSL-:72-003-110
Percent ,
a/
Maximum carbon
number of aliphatic
Maximum carbon Maximum carbon
number of total number of
organic oxygenated
Sample
1
2
3
vaporized
11.8
4.8
5.7
hydrocarbons
C15
C14
C12
material
C29
C27
C26
hydrocarbons
C27
C26
C25
a/ Based on weight of filter plus sample.
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16
Table 9. High Resolution Mass Spectrometric Data for Selected
Carcinogenic PNA's - Sample CSL-7:72-003-110.
Relative
m/e
228
252
254
256
267
268
278
279
302
178
202
Formula
C18H12
C20H12
C20H14
C20H16
C2QH13N
C21H16
C22H14
C2lV
C24H14
C14H10
C16H10
concentration
7
9
2
2
2
2
3
3
Additional PNA's
<1
7
Possible Compounds
Benzo (c) phenanthrene
Benzo (b) f luoranthene
Benzo ( j ) f luoranthene
Benzo (a) pyrene
Benz ( j ) aceanthrylene
(cholanthrene)
7 , 12-Dimethylbenz (a) anthracene
Dibenzo (c , g) carbazole
3-Methylcholanthrene
Dibenz (a , b ) anthracene
Dibenz (a, j)acridine
Dibenz (a, b)acridine
Dibenzo (a, b) pyrene
Dibenzo (a , i) pyrene
Dibenzo (b , def ) chrysene
Anthracene /phenanthrene
Pyrene/f luoranthene
a/ Only relative concentrations available at this time.
b/ Not detected.
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17
Table 10. Mass Spectrometric Analysis for PNA's in
Sample CSL-7 : 73-003-110.
Major structural types, including ,
alkyl derivatives % T. I. -
Naphthalenes 1.5
Acenaphthylenes/fluorenes 2.0
Acenaph thene s 1.8
Anthracenes/phenanthrenes 7.3
Phenylnaphthalenes 6.2
4-rings, peri-condensed 18.6
4-rings, cata-condensed 14.6
5-rings, peri-condensed 19.3
5-rings, cata-condensed 6.0
6-rings, peri-condensed 14.6
Binaphthyls 5.8
6-rings, cata-condensed 0.7
7-rings, peri-condensed 1.6
Total 100.0
a/ Percent of total ionization assumes equal sensitivity for all
components. Valid for comparison of similar samples.
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18
Table 11. High Resolution Mass Spectrometric Data for Selected
Carcinogenic PNA's in Methylene Chloride Extracts
of Ferroalloy Emission Samples CSL-7, 12, and 13.
CSL-7
CSL-12
CSL-13
Mass
228
252
254
256
267
268
278
279
302
178
202
Formula
C18H12
C20H12
C20H14
C20H16
C20H13N
C21H16
C22H14
C21H13N
C24H14
C14H10
C16H10
Relative concentrations
9
9
b/
1
b/
b/
b/
b/
b/
1.4
12.5
17
21
1
b/
b/
b/
2
b/
1
Additional
7
23
14
17
1
0.3
b/
2
2
b/
1
PNA's
12
21
Possible Compounds
Benzo (c)phenanthrene
Benzo (b) f luoranthene
Benzo ( j ) f luoranthene
Benzo(a)pyrene
Benz ( j ) aceanthrylene
(cholanthrene)
7 , 12-Dimethylbenz (a) anthracene
Dibenzo (c , g) carbazole
3-Me thy Icho lanthr ene
Dibenz (a, b) anthracene
Dibenz (a , j ) acr idine
Dibenz (a , b ) acridine
Dibenzo (a, b)pyrene
Dibenzo (a , i) pyrene
Dibenzo (b , def ) chrysene
Anthracene/phenanthrene
Pyrene / f luoranthene
a/ Only relative concentration available at this time.
b/ Not detected.
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19
Table 12. Mass Spectrometric Analyses of PNA's in Methylene Chloride
Extracts of Ferroalloy Emission Samples CSL-7, 12, and 13.
Major structural types, including
alkyl derivatives
CSL-7 CLS-12 CSL-13
Naphthalenes
Acenaphthylene s/fluorenes
Acenaphthenes
Anthracenes/phenanthrenes
Phenylnaphthalenes
4-rings, peri-condensed
cata-condensed
peri-condensed
cata-condensed
6-rings, peri-condensed
Binaphthyls
6-rings, cata-condensed
7-rings, peri-condensed
4-rings,
5-rings,
5-rings,
Percent of total ionization
10.6
7.2
26.5
18.0
18.6
4.9
7.5
5.0
1.6
12.0
4.3
28.3
21.0
23.3
2.6
5.6
2.7
0.2
1.6
1.2
16.5
4.7
26.8
17.7
19.4
2.7
5.7
3.4
0.2
0.3
Ratio
Unsubstituted aromatic rings
Substituted aromatic rings
0.8
3.64
2.87
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Table 13. Mass Spectral Information Derived from Sample Series 11593.
Sample
3-3
3-4
4-4
16-4
20-2
20-3
22-2
22-3
Particle
7-4
10-5
10-6
14-4
14-5
16-3
1
3
1
1
3
1
1
3
1
3
Origin
Percent
Vaporized
Open hearth furnace 2.1
Open hearth furnace 0.12
Coke oven 5.3
Basic oxygen furnace 3.2
Iron sintering plant 7.3
Iron sintering plant 37.8
Copper smelter
Copper smelter
Aluminum plant
Aluminum plant
c/
n.a.
c/
n.a.
1.3
5.2
Ceramics plant 2.4
Ceramics plant 2.1
Municipal incinerator 4.0
Municipal Incinerator 0.5
a/ All isomeric structures are possible
b/ Measurement doubtful
c/ n. a. - not available.
Summary of high resolution and low Ionizing voltage mass spectral data
Gases evolved at 300° C, 10~6 torrHydrocarbon Tormulas Identified a/
HCN, CH CN, HC1, CO , NO EtOH>
CH3COOH7 S02, COS, CO
HCN, CH CN, HC1, NO, NO , H S, CO ,
EtOH, CO, COS, S02, CS2
HCN, CH CN, CO, NO, H,S, CO,,NO,,
cn rr\ COS
Pyridine, C.-C7, aliphatic radials,
trace oxygenates
Pyridine, McPyridine; aliphatic hydro-
carbon radicals through C_
Six unidentified mass peaks ^ mass
102; trace oxygenates
Pyridine, Mepyridine, C7-C8 naphthenes,
aliphatic radicals through C,;
unidentified mass-peaks <"mass 109.
Pyrrole poss., trace oxygenates, trace
hydrocarbons through C_
C6H6' C10H8' C11C10' C14H10
C6H6' C10H8' C11H10' C14H10' C6H6°
As.O,
4 6
AS.O,
4 6
CHN, CO, NO, HC1, CO , NO,, SO,, Aromatic hydrocarbons; nitro- and sulfur
COS , H2S ^ z ^ .._/-__ ^-, ,_ -N
CHN, CO, NO, HC1, CO , NO , SO ,
COS ILL
heterocyclics (see table 1)
Similar to 16-3 in composition;
slightly lower carbon number distri-
bution for all classes of compounds
HCN, CO, NO, MeOH, HC1, SO , NO , Trace organics through C
H2S, COS i i J-U
HCN, CO, NO, HC1, CH CN, CO,, EtOH, Pyridine, trace organics through C
wn Qr> pr^Q u Q
INU,, ou,, uus, n,o
HCN,CO, NO, HC1, CH,CN, CO,,NO,, Pyrrole, phenol, aromatics through Clf.
S02, CS2 J aliphatic radicals through Cg
HCN, CO, NO, H S, HC1, CH CN, -CO,, Trace hydrocarbon
N02, COS, S02, CS2
to
C
-------
21
Table 14. Mass Spectral Analysis of EPA-TRW Sample 11593-16-4
Percent ,
3. /
Possible structural types total ionization
Benzenes 1.1
Naphthalenes 0.4
Acenaphthylenes; fluorenes 0.8
Acenaphthenes; biphenyls 1.0
Anthracenes; phenanthrenes 3.8
Phenylnaph thalenes 2.5
4-rings, peri-condensed 10.2
4-rings, cata-condensed 10.4
5-rings, peri-condensed 39.9
5-rings, cata-condensed 12.5
6-rings, peri-condensed 14.0
7-rings, peri-condensed 0.4
Carbazoles 0.9
Dibenzocarbazoles 0.9
Dibenzacridines 1.1
a/ Distribution of PNA's in portion of sample vaporized in the mass
spectrometer.
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22
Table 15. Semi-Quantitative Mass Spectral Analysis of Particulate Matter Col-
lected in Aluminum Plant; Integrated Peak Height Versus Time Curves
11593
Sample number
Percent vaporized
Particle size > y
Weiglit collected, mg.
Examples of structural types
3-ring aromatics
Phenylnaphthalenes
4-ring, peri-condensed
4-ring, cata-condensed
5-ring, peri-condensed
Phenylanthracenes
5-ring, cata-condensed
6-ring, peri-condensed (mass 276)
6-ring, peri-condensed (mass 302)
7-ring, peri-condensed (Coronene)
D inaph tho thiophene
Azapyrene + Benzocarbazole
Benzacridine
Carbazole
Acridine
Dibenzocarbazole
Dibenzacridine
Azabenzo[ghi]perylene
Azaperylene
16-3
4.5
1
983.3
Percent of
2.3
2.3
6.5
7.0
20.4
3.5
12.6
17.1
3.5
1.1
1.5
12.2
1.3
1.0
1.2
1.4
0.8
0.03
4.3
16-4
3.7
3
1,613.6
total ionization
0.8
5.4
7.5
7.0
12.4
12.0
13.3
3.7
2.5
0.9
1.6
12.5
5.7
1.9
3.2
0.4
3.1
2.1
4.0
-------
23
Table 16. Results of Mass Spectral Screening for Carcinogenic
PNA's - Series 11593: TRW Particulate Samples
16-3 16-4
x£/ x
X X
X X
X X
X X
X X
X X
X X
X X
a/ Entire sample series screened for carcinogenic PNA's. None
detected in samples of particulates from sources other than the
aluminum plant.
b_/ Molecular formulas verified by precise mass measurement.
a/
Sample
Nominal
Mass
228
252
254
256
267
268
278
279
302
Formula
C18H12
C20H12
C20H14
C20H16
C20H13N
C21H16
C22H14
CnH13N
C24H14
-------
50
40
LU
8 30
CH
Q
J 20
o
cr
UJ
§ 10
ID
0
,,,
,,,,,,
a Aliphatic
b Perhydroaromatic
c Aikylated aromatic
d Polynuclear aromatic
_ _ d
J I I I ___i. 1 I t I I i A 1 I I j i 1 I
10
15
20
25
30
NUMBER OF CARBON ATOMS
Figure 1. Limiting H/C values for several classes of hydrocarbon compounds.
-------
(/) *JV
O
1
< 40
LJ
§ 30
a:
Q
>
x 20
LJL
O
or
*** 1 0
S9
ID
-
-
~
~
-
.
-
^~
-
i i
i i i i i i i i i > i > i i i i i i i
'
,
i ' -
. i
i ,
i i
~
«
i
|
i
i
i i «
1 1 1 i
i i
,11
.
: A 1 1
Illl 1 1 1 1 1 i i . 1 1 1 1 1 1 1
0
10
15
20
25
30
NUMBER OF CARBON ATOMS
Figure 2. High-resolution mass spectrometry data for coke oven vapor,
run 2, stack 1.
N:
L-13
-------
26
Visitors
None.
Personal Mention
None.
APPENDIX II
Manuscripts in preparation and/or published.
None.
APPENDIX III
Nonexpendable items consisting of $100 or more.
Hone.
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-76-075
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Analysis of Polycyclic Organic Material in Coal, Coal
Ash, Fly Ash, and Other Fuel and Emission Samples
5. REPORT DATE
March 1976
6. PERFORMING ORGANIZATION CODE
7-AUTHOR(S)A.G. Sharkey, J.L. Schultz, C. White, and
R. Lett
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
U.S. Energy Research and Development Administration
Pittsburgh Energy Research Center
4800 Forbes Avenue
Pittsburgh. Pennsylvania 15213
10. PROGRAM ELEMENT NO.
1AB015; ROAP 21AXM-012
11. CONTRACT/GRANT NO.
IAG-D4-0501
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final; 7/74-6/75
14. SPONSORING AGENCY CODE
EPA-ORD
is. SUPPLEMENTARY NOTEsproject officer for this report is Larry D. Johnson, Mail Drop 62,
Ext 2557.
. ABSTRACT
report gives results of 2i high- resolution mass spectrometric investi-
gation to determine the major polynuclear aromatic hydrocarbons (PNAs) in samples
derived from various fuel conversion processes and related plant emissions. Studied
were particulate materials and extracts of hydrocarbons in the particulate materials
collected on filters placed in flue gas streams from coking, smelting, and similar
industrial operations. The analysis considered 14 highly carcinogenic PNAs, with
nine unique formulas . Additional quantitative data were obtained by low ionizing
voltage techniques for major aromatic hydrocarbon classes, where possible. The
gases evolved from the particulate samples were also identified.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDEDTERMS
c. COSATi Field/Group
Air Pollution
Analyzing
Polycyclic Compounds
Organic Compounds
Coal
Fly Ash
Industrial Processes
Flue Gases
Mass Spectres copy
Aromatic Polycy-
clic Hydrocarbons
Hydrocarbons
Gases
Carcinogens
Air Pollution Control
Stationary Sources
Coal Ash
Particulate
Fuel Conversion
13B
14B
07C
21D
21B
13H
07D
06E
13. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
20. SECURITY CLASS (TMspage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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