&EPA
United States
Environmental Protection
Agency
Environmental Sciences Research EPA-600 2-80-069
Laboratory April 1980
Research Triangle Park NC 27711
Research and Development
Quantitative
Analysis of
Polynuclear
Aromatic
Hydrocarbons in
Liquid Fuels
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental 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.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-80-069
April 1980
QUANTITATIVE ANALYSIS
OF
POLYNUCLEAR AROMATIC HYDROCARBONS
IN LIQUID FUELS
by
Radian Corporation
8500 Shoal Creek Boulevard
Austin, Texas 78766
EPA Contract No. 68-02-2446
Project Officer
James N. Braddock
Environmental Sciences Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
-------
DISCLAIMER
This report has been reviewed by the Environmental Sciences Research
Laboratory, U. S. Environmental Protection Agency, and approved for publica-
tion. Approval does not signify that the contents necessarily reflect the
views and policies of the U. S. Environmental Protection Agency, nor does
mention of trade names or commercial products contain endorsement or recom-
mendation for use.
ll
-------
ABSTRACT
Polynuclear aromatic hydrocarbons (PNA'*) , formed in combustion processes
with liquid hydrocarbon fuels, contribute to mobile source exhaust emissions,
Because correlation between PNA levels in automobile exhaust and pre-
existent PNAs in fuel has been demonstrated .'n previous work, a quanti-
tative analysis of 12 individual polynuclear aromatic hydrocarbons present
in various aircraft turbine, diesel, and gasoline test fuels was determined
in this project. The PNAs included phenanthrene, anthracene, fluoranthene,
pyrene, benzo(a)anthracene, chrysene, triphenylene, benzo(a)pyrene,
benzo(e)pyrene, benzo(g,h,i)perylene, coronene and anthanthrene. The
fuel samples were analyzed by combined gas chromatography/mass spectrometry
(GC-MS) after a preliminary isolation/concentration scheme. Liquid
crystal chromatographic columns were employed to resolve isomeric PNAs.
The results indicated that anthanthrene and coronene were not detected
in any of the samples analyzed. Although the detection limit for each
PNA in the samples varied, the detection limit of the method employed
was approximately Syg/gallon (1 ppb). The remaining ten PNAs were
found in levels ranging from 6ug/gallon (1.6 ppb = benzo(e)pyrene) to
3.1g/gallon (810,000 ppb = phenanthrene) of fuel. In general, the
concentration decreased with increasing molecular weight of the PNAs.
This report was submitted in fulfillment of Contract No. 68-02-2446 by
Radian Corporation under the sponsorship of the U.S. Environmental
Protection Agency. This report covers a period from October, 1976 to
October, 1978 and work was completed as of September, 1979.
iii
-------
CONTENTS
Abstract .............................
Figures ....... ,,.,,.,.,,,,,..,, ..... vi
Tables .............................. vii
Acknowledgments. ...,,•.,,,,,,,,,,,,, ...... viii
1. Introduction ...... ................. 1
2, Results, ,......,.,.,,,.,,,.,.,,,, 2
3. Discussion ....,,.,,. ......... . . . . , 6
Experimental procedures ................ 7
Quality control analyses ................ 15
Recommendations ....... , ............ 15
References ........... ..... ..... , ...... 17
Appendices ........ ..,.,,,..,,,..,,.... 13
A. Test Fuel description ................... 18
B. PNA analyses of liquid fuels ............... 23
-------
FIGURES
Number Page
1. Isolation and Concentration Scheme for PNAs in Liquid Fuels . . 7
2. Selected Ion Chromatograms From the Analysis of PNAs on
BBBT At Two GC Temperature Programming Conditions 12.
3. Typical Calibration Curve For Pyrene 14
vi
-------
TABLES
Number Page
1. Concentration of Polynuclear Aromatic Hydrocarbons
in Liquid Fuels 3
2. Pooled Standard Deviation for Duplicate Analyses 4
3. Recovery of Spiked Compounds 5
4. Summary of Extraction Procedures for Liquid Fuel Samples . . 9
5. Key Ions For the SIM Analysis of PNAs in Liquid Fuels .... 10
6. GC-MS Operating Conditions for Liquid Fuel Extracts 13
vii
-------
ACKNOWLEDGMENTS
The cooperation and assistance of Dr. James N. Bfaddock of the Environ-
mental Sciences Research Laboratory of the EPA is gratefully acknowledged.
The Radian Staff included Dr. Donald D. Rosebrook as Program Manager
and Ronald G. Oldham as Project Director. The GC-MS analyses were performed
by Dr. P. H. Lin. Acknowledgment is also given to J. L. Parr and B. J. May-
field who contributed significantly to the program.
viii
-------
SECTION 1
INTRODUCTION
In order to correlate polynuclear aromatic hydrocarbon (PNA) levels
in combustion source exhaust emissions with the concentrations of PNAs in
various liquid hydrocarbon fuels, the EPA contracted Radian Corporation to
determine the concentration of twelve specified PNAs in various test fuels.
The PNAs of interest include:
• Phenanthrene • Triphenylene
• Anthracene • Benzo(a)pyrene
• Flouranthene • Benzo(e)pyrene
• Pyrene • Benzo(g,h,i)perylene
a Benz(a)anthracene • Coronene
• Chrysene • Anthanthrene
'The approach employed for the analysis of the specified PNAs in each sample
was combined gas chromatography-mass spectrometry (GC-MS) with operation in
the selected ion monitoring mode. A preliminary isolation/concentration
scheme was employed to remove the PNAs from the hydrocarbon fuel matrix.
Isomeric PNAs were chromatographically resolved by utilizing liquid crystal
liquid phases.
A total of ten test fuels were analyzed during the program. Each fuel
was analyzed in duplicate. Blank samples were also analyzed.
The report presents the results from these analyses and describes the
procedures employed.
-------
SECTION 2
RESULTS
The results from the analyses of the ten fuel samples are presented in
Table 1. -All samples were analyzed in duplicate, and the results shown are
the average from the two determinations. The two Couch #5 samples (A and B)
were submitted to Radian as blind duplicates. The pooled standard deviation
of each compound was calculated by taking the square root of the average of
all the standard deviations squared. (This number represents the best esti-
mate of the variance between duplicate analyses for each compound.) These
pooled standard deviations for the replicate pairs are summarized in Table 2.
The absolute concentration of any compound should be within two statistical
deviations of the measured concentration 95% of the time (95% confidence
interval) and within one standard deviation 60% of the time. The data from
the blind duplicate samples support these pooled standard deviations. The
reported, concentration of all but two compounds (phenanthrene and pyrene)
are within one standard deviation of the mean concentration while these two
are within two standard deviations. Complete PNA results are given in Ap-
pendix B. A detailed description of the various test fuels is provided in
Appendix A.
Anthanthrene and coronene were not detected in any of the samples ana-
lyzed. Although the detection limit for each PNA in the samples varied, in
general, the detection limit of the method employed was approximately 5yg/
gallon (1 ppb). The remaining ten PNAs were found in levels ranging from
6yg/gallon (1.6 ppb) to 3.1g/gallon (810,000 ppb) of fuel. In general, the
concentration decreased with increasing molecular weight of the PNAs.
Samples were received and analyzed in three groups ranging from two to
six samples per group. A blank sample consisting of cyclohexane was analyzed
in duplicate with each sample set. In one of the blank samples, the com-
pounds phenanthrene and anthracene were detected at a concentration
corresponding to 360yg/gallon (96 ppb) and 12yg/gallon (3.1 ppb) respectively.
These levels were attributed to residual fuel in the glassware employed for
the extraction of the fuel samples EM-238-F and EM-239-F. PNAs were not
detected in any of the other blank samples analyzed.
All samples and cyclohexane blanks were spiked with 9-bromoanthracene,
djo-anthracene or indenopyrene in the range of 4 to 38yg/gallon (1 to 10 ppb)
before extraction to measure recovery. Table 3 presents recovery data for
the blanks and two fuels, Jet A Fuel - low sulfur and EM-240-F. The recovery
for the other samples could not be measured because of positive interference.
The average percent recovery was found to be 94.6% and the standard deviation
on individual recoveries was 17.0%. This recovery data can be utilized as an
indication of the variability of the analytical method. The spike compounds
were chosen to be chemically similar to the PNAs of interest. The excellent
recovery of the spike compounds indicates that the procedure employed did not
result in any losses of the PNAs of interest.
-------
TABLE 1. CONCENTRATION OF POLYNUCLEAR AROMATIC
HYDROCARBONS IN LIQUID FUELS
QeHlgnatton
Jit A Fuel.
Low Sulfur
Jet A Fuel,
High Sulfur
EM-218-F
DI-2J9-f
EH-240-F
DI-241-F
Qt-242-f
COUCH 12
COUCH *5A
COUCH lit
Phenentlirene
6,800
8.300
2,600,000
1,100,000
30,000
3,100,000
800,000
2,000,000
19,000
42,000
-
Anthracene
330
760
16,000
38,000
760
33,000
6,400
11,000
1,200
1,200
Flunranthane
43
180
95,000
49,000
610
61,000
20,000
76,000
6,800
7,800
1
Pyrene
68
290
38,000
36,000
200
33,000
7,600
120,000
21,000
10,000
:oncen tret 1cm,
Trlphenylcne
14
27
53,000
17,000
280
16,000
6,100
42,000
6,100
4,500
M/tallon*
Ueni(a)
anthracene
ND (<2)*
ND (<2)
34,000
13,000
210
13,000
2,300
28,000
2,600
2,000
Chryaane
11
11
110,000
16,000
310
24,000
3,300
53,000
4,500
4,500
8en»(e)
pyrene
6
43
S70
290
38
200
64
680
1,400
1,200
8emo(a)
pyienc
NO (<»
ND (<2)
160
260
280
170
76
330
800
720
B«nzo(g.h,l)
perylena
ND <<2)
ND (<2)
240
110
ND (<10)
68
ND <<10)
ir
30
18
Anthanthrcne
ND <<2>
ND (<2)
ND <<20)
ND (<20)
N"> <<20)
ND (<20)
ND (<20)
ND (<20)
ND (<20)
MO (<20)
Cor one ne
ND (<2)
ND (<2)
ND (<20>
ND (<2Ll)
ND (<:o)
ND (<20)
ND (<20)
ND (<20)
Nil (<10)
KD (<20)
NOTES: ' - Avara|« fro. duplicate «etc»lnatlon
* - N0(<«) - Not detected; X represent! th« detection limit for tha
conpaund la 'the aaa^itc analyzed.
-------
TABLE 2, POOLED STANDARD DEVIATION
FOR DUPLICATE ANALYSES
Compound
Number of
Duplicate Pairs
Pooled Standard
Deviation (%)
Phenanthrene
Fluoranthene
Benzo(e)pyrene
Pyrene
Benz(a)anthracene
Benzo(a)pyrene
Anthracene
Triphenylene
Chrysene
Benzo(g,h,i)perylene
10
10
10
10
8
8
10
10
10
6
18.5
12.2
14.2
20.8
20.9
25.3
37.1
35.5
35.3
3-3.3
-------
TABLE 3, RECOVERY OF SPIKED COMPOUNDS
Compound Spiked Sample Amount
Spiked Concentration, ppb Type Recovered, ppb
d. --Anthracene
dj --Anthracene
9-Bromoanthracene
9-Bromoanthracene
9-Bromoanthracene
9-Bromoanthracene
9-Bromoanthracene
9-Bromoanthracene
Indeno(l,2,3- c,d)pyrene
Indeno(l,2,3- c,d)pyrene
10.
10.
10.
10.
10.
10.
1.02
1.02
1.12
1.12
Jet A Fuel,
Low Sulfur
Jet A Fuel,
Low Sulfur
Blank
Blank
EM-240-F
EM-240-F
Blank
Blank
Blank
Blank
7.4
9.6
10.8
9.0
11.5
10.6
0.71
0.74
1.02
1.33
Percent
Recovered
74
96
108
90
115
106
70
78
91
118
-------
SECTION 3
DISCUSSION
EXPERIMENTAL
This program required the development and application of a multi-step
procedure to measure PNAs at the low ppb level in liquid fuels. The approach
that was utilized contained the following elements:
• isolation and concentration of the PNAs from the bulk sample matrix
by liquid-liquid extraction,
• identification of the specified PNAs by GC-MS, and
• quantification of identified PNAs by GC-MS.
Isolation and Concentration of PNAs From Liquid Fuels
An extraction scheme was developed to isolate and concentrate the PNAs
present in the liquid fuels. The procedure employed was a modification of
the method described by Matsushita (1972) and is illustrated in Figure 1.
The fuel sample (500 ml) was extracted three times with 300 ml of dimethyl-
sulfoxide (DMSO). An equal volume of cold 20% HC1 was then added to the com-
bined DMSO extracts. The resulting DMSO-HC1 mixture was extracted three
times with 900 ml of cyclohexane. The cyclohexane extracts were combined and
washed successively first with 200 ml of 5% sodium hydroxide followed by two
200 ml portions of distilled water. This extract was then concentrated by
removal of the cyclohexane by distillation. The extract was placed in a
round bottom flask in a heating mantle. A three-ball Snyder column was placed
on top of the flask as a distillation column. Distillation was conducted at
atmospheric pressure until all cyclohexane had been removed.
Initially, it was anticipated that a large concentration factor (500-
1000) would be required in order to achieve the desired sensitivity ( lug/
gallon). Therefore, it was anticipated that 500 ml of sample would be ex-
tracted and the solvent concentrated to 1 ml. With this procedure, PNAs
at one microgram per gallon in the fuel would be at a concentration of 130 ng/
ml in the concentrated extract.
-------
Concentrate
Extract
l.Add HC1
2.Extract
r
Cyclohexane
Extract
l.Wash with
NaOH
2.Wash with
HaO
Liquid
Fuel
Extract
with
DMSO
DMSO
Extract
with
Cvclohexane
Washed
Cyclohexane
Extract
Concentrated
PNA Extract
Analyze by
GC-MS
Aqueous
Wastes
DMSO-HCl
Discard
Discard
HFuel I
Discard
FIGURE 1. ISOLATION AND CONCENTRATION SCHEME FOR PNAs IN LIQUID FUELS
-------
However, this concentration factor could not readily be achieved in the samples.
Typically, the extraction and concentration steps removed 90 to 95% of the
fuel. The remaining 5 to 10% consisted of aromatic compounds which were not
removed by the procedure. For the first two samples analyzed, Jet A Fuel-Low
Sulfur and Jet A-High Sulfur Fuel, vacuum distillation was employed to provide
a higher concentration factor as illustrated in Table 4.
The PNAs were present in much higher levels than anticipated, frequently
in the ppm range. Also, the GOMS analysis technique was shown to be sensi-
tive to the low ppb range with only moderate concentration. Therefore, the
vacuum distillation step was omitted from the isolation scheme for the re-
maining samples. Table 4 summarizes the final volume obtained for each ex-
tract.
All samples were extracted in duplicate. Each sample was spiked prior
to extraction with either 9-bromoanthracene, dio-anthracene, or indenopyrene.
The spikes were, for the most part, added to the fuel to the 10 ppb level.
Two samples, Couch #5A and Couch #5B, were spiked to a 1 ppb level. Table 4
summarizes the spiking information for all samples analyzed.
Identification of PNAs
The liquid fuel concentrates were analyzed by combined gas chromatography/
mass spectrometry (GC-MS) using a Hewlett-Packard 5982A GC-MS system. The
mass spectral information was stored on magnetic discs for future interpre-
tation and reference.
The technique of selected ion monitoring (SIM) was employed for all
analyses. In this technique, the intensity of key ions was monitored during
the chromatographic separation. Identification of the desired compounds was
based on the appearance of these key ions at known gas chromatographic re-
tention times. A second criterion for identification was also employed during
the analysis. The relative intensity of the key ions for each compound had
to be within 20% of the intensity found from the analysis of a standard.
Table 5 lists the PNAs determined in this program along with the key ions
and their relative intensities employed in the analysis.
The twelve PNAs of interest consist of six series of isomers. Other
isomeric species of the desired compounds exist. For example, there are six
isomers of benzo(a)pyrene but only two (benzo(a)pyrene and benzo(e)pyrene)
were of interest in this program. In order to accurately measure each com-
pound, it was imperative that e_'ch isomeric specie be resolved.
A novel liquid crystal liquid phase, N,N'-bis(p-methoxy-benzylidene)
a,a'-bi-p-toluidine (BMBT), was studied for the chromatographic separation of
the PNA isomers. This packingj which had been reported by Janini (1975),
provides excellent resolution of certain PNA isomers.
-------
TABLE 4. SUMMARY OF EXTRACTION PROCEDURES FOR LIQUID FUEL SAMPLER
VO
Sample
Designation
Jet A Fuel - Lou Sulfur
Jet A Fuel - Low Sulfur
Jet A - High Sulfur
Jet A - High Sulfur
EM-238-F
EM- 2 38- F
EH-239-F
EM- 2 39- F
EH-240-F
EM-240-F
EM-241-F
EM-241-F
EM-242-F
EM-242-F
Couch 12
Couch 12
Couch *5A
Couch I5B
Radian
Sample Number
556-1
556-2
557-1
557-2
826-A
826-B
825-A
825-B
827-A
827-B
823-A
823-B
824-A
824-B
82 8- A
828-B
1556-A
1557-B
Date
Extracted
9/15/77
9/15/77
9/15/77
9/15/77 •
11/8/77
11/8/77
11/8/77
11/8/77
11/8/77
11/8/77
11/8/77
11/8/77
11/8/77
11/8/77
11/8/77
11/8/77
9/1/78
9/1/78
1
Spike <
d Anthracene
it
dioAnthracene
d|0Anthracene
dioAnthracene
9-Bromanthracene
9-Bronoanthracene
9-Broaioontbracene
9-Browo anthracene
9-Oromoanthracene
9-Bronoanthracene
9-Bronoanthracene
9-Bronoanthracene
9-Bromoanthracene
9-Bronoanthracene
9-Bronoanthracene
9-Bronoanthracene
9-Bronaanthracene
Indeno - Pyrene
9-Bromoanthracene
Indeno - Pyrene
Spiked (upb)
Concentration
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
1.01
1.12
1.01
1.12
Volume of
Concentrate, ml*
35 (2.4)2
33 (2.3)a
37 (1.0)'
25 (1.3)a
53
51
41
44
32
32
61
63
25
24
55 (2)a
57
55
66
NOTE:
- Volume of extract after rn«oval of cyclohexane) sample volume 500 nl
• (x) Volume of extract after vacuum distillation indicating final concentration volu
-------
TABLE 5. KEY IONS FOR THE SIM ANALYSIS OF PNAs IN LIQUID FUELS
Relative Relative Relative
Compound Mi Intensity M2 Intensity M3 Intensity
Phenantarene
Anthracene :
Fluoranthene
Pyrene
Benz (a) anthracene
Triphenylene
Chrysene
Benz o ( e ) p yr ene
Benzo (a) pyrene
Benzo (g , h, i) perylene
Anthanthrene
Coronene
178
178
202
202
228
228
228
252
252
276.
276
300
100%
100%
100%
100%
100%
100%
100%
100%
100%
100%
100%
100%
89
89
101
101
229
229
229
126.
126
138
138
150
17%
16%
23%
26%
19%
19%
19%
23%
23%
372
37%
64%
176
176
100
100
226
226
226
250
250
274
274
149
15%
15%
14%
17%
19%
23%
20%
16%
16%
27%
27%
46%
10
-------
Two additional liquid crystals recently developed (Janini, 1976, Janini,
1976) were also studied. These liquid phases, N,N'-bis(p-butoxy-benzylidene)
a,a'-bi-p-toluidine (BBBT) and N,N'-bis(p-phenyl-benzylidene) a,a'-bi-p-
toluidine (BPhBT), also provided excellent separation of certain PNA isomers.
These phases are commercially available from Supelco.
Each of the three liquid crystals have different characteristics. While
both BBBT and BMBT are satisfactory for 3 to 7 ring PNAs, BBBT has less col-
umn bleed at elevated temperatures. Chromatographic resolution on liquid
crystals is highly dependent on temperature, -ith the best resolution
achieved with the liquid crystal in the nematic state. BMBT and BBBT are
nematic in the temperature range of' 190° to 300°C, while BPhBT is nematic
in the temperature range of 260° to 400°C. Therefore, BPhBT is generally
limited to 5-7 ring compounds becasue of its temperature range. Early in
the study it was determined that slight variations in the temperature pro-
gramming conditions could cause drastic changes in resolution. Because of
this temperature dependence of the liquid crystals, it was very difficult to
resolve all of the PNA isomers in one analysis as illustrated in Figure 2.
Changes in the temperature programming will easily resolve either phenanthrene
and anthracene (m/e 178) or chrysene, triphenylene and benz(a)anthracene
(m/e 228). However, careful selection of the Chromatographic conditions was
required in order to separate all of these isomers in one analysis.
Therefore, it was decided to employ separate GC analyses for the
different isomeric species. The benefits from this approach were:
• the instrument gain could be adjusted to obtain maximum sensitivity
for the high molecular weight PNAs by allowing measurement of the
more abundant low molecular weight species separately,
• the best Chromatographic column for each group of isomers was employed,
thus improving the separation,
• temperature control was not critical, and
• the overall analysis time was often shortened.
Table 6 summarizes the Chromatographic conditions employed for all
analyses.
Quantification of Identified PNAs
Quantification of each PNA identified was achieved by examination of the
stored mass spectral data. For each compound, the areas under the intensity
profiles for each key ion were calculated employing the Hewlett-Packard data
system. The total mass of each compound injected was determined from a cali-
bration curve. A typical calibration curve is shown in Figure 3. Each
11
-------
HUE
GPtrr
-rn i mm it i11 ii rrmrnrmTmTrrrn-n 11111111 n n 1mi1 HI 11 i u i11
HIII i ii i m i' i
50 lt)0 ISO MO' «0 100 330 400 «0 500 5SO 000 190 700 ISO »00 850 900 S50
GC Conditions: 240 for 4 minutes
then 8°/minute to 280°C
TIME
SPECT
10
F
nTriTnrirrTTTrrrnriTrTTTTrTTTniiinintTrTTi'rTTTTriTnnTTiiiiiiiiiiiiMiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii
50 100 ISO ZOO Z90 300 330 480 450 500 S30 ODD 030 700 750 800 830 800 930 100010301^00
GC Conditions: 220° for 8 minutes
then 8°/minute to 290°C
FIGURE 2. SELECTED TON CHKOMATQGRAMS FROM THE ANALYSIS OF A STANDARD PNA MIXTURE ON BBBT
AT TWO Gg TEMPERATURE PROGJRAMMING CONDITIONS
PNAs 1) Phenanthcene, 2) Anthracene, 3) Fluoranthene, 4) Pyrene, 5) Triphenylene
6) Benz(a)anthracene, 7) Chrysene
-------
TABLE 6. GC-MS OPERATING CONDITIONS FOR LIQUID FUEL EXTRACTS
Initial Initial
Carrier Flow Rate Temperature Time
Column 1'acklng fias (ml /mill) (°C) (minutes)
ft' > V f.lass 1.5% RRBT He 30 200 It
on 100/120
Supclroport
6' x V RbiKS 1.5% IJBRT He 10 210 2
on 100/120
Supe looport
(>' x V Kl'iss 2.5% llliBT He 30 300
on 100/120
• Knpelcopnrt
2 x ',," glass 1.5% RI'liBT tin 30 280
on \ 00/1 20
Supi.'lcoport
fi x V l;lass 5% SP-2IOOH Hi- 30 200 0
II HMRTiu
on 100/120
Sitpel roport
(,' x V «l««s 1.5% nrhBT lie 30 270 0
on 100/120
Supolcnpoit
:>' x V p.liiss 1.5% lil'hlit He 10 2W
on 100/120
Supe Icoport
Final Program
Temperature Rate Samples
(°C) (c>C/mln) Analyzed
280 8 J«t A Fl'elt Lou Sulf"r
Jet A Fuel, High Sulfur
260 8 KM-238 EM-242
EH-239 Couch 12
EM-240
EM-241
300 - EM-338 EM-241
EM-239 EH- 24 2
EM-240 Couch «2
280 - EH-438 EM-2'il
EM-239 KM-242
EM-24 Couch l~
260 8 Couch 5A
Conch 51!
290 8 Couch 5A
Couch 511
290 - Couch 5A
Clinch 511
Isomers
Resolved
All
Phenanthrene , Anth
racene , Fluorau-
threne, I'yrene,
Chrysene, Beii7.(a)-
anthraireiie, Tri-
pheiiy lene
Bpnzo(a)pyr2ne
Benxo(e)pyr«Ji»i>
Henzo(fi,li.i)-
perylmu' ,
Aiuliantlircno
(ioronene
Phenanl Im'ne t
Ant hracenii
riuoranthroue
F'yrene
Bon?, (a ) ant hr. •»<•<• nr
('hrysene, Trl-
phenyl =>ne
Beuzo(a)pyreni*
Beozo (e)pyroiu*
Heii7.o(g,h, 1 )-
ppry lene
Ant hraiu^ue
Coronene
-------
100,000
Area units,
uiasti 202
10,000
10
Nanograms of Pyrene Injected
i
Figure 3. Typical Calibration Curve for Pyrene
iOO
-------
calibration curve was generated by analyzing a series of at least four
standards at varying concentrations, The concentration of each compound in
the sample was then calculated according to the following equation:
ppb = ^g PNA ™& concentrate
£ injected I sample extracted
The GC-MS-SIM technique employed is very sensitive with absolute lower
detection limits on the order of 100 pg/yil injected for each compound. How-
ever, the detection limit for each compound is also dependent on the background
(noise) of the ions measured. The detection limit, therefore, varied from
sample to sample, depending on the sample matrix and instrumental conditions.
Interferences
Prior to liquid-liquid extraction, each sample was spiked at the low
ppb level with selected compounds in order to demonstrate overall PNA recovery.
Analysis of several of the sample concentrates by SIM GC-MS for the spiked
component yielded data that corresponded to a recovery of >1000%. Further
analysis of these sample extracts by repetitive scan GC-MS revealed that
fragment and parent ions were present with significant intensity at virtually
all masses below m/e 300. This unresolved background prevented the accurate
measurement of the low level spiked compound in many of the sample extracts.
However, in all sample extracts where the background was not present, excel-
lent recovery of the spikes was demonstrated.
QUALITY CONTROL
The results from the quality control analyses (duplicate analyses and
spikes) indicated that all analyses were conducted in a manner consistent
with good analytical practice. Statistical tests were performed to deter-
mine whether the average of the variance of the percent recovered varied
between low and high concentrations or between spikes in blank and spikes in
actual samples. No statistically significant differences were observed.
A 95% confidence interval for the average percent recovered is 95.3±
12.49, or 83% to 108%. Therefore, there is no statistical evidence in a
bias in the extraction/analysis procedures.
Ninety-two pairs of measurements were analyzed to determine the random
variability of a single concentration determination. No evidence was found
that the percent variability depended on concentration or chemical species.
RECOMMENDATIONS AND CONCLUSIONS
The analytical scheme developed during this program was successfully
employed to determine the levels of the specified PNAs. The procedure
requires the use of sophisticated instrumentation and skilled analysts.
15
-------
Nevertheless, the advantages of specificity, sensitivity and accuracy are cur-
rently not realized by other analytical techniques.
The primary areas for improvement in the current analytical scheme are in
the chromatography and the preliminary isolation scheme. Additional investiga-
tion into liquid crystals should continue to improve the separation of the
various isomers. The combination of liquid crystals with traditional chromat-
ographic phases should be of particular interest.
The isolation scheme employed successfully isolated the PNAs from the
fuel matrix. However, other aromatic species were also carried through the
separation scheme. Additional effort directed towards removal of these
species should result in increased sensitivity.
16
-------
REFERENCES
1. Janini, G. M. , K. Johnston, and W. L. Zielinski, Jr. Use of nematic
liquid crystal for gas-liquid chromatographic separation of polyaro-
matic hydrocarbons. Analytical Chemistry 47(4):670-74, 1975.
2. Janini, G. M. , G. M. Muschik, and W. L. Zielinski, Jr. N,N'-Bis(p-
butoxybenzylidene)-a,a'-bi-p-toluidine: Thermally stable liquid crystal
for unique gas-liquid chromatography separations of polycyclic aromatic
hydrocarbons. Analytical Chemistry 48_(6) :809, 1976.
3. Janini, G. M., et al. Gas-liquid chromatographic evaluation and gas-
chromatography/mass spectrometric application of new high-temperature
liquid crystal stationary phases for polycyclic aromatic hydrocarbon
separations. Analytical Chemistry 48(13):1879, 1976.
4. Matsushita, H. , Y. Esumi, and A. Suzuki. Analysis of polynuclear hydro-
carbons in petroleum. Bunseki Kagaku 21(3);331-7, 1972.
17
-------
APPENDIX A
TEST FUEL DESCRIPTION
18
-------
TABLE A-l. TEST FUEL DESCRIPTION
Test Fuel Designation Type of Fuel
Jet A High Sulfur Aircraft turbine jet fuel
Where Used
Jet A Low Sulfur
Aircraft turbine jet fuel
Commercial
jet aircraft
EM-238-F
EM-239-F
EM-240-F
Diesel: No. 2-D smoke
test fuel
Diesel! National
average No, 2 fuel.
Diesel: No. 1 Jet
A fuel
Diesel-
powered
passenger
cars and
trucks.
Reference
Robertson, D. J., J. H.
Elwood, and R. H. Groth,
Chemical Composition of
Exhaust Particles from Gas
Turbine Engines. Final
report prepared by United
Technologies Corporation,
East Hartford, Conn., under
Contract No. 68-02-2450 to
the U. S. Environmental
Protection Agency, Research
Triangle Park, NC Publication
No. EPA-600/2-79-041, February
1979.
Braddock, J. N., and P. A.
Gabele, Emissions patterns of
diesel-powered passenger cars -
Part II. SAE Paper No. 770168
Detroit, February 1977.
Hare, C. T., and R. L. Bradow.
Characterization of heavv-duty
diesel gaseous and particulate
emissions, and effects of fuel
composition. SAE Paper No.
790490. Detroit, February 1979.
-------
TABLE A-2. TEST FUEL DESCRIPTION
Test Fuel Designation
Type of Fuel
Where Used
Reference
EM-241-F
EM-242-F
Couch No. 2
O
Couch 5A
Diesel: Minimum
Quality No. 2 fuel.
Diesel: Premium
Quality No. 2 fuel.
Diesel: Local
(Durham, NC)
No. 2 fuel.
Diesel: Local
(Durham, NC)
No. 2 fuel.
Diesel-
powered
cars and
trucks
/ Braddock, J. N., and P. A.
Gabele. Emissions patterns
of diesel-powered passenger
cars - Part II. SAE Paper No.
770168. Detroit 1977.
Hare, C. T., and R. L. Bradow,
Characterization of heavy-duty
diesel gaseous and particulate
emissions and effects of fuel
composition. SAE Paper No.
790490. Detroit, February 1979.
Hare, C. T., and T. M. Baines.
Characterization of particulate
and gaseous emissions from two
diesel automobiles as a function
of fuel and driving cycle. SAE
Paper No. 790424. Detroit, Feb-
\ ruary 1979.
-------
TABLE A-3. TEST FUEL ANALYSES
Analysis
API Gravity @ 60°F
Density, gm/cc
ASTM Distillation. F
IBP
10%
50%
90%
EP
FIA Analysis
*
% Saturates
% Olefins
% Aromatics
Cetane
Carbon, Weight %
Hydrogen, Weight %
Sulfur, Weight %
Jet A
High Sulfur
47.0
0,792
328
338
358
403
456
80.0
1.5
18.5
Jet A
Low Sulfur
47.3
0.791
EM-238-F
EMr-239-F
EM-240-F
336
344
363
410
455
79.1
1.6
19.3
0.25
0.007
35.9
0.845
394
424
498
600
658
74,5
0.3
25.2
48.6
83.6
14.72
0.27
35.9
0.844
369
428
496
576
624
82.4
0.4
17.2
48.7
83.12
14.96
0.23
43.9
0.804
344
362
397
458
506
N
83.1
2.4
14.5
47.4
83.98
14.86
0.04
-------
TABLE A-4, TEST FUEL ANALYSIS
ro
K)
Analysis
EM-241-F
EM-242-F
Couch No, 2
Couch No. 5A
Couch No. 5B
API Gravity @ 60°F
Density, gm/cc
ASTM Distillation, °F
IBP
10%
50%
90%
EA
FIA Analysis
% Saturates
% Olefins
% Aromatics
Cetane
Carbon, Weight %
Hydrogen, Weight %
Sulfur, Weight %
32.4
378
425
483
570
610
59.8
0.5
39.7
41.8
84.36
13.95
0.30
38.7
377
417
488
572
610
81.6
0.4
18.0
53.0
84.00
14.98
0.27
34.6
376
418
498
590
642
68.9
1.5
29.6
46.0
84.62
14.80
0.17
35.5
380
427
504
600
642
66.2
1.3
32.5
84.59
14.81
0.16
-------
APPENDIX B
PNA ANALYSES OF LIQUID FUELS
23
-------
TABLE B-l
CONCENTRATION OF POLYNUCLEAR AROMATIC HYDROCARBONS IN JET A FUEL - HIGH SULFUR
Concentration
Compound
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Triphenylene
Chrysene
Benzo(e)pyrene
pph
2,700
250
45
64
4
3
9
Analysis I
1 Mg/gal
10,000.
950.
170.
240.
.6 17.
t
.0 11.
.6 36.
Analysis 11
PPb
1,800.
150.
50.
87.
9.9
3.4
13.3
Mg/gal
6,800.
570.
190.
330.
37.
13.
50.
ppb
2,200.
200.
48.
76.
7.
3.
11.
Average
Mg/gal
8,300.
760.
180.
290.
2 27.
2 12.
4 43.
-------
TABLE B-2
CONCENTRATION OF POLYNUCLEAR AROMATIC HYDROCARBONS IN JET A FUEL, LOW SULFUR
Concentration
Analysis I
Compound
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Triphenylene
Chrysene
Benzo(e)pyrene
ppb
1,900.
130.
11.
13.
1.8
3.2
1.4
yg/gai
7,200.
490.
42.
49.
6.8
12.
5.3
Analysis II
ppb
1,800.
140.
14.
22.
5.3
2.4
1.9
Mg/gal
6,800.
530.
53.
83.
20.
9.1
7.2
ppb
1,800.
140.
12.
18.
3.
2.
1.
Average
yg/gal
6,800.
530.
45.
68.
6 14.
8 11.
6 6.1
K)
Ul
-------
TABLE B-3
CONCENTRATION OF POLYNUCLEAR AROMATIC HYDROCARBONS IN EM-238-F
N>
Concentration
Analysis I
Compound
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Triphenylene
Benz (a) anthracene
Chrysene
Benzo(e)pyrene
Benzo (a) pyrene
Benzo ( g , h , i) perylene
ppb
710,000.
1,900.
28,000.
10,000.
20,000.
12,000.
36,000.
160.
62.
62.
Hg/gal
2,700,000.
7,200.
110,000.
38,000.
76,000.
45,000.
140,000.
610.
240.
240.
Analysis 11
ppb
650,000.
6,700.
22,000.
11,000.
7,000.
5,300.
190,000.
140.
23.
63.
yg/gal
2,500,000.
25,000.
83,000.
42,000.
26,000.
20,000.
72,000.
530.
87.
240.
Average
ppb
680,000.
4,300.
25,000.
10,000.
14,000.
9,000.
28,000.
150.
42.
62.
Mg/gal
2,600,000.
16,000.
95,000.
38,000.
53,000.
34,000.
110,000.
570.
160.
240.
-------
TABLE B-4
CONCENTRATION OF POLYNUCLEAR AROMATIC HYDROCARBONS IN EM-239-F
Concentration
Analysis I
Compound
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Tr iphenylene
Benz (a) anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Benzo(g,h, i)perylene
ppb
380,000.
9,000.
13,000.
8,700.
4,000.
3,100.
2,800.
75.
58.
29.
Vig/gal
1,400,000.
34,000.
49,000.
33,000.
15,000.
12,000.
11,000.
280.
220.
110.
Analysis II
ppb
300,000.
11,000.
13,000.
7,400.
4,900.
3,900.
5,800.
79.
80.
31.
Mg/gal
1,100,000.
42,000.
49,000.
28,000.
19,000.
15,000.
22,000.
300.
300.
117.
Average
ppb
340,000.
10,000.
13,000.
8,000.
4,400.
3,500.
4,300.
77.
69.
30.
Mg/gal
1,300,000.
38,000.
49,000.
30,000.
17,000.
13,000.
16,000.
290.
260.
110.
-------
TABLE B-5
CONCENTRATION OF POLYNUCLEAR AROMATIC HYDROCARBONS IN EM-240-F
Concentration
Analysis I
Compound
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Triphenylene
Benz (a) anthracene
Chrysene
Benzo (e) pyrene
Benzo (a) pyrene
ppb
8,300.
180.
140.
51.
74.
55.
83.
9.0
7.1
yg/gai
31,000.
680.
530.
190.
280.
210.
310.
34.
27.
Analysis II
ppb
7,700.
210.
170.
54.
74.
56.
83.
12.
7.7
yg/gai
29,000
800.
640.
200.
280.
210.
310.
45.
29.
ppb
8,000.
200.
160.
52.
74.
56.
83.
10.
7.
Average
pg/gal
30,000.
760.
610.
200.
280.
210.
310.
38.
4 280.
oo
-------
vo
TABLE B-6
CONCENTRATION OF POLYNUCLEAR AROMATIC HYDROCARBONS IN EM-241-F
Concentration
Analysis I
Compound
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Trlphenylene
Benz (a) anthracene
Chrysene
Benzo ( e) pyrene
Benzo (a) pyrene
Benzo (g,h,i)perylene
ppb
700,000.
10,000.
14,000.
12,000.
3,900.
3,200.
5,600.
58.
40.
13.
Vlg/gal
2,700,000.
380,000.
53,000.
45,000.
15,000.
12,000.
21,000.
220.
150.
49.
Analysis II
ppb
920,000.
7,100.
18,000.
17,000.
4,500.
3,500.
6,800.
48.
47.
22.
Vlg/gal
3,500,000.
27,000.
68,000.
64,000.
17,000.
13,000.
26.000
180.
180.
83.
ppb
810,000.
8,600.
16,000.
14,000.
4,200.
3,400.
6,200.
53.
44.
18.
Average
Vlg/gal
3,100,000.
33,000
61,000.
53,000.
16,000.
13,000.
24,000.
200.
170.
68.
-------
TABLE B-7
CONCENTRATION OF POLYNUCLEAR AROMATIC HYDROCARBONS IN EM-242-F
CO
o
Concentration
Analysis I
Compound
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Triphenylene
Benz (a) anthracene
Chrysene
Benzo(e)pyrene
Benzo (a) pyrene
ppb
200,000.
900.
4,600.
2,000.
1,700.
600.
1,400.
17.
20.
Ug/gal
760,000.
3,400.
17,000.
7,600.
6,400.
2,300.
5,300.
64.
76.
Analysis II
ppb
220,000.
2,500.
5,700.
2,100.
1,600.
600.
1,500.
17.
21.
Mg/gal
830,000.
9,500.
22,000.
8,000.
6,100.
2,300.
5,700.
64.
80.
Average
ppb
210,000.
1,700.
5,200.
2,000.
1,600.
600.
1,400.
17.
20.
JJg/gal
800,000.
6,400.
20,000.
7,600.
6,100.
2,300.
5,300.
64.
76.
-------
TABLE B-8
CONCENTRATION OF POLYNUCLEAR AROMATIC HYDROCARBONS IN COUCH #2
Concentration
Analysis I
Compound
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Triphenylene
Benz (a) anthracene
Chrysene
Benzo(e)pyrene
Benzo (a) pyrene
Benzo(g,h, i)perylene
ppb
510,000.
3,200.
19,000.
26,000.
10,000.
8,100.
14,000.
130.
79.
43.
Mg/gal
1,900,000.
12,000.
72,000.
99,000.
38,000.
31,000.
53,000.
490.
300.
160.
Analysis II
ppb
570,000.
2,600.
21,000.
35,000.
11,000.
6,800.
14,000.
170.
98.
15.
Mg/gal
2,200,000.
9,900
80,000.
130,000.
42,000.
26,000.
53,000.
640.
370.
57.
Average
ppb
540,000.
2,900.
20,000.
31,000.
11,000.
7,500.
14,000.
150,
88.
29.
Mg/gal
2,000,000
11,000.
76,000.
120,000.
42,000.
28,000.
33,000.
570.
330.
110.
-------
TABLE B-9
CONCENTRATION OF POLYNUCLEAR AROMATIC HYDROCARBONS IN COUCH #5A
CO
Concentration
Analysis I
Compound
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Triphenylene
Benz (a)anthracene
Chrysene
Benzo (e) pyrene
Benzo (a) pyrene
Benzo (g , h , i) perylene
ppb
6,000.
330.
1,900.
6,600.
1,500.
660.
1,200.
380.
210.
6.7
Hg/gal
23,000.
1,200.
7,200.
25,000.
5,700.
2,500.
4,500.
1,400.
800.
25.
Analysis 11
ppb
3,900.
290.
1,700.
4,500.
1,600.
700.
1,300.
380.
210.
8.9
Mg/gal
15,000.
1,100.
6,500.
17,000.
6,100.
2,700.
4,900.
1,400.
800.
34.
Average
ppb
5,000.
310.
1,800.
5,600.
1,600.
680.
1,200.
380.
210.
7.8
yg/gai
19,000.
1,200.
6,800.
21,000.
6,100.
2,600.
4,500.
1,400.
800.
30.
-------
TABLE B-10
CONCENTRATION OF POLYNUCLEAR AROMATIC HYDROCARBONS IN COUCH #5B
u>
U)
Concentration
Analysis I
Compound
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Triphenylene
Benz (a) anthracene
Chrysene
Benzo (e) pyrene
Benzo (a) pyrene
Benzo (g , h , i) perylene
ppb
8,500.
250.
2,000.
3,100.
1,100.
520.
1,100.
320.
190.
8.8
Mg/gal
32,000.
950.
7,600.
12,000.
4,200.
2,000.
4,200.
1,200.
720.
33.
Analysis II
ppb
13,000.
360.
2,100.
2,200.
1,200.
540.
1,200.
320.
190.
11.
Mg/gal
49,000,
1,400.
8,000.
8,300.
4,500.
2,000.
4,500.
1,200.
720.
42.
Average
ppb
11,000.
300.
2,000.
2,600.
1,200.
530.
1,200.
320.
190.
9.9
JJg/gal
42,000.
1,200.
7,800,
10,000.
4,500.
2,000.
4,500.
1,200.
720.
38.
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-80-069
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
QUANTITATIVE ANALYSIS OF POLYNUCLEAR AROMATIC
HYDROCARBONS IN LIQUID FUELS
5. REPORT DATE
April 1980
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Jerry L. Parr
8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Radian Corporation
8500 Shoal Creek Boulevard
P.O. Box 9948
Austin, Texas 78766
10. PROGRAM ELEMENT NO.
1AD712 BC-04 (FY-77)
11. CONTRACT/GRANT NO.
Contract No. 68-02-2466
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory—RTF,NC
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final 10/76-10/78
14. SPONSORING AGENCY CODE
EPA/600/09
15. SUPPLEMENTARY NOTES
Polynuclear aromatic hydrocarbons (PNAs), formed in combustion processes
with liquid hydrocarbon fuels, contribute to mobile source exhaust emissions.
Because correlation between PNA levels in automobile exhaust and pre-
existent PNAs in fuel has been demonstrated in previous work, a quanti-
tative analysis of 12 individual polynuclear aromatic hydrocarbons present
. in various aircraft turbine, diesel, and gasoline test fuels was determined
in this project. The PNAs included phenanthrene, anthracene, fluoranthene,
pyrene, benzo(a)anthracene, chrysene, triphenylene, benzo(a)pyrene,
benzo(e)pyrene, benzo(g,h,i)perylene, coronene and anthanthrene. The
fuel samples were analyzed by combined gas chromatography/mass spectrometry
(GC-MS) after a preliminary isolation/concentration scheme. Liquid
crystal chromatographic columns were employed to resolve isomeric PNAs.
The results indicated that anthanthrene and coronene were not detected
in any of the samples analyzed. Although the detection limit for each
PNA in the samples varied, the detection limit of the method employed
was approximately 5yg/gallon (1 ppb). The remaining ten PNAs were
found in levels ranging from 6ug/gallon (1.6 ppb = benzo(e)pyrene) to
3.1g/gallon (810,000 ppb = phenanthrene) of fuel. In general, the
concentration decreased with increasing molecular weight of the PNAs.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
COSATI Field/Group
*
*
*
*
Air pollution
Aromatic polycyclic hydrocarbons
Quantitative analysis
Diesel Fuels
Gasoline
Gas chromatography
Mass spectrometry
13B
07C
07D
21D
14B
I. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (ThisReport)
UNCLASSIFIED
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20. SECURITY CLASS (This page)
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22. PRICE
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34
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