POLYNUCLEAR AROMATIC HYDROCARBONS by GC 5515

Table 1 MW: Table 1 CAS: Table 2 RTECS: Table 2

METHOD: 5515, Issue 2 EVALUATION: PARTIAL Issue 1: 15 May 1985

Issue 2: 15 August 1994

NIOSH: Table 3 PROPERTIES: Table 1

OSHA :

COMPOUNDS: acenaphthene benzo[ghi]perylene fluorene

acenaphthylene benzo[a]pyrene indeno[1,2,3-cd]pyrene
anthracene benzo[e]pyrene naphthalene
benz[a]anthracene chrysene phenanthrene
benzo[b]fluoranthene dibenz[a,h]anthracene pyrene
benzo[k]fluoranthene fluoranthene

SYNONYMS: PAH; PNA; also see Table 2.

SAMPLING MEASUREMENT

SAMPLER: FILTER + SORBENT METHOD: GAS CHROMATOGRAPHY, CAPILLARY

(2-µm, 37-mm PTFE + washed XAD-2, COLUMN, FID
100 mg/50 mg)
ANALYTE: compounds above
FLOW RATE: 2 L/min
EXTRACTION: 5 mL organic solvent appropriate to
VOL-MIN: 200 L sample matrix (step 7)
-MAX: 1000 L
INJECTION
SHIPMENT: transfer filters to culture tubes; wrap sorbent VOLUME: 4 µL; 10:1 split
and culture tubes in Al foil; ship @ 0 °C
COLUMN: 30 m x 0.32-mm ID, fused silica capillary,
SAMPLE 1-µm DB-5
STABILITY: unknown; protect from heat and UV radiation
TEMPERATURE-INJECTOR: 200 °C
FIELD BLANKS: 2 to 10 field blanks per set -DETECTOR: 250 °C
-PROGRAM: 130 to 290 °C @ 4 °C/min
MEDIA BLANKS: 6 to 10
GASES-CARRIER: He @ 1 mL/min
AREA SAMPLES: 8 replicates on preweighed filters for -MAKEUP: He @ 20 mL/min
solvent selection
LOD: ca. 0.3 to 0.5 µg per sample [1]

ACCURACY CALIBRATION: external standards in toluene

RANGE, LOD, and PRECISION (Sr): EVALUATION OF

RANGE STUDIED, ACCURACY, BIAS, and OVERALL
METHOD
PRECISION (ŜrT): not measured

APPLICABILITY: The working range for B[a]P is 3 to 150 µg/m 3 for a 400-L air sample. Specific sample sets may require
modification in filter extraction solvent, choice of measurement method, and measurement conditions.

INTERFERENCES: Any compound which elutes at the same GC retention time may interfere. Heat, ozone, NO 2, or UV light may
cause sample degradation.

OTHER METHODS: This revises P&CAM 183 [2]. The spectrophotometric methods, P&CAM 184 and 186 [2], have not been
revised. Method 5506 (HPLC) uses the same sampling technique and is more sensitive.

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 POLYNUCLEAR AROMATIC HYDROCARBONS by GC: METHOD 5515, Issue 2, dated 15 August 1994 - Page 2 of 7

REAGENTS: EQUIPMENT:

1. Filter extraction solvent: acetonitrile, benzene,* 1. Sampler:

cyclohexane, methylene chloride,* or other a. Filter. PTFE-laminated membrane filter,
appropriate solvents, pesticide grade (step 7). 2-µm pore size, 37-mm diameter (Gelman
2. Toluene, pesticide grade. Zefluor, Membrana, Pleasantown, CA, or
3. Water, distilled, deionized. equivalent), backed by a spacer (37-mm
4. PAH reference standards,* appropriate to the OD, 32-mm ID) cut from a cellulose
PAH-containing matrix sampled. support pad or SKC #225-23, in cassette
5. Calibration stock solution, 0.25 mg/mL.* filter holder.
Check purity of each PAH reference standard NOTE 1: If sampling is to be done in
by GC/FID, HPLC/fluorescence and/or melting bright sunlight, use opaque or
point. Purify, if necessary, by recrystallization. foil-wrapped cassettes to
Weigh 25 mg of each PAH into a 100-mL prevent sample degradation.
volumetric flask; dilute to volume with toluene. NOTE 2: Take filters to be preweighed
Stable six months if refrigerated and protected from the filter package and
from light. allow to equilibrate 24 h with
6. Helium, prepurified. laboratory atmosphere before
7. Hydrogen, dry. taring.
8. Air, filtered. b. Sorbent tube, connected to filter with
minimum length PVC tubing. Plastic caps
are required after sampling. Washed
XAD-2 resin (front = 100 mg; back = 50
mg) (Supelco ORBO 43 or equivalent).
Pressure drop at 2 L/min airflow 1.6 to 2
* See SPECIAL PRECAUTIONS. kPa (15 to 20 cm H 2O).
2. Personal sampling pump capable of operating
for 8 h at 2 L/min, with flexible connecting
tubing.
3. Aluminum foil.
4. Vial, scintillation, 20-mL, glass, PTFE-lined
cap.
5. Refrigerant, bagged.
6. Culture tubes, PTFE-lined screw cap, 13-mm
x 100-mm.
7. Forceps.
8. Filters, 0.45-µm, PTFE (for filtering sample
solutions).
9. Pipet, 5-mL.
10. Syringes or micropipets, 1- to 100-µL.
11. Ultrasonic bath.
12. Gas chromatograph with FID, electronic
integrator, and capillary column (page 5515-1).
13. Volumetric flasks, 10- and 100-mL.
14. Lighting in laboratory: incandescent or UV-
shielded fluorescent.

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S P E C I A L P R E C A U T I O N S : T r e a t b e n z e n e ,
m e t h y l e n e c h l o r i d e , a n d a l l p o l y n u c l e a r a r o m a t i c
h y d r o c a r b o n s a s c a r c i n o g e n s . N e a t c o m p o u n d s
s h o u l d b e w e i g h e d i n a g l o v e b o x . S p e n t s a m p l e s
a n d u n u s e d s t a n d a r d s a r e t o x i c w a s t e . R e g u l a r l y
c h e c k c o u n t e r t o p s a n d e q u i p m e n t w i t h " b l a c k
l i g h t " f o r f l u o r e s c e n c e a s a n i n d i c a t o r o f
contamination by PAH.

SAMPLING:

1. Calibrate each personal sampling pump with a representative sampler in line.

2. Take personal samples at 2 L/min for a total sample size of 200 to 1000 L. Take a concurrent
set of eight replicate area samples at 2 to 4 L/min on preweighed, 2-µm PTFE filters in an area
of highest expected PAH concentration.
NOTE: The area samples are needed for solvent selection (step 7).
3. Immediately after sampling, transfer the filter carefully with forceps to a scintillation vial. Hold
filter at edge to avoid disturbing the deposit. Cap the scintillation vial and wrap it in aluminum
foil.
NOTE: This step is necessary to avoid loss of analytes due to sublimation and degradation by
light.
4. Cap the sorbent tube and wrap it in aluminum foil.
5. Ship to laboratory in insulated container with bagged refrigerant.

SAMPLE PREPARATION:

NOTE: UV light may degrade PAH. Use yellow, UV-absorbing shields for fluorescent lights or use
incandescent lighting.
6. Refrigerate samples upon receipt at laboratory.
7. Determine optimum extraction solvent.
a. Allow the preweighed area filter samples to equilibrate 24 h with the laboratory atmosphere.
b. Weigh the area filters. Determine total weight collected on each.
c. Extract the first pair of area filters with acetronitrile, the second with benzene, the third with
cyclohexane, and the fourth with methylene chloride, according to step 8.
NOTE: Use alternate solvents, if appropriate. PAH of interest may be entrained within, and
adsorbed by, particulate matter collected on the filter. It is necessary to determine
the solvent which maximizes recovery of the PAH from each sample matrix. For
example, methylene chloride [3,4] and benzene:ethanol (4:1 v/v) [5] have been
recommended for extraction of PAH from diesel exhaust particulate.
d. Analyze the extracts for the PAH of interest (steps 10 through 18). Normalize the total
mass of PAH found to the mass of sample collected.
e. Choose the solvent which gives the highest recovery of PAH of interest. Use the solvent
chosen to extract the personal filter samples.
8. Extract filters.
a. Add 5.0 mL of the solvent chosen in step 7 to each scintillation vial containing a filter. Start
media and reagent blanks at this step.
b. Cap and let stand 15 to 20 min in an ultrasonic bath.
NOTE: Soxhlet extraction may be required when large amounts of highly adsorptive
particulate matter (e.g., fly ash or diesel soot) are present.
9. Desorb PAH from sorbent.
a. Score each sorbent tube with a file in front of the primary (larger) sorbent section. Break
tube at score line.
b. Transfer front glass wool plug and front sorbent section to a culture tube. Transfer back

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 POLYNUCLEAR AROMATIC HYDROCARBONS by GC: METHOD 5515, Issue 2, dated 15 August 1994 - Page 4 of 7

sorbent section and the middle glass wool plug to a second culture tube.
c. Add 5.0 mL toluene to each culture tube. Cap the culture tubes.
d. Allow samples to stand for 30 min. Swirl occasionally.
10. Filter all sample extracts through an 0.45-µm membrane filter.

CALIBRATION AND QUALITY CONTROL:

11. Calibrate daily with at least six working standards.

a. Dilute aliquots of calibration stock solution with toluene in 10-mL volumetric flasks (e.g., to 5,
1, 0.2, 0.05, and 0.005 µg/mL).
b. Intersperse working standards and samples in the measurements.
c. Prepare calibration graphs (peak area vs. µg of each PAH per sample).
12. Recovery and desorption efficiency.
a. Determine recovery (R) from filters and desorption efficiency (DE) from sorbent tubes at
least once for each lot of filters and sorbent tubes used in the range of interest.
(1) Filters. Using a microliter syringe or micropipette, spike four filters at each of five
concentration levels with calibration stock solution. Allow the filters to dry in the dark
overnight. Analyze the filters (steps 8, 10, and 14 through 16). Prepare graphs of R vs.
amounts found.
NOTE: This step may not be used for some highly adsorptive particulate matrices for
which calibration by the method of standard additions may be more accurate.
(2) Sorbent tubes. Transfer an unused front sorbent section to a culture tube. prepare a
total of 24 culture tubes in order to measure DE at five concentration levels plus blanks
in quadruplicate. Using a microliter syringe or micropipette, add calibration stock
solution directly to sorbent. Cap culture tubes and allow to stand overnight in the dark.
Analyze (steps 9, 10, and 14 through 16). Prepare graphs of DE vs. amounts found.
b. Check R and DE at two levels for each sample set, in duplicate. Repeat determination of R
and DE graphs if checks do not agree to within ±5% of DE graph.
13. Analyze at least three field blanks for each sample medium.

MEASUREMENT:

14. Set GC according to manufacturer's recommendations and to the conditions on page 5515-1.
15. Inject sample aliquot. Start temperature program.
16. Measure peak areas.
NOTE 1: Approximate retention times appear in Table 4.
NOTE 2: If peak area is above the calibration range, dilute with appropriate solvent,
reanalyze, and apply dilution factor in calculations.
NOTE 3: If sample has many interferences, additional sample cleanup may be necessary.
Many cleanup procedures have been published. Liquid-liquid partitioning between
cyclohexane and nitromethane [6,7] is widely used, but other techniques may be
more appropriate for specific samples.

CALCULATIONS:

17. Read the mass, µg (corrected for R or DE) of each analyte found on the filter (W) and front
sorbent (W f) and back sorbent (W b) sections, and on the average media blank filter (B) and front
sorbent (B f) and back sorbent (B b) sections from the calibration graphs.
18. Calculate concentration, C (mg/m 3), in air as the sum of the particulate concentration and the
vapor concentration using the actual air volume sampled, V (L).

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 POLYNUCLEAR AROMATIC HYDROCARBONS by GC: METHOD 5515, Issue 2, dated 15 August 1994 - Page 5 of 7

EVALUATION OF METHOD:

Owing to large interferences that occured while utilizing NIOSH Method P&CAM 206 for samples
collected during asphalt roofing operations, the gas chromatographic capillary column method was
developed. The GC method has been evaluated using several hundred field filter and sorbent tube
sampling trains. To date, no statistical studies have been initiated. Overall, standard spiked filters and
sorbent tubes have yielded reproducible measurement calibration graphs. The method has been
applied to the following sources with semi-quantitative results using three separate particulate extraction
solvents (benzene, cyclohexane, acetonitrile): aluminum reduction facilities, asphalt fume, coal
gasification plants, coal liquefaction plants, coal tar pitch, coke oven emissions, creosote treatment
facilities, diesel exhaust, graphite electrode manufacturing, petroleum pitch, and roofing tearoff operations.

REFERENCES:

[1] UBTL, Inc., NIOSH Sequence #4220-O (NIOSH, unpublished, August 10, 1984).
[2] NIOSH Manual of Analytical Methods, 2nd ed., Vol. 1, U.S. Department of Health, Education, and
Welfare, Publ. (NIOSH) 77-157-A (1977).
[3] Breuer, G. M. Anal. Lett., 17 (A11), 1293-1306 (1984).
[4] Zweidinger, R. B., S. B. Tejada, D. Dropkins, J. Huisingh, and L. Claxton. "Characterization of
Extractable Organics in Diesel Exhaust Particulate," paper presented at Symposium on Diesel
Particulate Emissions Measurement Characterization, Ann Arbor, MI (1978).
[5] Swarin, S. J. and R. L. Williams. "Liquid Chromatographic Determination of Benzo[a]pyrene in
Diesel Exhaust Particulate: Verification of the Collection and Analytical Methods," Polynuclear
Aromatic Hydrocarbons: Physical and Biological Effects, Bjorseth, A. and Dennis, Eds., Battelle
Press, pp. 771-790 (1980).
[6] Wise, S. A., et al. "Analytical Methods for the Determination of Polycyclic Aromatic Hydrocarbons
on Air Particulate Matter," Polynuclear Aromatic Hydrocarbons: Physical and Biological Chemistry ,
Cooke, Dennis and Fisher, Eds., Battelle Press, pp. 919-929 (1982).
[7] Novotny, M., M. L. Lee and K. D. Bartle. J. Chromatog. Sci., 12, 606-612 (1974).
[8] Backup Data Report for Method 5506, Analytical Report for NIOSH Sequence 4170 (NIOSH, DPSE,
MRSB, unpublished, March 16, 1984).
[9] Studt., P., Liebigs Ann. Chem., 528 (1978).
[10] Clar, E. Polycyclic Hydrocarbons , Academic Press (1964).
[11] Handbook of Chemistry and Physics, 62nd ed., CRC Press (1982).
[12] Beilstein 5 (1), 344.

METHOD REVISED BY:

B.R. Belinky, NIOSH/DPSE, and E.J. Slick; J.C. Holt, D.E. Bilak, and J.B. Perkins, DataChem
Laboratories, Inc., Salt Lake City, UT.

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Table 1. Formulae and physical properties.

MELTING BOILING
EMPIRICAL MOLECULAR POINT POINT
COMPOUND (by M.W.) FORMULA WEIGHT (°C)* (°C)* REF.

1. NAPHTHALENE C10H8 128.17 80.2 218 [10]

2. ACENAPHTHYLENE C12H8 152.20 92-93 265-275 [11]
3. ACENAPHTHENE C12H10 154.21 96.2 279 [11]
4. FLUORENE C13H10 166.22 116 293-295 [10]
5. ANTHRACENE C14H10 178.23 218 340 [10]
6. PHENANTHRENE C14H10 178.23 100 340 [10]
7. FLUORANTHENE C16H10 202.26 110 384* [10], [12]
8. PYRENE C16H10 202.26 156 393 [10]
9. BENZ[a]ANTHRACENE C18H12 228.29 162-167 435 [10]
10. CHRYSENE C18H12 228.29 255-256 448 [10]
11. BENZO[b]FLUORANTHENE C20H12 252.32 168 -- [10]
12. BENZO[k]FLUORANTHENE C20H12 252.32 217 480 [11]
13. BENZO[a]PYRENE C20H12 252.32 179 495 [10]
14. BENZO[e]PYRENE C20H12 252.32 178-179 -- [10]
15. BENZO[ghi]PERYLENE C22H12 276.34 273 -- [10]
16. INDENO[1,2,3-cd]PYRENE C22H12 276.34 161.5-163 530 [9]
17. DIBENZ[a,h]ANTHRACENE C22H14 278.35 267 524 [10]

*Many of these compounds will sublime.

Table 2. Synonyms.

COMPOUND (alphabetically) SYNONYMS

1. ACENAPHTHENE CAS# 83-32-9; RTECS# AB1000000

2. ACENAPHTHYLENE CAS# 208-96-8; RTECS# AB1254000
3. ANTHRACENE CAS# 120-12-7; RTECS# CA9350000
4. BENZ[a]ANTHRACENE 1,2-benzanthracene; benzo[b]phenanthrene; 2,3-
benzophenanthrene; tetraphene; CAS# 56-55-3; RTECS#
CV9275000
5. BENZO[b]FLUORANTHENE 3,4-benzofluoranthene; 2,3-benzofluoranthene;
benz[e]acephenanthrylene; B[b]F; CAS # 205-99-2; RTECS#
CU1400000
6. BENZO[k]FLUORANTHENE 11,12-benzofluoranthene; CAS# 207-08-9; RTECS# DF6350000
7. BENZO[ghi]PERYLENE 1,12-benzoperylene; CAS# 191-24-2; RTECS# DI6200500
8. BENZO[a]PYRENE 3,4-benzopyrene; 6,7-benzopyrene; B[a]P; BP; CAS# 50-32-8;
RTECS# DJ3675000
9. BENZO[e]PYRENE 1,2-benzopyrene; 4,5-benzopyrene; B[e]P; CAS# 192-97-2;
RTECS# DJ4200000
10. CHRYSENE 1,2-benzophenanthrene; benzo[a]phenanthrene; CAS# 218-01-9;
RTECS# GC0700000
11. DIBENZ[a,h]ANTHRACENE 1,2,5,6-dibenzanthracene; CAS# 53-70-3; RTECS# HN2625000
12. FLUORANTHENE benzo[jk]fluorene; Idryl; CAS# 206-44-0; RTECS# LL4025000
13. FLUORENE o-biphenylenemethane; CAS# 86-73-7; RTECS# LL5670000
14. INDENO[1,2,3-cd]PYRENE 2,3-phenylenepyrene; CAS# 193-39-5; RTECS# NK9300000
15. NAPHTHALENE naphthene; CAS# 91-20-3; RTECS# QJ0525000
16. PHENANTHRENE CAS# 85-01-8; RTECS# SF7175000
17. PYRENE benzo[def]phenanthrene; CAS# 129-00-0; RTECS# UR2450000

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Table 3. Exposure Limits.

COMPOUND (alphabetically) OSHA NIOSH ACGIH

1. ACENAPHTHENE -- -- --
2. ACENAPHTHYLENE -- -- --
3. ANTHRACENE 0.2 mg/m 3 -- --
4. BENZ[A]ANTHRACENE -- -- --
5. BENZO[B]FLUORANTHENE -- -- suspect carcinogen
6. BENZO[K]FLUORANTHENE -- -- --
7. BENZO[GHI]PERYLENE -- -- --
8. BENZO[A]PYRENE 0.2 mg/m 3 (benzene sol.) 0.1 mg/m 3 (cyclohexane sol.) suspect carcinogen
9. BENZO[E]PYRENE -- -- --
10. CHRYSENE 0.2 mg/m 3 (benzene sol.) lowest feasible, carcinogen suspect carcinogen
11. DIBENZ[A,H]ANTHRACENE -- -- --
12. FLUORANTHENE -- -- --
13. FLUORENE -- -- --
14. INDENO[1,2,3-CD]PYRENE -- -- --
15. NAPHTHALENE 10 ppm 10 ppm; STEL 15 ppm 10 ppm; STEL 15 ppm
16. PHENANTHRENE 0.2 mg/m 3 -- --
17. PYRENE -- -- --

Table 4. Approximate PAH retention times.

COMPOUND RETENTION TIME (min)*

1. NAPHTHALENE not available
2. ACENAPHTHALENE 7.66
3. ACENAPHTHENE 8.37
4. FLUORENE 10.5
5. PHENANTHRENE 15.0
6. ANTHRACENE 15.3
7. FLUORANTHENE 21.4
8. PYRENE 22.6
9. BENZ[a]ANTHRACENE 29.4
10. CHRYSENE 29.6
11. BENZO[e]PYRENE 36.4
12. BENZO[b]FLUORANTHENE 35.1
13. BENZO[k]FLUORANTHENE 35.2
14. BENZO[a]PYRENE 36.2
15. DIBENZ[a,h]ANTHRACENE 43.9
16. BENZO[ghi]PERYLENE 45.6
17. INDENO[1,2,3-cd]PYRENE 43.6

*NOTE: Actual retention times will vary with individual columns and column age.

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94