NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

 POLYNUCLEAR AROMATIC HYDROCARBONS in AIR by GC-MS SIM 5528

Formulae: Table 1 MW: Table 1 CAS: Table 1 RTECS: Table 1

METHOD: 5528, Issue 1 EVALUATION: FULL Issue 1: November 2021 

OSHA: Table 3

NIOSH REL: Table 3

PROPERTIES: Table 2 

SYNONYMS: Table 1

SAMPLING

SAMPLER: Filter + Sorbent tube (glass fiber filter, 

OVS-7 tube: 13-mm; XAD-7, 

 200 mg/100 mg)

FLOW RATE: 1 L/min

VOLUME MIN: 1 L

VOLUME MAX: 480 L (see Method Evaluation) 

SHIPMENT: Protect from light; standard

SAMPLE

STABILITY: at least 30 days at < 4°C [1] 

BLANKS: 10% (≥ 2) of samples

ACCURACY [1]

RANGE 

STUDIED: 0.25 to 75 μg/sample. Table 7

BIAS: Table 7

OVERALL

PRECISION Table 7

ACCURACY: Table 7

MEASUREMENT

TECHNIQUE: GAS CHROMATOGRAPHY-MASS 

SPECTROMETRY SELECTED ION 

MONITORING GC-MS SIM

ANALYTE: Table 1

INJECTION

VOLUME: 1 μL Splitless

CARRIER 

GAS: Helium @ 1.3 mL/min 

COLUMN: Phenyl arylene polymer (0.5 μm) film fused 

silica capillary column (30 m × 0.32 mm ID)

MASS SPEC: Tables 5 and 6

CALIBRATION: At least six media-spiked standards to 

cover the range

ESTIMATED LOD: 0.08 to 0.2 μg/sample (Table 8)

PRECISION Table 9 

APPLICABILITY: For analysis of PAHs in air. The working range for a 240-L air sample is 0.0011 to 2.0 mg/m3

. 

INTERFERENCES: Because of the mass-selective capabilities of GC-MS, interferences are not anticipated to have any impact on the 

analysis. At higher humidity levels (80% and above), the method range is shortened as samples at concentrations of 10 μg/sample 

do not quantitatively recover. 

OTHER METHODS: This method is similar to NIOSH 5515, with primary differences including a more efficient sampling device and 

the use of GC-MS SIM rather than GC-FID [2]. NIOSH 5506 (HPLC) uses the same sampling technique as NIOSH 5515 [3]
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NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

REAGENTS:

1. Desorbing solvent: Methylene chloride.

High Purity grade or equivalent.

2. Dilution solution: Methylene chloride

containing approximately 1 μg/mL of

internal standard(s). Prepare by adding 100

μL of internal standard spiking solution to

exactly 10 mL of methylene chloride. (Do

not reduce volume to compensate for the

100 μL added.)

3. Internal standard spiking solution:

naphthalene-D8, acenaphthene-D10,

phenanthrene-D10, chrysene-D12, and

perylene-D12 at about 100 μg/mL in

methylene chloride.

4. 16 PAHs, 1000 μg each in 1 mL solvent:

Naphthalene, Acenaphthylene,

Acenaphthene, Anthracene,

Benz[a]anthracene, Benzo[a]pyrene,

Benzo[b]fluoranthene, Benzo[ghi]perylene,

Benzo[k]fluoranthene, Chrysene,

Dibenz[a,h]anthracene, Fluoranthene,

Fluorene, Indeno[1,2,3-cd]pyrene,

Phenanthrene, Pyrene

5. Helium, UHP (carrier gas for GC-MS)

*See SPECIAL PRECAUTIONS.

EQUIPMENT:

1. Sampler: OVS-7 sampling tube with glass

fiber filter (glass tube, 11-mm i.d. × 13-mm

o.d. × 50-mm long, with the outlet end

drawn to a 6-mm o.d. × 15 to 25-mm-long

tube. The enlarged part of the tube contains

a 200-mg front section of 20/60 mesh XAD-7

sorbent held in place by an 11-mm o.d. glass

fiber filter (GFF) and a

polytetrafluoroethylene (PTFE) retaining

ring. The front section is separated from the

back section of 100-mg XAD-7 sorbent with

a short plug of polyurethane foam (PUF).

The back section is held in place by a long

plug of PUF. The sampler is available

commercially (See Figure 1).

2. Personal sampling pump, 0.5 to 2 L/min,

with flexible connecting tubing

3. 4-mL Amber glass vials with caps

4. 2-mL Amber GC vials with caps

5. Gas chromatograph-mass spectrometer

capable of selected ion monitoring, column,

autosampler, and data integrator (page

5528-1)

6. Microliter syringes

7. Ultrasonic water bath

8. Foil for shipping

SPECIAL PRECAUTIONS: Wear gloves, lab coat, and safety glasses while handling all chemicals. All work 

should be performed in a fume hood. Treat benzene, methylene chloride, and all polynuclear aromatic

hydrocarbons as carcinogens. Neat compounds should be weighed in a high efficiency fume hood or glove 

box. Spent samples and unused standards are toxic waste. Regularly check countertops and equipment with 

"black light" for fluorescence as an indicator of contamination by PAH.

SAMPLING:

1. Calibrate each personalsampling pump with a representative sampler in line.

2. Connect the sampler to personalsampling pump with flexible tubing. The samplershould be placed vertically

with the large end down, in the worker’s breathing zone, in such a manner that it does not impede worker

performance. Follow manufacturer’s instructions on use of OVS tube and holder.

3. Sample at an accurately known rate around 1 liter per minute for a total sample size of 1 to 480 liters

(maximum = 480 liters).

4. Upon completion of sampling, immediately cap both ends of the sampler and protect from light by wrapping

in foil. Pack securely for shipment.
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NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

SAMPLE PREPARATION:

5. Transfer the glassfiber filter and the frontsection to a 4-mL amber glass vial (Cf

). Transfer the back

section and foam plug which separatesthe front resin from the back resin (Ch) to a second 4-mL amber

glass vial.

6. Add 2 mL of methylene chloride to each vial. Cap the vial and shake well, then place in an ultrasonic

bath for at least thirty minutes.

7. Transfer an accurately measured aliquot of the desorbing solvent to a GC vial (e.g., 1.0 mL).

8. Spike with the internalstandard spiking solution to achieve an internalstandard concentration of

approximately 1 μg/mL (for example,spike 10 μL of internalstandard solution into a 1.0 mL aliquot of

desorption solvent).

CALIBRATION AND QUALITY CONTROL:

9. Calibrate with at leastsix working standards covering the expected concentration range of the samples.

a. Prepare each working standard by spiking a known amount of stock solution onto the glassfiber

filter and front XAD-7 resin from a blank OVS-7 sampler contained within a 4-mL amber glass

vial.

b. Add 2 mL of methylene chloride to each vial and desorb in the same manner asthe field samples

(steps 5-8 above).

c. Prepare at least two method blanks by adding 2 mL of methylene chloride to the glassfiber filter

and front XAD-7 resin from a blank OVS-7 sampler contained within a 4-mL amber glass vial and

desorbing in the same manner asthe field samples.

d. Analyze calibration standards and method blanks with field samples and laboratory control samples

(steps 11-12).

e. Prepare calibration graphs by plotting, for each working standard, the analyte relative response (peak

area of analyte divided by the peak area of the internalstandard in the same chromatogram) on the

y-axis vs. concentration of analyte on the x-axis. A linear or quadratic model may be utilized in

processing the analytical data. Quadratic models usually work best on GC-MS data. To confirm 

acceptability of the calibration curve, when each standard is inserted into the calibration equation, 

the value should be within ±20% of the expected value. 

f. Prepare laboratory Quality Control samples in duplicate with each sample set. 

g. Independently prepared quality control PAH solutions in dilution solution must be prepared at

concentrations within the analytical range.

h. Remove the cap from the large end of a sampler tube. Apply solution to face of glassfiber filter

(GFF).

NOTE: Spiking volume should not exceed 25 μL otherwise there might be wicking of the spiking

solution to the edges of the GFF and then behind the PTFE retainer ring. One way to avoid this

is to pull the retainer ring away from the GFF by a few millimeters prior to spiking the GFF.

i. Re-cap the samplers and allow to stand for a minimum of one hour. Transfer to a 4-mL amber glass 

vial and desorb in same manner as the field samples (steps 5-8).

j. Analyze these along with the field samples, blanks, and calibration standards(steps 11–12). QC values 

should normally be within ±20% of the spiked values. If not, the batch is considered out of control, 

the batch data discarded, and corrective actions taken before more samples are analyzed.

MEASUREMENT:

10. Set gas chromatograph and massspectrometer according to manufacturer’srecommendations and to

conditions given on page 5528-1 and in Table 5.

11. Inject sample aliquot with autosampler or manually (using solvent flush technique is not necessary if

internalstandards are used). See Table 4 for retention times of selected analytes.
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NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

NOTE: If peak area is greater than the range of the working standards, dilute an aliquot of the sample with 

desorbing solvent and reanalyze. Apply appropriate dilution factor in calculations.

12. Measure peak areas of analyte and internalstandard and compute analyte relative peak area by

dividing the peak area of the analyte by that of the internalstandard in the same chromatogram.

CALCULATIONS:

13. Determine the concentrations of the target analytesin μg/sample of respective analyte found in the

sample front section (Cf ) and back section (Cb ), and in the media blank front (Bf

) and back (Bb) sections

from the calibration graph.

NOTE: If Cb is greater than Cf /10, report breakthrough and possible sample loss.

14. Calculate concentration, C, of analyte in the air volume sampled, V (L):

C = (Cf + Cb) − (Bf + Bb)

V mg m3 ⁄ x dilution factor (if any)

EVALUATION OF METHOD [1]: 

Precision and accuracy were evaluated over six spiked concentration levels from 0.25 to 75 μg/sample. This 

range represented 1x the estimated analytical LOQ to 300× the estimated LOQ. Seven replicates were 

analyzed at each level. Precision and accuracy are given in Table 7. Data were not included where 

desorption was <75% or >125%. This meant the lower 4 levels of Acenaphthylene (0.25 μg-7.5 μg) and the 

lowest level of Benzo[a]pyrene (0.25 μg) were omitted. For definitions and mathematical formulae used for 

precision, accuracy, and bias, refer to the backup data report [1].

The average recoveries at the various concentration levels are shown in Table 8; the data not used for 

precision and accuracy are in bold type. 

Sample storage was evaluated up to 30 days at two different temperatures. OVS-7 samplers were spiked 

with 75 μg/sample for each PAH. Spiked samplers were stored at ambient temperature and at 4° C for 7, 10, 

14, 21, and 30 days and then analyzed. Recoveries for all analytes up to 30-day storage at both

temperatures were above 80%. 

OVS-7 sampler capacity or breakthrough was determined for up to 24 hours at 1-liter air per minute. No 

breakthrough was detected for any analyte up to the maximum time tested. All analytes appeared to be 

stable in storage up to 30 days on the OVS-7 sampler, but acenaphthylene exhibited breakdown during 

sampling over long time periods. Recoveries were 93% in 8 hours but dropped rapidly to about 80% in 16 

hours and to 74% in 24 hours. Therefore, it is recommended to sample for no more than 8 hours. 

Otherwise, acenaphthylene will be biased low due to degradation during sampling. Acenaphthenone was 

detected in the samples showing reduced recoveries for acenaphthylene.

The LOD and LOQ were determined by analyzing a series of standards with the data fitted to a quadratic 

curve [1]. The LOD and LOQ were estimated according to the Burkart Method [4]. Estimated LODs are given 

in Table 8. The limits of detection for this method are on average (except for anthracene) twice as low as 

for NIOSH 5506. The LOD for anthracene is comparable to NIOSH 5506 [3]. 

A humidity challenge was done at 10, 48, 96, and 192 μg per sample (n = 6) with a mixture of 16 PAHs at 

80% relative humidity [1]. Humid air was pulled through the loaded samples at 1 L/min for 8 hours. The 

samplers sat overnight before analysis. A Tukey [1] multiple comparison test indicated that the 10-μg level 
PAH in Air by GC-MS SIM: METHOD 5528, Issue 1, dated 10 November 2021 - Page 5 of 15 

NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

was statistically different from the other three levels; 70.5 to 78.5, 90.0 to 104.0, 78.0 to 86.0, and 80.9 to 

87.8% average recovery for the 16 PAHs at 10, 48, 96 and 192 μg per sample respectively.

A user check tested the method over the range of 0.5, 2.0, 5.0, and 20.0 μg per sample (n = 6) [1]. The LOD 

was 0.05 μg for 14 compounds, 0.06 μg for naphthalene, 0.08 μg for dibenzo[a,h]anthracene; LOQ was 0.17 

μg for 13 compounds, 0.19 μg for naphthalene, 0.26 for dibenzo[a,h]anthracene, and 0.18 μg for 

benzo[a]anthracene. Only benzo[a]pyrene had a recovery below 75%, at the 0.5 μg spike level. 

Additionally, 7 of the PAHs recovered below 90% at the lowest spike level (0.5 μg). Therefore, it is 

recommended that sample volume be maximized when a low PAH level is anticipated. The correlation 

coefficient was 0.990 or higher for all but naphthalene (0.970). A humidity challenge was also done, with 

10, 48, 96 and 192 μg samples at 80% relative humidity. As in the humidity challenge done during method 

development, the 10-μg samples were lower than 80% recovery.

REFERENCES:

[1] NIOSH [2005]. Back-up data report: Polynuclear aromatic hydrocarbons in air by GC-MS SIM. 

https://www.cdc.gov/niosh/nmam/datadoc.html 

[2] NIOSH [2003]. Method 5515: Polynuclear aromatic hydrocarbons by GC. In: Eller PM, Cassinelli ME, 

eds. NIOSH manual of analytical methods. 4th edition. Cincinnati, OH: U.S. Department of Health 

and Human Services, Centers for Disease Control and Prevention, National Institute for Occupational 

Safety and Health, DHHS (NIOSH) Publication No. 94-113.

[3] NIOSH [2003]. Method 5506: Polynuclear aromatic hydrocarbons by HPLC. In: Eller PM, Cassinelli 

ME, eds. NIOSH manual of analytical methods. 4th edition. Cincinnati, OH: U.S. Department of 

Health and Human Services, Centers for Disease Control and Prevention, National Institute for 

Occupational Safety and Health, DHHS (NIOSH) Publication No. 94-113.

[4] Burkart JA [1986]. General procedures for limit of detection calculationsin the industrial hygiene

chemistry laboratory. App Ind Hyg1(3):153-155.

[5] Rumble J [2019]. Handbook of physical properties of organic chemicals. Boca Raton, Florida: 

CRC/Lewis Publishers. https://hbcponline.com 

[6] NIOSH [ 1987]. Registry of toxic effects of chemical substances. U.S. Department of Health and Human 

Services, Centers for Disease Control, National Institute for Occupational Safety and Health, DHHS

(NIOSH) Publication No. 87-114.

[7] O’Neil M, ed. [2013]. Merck Index, 15th ed. Rahway, New Jersey: Merck and Co., Inc. 

https://www.rsc.org/merck-index 

[8] ACGIH [2020]. TLVs and BEIs based on the documentation of the Threshold LimitValuesfor chemical

substances and physical agents and Biological Exposure Indices. Cincinnati, Ohio: American

Conference of Governmental Industrial Hygienists. https://www.acgih.org 

[9] NIOSH [1992]. NIOSH recommendationsfor occupational safety and health. Cincinnati, OH:U.S. 

Department of Health and Human Services, Centers for Disease Control, National Institute for Occupational 

Safety and Health, DHHS (NIOSH) Publication. No. 92-100.

[10] Kim S, Chen J, Cheng T, Gindulyte A, He J, He S, Li Q, Shoemaker BA, Thiessen PA, Yu B, Zaslavsky L, 

Zhang J, Bolton EE [2019]. PubChem 2019 update: improved access to chemical data. Nucleic Acids 

Res. 8(47):D1102-D1109. https://pubchem.ncbi.nlm.nih.gov/
PAH in Air by GC-MS SIM: METHOD 5528, Issue 1, dated 10 November 2021 - Page 6 of 15 

NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

METHOD WRITTEN BY:

Dawn Farwick, NIOSH. Method developed by DataChem Laboratories, Inc., Salt Lake City, Utah under 

NIOSH Contract CDC-200-2001-0800.

Disclaimer: Mention of any company or product does not constitute endorsement by the National 

Institute for Occupational Safety and Health, Centers for Disease Control and Prevention. In addition, 

citations to websites external to NIOSH do not constitute NIOSH endorsement of the sponsoring 

organizations or their programs or products. Furthermore, NIOSH is not responsible for the content of 

these websites. All web addresses referenced in this document were accessible as of the publication date. 

Table 1. CAS Numbers, RTECS Numbers, and Synonyms

Compound

(alphabetically)

CAS

Number

RTECS

Number(1)

Other Names(2)

Acenaphthene 83-32-9 AB1000000 1,2-dihydroacenaphthylene; 1,8-ethylenenapthylene

Acenaphthylene 208-96-8 AB1254000 Acenaphthalene; cyclopenta[de]naphthalene

Anthracene 120-12-7 CA9350000

Benz[a]anthracene 56-55-3 CV9275000 1,2-benzanthracene; 2,3-benzphenanthrene; tetraphene

Benzo[b]fluoranthene 205-99-2 CU1400000 3,4-benzfluoranthene; 2,3-benzofluoranthene; benz[e]acephenanthrylene 

Benzo[k]fluoranthene 207-08-9 DF6350000 benzofluoranthene; 2,3,1’,8’-binaphthylene; dibenzo[bjk]fluorene

Benzo[ghi]perylene 191-24-2 DI6200500 1,12-benzoperylene

Benzo[a]pyrene 50-32-8 DJ3675000 3,4-benzopyrene; 6,7-benzopyrene 

Chrysene 218-01-9 GC0700000 1.2-benzophenanthrene; benzo[a]phenanthrene

Dibenz[a,h]anthracene 53-70-3 HN2625000 1,2,5,6-dibenzanthracene

Fluoranthene 206-44-0 LL4025000 benzo[jk]fluorene; 1,2-benzacenaphthene; Idryl

Fluorene 86-73-7 LL5670000 o-biphenylenemethane; 2,2’-methylenebiphenyl; 9H-fluorene

Indeno[1,2,3-cd]pyrene 193-39-5 NK9300000 2,3-phenylenepyrene

Naphthalene 91-20-3 QJ0525000 Naphthene, naphthalin

Phenanthrene 85-01-8 SF7175000 Phenanthracene

Pyrene 129-00-0 UR2450000 benzo[def]phenanthrene

(1) Registry of Toxic Effects of Chemical Substances [6].

(2) Alternate names taken from Merck Index [7] and PubChem [10].
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Table 2. Formulae and Physical Properties (1)

Compound (by MW) Empirical 

Formula

Molecular

Weight

Melting

Point °C (2)

Boiling

point°C (2)

Vapor Pressure

mm Hg(3) log P(4)

Naphthalene C10H8 128.17 80.2 218 0.085 3.30

Acenaphthylene C12H8 152.19 92.5 280 0.0048 3.94

Acenaphthene C12H10 154.21 95 279 0.0025 3.92

Fluorene C13H10 166.22 116 295 0.00842 3.77

Anthracene C14H10 178.23 218 342 2.67E-06 4.45

Phenanthrene C14H10 178.23 100 340 0.000112 4.46

Fluoranthene C16H10 202.26 110 384 9.22E-06 5.16

Pyrene C16H10 202.26 156 404 4.5E-06 4.88

Benz[a]anthracene C18H12 228.29 155-157 435 1.9E-06 5.76

Chrysene C18H12 228.29 254 448 6.23E-09 5.81

Benzo[b]fluoranthene C20H12 252.32 168 481 5E-07 5.78

Benzo[k]fluoranthene C20H12 252.32 217 480 9.65E-010 6.11

Benzo[a]pyrene C20H12 252.32 179 312 5.49E-09 6.13

Benzo[ghi]perylene C22H12 276.34 278 550 1E-010 6.63

Indeno[1,2,3-cd]pyrene C22H12 276.34 161.5-163 530 1.25E-010 6.70

Dibenz[a,h]anthracene C22H14 278.35 266 524 1E-010 (@ 20 °C) 6.65 

(1) Values Merck Index [7] and PubChem [10].

(2) Many of these compounds will sublime.

(3) Vapor pressure at 25 0C [5].

(4) Octanol-water partition coefficient [5].
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Table 3. Exposure Limits(1, 2, 3)

Compound

(alphabetically)

OSHA PEL NIOSH REL

Acenaphthene 0.2 mg/m3 (benzene soluble fraction) 0.1 mg/m3 (cyclohexane soluble fraction)

Acenaphthylene 0.2 mg/m3 (benzene soluble fraction) 0.1 mg/m3 (cyclohexane soluble fraction)

Anthracene 0.2 mg/m3 (benzene soluble fraction) 0.1 mg/m3 (cyclohexane soluble fraction)

Benz[a]anthracene 0.2 mg/m3 (benzene soluble fraction) 0.1 mg/m3 (cyclohexane soluble fraction)

Benzo[b]fluoranthene 0.2 mg/m3 (benzene soluble fraction) 0.1 mg/m3 (cyclohexane soluble fraction)

Benzo[k]fluoranthene 0.2 mg/m3 (benzene soluble fraction) 0.1 mg/m3 (cyclohexane soluble fraction)

Benzo[ghi]perylene 0.2 mg/m3 (benzene soluble fraction) 0.1 mg/m3 (cyclohexane soluble fraction)

Benzo[a]pyrene 0.2 mg/m3 (benzene soluble fraction) 0.1 mg/m3 (cyclohexane soluble fraction)

Chrysene

0.2 mg/m3 (benzene soluble fraction) 0.1 mg/m3 (cyclohexane soluble fraction)

Dibenz[a,h]anthracene 0.2 mg/m3 (benzene soluble fraction) 0.1 mg/m3 (cyclohexane soluble fraction)

Fluoranthene 0.2 mg/m3 (benzene soluble fraction) 0.1 mg/m3 (cyclohexane soluble fraction)

Fluorene 0.2 mg/m3 (benzene soluble fraction) 0.1 mg/m3 (cyclohexane soluble fraction)

Indeno[1,2,3-cd]pyrene 0.2 mg/m3 (benzene soluble fraction) 0.1 mg/m3 (cyclohexane soluble fraction)

Naphthalene 10 ppm (50 mg/m3

) 10 ppm (50 mg/m3); STEL 15 ppm (75 mg/m3)

Phenanthrene 0.2 mg/m3 (benzene soluble fraction) 0.1 mg/m3 (cyclohexane soluble fraction)

Pyrene 0.2 mg/m3 (benzene soluble fraction) 0.1 mg/m3 (cyclohexane soluble fraction)

(1) OSHA Recommendations for Occupational Safety and Health [10]. 

(2) NIOSH Recommendations for Occupational Safety and Health [10].

(3) STEL = short term exposure limit [10]. 
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Table 4. Approximate PAHRetentionTimes (1)

Compound (by elution order) Approximate RetentionTime

(minutes)

Naphthalene-D8 6.26

Naphthalene 6.28

Acenaphthylene 8.74

Acenaphthene-D10 9.02

Acenaphthene 9.04

Fluorene 9.95

Phenanthrene-D10 11.65

Phenanthrene 11.69

Anthracene 11.79

Fluoranthene 13.82

Pyrene 14.17

Benz[a]anthracene 15.90

Chrysene-D12 15.92

Chrysene 15.96

Benzo[b]fluoranthene 17.83

Benzo[k]fluoranthene 17.89

Benzo[a]pyrene 18.58

Perylene-D12 18.70

Indeno[1,2,3-cd]pyrene 21.95

Dibenz[a,h]anthracene 22.04

Benzo[ghi]perylene 22.95

(1) Actual retention times will vary with individual columns and column age.

Table 5. Mass Spectrometer Parameters for SIM operation (1)

Start Time (minutes)

Dwell

Time

(ms)

Ions (m/z) to monitor

Group 1 1 minute before naphthalene (~5.5 min) 30 136, 128, 129, 126, 64

Group 2 1 minute after naphthalene (~7.5 min) 30 164, 152, 150, 153, 76, 154, 166,165, 167, 82

Group 3 1 minute after fluorene (~11 min) 30 188, 178, 179, 176, 89, 202, 200,203, 101

Group 4 1 minute before fluoranthene (~13 min) 30 240, 202, 200, 203, 101, 228,229, 226, 114

Group 5 1 minute after chrysene (~17.3 min) 30 264, 252, 253, 250, 126

Group 6 1.5 min after benzo(a)pyrene (~21 min) 30 276, 277, 274, 138, 278, 279,139

(1) These parameters monitor several ions for each PAH, which increases the certainty of the identification with 

minimal, if any, sacrifice of sensitivity.
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Table 6. Quantitation Ions andInternal Standard References(1)

Compound

(by elution order)

Quantitation

ion (m/z)

Secondary

Ions (m/z)

Internal

Standard Reference

Naphthalene-D8 136 n/a n/a

Naphthalene 128 129, 126, 64 Naphthalene-D8

Acenaphthylene 152 153, 150, 76 Acenaphthene-D10

Acenaphthene-D10 164 n/a n/a

Acenaphthene 153 154, 152, 150, 76 Acenaphthene-D10

Fluorene 166 167, 165, 164, 82 Acenaphthene-D10

Phenanthrene- D10 188 n/a n/a

Phenanthrene 178 179, 176, 89 Phenanthrene- D10

Anthracene 178 179, 176, 89 Phenanthrene- D10

Fluoranthene 202 203, 200, 101 Phenanthrene- D10

Pyrene 202 203, 200, 101 Chrysene- D12

Benz[a]anthracene 228 229, 226, 114 Chrysene- D12

Chrysene- D12 240 n/a n/a

Chrysene 228 229, 226, 114 Chrysene- D12

Benzo[b]fluoranthene 252 253, 250, 126 Perylene- D12

Benzo[k]fluoranthene 252 253, 250, 126 Perylene- D12

Benzo[a]pyrene 252 253, 250, 126 Perylene- D12

Perylene- D12 264 n/a n/a

Indeno[1,2,3-cd] pyrene 276 277, 274, 138 Perylene- D12

Dibenz[a,h]anthracene 278 279, 276, 139 Perylene- D12

Benzo[ghi]perylene 276 277, 274, 138 Perylene- D12

(1) Quantitation is performed using the single ion listed above as the quantitation ion. The secondary

ions are included so that an abbreviated mass spectrum can be established for identity confirmation.
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Table 7. Precision, Accuracy and Bias for 16 PAHs (1,3)

Compound

(alphabetically)

Range For

Calculation(2)

(μg/sample)

Bias (B) Overall Accuracy (A)

95% Upper 

Confidence Limit 

of Accuracy

Acenaphthene 0.25 - 75 -0.162 0.057 0.256 0.284

Acenaphthylene 25 - 75 -0.217 0.058 0.312 0.370

Anthracene 0.25 - 75 -0.243 0.058 0.338 0.367

Benz[a]anthracene 0.25 - 75 -0.139 0.059 0.236 0.265

Benzo[b]fluoranthene 0.25 - 75 -0.126 0.059 0.223 0.252

Benzo[k]fluoranthene 0.25 - 75 -0.170 0.060 0.268 0.298

Benzo[ghi]perylene 0.25 - 75 -0.140 0.072 0.258 0.293

Benzo[a]pyrene 0.75 - 75 -0.235 0.060 0.334 0.367

Chrysene 0.25 - 75 -0.147 0.057 0.241 0.269

Dibenz[a,h]anthracene 0.25 - 75 -0.133 0.076 0.257 0.295

Fluoranthene 0.25 - 75 -0.126 0.060 0.225 0.254

Fluorene 0.25 - 75 -0.151 0.057 0.245 0.273

Indeno[1,2,3-cd]pyrene 0.25 - 75 -0.195 0.070 0.310 0.344

Naphthalene 0.25 - 75 -0.143 0.062 0.245 0.275

 Phenanthrene 0.25 - 75 -0.137 0.056 0.229 0.257

Pyrene 0.25 - 75 -0.138 0.065 0.245 0.277

Precision

(1) Backup Data Report [1]; with pump error correction

(2) Range for calculation is the range over which the precision, bias, and accuracy were calculated. Range studied

was 0.25 to 75.0 μg/sample for all 16 PAHs.

(3) Data was not included where desorption was <75% or >125%; therefore:

Acenaphthylene: Omits 4 lower levels (0.25-7.5)

Benzo[a]pyrene: Omits lowest level (0.25)
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NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

Table 8. Limits of Detection and Average Percent Recoveries by Concentration Level 

(μg/sample) (1,3)

Compound

(alphabetically)

LOD(2)

Avg % 

Recovery at 

0.25 

(μg/sample)

Avg % 

Recovery 

at 0.75 

(μg/sample)

Avg % 

Recovery at 

2.50 

(μg/sample)

Avg % 

Recovery 

at 7.50 

(μg/sample)

Avg % 

Recovery at 

25.0 

(μg/sample)

Avg % 

Recovery at 

75.0 

(μg/sample)

Acenaphthene 0.08 97.1 92.6 96.1 87.6 93.8 83.8

Acenaphthylene 0.08 64.7 71.0 57.9 67.5 87.0 78.3

Anthracene 0.08 75.7 83.1 89.0 86.3 97.4 84.1

Benz[a]anthracene 0.08 86.7 86.1 94.7 92.1 103 86.4

Benzo[b]fluoranthene 0.08 92.8 91.6 95.7 91.7 104 87.4

Benzo[k]fluoranthene 0.1 83.0 86.3 101 91.0 97.5 86.7

Benzo[ghi]perylene 0.08 87.9 86.0 104 102 109 91.7

Benzo[a]pyrene 0.1 70.1 76.5 85.8 87.4 103 85.1

Chrysene 0.08 96.9 92.5 99.7 86.4 94.3 85.3

Dibenz[a,h]anthracene 0.1 86.7 87.3 105 102 109 89.0

Fluoranthene 0.08 95.1 92.6 97.8 91.9 105 87.4

Fluorene 0.08 95.7 92.3 98.2 90.8 97.4 85.0

Indeno[1,2,3-cd]pyrene 0.2 80.5 81.4 86.1 90.9 103 91.0

Naphthalene 0.1 110 96.3 101 87.6 95.1 85.7

Phenanthrene 0.08 97.1 92.3 99.6 90.1 98.6 86.3

Pyrene 0.08 92.3 91.4 92.7 89.3 99.1 86.2

(1) Backup Data Report [1]

(2) Limit of Detection in μg/sample determined from calibration curve using the method of Burkart [4].

Average percent recovery for seven replicates at each concentration level.

(3) Recoveries less than 75% are in bold text. Data from those levels were not used in accuracy, precision and bias 

calculations found in Table 7.

The data presented in Table 9 is from the user check and does not contain a correction for pump error. It is 

therefore Sr. This experiment was run at a different time by a different lab than the data presented in Table 

7. The samples were spiked at different ranges and as a liquid injection with no air pulled through. 
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NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

Table 9. Method Bias, Accuracy and Precision (1,2)

Compound

(alphabetically)

Range For

Calculation(2)

(μg/sample)

Bias 

(B)

Precision 

(Sr)

Accuracy 

(A)

95% Upper 

Confidence Limit 

of Accuracy

Acenaphthene 0.5-20 -0.012 0.066 0.131 0.178

Acenaphthylene 0.5-20 -0.113 0.077 0.240 0.295

Anthracene 0.5-20 -0.207 0.0972 0.367 0.436

Benz[a]anthracene 0.5-20 -0.207 0.095 0.363 0.431

Benzo[b]fluoranthene 0.5-20 -0.207 0.080 0.338 0.395

Benzo[k]fluoranthene 0.5-20 -0.042 0.062 0.144 0.188

Benzo[ghi]perylene 0.5-20 -0.018 0.062 0.127 0.172

Benzo[a]pyrene 2-20 -0.141 0.081 0.273 0.343

Chrysene 0.5-20 0.019 0.057 0.117 0.159

Dibenz[a,h]anthracene 0.5-20 -0.097 0.118 0.290 0.374

Fluoranthene 0.5-20 -0.16 0.087 0.302 0.364

Fluorene 0.5-20 0.025 0.105 0.212 0.287

Indeno[1,2,3-cd]pyrene 0.5-20 -0.217 0.144 0.453 0.555

Naphthalene 0.5-20 -0.038 0.071 0.157 0.213

Phenanthrene 0.5-20 -0.034 0.062 0.138 0.188

Pyrene 0.5-20 0.082 0.055 0.174 0.213

1) These data are from the user check performed after method development.

2) All samples at the lowest spike level of Benzo[a]pyrene (0.5 μg) gave results < 75% and were excluded from the

calculation. Range studied was 0.5-20 μg/sample for all PAHs.
PAH in Air by GC-MS SIM: METHOD 5528, Issue 1, dated 10 November 2021 - Page 14 of 15 

NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

Figure 1. OVS-7 Sampler
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NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

Figure 2. Sample Chromatogram. Identification of GC peaks is given in Table 4 by retention time.