NIOSH Manual of Analytical Methods (NMAM) 5th Edition 

BACKUP DATA REPORT 

 NIOSH Method No. 5528

Title: Polynuclear aromatic hydrocarbons in air by GC-MS SIM 

Analyte: Naphthalene, Acenaphthylene, Acenaphthene, Fluorene, Phenanthrene, 

Anthracene, Fluoranthene, Pyrene, Benz[a]anthracene, Chrysene, 

Benzo[b]fluoranthene, Benzo[k]fluoranthene, Benzo[a]pyrene, Indeno[1,2,3-cd]pyrene, 

Dibenz[a,h]anthracene, Benzo[g,h,i]perylene 

Author: Dawn Farwick

Developer: Method developed by DataChem under contract CDC-200-2001-0800

 Date: October 6, 2021

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. 
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I. INTRODUCTION AND BACKGROUND 

Polynuclear Aromatic Hydrocarbons (PAHs) are some of the most widespread environmental 

contaminants. PAHs are formed by virtually all types of combustion, with possible sources of PAH 

exposure including automobile exhaust, factory smokestack exhaust, and even the family backyard 

barbecue. 

Most exhaust contains a whole host of various PAH compounds, and for this reason it has 

historically been difficult to use epidemiological data to determine toxicity of individual polynuclear 

aromatic hydrocarbons. Not all PAHs have the same toxicity; some are relatively harmless compared 

to others. Recent science has focused on benzo[a]pyrene as perhaps the most toxic of these 16 

PAHs. Benzo[a]pyrene is metabolized in mammalian tissue to a highly carcinogenic bay-region diol 

epoxide [1]. Much work has yet to be done on the toxicity of individual PAHs, but it is nonetheless 

clear that exposure to PAHs is detrimental to human health. Because of their different toxic natures, it 

is important to have analytical methods which can reliably detect and differentiate PAHs. 

There are several published methods for the analysis of PAHs in air. NIOSH Method 5506 

uses a filter and an XAD-2 sorbent tube followed by HPLC with fluorescence and/or UV detection [2].

NIOSH Method 5515 uses the same sampling device followed by gas chromatography with an FID 

detector [3]. 

The introduction of the OSHA Versatile Sampler (OVS) in the 1980’s provided an opportunity 

for easier sampling of workplace exposures and a greater capacity for trapping organic vapors and 

submicron particles [4]. The sampling device used in NIOSH Methods 5506 and 5515 is a filter 

cassette, spacer ring, and sorbent tube, all connected in series. This multi-part device is somewhat 

bulky and inconvenient to use compared to the one-piece OVS sampler. Furthermore, the sorbent 

tube of Method 5506/5515 contains about one-third the sorbent of the OVS tube [2,3]. 

Due to the relatively broader peaks inherent in HLPC (when compared to GC), it is 

sometimes more difficult to properly resolve isomeric pairs when analyzing by HPLC. 

Benzo[e]pyrene, for example, was included in the Method 5506 target compound list not because it 

was an analyte of concern, but rather because it was necessary to demonstrate that the HPLC 

system could separate the relatively innocuous benzo[e]pyrene from its highly toxic cousin 

benzo[a]pyrene. GC analysis has sharper peaks and does not have this problem with peak resolution, 

making it a preferred choice in analytical instrumentation for this class of compounds. HPLC was 

used because of the sensitivity using fluorescence detection. Since then, GC/MS advances have 

allowed comparable limits of detection. 

Considering the above-mentioned issues, a method using the more compact OVS sampling 

device with more specific analytical analysis was investigated. Gas chromatography/mass 

spectrometry (GC/MS) was chosen for study because of its ability to use the mass-spectral fingerprint 

for reliable identification even in the most complex of matrices. The use of selected-ion monitoring 

(SIM), scanning as many as ten ions at a time, could give detection limits rivaling those of Methods 
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5506/5515 while still collecting enough mass spectral data to obtain a reliable mass spectrum for 

identity confirmation. The remainder of this report documents the development of a method for 

analysis of PAHs using an OVS sampler followed by GC/MS SIM analysis. This method has been 

assigned the number NIOSH 5528 [5].

II. REAGENTS AND MATERIALS 

Presented in Table 1 is the list of reagents and solvents used for this method development. 

Table 1. List of Chemicals 

Chemical Vendor CAS # Purity Lot # 

Methylene Chloride Burdick & Jackson 75-09-2 

High 

Purity C0173 

Naphthalene-D8 Cambridge Isotope Labs 1146-65-2 99% P-7172 

Acenaphthene-D10 MSD Isotopes 15067-26-2 98.7% 5693-M 

Phenanthrene-D10 Cambridge Isotope Labs 1517-22-2 98% P-7101 

Chrysene-D12 Cambridge Isotope Labs 1719-03-5 98% P-6241 

Perylene-D12 Cambridge Isotope Labs 1520-96-3 98% P-8438 

PAH mixture Absolute Standards (10007) Various N/A 111804 

III. SELECTION OF SAMPLING MEDIA 

After some preliminary laboratory studies of samplers using various media (XAD-2, 

Chromosorb-6, Florisil®, XAD-7, and Tenax), it was determined that an OVS sampler with XAD-7 

would be the most appropriate sampler [6]. 

OVS Sampler 

 The OVS device used has a glass fiber filter (GFF) of 13-mm diameter with front and backup 

sections of sorbent separated by polyurethane foam. Devices used in the study were purchased from 

SKC (OVS-7, catalog number 226-57). Figure 1 is a picture of this device [7]. 

Figure 1. OVS-7 Sampler 
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Most published analytical methods for PAHs do not specify the use of XAD-7, favoring 

instead XAD-2 or polyurethane foam (PUF). The XAD-2 resin is a styrene divinylbenzene polymer, 

and the XAD-7 resin is an acrylate-based polymer. XAD-2 has polyphenyl alkane breakdown 

products which can interfere with the detection of PAHs, especially alkyl substituted PAHs. XAD-7, 

however, presented a cleaner chromatographic background than the XAD-2 and showed good 

desorption efficiency. XAD-7 has a dipole moment of 1.8, pore size of 90 Angstroms (mesh 20 to 60), 

and a surface area of 450 m2/gram.[8]

IV. USE OF SELECTED ION MONITORING (SIM) AND INSTRUMENT CONDITIONS 

This GC/MS method can be run in full-scan mode, monitoring every ion ranging from massto-charge 35 through 500. In fact, full scan mode would be the most desirable approach if there is a 

need to identify PAH components outside the target-compound list. There are some instances in 

which alkyl-substituted PAHs may be of more concern than the parent PAH. As more toxicity data 

become available over the coming years, it may be needed to expand the analyte list or at least to 

use mass-spectral data for tentative identifications of non-target analytes. The only disadvantage to 

running in full-scan mode would be a higher limit of detection, but this method is written with the 

assumption that the emphasis lies on obtaining the lowest reasonable detection limit and that there is 

no need to identify PAH components outside the list of target analytes. 

 This method specifies the use of SIM and the monitoring of as many as ten ions in a single 

scan. The extra ions are included so that an abbreviated mass spectrum may be obtained to provide 

additional data for confirmation (or rejection) of the PAH identification. It is often assumed by analysts 

that this choice to monitor more ions represents a major trade-off in terms of sensitivity versus the 

alternative of monitoring one ion only. This assumption seems logical. If the mass spectrometer 

spends half a second scanning ten ions, then it ought to be able to give a ten-fold increase in 

sensitivity if it were to spend that same half-second scanning a single ion instead of ten. The 

assumption is logical, but it is not supported by the data, at least not on the instrumentation used for 

method development (Agilent 5972 and 5973). In truth, there is no significant difference in sensitivity 

between monitoring a single ion versus ten. 

A test was performed to see what degree of sensitivity improvements can be made by 

running in SIM mode over full scan. A PAH standard at 2 μg/mL was injected four times at each of 

three different operating conditions. The three operating conditions were full scan, SIM mode 

monitoring one ion only, and SIM mode monitoring about 9 ions. The samples were injected in 

random, interspersed order. 

The results, displayed in Table 2 below, show that a two-fold increase in sensitivity can be 

gained by using SIM mode over full scan, as measured by peak areas. It further shows that it does 

not make any difference in dropping to one ion versus nine; an interesting result because one would 
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expect that a greater dwell time (or the same dwell time but many more cycles per second) would 

result in greater sensitivity. It does not. 

 

Table 2. Areas of Naphthalene Peaks in Three SIM/Scan Conditions 

 Full Scan Mode SIM Mode 1 ion SIM Mode 9 ion 

Replicate 1.53 scans/sec 20 cycles/sec 2.4 cycles/sec 

#1 325,088 856,985 726,988 

#2 376,578 649,654 717,072 

#3 382,163 794,097 637,035 

#4 298,324 573,070 793,673 

 

Average 345,538 718,452 718,692 

An additional experiment was performed to measure sensitivity variations in a slightly 

different manner. It was theorized that using peak areas to measure sensitivity was the best 

approach. To test for this, consecutively lower concentration standards were analyzed to check for a 

difference in sensitivity. No difference was observed. There was no concentration level at which the 

one-ion analysis showed a peak when the 9-ion analysis did not. Both sets of SIM parameters 

reached the point where signal-to-noise levels were less than two at the same concentration level. 

This experiment confirmed that there is no increase in sensitivity by monitoring a single ion rather 

than nine. 

 A few experiments were performed in which the dwell time was varied from 10 to 800 

milliseconds (ms). No significant difference in sensitivity was noted from one parameter to another. 

The only notable difference was the extreme case of 800-ms dwell times resulted in poor peaks 

shapes from too few scans to define the GC peak. The 30-ms dwell time gave the best peak shapes, 

which agrees with the manufacturer’s recommendation for SIM analysis of more than three ions. 

Instrument Conditions 

The systems used consisted of an Agilent Technologies Model 5890 gas chromatograph with 

a Model 5972 mass spectrometer or an Agilent Technologies Model 6890 gas chromatograph with a 

Model 5973 mass spectrometer. The column used was a fused silica capillary column (DB-5ms, 30m 

× 0.32mm I.D., 0.5 μm film). 

GC programming was as follows: 

o Temperature program: 50 C for one minute; 25 C/minute until 130 C; 

13 C/minute until 240 C; 22 C/minute until 300 C; hold for 7 minutes 

o Injector temperature: 280 C 

o MS transfer line: 310 C 

o Injection volume: 1 μL; splitless time of 0.5 minutes 

o constant pressure at 1.3 mL/minute 

 
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Chromatogram Analysis

A list of typical retention times using the conditions described above is shown in Table 3. 

Figure 2 displays a typical chromatogram when the previously described conditions are employed. 

Refer to Table 3 for elution order of the peaks. The retention times will vary according to the age of 

the individual GC columns. For example, a proper injection port maintenance normally includes 

trimming a few inches from the front of the column, thus an older column will be somewhat shorter 

than a new column and will have earlier elution times. 

Table 3. Typical Retention Times. 

Compound Approximate Retention 

Time (minutes) 

Naphthalene 6.28

Acenaphthylene 8.74

Acenaphthene 9.04

Fluorene 9.95

Phenanthrene 11.69 

Anthracene 11.79 

Fluoranthene 13.82 

Pyrene 14.17 

Benz[a]anthracene 15.90 

Chrysene 15.96 

Benzo[b]fluoranthene 17.83 

Benzo[k]fluoranthene 17.89 

Benzo[a]pyrene 18.58 

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

Dibenz[a,h]anthracene 22.04 

Benzo[ghi]perylene 22.95 
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Figure 2. Typical Chromatogram 

The mass spectrometer is operated in Selected-Ion Monitoring (SIM) mode using a dwell time of 30 

ms for each ion. Six different SIM windows are used as shown in Table 4. Table 5 lists ions to use for 

quantitation, ions for spectral confirmation and internal standard references.

Table 4. SIM Parameters. 

 Start Time (minutes) Dwell 

Time (ms) Ions 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
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Table 5. Quantitation Ions, Secondary Ions and Internal Standard References. 

Compound Quantitation ion Secondary Ions Internal Standard Ref. 

Naphthalene 128 129, 127, 126, 64 Naphthalene-D8

Acenaphthylene 152 153, 150, 76 Acenaphene-D10

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

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

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 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

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

Naphthalene- D8 136 N/A N/A 

Acenaphene-D10 164 N/A N/A 

Phenanthrene-D10 188 N/A N/A 

Chrysene-D12 240 N/A N/A 

Perylene-D12 264 N/A N/A 

V. CALIBRATION AND SAMPLE PREP

Preparation of Primary Stock and Internal Standard Solutions 

The desorption fluid was methylene chloride (high purity). Standards were prepared by 

spiking the appropriate volume of Absolute Standards mixture 10007 (or a dilution of this solution). An 

internal standard solution consisting of naphthalene-D8, acenaphthene-D10, phenanthrene-D10, 

chrysene-D12, and perylene-D12 was prepared at a concentration of 2000 μg/mL in methylene 

chloride. Analysis presumably could be performed using a single internal standard rather than five, 

but with so many analytes there is a benefit in having an internal standard for each section of the 

chromatogram. These deuterated internal standards are readily available commercially. 

Calibration

 To quantify the concentrations of target analytes present in samples, a calibration curve is 

constructed with nine working standards (six concentration levels, with two replicates for each of the 

lower three levels) covering the anticipated concentration range of the samples. The working 

standards are prepared by spiking known amounts of the PAH mixture (or a dilution of it) onto the 
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filter and front resin of a fresh OVS tube. Two milliliters of methylene chloride are added, and the 

working standards are desorbed for at least thirty minutes in an ultrasonic bath. An aliquot of the 

desorbate is placed in a GC vial and spiked with the internal standard solution to yield a concentration 

of 1.0 μg/mL for each internal standard. After analyzing the standards, a calibration graph is 

generated for each analyte by plotting the normalized analyte response (peak area of analyte divided 

by the peak area of the internal standard on the same chromatogram) on the y-axis vs. concentration 

of analyte on the x-axis. 

 Since this method specifies the use of media standards, there is no need to perform 

desorption efficiency studies. 

Sample Preparation 

The filter and front section of the OVS-7 tube are placed into an amber 4-mL screw-top vial. 

The backup resin (including foam plug which separates the front resin from the back) is placed in a 

separate vial. Two milliliters of methylene chloride are then added to each vial and the vials are 

desorbed in an ultrasonic bath for at least 30 minutes. 

VI. SAMPLER CAPACITY AND BREAKTHROUGH STUDY 

The OVS devices are recommended for a sampling rate of 1 liter per minute, which differs 

from the 2-liter-per-minute rate specified in other NIOSH PAH methods. It was felt there was some 

benefit in keeping the same sample volume used in other methods to allow for a comparison of the 

methods/samplers. The OVS tubes were therefore sampled at 1 liter per minute for 4, 8, 12, 16, 20, 

and 24 hours. 

It is recommended that the spiking level be equal to twice the PEL [9]. Currently, there are 

not PEL values for all PAHs, but several of them have a PEL of 0.2 mg/m3. Assuming this PEL 

applies for all analytes, and further assuming a typical air volume for this method would be about 

1000 liters of air (8 hours × 2 L/min × 60 min/hr = 960 L), the amount to spike on each filter was 

determined to be 400 μg of each PAH. 

400 μg/ 1000 L × 1000 L / m3 × 1 mg / 1000 μg = 0.4 mg/m3. 

This was accomplished by spiking 200 μL of the Absolute Standards mix #10007 which was 

at a concentration of 2000 μg/mL. It was not advisable to spike more than 25 μL because of potential 

problems with the spiking solution pooling around the edge of the filter and being aspirated around 

the filter, resulting in anomalous breakthrough numbers, so spiking was accomplished by spiking 25 

μL at a time, then waiting for the solvent to dry before spiking again, 8 times, until the full amount was 

delivered. Six replicates were made at each level. 
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Figures 3 through 7 show graphical representations of the breakthrough characteristics of the 

first five analytes. A tabular summary of the entire study is presented in Tables 6-11.

Figure 3. Naphthalene on OVS with XAD-7.

Naphthalene

0

10

20

30

40

50

60

70

80

90

100

110

4, 8, 12, 16, 20 and 24 hours

% in backup

%recovery

 

Figure 4. Acenaphthylene on OVS with XAD-7.

Acenaphthylene

0

10

20

30

40

50

60

70

80

90

100

4, 8, 12, 16, 20 and 24 hours

% in backup

%recovery
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Figure 5. Acenaphthene on OVS with XAD-7.

Acenaphthene

0

10

20

30

40

50

60

70

80

90

100

4, 8, 12, 16, 20 and 24 hours

% in backup

%recovery

Figure 6. Fluorene on OVS with XAD-7.

Fluorene

0

10

20

30

40

50

60

70

80

90

100

4, 8, 12, 16, 20 and 24 hours

% in backup

%recovery
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Figure 7. Phenanthrene on OVS with XAD-7.

Phenanthrene

0

10

20

30

40

50

60

70

80

90

100

4, 8, 12, 16, 20 and 24 hours

% in backup

%recovery

Table 6. Breakthrough at Four Hours 

(average of 6 replicates; units of concentration are μg/sampler) 

Analyte Filter 

Front 

resin 

Back 

resin cassette total 

% in 

backup %rec 

Naphthalene 1.95 394 1.07 0.0740 397 0.3 99.3

Acenaphthylene 3.78 387 0.616 0.0543 392 0.2 97.9

Acenaphthene 4.87 381 0.754 0.0743 386 0.2 96.6

Fluorene 63.1 324 0.694 1.88 390 0.2 97.5

Phenanthrene 127 247 0.548 3.15 378 0.1 94.4

Anthracene 200 178 0.412 4.79 383 0.1 95.7

Fluoranthene 201 195 0.460 4.99 401 0.1 100

Pyrene 173 163 0.435 4.54 341 0.1 85.3

Benzo[a]anthracene 185 140 0.211 4.06 329 0.1 82.2

Chrysene 225 173 0.541 6.33 405 0.1 101

Benzo[b]fluoranthene 191 144 0.232 3.80 339 0.1 84.6

Benzo[k]fluoranthene 205 155 0.445 4.74 365 0.1 91.4

Benzo[a]pyrene 195 145 0.273 4.22 345 0.1 86.3

Indeno[1,2,3-cd]pyrene 210 154 0.316 4.11 369 0.1 92.2

Dibenz[a,h]anthracene 218 159 0.241 4.52 382 0.1 95.5

Benzo[ghi]perylene 221 163 0.326 4.77 389 0.1 97.3
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Table 7. Breakthrough at Eight Hours 

 (average of 6 replicates; units of concentration are μg/sampler) 

Analyte Filter

Front 

resin

Back 

resin cassette total

% in 

backup %rec

Naphthalene 1.26 396 1.40 0.134 399 0.4 99.7

Acenaphthylene 3.86 368 0.871 0.193 373 0.2 93.3

Acenaphthene 5.30 375 1.07 0.280 382 0.3 95.4

Fluorene 54.5 325 0.869 1.15 381 0.2 95.3

Phenanthrene 115. 255 0.668 1.71 372 0.2 93.1

Anthracene 204. 172 0.506 2.71 380 0.1 95.0

Fluoranthene 207 191 0.586 2.83 401 0.1 100

Pyrene 178 162 0.545 2.59 343 0.2 85.7

Benzo[a]anthracene 191 129 0.244 1.83 322 0.1 80.4

Chrysene 242 165 0.678 3.95 411 0.2 103 

Benzo[b]fluoranthene 202 136 0.257 1.84 340 0.1 85.0

Benzo[k]fluoranthene 221 147 0.511 2.74 372 0.1 92.9

Benzo[a]pyrene 207 136 0.348 2.22 345 0.1 86.2

Indeno[1,2,3-cd]pyrene 221 144 0.388 2.46 368 0.1 92.1

Dibenz[a,h]anthracene 231 148 0.286 2.19 382 0.1 95.4

Benzo[ghi]perylene 232 152 0.427 2.47 387 0.1 96.7

 

 Table 8. Breakthrough at Twelve Hours 

 (average of 6 replicates; units of concentration are μg/sampler) 

Analyte Filter

Front 

resin

Back 

resin cassette total

% in 

backup %rec

Naphthalene 0.888 389 3.57 0.328 394 0.9 98.5

Acenaphthylene 1.97 310 2.21 0.116 314 0.7 78.5

Acenaphthene 2.84 366 2.90 0.159 372 0.8 93.0

Fluorene 34.0 327 3.17 1.51 365 0.9 91.3

Phenanthrene 78.5 269 2.91 3.18 353 0.8 88.3

Anthracene 170 173 1.53 5.56 350 0.4 87.6

Fluoranthene 156 191 1.66 5.43 355 0.5 88.7

Pyrene 150 168 1.60 5.56 326 0.5 81.4

Benzo[a]anthracene 172 131 0.966 4.80 308 0.3 77.0

Chrysene 199 151 1.50 7.76 359 0.4 89.8

Benzo[b]fluoranthene 201 149 1.08 5.30 357 0.3 89.3

Benzo[k]fluoranthene 206 153 1.32 6.64 368 0.4 91.9

Benzo[a]pyrene 191 144 1.19 5.94 343 0.3 85.7

Indeno[1,2,3-cd]pyrene 194 154 1.35 5.86 355 0.4 88.6

Dibenz[a,h]anthracene 197 151 1.22 6.02 355 0.3 88.6

Benzo[ghi]perylene 199 156 1.45 6.48 363 0.4 90.8
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Table 9. Breakthrough at Sixteen Hours 

(average of 6 replicates; units of concentration are μg/sampler) 

Analyte Filter

Front 

resin

Back 

resin cassette total

% in 

backup %rec

Naphthalene 1.22 413 1.38 0.147 415 0.3 104 

Acenaphthylene 2.83 315 0.122 0.102 319 0.0 79.6

Acenaphthene 4.47 389 0.194 0.157 394 0.0 98.5

Fluorene 39.30 350 0.189 2.34 392 0.0 97.9

Phenanthrene 84.1 288 0.228 4.44 376 0.1 94.1

Anthracene 183 181 0.169 8.71 373 0.0 93.1

Fluoranthene 162 207 0.200 8.17 378 0.1 94.4

Pyrene 159 179 0.228 8.06 346 0.1 86.6

Benzo[a]anthracene 181 136 0.089 8.86 325 0.0 81.3

Chrysene 216 160 0.269 11.5 388 0.1 97.1

Benzo[b]fluoranthene 216 163 0.120 10.5 389 0.0 97.4

Benzo[k]fluoranthene 227 167 0.213 11.3 405 0.1 101

Benzo[a]pyrene 203 153 0.140 10.5 367 0.0 91.7

Indeno[1,2,3-cd]pyrene 215 165 0.215 11.0 391 0.1 97.7

Dibenz[a,h]anthracene 217 159 0.133 11.0 388 0.0 97.0

Benzo[ghi]perylene 222 170 0.242 11.7 404 0.1 101

 Table 10. Breakthrough at Twenty Hours 

 (average of 6 replicates; units of concentration are μg/sampler) 

Analyte Filter

Front 

resin

Back 

resin cassette total

% in 

backup %rec

Naphthalene 1.87 389 3.67 0.191 394 0.9 98.6

Acenaphthylene 1.72 297 0.431 0.288 300 0.1 75.0

Acenaphthene 2.80 368 0.585 0.439 371 0.2 92.9

Fluorene 35.0 340 0.213 1.05 377 0.1 94.2

Phenanthrene 75.4 301 0.0973 1.58 378 0.0 94.6

Anthracene 180 196 0.0587 3.18 378 0.0 94.6

Fluoranthene 163 225 0.0480 3.18 391 0.0 97.9

Pyrene 151 189 0.0460 3.07 343 0.0 85.8

Benzo[a]anthracene 182 149 0.0137 3.11 335 0.0 83.7

Chrysene 219 172 0.0470 5.21 396 0.0 99.0

Benzo[b]fluoranthene 197 166 0.0237 3.57 367 0.0 91.7

Benzo[k]fluoranthene 210 170 0.0690 4.51 385 0.0 96.2

Benzo[a]pyrene 197 159 0.0403 3.88 360 0.0 90.1

Indeno[1,2,3-cd]pyrene 228 202 0.0783 4.31 434 0.0 109 

Dibenz[a,h]anthracene 234 196 0.0550 4.46 434 0.0 109 

Benzo[ghi]perylene 237 208 0.0847 4.91 450 0.0 112
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 Table 11. Breakthrough at Twenty-Four Hours 

 (average of 6 replicates; units of concentration are μg/sampler) 

Analyte Filter

Front 

resin

Back 

resin cassette total

% in 

backup %rec

Naphthalene 0.537 405 2.82 0.0937 409 0.7 102

Acenaphthylene 0.923 296 0.139 0.0280 297 0.0 74.2

Acenaphthene 1.66 382 0.223 0.0467 384 0.1 96.1

Fluorene 34.6 350 0.110 1.32 386 0.0 96.6

Phenanthrene 77.5 310 0.0810 2.61 390 0.0 97.5

Anthracene 184. 197 0.0400 5.04 387 0.0 96.6

Fluoranthene 162 235 0.0730 5.04 402 0.0 101 

Pyrene 154 197 0.0733 4.87 356 0.0 89.1

Benzo[a]anthracene 187 150 0.0237 4.82 338 0.0 84.5

Chrysene 229 172 0.0833 7.45 408 0.0 102

Benzo[b]fluoranthene 201 167 0.0350 5.44 373 0.0 93.3

Benzo[k]fluoranthene 217 170 0.116 6.63 394 0.0 98.5

Benzo[a]pyrene 202 158 0.0517 5.91 365 0.0 91.4

Indeno[1,2,3-cd]pyrene 244 199 0.120 6.65 450 0.0 112

Dibenz[a,h]anthracene 252 193 0.0837 7.01 452 0.0 113

Benzo[ghi]perylene 258 207 0.132 7.63 474 0.0 118

A noteworthy observation is the fact that recovery of acenaphthylene on the overall sampler 

drifts downward over time to below 80%. The subsequent section addresses this observation 

in more detail. 

VII. THE TROUBLE WITH ACENAPHTHYLENE 

As can be seen in Figure 4 above, recovery of acenaphthylene on the OVS-7 sampler 

decayed over time to less than 80%. Recovery of 70-75% is beyond the range of what one would 

expect to be written off as experimental error. 

Since there is no appreciable amount (above the LOD) of analyte showing up in the backup 

section, it is assumed that the acenaphthylene is not being drawn out the back end of the sampler. A 

more logical hypothesis is that this analyte is undergoing oxidation or photolysis over time. A full-scan 

analysis of the desorbate from the front resin section from one of the 24-hour samplers shows 

evidence that oxidation reactions are indeed taking place. 

Figure 8 shows the structure of acenaphthylene. Figure 9 shows the probable chemical 

structure of one of the observed breakdown products. The identity of this breakdown product is based 

on interpretation of the mass spectral data utilizing a library search of the NBS spectral database. The 

chromatogram is presented in Figure 10. 
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Figure 8. Chemical Structure of Acenaphthylene. 

Figure 9. Structure of Degradation Product at RT 10.780 minutes (Acenaphthenone) 

Figure 10. Full Scan Chromatogram of an OVS/XAD-7 Sampled for 24 Hours 

An examination of these full scan data gives evidence that acenaphthylene may in fact be 

degrading to one or more reaction products during sampling. The evidence is not conclusive; for 

example, some of these breakdown products appear to be fluorene derivatives, yet fluorene recovery 

is not significantly inhibited over time. The presence of acenaphthenone as a breakdown product 

does, however, provide substantiation that acenaphthylene loss may be a result of degradation 
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reactions during the sampling event even though the precise nature of the acenaphthylene 

degradation remained unknown. A brief experiment was conducted to determine whether the 

degradation of acenaphthylene could be avoided by protecting the sampler from light. Six OVS-7 

tubes were spiked with acenaphthylene and sampled for 24 hours under the same conditions used in 

the breakthrough study. Another six devices were then spiked with acenaphthylene and protected 

from light for the 24-hour sampling time. The results were somewhat inconclusive, with the protected 

tubes showing slightly better acenaphthylene recovery (about 14% better); however, both batches 

showed evidence of breakdown. For example, reaction product acenaphthenone was detected in 

both the protected and the unprotected sampling devices. 

 Regardless of the impact of light, it is not realistic to expect that an industrial hygienist in the 

field would be able to protect the OVS tube from light during a sampling event, and for this reason no 

further investigation into the causes of acenaphthylene degradation was undertaken. End users of the 

data should understand that breakdown of this analyte does occur during sampling and that reported 

concentrations of acenaphthylene will likely be biased somewhat low. 

 Because of these results/observations, an 8-hr sampling time is the maximum recommended. 

VIII. LIMIT OF DETECTION AND QUANTITATION STUDY 

The limit of detection (LOD) for this method lies somewhere between 0.08 and 0.4 

μg/sample. It is possible to see GC peaks for most analytes at a level below 0.08 μg/sample, but 

there are some problems inherent with going too low in the calibration range. One results from the 

ubiquitous nature of PAHs; namely that some PAHs will often be detected in the media blanks at 

levels very much below 0.08 μg/sample. Another problem is that peak shapes tend to deteriorate at 

extremely low concentration levels. This poses a problem particularly for isomeric pairs that elute 

closely together. These include benzo[b]- and benzo[k]fluoranthene as well as benz[a]anthracene and 

chrysene. The worst of these is the benz[a]anthracene/chrysene pair, which becomes increasingly 

difficult to separate at the lower levels and increasingly distorted in terms of peak-area proportionality. 

Indeno[1,2,3-cd]pyrene is also problematic because its peak (base peak of m/z = 276) has a hump 

produced by the dibenz[a,h]anthracene peak, which has a 276 ion as one of the minor ions in its 

spectrum. At the higher levels this hump can be distinguished and excluded from the integrated area. 

In the lower levels it cannot. 

Figures 11 through 14 demonstrate some of these problems, which arise from calibrating at 

too low a concentration level. 
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Figure 11. Benz[a]anthracene and Chrysene in a High Standard 

Figure 12. Benz[a]anthracene and Chrysene in a Low Standard 
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Figure 13. Indeno[1,2,3-cd]pyrene in a High Standard 

Figure 14. Indeno[1,2,3-cd]pyrene in a Low Standard 

Based upon the experience gained from method development experiments and from analysis 

of a moderate number of field samples submitted by NIOSH during the term of the method 

development, it has been determined that the optimal LOD target is about 0.1 μg/sample for most of 

the PAHs on the target analyte list. Using calibration standards prepared at concentrations of 0.08, 

0.12, 0.4, 4, 10 and 40 μg/sample and applying the Burkart Method [10] for statistical calculations, an 

LOD ranging from 0.08 to 0.4 μg/sample is generally obtainable for the various analytes. The 

resulting limit of quantitation (LOQ) is defined as 3.33 times the LOD, with results in LOQ values 

ranging from 0.3 to 1 μg/sample. The LOD and LOQ will vary from batch to batch depending on the 

statistics of each individual calibration curve. 

IX. LONG-TERM STABILITY STUDY 

This experiment is designed to assess the stability of target analytes over time. Forty-three 

OVS tubes were spiked with 4.0 μL of the PAH mixture (Absolute Standards mix 10007 at 2000 
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μg/mL), which corresponded to a level of about 30 times the LOQ, or about 8 μg/sample. Seven of 

these samplers were desorbed immediately and analyzed the same day. The remaining samplers 

were divided into two groups. One group was stored at room temperature and the other refrigerated 

at 4 C. 

After seven days, six of the refrigerated samples and six of the ambient-stored samples were 

desorbed and analyzed. On Days 10, 14, and 21, three of each were desorbed and analyzed, and on 

Day 30, six of each were desorbed and analyzed. 

The results are shown in Tables 12-24. All analytes are stable for up to thirty days from 

sampling as all average recoveries are greater than 80%. Refrigeration is not required for stability. 

However, it should be noted that at nearly every sampling point, the recovery from the refrigerated 

samples is a bit better. Therefore, it is recommended that the samples be refrigerated upon arrival at 

the laboratory. 

Even the problematic acenaphthylene was shown to be stable under storage for up to thirty 

days. Unlike the precision and accuracy study (discussed in the subsequent section) in which air was 

drawn through the samplers for four hours prior to analysis, these stability-study samplers were 

spiked and then immediately capped for storage. The fact that acenaphthylene exhibits good storage 

stability gives evidence that it is the passage of air through the sampler which is the likely cause of 

degradation seen in other experiments. Acenaphthylene does not appear to degrade under anaerobic 

storage. 

 Table 12. Sample Storage Stability on Day Zero (as % recovery) 

Analyte #1 #2 #3 #4 #5 #6 #7 Average 

Naphthalene 91.9 93.4 97.3 94.6 91.6 90.0 108 95.2

Acenaphthylene 92.1 87.5 91.4 93.7 88.4 86.9 108 92.6

Acenaphthene 91.6 89.8 94.6 94.6 86.2 91.3 108 93.7

Fluorene 92.3 88.7 90.3 94.8 83.1 85.3 107 91.7

Phenanthrene 94.1 88.5 91.9 92.1 89.5 83.8 106 92.3

Anthracene 92.7 94.1 90.5 90.7 89.4 89.8 107 93.5

Fluoranthene 90.8 90.8 92.8 85.8 89.5 88.3 108 92.3

Pyrene 90.0 84.0 87.6 97.3 95.5 86.9 110 93.0

Benzo[a]anthracene 90.1 88.9 92.1 92.3 91.9 83.5 109 92.6

Chrysene 95.6 88.5 92.8 101.7 90.0 86.1 105 94.2

Benzo[b]fluoranthene 91.7 93.4 97.3 90.7 87.7 87.7 109 93.9

Benzo[k]fluoranthene 93.3 90.1 95.7 90.0 89.8 87.9 107 93.3

Benzo[a]pyrene 91.4 95.0 94.1 92.0 91.8 91.6 109 94.9

Indeno[1,2,3-cd]pyrene 88.8 93.4 90.4 89.5 91.5 84.2 113 92.9

Dibenz[a,h]anthracene 90.3 93.3 91.9 86.7 94.7 87.8 110 93.5

Benzo[ghi]perylene 87.2 95.0 90.3 92.9 97.0 89.9 113 95.0
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Table 13. Sample Storage Stability at Ambient Temperature on Day Seven 

(as % recovery)

Analyte #1 #2 #3 #4 #5 #6 Average

Naphthalene 89.4 84.3 89.0 89.8 88.5 91.6 88.8

Acenaphthylene 82.1 87.0 83.0 88.2 86.5 91.8 86.4

Acenaphthene 82.4 87.1 81.6 89.1 88.9 93.6 87.1

Fluorene 85.8 86.6 86.2 93.7 84.7 87.0 87.3

Phenanthrene 88.0 85.2 92.1 88.7 89.0 91.1 89.0

Anthracene 93.7 92.5 94.4 98.1 93.4 94.4 94.4

Fluoranthene 85.4 86.1 92.6 89.4 87.9 83.6 87.5

Pyrene 91.5 97.7 96.0 92.2 93.9 98.0 94.9

Benzo[a]anthracene 86.5 85.9 92.8 85.3 85.5 87.7 87.3

Chrysene 85.3 92.2 93.6 89.9 92.7 91.5 90.8

Benzo[b]fluoranthene 91.5 90.0 98.4 96.3 92.3 91.0 93.3

Benzo[k]fluoranthene 93.2 94.6 97.1 93.5 92.9 96.8 94.7

Benzo[a]pyrene 92.5 90.5 95.9 93.6 90.5 95.5 93.1

Indeno[1,2,3-cd]pyrene 88.2 93.0 99.1 89.4 93.6 94.9 93.0

Dibenz[a,h]anthracene 87.1 90.7 99.2 88.6 89.8 93.3 91.4

Benzo[ghi]perylene 93.0 96.3 105 93.8 93.5 99.5 96.8

Table 14. Sample Storage Stability under Refrigeration on Day Seven 

(as % recovery)

Analyte #1 #2 #3 #4 #5 #6 Average

Naphthalene 91.6 89.9 87.4 86.0 93.2 93.1 90.2

Acenaphthylene 87.5 94.7 91.9 86.2 91.0 95.0 91.1

Acenaphthene 88.3 91.8 90.2 85.1 92.5 92.7 90.1

Fluorene 83.8 88.2 87.5 84.4 90.9 92.8 87.9

Phenanthrene 88.9 96.7 91.0 88.4 89.5 90.7 90.9

Anthracene 98.4 101 96.6 94.9 92.3 96.7 96.7

Fluoranthene 88.4 94.1 91.8 89.1 88.7 92.0 90.7

Pyrene 96.6 91.7 91.0 91.6 99.2 96.8 94.5

Benzo[a]anthracene 89.9 86.8 87.0 86.3 92.8 91.7 89.1

Chrysene 92.4 91.6 87.9 89.1 94.9 95.9 91.9

Benzo[b]fluoranthene 92.2 93.1 95.3 87.7 92.7 93.4 92.4

Benzo[k]fluoranthene 95.6 93.9 105 89.9 97.8 101 97.1

Benzo[a]pyrene 95.3 95.4 97.8 91.6 99.9 99.3 96.5

Indeno[1,2,3-cd]pyrene 92.7 94.3 97.9 87.2 97.8 101 95.1

Dibenz[a,h]anthracene 95.7 94.4 95.7 86.1 95.6 100 94.6

Benzo[ghi]perylene 98.8 97.3 100 85.4 100 107 98.1
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 Table 15. Sample Storage Stability at Ambient Temperature 

 on Day Ten (as % recovery)

Analyte #1 #2 #3 Average 

Naphthalene 87.2 84.5 82.3 84.6

Acenaphthylene 84.4 80.9 77.8 81.0

Acenaphthene 84.5 80.6 80.0 81.7

Fluorene 86.0 83.1 82.2 83.8

Phenanthrene 86.1 83.4 81.3 83.6

Anthracene 84.9 81.8 82.3 83.0

Fluoranthene 86.2 80.8 82.1 83.0

Pyrene 86.0 86.4 85.9 86.1

Benzo[a]anthracene 83.7 82.1 81.4 82.4

Chrysene 84.8 82.3 80.0 82.4

Benzo[b]fluoranthene 94.3 83.9 84.8 87.7

Benzo[k]fluoranthene 91.6 81.8 84.7 86.0

Benzo[a]pyrene 84.2 80.6 80.2 81.7

Indeno[1,2,3-cd]pyrene 72.2 93.1 82.7 82.6

Dibenz[a,h]anthracene 70.0 94.3 78.3 80.9

Benzo[ghi]perylene 66.6 95.4 80.7 80.9

 Table 16. Sample Storage Stability under Refrigeration on 

 Day Ten (as % recovery)

Analyte #1 #2 #3 Average 

Naphthalene 88.7 86.9 91.4 89.0

Acenaphthylene 85.6 87.5 89.9 87.7

Acenaphthene 86.7 88.8 91.0 88.8

Fluorene 89.0 86.3 89.9 88.4

Phenanthrene 86.2 87.3 91.9 88.4

Anthracene 84.0 87.1 90.6 87.2

Fluoranthene 83.0 85.6 89.6 86.1

Pyrene 91.5 95.1 90.3 92.3

Benzo[a]anthracene 88.2 87.3 88.0 87.8

Chrysene 86.3 88.9 91.5 88.9

Benzo[b]fluoranthene 92.0 89.1 92.7 91.2

Benzo[k]fluoranthene 90.4 90.5 93.7 91.5

Benzo[a]pyrene 85.5 86.0 91.1 87.5

Indeno[1,2,3-cd]pyrene 87.2 84.8 86.1 86.0

Dibenz[a,h]anthracene 84.1 86.0 87.8 86.0

Benzo[ghi]perylene 83.9 88.6 92.1 88.2
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 Table 17. Sample Storage Stability at Ambient Temperature 

 on Day Fourteen (as % recovery)

Analyte #1 #2 #3 Average 

Naphthalene 77.9 101 73.6 84.1

Acenaphthylene 83.4 107 77.3 89.2

Acenaphthene 82.4 108 78.1 89.6

Fluorene 80.0 108 76.4 88.0

Phenanthrene 81.6 108 76.3 88.7

Anthracene 81.5 108 72.9 87.4

Fluoranthene 81.7 106 74.7 87.3

Pyrene 76.6 102 87.0 88.7

Benzo[a]anthracene 81.6 104 72.0 85.8

Chrysene 78.4 107 77.9 87.7

Benzo[b]fluoranthene 79.1 119 64.8 87.6

Benzo[k]fluoranthene 76.6 127 65.7 89.6

Benzo[a]pyrene 79.0 113 73.1 88.4

Indeno[1,2,3-cd]pyrene 73.1 123 89.0 95.2

Dibenz[a,h]anthracene 75.6 122 88.1 95.2

Benzo[ghi]perylene 76.1 119 85.2 93.4

 Table 18. Sample Storage Stability under Refrigeration on 

 Day Fourteen (as % recovery)

Analyte #1 #2 #3 Average 

Naphthalene 83.9 78.3 106 89.5

Acenaphthylene 89.7 82.9 110 94.1

Acenaphthene 89.5 82.2 108 93.2

Fluorene 88.5 81.6 99.5 89.9

Phenanthrene 89.3 81.9 104 91.8

Anthracene 89.0 80.7 94.3 88.0

Fluoranthene 89.5 81.7 104 91.7

Pyrene 87.2 79.3 101 89.0

Benzo[a]anthracene 88.9 81.3 79.9 83.4

Chrysene 87.9 79.3 83.9 83.7

Benzo[b]fluoranthene 74.4 78.8 90.5 81.2

Benzo[k]fluoranthene 71.4 80.7 98.1 83.4

Benzo[a]pyrene 80.4 81.3 88.0 83.2

Indeno[1,2,3-cd]pyrene 69.8 88.3 91.9 83.3

Dibenz[a,h]anthracene 69.9 88.0 98.1 85.3

Benzo[ghi]perylene 70.4 81.3 114 88.7
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 Table 19. Sample Storage Stability at Ambient Temperature 

 on Day Twenty One (as % recovery)

Analyte #1 #2 #3 Average 

Naphthalene 85.8 87.0 88.8 87.2

Acenaphthylene 90.7 92.4 94.0 92.3

Acenaphthene 94.5 88.5 92.5 91.8

Fluorene 97.0 91.6 96.3 94.9

Phenanthrene 94.5 95.1 94.9 94.8

Anthracene 93.8 94.4 91.8 93.3

Fluoranthene 84.3 88.5 84.2 85.7

Pyrene 92.3 94.9 91.4 92.8

Benzo[a]anthracene 85.9 88.3 85.9 86.7

Chrysene 93.8 95.6 94.6 94.7

Benzo[b]fluoranthene 94.3 86.5 88.4 89.7

Benzo[k]fluoranthene 101 94.3 96.4 97.2

Benzo[a]pyrene 95.3 91.3 93.0 93.2

Indeno[1,2,3-cd]pyrene 92.9 81.3 86.7 87.0

Dibenz[a,h]anthracene 93.6 87.8 88.2 89.9

Benzo[ghi]perylene 98.8 86.6 90.8 92.1

 Table 20. Sample Storage Stability under Refrigeration on 

 Day Twenty One (as % recovery)

Analyte #1 #2 #3 Average 

Naphthalene 93.0 87.9 96.3 92.4

Acenaphthylene 99.4 94.8 92.7 95.6

Acenaphthene 98.0 91.1 93.1 94.1

Fluorene 103 93.7 96.2 97.7

Phenanthrene 103 96.1 95.3 98.0

Anthracene 103 94.6 93.9 97.0

Fluoranthene 105 94.8 93.6 97.9

Pyrene 101 95.3 94.5 97.0

Benzo[a]anthracene 93.5 90.3 86.2 90.0

Chrysene 99.9 93.6 98.3 97.3

Benzo[b]fluoranthene 95.4 95.2 95.5 95.4

Benzo[k]fluoranthene 106 101 97.1 102 

Benzo[a]pyrene 99.8 96.5 95.5 97.3

Indeno[1,2,3-cd]pyrene 93.3 89.7 88.3 90.4

Dibenz[a,h]anthracene 97.8 88.0 91.8 92.5

Benzo[ghi]perylene 101 92.0 92.2 95.1
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Table 21. Sample Storage Stability at Ambient Temperature on 

 Day Thirty (as % recovery)

Analyte #1 #2 #3 #4 #5 #6 Average 

Naphthalene 85.2 86.1 88.6 94.8 87.6 90.7 88.8

Acenaphthylene 92.4 98.2 95.0 101 97.4 96.7 96.7

Acenaphthene 92.7 97.8 94.8 99.5 96.3 98.1 96.5

Fluorene 92.4 103 93.7 102 98.9 102 98.5

Phenanthrene 95.6 99.4 97.2 102 92.8 101 98.1

Anthracene 95.9 97.0 97.0 104 95.2 98.7 97.9

Fluoranthene 97.8 101 86.1 102 94.9 101 97.2

Pyrene 90.6 97.1 95.0 95.0 90.0 97.6 94.2

Benzo[a]anthracene 91.2 96.0 86.3 97.4 88.0 93.6 92.1

Chrysene 90.9 94.4 96.1 101 95.6 98.2 96.0

Benzo[b]fluoranthene 90.0 95.1 92.5 102 89.2 97.1 94.2

Benzo[k]fluoranthene 95.1 99.5 99.2 101 93.2 98.1 97.6

Benzo[a]pyrene 90.7 97.2 96.6 101 92.8 96.2 95.8

Indeno[1,2,3-cd]pyrene 90.9 96.3 92.7 98.4 93.9 93.5 94.3

Dibenz[a,h]anthracene 89.2 94.1 90.9 98.8 91.1 96.4 93.4

Benzo[ghi]perylene 89.7 97.4 94.2 101 91.3 95.6 94.9

Table 22. Sample Storage Stability under Refrigeration on Day Thirty 

(as % recovery)

Analyte #1 #2 #3 #4 #5 #6 Average 

Naphthalene 87.2 88.9 89.4 98.5 92.7 87.3 90.6

Acenaphthylene 94.2 95.0 94.0 105 96.4 98.2 97.1

Acenaphthene 94.3 95.8 95.1 104 96.3 95.4 96.9

Fluorene 96.5 98.4 98.4 109 96.3 98.1 99.5

Phenanthrene 91.5 93.9 96.2 107 101 101 98.4

Anthracene 94.4 93.3 98.2 106 99.0 101 98.5

Fluoranthene 86.1 84.3 96.6 108 96.7 88.9 93.3

Pyrene 88.9 89.7 92.2 99.6 93.2 96.0 93.3

Benzo[a]anthracene 90.8 90.7 89.9 99.9 94.1 91.6 92.8

Chrysene 91.3 96.3 96.5 105 97.7 97.1 97.4

Benzo[b]fluoranthene 93.4 95.1 96.0 108 94.1 93.2 96.6

Benzo[k]fluoranthene 95.3 95.1 103 105 100 102 100

Benzo[a]pyrene 96.0 95.4 97.4 106 96.4 97.4 98.1

Indeno[1,2,3-cd]pyrene 92.5 91.3 94.4 104 93.9 97.3 95.5

Dibenz[a,h]anthracene 96.1 94.8 95.4 104 92.7 96.4 96.6

Benzo[ghi]perylene 93.7 93.2 97.2 108 95.1 99.8 97.8
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Table 23. Average Storage Stabilities Relative to Day Zero Recoveries 

At Ambient Temperature (as % recovery)

Analyte 0 day 7 day 10 day 14 day 21 day 30 day 

Naphthalene 100 93.3 88.9 88.3 91.6 93.3 

Acenaphthylene 100 93.3 87.5 96.3 99.7 104

Acenaphthene 100 93.0 87.2 95.6 98.0 103 

Fluorene 100 95.2 91.4 96.0 104 107 

Phenanthrene 100 96.4 101 96.1 103 106 

Anthracene 100 101 99.5 93.5 99.8 105 

Fluoranthene 100 94.8 101 94.6 92.8 105 

Pyrene 100 91.3 103 95.4 99.8 101 

Benzo[a]anthracene 100 94.3 89.0 92.7 93.6 99.5 

Chrysene 100 96.4 87.5 93.1 101 102 

Benzo[b]fluoranthene 100 99.4 93.4 93.3 95.5 100 

Benzo[k]fluoranthene 100 102 92.2 96.0 104 105 

Benzo[a]pyrene 100 98.1 86.1 93.2 98.2 101 

Indeno[1,2,3-cd]pyrene 100 100 88.9 103 93.6 102 

Dibenz[a,h]anthracene 100 97.8 86.5 102 96.1 99.9 

Benzo[ghi]perylene 100 102 85.2 98.3 96.9 99.9 

Table 24. Average Long-Term Storage Stabilities Relative to Day 

 Zero Recoveries at Refrigerated Temperature (as % recovery)

Analyte 0 day 7 day 10 day 14 day 21 day 30 day 

Naphthalene 100 94.7 93.5 94.0 97.1 95.2 

Acenaphthylene 100 98.4 94.7 102 103 105 

Acenaphthene 100 96.2 94.8 99.5 100 103 

Fluorene 100 95.9 96.4 98.0 107 109 

Phenanthrene 100 98.5 95.8 99.5 106 107 

Anthracene 100 103 93.3 94.1 104 105 

Fluoranthene 100 98.3 93.3 99.3 106 101 

Pyrene 100 102 99.2 95.7 104 100 

Benzo[a]anthracene 100 96.2 94.8 90.1 97.2 100 

Chrysene 100 97.6 94.4 88.9 103 103 

Benzo[b]fluoranthene 100 98.4 97.1 86.5 102 103 

Benzo[k]fluoranthene 100 104 98.1 89.4 109 107 

Benzo[a]pyrene 100 102 92.2 87.7 103 103 

Indeno[1,2,3-cd]pyrene 100 102 92.6 89.7 97.3 103 

Dibenz[a,h]anthracene 100 101 92.0 91.1 98.9 103 

Benzo[ghi]perylene 100 103 92.8 93.4 100 103 
Backup Data Report for NMAM 5528: Polynuclear aromatic hydrocarbons in air by GC-MS SIM- dated 06

October 2021 - Page 27 of 60

NIOSH Manual of Analytical Methods (NMAM) 5th Edition

IX. PRECISION, ACCURACY, AND BIAS STUDY 

A study was performed to determine the precision, accuracy, and bias of the method. 

Concentration levels ranging from this study’s LOQ to 300× LOQ were used. Seven samplers at each 

of the following levels were spiked with target compounds to produce the desired concentrations: 0.25 

μg/sample, 0.75 μg/sample, 2.50 μg/sample, 7.50 μg/sample, 25.0 μg/sample, and 75.0 μg/sample. 

The OVS-7 tubes were then placed in an environmental chamber and air was drawn through each 

sampler at a rate of 1 liter per minute for four hours. The samples were prepared and analyzed 

according to the method. Table 25 displays the average recoveries of the analytes over the ranges 

studied. Following Table 25 are tables for each analyte (Tables 26-41). These tables contain the 

recoveries for each replicate for each of the six concentration levels used. The recoveries are given in 

μg/sample (sample being 1 mL) and in percent recovery. 

Table 25. Average percent recoveries over various levels 

Analyte 

(by retention time) 

0.25 

(μg/sample) 

0.75 

(μg/sample) 

2.50 

(μg/sample) 

7.5 

(μg/sample) 

25.0 

(μg/sample) 

75.0 

(μg/sample) 

Pooled 

CV

Naphthalene 110 96.3 101 87.6 95.1 85.7 0.0305 

Acenaphthylene 64.7 71.0 57.9 67.5 87.0 78.3 0.0340 

Acenaphthene 97.1 92.6 96.1 87.6 93.8 83.8 0.0258 

Fluorene 95.7 92.3 98.2 90.8 97.4 85.0 0.0309 

Phenanthrene 97.1 92.3 99.6 90.1 98.6 86.3 0.0249 

Anthracene 75.7 83.1 89.0 86.3 97.4 84.1 0.0323 

Fluoranthene 95.1 92.6 97.8 91.9 105 87.4 0.0367 

Pyrene 92.3 91.4 92.7 89.3 99.1 86.2 0.0474 

Benz[a]anthracene 86.7 86.1 94.7 92.1 103 86.4 0.0352 

Chrysene 96.9 92.5 99.7 86.4 94.3 85.3 0.0315 

Benzo[b]fluoranthene 92.8 91.6 95.7 91.7 104 87.4 0.0294 

Benzo[k]fluoranthene 83.0 86.3 101 91.0 97.5 86.7 0.0387 

Benzo[a]pyrene 70.1 76.5 85.8 87.4 102 85.1 0.0370 

Indeno[1,2,3-c,d]pyrene 80.5 81.4 86.1 90.9 103 91.0 0.0545 

Dibenz[a,h]anthracene 86.7 87.3 105 102 109 89.0 0.0463 

Benzo[ghi]perylene 87.9 86.0 104 102 109 91.7 0.0493 

(1) Recoveries less than 75% are highlighted in bold numerals. (See comments in following text.) 

(2) This table summarizes data in Tables 26-42
Backup Data Report for NMAM 5528: Polynuclear aromatic hydrocarbons in air by GC-MS SIM- dated 06 October 2021 - Page 28 of 60

NIOSH Manual of Analytical Methods (NMAM) 5th Edition

TABLE 26. ACENAPHTHENE RECOVERY FROM SPIKED MEDIA (Weathered for 4 hours at 1 L/min) 

 Int Std: Acenaphthene-D10; Quant. ion (m/z): 153

Applied 0.250 

(μg/sample) 

Applied 0.750 

(μg/sample) 

Applied 2.50 

(μg/sample) 

Applied 7.50 

(μg/sample) 

Applied 25.0 

(μg/sample) 

Applied 75.0 

(μg/sample) 

Found Percent Found Percent Found Percent Found Percent Found Percent Found Percent 

Replicate μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery 

1 0.242 96.8 0.666 88.8 2.36 94.2 6.92 92.2 22.7 90.6 65.6 87.5 

2 0.254 102 0.688 91.7 2.48 99.0 6.39 85.2 22.9 91.8 60.4 80.5 

3 0.242 96.8 0.684 91.2 2.49 99.5 6.66 88.8 23.0 92.1 62.3 83.1 

4 0.238 95.2 0.716 95.5 2.39 95.8 6.61 88.2 24.0 96.1 61.4 81.9 

5 0.240 96.0 0.716 95.5 2.30 91.9 6.40 85.3 24.0 96.0 62.3 83.1 

6 0.242 96.8 0.682 90.9 2.36 94.3 6.92 92.2 23.5 94.1 64.4 85.9 

7 0.242 96.8 0.710 94.7 2.44 97.5 6.10 81.3 23.9 95.8 63.5 84.6 

average = 0.243 97.1 0.695 92.6 2.40 96.1 6.57 87.6 23.4 93.8 62.8 83.8 

std dev = 0.00515 2.06 0.0195 2.60 0.0696 2.79 0.299 3.99 0.570 2.28 1.78 2.38 

TABLE 27. ANTHRACENE RECOVERY FROM SPIKED MEDIA (Weathered for 4 hours at 1 L/min) 

Int Std: Phenanthrene-D10; Quant. ion (m/z):178

Applied 0.250 

(μg/sample) 

Applied 0.750 

(μg/sample) 

Applied 2.50 

(μg/sample) 

Applied 7.50 

(μg/sample) 

Applied 25.0 

(μg/sample) 

Applied 75.0 

(μg/sample) 

Found Percent Found Percent Found Percent Found Percent Found Percent Found Percent 

Replicate μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery 

1 0.196 78.4 0.646 86.1 2.20 87.92 6.90 92.00 23.8 95.15 64.8 86.4 

2 0.196 78.4 0.600 80.0 2.31 92.32 6.39 85.23 23.6 94.50 60.5 80.7 

3 0.180 72.0 0.632 84.3 2.30 91.84 6.41 85.47 23.6 94.55 62.5 83.4 

4 0.198 79.2 0.604 80.5 2.21 88.32 6.55 87.36 24.9 99.59 62.3 83.1 

5 0.176 70.4 0.644 85.9 2.11 84.64 6.28 83.79 25.1 100.25 62.5 83.4 

6 0.192 76.8 0.608 81.1 2.19 87.60 6.69 89.20 24.7 98.78 64.9 86.5 

7 0.186 74.4 0.630 84.0 2.25 90.00 6.09 81.20 24.8 99.15 64.0 85.3 

average = 0.189 75.7 0.623 83.1 2.22 88.95 6.47 86.32 24.4 97.43 63.1 84.1 

std dev = 0.00863 3.45 0.0192 2.56 0.0667 2.6667 0.267 3.5636 0.641 2.5634 1.56 2.08 
Backup Data Report for NMAM 5528: Polynuclear aromatic hydrocarbons in air by GC-MS SIM- dated 06 October 2021 - Page 29 of 60

NIOSH Manual of Analytical Methods (NMAM) 5th Edition

TABLE 28. ACENAPHTHYLENE RECOVERY FROM SPIKED MEDIA (Weathered for 4 hours at 1 L/min) 

Int Std: Acenaphthene-D10; Quant. ion (m/z): 152 

Applied 0.250 

(μg/sample) 

Applied 0.750 

(μg/sample) 

Applied 2.50 

(μg/sample) 

Applied 7.50 

(μg/sample) 

Applied 25.0 

(μg/sample) 

Applied 75.0 

(μg/sample) 

Found Percent Found Percent Found Percent Found Percent Found Percent Found Percent 

Replicate μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery 

1 0.180 72.0 0.548 73.1 1.42 57.0 5.49 73.3 20.2 80.7 61.4 81.8 

2 0.162 64.8 0.456 60.8 1.55 61.9 4.97 66.3 21.5 85.9 56.2 74.9 

3 0.156 62.4 0.574 76.5 1.56 62.5 5.12 68.2 21.5 85.9 58.5 78.0 

4 0.160 64.0 0.496 66.1 1.51 60.6 5.22 69.6 21.9 87.7 57.5 76.7 

5 0.148 59.2 0.522 69.6 1.22 48.9 4.77 63.7 22.4 89.5 58.1 77.5 

6 0.164 65.6 0.554 73.9 1.44 57.5 5.19 69.2 22.1 88.4 60.5 80.7 

7 0.162 64.8 0.576 76.8 1.43 57.0 4.68 62.4 22.7 90.6 58.9 78.6 

average = 0.162 64.7 0.532 71.0 1.45 57.9 5.06 67.5 21.7 87.0 58.7 78.3 

std dev = 0.00969 3.88 0.0440 5.87 0.115 4.61 0.278 3.71 0.814 3.25 1.77 2.36 

TABLE 29. BENZ[a]ANTHRACENE RECOVERY FROM SPIKED MEDIA (Weathered for 4 hours at 1 L/min) 

 Int Std: Chrysene-D12; Quant. ion (m/z): 228

Applied 0.250 

(μg/sample) 

Applied 0.750 

(μg/sample) 

Applied 2.50 

(μg/sample) 

Applied 7.50 

(μg/sample) 

Applied 25.0 

(μg/sample) 

Applied 75.0 

(μg/sample) 

Found Percent Found Percent Found Percent Found Percent Found Percent Found Percent 

Replicate μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery 

1 0.224 89.6 0.644 85.9 2.35 94.1 7.15 95.3 24.37 97.5 66.4 88.6 

2 0.230 92.0 0.634 84.5 2.49 99.5 6.70 89.4 24.9 99.4 62.1 82.8 

3 0.216 86.4 0.622 82.9 2.41 96.3 6.84 91.3 25.2 101 62.6 83.5 

4 0.212 84.8 0.632 84.3 2.31 92.4 7.13 95.0 26.5 106 65.1 86.8 

5 0.204 81.6 0.672 89.6 2.33 93.0 6.79 90.6 26.7 107 64.1 85.5 

6 0.218 87.2 0.634 84.5 2.38 95.1 7.18 95.7 26.3 105 67.2 89.7 

7 0.214 85.6 0.682 90.9 2.32 92.6 6.54 87.2 26.6 107 66.0 88.1 

average = 0.217 86.7 0.646 86.1 2.37 94.7 6.90 92.1 25.8 103 64.8 86.4 

std dev = 0.00840 3.36 0.0225 3.00 0.0635 2.54 0.251 3.34 0.956 3.82 1.96 2.61 
Backup Data Report for NMAM 5528: Polynuclear aromatic hydrocarbons in air by GC-MS SIM- dated 06 October 2021 - Page 30 of 60

NIOSH Manual of Analytical Methods (NMAM) 5th Edition

TABLE 30. BENZO[b]FLUORANTHENE RECOVERY FROM SPIKED MEDIA (Weathered for 4 hours at 1 L/min) 

Int Std: Perylene-D12; Quant. ion (m/z): 252

Applied 0.250 

(μg/sample) 

Applied 0.750 

(μg/sample) 

Applied 2.50 

(μg/sample) 

Applied 7.50 

(μg/sample) 

Applied 25.0 

(μg/sample) 

Applied 75.0 

(μg/sample) 

Found Percent Found Percent Found Percent Found Percent Found Percent Found Percent 

Replicate μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery 

1 0.232 92.8 0.664 88.5 2.39 95.6 7.06 94.2 24.3 97.4 67.7 90.2 

2 0.244 97.6 0.676 90.1 2.46 98.3 6.71 89.5 25.2 101 63.3 84.4 

3 0.234 93.6 0.694 92.5 2.46 98.6 6.87 91.6 25.4 101 63.6 84.8 

4 0.228 91.2 0.682 90.9 2.32 93.0 6.97 93.0 26.8 107 64.6 86.1 

5 0.224 89.6 0.704 93.9 2.44 97.5 6.66 88.8 27.1 108 65.0 86.6 

6 0.226 90.4 0.668 89.1 2.36 94.4 7.25 96.7 26.2 105 67.7 90.2 

7 0.236 94.4 0.720 96.0 2.32 92.6 6.64 88.5 27.4 110 66.9 89.3 

average = 0.232 92.8 0.687 91.6 2.39 95.7 6.88 91.7 26.1 104 65.5 87.4 

std dev = 0.00683 2.73 0.0203 2.70 0.0620 2.48 0.231 3.08 1.12 4.50 1.86 2.48 

TABLE 31. BENZO[k]FLUORANTHENE RECOVERY FROM SPIKED MEDIA (Weathered for 4 hours at 1 L/min) 

Int Std: Perylene-D12; Quant. ion (m/z): 252

Applied 0.250 

(μg/sample) 

Applied 0.750 

(μg/sample) 

Applied 2.50 

(μg/sample) 

Applied 7.50 

(μg/sample) 

Applied 25.0 

(μg/sample) 

Applied 75.0 

(μg/sample) 

Found Percent Found Percent Found Percent Found Percent Found Percent Found Percent 

Replicate μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery 

1 0.214 85.6 0.642 85.6 2.49 99.6 6.95 92.7 23.0 91.9 67.2 89.7 

2 0.230 92.0 0.640 85.3 2.59 104 6.71 89.4 23.8 95.2 62.4 83.2 

3 0.204 81.6 0.642 85.6 2.57 103 6.95 92.7 23.9 95.8 63.7 85.0 

4 0.208 83.2 0.656 87.5 2.41 96.4 6.93 92.4 24.5 98.1 65.3 87.1 

5 0.206 82.4 0.660 88.0 2.56 102 6.56 87.5 25.0 100 62.7 83.6 

6 0.190 76.0 0.634 84.5 2.57 103 7.14 95.2 25.0 100 67.6 90.1 

7 0.200 80.0 0.658 87.7 2.46 98.5 6.55 87.3 25.4 101 66.5 88.6 

average = 0.207 83.0 0.647 86.3 2.52 100 6.83 91.0 24.4 97.5 65.1 86.7 

std dev = 0.0124 4.97 0.0103 1.37 0.0679 2.71 0.224 2.99 0.849 3.39 2.14 2.86 
Backup Data Report for NMAM 5528: Polynuclear aromatic hydrocarbons in air by GC-MS SIM- dated 06 October 2021 - Page 31 of 60

NIOSH Manual of Analytical Methods (NMAM) 5th Edition

TABLE 32. BENZO[ghi]PERYLENE RECOVERY FROM SPIKED MEDIA (Weathered for 4 hours at 1 L/min) 

Int Std: Perylene-D12; Quant. ion (m/z): 276

Applied 0.250 

(μg/sample) 

Applied 0.750 

(μg/sample) 

Applied 2.50 

(μg/sample) 

Applied 7.50 

(μg/sample) 

Applied 25.0 

(μg/sample) 

Applied 75.0 

(μg/sample) 

Found Percent Found Percent Found Percent Found Percent Found Percent Found Percent 

Replicate μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery 

1 0.236 94.4 0.628 83.7 2.63 105 8.00 107 25.5 102 69.8 93.0 

2 0.226 90.4 0.644 85.9 2.61 104 7.79 104 25.7 103 65.5 87.3 

3 0.212 84.8 0.618 82.4 2.61 104 7.58 101 26.0 104 69.5 92.6 

4 0.216 86.4 0.612 81.6 2.59 104 7.78 104 28.8 115 66.1 88.2 

5 0.200 80.0 0.712 94.9 2.47 98.6 7.61 101 28.2 113 66.9 89.3 

6 0.244 97.6 0.634 84.5 2.71 108 8.02 107 27.7 111 73.3 97.7 

7 0.204 81.6 0.668 89.1 2.66 106 6.66 88.9 28.7 115 70.6 94.2 

average = 0.220 87.9 0.645 86.0 2.61 104 7.64 102 27.2 109 68.8 91.7 

std dev = 0.0164 6.54 0.0348 4.63 0.0744 2.98 0.461 6.15 1.45 5.78 2.78 3.70 

TABLE 33. BENZO[a]PYRENE RECOVERY FROM SPIKED MEDIA (Weathered for 4 hours at 1 L/min) 

Int Std: Perylene-D12; Quant. ion (m/z): 252

Applied 0.250 

(μg/sample) 

Applied 0.750 

(μg/sample) 

Applied 2.50 

(μg/sample) 

Applied 7.50 

(μg/sample) 

Applied 25.0 

(μg/sample) 

Applied 75.0 

(μg/sample) 

Found Percent Found Percent Found Percent Found Percent Found Percent Found Percent 

Replicate μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery 

1 0.188 75.2 0.576 76.8 2.16 86.4 6.76 90.1 24.1 96.4 65.6 87.5 

2 0.190 76.0 0.560 74.7 2.26 90.3 6.56 87.5 24.8 99.2 61.1 81.5 

3 0.172 68.8 0.584 77.9 2.20 88.2 6.63 88.4 25.3 101 62.6 83.4 

4 0.178 71.2 0.556 74.1 2.02 81,0 6.78 90.4 26.3 105 63.2 84.3 

5 0.162 64.8 0.616 82.1 2.11 84.2 6.33 84.4 26.7 107 62.7 83.6 

6 0.176 70.4 0.556 74.1 2.17 86.8 6.80 90.7 26.1 104 66.5 88.7 

7 0.160 64.0 0.566 75.5 2.10 83.8 6.03 80.4 26.8 107 65.1 86.9 

average = 0.175 70.1 0.573 76.5 2.15 85.8 6.55 87.4 25.7 103 63.8 85.1 

std dev = 0.0116 4.64 0.0215 2.87 0.0771 3.08 0.284 3.78 1.01 4.04 1.95 2.60 
Backup Data Report for NMAM 5528: Polynuclear aromatic hydrocarbons in air by GC-MS SIM- dated 06 October 2021 - Page 32 of 60

NIOSH Manual of Analytical Methods (NMAM) 5th Edition

TABLE 34. CHRYSENE RECOVERY FROM SPIKED MEDIA (Weathered for 4 hours at 1 L/min) 

INT STD: Chrysene-D12; Quant. ion (m/z): 228

Applied 0.250 

(μg/sample) 

Applied 0.750 

(μg/sample) 

Applied 2.50 

(μg/sample) 

Applied 7.50 

(μg/sample) 

Applied 25.0 

(μg/sample) 

Applied 75.0 

(μg/sample) 

Found Percent Found Percent Found Percent Found Percent Found Percent Found Percent 

Replicate μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery 

1 0.244 97.6 0.656 87.5 2.50 100 7.02 93.6 22.5 89.9 66.4 88.5 

2 0.254 102 0.708 94.4 2.55 102 6.57 87.6 22.8 91.4 61.9 82.6 

3 0.238 95.2 0.686 91.5 2.52 101 6.74 89.8 23.1 92.4 62.5 83.4 

4 0.240 96.0 0.690 92.0 2.40 96.0 6.70 89.3 24.1 96.3 63.0 84.1 

5 0.234 93.6 0.712 94.9 2.45 97.9 6.40 85.3 24.1 96.4 630 84.0 

6 0.240 96.0 0.698 93.1 2.48 99.4 7.05 940 24.2 96.7 66.0 87.9 

7 0.246 98.4 0.708 94.4 2.54 102 6.46 86.1 24.3 97.3 64.8 86.4 

average = 0.242 96.9 0.694 92.5 2.50 99.7 6.70 89.4 23.6 94.3 63.9 85.3 

std dev = 0.00647 2.59 0.0194 2.59 0.0538 2.15 0.255 3.40 0.752 3.01 1.75 2.33 

TABLE 35. DIBENZ[a,h]ANTHRACENE RECOVERY FROM SPIKED MEDIA (Weathered for 4 hours at 1 L/min) 

Int Std: Perylene-D12; Quant. ion (m/z): 278

Applied 0.250 

(μg/sample) 

Applied 0.750 

(μg/sample) 

Applied 2.50 

(μg/sample) 

Applied 7.50 

(μg/sample) 

Applied 25.0 

(μg/sample) 

Applied 75.0 

(μg/sample) 

Found Percent Found Percent Found Percent Found Percent Found Percent Found Percent 

Replicate μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery 

1 0.224 89.6 0.660 88.0 2.65 106 8.10 108 25.1 100 68.2 90.9 

2 0.222 88.8 0.680 90.7 2.60 104 7.77 104 26.8 107 63.8 85.1 

3 0.218 87.2 0.604 80.5 2.59 104 7.58 101 26.0 104 66.9 89.2 

4 0.206 82.4 0.554 73.9 2.64 106 7.80 104 28.8 115 64.9 86.6 

5 0.186 74.4 0.736 98.1 2.47 98.7 7.66 102 27.8 111 64.0 85.3 

6 0.2400 96.0 0.646 86.1 2.75 110 7.99 107 27.3 109 70.9 94.6 

7 0.222 88.8 0.704 93.9 2.68 107 6.81 90.8 28.3 113 68.3 91.1 

average = 0.217 86.7 0.655 87.3 2.63 105 7.67 102 27.2 109 66.7 89.0 

std dev = 0.0169 6.75 0.0612 8.16 0.0872 3.49 0.422 5.63 1.30 5.21 2.62 3.49 
Backup Data Report for NMAM 5528: Polynuclear aromatic hydrocarbons in air by GC-MS SIM- dated 06 October 2021 - Page 33 of 60

NIOSH Manual of Analytical Methods (NMAM) 5th Edition

TABLE 36. FLUORANTHENE RECOVERY FROM SPIKED MEDIA (Weathered for 4 hours at 1 L/min) 

Int Std: Phenanthrene-D10; Quant. ion (m/z): 202

Applied 0.250 

(μg/sample) 

Applied 0.750 

(μg/sample) 

Applied 2.50 

(μg/sample) 

Applied 7.50 

(μg/sample) 

Applied 25.0 

(μg/sample) 

Applied 75.0 

(μg/sample) 

Found Percent Found Percent Found Percent Found Percent Found Percent Found Percent 

Replicate μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery 

1 0.244 97.6 0.698 93.1 2.38 95.4 7.37 98.3 26.6 106 68.2 91.0 

2 0.246 98.4 0.696 92.8 2.57 103 6.81 90.9 25.0 100 63.5 84.7 

3 0.236 94.4 0.682 90.9 2.48 99.0 7.05 94.1 25.8 103 64.8 86.4 

4 0.248 99.2 0.674 89.9 2.42 96.9 6.87 91.7 26.7 107 64.2 85.7 

5 0.222 88.8 0.692 92.3 2.38 95.0 6.66 88.8 26.5 106 64.1 85.5 

6 0.234 93.6 0.672 89.6 2.38 95.2 7.11 94.8 26.6 106 67.8 90.4 

7 0.234 93.6 0.748 99.7 2.51 100 6.39 85.2 25.7 103 65.9 87.9 

average = 0.238 95.1 0.695 92.6 2.45 97.8 6.90 91.9 26.1 105 65.5 87.4 

std dev = 0.00905 3.62 0.0257 3.43 0.0762 3.05 0.320 4.27 0.629 2.52 1.85 2.46 

TABLE 37. FLUORENE RECOVERY FROM SPIKED MEDIA (Weathered for 4 hours at 1 L/min) 

Int Std: Phenanthrene-D10; Quant. ion (m/z): 166

Applied 0.250 

(μg/sample) 

Applied 0.750 

(μg/sample) 

Applied 2.50 

(μg/sample) 

Applied 7.50 

(μg/sample) 

Applied 25.0 

(μg/sample) 

Applied 75.0 

(μg/sample) 

Found Percent Found Percent Found Percent Found Percent Found Percent Found Percent 

Replicate μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery 

1 0.244 97.6 0.674 89.9 2.42 97.0 7.26 96.8 23.9 95.7 66.0 88.1 

2 0.246 98.4 0.702 93.6 2.56 103 6.62 88.2 23.6 94.5 61.3 81.8 

3 0.238 95.2 0.678 90.4 2.52 101 6.86 91.4 23.8 95.2 63.2 84.3 

4 0.240 96.0 0.694 92.5 2.43 97.2 6.86 91.4 24.8 99.0 62.9 83.9 

5 0.226 90.4 0.704 93.9 2.37 95.0 6.69 89.3 25.1 101 63.2 84.3 

6 0.238 95.2 0.678 90.4 2.38 95.0 7.08 94.4 24.6 98.3 65.3 87.1 

7 0.242 96.8 0.714 95.2 2.49 99.5 6.31 84.1 24.7 98.7 63.9 85.2 

average = 0.239 95.7 0.692 92.3 2.45 98.2 6.81 90.8 24.4 97.4 63.7 85.0 

std dev = 0.00652 2.61 0.0155 2.07 0.0729 2.91 0.311 4.14 0.576 2.30 1.57 2.09 
Backup Data Report for NMAM 5528: Polynuclear aromatic hydrocarbons in air by GC-MS SIM- dated 06 October 2021 - Page 34 of 60

NIOSH Manual of Analytical Methods (NMAM) 5th Edition

TABLE 38. INDENO[1,2,3-c,d]PYRENE RECOVERY FROM SPIKED MEDIA (Weathered for 4 hours at 1 L/min) 

Int Std: Perylene-D12; Quant. ion (m/z): 276

Applied 0.250 

(μg/sample) 

Applied 0.750 

(μg/sample) 

Applied 2.50 

(μg/sample) 

Applied 7.50 

(μg/sample) 

Applied 25.0 

(μg/sample) 

Applied 75.0 

(μg/sample) 

Found Percent Found Percent Found Percent Found Percent Found Percent Found Percent 

Replicate μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery 

1 0.214 85.6 0.592 78.9 2.17 86.9 7.14 95.2 23.8 95.4 69.7 92.9 

2 0.212 84.8 0.642 85.6 2.14 85.7 6.89 91.9 25.3 101 64.9 86.6 

3 0.198 79.2 0.578 77.1 2.14 85.4 6.86 91.5 24.7 98.8 67.9 90.5 

4 0.196 78.4 0.530 70.7 2.09 83.4 6.95 92.6 27.2 109 66.5 88.6 

5 0.180 72.0 0.654 87.2 2.08 83.3 6.87 91.7 26.1 105 66.4 88.5 

6 0.216 86.4 0.644 85.9 2.28 91.2 7.15 95.3 25.6 102 72.2 96.3 

7 0.192 76.8 0.632 84.3 2.17 86.9 5.90 79.0 27,0 108 70.7 94.2 

average = 0.201 80.5 0.610 81.4 2.15 86.1 6.82 91.0 25.7 103 68.3 91.1 

std dev = 0.0134 5.34 0.0454 6.05 0.0668 2.67 0.426 5.68 1.21 4.83 2.63 3.51 

TABLE 39. NAPHTHALENE RECOVERY FROM SPIKED MEDIA (Weathered for 4 hours at 1 L/min) 

Int Std: Naphthalene-D8; Quant. ion (m/z): 128

Applied 0.250 

(μg/sample) 

Applied 0.750 

(μg/sample) 

Applied 2.50 

(μg/sample) 

Applied 7.50 

(μg/sample) 

Applied 25.0 

(μg/sample) 

Applied 75.0 

(μg/sample) 

Found Percent Found Percent Found Percent Found Percent Found Percent Found Percent 

Replicate μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery 

1 0.272 109 0.682 90.9 2.45 98.2 6.88 91.7 22.9 91.7 66.7 88.9 

2 0.278 111 0.720 96.0 2.57 103 6.45 86.1 23.3 93.2 61.3 81.8 

3 0.266 106 0.698 93.1 2.58 103 6.67 88.9 23.4 93.8 63.5 84.7 

4 0.272 109 0.730 97.3 2.51 100 6.64 88.5 24.3 97.2 63.0 84.0 

5 0.262 105 0.740 98.7 2.41 96.6 6.36 84.8 24.4 97.7 64.0 85.3 

6 0.304 122 0.716 95.5 2.54 102 6.90 92.0 23.9 95.7 65.7 87.6 

7 0.272 109 0.772 103 2.53 101 6.08 81.1 24.1 96.6 65.4 87.3 

average = 0.275 110 0.723 96.3 2.51 101 6.57 87.6 23.8 95.1 64.2 85.7 

std dev = 0.0137 5.48 0.0292 3.89 0.0614 2.45 0.292 3.90 0.568 2.27 1.84 2.45 
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NIOSH Manual of Analytical Methods (NMAM) 5th Edition

TABLE 40. PHENANTHRENE RECOVERY FROM SPIKED MEDIA (Weathered for 4 hours at 1 L/min) 

Int Std: Phenanthrene-D10; Quant. ion (m/z): 178

Applied 0.250 

(μg/sample) 

Applied 0.750 

(μg/sample) 

Applied 2.50 

(μg/sample) 

Applied 7.50 

(μg/sample) 

Applied 25.0 

(μg/sample) 

Applied 75.0 

(μg/sample) 

Found Percent Found Percent Found Percent Found Percent Found Percent Found Percent 

Replicate μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery 

1 0.246 98.4 0.680 90.7 2.46 98.3 7.08 94.4 23.7 94.6 66.7 88.9 

2 0.252 101 0.690 92.0 2.54 102 6.71 89.5 24.1 96.2 62.4 83.2 

3 0.240 96.0 0.672 89.6 2.55 102 6.73 89.7 24.1 96.3 64.0 85.3 

4 0.242 96.8 0.694 92.5 2.48 99.3 6.82 91.0 25.2 101 64.2 85.6 

5 0.230 92.0 0.710 94.7 2.40 96.0 6.56 87.4 25.3 101 64.1 85.4 

6 0.248 99.2 0.688 91.7 2.49 99.5 7.09 94.6 24.9 99.7 66.7 88.9 

7 0.242 96.8 0.710 94.7 2.52 101 6.33 84.4 25.3 101 65.4 87.2 

average = 0.243 97.1 0.692 92.3 2.49 99.6 6.759 90.1 24.6 98.6 64.8 86.3 

std dev = 0.00701 2.80 0.0142 1.90 0.0514 2.05 0.273 3.64 0.698 2.79 1.58 2.10 

TABLE 41. PYRENE RECOVERY FROM SPIKED MEDIA (Weathered for 4 hours at 1 L/min) 

Int Std: Chrysene-D12; Quant. ion (m/z): 202

Applied 0.250 

(μg/sample) 

Applied 0.750 

(μg/sample) 

Applied 2.50 

(μg/sample) 

Applied 7.50 

(μg/sample) 

Applied 25.0 

(μg/sample) 

Applied 75.0 

(μg/sample) 

Found Percent Found Percent Found Percent Found Percent Found Percent Found Percent 

Replicate μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery μg/sample Recovery 

1 0.238 95.2 0.634 84.5 2.31 92.4 6.82 91.0 23.0 92.0 66.4 88.5 

2 0.246 98.4 0.676 90.1 2.45 98.0 6.53 87.0 24.9 99.5 620 82.7 

3 0.220 88.0 0.658 87.7 2.38 95.3 6.81 90.8 25.2 101 63.9 85.1 

4 0.244 97.6 0.758 101 2.26 90.6 6.82 91.0 25.3 102 61.6 82.1 

5 0.218 87.2 0.700 93.3 2.27 91.0 6.37 84.9 24.8 99.2 64.5 86.0 

6 0.224 89.6 0.714 95.2 2.31 92.5 7.28 97.0 24.8 99.3 67.5 90.0 

7 0.226 90.4 0.660 88.0 2.24 89.4 6.24 83.3 25.4 102 66.7 89.0 

average = 0.231 92.3 0.686 91.4 2.32 92.7 6.70 89.3 24.8 99.1 64.6 86.2 

std dev = 0.0116 4.64 0.0417 5.56 0.0744 2.98 0.347 4.63 0.812 3.25 2.33 3.11 
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NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Method for Processing the Data 

Recovery data less than 75% were not used in any statistical analysis. Overall precision, accuracy, and bias (Sr

2

) 

were calculated using the relationships described in Bartley [11], using the data from Tables 26-42. Identical calculations 

were made for Method precision, accuracy, and bias (Sr1) using data only from the user check. A description of the user 

check and the data tables are presented in Appendix A at the end of this report. 

As noted in Bartley [11, p. 363] the relationship between bias (B), accuracy (A), and precision (

rT S

) may 

formulated as 

rT rT

B A B A

S S



    + − =  −         

(1)

where 



is the standard normal distribution function and SrT (a measure of precision) is the true relative standard 

deviation. Accuracy was computed with α = 0.95 and was estimated using the formula presented in Bartley [11, p. 359] 

( )

1

2 2 2

1 /2 , | |

| | ,

rT

rT

rT

S

A u B S B

u

B u S otherwise







+

 

 

=  +         

  +   

Specifically, for 

( ) 1 /2 0.975 u u 1.96 +

= =

and for 

0.95 u u 1.645 

= =

as presented in (A3) in NIOSH [12], the estimate of 

accuracy, 

A

ˆ

, was computed as

1

2 2 2

ˆ

ˆ ˆ ˆ ˆ 1.96 , | |

1.645

ˆ ˆ

| | 1.645 ,

rT

rT

rT

S

A B S B

B S otherwise

 

   

=  +         

  +   

(2)

The estimated precision, 

ˆ

SrT

, was calculated as in NIOSH [12, p. 57] 

( )

( )

( )( )

( )

2

2

1 1

1 1

ˆ

1 ˆ 1

ˆ ˆ

1 1

i

i

k k i rTi i

rT pool k k

i i

i i

i i

S

n

C n S

S S

n n = =

= =

 

−  

−

 

= = =

− −

 

 

 (3)

if Bartlett’s test did not reject homogeneity of the true relative standard deviations 

ˆ

i

Ti

S

C

       

over the k concentrations where 

ni = number of observations for i

th concentration, 
Backup Data Report for NMAM 5528: Polynuclear aromatic hydrocarbons in air by GC-MS SIM- dated 06 October 2021 - Page 37 of 60

NIOSH Manual of Analytical Methods (NMAM) 5th Edition

 k = number of concentrations, 

ˆ

i

S

= standard deviation of observations at i

th concentration, and 

CTi

= known i

th concentration. 

If, on the other hand, Bartlett’s test did reject homogeneity of the true relative standard deviations are set 

 

  S S

ˆ ˆ

rT

= max ri

.

To calculate the bias, B, the bias for each measurement, yij, was computed as 

ij Ti

ij

Ti

x C

y

C

−

=

where 

ij x

= the j

th measurement for the ith concentration (run). Letting

1

.

j n

ij

j

i

i

y

y

n

=

=

=



 calculate the sum of squares within 

each concentration as SSwithin = ( )2

.

1 1

i k j n

ij i

i j

y y

= =

= =

 − and the error mean square = 

1

within

i k

i

i

SS MSE

n k

=

=

=

 

−     

. Next, calculate the 

sum of squares between concentrations as SSbetween = 

( )

2

. ..

1

i k

i i

i

n y y

=

=

 − and the treatment (concentration) mean square = 

1

MSTR SSbetween

k

=

−

. Then use a straightforward ANOVA, as shown in [12, p.51] and Neter Wasserman, Kutner [13], 

calculating 

MSTR F

MSE

=

with (k – 1) and

1

i k

i

i

n k

=

=

 

−     

degrees of freedom using SAS PROC GLM. If different 

concentrations were judged to have equivalent biases, then

.

1

..

ˆ

i k

i

i

y

B y

k

=

= = =



.

However, if the different concentrations were judged not to have equivalent biases, then 

i.

y

was chosen such that 

i k . max ,...,   1. . y y y =

and set 

.

ˆ

B y =

i

.

Note that the value of bias was chosen based on it having the largest absolute value, but the actual of 

B

ˆ

could be 

negative or positive. The 95% upper confidence limit of accuracy was calculated according to the formula (A4) given in 

NIOSH [12, p. 44]. These results are presented in Tables 42 and 43. 
Backup Data Report for NMAM 5528: Polynuclear aromatic hydrocarbons in air by GC-MS SIM- dated 06 October 2021 - Page 38 of 60

NIOSH Manual of Analytical Methods (NMAM) 5th Edition

 Table 42. Overall Bias, Accuracy and Precision (1,2)

Compound 

(alphabetically) 

Range For 

Calculation(3) 

(μg/sample) 

Bias (B) Overall 

Precision (SrT ̅̅̅̅) 

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 2.5 - 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 

 

(1) 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) 

 (2) Data includes 5% pump error correction 

(3) 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. 
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NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Table 43. Method Bias, Accuracy and Precision 

(1,2)

Analyte 

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 

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

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

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

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

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

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) This data is from the user check performed after method development. See Appendix 1 for discussion of 

experiments and data tables. 

(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. 

X. SUMMARY 

Data for most analytes derived during the method development met NIOSH criteria for precision, bias, and 

accuracy in all studies performed [9, 11, 12]. The method proved to be rugged for most analytes, with acenaphthylene 

being a notable exception due to its degradation during sampling. 

A user check has been performed on this method, and the results are located in Appendix 1. 
Backup Data Report for NMAM 5528: Polynuclear aromatic hydrocarbons in air by GC-MS SIM- dated 06 October 2021 - Page 40 of 60

NIOSH Manual of Analytical Methods (NMAM) 5th Edition

XI. REFERENCES 

[1] Wood AW, Levin W, Chang RL, Yagi H, Thakker DR, Lehr RE, Jerina DM, Conney AH [1979]. Bay-Region 

activation of carcinogenic polycyclic hydrocarbons. In: Jones PW, Leber P, eds. Polynuclear aromatic 

hydrocarbons. Ann Arbor, MI: Ann Arbor Science Publishers, Inc. 

[2] NIOSH [1994]. Polynuclear aromatic hydrocarbons by HPLC: Method 5506. In: Eller PM, Cassinelli ME, eds. 

NIOSH manual of analytical methods, 4th edition. Cincinnati, OH: 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 [1994]. Polynuclear aromatic hydrocarbons by GC: Method 5515. In: Eller PM, Cassinelli ME, eds. NIOSH 

Manual of Analytical Methods, 4th edition. Cincinnati, OH: 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] OSHA [1983, 1986]. 2,4-Dintrotoluene and/or 2,4,6-Trinitrotoluene: Method 44 and Chlorpyrifos, DDVP, diazinon, 

malathion, and parathion: Method 62. Salt Lake City, UT: U.S. Department of Labor, Occupational Safety and 

Health Administration. 

[5] NIOSH [2021]. Polynuclear aromatic hydrocarbons in air by GC-MS SIM: Method 5528. In: Andrews RA, 

O’Connor PF. NIOSH Manual of Analytical Methods, 5th edition. Cincinnati, OH: Department of Health and Human 

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

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

[6] DataChem Laboratories [2005]. Polynuclear aromatic hydrocarbons in air by GC-MS SIM: Method 5528 Backup 

Data Report. By: Hendricks RA, Reynolds JM, Perkins JB. Salt Lake City, UT: DataChem Laboratories, Inc. 

NIOSH contract CDC-200-2001-0800. LIMS Sequence 10313. Unpublished. 

[7] SKC Inc [2005]. Eighty Four, PA. www.skcinc.com

[8] Sigma-Aldrich [1998]. St Louis, MO. https://www.sigmaaldrich.com/content/dam/sigmaaldrich/docs/Sigma/Product_Information_Sheet/1/xad7pis.pdf

[9] NIOSH [1995]. Guidelines for air and analytical method development and evaluation. By: Kennedy ER, Fishbach 

TJ, Song R, Eller PM, Shulman, SA. Cincinnati, OH: Department of Health and Human Services, Centers for 

Disease Control and Prevention, National Institute for Occupational Safety and Health, DHHS (NIOSH) Publication 

No. 95-117.

[10] Burkart JA [1986]. General procedures for limit of detection calculations in industrial hygiene chemistry laboratory. 

App Ind Hyg 1(3):153-155. 

[11] Bartley DL [2001]. Definition and assessment of sampling and analytical accuracy. Annals Occ Hyg. 45:357-364. 

[12] NIOSH [2012]. Components for evaluation of direct-reading monitors for gases and vapors. Cincinnati, OH: 

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

Occupational Safety and Health, DHHS (NIOSH) Publication No. 2012-162. 

[13] Neter J, Wasserman W, Kutner MH. [1990]. Applied linear statistical models, 3rd ed. Boston, MA: Irwin. 
Backup Data Report for NMAM 5528: Polynuclear aromatic hydrocarbons in air by GC-MS SIM- dated 06 October 2021 - Page 41 of 60

NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Appendix 1. User Check 

User check samples were prepared by the Quality Assurance group of the NIOSH/DART contract laboratory, 

BVNA (contract 200-2011-39202, sequence #11571), to evaluate NIOSH Method 5528. Six tubes at 4 spiking levels (0.5, 

2, 5, and 20 μg) were prepared, for a total of twenty-four OVS-7 samples, for each of the 16 PAHs in the method. 

Samples for LOD/LOQ determination were also prepared and analyzed. The procedure followed by the laboratory for 

sample analysis was as given in the method. Results are presented in Tables 1-1 through 1-17. 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). The user check was successful. 

To check for humidity interference, additional experiments were performed by NIOSH/DART contract laboratory 

BVNA (contract 200-2011-39202, sequence #11760). Sample spikes were prepared at five different levels of 0, 10, 48, 96 

and 192 μg for each PAH in the method. Each level was composed of six replicate spikes. After the OVS-7 sampling 

tubes were spiked at the various levels, 80% relative humidity air was drawn through them. The spiked tubes were placed 

on an air-sampling manifold. The flow rate of the manifold was adjusted to 1 liter per minute (LPM). After the flow rate for 

the individual tubes was set, each tube was connected to a Miller/Nelson atmosphere generator to produce the humid air 

that would be drawn through the tubes. The tubes had the humid air drawn across them for 480 minutes. After sampling 

was performed, the tubes were placed in freezer storage conditions. The tubes sat overnight before desorption was done. 

The procedure followed by the laboratory for sample analysis was as given in the method. The results for the humidity test 

are presented in Tables 1-18 through 1-21. For 11 of the 16 PAHs tested, results at the lowest spiking level, 10 

μg/sample, were low. Therefore, when sampling an atmosphere high in humidity where the PAH level is expected to be 

low, be aware that results may be biased low. All other results for the humidity test were acceptable. 

All samples (user check and humidity user check) were analyzed under the instrument parameters listed below: 

• Instrument: Hewlett Packard Model 6890 GC/Hewlett Packard Model 5972 MS 

• Column: Phenomenex ZB-5MS, 30 meter, 0.25-mm ID with a 0.25 μm film thickness (Catalog# 7GH-G010-11-

GGC) 

• Column Flow: Pressure program, approximately 1.0 mL/min 

• Injection Temperature: 280 oC 

• Injection Volume: 1 μL 

• Oven Temperature Profile: 

• Initial Temperature: 100 oC 

• Initial Hold Time: 0.5 minutes 

• Temperature Program Rate: 12 oC/minute 

• Temperature: 290 oC 

• Hold Time: 1.0 minutes 

• Temperature Program Rate: 20 oC/minute 

• Final Temperature: 320 oC 

• Final Hold Time: 3.0 minutes 

• MS Operating Parameters: SIM mode 
Backup Data Report for NMAM 5528: Polynuclear aromatic hydrocarbons in air by GC-MS SIM- dated 06 October 2021 - Page 42 of 60

NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Table 1-1. LOD/LOQ results 

Compound 

LOD 

(μg/sample) 

LOQ 

(μg/sample) 

Analytical Range 

(μg/sample) 

Acenaphthene 0.05 0.17 0.05 to 30 

Acenaphthylene 0.05 0.17 0.05 to 30 

Anthracene 0.05 0.17 0.05 to 30 

Benzo[a]anthracene 0.05 0.18 0.05 to 30 

Benzo[a]pyrene 0.05 0.17 0.05 to 30 

Benzo[b]fluoranthene 0.05 0.17 0.05 to 30 

Benzo[ghi]perylene 0.05 0.17 0.05 to 30 

Benzo[k]fluoranthene 0.05 0.17 0.05 to 30 

Chrysene 0.05 0.17 0.05 to 30 

Dibenz[a,h]anthracene 0.08 0.26 0.08 to 30 

Fluoranthene 0.05 0.17 0.05 to 30 

Fluorene 0.05 0.17 0.05 to 30 

Indeno[1,2,3-cd]pyrene 0.05 0.17 0.05 to 30 

Naphthalene 0.06 0.19 0.06 to 30 

Phenanthrene 0.05 0.17 0.05 to 30 

Pyrene 0.05 0.17 0.05 to 30 
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NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Table 1-2. Recovery results for Acenaphthene

Analyte Concentration (μg) Spike (μg) % Recovery 

Acenaphthene 19.4 20 96.8

Acenaphthene 20.6 20 103

Acenaphthene 20.5 20 103

Acenaphthene 20.9 20 105

Acenaphthene 19.7 20 98.4 Avg recovery 101

Acenaphthene 20.4 20 102 Std Dev 3.00

Acenaphthene 4.59 5 91.8

Acenaphthene 5.24 5 105 

Acenaphthene 5.49 5 110 

Acenaphthene 5.47 5 109

Acenaphthene 5.27 5 105 Avg recovery 103

Acenaphthene 4.76 5 95.2 Std Dev 7.51

Acenaphthene 2.28 2 114

Acenaphthene 2.0 2 100

Acenaphthene 1.91 2 95.5

Acenaphthene 1.80 2 90.0

Acenaphthene 1.98 2 99.0 Avg recovery 97.6

Acenaphthene 1.74 2 87.0 Std Dev 9.50

Acenaphthene 0.43 0.5 86.0

Acenaphthene 0.48 0.5 96.0

Acenaphthene 0.48 0.5 96.0

Acenaphthene 0.49 0.5 98.0

Acenaphthene 0.46 0.5 92.0 Avg recovery 93.7

Acenaphthene 0.47 0.5 94.0 Std Dev 4.27
Backup Data Report for NMAM 5528: Polynuclear aromatic hydrocarbons in air by GC-MS SIM- dated 06 October 2021 - Page 44 of 60

NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Table 1-3. Recovery results for Acenaphthylene

Analyte Concentration (μg) Spike (μg) % Recovery 

Acenaphthylene 20.2 20 100

Acenaphthylene 21.4 20 107 

Acenaphthylene 21.4 20 107 

Acenaphthylene 21.8 20 109

Acenaphthylene 20.5 20 102 Avg recovery 105

Acenaphthylene 21.3 20 107 Std Dev 3.37

Acenaphthylene 4.98 5 99.6

Acenaphthylene 5.67 5 113

Acenaphthylene 5.98 5 120

Acenaphthylene 5.98 5 120

Acenaphthylene 5.70 5 114 Avg recovery 110

Acenaphthylene 4.81 5 96.2 Std Dev 10.1 

Acenaphthylene 2.26 2 113

Acenaphthylene 1.99 2 99.5

Acenaphthylene 1.91 2 95.5

Acenaphthylene 1.78 2 89.0

Acenaphthylene 1.96 2 98.0 Avg recovery 96.4

Acenaphthylene 1.67 2 83.5 Std Dev 10.1

Acenaphthylene 0.41 0.5 82.0

Acenaphthylene 0.44 0.5 88.0

Acenaphthylene 0.44 0.5 88.0

Acenaphthylene 0.46 0.5 92.0

Acenaphthylene 0.48 0.5 96.0 Avg recovery 88.7

Acenaphthylene 0.43 0.5 86.0 Std Dev 4.84
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NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Table 1-4. Recovery results for Anthracene 

Analyte Concentration (μg) Spike (μg) % Recovery 

Anthracene 18.9 20 94.4

Anthracene 20.7 20 103

Anthracene 20.4 20 102 

Anthracene 20.3 20 101

Anthracene 19.8 20 99.2 Avg recovery 100

Anthracene 20.0 20 99.8 Std Dev 3.13

Anthracene 4.60 5 92.0

Anthracene 5.19 5 104

Anthracene 5.48 5 110

Anthracene 5.44 5 109

Anthracene 5.38 5 108 Avg recovery 103

Anthracene 4.68 5 93.6 Std Dev 7.84

Anthracene 2.19 2 110

Anthracene 1.86 2 93.0

Anthracene 1.81 2 90.5

Anthracene 1.70 2 85.0

Anthracene 1.88 2 94.0 Avg recovery 92.3

Anthracene 1.63 2 81.5 Std Dev 9.72

Anthracene 0.39 0.5 78.0

Anthracene 0.40 0.5 80.0

Anthracene 0.39 0.5 78.0

Anthracene 0.40 0.5 80.0

Anthracene 0.41 0.5 82.0 Avg recovery 79.3

Anthracene 0.39 0.5 78.0 Std Dev 1.63
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NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Table 1-5. Recovery results for Benzo[a]anthracene 

Analyte Concentration (μg) Spike (μg) % Recovery 

Benzo[a]anthracene 19.7 20 98.6 

Benzo[a]anthracene 21.0 20 105

Benzo[a]anthracene 21.1 20 105

Benzo[a]anthracene 21.7 20 108

Benzo[a]anthracene 21.1 20 105 Avg recovery 105

Benzo[a]anthracene 21.3 20 106 Std Dev 3.29

Benzo[a]anthracene 4.88 5 97.6

Benzo[a]anthracene 5.61 5 112

Benzo[a]anthracene 5.60 5 112

Benzo[a]anthracene 5.78 5 116 

Benzo[a]anthracene 5.57 5 111 Avg recovery 108

Benzo[a]anthracene 4.86 5 97.2 Std Dev 8.09

Benzo[a]anthracene 2.49 2 125

Benzo[a]anthracene 1.99 2 99.5

Benzo[a]anthracene 1.94 2 97.0

Benzo[a]anthracene 1.76 2 88.0

Benzo[a]anthracene 1.86 2 93.0 Avg recovery 96.9

Benzo[a]anthracene 1.59 2 79.5 Std Dev 15.3 

Benzo[a]anthracene 0.38 0.5 76.0

Benzo[a]anthracene 0.39 0.5 78.0

Benzo[a]anthracene 0.38 0.5 76.0

Benzo[a]anthracene 0.38 0.5 76.0

Benzo[a]anthracene 0.38 0.5 76.0 Avg recovery 79.3

Benzo[a]anthracene 0.47 0.5 94.0 Std Dev 7.23
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NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Table 1-6. Recovery results for Benzo[a]pyrene

Analyte Concentration (μg) Spike (μg) % Recovery

Benzo[a]pyrene 19.2 20 96.2 

Benzo[a]pyrene 20.3 20 102 

Benzo[a]pyrene 20.4 20 102

Benzo[a]pyrene 20.9 20 104

Benzo[a]pyrene 19.4 20 97.2 Avg recovery 100

Benzo[a]pyrene 20.2 20 101 Std Dev 3.11

Benzo[a]pyrene 4.52 5 90.4

Benzo[a]pyrene 5.17 5 103

Benzo[a]pyrene 5.53 5 111 

Benzo[a]pyrene 5.20 5 104

Benzo[a]pyrene 5.29 5 106 Avg recovery 101

Benzo[a]pyrene 4.58 5 91.6 Std Dev 8.13

Benzo[a]pyrene 2.09 2 105

Benzo[a]pyrene 1.78 2 89.0

Benzo[a]pyrene 1.72 2 86.0

Benzo[a]pyrene 1.51 2 75.5

Benzo[a]pyrene 1.72 2 86.0 Avg recovery 85.9

Benzo[a]pyrene 1.49 2 74.5 Std Dev 10.9

Benzo[a]pyrene 0.33 0.5 66.0

Benzo[a]pyrene 0.35 0.5 70.0

Benzo[a]pyrene 0.34 0.5 68.0

Benzo[a]pyrene 0.35 0.5 70.0

Benzo[a]pyrene 0.33 0.5 66.0 Avg recovery 69.0

Benzo[a]pyrene 0.37 0.5 74.0 Std Dev 3.03
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NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Table 1-7. Recovery results for Benzo[b]fluoranthene

Analyte Concentration (μg) Spike (μg) % Recovery 

Benzo[b]fluoranthene 18.5 20 92.5

Benzo[b]fluoranthene 19.7 20 98.5

Benzo[b]fluoranthene 19.8 20 98.9 

Benzo[b]fluoranthene 20.2 20 101 

Benzo[b]fluoranthene 19.1 20 95.7 Avg recovery 97.3

Benzo[b]fluoranthene 19.4 20 97.2 Std Dev 2.93

 Benzo[b]fluoranthene 4.37 5 87.4

Benzo[b]fluoranthene 4.98 5 99.6

Benzo[b]fluoranthene 5.24 5 105 

Benzo[b]fluoranthene 4.94 5 98.8

Benzo[b]fluoranthene 4.95 5 99.0 Avg recovery 96.4

Benzo[b]fluoranthene 4.43 5 88.6 Std Dev 6.86

Benzo[b]fluoranthene 2.21 2 111

Benzo[b]fluoranthene 1.84 2 92.0

Benzo[b]fluoranthene 1.76 2 88.0

Benzo[b]fluoranthene 1.50 2 75.0

Benzo[b]fluoranthene 1.72 2 86.0 Avg recovery 87.7

Benzo[b]fluoranthene 1.49 2 74.5 Std Dev 13.2

Benzo[b]fluoranthene 0.37 0.5 74.0

Benzo[b]fluoranthene 0.40 0.5 80.0

Benzo[b]fluoranthene 0.39 0.5 78.0

Benzo[b]fluoranthene 0.40 0.5 80.0

Benzo[b]fluoranthene 0.38 0.5 76.0 Avg recovery 79.3

Benzo[b]fluoranthene 0.44 0.5 88.0 Std Dev 4.84
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NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Table 1-8. Recovery results for Benzo[ghi]perylene

Analyte Concentration (μg) Spike (μg) % Recovery

Benzo[ghi]perylene 19.1 20 95.6

Benzo[ghi]perylene 20.3 20 102 

Benzo[ghi]perylene 20.1 20 100

Benzo[ghi]perylene 20.8 20 104 

Benzo[ghi]perylene 19.5 20 97.3 Avg recovery 99.7

Benzo[ghi]perylene 19.9 20 99.6 Std Dev 2.98

Benzo[ghi]perylene 4.23 5 84.6

Benzo[ghi]perylene 4.88 5 97.6

Benzo[ghi]perylene 5.35 5 107

Benzo[ghi]perylene 4.93 5 98.6

Benzo[ghi]perylene 5.0 5 100 Avg recovery 97.5

Benzo[ghi]perylene 4.86 5 97.2 Std Dev 7.27

Benzo[ghi]perylene 2.24 2 112

Benzo[ghi]perylene 2.04 2 102

Benzo[ghi]perylene 1.93 2 96.5

Benzo[ghi]perylene 1.74 2 87.0

Benzo[ghi]perylene 1.97 2 98.5 Avg recovery 97.5

Benzo[ghi]perylene 1.78 2 89.0 Std Dev 9.11

Benzo[ghi]perylene 0.47 0.5 94.0

Benzo[ghi]perylene 0.50 0.5 100

Benzo[ghi]perylene 0.50 0.5 100

Benzo[ghi]perylene 0.51 0.5 102

Benzo[ghi]perylene 0.48 0.5 96.0 Avg recovery 98.0

Benzo[ghi]perylene 0.48 0.5 96.0 Std Dev 3.10
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NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Table 1-9. Recovery results for Benzo[k]fluoranthene

Analyte Concentration (μg) Spike (μg) % Recovery

Benzo[k]fluoranthene 17.9 20 89.4 

Benzo[k]fluoranthene 19.1 20 95.5

Benzo[k]fluoranthene 19.4 20 96.8 

Benzo[k]fluoranthene 19.9 20 99.3 

Benzo[k]fluoranthene 18.2 20 91.0 Avg recovery 94.6

Benzo[k]fluoranthene 19.1 20 95.5 Std Dev 3.70

Benzo[k]fluoranthene 4.32 5 86.4

Benzo[k]fluoranthene 5.02 5 100

Benzo[k]fluoranthene 5.51 5 110

Benzo[k]fluoranthene 5.03 5 101 

Benzo[k]fluoranthene 5.23 5 105 Avg recovery 99.1

Benzo[k]fluoranthene 4.62 5 92.4 Std Dev 8.53

Benzo[k]fluoranthene 2.17 2 109

Benzo[k]fluoranthene 1.95 2 97.5

Benzo[k]fluoranthene 1.88 2 94.0

Benzo[k]fluoranthene 1.74 2 87.0

Benzo[k]fluoranthene 1.98 2 99.0 Avg recovery 95.8

Benzo[k]fluoranthene 1.77 2 88.5 Std Dev 7.85

Benzo[k]fluoranthene 0.45 0.5 90.0

Benzo[k]fluoranthene 0.47 0.5 94.0

Benzo[k]fluoranthene 0.47 0.5 94.0

Benzo[k]fluoranthene 0.48 0.5 96.0

Benzo[k]fluoranthene 0.47 0.5 94.0 Avg recovery 93.7

Benzo[k]fluoranthene 0.47 0.5 94.0 Std Dev 1.97
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NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Table 1-10. Recovery results for Chrysene

Analyte Concentration (μg) Spike (μg) % Recovery

Chrysene 18.4 20 91.9 

Chrysene 19.7 20 98.3 

Chrysene 19.7 20 98.7

Chrysene 20.1 20 101. 

Chrysene 19.3 20 96.5 Avg recovery 97.4

Chrysene 19.7 20 98.7 Std Dev 3.02

Chrysene 4.46 5 89.2

Chrysene 5.00 5 100

Chrysene 5.34 5 107 

Chrysene 5.29 5 106 

Chrysene 5.16 5 103 Avg recovery 99.9

Chrysene 4.72 5 94.4 Std Dev 6.90

Chrysene 2.37 2 119

Chrysene 2.08 2 104

Chrysene 1.99 2 99.5

Chrysene 2.05 2 103 

Chrysene 2.14 2 107 Avg recovery 105

Chrysene 1.95 2 97.5 Std Dev 7.48

Chrysene 0.52 0.5 104

Chrysene 0.53 0.5 106

Chrysene 0.52 0.5 104

Chrysene 0.56 0.5 112

Chrysene 0.53 0.5 106 Avg recovery 105

Chrysene 0.50 0.5 100 Std Dev 3.93
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NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Table 1-11. Recovery results for Dibenz[a,h]anthracene

Analyte Concentration (μg) Spike (μg) % Recovery

Dibenz[a,h]anthracene 20.0 20 99.8

Dibenz[a,h]anthracene 21.0 20 105

Dibenz[a,h]anthracene 21.0 20 105

Dibenz[a,h]anthracene 21.7 20 108

Dibenz[a,h]anthracene 20.3 20 102 Avg recovery 104

Dibenz[a,h]anthracene 20.7 20 104 Std Dev 3.05

Dibenz[a,h]anthracene 4.63 5 92.6

Dibenz[a,h]anthracene 5.29 5 106 

Dibenz[a,h]anthracene 5.69 5 114 

Dibenz[a,h]anthracene 5.24 5 105 

Dibenz[a,h]anthracene 5.34 5 107 Avg recovery 105

Dibenz[a,h]anthracene 5.25 5 105 Std Dev 6.85

Dibenz[a,h]anthracene 2.39 2 120

Dibenz[a,h]anthracene 2.16 2 108

Dibenz[a,h]anthracene 2.01 2 101 

Dibenz[a,h]anthracene 1.76 2 88.0

Dibenz[a,h]anthracene 2.03 2 102 Avg recovery 101

Dibenz[a,h]anthracene 1.79 2 89.5 Std Dev 11.8

Dibenz[a,h]anthracene 0.45 0.5 90.0

Dibenz[a,h]anthracene 0.47 0.5 94.0

Dibenz[a,h]anthracene 0.44 0.5 88.0

Dibenz[a,h]anthracene 0.47 0.5 94.0

Dibenz[a,h]anthracene 0.44 0.5 88.0 Avg recovery 90.3

Dibenz[a,h]anthracene 0.44 0.5 88.0 Std Dev 2.94
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NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Table 1-12. Recovery results for Fluoranthene

Analyte Concentration (μg) Spike (μg) % Recovery

Fluoranthene 19.2 20 96

Fluoranthene 21.1 20 105

Fluoranthene 20.6 20 103

Fluoranthene 20.7 20 103

Fluoranthene 20.2 20 101 Avg recovery 102

Fluoranthene 20.6 20 103 Std Dev 3.24

Fluoranthene 4.51 5 90.2

Fluoranthene 5.30 5 106

Fluoranthene 5.63 5 113 

Fluoranthene 5.40 5 108

Fluoranthene 5.74 5 115 Avg recovery 104

Fluoranthene 4.73 5 94.6 Std Dev 9.89

Fluoranthene 2.34 2 117

Fluoranthene 1.88 2 94.0

Fluoranthene 1.89 2 94.5

Fluoranthene 1.70 2 85.0

Fluoranthene 1.87 2 93.5 Avg recovery 94.3

Fluoranthene 1.63 2 81.5 Std Dev 12.4 

Fluoranthene 0.40 0.5 80.0

Fluoranthene 0.42 0.5 84.0

Fluoranthene 0.40 0.5 80.0

Fluoranthene 0.42 0.5 84.0

Fluoranthene 0.40 0.5 80.0 Avg recovery 84.0

Fluoranthene 0.48 0.5 96.0 Std Dev 6.20
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NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Table 1-13. Recovery results for Fluorene

Analyte Concentration (μg) Spike (μg) % Recovery

Fluorene 19.6 20 97.9

Fluorene 20.9 20 104

Fluorene 20.6 20 103

Fluorene 21.0 20 105

Fluorene 19.9 20 99.5 Avg recovery 102

Fluorene 20.6 20 103 Std Dev 2.87

Fluorene 4.67 5 93.4

Fluorene 5.28 5 106

Fluorene 5.55 5 111

Fluorene 5.51 5 110

Fluorene 5.27 5 105 Avg recovery 105

Fluorene 5.26 5 105 Std Dev 6.29

Fluorene 2.47 2 123.5 

Fluorene 2.16 2 108

Fluorene 2.09 2 104.5 

Fluorene 1.99 2 99.5

Fluorene 2.14 2 107 Avg recovery 106

Fluorene 1.84 2 92.0 Std Dev 10.5

Fluorene 0.47 0.5 94.0

Fluorene 0.49 0.5 98.0

Fluorene 0.49 0.5 98.0

Fluorene 0.49 0.5 98.0

Fluorene 0.48 0.5 96.0 Avg recovery 97.0

Fluorene 0.49 0.5 98.0 Std Dev 1.67
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NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Table 1-14. Recovery results for Indeno[1,2,3-cd]pyrene 

Analyte Concentration (μg) Spike (μg) % Recovery

Indeno[1,2,3-cd]pyrene 19.7 20 98.4

Indeno[1,2,3-cd]pyrene 20.7 20 103

Indeno[1,2,3-cd]pyrene 20.8 20 104

Indeno[1,2,3-cd]pyrene 21.2 20 106

Indeno[1,2,3-cd]pyrene 20.2 20 101 Avg recovery 102

Indeno[1,2,3-cd]pyrene 20.4 20 102 Std Dev 2.69

Indeno[1,2,3-cd]pyrene 4.39 5 87.8

Indeno[1,2,3-cd]pyrene 4.91 5 98.2

Indeno[1,2,3-cd]pyrene 5.27 5 105

Indeno[1,2,3-cd]pyrene 4.93 5 98.6

Indeno[1,2,3-cd]pyrene 4.9 5 98.0 Avg recovery 97.3

Indeno[1,2,3-cd]pyrene 4.8 5 96.0 Std Dev 5.67

Indeno[1,2,3-cd]pyrene 2.2 2 110

Indeno[1,2,3-cd]pyrene 1.98 2 99.0

Indeno[1,2,3-cd]pyrene 1.82 2 91.0

Indeno[1,2,3-cd]pyrene 1.49 2 74.5

Indeno[1,2,3-cd]pyrene 1.63 2 81.5 Avg recovery 88.3

Indeno[1,2,3-cd]pyrene 1.48 2 74.0 Std Dev 14.4

Indeno[1,2,3-cd]pyrene 0.39 0.5 78.0

Indeno[1,2,3-cd]pyrene 0.39 0.5 78.0

Indeno[1,2,3-cd]pyrene 0.38 0.5 76.0

Indeno[1,2,3-cd]pyrene 0.40 0.5 80.0

Indeno[1,2,3-cd]pyrene 0.38 0.5 76.0 Avg recovery 78.3

Indeno[1,2,3-cd]pyrene 0.41 0.5 82.0 Std Dev 2.34
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NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Table 1-15. Recovery results for Naphthalene 

Analyte Concentration (μg) Spike (μg) % Recovery

Naphthalene 18.6 20 93.0 

Naphthalene 20.1 20 101 

Naphthalene 20.2 20 101 

Naphthalene 20.5 20 103 

Naphthalene 19.8 20 99.2 Avg recovery 99.3

Naphthalene 20.0 20 99.9 Std Dev 3.33

Naphthalene 4.48 5 89.6

Naphthalene 5.08 5 102 

Naphthalene 5.27 5 105

Naphthalene 5.35 5 107

Naphthalene 5.16 5 103 Avg recovery 99.9

Naphthalene 4.63 5 92.6 Std Dev 7.12

Naphthalene 2.28 2 114

Naphthalene 1.99 2 99.5

Naphthalene 1.89 2 94.5

Naphthalene 1.70 2 85.0

Naphthalene 1.95 2 97.5 Avg recovery 95.4

Naphthalene 1.69 2 84.5 Std Dev 10.9

Naphthalene 0.41 0.5 82.0

Naphthalene 0.46 0.5 92.0

Naphthalene 0.47 0.5 94.0

Naphthalene 0.46 0.5 92.0

Naphthalene 0.45 0.5 90.0 Avg recovery 89.7

Naphthalene 0.44 0.5 88.0 Std Dev 4.27
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NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Table 1-16. Recovery results for Phenanthrene 

Analyte Concentration (μg) Spike (μg) % Recovery

Phenanthrene 18.5 20 92.3 

Phenanthrene 20.0 20 100

Phenanthrene 19.9 20 99.7 

Phenanthrene 19.9 20 99.6 

Phenanthrene 19.5 20 97.5 Avg recovery 97.8

Phenanthrene 19.5 20 97.6 Std Dev 2.94

Phenanthrene 4.43 5 88.6

Phenanthrene 4.99 5 99.8

Phenanthrene 5.31 5 106

Phenanthrene 5.21 5 104

Phenanthrene 5.20 5 104 Avg recovery 99.3

Phenanthrene 4.65 5 93 Std Dev 7.04

Phenanthrene 2.25 2 113

Phenanthrene 1.92 2 96.0

Phenanthrene 1.86 2 93.0

Phenanthrene 1.78 2 89.0

Phenanthrene 1.99 2 99.5 Avg recovery 96.2

Phenanthrene 1.74 2 87.0 Std Dev 9.20

Phenanthrene 0.44 0.5 88.0

Phenanthrene 0.48 0.5 96.0

Phenanthrene 0.46 0.5 92.0

Phenanthrene 0.48 0.5 96.0

Phenanthrene 0.46 0.5 92.0 Avg recovery 93.0

Phenanthrene 0.47 0.5 94.0 Std Dev 3.03
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NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Table 1-17. Recovery results for Pyrene 

Analyte Concentration (μg) Spike (μg) % Recovery

Pyrene 18.1 20 90.4

Pyrene 18.9 20 94.5

Pyrene 19.3 20 96.6 

Pyrene 19.6 20 98.1 

Pyrene 19.0 20 95.2 Avg recovery 95.3

Pyrene 19.4 20 97.0 Std Dev 2.71

Pyrene 4.39 5 87.8

Pyrene 4.95 5 99.0

Pyrene 5.18 5 104 

Pyrene 5.25 5 105

Pyrene 5.05 5 101 Avg recovery 99.2

Pyrene 4.93 5 98.6 Std Dev 6.11

Pyrene 2.46 2 123

Pyrene 2.19 2 110 

Pyrene 2.08 2 104

Pyrene 2.10 2 105

Pyrene 2.20 2 110 Avg recovery 108

Pyrene 1.96 2 98.0 Std Dev 8.44

Pyrene 0.51 0.5 102

Pyrene 0.53 0.5 106

Pyrene 0.53 0.5 106

Pyrene 0.53 0.5 106

Pyrene 0.53 0.5 106 Avg recovery 104

Pyrene 0.50 0.5 100 Std Dev 2.66
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NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Table 1-18. Humidity recovery results for 10 μg spike on tube 

Analyte Amount 

Spiked (μg) 

Average 

Recovery (%) 

Standard 

Deviation 

Naphthalene 10 74.3 6.34

Acenaphtylene 10 72.4 6.94

Acenaphthene 10 73.1 6.74

Fluorene 10 75.0 7.56

Phenanthrene 10 75.4 7.26

Anthracene 10 73.5 6.88

Fluoranthene 10 75.5 8.27

Pyrene 10 76.0 6.99

Benz[a]anthracene 10 72.6 6.89

Chrysene 10 78.5 6.84

Benzo[b]fluoranthene 10 70.4 6.63

Benzo[k]fluoranthene 10 77.9 7.96

Benzo[a]pyrene 10 70.5 6.91

Indeno[1,2,3-c,d]pyrene 10 67.8 5.43

Dibenz[a,h]anthracene 10 71.1 7.04

Benzo[ghi]perylene 10 72.6 5.75

Table 1-19. Humidity recovery results for 48 μg spike on tube

Analyte Amount 

Spiked (μg) 

Average 

Recovery (%) 

Standard 

Deviation 

Naphthalene 48 91.2 3.73

Acenaphtylene 48 91.7 4.46

Acenaphthene 48 94.5 4.70

Fluorene 48 94.2 4.70

Phenanthrene 48 95.4 5.73

Anthracene 48 98.1 6.04

Fluoranthene 48 95.0 5.88

Pyrene 48 95.0 6.42

Benz[a]anthracene 48 95.9 5.12

Chrysene 48 95.8 6.44

Benzo[b]fluoranthene 48 100 5.88

Benzo[k]fluoranthene 48 96.8 6.70

Benzo[a]pyrene 48 90.0 6.28

Indeno[1,2,3-c,d]pyrene 48 96.7 6.74

Dibenz[a,h]anthracene 48 92.6 5.90

Benzo[ghi]perylene 48 104 5.45
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NIOSH Manual of Analytical Methods (NMAM) 5th Edition

Table 1-20. Humidity recovery results for 96 μg spike on tube

Analyte Amount 

Spiked (μg) 

Average 

Recovery (%) 

Standard 

Deviation 

Naphthalene 96 78.0 2.05

Acenaphthylene 96 83.4 1.77

Acenaphthene 96 81.5 1.96

Fluorene 96 82.7 1.87

Phenanthrene 96 82.5 1.75

Anthracene 96 84.0 1.56

Fluoranthene 96 86.0 1.99

Pyrene 96 82.9 1.90

Benz[a]anthracene 96 83.0 1.41

Chrysene 96 81.7 1.91

Benzo[b]fluoranthene 96 85.1 2.79

Benzo[k]fluoranthene 96 85.1 2.62

Benzo[a]pyrene 96 85.6 1.68

Indeno[1,2,3-c,d]pyrene 96 78.9 3.03

Dibenz[a,h]anthracene 96 86.1 3.06

Benzo[ghi]perylene 96 80.1 4.36

Table 1-21. Humidity recovery results for 192 μg spike on tube

Analyte Amount 

Spiked (μg) 

Average 

Recovery (%) 

Standard 

Deviation 

Naphthalene 192 79.8 2.67

Acenaphthylene 192 84.0 3.50

Acenaphthene 192 83.9 2.27

Fluorene 192 84.7 1.70

Phenanthrene 192 80.9 2.11

Anthracene 192 83.1 3.55

Fluoranthene 192 85.3 3.54

Pyrene 192 83.3 2.91

Benz[a]anthracene 192 86.0 2.72

Chrysene 192 81.7 2.22

Benzo[b]fluoranthene 192 86.6 2.18

Benzo[k]fluoranthene 192 82.7 3.00

Benzo[a]pyrene 192 87.8 2.53

Indeno[1,2,3-c,d]pyrene 192 81.2 2.29

Dibenz[a,h]anthracene 192 87.0 2.65

Benzo[ghi]perylene 192 81.3 2.06