NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

NIOSH Manual of Analytical Methods (NMAM) 5th Edition 

BACKUP DATA REPORT 

NIOSH Method No. 1453

Title: Vinyl Acetate

Analyte: Vinyl Acetate

Author/developer:Paula Fey O’Connor, Yvonne Gagnon, 

H. Amy Feng and Kevin Ashley

Date: December, 2012

Note: Method revised due to availability of sorbent tubes 

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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BACKUP DATA REPORT – NIOSH 1453 Issue 3, Dec. 2012

Backup Data Report for Revised Vinyl Acetate Analytical Method, NMAM 1453

Paula Fey O’Connor, Yvonne Gagnon, H. Amy Feng and Kevin Ashley

RATIONALE: Revision of this method became necessary due to changes in supplies of sorbent tubes 

provided by manufacturers. It was necessary to reevaluate the method using currently commercially available 

sorbent tubes, which replaced those used in previous method evaluations, ORBO-90. 

Carbon molecular sieve sampling tubes (ORBO-92 adsorbent tube, 160/80 mg., Supelco) were loaded 

with known amounts of vinyl acetate. These tubes were desorbed with 1 mL of methylene chloride/methanol 

(95:5 v/v) for 30 minutes and analyzed by gas chromatography (GC) with flame ionization detection (FID). The 

GC analytical parameters were as follows:

Gas Chromatograph: Hewlett-Packard Model 5890A equipped with a flame ionization detector 

Injector Temperature: 210 °C 

Detector Temperature: 260 °C 

Column: 30 m x 0.32 mm fused silica capillary column coated internally with 1.00 μm

(5% - Phenyl)-methylpolysiloxane

Oven Condition: 35 °C hold 5 minutes; 5 °C/minute to 50 °C, hold one minute

 Carrier Gas: Nitrogen, split flow 21.0 mL/min

Experiments and statistical computations were carried out in accordance with E. R. Kennedy et al., Guidelines 

for Air Sampling and Analytical Development and Evaluation, CDC/NIOSH: Cincinnati (1995); DHHS (NIOSH) 

Publ. No. 95-117. A summary of the calculations performed and the data obtained follows.
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A. Precision, Bias, & Accuracy Study

Two sets of data: spikes and generated samples

Data were collected using spiked sample tubes as well as samples collected using generated test atmospheres.

1. Analysis of spiked samples was used to calculate CV1 based on mean % recovery

2. Sampling and analysis data from generated test atmospheres was used to (a) calculate CV2 based

on pooled mean values, and (b) calculate mean bias and method accuracy.

User check procedures

The User Check study was carried out in accordance with CEMB SOP 504. 

Bias Precision and Accuracy Estimation

For details on procedures used for data evaluation, refer to NMAM Chapter P & Documentation of the

NIOSH Validation Tests (77-185): 

CV1: CV based on spiked samples - Experimental error due to analysis

CV2: CV based on generated data - Experimental error due to sampling and analysis 

(CVp)**2=(0.05)**2=0.0025 - Uncertainty component due to sampling pump error

CVT: CV total

(CVT)**2=(CV2)**2+(CVp)**2

CV_ADE=Square root[(n+1/n)]*CV1 

Tables summarizing the performance data hereby follow: 
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Vinyl Acetate

Analytical – Desorption Efficiencies (D.E.) – Data summary

Obs sequence LOD LOQ sample found level Taken % Recovery

1 10898-CA 0.5 1.6 5 45.2 1 46.7 96.788

2 10898-CA 0.5 1.6 6 43.4 1 46.7 92.9336

3 10898-CA 0.5 1.6 13 40.6 1 46.7 86.9379

4 10898-CA 0.5 1.6 18 43.3 1 46.7 92.7195

5 10898-CA 0.5 1.6 20 45.4 1 46.7 97.2163

6 10898-CA 0.5 1.6 21 46 1 46.7 98.5011

7 10898-CA 0.5 1.6 2 88.2 2 93.4 94.4325

8 10898-CA 0.5 1.6 4 90.6 2 93.4 97.0021

9 10898-CA 0.5 1.6 8 87.5 2 93.4 93.6831

10 10898-CA 0.5 1.6 12 86.4 2 93.4 92.5054

11 10898-CA 0.5 1.6 17 86.5 2 93.4 92.6124

12 10898-CA 0.5 1.6 19 88.6 2 93.4 94.8608

13 10898-CA 0.5 1.6 3 189 3 205.5 91.9708

14 10898-CA 0.5 1.6 9 201 3 205.5 97.8102

15 10898-CA 0.5 1.6 11 195 3 205.5 94.8905

16 10898-CA 0.5 1.6 14 183 3 205.5 89.0511

17 10898-CA 0.5 1.6 15 191 3 205.5 92.944

18 10898-CA 0.5 1.6 16 201 3 205.5 97.8102

Mean % recovery, Grubb test, 95% CI of mean % recovery

Level Taken mean m_found std n cv outlier LL UL

1 46.7 94.1827 43.983 4.26208 6 0.045253 no 90.3913 97.9742

2 93.4 94.1827 87.967 1.67334 6 0.017767 no 92.6942 95.6713

3 205.5 94.0795 193.333 3.45007 6 0.036672 no 91.0104 97.1486

Bias RSD, and RSD (CV)

n k % Recovery est_bias est_rsd (CV_1) (CV_1)**2 CV_ADE

3 1 94.16 -0.05852 0.020299 0.001236 0.023439
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Sampling and Analysis – Data summary

Obs Level sample Humidity Front Back Found Taken flow_rate % Recovery

1 1 1 L 85.2 0 85.2 89 98.4 95.8

2 1 2 L 91.3 0 91.3 89 105 103

3 1 3 L 89.9 0 89.9 89 96.3 101

4 1 4 L 90.2 0 90.2 89 94 101

5 1 1 H 81.5 0 81.5 89 98.1 91.6

6 1 2 H 85.3 0 85.3 89 102 95.9

7 1 3 H 79.3 0 79.3 89 99 89.2

8 1 4 H 82.3 0 82.3 89 99 92.5

9 2 1 L 199 0 199 200 102 99.5

10 2 2 L 196 0 196 200 101 98

11 2 3 L 205 0 205 200 93.9 103

12 2 4 L 202 0 202 200 106 101

13 2 1 H 175 0 175 200 103 87.5

14 2 2 H 188 0 188 200 96.9 94

15 2 3 H 201 0 201 200 106 101

16 2 4 H 174 0 174 200 91.7 87

17 3 1 L 530 0 530 623 103 85.1

18 3 2 L 561 0 561 623 104 90

19 3 3 L 573 0 573 623 106 92

20 3 4 L 576 0 576 623 95.8 92.5

21 3 1 H 626 0 626 623 92.5 100

22 3 2 H 620 0 620 623 102 99.5

23 3 3 H 614 0 614 623 108 98.6

24 3 4 H 632 0 632 623 99.7 101

25 4 1 L 1050 0 1050 1110 106 94.6

26 4 2 L 1000 0 1000 1110 100 90.1

27 4 3 L 1090 0 1090 1110 101 98.2

28 4 4 L 1110 0 1110 1110 100 100

29 4 1 H 1040 0 1040 1110 96.8 93.7

30 4 2 H 1130 0 1130 1110 97.6 102

31 4 3 H 1040 0 1040 1110 101 93.7

32 4 4 H 1110 0 1110 1110 98.3 100
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Mean % recovery, Grubb test, 95% CI of mean % recovery

Humidity level Taken m_found m_recovery n CV_found outlier LL UL

H 1 89 82.1 92.3 4 0.030 no 89.28 95.32

H 2 200 184.5 92.375 4 0.069 no 85.21 99.54

H 3 623 623 99.775 4 0.012 no 98.68 100.87

H 4 1110 1080 97.35 4 0.043 no 92.67 102.03

L 1 89 89.15 100.2 4 0.03 no 96.84 103.56

L 2 200 200.5 100.375 4 0.019 no 98.05 102.70

L 3 623 560 89.9 4 0.038 no 86.22 93.58

L 4 1110 1062.5 95.725 4 0.046 no 90.96 100.49

Bias, RSD, Accuracy Estimates and 95 % CI Estimates

%rRecovery n (CV2)**2 CV2 CVT

96 8 0.00156 0.0395 0.063731

n K est_bias est_rsd Accuracy Acc_U95

8 2 -0.04022 0.039518 0.10523 0.14127

Conclusion: Based on the bias, precision, and accuracy results, this method meets the NIOSH criteria for 

method accuracy (Kennedy et al., 1995).

B. Sample Storage Stability Study

Spiked samples of vinyl acetate were stored at two temperatures: room temperature and 4 °C, and at two 

concentration levels: ‘Low’ (187 micrograms) and ‘High’ (747 micrograms). For the room temperature, data 

were collected at days 1 and 7. For the cold temperature, data were collected for days 1,7,14, and 30.

Analysis of Variance (ANOVA) procedures followed by Tukey’s multiple comparison technique was used to test 

for difference in recovery among the storage days (1, 7, 14, 30). The test was performed at the 5%

significance level.

Statistically significant differences were found:

1. 4 °C and high concentration, the recovery of day 30 is higher than those of days 1, 7, 14.

2. 4 °C and low concentration, the recovery of days 30 and 14 are higher than those of the days 1, 7.
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When day 30 was excluded, the ANOVA shows no statistically significant difference in % recovery among days

1, 7, and 14 except for one case: cold temperature and low concentration, the recovery of days 14 remains 

higher than those of the days 1, 7.

However, the individual % recovery of day 30 results are mostly with the acceptable ranges of the 90%-110% 

with two exceptions (112%* and 111%* at the 4 °C -High loading). In any case, the mean percent recoveries 

are all in the acceptable ranges of the 90%-110% **. This leads to a conclusion of acceptable recovery for up 

to 1 month storage

Vinyl Acetate – User check Storage Data

Obs temp Level day Samp Result

μg

Spiked

μg

Recovery pt_bias

1 C H 1 ‘1-1 760 747 101.74 1.7403

2 C H 1 ‘1-2 681 747 91.165 -8.8353

3 C H 1 ‘1-3 703 747 94.11 -5.8902

4 C H 1 ‘1-4 691 747 92.503 -7.4967

5 C H 1 ‘1-5 696 747 93.173 -6.8273

6 C H 7 ‘2-1 748 747 100.134 0.1339

7 C H 7 ‘2-2 711 747 95.181 -4.8193

8 C H 7 ‘2-3 727 747 97.323 -2.6774

9 C H 7 ‘2-4 770 747 103.079 3.079

10 C H 7 ‘2-5 727 747 97.323 -2.6774

11 C H 14 ‘3-1 632 747 84.605 -15.3949

12 C H 14 ‘3-2 674 747 90.228 -9.7724

13 C H 14 ‘3-3 680 747 91.031 -8.9692

14 C H 14 ‘3-4 696 747 93.173 -6.8273

15 C H 14 ‘3-5 769 747 102.945 2.9451

16 C H 30 ‘4-1 837 747 112.048* 12.0482

17 C H 30 ‘4-2 753 747 100.803 0.8032

18 C H 30 ‘4-3 807 747 108.032 8.0321

19 C H 30 ‘4-4 786 747 105.221 5.2209

20 C H 30 ‘4-5 833 747 111.513* 11.5127

21 C L 1 ‘1-1 171 187 91.444 -8.5561

22 C L 1 ‘1-2 176 187 94.118 -5.8824

23 C L 1 ‘1-3 173 187 92.513 -7.4866

24 C L 1 ‘1-4 167 187 89.305 -10.6952

25 C L 1 ‘1-5 171 187 91.444 -8.5561

26 C L 7 ‘2-1 173 187 92.513 -7.4866

27 C L 7 ‘2-2 173 187 92.513 -7.4866

28 C L 7 ‘2-3 171 187 91.444 -8.5561

29 C L 7 ‘2-4 174 187 93.048 -6.9519
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30 C L 7 ‘2-5 173 187 92.513 -7.4866

31 C L 14 ‘3-1 184 187 98.396 -1.6043

32 C L 14 ‘3-2 185 187 98.93 -1.0695

33 C L 14 ‘3-3 193 187 103.209 3.2086

34 C L 14 ‘3-4 184 187 98.396 -1.6043

35 C L 14 ‘3-5 190 187 101.604 1.6043

36 C L 30 ‘4-1 189 187 101.07 1.0695

37 C L 30 ‘4-2 195 187 104.278 4.2781

38 C L 30 ‘4-3 190 187 101.604 1.6043

39 C L 30 ‘4-4 188 187 100.535 0.5348

40 C L 30 ‘4-5 202 187 108.021 8.0214

41 R H 1 ‘1-1 690 747 92.369 -7.6305

42 R H 1 ‘1-2 684 747 91.566 -8.4337

43 R H 1 ‘1-3 712 747 95.315 -4.6854

44 R H 1 ‘1-4 705 747 94.378 -5.6225

45 R H 1 ‘1-5 701 747 93.842 -6.158

46 R H 7 ‘2-1 661 747 88.487 -11.5127

47 R H 7 ‘2-2 739 747 98.929 -1.071

48 R H 7 ‘2-3 688 747 92.102 -7.8983

49 R H 7 ‘2-4 782 747 104.685 4.6854

50 R H 7 ‘2-5 684 747 91.566 -8.4337

51 R L 1 ‘1-1 181 187 96.791 -3.2086

52 R L 1 ‘1-2 173 187 92.513 -7.4866

53 R L 1 ‘1-3 165 187 88.235 -11.7647

54 R L 1 ‘1-4 171 187 91.444 -8.5561

55 R L 1 ‘1-5 193 187 103.209 3.2086

56 R L 7 ‘2-1 183 187 97.861 -2.139

57 R L 7 ‘2-2 186 187 99.465 -0.5348

58 R L 7 ‘2-3 186 187 99.465 -0.5348

59 R L 7 ‘2-4 189 187 101.07 1.0695

60 R L 7 ‘2-5 190 187 101.604 1.6043

Summary Statistics of percent recovery

temp level day Mean

% Recovery

Min max N Std

C H 1 94.538 91.165 101.74 5 4.166

C H 7 98.608 95.181 103.079 5 3.056

C H 14 92.396 84.605 102.945 5 6.692

C H 30 107.523** 100.803 112.048 5 4.667

C L 1 91.765 89.305 94.118 5 1.757

C L 7 92.406 91.444 93.048 5 0.586

C L 14 100.107** 98.396 103.209 5 2.185

C L 30 103.102** 100.535 108.021 5 3.104
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R H 1 93.494 91.566 95.315 5 1.517

R H 7 95.154 88.487 104.685 5 6.552

R L 1 94.438 88.235 103.209 5 5.78

R L 7 99.893 97.861 101.604 5 1.484

C. Review of User Check for NMAM Method 1453-3, Vinyl Acetate

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

order to evaluate the update of NIOSH Method 1453 (Vinyl Acetate). A total of twenty-one ORBO 92 sample 

tubes were spiked with vinyl acetate on January 13, 2009. The NIOSH contract industrial hygiene laboratory 

(Bureau Veritas) analyzed the samples on February 5, 2009. The procedure followed by the laboratory was as 

given in the method.

The limit of detection (LOD) was 0.5 μg/sample and the limit of quantitation (LOQ) was 1.6 μg/sample for vinyl 

acetate. The laboratory method blanks were none detected for vinyl acetate. The recoveries for the

laboratory control samples were acceptable for vinyl acetate at 99.5%. The blind spikes were within the 

default limits of 80%-120% for vinyl acetate. Replicate analyses were within the 20% acceptable limit.

The table below summarizes the data from the independent laboratory report for vinyl acetate:

Ave

Sample ID 

VA NMAM - 1

Spiked Amt

0 μg

Amt found

ND

Recovery

N/A

Recovery RSD

VA NMAM - 7

VA NMAM - 10

0 μg

0 μg

ND 

ND

N/A 

N/A

VA NMAM - 5 46.7 μg 45.2 μg 96.8%

VA NMAM - 6 46.7 μg 43.4 μg 92.9%

VA NMAM - 13 46.7 μg 40.6 μg 86.9%

VA NMAM - 18 46.7 μg 43.3 μg 92.7%

VA NMAM - 20 46.7 μg 45.4 μg 97.2%

VA NMAM - 21 46.7 μg 46.0 μg 98.5% 94.2% 4.5%

VA NMAM - 2 93.4 μg 88.2 μg 94.4%

VA NMAM - 4 93.4 μg 90.6 μg 97.0%

VA NMAM - 8 93.4 μg 87.5 μg 93.7%

VA NMAM - 12 93.4 μg 86.4 μg 92.5%

VA NMAM - 17 93.4 μg 96.5 μg 103.3%

VA NMAM - 19 93.4 μg 88.6 μg 94.9% 96.0% 4.1%

VA NMAM - 3 205.5 μg 189 μg 92.0%

VA NMAM - 9 205.5 μg 201 μg 97.8%

VA NMAM - 11 205.5 μg 195 μg 94.9%

VA NMAM - 14 205.5 μg 183 μg 89.1%

VA NMAM - 15 205.5 μg 191 μg 92.9%

VA NMAM - 16 205.5 μg 201 μg 97.8% 94.1% 3.7%
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Overall this user check to update NMAM 1453 showed excellent performance, and the user check has been 

passed and is acceptable. It is recommended that the draft 3rd issue of method 1453 be accepted and placed 

into NMAM for publication.

19 December 2012