NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

 

Volatile Organic Compounds, C1 to C10, Canister Method 3900

Formula: Table 1 MW: Table 1 CAS: Table 1 RTECS: Table 1

METHOD: 3900, Issue 1 EVALUATION: FULL Issue 1: 30 August 2018

OSHA: Table 3

NIOSH REL: Table 3 

Other OELs: [1-3]

PROPERTIES: Table 1

ANALYTES: ethanol, 2-propanol, acetone, 2,3-butanedione, 2,3-pentanedione, 2,3-hexanedione, dichloromethane, 

trichloromethane, hexane, benzene, toluene, ethylbenzene, o-xylene, m,p-xylene, methyl methacrylate, α-pinene, d-limonene

SAMPLING

SAMPLER: FUSED-SILICA LINED STAINLESS STEEL 

CANISTER, 6 L, 450, or 400 mL

FLOW RATE: 0.06 to 50 mL/min. See SAMPLING section

VOL-MIN: Depends on canister volume. See 

SAMPLING section

SHIPMENT: Routine

SAMPLE

STABILITY: 58 days @ 25 °C (30 days for ethanol, 

2-propanol, and acetone @ 10 ppb; 21 days 

for α-pinene and d-limonene @ 0.8 ppm)

BLANKS: 1 field blank per set

ACCURACY

RANGE 

STUDIED: Tables 4a and 4b 

BIAS: Tables 4a and 4b

OVERALL

PRECISION (SS�rrrr): Tables 4a and 4b 

ACCURACY: Tables 4a and 4b 

MEASUREMENT

TECHNIQUE: GAS CHROMATOGRAPHY, MASS 

SPECTROMETRY

ANALYTE: Compounds listed in Table 1

PRECONCENTRATION 

VOLUME: 25 to 500 mL injection (ppblevels) for a 6L canister, 25 to 250 mL 

injection (ppb-levels) for a 400/450 mL 

canister, 1 mL loop (ppm-levels)

PRECONCENTRATION 

CONDITIONS: Module 1 (empty): 

Focused @ -20° C, desorbed @ 10° C, baked 

@ 150° C (7 min); Module 2 (glass beads): 

Focused @ -80° C, desorbed @ 180° C, 

baked @ 190° C; Module 3 (focuser): 

Focused @ -150° C.

GC/MS 

CONDITIONS: Injection: preconcentrator transfer line 100°C

Detector: 280° C 

Column: 35° C (2 min hold) to 170° C (ramp 

8°C/min), ramp 20° C/min to 220° C (3 min 

hold)

MS Source: 230° C 

Quadrupole: 150° C 

Solvent delay: 4.5 min

MS Scan: 35-350 amu

CARRIER GAS: Helium, 1 mL/min

COLUMN: Capillary, fused silica, 60 m x 0.32-mm ID; 1-

μm film 100% dimethylpolysiloxane

CALIBRATION: Gas phase analytes in canisters

RANGE: Tables 4a and 4b

ESTIMATED LOD: Tables 4a and 4b

PRECISION (SS�rr): Tables 4a and 4b

APPLICABILITY: The method was developed for measuring a range of volatile organic compounds in healthcare settings [4], but 

may be used in other occupational settings. The method was developed to measure the following analytes: ethanol, acetone, 2-

propanol, dichloromethane, hexane, trichloromethane, 2,3-butanedione, 2,3-pentanedione, and 2,3-hexanedione, benzene, 

methyl methacrylate, toluene, ethylbenzene, m,p-xylene, o-xylene, α-pinene, and d-limonene. The working range is 0.24 to 22 ppb 
Volatile Organic Compounds, C1 to C10, Canister Method: METHOD 3900, Issue 1, dated 30 August 2018 - Page 2 of 14

NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

for ppb-level analysis and 0.07 to 2.0 ppm for ppm-level analysis depending on analyte (Table 4a). This method may be applicable 

for other volatile organic compounds that exhibit acceptable stability, bias, precision and accuracy. Alternate detectors (e.g., flame 

ionization detector, electron capture detector, thermal conductivity detector, time-of-flight or quadrupole time-of-flight mass 

spectrometer), canister volumes, GC columns, internal standards and equipment may be used after method performance has been 

assessed and shown to be within acceptable limits. Training on pressure dilution techniques and preconcentration systems as well 

as proficiency testing should be periodically conducted to ensure operating laboratories maintain optimal canister method 

performance.

INTERFERENCES: Other compounds with similar retention times and quantitation ions may interfere (e.g., alcohols, ketones, 

aromatics, beta-pinene). For example, vinyl acetate has the same molecular weight as 2,3-butanedione and has the same retention 

time elution on the recommended column. High humidity samples that are pressurized may form condensed water causing losses 

of water-soluble compounds. Water content should be managed during preconcentration of the sample by purging traps with 

helium, reducing the sample injection volume onto the preconcentrator, or splitting the sample stream prior to concentration 

and/or gas chromatograph injection. 

OTHER METHODS: This is a method for the determination of VOCs, C1 to C10, in mixed exposure environments. The method has 

been modified from the Environmental Protection Agency (EPA) method TO-15 to include specific chemicals and low-ppm 

concentration volatile analysis [5]. ASTM D5466 is also available as guidance for canister sampling and analysis [6].

REAGENTS:

1. Ethanol, reagent grade*

2. 2-Propanol, reagent grade*

3. Acetone, reagent grade*

4. 2,3-Butanedione, reagent grade*

5. 2,3-Pentanedione, reagent grade*

6. 2,3-Hexanedione, reagent grade*

7. Dichloromethane, reagent grade*

8. Trichloromethane, reagent grade*

9. Hexane, reagent grade*

10. Benzene, reagent grade*

11. Toluene, reagent grade*

12. Ethylbenzene, reagent grade*

13. o-Xylene, reagent grade*

14. m-Xylene, reagent grade*

15. p-Xylene, reagent grade*

16. Methyl methacrylate, reagent grade*

17. α-Pinene, reagent grade

18. d-Limonene, reagent grade*

19. Ultra-high purity air

20. Ultra-high purity nitrogen

21. Ultra-high purity helium

22. Internal standard cylinder @ 20 ppb 

(bromochloromethane; 1,4-difluorobenzene; 

chlorobenzene-d5; and 

bromofluorobenzene)

23. Distilled, deionized water, 18 MOhm, low VOC 

content

*See SPECIAL PRECAUTIONS.

EQUIPMENT:

1. Gas chromatograph/mass spectrometer 

system capable of attaching to 

preconcentrator system 

2. Whole-air preconcentrator system capable of 

variable injection volumes from 25 to 500 mL

3. Canister autosampler with 1-mL loop 

injection system

4. Gas dilution system capable of measuring 

pressure transfers

5. Heated canister cleaning system capable of 

evacuating canister to 0.0066 kPa prior to 

sampling and cycling between vacuum and 

humidified gas 

6. Capillary or diaphragm flow controller for 

restricted flow sampling, or fitting for 

instantaneous sampling with 2-μm, sintered, 

stainless steel particle filter 

7. 400 mL, 450 mL, or 6 L fused-silica lined 

coated canisters

8. Gas-tight syringes, 2.5 mL, 1 mL, 250 μL, 100 

μL, 25 μl and 10 μL

9. Disposable glass pipets

10. 2 L glass bulb

 

SPECIAL PRECAUTIONS: Dichloromethane and trichloromethane are confirmed animal carcinogens and 

benzene is a confirmed human carcinogen (see International Agency for Research on Cancer (IARC)). 

Terpenes are flammable and considered irritants. Perform all standards preparation in a well-ventilated 
Volatile Organic Compounds, C1 to C10, Canister Method: METHOD 3900, Issue 1, dated 30 August 2018 - Page 3 of 14

NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

hood. Wear appropriate personal protective equipment during sampling activities and analysis. It is 

essential that suitable gloves, eye protection, laboratory coat, etc. be used when working with the 

chemicals.

SAMPLING:

1. Evacuate canister to 0.0066 kPa prior to sampling. 

2. Sampling may be performed with a flow controller (e.g., diaphragm or capillary) into a large canister 

(e.g., 6 L) for area sampling or a small canister (e.g., 400 or 450 mL) for personal sampling. Selection of 

the appropriate flow controller and flow rate will depend upon the size of canister being used and 

sampling period that is necessary to characterize exposures.

3. For diaphragm flow controllers, follow the manufacturers procedures for calibration to an appropriate 

flow rate (e.g., 10 mL/min for a 6 L canister for an 8-hour work shift) prior to each day of sampling; the 

final pressure in the canister should be less than 84.1 kPa. 

4. For capillary flow controllers, the flow is governed by the length and internal diameter of the capillary. 

Use a flow controller that will fill the can volume to 30.4 kPa during your sampling period. Do not 

exceed a final sample pressure of 50.6 kPa. 

5. Use a 2-μm, sintered, stainless steel particle filter to protect the flow controllers and canisters when 

sampling in dusty atmospheres. 

SAMPLE PREPARATION:

6. For ppb-level analysis, attach the canister to the preconcentrator via an autosampler or direct transfer 

line. If sample needs to be pressurized to increase sample volume prior to analysis, perform pressure 

dilution with ultra-high purity (UHP) nitrogen or air and apply dilution factors in calculation. Final 

sample pressure after analysis should be greater than 50.6 kPa to limit potential for sample dilution due 

to system leakage. 

7. For ppm-level analysis, pressurize the canister (e.g., 152 kPa or follow instrument manufacturer’s 

recommendation) in order to obtain a sufficient excess pressure to flush the 1 mL loop. An alternative to 

using the loop for quantitation could be running a loop or low volume injection of the canister to 

investigate the analyte concentration range. Then, perform pressure dilutions into ppb-level calibration 

curve.

NOTE: Allow samples or calibration standards that are pressurized a minimum of 6 hours to equilibrate 

prior to analysis. Pressure dilutions greater than 50x should be performed with successive 

dilutions into additional canisters with equilibration time allowed at each step. 

CALIBRATION AND QUALITY CONTROL:

8. Tune the mass spectrometer and calibrate with standards over the range 1 to 20 ppb (25 to 500 mL 

nominal injection volume) and 0.2 to 2 ppm (1 mL loop flushed with 100 mL of sample). Five to seven 

calibration points within the dynamic range should be used. Internal standard (50 mL at 20 ppb) is 

added to the preconcentrator prior to standard or sample transfer. 

9. A mixture of the analytes must be produced before gas-phase standard preparation. 

10. Gas-phase standards may be prepared in 2 L glass bulbs by adding a known volume of a neat chemical 

mixture (see Calculation section) to the vessels. The mass injected into the bulb is determined from the 

concentration of analyte in the mixture and the volume of mixture delivered to the vessel. 

NOTE: Alcohols and ketones may react in the presence of heat. The heated-bulb preparation method is 

not recommended for alcohols and ketones when prepared in the same heated bulb as the 

reaction will change the gas concentration produced. Two alternatives to the heated-bulb 
Volatile Organic Compounds, C1 to C10, Canister Method: METHOD 3900, Issue 1, dated 30 August 2018 - Page 4 of 14

NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

preparation method are generation without heat in a large inert bag (e.g., tedlar) protected from 

light or purchasing a calibration cylinder from a reference material supplier.

11. The vessel is heated to 60° C for 30 minutes and allowed to cool to room temperature before a small gas 

volume is transferred to evacuated-calibration canisters via a gas-tight syringe. An alternative to

standard preparation by a heated glass bulb is to purchase gas standards at known concentrations and 

use a gas dilution system to measure pressure transfers. Gas standards should be purchased from a 

reputable, accredited reference material producer (e.g., ISO 17034 [7] accreditation recommended). A 

gas standard at approximately 2 ppm of each of the 17 compounds (balance nitrogen) has been stable 

for 2 years in a pressurized aluminum cylinder with only a ± 2% deviation from the original certified 

value.

12. Add 80 μl of clean distilled water to an evacuated 6 L canister, add gas standard, and dilute with UHP

nitrogen or air to 172 kPa (i.e., ~40%RH). 

13. Develop response factors for each analyte to the closest internal standard using the mass spectrometer 

quantitation software and the appropriate quantitation (primary) ion. Response factors (RF) are 

calculated as follows [8]:

RRRR = AAxx ∗ CCiiii

AAiiii ∗ CCxx

Where:

Ax = area of the quantitation ion for the analyte (counts);

Ais = area of the quantitation ion for the internal standard (counts);

Cis = concentration of internal standard (ppb); and

Cx = concentration of the analyte (ppb).

14. A humidified (e.g., ~40%RH) laboratory blank and humidified (e.g., ~40%RH) 10 ppb check standard 

must be analyzed within a 24 hour period of sample analysis. Perform a full calibration when the check 

standard falls outside established acceptance criteria as developed by the laboratory. Check standard 

recoveries of 90% to 110% are achievable but may be higher or lower depending on instrumentation. A 

replicate sample analysis should be conducted every 10 samples, when possible, to assess 

measurement repeatability. A check standard should be analyzed near the end of the analytical 

sequence to ensure recoveries of each compound are within 80% to 120%. 

MEASUREMENT:

15. Set preconcentrator/GC/MS according to manufacturer’s recommendations and to conditions given on 

page 3900-1. 

16. Inject 50 mL of internal standard at 20 ppb.

17. Inject between 200 and 500 mL of sample for ppb-level analysis and 1 mL of sample for ppm-level 

analysis. Alternative injection volumes may be used as long as performance is verified prior to sample 

analysis.

NOTE 1: If peak area is above linear range of the working standards, dilute with UHP nitrogen using a 

gas dilution system or inject smaller sample volumes, reanalyze and apply the appropriate 

dilution factor in calculations. 

NOTE 2: m- and p-Xylene isomers co-elute on the specified column and should be analyzed/reported 

together. 

CALCULATIONS:

18. Calculation for the concentration of analyte in calibration standard (Cbulb; ppm) in the glass bulb:

CCbbbbbbbb = CCaaVVmmYY ∗ 22.4

MMWW ∗ VVbbbbbbbb

∗ TT

273.15 ∗ 760

PP
Volatile Organic Compounds, C1 to C10, Canister Method: METHOD 3900, Issue 1, dated 30 August 2018 - Page 5 of 14

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Where:

Ca = concentration of analyte in the mixture (mg/mL);

Vm = volume of mixture injected in bulb (mL);

Y = purity of analyte (scale 0 to 1);

MWs = molecular weight of analyte (g/mol);

Vbulb = volume of glass bulb (m3

) determined experimentally;

Tlab = temperature of the laboratory (K);

Plab = pressure of the lab (mm Hg). 

NOTE: 760 is assuming standard atmospheric pressure. 273.15 is International Union of Pure and 

Applied Chemistry (IUPAC) standard temperature and 22.4 is molar volume at STP.

19. Transfer a small aliquot of the gas from the bulb to an evacuated canister for calibration standards. 

20. Calculate the final concentration in the canister (Cfinal; ppb) based on:

CCff ff = CCbbbbbbbb ∗ 1000 ∗ VViiiiii

VVcccc

∗ PP aaaa

PPff

Where:

Cbulb = concentration in glass bulb (ppm);

Vinj = volume transferred to the canister (mL);

Vcan = volume of the canister (mL);

Patm=atmospheric pressure (kPa); and

Pf = final canister pressure (kPa).

21. Determine the analyte concentration (Cx) in ppb or ppm according to the following equation:

CCxx = AAxx ∗ CCiiii

AAiiii ∗ RRRR

Where:

Ax = area of the primary ion for the analyte (counts);

Ais = area of the primary ion for the internal standard (counts);

Cis = concentration of internal standard (ppb);

RF = response factor calculated using linear regression.

Note: Most data analysis software packages will calculate analyte concentration provided you 

enter the calibration information in the quantification database. Blank correction may be 

necessary when instrument or field blank results are consistent and above the analyte detection 

limit.

22. Dilution factors (ratio of final volume to initial volume) must be applied to standards or samples as 

applicable.

EVALUATION OF METHOD:

Method Accuracy

Bias, precision, accuracy and stability for 14 volatile organic compounds (ethanol, acetone, 2-propanol, 

dichloromethane, hexane, trichloromethane, benzene, methyl methacrylate, toluene, ethylbenzene, m,pxylene, o-xylene, α-pinene, and d-limonene) at ppb-level and ppm-level concentrations [4] were 

determined using Kennedy et al. [9]. Three additional analytes (2,3-butanedione, 2,3-pentanedione, and 
Volatile Organic Compounds, C1 to C10, Canister Method: METHOD 3900, Issue 1, dated 30 August 2018 - Page 6 of 14

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2,3-hexanedione) were added to the target list after this study and accuracy has been assessed during 

chamber studies (see section below). The upper and lower 95% confidence limits of the average bias were 

calculated (i.e., ±1.96*standard error). To be acceptable either both bias limits must have an absolute value 

less than 10%, or an absolute value of 10% must fall between the limits. For a method to meet the NIOSH 

“25% accuracy” criterion, the 95% confidence statistic for accuracy estimated with the hyperbolic 

approximation formula must be below 25%. The stability metric is a measure of bias comparing average 

concentration on day 30 or greater to average concentration on day zero; the absolute value of the 

stability metric must be less than 10% to be acceptable. Day 30 stability was obtained from LeBouf et al. 

[4]. Day 58 stability was obtained from NIOSH [10]. While method performance varied by analyte, the 

validation results demonstrate that this method is a viable air sampling and analytical methodology for 

measuring a wide range of air concentrations of select volatile organic compounds in mixed exposure 

environments. 

For the preconcentration method used to measure ppb-level concentrations, all accuracy criteria were 

within acceptable limits for 16 of the 17 target analytes (Table 4a). 2-Propanol failed the 95% accuracy 

criterion at ppb-level concentrations and accuracy validation results are considered inconclusive, perhaps 

because the water management step in the preconcentration may have affected the concentrations of this 

analyte due to its polar nature. Ethanol, however, passed the accuracy criterion despite its similar polarity. 

Bias was acceptable for all 17 analytes. The average bias values for 2-propanol and methyl methacrylate 

were greater than 10% but still within acceptable parameters when 95% confidence limits were calculated; 

further evaluation to confirm or refute this excessive bias result is warranted, particularly because bias 

values may have been influenced by error introduced during the preparation of standards (e.g., liquid 

injection into glass bulb or concentration dilution). Storage stability of the 17 analytes was confirmed for 

58 days at approximately 10 ppb for most analytes with the exception of ethanol, 2-propanol, and acetone 

(stable for 30 days) (Table 4a) [4, 10].

Because trichloromethane failed Bartlett’s test of homogeneity [9] (i.e., precision varied across 

concentrations) for ppb-level, the accuracy value for this analyte displayed in Table 4a was not calculated 

based on a value for precision that was pooled across all concentrations investigated. Rather, the accuracy 

value was calculated based on the worst-case concentration-specific precision and bias and a modified 

accuracy calculation that accounts for the reduced degrees of freedom. Further investigation of the 

precision for trichloromethane using the ppb-level method is warranted. In the meantime, the method can 

be used to quantify this analyte, but the analyst must be cognizant of the concentration-dependence of 

measurement variability.

For the loop method used to measure ppm-level concentrations, all accuracy and bias criterion were 

within acceptable limits for each analyte (Table 4b). Bartlett’s test demonstrated that measurement 

precision was non-homogeneous over concentrations for both dichloromethane and methyl methacrylate. 

The accuracy values for these two analytes were calculated based on the worst-case concentration-specific 

precision and bias and a modified accuracy calculation that accounts for the reduced degrees of freedom.

All analytes were stable for 30 days, except α-pinene and d-limonene, which remained stable for 21 days

(Table 4b). The shorter acceptable storage time for α-pinene and d-limonene may be due to losses from 

chemical reactions with other components of canister contents, particularly oxidizing species such as 

ozone or hydroxyl and nitrate radicals naturally found in indoor air [11, 12].

Inter-laboratory Study

An inter-laboratory study was conducted to estimate precision from nine laboratories [10]. Laboratories 

were recruited from American Industrial Hygiene Association (AIHA)-accredited or National Environmental 

Laboratory Accreditation Program (NELAP)-accredited laboratories which had the experience and 

equipment necessary to analyze canister samples. Precision estimates for repeatability ranged from 0.04 to 

0.55 at ppb concentrations and from 0.1 to 0.47 for ppm concentrations. Precision estimates for 
Volatile Organic Compounds, C1 to C10, Canister Method: METHOD 3900, Issue 1, dated 30 August 2018 - Page 7 of 14

NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

reproducibility ranged from 0.1 to 0.62 at ppb concentrations and from 0.19 to 0.58 at ppm concentrations, 

depending on analyte and nominal level. Plots of h and k statistics which measure between and within 

laboratory consistency indicated inconsistencies with reported results from laboratories 5, 6, and 7. These 

laboratories were investigated to determine the cause of the inconsistent results. Issues with storage time 

and adherence to the method protocol were encountered but results were retained due to the low 

number of laboratories participating. Training on pressure dilution techniques and preconcentration 

systems as well as proficiency testing should be periodically conducted to ensure operating laboratories 

maintain optimal canister method performance.

Chamber Studies

The canister method was challenged in laboratory chamber studies [10] under varying environmental 

conditions and concentrations of alpha-diketones to assess sampling and analytical accuracy following 

ASTM D6246 [13]. The following conditions were assessed: temperature, humidity, wind speed, and 

concentration. Bias pulse tests were performed to assess the bias associated with a known drop in flow rate 

(~13% over the sampling period) for capillary flow controllers. Flow rate bias (bias pulse) was assessed 

using the difference in measurements for peak exposures occurring at the beginning and end of the 

sampling period. Tests were also performed to assess inter-day and inter-sampler variation. A dynamic 

volatile organic compound generation and sampling system was used to produce known concentrations 

of challenge agents in a glass sampling chamber with 18 sampling ports. The system was placed in a large 

walk-in environmental control chamber to regulate temperature. Capillary flow controllers were 

constructed using Swagelok connections and deactivated fused-silica tubing to collect air samples at 15 

mL/min for 15 minutes into a 450 mL canister to test the maximum recommended sampling fill pressure of 

50.6 kPa. Canisters were pressurized with ultra-high purity nitrogen and analyzed using an 

autosampler/preconcentrator system attached to a gas chromatograph/mass spectrometer. Results were 

corrected for pressure dilution and compared to a theoretical concentration calculated from flow dilution 

of the gas standard used in the generation system. Accuracy was calculated for each target analyte for all 

conditions combined. Variance estimates for each factor influencing accuracy were used to apportion the 

relative influence of each test condition on the overall performance of the method. Upper confidence 

limits on accuracy (A95) were below 0.25 for all analytes: 0.085 for diacetyl, 0.142 for 2,3-pentanedione, and 

0.194 for 2,3-hexanedione. Overall precision was largest for 2,3-hexanedione at 0.061 with 27.4% of the 

total variance due to inter-day variability. The peak exposure condition (i.e., effect of a bias pulse given the 

flow rate drop over the sampling period) accounted for less than 6% of the variability regardless of analyte, 

meaning the known drop in flow rate from the capillary flow controller did not overly influence air 

sampling results. Additional VOCs (ethanol, acetone, isopropyl alcohol, dichloromethane, 

trichloromethane, methyl methacrylate, hexane, benzene, toluene, xylenes, α-pinene, d-limonene) were 

present during low and high humidity trials to assess the effect of humidity on method performance. For 

the high humidity trial (n=10), A95 for the additional VOCs were below 0.25 except for ethanol and methyl 

methacrylate. For the low humidity trial (n=5), A95 for the additional VOCs were below 0.25 except for 

ethanol and isopropyl alcohol. Canister method is a reliable, robust sampling and analytical method that 

may be used for a variety of analytes (e.g., C1 to C10) under varying environmental conditions. 

Flow Controllersfor Personal Sampling

Diaphragm flow controllers are heavy due to the stainless steel body holding the diaphragm making them 

inconvenient for personal sampling. The capillary flow controllers are light weight and provide a broad 

dynamic range of flow rates that enables full-shift (8-12 hours) sample collection in a 400/450mL canister 

[8]. With capillary flow controllers, the flow is governed by the length and internal diameter of the capillary 

and the pressure in the canister [8, 14]. As the canister fills with sample, the pressure differential between 

the atmosphere and the inside of the canister decreases. This decrease causes a slight, non-linear 

reduction in flow rate over time. The effect of the change can be mitigated by keeping the final sample 

volume in the canister at around 30% (but no greater than 50%). The effect of a known, decrease in flow 
Volatile Organic Compounds, C1 to C10, Canister Method: METHOD 3900, Issue 1, dated 30 August 2018 - Page 8 of 14

NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

rate on bias has been assessed and will not overly influence time-integrated measurements of analyte 

concentration even when a peak concentration at the beginning or end of the sampling period is collected 

[10, 14].

Additional Guidance

Follow EPA guidelines for cleaning canisters, sampling train cleanliness, canister cleanliness, leak testing, 

and canister pressurization [5, 15]. Do not clean fused silica lined canisters with humidified air and heat 

above 80°C. Use humidified nitrogen and heat to clean fused silica lined canisters. ASTM D5466 is also 

available as guidance for canister sampling and analysis [6]. 

REFERENCES:

[1] ACGIH [2018]. TLVs® and BEIs® based on the documentation of the Threshold Limit Values for 

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

Conference of Governmental Industrial Hygienists. 

[2] Permanent Senate Commission for the Investigation of Health Hazards of Chemical Compounds in 

the Work Area [2016]. List of MAK and BAT values 2016; Maximum Concentrations and Biological 

Tolerance Values at the Workplace. Weinheim, Germany: Wiley-VCH Verlag GmbH & Co., 

https://dx.doi.org/10.1002/9783527805983. 

[3] Institute for Occupational Safety and Health of the German Social Accident Insurance (IFA) [2017]. 

GESTIS international limit values, http://limitvalue.ifa.dguv.de/. 

[4] LeBouf RF, Stefaniak AB, Virji MA [2012]. Validation of evacuated canisters for sampling volatile 

organic compounds in healthcare settings. J Environ Monit 14(3):977-983.

[5] EPA [1999]. Compendium Method TO-15: Determination of volatile organic compounds (VOCs) in air 

collected in specially-prepared canisters and analyzed by gas chromatography/mass spectrometry 

(GC/MS). Cincinnati, OH, U.S. Environmental Protection Agency, EPA/625/R-96/010b.

[6] ASTM [2015]. Standard test method for determination of volatile organic compounds in atmospheres 

(canister sampling methodology). West Conshohocken, PA: ASTM International, ASTM D5466 – 15.

[7] ISO [2016]. General requirements for the competence of reference material producers. Geneva, 

Switzerland: International Organization for Standardization, ISO 17034. 

[8] Rossner A, Farant JP [2002]. Development of a flow controller for long-term sampling of gases and 

vapors using evacuated canisters. Environ Sci Technol 36:4912-4920.

[9] NIOSH [1995]. Guidelines for air sampling and analytical method development and evaluation. By

Kennedy ER, Fischbach TJ, Song R, Eller PM, Shulman SA. Cincinnati, OH: U.S. Department of Health 

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

Safety and Health, DHHS (NIOSH) Publication No. 95-117.

[10] NIOSH [2018]. NIOSH 3900 Backup Data Report. By LeBouf RF, Feng A, Shulman SA. Cincinnati, OH: 

U.S. 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/datadoc.html.

[11] Atkinson R, Arey J [2003]. Gas-phase tropospheric chemistry of biogenic volatile organic compounds: 

a review. Atmos Environ 37:S197-S219.

[12] Forester C, Wells J [2009]. Yields of carbonyl products from gas-phase reactions of fragrance 

compounds with OH radical and ozone. Environ Sci Technol 43:3561-3568.
Volatile Organic Compounds, C1 to C10, Canister Method: METHOD 3900, Issue 1, dated 30 August 2018 - Page 9 of 14

NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

[13] ASTM [2013]. Standard practice for the evaluating the performance of diffusive samplers. West 

Conshohocken, PA: ASTM International, ASTM D6246 – 08.

[14] Rossner A, Wick DP [2005]. A field study to assess the long-term sampling feasibility of evacuated 

canisters and the development of a mathematical model to analyze potential sampling bias. J Occ 

Environ Hyg 2:474-480.

[15] EPA [1999]. Compendium Method TO-14A: Determination of volatile organic compounds (VOCs) in 

ambient air using specially prepared canisters with subsequent analysis by gas chromatography. 

Cincinnati, OH, US Environmental Protection Agency, EPA/625/R-96/010b.

[16] Code of Federal Regulations [2017]. Title 29 (Labor), Part 1910 (Occupational Safety and Health 

Standards); 29 CFR 1910.1000 Table Z-1; US Government Printing Office, Washington DC.

[17] NIOSH [2010]. Pocket guide to chemical hazards. Cincinnati, OH: U.S. Department of Health and 

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

Safety and Health, DHHS (NIOSH) Publication No. 2010-168c.

METHOD WRITTEN BY:

Ryan F LeBouf, PhD, CIH. CDC/NIOSH, Respiratory Health Division.

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

Institute for Occupational Safety and Health (NIOSH), Centers for Disease Control and Prevention (CDC). 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.
Volatile Organic Compounds, C1 to C10, Canister Method: METHOD 3900, Issue 1, dated 30 August 2018 - Page 10 of 14

NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

TABLE 1. SYNONYMS, FORMULAE, MOLECULAR WEIGHTS AND PHYSICAL PROPERTIES

IUPAC Name /

Synonym CAS # / RTECS

Empirical 

formula

Molecular 

Weight

Boiling 

Point 

(°C)

Vapor 

Pressure 

@ 20° C 

(mm Hg)

Vapor 

Pressure 

@ 20° C 

(kPa)

ethanol / ethyl 

alcohol

64-17-5/ 

KQ6300000

C2H6O 46.07 78.3 44 5.87

2-propanol / 

isopropyl alcohol

67-63-0/ 

NT8050000

C3H8O 60.1 82.3 33 4.4

acetone / 2-

propanone

67-64-1/ 

AL3150000

C3H6O 58.08 56.1 180 24

2,3-butanedione / 

diacetyl

431-03-8/ 

EK2625000

C4H6O2 86.09 88 52.2 6.96

2,3-pentanedione

/ acetyl propionyl

600-14-6/ 

SA1850000

C5H8O2 100.12 110-

112

21.4 2.85

2,3-hexanedione / 

acetyl butyryl

3848-24-6 C6H10O2 114.14 128 10 1.33

dichloromethane / 

methylene 

chloride

75-09-2/ 

PA8050000

CH2Cl2 84.93 40 350 46.7

trichloromethane / 

chloroform

67-66-3 CHCl3 119.38 61.2 160 21.3

hexane / n-hexane 110-54-3/ 

MN9275000

C6H14 86.18 68.7 124 16.5

benzene / benzol 71-43-2/ 

CY1400000

C6H6 78.11 80.1 75 10

toluene / 

methylbenzene

108-88-3/ 

XS5250000

C7H8 92.14 110.6 22 2.93

ethylbenzene / 

phenylethane

100-41-4/ 

DA0700000

C8H10 106.17 136.2 7 0.93

o-xylene / 1,2-

dimethylbenzene

95-47-6/ 

ZE2450000

C8H10 106.17 144.5 7 0.93

m-xylene / 1,3-

dimethylbenzene

108-38-3/ 

ZE2275000

C8H10 106.17 139.1 9 1.2

p-xylene / 1,4-

dimethylbenzene

106-42-3/ 

ZE2625000

C8H10 106.17 138.2 9 1.2

methyl-2-methyl2-propenate / 

methyl 

methacrylate 

80-62-6/

OZ5075000

C5H8O2 100.12 100.5 29 3.87

4,6,6-

trimethylbicyclo[3.

1.1]hept-3-ene / αpinene / 2-pinene

80-56-8/ 

DT7000000

C10H16 136.23 156.2 4.75 

(25° C)

0.63

(4R)-1-methyl-4-

prop-1-en-2-

ylcyclohexene / dlimonene / pmentha-1,8-diene, 

("R")

5989-27-5/ 

OS8100000

C10H16 136.23 178 1.43 0.19
Volatile Organic Compounds, C1 to C10, Canister Method: METHOD 3900, Issue 1, dated 30 August 2018 - Page 11 of 14

NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

TABLE 2. CHARACTERISTIC MASSES (M/Z) USED FOR QUANTITATION

Substance

Primary

Ion

Secondary

Ion

ethanol 45 46, 43

2-propanol 45 43

acetone 43 58

2,3-butanedione 86 43

2,3-pentanedione 100 57, 43

2,3-hexanedione 71 43, 114

dichloromethane 84 49, 86

trichloromethane 83 85, 47

hexane 57 41, 43

benzene 78 77, 52

toluene 91 92

ethylbenzene 91 106

o-xylene 91 106, 105

m,p-xylene 91 106, 105

methyl methacrylate 69 41, 100

α-pinene 93 91, 92

d-limonene 68 93, 67

bromochloromethaneA 130 49, 93

1,4-difluorobenzeneA 114 63, 88

chlorobenzene-d5A 117 82, 119 Ainternal standards

TABLE 3. EXPOSURE LIMITS (PPM) [16,17]

Substance

OSHA 

TWA

OSHA 

Peak

NIOSH 

TWA

NIOSH 

STEL

mg/m3 

per ppm

ethanol 1000 - 1000 - 1.89

2-propanol 400 400 500 2.46

acetone 1000 - 250 - 2.38

2,3-butanedione - - 0.005 0.025 3.52

2,3-pentanedione - - 0.0093 0.031 4.09

2,3-hexanedione - - - - 4.67

dichloromethane 25 125 N/AA (caB

) 3.47

trichloromethane - 50 - 2 (60 min) 4.88

hexane 500 - 50 - 3.53

benzene 1 5 0.1 (ca) 1 (ca) 3.19

toluene 200 500 100 150 3.77

ethylbenzene 100 - 100 125 4.34

o-xylene 100 - 100 150 4.34

m-xylene 100 - 100 150 4.34

p-xylene 100 - 100 150 4.34

methyl methacrylate 100 - 100 - 4.09

α-pinene - - - - 5.57

d-limonene - - - - 5.57 AN/A = not applicable

B

ca = carcinogen
Volatile Organic Compounds, C1 to C10, Canister Method: METHOD 3900, Issue 1, dated 30 August 2018 - Page 12 of 14

NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

TABLE 4A. RANGE, OVERALL BIAS, PRECISION AND ACCURACY FOR PPB LEVELS [4, 10]

Substance

Range of 

generated 

samples

Overall 

Bias (%)

Overall 

Precision 

(SrT)

Overall 

Accuracy 

(%)

58 day 

Stability (%)

ethanol 1.3 - 9.9 -9.3 0.058 ±22.2 -0.5 (30 days)

2-propanol 1.3 - 10.0 -12.3 0.098 ±28.9 7.8 (30 days)

acetone 1.3 - 10.0 -3.2 0.064 ±18.6 3.1 (30 days)

2,3-butanedione 21.5 - 381 2.2 0.032 ±8.5 4.1

2,3-pentanedione 20.8 - 377 4.8 0.048 ±14.2 2.7

2,3-hexanedione 20.4 - 368 -6.0 0.061 ±19.4 -2.9

dichloromethane 1.3 - 9.8 2.9 0.017 ±7.1 0.22

trichloromethane 1.3 - 9.8 -0.3 0.020* ±16.5* 3.1

hexane 1.3 - 9.9 -0.1 0.020 ±5.5 3.6

benzene 1.3 - 9.8 -3.0 0.022 ±8.3 3.6

toluene 1.3 - 9.9 -4.0 0.020 ±8.6 1.6

ethylbenzene 1.3 - 9.9 -4.4 0.020 ±9.1 -0.6

o-xylene 1.3 - 9.8 -6.0 0.027 ±12.3 -3.5

m,p-xylene 1.3 - 9.8 -6.7 0.025 ±12.6 -8.1

methyl methacrylate 1.3 - 9.9 -10.2 0.066 ±24.9 1.5

α-pinene 1.3 - 9.8 -4.7 0.028 ±11.4 -3.3

d-limonene 1.3 - 9.8 -4.6 0.069 ±21.1 -1.9

*worst-case precision estimate since failed Bartlett’s test of homogeneity of variance across concentrations

SrT = pooled precision as relative standard deviation across multiple concentration levels

Overall Accuracy=upper confidence limit on accuracy, A95

Stability (%) = ((Concentration at storage day)/(Concentration at day 0)-1)*100%
Volatile Organic Compounds, C1 to C10, Canister Method: METHOD 3900, Issue 1, dated 30 August 2018 - Page 13 of 14

NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

TABLE 4B. RANGE, OVERALL BIAS, PRECISION AND ACCURACY FOR PPM-LEVELS [4]

Substance

Range of 

generated 

samples

Overall 

Bias (%)

Overall 

Precision 

(SrT)

Overall 

Accuracy 

(%)

30 day Stability 

(%)

ethanol 0.81 - 1.8 9.4 0.028 ±17.0 -9.2

2-propanol 0.82 - 1.8 8.9 0.027 ±16.1 -2.9

acetone 0.82 - 1.8 8.7 0.019 ±13.8 -1.6

dichloromethane 0.79 - 1.8 3.0 0.041* ±17.8* -4.7

trichloromethane 0.80 - 1.8 5.7 0.012 ±8.9 -1.9

hexane 0.81 - 1.8 6.1 0.012 ±9.4 0.1

benzene 0.80 - 1.8 6.3 0.011 ±9.3 7.3

toluene 0.81 - 1.8 5.5 0.015 ±9.3 6.4

ethylbenzene 0.81 - 1.8 4.7 0.017 ±9.2 0.8

o-xylene 0.80 - 1.8 5.4 0.019 ±10.3 -0.3

m,p-xylene 0.80 - 1.8 3.9 0.019 ±8.8 -2.1

methyl methacrylate 0.81 - 1.8 5.7 0.016* ±15.6* 1.4

α-pinene 0.81 - 1.8 6.7 0.022 ±12.5 0.1 (21 days)

d-limonene 0.80 - 1.8 13.1 0.039 ±24.0 -0.03 (21 days)

*worst-case precision estimate since failed Bartlett’s test of homogeneity of variance across concentrations

SrT = pooled precision as relative standard deviation across multiple concentration levels

Overall Accuracy=upper confidence limit on accuracy, A95

Stability (%) = ((Concentration at storage day)/(Concentration at day 0)-1)*100%

TABLE 5A. LIMITS OF DETECTION (LOD), MEASUREMENT RANGE, AND PRECISION FOR PPB-LEVELS [4, 10]

Substance LOD (ppb) Range (ppb) Precision (RMSEA) Linearity R2

ethanol 0.4 0.25 – 21.4 0.272 0.999

2-propanol 0.5 0.27 – 22.0 0.077 0.998

acetone 0.4 0.27 – 20.6 0.080 0.999

2,3-butanedione* 0.3 0.26 – 21.0 0.033 0.999

2,3-pentanedione* 0.2 0.24 – 18.4 0.148 0.999

2,3-hexanedione* 0.4 0.24 – 18.0 0.238 0.999

dichloromethane 0.2 0.26 – 20.8 0.049 0.999

trichloromethane 0.1 0.27 – 21.6 0.044 0.999

hexane 0.2 0.27 – 21.8 0.030 0.999

benzene 0.2 0.27 – 21.6 0.032 0.999

toluene 0.3 0.27 – 21.4 0.023 0.999

ethylbenzene 0.3 0.26 – 21.0 0.019 0.999

o-xylene 0.3 0.26 – 21.0 0.019 0.999

m,p-xylene 0.4 0.27 – 22.0 0.015 0.999

methyl methacrylate 0.5 0.25 – 20.4 0.035 0.999

α-pinene 0.5 0.26 – 21.0 0.019 0.999

d-limonene 0.8 0.26 – 20.8 0.136 0.999

*Selected ion monitoring mode used to improve detection limits ARMSE= root mean square error
Volatile Organic Compounds, C1 to C10, Canister Method: METHOD 3900, Issue 1, dated 30 August 2018 - Page 14 of 14

NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

TABLE 5B. LIMITS OF DETECTION (LOD), MEASUREMENT RANGE, AND PRECISION FOR PPM-LEVELS [4] 

Substance LOD (ppm) Range (ppm) Precision (SEEA) Linearity R2

ethanol 0.2 0.07 - 1.9 0.058 0.998

2-propanol 0.2 0.07 - 2.0 0.066 0.998

acetone 0.3 0.08 - 2.0 0.071 0.998

dichloromethane 0.4 0.15 - 1.9 0.099 0.999

trichloromethane 0.3 0.11 - 1.9 0.093 0.999

hexane 0.2 0.11 - 2.0 0.072 0.999

benzene 0.2 0.11 - 1.9 0.064 0.999

toluene 0.3 0.11 - 1.9 0.101 0.998

ethylbenzene 0.3 0.11 - 1.9 0.108 0.998

o-xylene 0.1 0.11 - 1.3 0.031 0.998

m,p-xylene 0.3 0.11 - 1.9 0.110 0.998

methyl methacrylate 0.2 0.11 - 1.9 0.089 0.998

α-pinene 0.3 0.11 - 1.9 0.116 0.999

d-limonene 0.4 0.11 - 1.9 0.156 0.999 ASEE = standard error of estimate from regression curve