United States

Enivronmental Protection

Agency

Center for Environmental

Research Information

EPA/625/R-96/010b

January 1999

Research and Development

EPA Compendium of Methods for 

the Determination of Toxic 

Organic Compounds in 

Ambient Air - Second Edition 
Compendium of Methods

for the 

Determination of Toxic Organic

Compounds in Ambient Air

Second Edition

U. S. Environmental Protection Agency

Office of Research and Development

National Risk Management Research Laboratory

Center for Environmental Research Information

Cincinnati, Ohio 45268

January 1999
ii

Disclaimer

The information in this document has been compiled wholly or in part by the United

States Environmental Protection Agency under contract No. 68-C3-0315, W.A. 3-10

to Eastern Research Group (ERG). The work was performed by Midwest Research

Institute (MRI) under subcontract to ERG. It has been subjected to Agency’s peer

and administrative review, and it has been approved for publication as an EPA

document. Mention of trade names or commercial products does not constitute

endorsement or recommendation for use.

It is further noted that the test methods compiled here are working compilations

subject to on-going review and update. It is recommended that the reader refer to

the “AMTIC, Air Toxics” section of EPA’s OAQPS Technology Transfer Network

web site at http://www.epa.gov/ttn/amtic/airtox.html to obtain the latest updates,

corrections, and/or comments to these test methods. 
iii

FOREWORD

The U. S. Environmental Protection Agency is charged by Congress with protecting the

Nation's land, air, and water resources. Under a mandate of national environmental laws, the Agency

strives to formulate and implement actions leading to a compatible balance between human activities

and the ability of natural systems to support and nurture life. To meet this mandate, EPA's research

program is providing data and technical support for solving environmental problems today and

building a science knowledge base necessary to manage our ecological resources wisely, understand

how pollutants affect our health, and prevent or reduce environmental risks in the future.

The National Risk Management Research Laboratory (NRMRL) is the Agency's center for

investigation of technological and management approaches for reducing risks from threats to human

health and the environment. The focus of the Laboratory's research program is on methods for the

prevention and control of pollution to air, land, water, and subsurface resources; protection of water

quality in public water systems; remediation of contaminated sites and ground water; and prevention

and control of indoor air pollution. The goal of this research effort is to catalyze development and

implementation of innovative, cost-effective environmental technologies; develop scientific and

engineering information needed by EPA to support regulatory and policy decisions; and provide

technical support and information transfer to ensure effective implementation of environmental

regulations and strategies.

Measurement of organic pollutants in ambient air is often difficult, in part because of the

variety of organic substances of potential concern, the variety of potential techniques for sampling

and analysis, and the lack of standardized and documented methods. Consequently, NRMRL has

developed a Second Edition of the Compendium of Methods for the Determination of Toxic Organic

Compounds in Ambient Air to assist Federal, State, and local regulatory personnel in developing and

maintaining necessary expertise and up-to-date monitoring technology for characterizing organic

pollutants in the ambient air. The Compendium contains a set of 17 peer reviewed, standardized

methods for the determination of volatile, semi-volatile, and selected toxic organic pollutants in the

air. The 17 methods in the Second Edition have been compiled from the best elements of methods

developed or used by various research or monitoring organizations and of which EPA has experience

in use of the methodology during various field monitoring programs over the last several years. As

with the previous Compendia of methods, these methods are provided only for consideration by the

user for whatever potential applications for which they may be deemed appropriate. In particular,

these methods are not intended to be associated with any specific regulatory monitoring purpose and

are specifically offered with no endorsement for fitness or recommendation for any particular

application.

This publication has been prepared in support of NRMRL's goal to provide technical support

and information transfer. It is published and made available by EPA's Office of Research and

Development to assist the user community and to link researchers with their clients.

E. Timothy Oppelt, Director

National Risk Management Research Laboratory
iv
v

TABLE OF CONTENTS

Page

Method TO-1: Method for the Determination of Volatile Organic ..........

Compounds (VOCs) in Ambient Air Using Tenax® Adsorption

and Gas Chromatography/Mass Spectrometry (GC/MS)

1-1 through 1-2

Method TO-2: Method for the Determination of Volatile Organic ..........

Compounds (VOCs) in Ambient Air by Carbon Molecular

Sieve Adsorption and Gas Chromatography/Mass Spectrometry

(GC/MS)

2-1 through 2-2

Method TO-3: Method for the Determination of Volatile Organic ..........

Compounds in Ambient Air Using Cryogenic Preconcentration

Techniques and Gas Chromatography with Flame Ionization

and Electron Capture Detection

3-1 through 3-2

Method TO-4A: Determination of Pesticides and Polychlorinated ............

Biphenyls in Ambient Air Using high Volume Polyurethane

Foam (PUF) Sampling Followed by Gas Chromatographic/Multi-Detector Detection (GC/MD)

4A-1 through 4A-44

Method TO-5: Determination of Aldehydes and Ketones in Ambient ........

Air Using High Performance Liquid Chromatography (HPLC)

5-1 through 5-2

Method TO-6: Determination of Phosgene in Ambient Air Using High ......

Performance Liquid Chromatography (HPLC)

6-1 through 6-2

Method TO-7: Method for the Determination of ........................

N-nitrosodimethylamine (NDMA) in Ambient Air Using Gas

Chromatography

7-1 through 7-2

Method TO-8: Method for the Determination of Phenol and ...............

Methylphenols (Cresols) in Ambient Air Using High

Performance Liquid Chromatography 

8-1 through 8-2

Method TO-9A: Determination of Polychlorinated, Polybrominated ..........

And Brominated/Chlorinated Dibenzo-p-Dioxins And

Dibenzofurans In Ambient Air

9A-1 through 9A-90
TABLE OF CONTENTS (continued)

Page

vi

Method TO-10A: Determination Of Pesticides And Polychlorinated ...........

Biphenyls In Ambient Air Using Low Volume Polyurethane

Foam (PUF) Sampling Followed By Gas

Chromatographic/Multi-Detector Detention (GC/MD)

10A-1 through 10A-32

Method TO-11A: Determination of Formaldehyde in Ambient Air Using .......

Adsorbent Cartridge Followed by High Performance Liquid

Chromatography (HPLC)

11A-1 through 11A-51

Method TO-12: Method for the Determination of Non-methane Organic ......

Compounds (NMOC) in Ambient Air Using Cryogenic

Preconcentration and Direct Flame Ionization Detection

(PDFID)

12-1 through 12-2

Method TO-13A: Determination of Polycyclic Aromatic Hydrocarbons ........

(PAHs) in Ambient Air Using Gas Chromatographic/Mass

Spectrometry (GC/MS)

13A-1 through 13A-78

Method TO-14A: Determination Of Volatile Organic Compounds (VOCs) .....

In Ambient Air Using Specially Prepared Canisters With

Subsequent Analysis By Gas Chromatography

14A-1 through 14A-86

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)

15-1 through 15-62

Method TO-16: Long-Path Open-Path Fourier Transform Infrared ..........

Monitoring Of Atmospheric Gases

16-1 through 16-40

Method TO-17: Determination of Volatile Organic Compounds in ...........

Ambient Air Using Active Sampling Onto Sorbent Tubes

17-1 through 17-49
January 1999 Compendium of Methods for Toxic Organic Air Pollutants Page 1-1

EPA/625/R-96-010b

Compendium of Methods

for the Determination of

Toxic Organic Compounds

in Ambient Air

Second Edition

Compendium Method TO-1

Method for the Determination of Volatile Organic Compounds 

(VOCs) in Ambient Air Using Tenax® Adsorption and 

Gas Chromatography/Mass Spectrometry (GC/MS)

Summary of Method

Compendium Method TO-1 involves drawing ambient air through a cartridge containing

~1-2 grams of Tenax®. Selected VOCs are trapped on the resin, while highly volatile organic

compounds and most inorganic atmospheric constituents pass through the cartridge. The cartridge

is then transferred to the laboratory and analyzed.

For analysis, the cartridge is placed in a heated chamber and purged with an inert gas, which

transfers the VOCs from the cartridge onto a cold trap and subsequently onto the front of the GC

column. The column is first held at low temperature (e.g., -70EC), then the column temperature is

uniformly increased (temperature programmed). The components eluting from the column are

identified and quantified by mass spectrometry. Component identification is normally accomplished

using a library search routine on the basis of the GC retention time and mass spectral characteristics.

Less sophisticated detectors (e.g., electron capture or flame ionization) may be used for certain

applications, but their suitability for a given application must be verified by the user. Due to the

complexity of ambient air samples, only high resolution (i.e., capillary) GC techniques are considered

to be acceptable in this method.

Sources of Methodology

Method TO-1 has not been revised. Therefore, the original method is not repeated in the

Second Edition of the Compendium. Method TO-1 is contained in the original Compendium of

Methods for the Determination of Toxic Organic Compounds in Ambient Air, EPA-600/4-89-017,

which may be purchased in hard copy from: National Technical Information Service, 5285 Port

Royal Road, Springfield, VA 22161; Telephone: 703-487-4650; Fax: 703-321-8547; E-Mail:

info@ntis.fedworld.gov; Internet: www.ntis.gov. Order number: PB90-116989. The TO-methods

may also be available from various commercial sources.
Method TO-1 VOCs

Page 1-2 Compendium of Methods for Toxic Organic Air Pollutants January 1999

Electronic versions of the individual unrevised Compendium (TO-) Methods are available for

downloading from the "AMTIC, Air Toxics" section of EPA's OAQPS Technology Transfer Network

via the Internet at the “AMTIC, Air Toxics” section of the TTNWeb:

http://www.epa.gov/ttn/amtic/airtox.html

Methods TO-1 to TO-13 are now posted in the portable document format (PDF).

The downloaded files can be read using an Acrobat Reader. Acrobat readers are

available from Adobe , free of charge, at: ®

http://www.adobe.com/prodindex/acrobat/readstep.html

and are required to read Acrobat (PDF) files. Readers are available for Windows,

MacIntosh, and DOS.
January 1999 Compendium of Methods for Toxic Organic Air Pollutants Page 2-1

EPA/625/R-96/010b

Compendium of Methods

for the Determination of

Toxic Organic Compounds

in Ambient Air

Second Edition

Compendium Method TO-2

Method for the Determination of Volatile Organic Compounds (VOCs)

in Ambient Air by Carbon Molecular Sieve Adsorption and Gas

Chromatography/Mass Spectrometry (GC/MS)

Summary of Method

Compendium Method TO-2 is similar to Compendium Method TO-1 except the adsorbent

is a carbon molecular sieve (CMS) rather than Tenax®. The use of CMS allows some of the more

volatile organics (i.e., vinyl chloride) to be captured and analyzed.

Method TO-2 is suitable for the determination of certain nonpolar VOCs having boiling points

in the range of -15EC to 120EC. The analytical detection limit varies with the analyte. Detection

limits of 0.01 to 1 ppbv are achievable using a 20-liter sample.

Sampling involves drawing ambient air through a cartridge containing ~0.4 g of a CMS

adsorbent. Volatile organic compounds are captured on the adsorbent while major inorganic

atmospheric constituents pass through (or are only partially retained). After sampling, the cartridge

is returned to the laboratory for analysis. Prior to analysis the cartridge is purged with 2 to 3 liters

of pure, dry air (in the same direction as sample flow) to remove adsorbed moisture.

Similar to Compendium Method TO-1, the cartridge is heated to 350E to 400EC, under

helium purge, and the desorbed organic compounds are collected in a specially designed cryogenic

trap. The collected organics are then flash evaporated onto a capillary column GC/MS system (held

at -70EC). The individual components are identified and quantified during a temperature programmed

chromatographic run.

Similar to Compendium Method TO-1, contamination of the CMS, breakthrough, and antifact

formation are potential weaknesses of the methodology. Method TO-2 also involves a single analysis.
Method TO-2 VOCs

Page 2-2 Compendium of Methods for Toxic Organic Air Pollutants January 1999

Sources of Methodology

Method TO-2 has not been revised. Therefore, the original method is not repeated in the

Second Edition of the Compendium. Method TO-2 is contained in the original Compendium of

Methods for the Determination of Toxic Organic Compounds in Ambient Air, EPA-600/4-89-017,

which may be purchased in hard copy from: National Technical Information Service, 5285 Port

Royal Road, Springfield, VA 22161; Telephone: 703-487-4650; Fax: 703-321-8547; E-Mail:

info@ntis.fedworld.gov; Internet: www.ntis.gov. Order number: PB90-116989. The TO-methods

may also be available from various commercial sources.

Electronic versions of the individual unrevised Compendium (TO-) Methods are available for

downloading from the "AMTIC, Air Toxics" section of EPA's OAQPS Technology Transfer Network

via the Internet at the “AMTIC, Air Toxics” section of the TTNWeb:

http://www.epa.gov/ttn/amtic/airtox.html

Methods TO-1 to TO-13 are now posted in the portable document format (PDF).

The downloaded files can be read using an Acrobat Reader. Acrobat readers are

available from Adobe , free of charge, at: ®

http://www.adobe.com/prodindex/acrobat/readstep.html

and are required to read Acrobat (PDF) files. Readers are available for Windows,

MacIntosh, and DOS.
January 1999 Compendium of Methods for Toxic Organic Air Pollutants Page 3-1

EPA/625/R-96/010b

Compendium of Methods

for the Determination of

Toxic Organic Compounds

in Ambient Air

Second Edition

Compendium Method TO-3

Method for the Determination of Volatile Organic Compounds in

Ambient Air Using Cryogenic Preconcentration Techniques and Gas

Chromatography with Flame Ionization and Electron Capture Detection

Summary of Method

Compendium Method TO-3 involves the in situ collection of VOCs having boiling points in

the range of -10E to 200EC in a cryogenic trap constructed of copper tubing packed with glass beads.

The collection trap is submerged in either liquid nitrogen or liquid argon. Liquid argon is highly

recommended because of the safety hazard associated with liquid oxygen. With the sampling valve

in the fill position, an air sample is admitted into the trap by a volume measuring apparatus. In the

meantime, a GC column oven is cooled to a subambient temperature (-50EC) for sample analysis.

Once sample collection is completed, the value is switched so that the carrier gas sweeps the VOCs

in the trap onto the head of the cooled GC column. Simultaneously, the liquid cryogen is removed,

and the trap is heated to assist the sample transfer process. The GC column is temperature

programmed, and the component peaks eluting from the columns are identified and quantified using

flame ionization and/or electron capture detection. Alternative detectors (e.g., photoionization) can

be used as appropriate. An automated system incorporating these various operations as well as the

data processing function is described in the method. Due to the complexity of ambient air samples,

high resolution (capillary column) GC techniques are recommended. However, when highly selective

detectors (such as the electron capture detector) are employed, packed column technology without

cryogenic temperature programming can be effectively used in some cases.

Sources of Methodology

Method TO-3 has not been revised. Therefore, the original method is not repeated in the

Second Edition of the Compendium. Method TO-3 is contained in the original Compendium of

Methods for the Determination of Toxic Organic Compounds in Ambient Air, EPA-600/4-89-017,

which may be purchased in hard copy from: National Technical Information Service, 5285 Port

Royal Road, Springfield, VA 22161; Telephone: 703-487-4650; Fax: 703-321-8547; E-Mail:

info@ntis.fedworld.gov; Internet: www.ntis.gov. Order number: PB90-116989. The TO-methods

may also be available from various commercial sources.
Method TO-3 VOCs

Page 3-2 Compendium of Methods for Toxic Organic Air Pollutants January 1999

Electronic versions of the individual unrevised Compendium (TO-) Methods are available for

downloading from the "AMTIC, Air Toxics" section of EPA's OAQPS Technology Transfer Network

via the Internet at the “AMTIC, Air Toxics” section of the TTNWeb:

http://www.epa.gov/ttn/amtic/airtox.html

Methods TO-1 to TO-13 are now posted in the portable document format (PDF).

The downloaded files can be read using an Acrobat Reader. Acrobat readers are

available from Adobe , free of charge, at: ®

http://www.adobe.com/prodindex/acrobat/readstep.html

and are required to read Acrobat (PDF) files. Readers are available for Windows,

MacIntosh, and DOS.
January 1999 Compendium of Methods for Toxic Organic Air Pollutants Page 5-1

EPA/625/R-96/010b

Compendium of Methods

for the Determination of

Toxic Organic Compounds

in Ambient Air

Second Edition

Compendium Method TO-5

Determination of Aldehydes and Ketones in Ambient Air Using 

High Performance Liquid Chromatography (HPLC)

Summary of Method

Compendium Method TO-5 involves drawing ambient air through a midget impinger

containing 10 mL of 2N HCl/0.05% 2,4-dinitrophenylhydrazine (DNPH reagent) and 10 mL of

isooctane. Aldehydes and ketones readily form stable 2,4-dinitrophenylhydrazones (DNPH

derivatives).

After sampling, the impinger solution is placed in a screw-capped vial having a Teflon®-lined

cap and returned to the laboratory for analysis. The DNPH derivatives are recovered by removing

the isooctane layer, extracting the aqueous layer with 10 mL of 70/30 hexane/methylene chloride, and

combining the organic layers.

The combined organic layers are evaporated to dryness under a steam of nitrogen and the

residue dissolved in methanol. The DNPH derivatives are determined using reversed phase HPLC

with an ultraviolet (UV) adsorption detector operated at 370 nm.

Sources of Methodology

Method TO-5 has not been revised. Therefore, the original method is not repeated in the

Second Edition of the Compendium. Method TO-5 is contained in the original Compendium of

Methods for the Determination of Toxic Organic Compounds in Ambient Air, EPA-600/4-89-017,

which may be purchased in hard copy from: National Technical Information Service, 5285 Port

Royal Road, Springfield, VA 22161; Telephone: 703-487-4650; Fax: 703-321-8547; E-Mail:

info@ntis.fedworld.gov; Internet: www.ntis.gov. Order number: PB90-116989. The TO-methods

may also be available from various commercial sources.

Electronic versions of the individual unrevised Compendium (TO-) Methods are available for

downloading from the "AMTIC, Air Toxics" section of EPA's OAQPS Technology Transfer Network

via the Internet at the “AMTIC, Air Toxics” section of the TTNWeb:
Method TO-5 Carbonyl(s)

Page 5-2 Compendium of Methods for Toxic Organic Air Pollutants January 1999

http://www.epa.gov/ttn/amtic/airtox.html

Methods TO-1 to TO-13 are now posted in the portable document format (PDF).

The downloaded files can be read using an Acrobat Reader. Acrobat readers are

available from Adobe , free of charge, at: ®

http://www.adobe.com/prodindex/acrobat/readstep.html

and are required to read Acrobat (PDF) files. Readers are available for Windows,

MacIntosh, and DOS.
January 1999 Compendium of Methods for Toxic Organic Air Pollutants Page 6-1

EPA/625/R-96/010b

Compendium of Methods

for the Determination of

Toxic Organic Compounds

in Ambient Air

Second Edition

Compendium Method TO-6

Determination of Phosgene in Ambient Air Using 

High Performance Liquid Chromatography (HPLC)

Summary of Method

Compendium Method TO-6 involves drawing an air sample through a midget impinger

containing 10 mL of 2% aniline/toluene (2/98 by volume). Phosgene readily reacts with aniline to

form carbanilide (1,3-diphenylurea), which is stable indefinitely. After sampling, the impinger

contents are transferred to a screw-capped vial having a Teflon-lined cap and returned to the

laboratory for analysis. The solution is taken to dryness by heating to 60EC on an aluminum heating

block under a gentle stream of pure nitrogen gas. The residue is dissolved in 1 mL of acetonitrile.

Carbanilide is determined in the acetonitrile solution using reverse-phase HPLC with an ultraviolet

(UV) absorbance detector operating at 254 nm. Precision for phosgene spiked into a clean air stream

is ±15-20% relative standard deviation. Recovery is quantitative within that precision, down to less

than 3 ppbv.

Sources of Methodology

Method TO-6 has not been revised. Therefore, the original method is not repeated in the

Second Edition of the Compendium. Method TO-6 is contained in the original Compendium of

Methods for the Determination of Toxic Organic Compounds in Ambient Air, EPA-600/4-89-017,

which may be purchased in hard copy from: National Technical Information Service, 5285 Port

Royal Road, Springfield, VA 22161; Telephone: 703-487-4650; Fax: 703-321-8547; E-Mail:

info@ntis.fedworld.gov; Internet: www.ntis.gov. Order number: PB90-116989. The TO-methods

may also be available from various commercial sources.

Electronic versions of the individual unrevised Compendium (TO-) Methods are available for

downloading from the "AMTIC, Air Toxics" section of EPA's OAQPS Technology Transfer Network

via the Internet at the “AMTIC, Air Toxics” section of the TTNWeb:

http://www.epa.gov/ttn/amtic/airtox.html
Method TO-6 Phosgene

Page 6-2 Compendium of Methods for Toxic Organic Air Pollutants January 1999

Methods TO-1 to TO-13 are now posted in the portable document format (PDF).

The downloaded files can be read using an Acrobat Reader. Acrobat readers are

available from Adobe , free of charge, at: ®

http://www.adobe.com/prodindex/acrobat/readstep.html

and are required to read Acrobat (PDF) files. Readers are available for Windows,

MacIntosh, and DOS.
January 1999 Compendium of Methods for Toxic Organic Air Pollutants Page 7-1

EPA/625/R-96/010b

Compendium of Methods

for the Determination of

Toxic Organic Compounds

in Ambient Air

Second Edition

Compendium Method TO-7

Method for the Determination of N-nitrosodimethylamine (NDMA) 

in Ambient Air Using Gas Chromatography 

Summary of Method

Compendium Method TO-7 involves drawing ambient air through a Thermosorb/N adsorbent

cartridge at a rate of approximately 2 L per minute for an appropriate period of time. Breakthrough

has been shown not to be a problem with total sampling volumes of 300 L (i.e., 150 minutes at 2 L

per minute) or less. The selection of Thermosorb/N adsorbent over Tenax® GC, was due, in part,

to recent laboratory studies indicating artifact formation on Tenax® from the presence of oxides of

nitrogen in the sample matrix.

After sampling, the cartridge is plugged and returned to the laboratory for analysis. In the

laboratory, the cartridge is pre-eluted with 5 mL of methylene chloride (in the same direction as

sample flow) to remove interferences. Residual methylene chloride is removed by purging the

cartridge with air in the same direction. The cartridge is then eluted, in the reverse direction, with

2 mL of acetone. This eluate is collected in a screw-capped vial and refrigerated until analysis.

NDMA is determined by GC/MS using a Carbowax 20M capillary column. NDMA is quantified from

the response of the m/e 74 molecular ion using an external standard calibration method.

Sources of Methodology

Method TO-7 has not been revised. Therefore, the original method is not repeated in the

Second Edition of the Compendium. Method TO-7 is contained in the original Compendium of

Methods for the Determination of Toxic Organic Compounds in Ambient Air, EPA-600/4-89-017,

which may be purchased in hard copy from: National Technical Information Service, 5285 Port

Royal Road, Springfield, VA 22161; Telephone: 703-487-4650; Fax: 703-321-8547; E-Mail:

info@ntis.fedworld.gov; Internet: www.ntis.gov. Order number: PB90-116989. The TO-methods

may also be available from various commercial sources.
Method TO-7 NDMA

Page 7-2 Compendium of Methods for Toxic Organic Air Pollutants January 1999

Electronic versions of the individual unrevised Compendium (TO-) Methods are available for

downloading from the "AMTIC, Air Toxics" section of EPA's OAQPS Technology Transfer Network

via the Internet at the “AMTIC, Air Toxics” section of the TTNWeb:

http://www.epa.gov/ttn/amtic/airtox.html

Methods TO-1 to TO-13 are now posted in the portable document format (PDF).

The downloaded files can be read using an Acrobat Reader. Acrobat readers are

available from Adobe , free of charge, at: ®

http://www.adobe.com/prodindex/acrobat/readstep.html

and are required to read Acrobat (PDF) files. Readers are available for Windows,

MacIntosh, and DOS.
January 1999 Compendium of Methods for Toxic Organic Air Pollutants Page 8-1

EPA/625/R-96/010b

Compendium of Methods

for the Determination of

Toxic Organic Compounds

in Ambient Air

Second Edition

Compendium Method TO-8

Method for the Determination of Phenol and Methylphenols (Cresols) 

in Ambient Air Using High Performance Liquid Chromatography 

Summary of Method

Compendium Method TO-8 involves drawing ambient air through two midget impingers, each

containing 15 mL of 0.1 N NaOH. The phenols are trapped as phenolates. The impinger solutions

are placed in a vial with a Teflon®-lined screw cap and returned to the laboratory for analysis. The

solution is cooled in an ice bath and adjusted to a pH <4 by addition of 1 mL of 5% sulfuric acid

(V/V). The sample is adjusted to a final volume of 25 mL with distilled water. The phenols are

determined using reverse-phase HPLC with either ultraviolet (UV) absorption detection at 274 nm,

electrochemical detection, or fluorescence detection. In general, the UV detection approach should

be used for relatively clean samples.

Sources of Methodology

Method TO-8 has not been revised. Therefore, the original method is not repeated in the

Second Edition of the Compendium. Method TO-8 is contained in the original Compendium of

Methods for the Determination of Toxic Organic Compounds in Ambient Air, EPA-600/4-89-017,

which may be purchased in hard copy from: National Technical Information Service, 5285 Port

Royal Road, Springfield, VA 22161; Telephone: 703-487-4650; Fax: 703-321-8547; E-Mail:

info@ntis.fedworld.gov; Internet: www.ntis.gov. Order number: PB90-116989. The TO-methods

may also be available from various commercial sources.

Electronic versions of the individual unrevised Compendium (TO-) Methods are available for

downloading from the "AMTIC, Air Toxics" section of EPA's OAQPS Technology Transfer Network

via the Internet at the “AMTIC, Air Toxics” section of the TTNWeb:

http://www.epa.gov/ttn/amtic/airtox.html
Method TO-8 Cresols

Page 8-2 Compendium of Methods for Toxic Organic Air Pollutants January 1999

Methods TO-1 to TO-13 are now posted in the portable document format (PDF).

The downloaded files can be read using an Acrobat Reader. Acrobat readers are

available from Adobe , free of charge, at: ®

http://www.adobe.com/prodindex/acrobat/readstep.html

and are required to read Acrobat (PDF) files. Readers are available for Windows,

MacIntosh, and DOS.
January 1999 Compendium of Methods for Toxic Organic Air Pollutants Page 12-1

EPA/625/R-96/010b

Compendium of Methods

for the Determination of

Toxic Organic Compounds

in Ambient Air

Second Edition

Compendium Method TO-12

Method for the Determination of Non-Methane Organic Compounds

(NMOC) in Ambient Air Using Cryogenic Preconcentration and 

Direct Flame Ionization Detection (PDFID)

Summary of Method

Compendium Method TO-12 combines a cryogenic concentration technique for trapping

organics in the ambient air (similar to Compendium Method TO-3) coupled to a highly sensitive and

simple flame ionization detector (FID) to determine non-speciated total NMOC concentrations in the

ambient air.

In Compendium Method TO-12, a whole air sample is either extracted directly from the

ambient air and analyzed on-site by the GC system or collected into a precleaned specially-treated

canister and analyzed off-site.

The analysis requires drawing a fixed-volume portion of the extracted sample air, at a low

flow rate, through a glass-bead filled trap that is cooled to approximately -186EC with liquid argon.

The cryogenic trap simultaneously collects and concentrates the NMOC (either via condensation or

adsorption) while allowing the methane, nitrogen, oxygen, etc. to pass through the trap without

retention. The system is dynamically calibrated so that the volume of sample passing through the trap

does not have to be quantitatively measured, but must be precisely repeatable between the calibration

and the analytical phases.

After the fixed-volume air sample has been drawn through the trap, a helium carrier gas flow

is diverted to pass through the trap, in the opposite direction to the sample flow, and into an FID.

When the residual air and methane have been flushed from the trap and the FID baseline restabilizes,

the cryogen is removed and the temperature of the trap is raised to approximately 90EC.

The NMOC previously collected in the trap revolatilize due to the increase in temperature and

are carried into the FID, resulting in a response peak or peaks from the FID. The area of the peak

or peaks is integrated, and the integrated value is translated to concentration units via a previously

obtained calibration curve relating integrated peak areas with known concentrations of propane.
Method TO-12 NMOC

Page 12-2 Compendium of Methods for Toxic Organic Air Pollutants January 1999

By convention, concentrations of NMOC are reported in units of parts per million carbon

(ppmC), which, for a specific compound, is the concentration by volume (ppmv) multiplied by the

number of carbon atoms in the compound.

Sources of Methodology

Method TO-12 has not been revised. Therefore, the original method is not repeated in the

Second Edition of the Compendium. Method TO-12 is contained in the original supplement of

Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air, EPA600/4-89-017, which may be purchased in hard copy from: National Technical Information Service,

5285 Port Royal Road, Springfield, VA 22161; Telephone: 703-487-4650; Fax: 703-321-8547; EMail: info@ntis.fedworld.gov; Internet: www.ntis.gov. Order number: PB90-116989. The TOmethods may also be available from various commercial sources.

Electronic versions of the individual unrevised Compendium (TO-) Methods are available for

downloading from the "AMTIC, Air Toxics" section of EPA's OAQPS Technology Transfer Network

via the Internet at the “AMTIC, Air Toxics” section of the TTNWeb:

http://www.epa.gov/ttn/amtic/airtox.html

Methods TO-1 to TO-13 are now posted in the portable document format (PDF).

The downloaded files can be read using an Acrobat Reader. Acrobat readers are

available from Adobe , free of charge, at: ®

http://www.adobe.com/prodindex/acrobat/readstep.html

and are required to read Acrobat (PDF) files. Readers are available for Windows,

MacIntosh, and DOS.
United States Center for Environmental

Environmental Protection Research Information

Agency

Research and Development EPA-625/SR-96/010b January 1999

EPA Project Summary1

Compendium of Methods for the

Determination of Toxic Organic Compounds

in Ambient Air--Second Edition

This Project Summary is the announcement of the availability of the Second Edition of the

Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air. This

Second Edition of the Compendium has been prepared to provide regional, state and local

environmental regulatory agencies with step-by-step sampling and analysis procedures for the

determination of selected toxic organic pollutants in ambient air. It is designed to assist those

persons responsible for sampling and analysis of hazardous air pollutants (HAPs) in complying

with the requirements of Title III of the Clean Air Act.

Determination of pollutants in ambient air is a complex task, primarily because of the wide

variety of compounds of interest coupled with the lack of standardized sampling and analysis

procedures. Many toxic organics can be sampled and analyzed by several techniques, often with

different interferences and detection limitations. This revised Compendium presents a set of

17 methods in a standardized format with a variety of applicable sampling methods, as well as

several analytical techniques, for specific classes of organic pollutants, as appropriate to the

specific pollutant compound, its level, and potential interferences. Consequently, this treatment

allows the user flexibility in selecting alternatives to complement his or her background and

laboratory capability. These methods may be modified from time to time as advancements are

made.

 

This Project Summary was developed jointly by the U. S. Environmental Protection

Agency (EPA) Center for Environmental Research Information (CERI), National Risk Management

Research Laboratory (NRMRL), Office of Research and Development (ORD), Cincinnati, OH and

ORD’s National Exposure Research Laboratory (NERL) at Research Triangle Park, NC to alert

potential users of the availability of the updated Compendium that is fully documented in a

separate report of the same title (see Project Report ordering information at back).

Introduction

The Clean Air Act Amendments of 1990 (CAAA of 1990) have significantly increased the

responsibilities of both federal and state agency programs for evaluating and maintaining air

emissions compliance. In turn, this increased responsibility has generated a need for more

1

Written by: William T. “Jerry” Winberry, Jr., EnviroTech Solutions, 1502 Laughridge Drive, Cary,

NC 27511, (919)-467-2785, email: jwinberry@mindspring.com.
Page -2-

personnel trained to interpret, enforce, and respond to regulatory initiatives. Consequently, the

Agency has restructured its technology transfer program to more effectively provide technical

assistance in the form of publication of technical documents, presentations and workshops, and

development of tools to assist Agency personnel in keeping their skills up-to-date so that they may

efficiently cope with the many changes evolving in new programs, equipment, sampling and

analytical methodology, and available enforcement tools.

Limited guidance has been available to state and local agencies or to other organizations

concerned with the determination of toxic organic compounds in ambient air. As a result, state

and local agencies and others responding to air pollution problems have had to develop their own

monitoring strategies, including selection of monitoring methods, sampling plan design, and

specific procedures for sampling, analysis, logistics, calibration and quality control. For the most

part, these procedures were based on professional judgments rather than adherence to any

documented uniform guidelines. Many governmental agencies and professional or research

organizations have developed ambient air monitoring methods and procedures, mostly to respond

to specialized needs. But these methods and procedures have, in general, been neither

standardized nor readily available to other agencies involved with ambient air monitoring for

organic hazardous air pollutants (HAPs).

To meet these needs, EPA's ORD, through CERI and NERL has supported technology

transfer programs involving standardized, peer reviewed monitoring methods for regulatory and

industrial personnel via publications of Compendia methods. Other recent or upcoming documents

in this series are:

• Compendium of Methods for the Determination of Inorganic Compounds in

Ambient Air, EPA 625/R-96/010a, January 1999. (This publication is

scheduled for release during the first half of 1999).

• Compendium of Methods for the Determination of Air Pollutants in Indoor

Air, EPA 600/4-90-010, April 1990.

These Compendia have historically assisted Federal, State, and local regulatory personnel

in developing and maintaining necessary expertise and up-to-date technology involving sampling

and analysis of both inorganic and organic HAPs. However, since the publication of these

documents, new technology has been introduced to cope with the monitoring requirements

identified in the Amendments, thus creating the need for updating many of the methods in the

existing Organic Compendium.

The methods in the Second Edition have been compiled from the best elements of

methods developed or used by various research or monitoring organizations. They are presented

in a standardized format, and each one has been extensively reviewed by several technical

experts having expertise in the methodology presented.

Structure of the Second Edition of the Compendium

This Second Edition has been prepared to provide regional, state and local environmental

regulatory agencies, as well as other interested parties, with specific guidance on the

determination of selected toxic organic compounds in ambient air. A visual guide to the

organization of the Compendium for specific methods covering a variety of organic compounds is

illustrated in Figure 1.
SPECIFIC

TO-8

TO-9A

TO-10A

TO-11A

TO-12

TO-13A

TO-14A

CRESOLS / PHENOLS

DIOXINS

PESTICIDES

FORMALDEHYDE

NMOC

SEMI-VOLATILES

VOLATILES (-158E to 170EC)

TO-7

TO-6

TO-5

TO-4A

TO-3

TO-2

TO-1

SEMIVOLATILES

N-NITROSODIMETHYLAMINE

PHOSGENE

ALDEHYDES / KETONES

PESTICIDES / PCBs

VOLATILES (-10EC to 200EC)

VOLATILES (-15EC to 120EC)

VOLATILES (80EC to 200EC)

TO-15

VOLATILES

(-50E to 170EC)

TO-16

VOLATILES

(80E to 200EC)

TO-17 

VOLATILES

(-158E to 200EC)

VOLATILES

Page -3-

Figure 1. A visual guide to the organization of the Second Edition of the Organic

Compendium.

Those methods assigned the "A" notation are methods which were published in the First

Edition (Compendium Methods TO-1 through TO-14) of the Compendium and have now been

updated due to technological advances in either the sampling or analysis methodology. In

addition, three new methods (Compendium Methods TO-15 through TO-17) have been added to

make the complete Second Edition of the Compendium. These methods were added due to their

advanced technology application involving specially treated canisters (Compendium

Method TO-15), long-path (open-path) fourier transform infrared spectroscopy (Compendium

Method TO-16), and multibed sorbent techniques (Compendium Method TO-17). The methods

which are neither new or modified are not reproduced in the Second Edition in order to save

space. This decision was based on the fact that they are not as likely to be used as the revised or

new methods.

A list of methods contained in the Second Edition of the Compendium is presented in

Table 1. This listing provides a brief indication of the type of compounds to which the method is

applicable, the type of sample collection device used, and the type of analytical methodology for

which the sample collection system was designed for compatibility. Finally, a listing of the

advantages and disadvantages of the methods in the Second Edition of the Compendium are

documented in Table 2.
Page -4-

TABLE 1. LIST OF METHODS IN SECOND EDITION OF THE COMPENDIUM

Compendium

Method No.

Type of Compounds

Determined Sample Collection Device

Analytical

Methodology1

TO-12 Volatile organic compounds Tenax® solid sorbent GC/MS

TO-22 Volatile organic compounds Molecular sieve sorbent GC/MS

TO-32 Volatile organic compounds Cryotrap GC/FID

TO-4A Pesticides/PCBs Polyurethane foam GC/MD

TO-52 Aldehydes/Ketones Impinger HPLC

TO-62 Phosgene Impinger HPLC

TO-72 Anilines Adsorbent GC/MS

TO-82 Phenols Impinger HPLC

TO-9A Dioxins Polyurethane foam HRGC/HRMS

TO-10A Pesticides/PCBs Polyurethane foam GC/MD

TO-11A Aldehydes/ketones Adsorbent HPLC

TO-122 Non-methane organic

compounds (NMOC)

Canister or

on-line

FID

TO-13A Polycyclic aromatic

hydrocarbons

Polyurethane foam GC/MS

TO-14A Volatile organic compounds

(nonpolar)

Specially-treated canister GC/MS and GC/MD

TO-15 Volatile organic compounds

(polar/nonpolar)

Specially-treated canister GC/MS

TO-16 Volatile organic compounds Open path monitoring FTIR

TO-17 Volatile organic compounds Single/multi-bed adsorbent GC/MS, FID, etc.

GC/MS = Gas chromatography/mass spectrometry. 1

GC/FID = Gas chromatography/flame ionization detector.

HPLC = High performance liquid chromatography.

GC/MD = Gas chromatography/multi-detector.

GC/IT = Gas chromatography/ion trap detector.

FTIR = Fourier transform infrared spectroscopy.

HRGC/HRMS = High resolution gas chromatography/high resolution mass spectrometry.

Methods denoted by "2" have not been changed since their publication in the First Edition of the Compendium, so the full content of these 2

methods is not repeated in this Second Edition. Therefore, the full content of these methods must be obtained from the original

Compendium (EPA 600/4-89-017).
Page -5-

TABLE 2. COMPENDIUM METHODS CHARACTERISTICS

Method Compounds Sampling and Analysis Detection

Desig. Determined Approach Limit Advantages Disadvantages

Types of

1

TO-1 VOCs 0.01-100 • Good data base. • Highly volatile compounds and certain polar

(See also sampled. • Rigorous clean-up of adsorbent required.

Methods [e.g., benzene, • Water vapor is not collected. • No possibility of multiple analysis.

TO-14A, toluene, xylenes] • Wide variety of compounds • Low breakthrough volumes for some compounds.

TO-15, collected. • Desorption of some compounds difficult.

and • Low detection limits. • Structural isomers are the most common

TO-17) • Standard procedures available. interferences.

(80E to 200EC) ppbv • Large volume of air can be compounds are not collected.

TENAX-GC ADSORPTION

AND GC/MS OR GC/FID

ANALYSIS

Ambient air is drawn through

organic polymer sorbent

where certain compounds

are trapped. The cartridge

is transferred to the

laboratory, thermally

desorbed and analyzed

using GC/MS or GC/FID.

• Practical for field use. • Contamination of adsorbent and blank

contaminants may be a problem.

• Artifact formation.

TO-2 Highly volatile 0.1-200 • Trace levels of volatile organic • Some trace levels of organic species are difficult to

(See also (-15E to +120EC) concentrated on sorbent material. • Structural isomers are common interferences.

Methods • Efficient collection of polar • Water is collected and can de-activate adsorption

TO-14A, [e.g., vinyl chloride, compounds. sites.

TO-15, chloroform, • Wide range of application. • Thermal desorption of some compounds may be

and chlorobenzene] • Highly volatile compounds are difficult.

TO-17) adsorbed.

VOCs ppbv compounds are collected and recover from the sorbent.

CARBON MOLECULAR

SIEVE ADSORPTION AND

GC/MS OR GC/FID

ANALYSIS

Selected volatile organic

compounds are captured on

carbon molecular sieve

adsorbents. Compounds are

thermally desorbed and

analyzed by GC/MS or

GC/FID techniques.

• Easy to use in field.

TO-3 VOCs nonpolar 0.1-200 • Collects wide variety of volatile • Moisture levels in air can cause freezing problems

(See also • Standard procedures are available. • Difficult to use in field.

Methods [e.g., vinyl chloride, • Contaminants common to • Expensive.

TO-14A, methylene chloride, adsorbent materials are avoided. • Integrated sampling is difficult.

TO-15, acrylonitrile] • Low blanks. • Compounds with similar retention times will interfere.

and • Consistent recoveries.

TO-17) • Large data base.

(-10E to +200EC) ppbv organic compounds. with cryogenic trap.

CRYOGENIC

PRECONCENTRATION AND

GC/FID/ECD ANALYSIS

Vapor phase organics are

condensed in a cryogenic

trap. Carrier gas transfers

the condensed sample to a

GC column. Adsorbed

compounds are eluted from

the GC column and

measured by FID or ECD.

TO-4 Pesticides/PCBs 0.2pg/m - • Low detection limits. • Breakdown of PUF adsorbent may occur with polar

(See also [e.g., PCBs, pesticides/PCBs • Contamination of glassware may limit detection

Method 4,4-DDE, DDT, • PUF reusable. limits.

TO-10A) DDD] • Low blanks. • Loss of some semi-volatile organics during storage.

HIGH VOL FILTER AND PUF

ADSORBENT FOLLOWED

BY GC/FID/ECD OR GC/MS

DETECTION

Pesticides/PCBs trap on filter

and PUF adsorbent trap. 

Trap returned to lab, solvent

extracted and analyzed by

GC/FID/ECD or GC/MS.

3

200 ng/m • Effective for broad range of extraction solvents. 3

• Excellent collection and retention • Extraneous organics may interfere.

efficiencies for common pesticides • Difficulty in identifying individual pesticides and

and PCBs. PCBs if using ECD.
Page -6-

TABLE 2. (CONTINUED)

Method Compounds Sampling and Analysis Detection

Desig. Determined Approach Limit Advantages Disadvantages

Types of

1

TO-5 Aldehydes and 1-50 ppbv • Specific for aldehydes and • Sensitivity limited by reagent purity.

(See also • Good stability for derivative sampling.

Method [e.g., formaldehyde, compounds formed in the • Isomeric aldehydes and ketones may be unresolved

TO-11A) acetaldehyde, impingers. by the HPLC system.

ketones ketones. • Potential for evaporation of liquid over long term

acrolein] • Low detection limits.

DNPH LIQUID IMPINGER

AND HPLC/UV ANALYSIS

Air sample is drawn through

dinitrophenylhydrazine

(DNPH) impinger solution

using a low volume pump. 

The solution is analyzed

using HPLC with a UV

detector.

TO-6 Phosgene ANILINE/TOLUENE LIQUID 1-50 ppbv • Good specificity. • Chloroformates and acidic materials may interfere.

IMPINGER AND HPLC/UV

ANALYSIS

Ambient air is drawn through

a midget impinger containing

10 mL of 2/98 aniline/toluene

(v/v). The phosgene reacts

with aniline to form 1,3-

diphenylurea and is analyzed

using reverse-phase HPLC

with a UV absorbance

detector operating at

254 nm.

• Good stability for derivative • Contamination of aniline reagents may be a source

compounds formed in the of interference.

impingers. • Use of midget impingers in field application may not

• Low detection limits. be practical.

TO-7 N-Nitroso 1-50 ppbv • Good specificity. • Compounds with similar GC retention times and

dimethylamine • Good stability for derivative detectable MS ions may interfere.

THERMOSORB/N

CARTRIDGE WITH GC/MS

ANALYSIS

Ambient air is drawn through

a cartridge containing

Thermosorb/N adsorbent to

trap N-nitrosodimethylamine. 

The cartridge is returned to

the lab and eluted with 5 mL

of dichloromethane. The

cartridge is then eluted in

reverse direction with 2 mL of

acetone. The

N-nitrosodimethylamine is

then determined by GC/MS.

compounds formed on the • Specificity is a limiting factor if looking for other

cartridge. organic amines.

• Low detection limit for

n-nitrosodimethylamine.

• Placement of sorbent as first

component in sample train

minimizes contamination.

• Sampling system portable and

lightweight.

TO-8 Cresol/phenol SODIUM HYDROXIDE LIQUID 1-250 ppb • 4,6-dinitro-2-methylphenol specific • Compounds having the same HPLC retention times

IMPINGER AND HPLC/UV

DETECTION

Ambient air is drawn through

two midget impingers. 

Phenols are trapped as

phenolates in NaOH solution

which is returned to the lab

and analyzed by HPLC.

to class of compounds. will interfere with this method.

• Good stability. • Phenolic compounds of interest may be oxidized

• Detects non-volatile as well as during sampling.

volatile phenol compounds. • Limited sensitivity.
Page -7-

TABLE 2. (CONTINUED)

Method Compounds Sampling and Analysis Detection

Desig. Determined Approach Limit Advantages Disadvantages

Types of

1

TO-9A Dioxin/Furan/PCBs PUF ADSORBENT 0.25-5000 • Cartridge is reusable. • Analytical interferences may occur from PCBs,

CARTRIDGE AND HRGC/

HRMS ANALYSIS

Ambient air is drawn through

a glass fiber filter and a

polyurethane foam (PUF)

adsorbent cartridge by

means of a high volume

sampler. The filter and PUF

cartridge are returned to the

laboratory and extracted

using toluene. The extract is

concentrated using the

Kuderna-Danish technique,

diluted with hexane, and

cleaned up using column

chromatography. The

cleaned extract is then

analyzed by high resolution

gas chromatography/high

resolution mass spectrometry

(HRGC/HRMS).

pg/m • Excellent detection limits. methoxybiphenyls, chlorinated 3

• Easy to preclean and extract. hydroxydiphenylethers, naphthalenes, DDE, and

• Excellent collection and retention DDT with similar retention times and mass fractions.

efficiencies. • Inaccurate measurement Ds/Fs are retained on

• Broad database. particulate matter and may chemically change

• Proven methodology. during sampling and storage.

• Analytical equipment required (HRGC/HRMS) is

expensive and not readily available.

• Operator skill level important.

• Complex preparation and analysis process.

• Can't separate particles from gaseous phase.

TO-10A Pesticides 1-100 • Easy field use. • ECD and other detectors (except the MS) are

[e.g., heptachlor, • Easy to clean. other than target analytes.

chlordane, dieldrin, • Effective for broad range of • PCBs, dioxins and furans may interfere.

aldrin] compounds. • Certain organochlorine pesticides (e.g., chlordane)

PUF ADSORBENT

CARTRIDGE AND

GC/ECD/PID/FID ANALYSIS

A low-volume sample

(1-5 L/min) is pulled through

a polyurethane foam (PUF)

plug to trap organochlorine

pesticides. After sampling,

the plug is returned to the

laboratory, extracted and

analyzed by GC coupled to

multi-detectors (ECD, PID,

FID, etc.).

ng/m • Proven methodology. subject to responses from a variety of compounds 3

• Portability. are complex mixtures and can make accurate

• Good retention of compounds. quantitation difficult.

• May not be sensitive enough for all target analytes in

ambient air.
Page -8-

TABLE 2. (CONTINUED)

Method Compounds Sampling and Analysis Detection

Desig. Determined Approach Limit Advantages Disadvantages

Types of

1

TO-11A Formaldehyde 0.5-100 • Placement of sorbent as first • Isometric aldehydes and ketones and other

(other aldehydes/ ppbv element in the sampling train compounds with the same HPLC retention time as

ketones) minimizes contamination. formaldehyde may interfere.

[e.g., formaldehyde, • Proven technology. ozone denuder is not employed.

acetaldehyde, • Sampling system is portable and • Liquid water captured on the DNPH cartridge during

acrolein] light weight. sampling may interfere.

DNPH-CARTRIDGE AND

HPLC/UV DETECTION

An ambient air sample is

drawn through a

commercially-coated DNPH

cartridge at a rate of 500-

1200 mL/minute. The

cartridges are returned to the

laboratory in screw-cap glass

vials. The cartridges are then

removed from the vials and

washed with acetonitrile by

gravity feed elution. The

eluate is diluted volumetrically

and an aliquot is removed for

determination of the DNPHformaldehyde derivative by

isocratic reverse phase

HPLC with UV detection at

350 nm.

• Large database. • Carbonyls on the DNPH cartridge may degade if an

• O3 and UV light deteriorates trapped carbonyls on

cartridge.

TO-12 NMOC (non- 0.1-200 • Standard procedures are available. • Moisture levels in air can cause freezing problems.

methane organic ppmvC • Contaminants common to • Non-speciated measurement.

compounds) adsorbent materials are avoided. • Precision is limited.

CANISTER SAMPLING--

CRYOGENIC PRECONCENTRATION AND FID

DETECTION

Ambient air is drawn into a

cryogenic trap where the

non-methane organic

compounds (NMOCs) are

concentrated. The trap is 

heated to move the NMOCs

to the FID. Concentration of

NMOCs is determined by

integrating under the broad

peak. Water correction is

necessary.

• Low blanks.

• Consistent recoveries.

• Large data base.

• Good sensitivity.

• Useful for screening areas or

samples.

• Analysis much faster than GC.
Page -9-

TABLE 2. (CONTINUED)

Method Compounds Sampling and Analysis Detection

Desig. Determined Approach Limit Advantages Disadvantages

Types of

1

TO-13A PAHs 0.5-500 • Allows for sample dilution if • Method has interferences due to contamination of

[e.g., analysis. hardware.

benzo(a)pyrene, • Repeated analysis is possible. • Coeluting contaminants may cause interference with

naphthalene, • High-volume sampling provides for target analytes.

fluorene] lower detection limits. • Heat, ozone, NO , and ultraviolet light may cause

PUF OR XAD-2 ADSORBENT

CARTRIDGE AND GC/MS

ANALYSIS

Ambient air is drawn through

a glass fiber filter and a

polyurethane foam (PUF) or

XAD-2 adsorbent cartridge

by means of a high volume

sampler. The filter and PUF

cartridge are extracted using

10% diethyl ether. The

extract is concentrated using

Kuderna-Danish technique,

diluted, and cleaned up using

column chromatography. 

The cleaned extract is then

analyzed by gas

chromatography/mass

spectrometry (GC/MS).

ng/m concentration is too high during solvents, reagents, glassware, and sampling 3

• Filter and PUF are low cost. sample degradation.

2

TO-14A VOCs 0.2-25 • Best method for broad speciation • Limited to non-polar compounds due to use of

(non-polar) ppbv of unknown trace volatile organics. permeation type dryer.

[e.g., toluene, • Good QA/QC database. decompose through interaction with container walls.

benzene, • Proven field and analytical • Water condensation at high humidity may be a

chlorobenzene] technology. problem at high concentrations (ppm).

SPECIALLY-PREPARED

CANISTER AND GC/FID/ECD

OR GC/MS DETECTION

Whole air samples are

collected in an evacuated

stainless steel canister.

VOCs are concentrated in

the laboratory with cryogen

trap. VOCs are revolatilized,

separated on a GC column,

and passed to one or more

detectors for identification

and quantitation.

• Simple sampling approach. • Sample components may be adsorbed or

• Complex equipment preparation required.

• Expensive analytical equipment.

TO-15 VOCs 0.2-25 • Incorporates a multisorbent/ dry • Expensive analytical equipment.

(polar/non-polar) ppbv purge technique or equivalent for • Operator skill level important.

[e.g., methanol, addressing a more extensive set of

benzene, xylene, compounds.

nitrobenzene] • Establishes method performance

SPECIALLY-PREPARED

CANISTER AND GC/MS

ANALYSIS

Whole air samples are

collected in a speciallyprepared canister. VOCs are

concentrated on a solid

sorent trap or other

arrangement, refocused on a

second trap, separated on a

GC column, and passed to

an MS detector for

identification and

quantification.

water management thereby

criteria for acceptance of data.

• Provides enhanced provisions for

quality control.

• Unique water management

approach allows analysis for polar

VOCs.
Page -10-

TABLE 2. (CONTINUED)

Method Compounds Sampling and Analysis Detection

Desig. Determined Approach Limit Advantages Disadvantages

Types of

1

TO-16 VOCs (polar/non- 25-500 • Open path analysis maintains • High level of operator skill level required.

polar) ppbv integrity of samples. • Requires spectra interpretation.

[e.g., alcohols, and time. • Higher detection limits than most alternatives.

ketones, benzene, • Path-integrated pollutant • Must be skilled in computer operation.

toluene, o-xylene, concentration measurement • Substantial limitations from ambient CO and

chlorobenzene] minimizes possible sample humidity levels associated with spectral analysis.

FTIR OPEN PATH SPECTROSCOPY

VOCs are monitored using

real-time long-path openpath fourier transform

infrared spectroscopy (FTIR).

• Multi-gas analysis saves money • Limited spectra library available.

contamination, and provides realtime pollutant concentration..

• Applicability for special survey

monitoring.

• Monitoring at inaccessible areas

possible using open-path FTIR.

2

TO-17 VOCs 0.2-25 • Placement of the sorbent as the • Distributed volume pairs required for quality

(polar/non-polar) ppbv first element minimizes assurance.

[e.g., alcohols, train components. • No possibility of multiple analysis.

ketones, benzene, • Large selection of sorbents to • Must purchase thermal desorption unit for analysis.

toluene, o-xylene, match with target analyte list. • Desorption of some VOCs is difficult.

chlorobenzene] • Includes polar VOCs. • Contamination of adsorbent can be a problem.

MULTI-BED ADSORBENT

TUBE FOLLOWED BY

GC/MS

Ambient air is drawn through

a multi-bed sorbent tube

where VOCs are trapped. 

The cartridge is returned to

the laboratory, thermally

desorbed and analyzed by

GC/MS or other methods.

contamination from other sample • Rigorous clean-up of sorbent required.

• Better water management using

hydrophobic sorbents than

Compendium Method TO-14A.

• Large database, proven

technology.

• Size and cost advantages in

sampling equipment.

Number in parenthesis is the boiling point range of the organics applicable to that Compendium Method. 1
Page -11-

The following is a brief overview of important technical changes/additions that have been

made to those methods which have been updated or added to comprise the Second Edition of

the Organic Compendium.

Compendium Method TO-4A

(Pesticides/PCBs)

• Incorporates an extensive update of quality assurance (QA) requirements involving the

sampling mechanism.

• Allows a multi-detector approach for quantifying analytes on the target compound list (TCL).

• Establishes method performance criteria for acceptance of data, allowing the use of

alternative but equivalent sampling and analytical equipment.

• Provides specific procedures for sample clean-up, employing solid phase extraction using

silica, alumina or florisil.

• A detailed discussion associated with method performance criteria involving surrogate

recoveries, laboratory method blanks, GC column performance and minimum detection limits

is provided.

Compendium Method TO-9A

(Dioxins/Furans)

• Includes guidance associated with the use of benzene or toluene as the extraction solvent.

• Provides extensive guidance associated with field operation and quality assurance checks

involving the high-volume sampler.

• Presents extracted ion current profiles (EICP) for selected dioxins and furans.

• Discusses method performance criteria involving surrogate recoveries, laboratory method

blanks, GC column performance, laboratory control spikes, matrix spikes, and minimum

detection limits determination.

• Provides specific procedures for sample clean-up employing solid phase extraction using

silica, alumina, and carbon adsorbents.

Compendium Method TO-10A

(Pesticides/PCBs)

• Provides guidance on determining sampling efficiency (SE), retention efficiency (RE), and

dynamic retention efficiency (RE ). d

• Recommends specific detectors for common pesticides and PCBs.

• Gives construction specifications for both PUF and PUF/XAD-2 adsorbent cartridges.

• Includes recent laboratory evaluation of sampling efficiencies for organochlorine pesticides,

PCBs, ureas, triazines and pyethrins.

• Describes generator used in determining sampling efficiencies.

Compendium Method TO-11A

(Formaldehyde)

• Includes new material from EPA's Technical Assistance Document (TAD) on enhanced ozone

monitoring.

• Adds design and construction specifications for an ozone denuder and scrubber.

• Reviews commercially-prepared low pressure drop adsorbent cartridges.

• Discusses sampler design for sequential sampling and heated inlet.
Page -12-

• Provides guidance on sorbent selection (C vs. silica gel). 18

• Illustrates the application of ozone denuder or scrubber to the field sampling system.

• Updates of HPLC procedures for column alternatives to quantitate up to 14 carbonyl

compounds.

Compendium Method TO-13A

(Semi-volatiles)

• Incorporates an extensive update of quality assurance (QA) requirements involving sampling

mechanism.

• Allows only gas chromatography/mass spectrometry (GC/MS) approach specified for

quantifying analytes on the target compound list (TCL).

• Establishes method performance criteria for acceptance of data, allowing the use of alternative

but equivalent sampling and analytical equipment.

• Provides specific procedures for sample clean-up, employing solid phase extraction.

• Provides detailed discussion of method performance evaluation (PE) standard and recoveries,

laboratory method blanks, GC column performance and minimum detection limits

requirements.

Compendium Method TO-14A

(VOCs - non-polar)

• Excludes alternative "water management" technique in lieu of permeation dryers.

• Expands canister requirements to include specially-prepared canisters.

• Provides for gas chromatography coupled to an ion trap detector.

Compendium Method TO-15

(VOCs - polar/non-polar)

• Addresses a more extensive set of compounds (the VOCs mentioned in Title III of the CAAA of

1990).

• The analytical methodology emphasizes GC/MS as the means to identify and quantitate target

compounds.

• Establishes method performance criteria for acceptance of data, allowing the use of alternate

but equivalent sampling and analytical equipment.

• Uses a multisorbent/dry purge technique or equivalent for water management.

Compendium Method TO-16

(VOCs - polar/non-polar)

• Describes the use of an FT-IR system to measure pollutants using a long, open air path. 

• Provides measurement of the path-average atmospheric concentrations of various organic

gases.

• Methodology discussed in Compendium Method TO-16 provides the following advantages for

field application:

 -- The integrity of the sample is assured, since no sampling actually occurs.

 -- Multi-gas analysis is possible with a single field spectrum.

 -- Path-integrated pollutant concentrations are obtained.

 -- Spatial survey monitoring of industrial facilities is possible if scanning optics are used.
Page -13-

 -- Coadding of spectra to improve detection capabilities is easily performed.

 -- Rapid temporal scanning of line-of-site or multiple lines-of-sight is possible.

 -- Monitoring of otherwise inaccessible areas is possible.

Compendium Method TO-17

(VOCs - polar/non-polar)

• The use of solid adsorbents in multisorbent tubes for concentrating VOCs from the ambient air

is presented as part of EPA's program for methods development of automated gas

chromatographs.

• Uses sorbent tubes with single or multisorbent packings.

• Compendium Method TO-17, collection of VOCs in ambient air samples by passage through

solid sorbent packings, provides numerous advantages, including:

-- The small size and light weight of the sorbent packing and attendant equipment allows for

field application.

-- The placement of the sorbent packing as the first element (with the possible exception of a

filter or chemical scrubber for ozone) in the sampling train reduces the possibility of 

contamination from upstream elements.

-- The availability of a large selection of sorbents enables matching sorbents with a target set

of compounds, including polar VOC.

-- The method provides for the possibility of water management using a combination of

hydrophobic sorbents (to cause water breakthrough while sampling), dry gas purge of

water from the sorbent after sampling, and splitting of the sample during analysis.

-- Technology is based on a large amount of literature associated with the use of sorbent

sampling and thermal desorption for monitoring of workplace air, particularly from the

Health and Safety Executive in the United Kingdom.

Ordering Information

The First Edition of the Compendium was published over a period of four years in four separate

EPA documents. They are:

• Original Compendium (Methods TO-1 through TO-5), EPA 600/4-84-041, April 1984.

• First Supplement (Methods TO-6 through TO-9), EPA 600/4-87-006, September 1986.

• Second Supplement (Methods TO-10 through TO-14), EPA 600/4-89-018, June 1988.

• Full Compendium (Methods TO-1 through TO-14), EPA 600/4-89-017, June 1988. 

Please Note: The Second Edition of the Compendium does not contain Methods TO-1, 2, 3, 5, 6, 7, 8, and

12. These methods, which were not updated because there were no significant technological advances

made in them, can be found in their entirety in the First Edition only. The Second Edition contains only:

a) the updated methods (methods assigned with an "A" in Table 1 from the First Edition which includes

Compendium Methods TO-4A, TO-9A, TO-10A, TO-11A, TO-13A, and TO-14A); and b) the three new

methods, Compendium Methods TO-15, TO-16, and TO-17.

These documents, including the Second Edition, may be purchased in hard copy from: 

National Technical Information Service (NTIS)

5285 Port Royal Road, Springfield, VA 22161

Telephone: 703-487-4650; FAX: 703-321-8547

E-mail:Info @ NTIS.FEDWORLD.GOV

INTERNET: http://www.ntis.gov.
Page -14-

 U.S. EPA: Office of Air Quality Planning and Standards (OAQPS)

Electronic versions of the individual unrevised Compendium (TO-) Methods are available

for downloading from the "AMTIC, Air Toxics" section of EPA's OAQPS Technology Transfer

Network via the Internet at the “AMTIC, Air Toxics” section of the TTNWeb:

http://www.epa.gov/ttn/amtic/airtox.html

Methods TO-1 to TO-17 are now posted in the portable document format (PDF). 

The downloaded files can be read using an Acrobat Reader. Acrobat readers are

available from Adobe , free of charge, at: ®

http://www.adobe.com/prodindex/acrobat/readstep.html

and are required to read Acrobat (PDF) files. Readers are available for Windows,

MacIntosh, and DOS.

 U.S. EPA: Office of Research and Development (ORD), 

 Center for Environmental Research Information (CERI)

New technology transfer documents may be ordered on-line through the CERI Technology

Transfer web site - “http://www.epa.gov/ttbnrmrl/”. Once the web site has been accessed, click on

the publication list and follow the menu-driven ordering instructions. 

Acknowledgements

The Second Edition of the Compendium of Methods for the Determination of Toxic

Organic Compounds in Ambient Air (EPA/625/R-96/010b) was prepared under Contract

No. 68-C3-0315, WA No. 3-10, by Midwest Research Institute (MRI), as a subcontractor to

Eastern Research Group, Inc. (ERG), and under the sponsorship of the EPA. Justice A. Manning,

John O. Burckle, Scott Hedges, Center for Environmental Research Information, and Frank F.

McElroy, National Exposure Research Laboratory , all in EPA’s Office of Research and

Development, were responsible for overseeing the preparation of the Second Edition of the

Compendium. Invaluable support was also provided by the following members of the

Compendium Workgroup:

John O. Burckle, U.S. EPA, ORD, NRMRL, Cincinnati, OH

James L. Cheney, U.S. Army Corps of Engineers, Omaha, NB

Michael Davis, U.S. EPA, Region 7, Kansas City, KS

Joseph B. Elkins Jr., U.S. EPA, OAQPS, Research Triangle Park, NC

Robert G. Lewis, U.S. EPA, ORD, NERL, Research Triangle Park, NC

William A. McClenny, U.S. EPA, ORD, NERL, Research Triangle Park, NC

Heidi Schultz, ERG, Lexington, MA

William T. "Jerry" Winberry, Jr., EnviroTech Solutions, Cary, NC