ASTM D6345-98

Standard Guide for Selection of Methods for Active, Integrative Sampling of Volatile Organic Compounds in Air

SCOPE
1.1 This guide provides assistance in the selection of active integrative sampling methods, in which the volatile organic analytes are collected from air over a period of time by drawing the air into the sampling device, with subsequent recovery for analysis. Where available, specific ASTM test methods and practices are referenced.
1.2 Guidance is provided for the selection of active sampling methods based either on collection of an untreated air sample (whole air samples) or selective sampling using sorbent concentration techniques that selectively concentrate components in air. Advantages and disadvantages of specific collection vehicles are presented.
1.3 This guide does not cover the use of cryogenically cooled field sampling devices used in some automated analysis systems. Detailed instructions for cryogenic recovery of compounds captured as whole air samples or thermally desorbed from sorbents are typically covered in standard methods for sample analysis and are beyond the scope of this guide.
1.4 Both thermal and solvent desorption techniques for sample recovery are discussed.
1.5 Organic compounds are classified on the basis of vapor pressure as very volatile, volatile, semivolatile and nonvolatile. Physical characteristics of many volatile organic compounds (VOCs) are provided to aid in selection of sampling techniques for VOC measurement. Semivolatile and nonvolatile organic compounds are defined in the guide to help guide users avoid misidentifying compounds that are not covered in this guide.
1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

General Information

• Status: Historical
• Publication Date: 09-Nov-1998
• ICS: 13.040.99 - Other standards related to air quality
• Technical Committee: D22 - Air Quality
• Drafting Committee: D22.05 - Indoor Air

Relations

• Replaced By: ASTM D6345-98(2003) - Standard Guide for Selection of Methods for Active, Integrative Sampling of Volatile Organic Compounds in Air
• Effective Date: 01-Oct-2003
• Referred By: ASTM D6670-18 - Standard Practice for Full-Scale Chamber Determination of Volatile Organic Emissions from Indoor Materials/Products
• Effective Date: 10-Nov-1998
• Referred By: ASTM D8141-22 - Standard Guide for Selecting Volatile Organic Compounds (VOCs) and Semi-Volatile Organic Compounds (SVOCs) Emission Testing Methods to Determine Emission Parameters for Modeling of Indoor Environments
• Effective Date: 10-Nov-1998

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D 6345 – 98
Standard Guide for
Selection of Methods for Active, Integrative Sampling of
Volatile Organic Compounds in Air
This standard is issued under the fixed designation D 6345; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope D 1356 Terminology Relating to Sampling and Analysis of
Atmospheres
1.1 This guide provides assistance in the selection of active
D 1357 Practice for Planning the Sampling of the Ambient
integrative sampling methods, in which the volatile organic
Atmosphere
analytes are collected from air over a period of time by drawing
D 3686 Practice for Sampling Atmospheres to Collect Or-
the air into the sampling device, with subsequent recovery for
ganic Compound Vapors (Activated Charcoal Tube
analysis. Where available, specific ASTM test methods and
Method)
practices are referenced.
D 3687 Practice for Analysis of Organic Compound Vapors
1.2 Guidance is provided for the selection of active sam-
Collected by the Activated Charcoal Tube Adsorption
pling methods based either on collection of an untreated air
Method
sample (whole air samples) or selective sampling using sorbent
D 5197 Test Method for Determination of Formaldehyde
concentration techniques that selectively concentrate compo-
and Other Carbonyl Compounds in Air (Active Sampler
nents in air. Advantages and disadvantages of specific collec-
Methodology)
tion vehicles are presented.
D 5466 Test Method for Determination of Volatile Organic
1.3 This guide does not cover the use of cryogenically
Chemicals in Atmospheres (Canister Sampling Methodol-
cooled field sampling devices used in some automated analysis
ogy)
systems. Detailed instructions for cryogenic recovery of com-
D 5953M Test Method for Determination of Non-Methane
pounds captured as whole air samples or thermally desorbed
Organic Compounds (NMOC) in Ambient Air Using
from sorbents are typically covered in standard methods for
Cryogenic Preconcentration and Direct Flame Ionization
sample analysis and are beyond the scope of this guide.
Detection Method (Metric)
1.4 Both thermal and solvent desorption techniques for
D 6196 Practice for Selection of Sorbents and Pumped
sample recovery are discussed.
Sampling/Thermal Desorption Analysis Procedures for
1.5 Organic compounds are classified on the basis of vapor
Volatile Organic Compounds in Air
pressure as very volatile, volatile, semivolatile and nonvolatile.
Physical characteristics of many volatile organic compounds
3. Terminology
(VOCs) are provided to aid in selection of sampling techniques
3.1 Definitions—For definitions of terms used in this guide
for VOC measurement. Semivolatile and nonvolatile organic
refer to Terminology D 1356.
compounds are defined in the guide to help guide users avoid
3.2 Definitions of Terms Specific to This Standard:
misidentifying compounds that are not covered in this guide.
3.2.1 cryofocus—the process of concentrating compounds
1.6 This standard does not purport to address all of the
from an air sample for subsequent analysis by collection on a
safety concerns, if any, associated with its use. It is the
trap cooled with a cryogen to very low temperatures (for
responsibility of the user of this standard to establish appro-
example, -186°C).
priate safety and health practices and determine the applica-
3.2.1.1 Discussion—Cryogenic traps used for cryofocusing
bility of regulatory limitations prior to use.
are typically U-shaped stainless steel tubes filled with glass
2. Referenced Documents beads or other inert material. An example of such a cryofocus-
ing trap is given in Test Method D 5933M. Compounds are
2.1 ASTM Standards:
typically released from cryogenic traps into the analytical
This guide is under the jurisdiction of ASTM Committee D-22 on Sampling and
Analysis of Atmospheres and is the direct responsibility of Subcommittee D22.05
on Indoor Air.
Current edition approved Nov. 10, 1998. Published January 1999. Annual Book of ASTM Standards, Vol. 11.03.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D 6345
system by rapid heating to elevated temperatures. Sorbent- methods for VOC measurement as well a discussion of the
filled tubes cooled to sub-ambient temperatures (for example, limitations of typical methods.
-30°C) have also been used for this purpose. 4.2 This guide should be used during the planning stages of
an air monitoring program along with other applicable guides
3.2.2 very volatile organic compounds (VVOCs)—Low mo-
and practices (for example, D 1357) to select ASTM or other
lecular weight organic compounds that possess vapor pressures
appropriate methods.
greater than 15 kPa at 25°C and boiling points typically below
30°C.
5. Characteristics of Organic Compounds
5.1 Physical and chemical characteristics of VOCs are
4. Significance and Use
available from numerous references (1, 2, 3, 4). The properties
4.1 This guide provides a broad perspective on techniques of the VOCs listed under the Clean Air Act of 1990 (5) are
presented in Table 1 and Table 2.
that can be used by environmental managers for selecting VOC
air monitoring methods. It summarizes various methods for
measurement of VOC in air derived from a variety of sources
and experiences and incorporates them into condensed guide-
The boldface numbers in parentheses refer to the list of references at the end of
lines. This guide provides a common basis for selecting this standard.
A,B
TABLE 1 Properties of Clean Air Act Very Volatile Organic HAPs
Vapor Boiling Water
Pressure Point Solubility (g/L Customary Reactivity in
Compound CAS No. (kPa at 25°C) (°C) at °C) Classification Air
Acetaldehyde 75-07-0 127 21 33.0 / 25 Polar
Acrolein 107-02-8 29 53 >100 /21 Polar Reactive
Allyl chloride 107-05-1 45 45 19.5 / 20 Non-Polar
1.3-Butadiene 106-99-0 267 -5 Insoluble Non-Polar Reactive (?)
Carbon disulfide 75-15-0 35 47 <1 / 20 Non-polar
Carbonyl sulfide 463-58-1 493 -50 >100 / 20 Polar
Chloroform 67-66-3 21 61 0.85 / 20-24 Non-Polar
Chloromethly methyl 107-30-2 30 59 Reacts Polar Reactive
ether
Chloroprene 126-99-8 30 59 Slightly soluble Non-Polar
Diazomethane 334-88-3 373 -23 Reacts Polar Highly reactive
1,1-Dimethylhydrazine 57-14-7 21 63 Reacts Non-Polar Reactive (?)
1,2-Epoxybutane 106-88-7 22 63 >100 / 17 Polar Reactive
Ethyl chloride 75-00-3 133 13 >100 / 20 Non-Polar
Ethyleneimine 151-56-4 21 56 Miscible Polar Reactive (?)
Ethylene oxide 75-21-8 147 11 Miscible Polar Reactive
Ethylidene dichloride 75-34-3 31 57 <1 / 20 Non-Polar
Formaldehyde 50-00-0 360 -20 >100 / 20.5 Polar
Hexane 110-54-3 16 69 <1 / 16.5 Non-Polar
Methyl bromide 74-83-9 240 4 Slightly soluble Non-Polar Pesticide
Methyl chloride 74-87-3 507 -24 Slightly soluble Non-Polar
Methyl iodide 74-88-4 53 42 10-50 / 18 Non-Polar
Methyl isocyanate 624-83-9 46 60 Reacts Polar Highly reactive
tert-butyl ether 1634-04-4 33 55 Soluble Polar
Methyl
Methylene chloride 75-09-2 47 40 10-50 / 21 Non-Polar
Phosgene 75-44-5 160 8 Slightly soluble Polar Reactive (?)
Propionaldehyde 123-38-6 31 49 50-100 / 18 Polar Reactive
Propylene oxide 75-56-9 59 34 400 / 20 Polar Reactive
1,2-Propyleneimine 75-55-8 15 66 >100 / 19 Polar Highly reactive (?)
Vinyl bromide 593-60-2 147 16 Insoluble Non-Polar
Vinyl chloride 75-01-4 427 -14 Slightly soluble Non-Polar
Vinylidene chloride 75-35-4 67 32 5-10 / 21 Non-Polar
A
Compounds with vapor pressures > 15 kPa.
B
Data taken from Ref. (3).
A,B
TABLE 2 Properties of Clean Air Act Volatile Organic HAP
Vapor
Pressure Water
(kPa at Boiling Point Solubility Customary Reactivity
Compound CAS No. 25°C) (°C) (g/L at °C) Classification in Air
Acetonitrile 75-05-8 9.86 82 >100 / 22 Polar
Acetophenone 98-86-2 0.13 202 6.3 / 25 Polar
Acrylamide 79-06-1 0.07 125/25 mm >100 / 22 Polar Reactive
Acrylic acid 79-10-7 0.43 141 >100 / 17 Polar
D 6345
TABLE 2 Continued
Vapor
Pressure Water
(kPa at Boiling Point Solubility Customary Reactivity
Compound CAS No. 25°C) (°C) (g/L at °C) Classification in Air
Acrylonitrile 107-13-1 13.33 77 716.0 / 254 Polar
Aniline 62-53-3 0.09 184 1.0 / 254 Polar
o-Anisidine 90-04-0 0.01 224.0 <0.1 / 19 Polar Reactive
Benzene 71-43-2 10.13 80 1-5 / 18 Non-Polar
Benzyl chloride 100-44-7 0.13 179 Reacts Non-polar Reactive(?)
Bis (chloromethyl) 542-88-1 4.00 104 Reacts Polar Reactive
ether
Bromoform 75-25-2 0.75 149 <0.1 / 22.5 Non-Polar
Carbon tetrachloride 56-23-5 12.00 77 <1 / 21 Non-Polar
Catechol 120-80-9 0.03 240 >100 / 21.5 Polar
Chloroacetic acid 79-11-8 0.09 189 >100 / 20 Polar
Chlorobenzene 108-90-7 1.17 132 <1 / 20 Non-Polar
o-Cresol 95-48-7 0.03 191 25.9 / 25 Polar
Cumene 98-82-8 0.43 153 Insoluble Non-Polar
1,2-Dibromo-3- 96-12-8 0.11 196 <0.1 / 18 Non-Polar
chloropropane
1,4-Dichlorobenzene 106-46-7 0.08 173 <1 / 23 Non-Polar
Dichloroethyl ether 111-44-4 0.09 178 Reacts Polar Reactive(?)
1,3-Dichloropropene 542-75-6 3.71 112 <0.1 / 16.5 Non-Polar
Diethyl sulfate 64-67-5 0.04 208 Reacts Polar Reactive(?)
N,N-Dimethylaniline 121-69-7 0.07 192 <1 / 21 Polar
Dimethylcarbamyl 79-44-7 0.65 166 Reacts Polar Highly reactive
chloride
N,N- 68-12-2 0.36 153 >100 / 22 Polar
Dimethyformamide
Dimethyl sulfate 77-78-1 0.13 188 >100 / 20 Polar Reactive(?)
1,4-Dioxane 123-91-1 4.93 101 >100 / 20 Polar
Epichlorohydrin 106-89-8 1.60 117 50-100- / 22 Polar Highly reactive
Ethyl acrylate 140-88-5 3.91 100 4.2 / 204 Polar
Ethylbenzene 100-41-4 0.93 136 <1 / 23 Non-Polar
Ethyl carbamate 51-79-6 0.07 183 >100 / 22 Polar
Ethyl dibromide 106-93-4 1.47 132 <1 / 21 Non-Polar Pesticide
Ethylene dichloride 107-06-2 8.20 84 5-10 / 19 Non-Polar Pesticide
Hexachlorobutadiene 87-68-3 0.05 215 <0.1 / 22 Non-Polar
Hexachloroethane 67-72-1 0.05 Sublimes at 186 <1 / 21 Non-Polar
Hexamethylphosphoramide 680-31-9 0.01 233 >100 / 18 Polar
Isophorone 78-59-1 0.05 215 0.1-1 / 18 Polar
Methanol 67-56-1 12.26 65 >100 / 21 Polar
Methyl chloroform 71-55-6 13.33 74 <1 / 20 Non-Polar
Methyl ethyl ketone 78-93-3 10.33 80 >100 / 19 Polar
Methylhydrazine 60-34-3 6.61 88 <1 / 24 Non-Polar Highly reactive
Methyl isobutyl ketone 108-10-1 0.80 117 1-5 / 21 Polar
Methyl methacrylate 80-62-6 3.73 101 15.9 / 20 Polar
Nitrobenzene 98-95-3 0.02 211 1.9 / 25 Polar
2-Nitropropane 79-46-9 1.33 120 1.7 / 20 Polar
N-Nitroso-N- 684-93-5 1.33 124 <1 / 18 Polar Reactive
methylurea
N-Nitrosodimethylamine 62-75-9 0.49 152 >100 / 19 Polar Reactive
N-Nitrosomorpholine 59-89-2 0.04 225 >100 / 19 Polar
Phenol 108-95-2 0.03 182 50-100- / 19 Polar
1,3-Propane sultone 1120-71-4 0.27 180/30 mm 0.1 Polar Reactive(?)
Beta-Propiolactone 57-57-8 0.45 Decomposes at 162 37.0 / 20 Polar
Propylene dichloride 78-87-5 5.60 97 <0.1 / 21.5 Non-Polar Pesticide
Quinoline 91-25-5 0.01 238 <0.1 / 22.5 Polar
Styrene 100-42-5 0.88 145 <1 / 19 Non-Polar
Styrene oxide 96-09-3 0.04 194 <1 / 19.5 Polar Highly reactive
1,1,2,2- 79-34-5 0.67 146 <0.1 / 22 Non-Polar
Tetrachloroethane
Tetrachloroethylene 127-18-4 1.87 121 <0.1 / 17 Non-Polar
Toluene 108-88-3 2.93 111 <1 / 18 Non-Polar
o-Toluidine 95-53-4 0.01 200 5-10 / 15 Polar
1,2,4-Trichlorobenzene 120-82-1 0.02 213 <1 / 21 Non-Polar
1,1,2-Trichloroethane 79-00-5 2.53 114 1-5 / 20 Non-Polar
Trichloroethylene 79-01-6 2.67 87 <1 / 21 Non-Polar
Triethylamine 121-44-8 7.20 90 Soluble Polar Reactive (?); strong base
2,2,4-Trimethyl 540-84-1 5.41 99 Insoluble Non-polar
pentane
Vinyl acetate 108-05-4 11.06 72 Insoluble Polar
o-Xylene 95-47-6 0.67 144 Insoluble Non-Polar
m-Xylene 108-38-3 0.80 139 Insoluble Non-Polar
p-Xylene 106-42-3 0.87 138 Insoluble Non-Polar
D 6345
A 2
Compounds with vapor pressures between 10 and 15 kPa.
B
Data taken from Ref. (4).
K (20°C). The standard molar volume at this temperature is 24.1 L/mol.
5.2 Organic compounds can be divided into four groups
based on volatility (1).
6. Selection of Sampling Methods for VOCs
5.2.1 VOCs with vapor pressures above 15 kPa at 25°C
(boiling points typically below 30°C) are sometimes referred to 6.1 The first criteria for selection of an appropriate method
as very volatile organic compounds (VVOCs). At room tem- for sampling are the physical and chemical characteristics of
perature and atmospheric pressure, VVOCs are present in the
the compounds to be monitored. Once the analyte has been
gas phase in air. Due to their high vapor pressures, VVOCs are characterized as a volatile compound, the appropriate measure-
generally more difficult to collect and retain on sorbents than
ment method (sampling and analysis) is chosen. Sampling
other VOCs. methods can be active or passive.
5.2.2 Volatile organic compounds typically have vapor pres- 6.1.1 Active methods employ some means of setting and
-2
sures above 10 kPa at 25°C (typical boiling points from about controlling the air sampling rate (for example pump, syringe,
30 to 180°C). VOCs with boiling points at the upper end of the or other vacuum source with a flow-controller).
range still have a significant vapor pressure at room tempera- 6.1.2 Passive/diffusive sampling methods have sampling
ture and atmospheric pressure. At room temperature and rates that depend on the molecular diffusion rate, sampling
atmospheric pressure VOCs are present in the gas phase in air. temperature, length and area of the diffusive path, and other
conditions.
5.2.3 Semivolatile organic compounds (SVOCs) typically
-2 -8
6.1.3 Active sampling methods can be divided into three
have vapor pressures between 10 and 10 kPa at 25°C
(typical boiling points from 180 to 350°C). SVOCs may be broad types: whole air methods which use canisters, bags, or
syringes; sorbent collection methods; and specialized sampling
present in both the vapor and particulate phases (1).
methods for reactive compounds.
5.2.4 Nonvolatile organic compounds have vapor pressures
-8
6.1.4 Sampling can also be integrative (accumulative) or
below 10 kPa at 25°C (boiling points typically above 300°C).
continuous (real-time).
Nonvolatile organic compounds occur primarily in the particu-
6.2 Whole Air Sampling:
late phase.
6.2.1 If the VOC of interest is relatively stable, and volatile
NOTE 1—Boiling points are not reliable predictors of volatility. Some
enough to be recovered from an inert container, then whole air
compounds that boil above 300°C are volatile at room temperature.
sampling may be a valid choice. The major advantage of whole
5.3 The polarity, water solubility, and reactivity of a VOC air sampling is the ability to trap the most volatile compounds,
are
...