ASTM D5466-01(2007)
(Test Method)Standard Test Method for Determination of Volatile Organic Chemicals in Atmospheres (Canister Sampling Methodology)
Standard Test Method for Determination of Volatile Organic Chemicals in Atmospheres (Canister Sampling Methodology)
SCOPE
1.1 This test method describes a procedure for sampling and analysis of volatile organic compounds (VOCs) in ambient, indoor, or workplace atmospheres. The test method is based on the collection of air samples in stainless steel canisters with specially treated (passivated) interior surfaces. For sample analysis, a portion of the sample is subsequently removed from the canister and the collected VOCs are selectively concentrated by adsorption or condensation onto a trap, subsequently released by thermal desorption, separated by gas chromatography, and measured by a mass spectrometric detector or other detector(s). This test method describes procedures for sampling into canisters to final pressures both above and below atmospheric pressure (respectively referred to as pressurized and subatmospheric pressure sampling).
1.2 This test method is applicable to specific VOCs that have been tested and determined to be stable when stored in canisters. Numerous compounds, many of which are chlorinated VOCs, have been successfully tested for storage stability in pressurized canisters (1-4). Although not as extensive, documentation is also available demonstrating stability of VOCs in subatmospheric pressure canisters. While initial studies were concentrated on non-polar VOCs, information on storage stability has been extended to many polar compounds as well (5-7).
1.3 The procedure for collecting the sample involves the use of inlet lines and air filters, flow rate regulators for obtaining time-integrated samples, and in the case of pressurized samples, an air pump. Canister samplers have been designed to automatically start and stop the sample collection process using electronically actuated valves and timers (8-10). A weatherproof shelter is required if the sampler is to be used outside.
1.4 The organic compounds that have been successfully measured at single-digit parts-per-billion by volume (ppbv) levels with this test method are listed in Table 1. This test method is applicable to VOC concentrations ranging from the detection limit to 300 ppbv. Above this concentration, samples require dilution with dry ultra-high-purity nitrogen or air.
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. Safety practices should be part of the user's SOP manual.
General Information
Relations
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: D5466 − 01(Reapproved 2007)
Standard Test Method for
Determination of Volatile Organic Chemicals in
Atmospheres (Canister Sampling Methodology)
This standard is issued under the fixed designation D5466; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope 1.4 The organic compounds that have been successfully
measured at single-digit parts-per-billion by volume (ppbv)
1.1 Thistestmethoddescribesaprocedureforsamplingand
levels with this test method are listed in Table 1. This test
analysis of volatile organic compounds (VOCs) in ambient,
method is applicable to VOC concentrations ranging from the
indoor,orworkplaceatmospheres.Thetestmethodisbasedon
detection limit to 300 ppbv.Above this concentration, samples
the collection of air samples in stainless steel canisters with
require dilution with dry ultra-high-purity nitrogen or air.
specially treated (passivated) interior surfaces. For sample
1.5 This standard does not purport to address all of the
analysis,aportionofthesampleissubsequentlyremovedfrom
safety concerns, if any, associated with its use. It is the
the canister and the collected VOCs are selectively concen-
responsibility of the user of this standard to establish appro-
trated by adsorption or condensation onto a trap, subsequently
priate safety and health practices and determine the applica-
released by thermal desorption, separated by gas
bility of regulatory limitations prior to use. Safety practices
chromatography, and measured by a mass spectrometric detec-
should be part of the user’s SOP manual.
tor or other detector(s). This test method describes procedures
for sampling into canisters to final pressures both above and
2. Referenced Documents
below atmospheric pressure (respectively referred to as pres-
surized and subatmospheric pressure sampling).
2.1 ASTM Standards:
D1356Terminology Relating to Sampling and Analysis of
1.2 This test method is applicable to specific VOCs that
Atmospheres
have been tested and determined to be stable when stored in
D1357Practice for Planning the Sampling of the Ambient
canisters. Numerous compounds, many of which are chlori-
Atmosphere
natedVOCs,havebeensuccessfullytestedforstoragestability
E260Practice for Packed Column Gas Chromatography
in pressurized canisters (1-4). Although not as extensive,
E355PracticeforGasChromatographyTermsandRelation-
documentation is also available demonstrating stability of
ships
VOCs in subatmospheric pressure canisters. While initial
studies were concentrated on non-polar VOCs, information on
2.2 Other Documents:
storage stability has been extended to many polar compounds
U.S. Environmental Protection Agency, Compendium of
as well (5-7).
Methods for the Determination to Toxic Organic Com-
pounds inAmbientAir, Method TO-14A, EPA600/R-96/
1.3 Theprocedureforcollectingthesampleinvolvestheuse
010b
of inlet lines and air filters, flow rate regulators for obtaining
time-integrated samples, and in the case of pressurized
3. Terminology
samples,anairpump.Canistersamplershavebeendesignedto
automaticallystartandstopthesamplecollectionprocessusing
3.1 Definitions—For definitions of terms used in this test
electronically actuated valves and timers (8-10). A weather-
method, refer to Terminology D1356. Other pertinent abbre-
proof shelter is required if the sampler is to be used outside. viationsandsymbolsaredefinedwithinthispracticeatpointof
use.
This test method is under the jurisdiction of ASTM Committee D22 on Air 3.2 Definitions of Terms Specific to This Standard:
Quality and is the direct responsibility of Subcommittee D22.05 on Indoor Air.
Current edition approved April 1, 2007. Published June 2007. Originally
approved in 1993. Last previous edition approved in 2001 as D5466–01. DOI:
10.1520/D5466-01R07. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
This test method is based on EPA Compendium Method TO-14, “The contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Determination of Volatile Organic Compounds (VOCs) in Ambient Air Using Standards volume information, refer to the standard’s Document Summary page on
SUMMAPassivated Canister Sampling and Gas ChromatographicAnalysis,” May the ASTM website.
1988. Available from the U.S. Dept. of Commerce, National Technical Information
Theboldfacenumbersinparenthesesrefertothelistofreferencesattheendof Service, Port Royal Road, Springfield, VA 22161 or http://www.cpa.gov/ttn/amtic/
the standard. airtox.html.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5466 − 01 (2007)
TABLE 1 Typical Volatile Organic Compounds Determined by the Canister Method
Molecular
Compound (Synonym) Formula Boiling Point (°C) Melting Point (°C) CAS Number
Weight
Freon 12 (Dichlorodifluoromethane) Cl CF 120.91 −29.8 −158.0
2 2
Methyl chloride (Chloromethane) CH Cl 50.49 −24.2 −97.1 74-87-3
Freon 114 (1,2-Dichloro-1,1,2,2-tetrafluoroethane) ClCF CClF 170.93 4.1 −94.0
2 2
Vinyl chloride (Chloroethylene) CH =CHCl 62.50 −13.4 −1538.0 75-01-4
Methyl bromide (Bromomethane) CH Br 94.94 3.6 −93.6 74-83-9
Ethyl chloride (Chloroethane) CH CH Cl 64.52 12.3 −136.4 75-00-3
3 2
Freon 11 (Trichlorofluoromethane) CCl F 137.38 23.7 −111.0
Vinylidene chloride (1,1-Dichloroethene) C H Cl 96.95 31.7 −122.5 75-35-4
2 2 2
Dichloromethane (Methylene chloride) CH Cl 84.94 39.8 −95.1 75-09-2
2 2
Freon 113 (1,1,2-Trichloro-1,2,2-trifluoroethane) CF ClCCl F 187.38 47.7 −36.4
2 2
1,1-Dichloroethane CH CHCl 98.96 57.3 −97.0 74-34-3
3 2
cis-1,2-Dichloroethylene CHCl=CHCl 96.94 60.3 −80.5
Chloroform (Trichloromethane) CHCl 119.38 61.7 −63.5 67-66-3
1,2-Dichloroethane (Ethylene dichloride) ClCH CH Cl 98.96 83.5 −35.3 107-06-2
2 2
Methyl chloroform (1,1,1,-Trichloroethane) CH CCl 133.41 74.1 −30.4 71-55-6
3 3
Benzene C H 78.12 80.1 5.5 71-43-2
6 6
Carbon tetrachloride (Tetrachloromethane) CCl 153.82 76.5 −23.0 56-23-5
1,2-Dichloropropane (Propylene dichloride) CH CHClCH Cl 112.99 96.4 −100.4 78-87-5
3 2
Trichloroethylene (Trichloroethene) ClCH=CCl 131.29 87 −73.0 79-01-6
cis-1,3-Dichloropropene (cis-1,3-dichloropropylene) CH CC=CHCl 110.97 76
trans-1,3-Dichloropropene (trans-1,3-Dichloropropylene) ClCH CH=CHCl 110.97 112.0
1,1,2-Trichloroethane (Vinyl trichloride) CH ClCHCl 133.41 113.8 −36.5 79-00-5
2 2
Toluene (Methyl benzene) C H CH 92.15 110.6 −95.0 108-88-3
6 5 3
1,2-Dibromoethane (Ethylene dibromide) BrCH CH Br 187.88 131.3 9.8 106-93-4
2 2
Tetrachloroethylene (Perchloroethylene) Cl C=CCl 165.83 121.1 −19.0 127-18-4
2 2
Chlorobenzene C H Cl 112.56 132.0 −45.6 108-90-7
6 5
Ethylbenzene C H C H 106.17 136.2 −95.0 100-41-4
6 5 2 5
m-Xylene (1,3-Dimethylbenzene) 1,3-(CH ) C H 106.17 139.1 −47.9
3 2 6 4
p-Xylene (1,4-Dimethylxylene) 1,4-(CH ) C H 106.17 138.3 13.3
3 2 6 4
Styrene (Vinyl benzene) C H CH=CH 104.16 145.2 −30.6 100-42-5
6 5 2
1,1,2,2-Tetrachloroethane CHCl CHCl 167.85 146.2 −36.0 79-34-5
2 2
o-Xylene (1,2-Dimethylbenzene) 1,2-(CH ) C H 106.17 144.4 −25.2
3 2 6 4
1,3,5-Trimethylbenzene (Mesitylene) 1,3,5-(CH ) C H 120.20 164.7 −44.7 108-67-8
3 3 6 6
1,2,4-Trimethylbenzene 1,2,4-(CH ) C H 120.20 169.3 −43.8 95-63-6
3 3 6 6
m-Dichlorobenzene (1,3-Dichlorobenzene) 1,3-Cl C H 147.01 173.0 −24.7 541-73-1
2 6 4
Benzyl chloride (α-Chlorotoluene) C H CH Cl 126.59 179.3 −39.0 100-44-7
6 5 2
o-Dichlorobenzene (1,2-Dichlorobenzene) 1,2-Cl C H 147.01 180.5 −17.0 95-50-1
2 6 4
p-Dichlorobenzene (1,4-Dichlorobenzene) 1,4-Cl C H 147.01 174.0 53.1 106-46-7
2 6 4
1,1,2,3,4,4–Hexachloro–1,3-butadiene Cl C 260.76 215 -21.0 7-68-3
6 4
3.2.1 absolute canister pressure— Pg + Pa, where Pg 3.2.6 gage pressure—pressure measured above ambient at-
=gagepressureinthecanister.(kPa,psi)and Pa=barometric mospheric pressure (as opposed to absolute pressure). Zero
pressure. gage pressure is equal to ambient atmospheric (barometric)
pressure.
3.2.2 absolute pressure—pressure measured with reference
toabsolutezeropressure(asopposedtoatmosphericpressure),
3.2.7 megabore column—chromatographic column having
usually expressed as kPa, mm Hg, or psia.
an internal diameter (I.D.) greater than 0.50 mm.
3.2.3 certification—the process of demonstrating with hu-
3.2.7.1 Discussion—The Megabore column is a trademark
mid zero air and humid calibration gases that the sampling
of the J&W Scientific Co. For purposes of this test method,
systems components and the canister will not change the
Megabore refers to chromatographic columns with 0.53 mm
concentrations of sampled and stored atmospheres.
I.D.
3.2.4 cryogen—a refrigerant used to obtain very low tem-
3.2.8 MS-SCAN—theGCiscoupledtoaMassSpectrometer
peratures in the cryogenic trap of the analytical system. A
(MS) programmed to scan all ions over a preset range
typical cryogen is liquid argon (bp−185.7°C) or liquid nitro-
repeatedly during the GC run.
gen (bp−195°C).
3.2.8.1 Discussion—As used in the current context, this
3.2.5 dynamic calibration—calibration of an analytical sys-
procedure serves as a qualitative identification and character-
temusingcalibrationgasstandardconcentrationsgeneratedby
ization of the sample.
diluting known concentration compressed gas standards with
3.2.9 MS-SIM—the GC is coupled to a MS programmed to
purified, humidified inert gas.
acquire data for only specified ions and to disregard all others.
3.2.5.1 Discussion—Such standards are in a form identical
Thisisperformedusingselectedionmonitoring(SIM)coupled
or very similar to the samples to be analyzed. Calibration
standards are introduced into the inlet of the sampling or to retention time discriminators. The GC-SIM analysis pro-
vides quantitative results for selected constituents of the
analytical system in the same manner as authentic field
samples. sample gas as programmed by the user.
D5466 − 01 (2007)
TABLE 2 Ion/Abundance and Expected Retention Time for
3.2.10 pressurized sampling—collection of an air sample in
Selected VOCs Analyzed by GC-MS-SIM
a canister with a (final) canister pressure above atmospheric
Ion/
pressure, using a sample pump.
Expected
Abundance
Compound Retention
(amu/%
3.2.11 qualitative accuracy—the ability of an analytical
Time (min)
base peak)
system to correctly identify compounds.
Freon 12 (Dichlorodifluoromethane) 85/100 5.01
3.2.12 quantitative accuracy—the ability of an analytical
87/31
Methyl chloride (Chloromethane) 50/100 5.69
system to correctly measure the concentration of an identified
52/34
compound.
Freon 114 (1,2-Dichloro-1,1,2,2-tetrafluoroethane) 85/100 6.55
135/56
3.2.13 static calibration—calibration of an analytical sys-
87/33
tem using standards in a form different than the samples to be
Vinyl chloride (Chloroethene) 62/100 6.71
analyzed.
27/125
64/32
3.2.13.1 Discussion—An example of a static calibration
Methyl bromide (Bromomethane) 94/100 7.83
would be injecting a small volume of a high concentration
96/85
standard directly onto a GC column, bypassing the sample Ethyl chloride (Chloroethane) 64/100 8.43
29/140
extraction and preconcentration portion of the analytical sys-
27/140
tem.
Freon 11 (Trichlorofluoromethane) 101/100 9.97
103/67
3.2.14 subatmospheric sampling—collection of an air
Vinylidene chloride (1,1-Dichloroethylene) 61/100 10.93
sample in an evacuated canister to a (final) canister pressure
96/55
63/31
below atmospheric pressure, with or without the assistance of
Dichloromethane (Methylene chloride) 49/100 11.21
a sampling pump.
84/65
3.2.14.1 Discussion—The canister is filled as the internal
86/45
Freon 113 (1,1,2-Trichloro-1,2,2-trifluoroethane) 151/100 11.60
canister pressure increases to ambient or near ambient pres-
101/140
sure. An auxiliary vacuum pump may be used as part of the
103/90
sampling system to flush the inlet tubing prior to or during
1,1-Dichloroethane 63/100 12.50
27/64
sample collection.
65/33
cis-1,2-Dichloroethylene 61/100 13.40
4. Summary of Test Method 96/60
98/44
4.1 The method described is taken from published work
Chloroform (Trichloromethane) 83/100 13.75
85/65
(1-22) and is the basis of EPACompendium Method TO-14A.
47/35
It has been used since the early 1980s in studies to establish
1,2-Dichloroethane (Ethylene dichloride) 62/100 14.39
long term trends in certain atmospheric gases (11), to deter-
27/70
64/31
mine the prevalence and extent ofVOC contributions to ozone
Methyl chloroform (1,1,1-Trichloroethane) 97/100 14.62
production (12), and to assess the toxicity of VOCs in the
99/64
ambient air (13, 14).
61/61
Benzene 78/100 15.04
4.2 Bothsubatmosphericpressureandpressurizedsampling
77/25
50/35
modesuseanevacuatedcanister.Asamplinglinelessthan2%
Carbon tetrachloride (Tetrachloromethane) 117/100 15.18
of the volume of the canister or a pump-ventilated sample line
119/97
are used during sample collection. Pressurized sampling re-
1,2-Dichloropropane (Propylene dichloride) 63/100 15.83
41/90
quires an additional pump to provide positive pressure to the
62/70
sample canister. A sample of air is drawn through a sampling
Trichloroethylene (Trichloroethene) 130/100 16.10
traincomprisingcomponentsthatregulatetherateandduration
132/92
of sampling into a precleaned and pre-evacuated passivated 95/87
cis-1,3-Dichloropropene 75/100 16.96
canister.
39/70
77/30
4.3 After the air sample is collected, the canister isolation
trans-1,3-Dichloropropene 75/100 17.49
valve is closed, the canister is removed from the sampler, an
39/70
identification tag is attached to the canister, and the canister is 77/30
1,1,2-Trichloroethane (Vinyl trichloride) 97/100 17.61
transported to a laboratory for analysis.
83/90
61/82
4.4 Upon receipt at the laboratory, the data on the canister
Toluene (Methyl benzene) 91/100 17.86
tag are recorded and the canister is attached to a pressure gage
92/57
which will allow accurate measurement of the final canister
1,2-Dibromoethane (Ethylene dibromide) 107/100 18.48
109/96
pressure. During analysis, water vapor may be reduced in the
27/115
gasstreambyapermeablemembranedryer(ifapplicable),and
Tetrachloroethylene (Perchloroethylene) 166/100 19.01
theVOCsarethenconcentratedbycollectiononasorbenttrap
164/74
131/60
or in a cryogenically-cooled trap. The temperature of the trap
Chlorobenzene 112/100 19.73
is raised and the VOCs originally collected in the trap are
77/62
revolatilized, separated on a GC column, and then detected by
D5466 − 01 (2007)
TABLE 2 Continued
(6)Quantitative determination of compounds on calibra-
Ion/
tion list, and
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.