ASTM D6209-98(2004)
(Test Method)Standard Test Method for Determination of Gaseous and Particulate Polycyclic Aromatic Hydrocarbons in Ambient Air (Collection on Sorbent-Backed Filters with Gas Chromatographic/Mass Spectrometric Analysis)
Standard Test Method for Determination of Gaseous and Particulate Polycyclic Aromatic Hydrocarbons in Ambient Air (Collection on Sorbent-Backed Filters with Gas Chromatographic/Mass Spectrometric Analysis)
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1.1 This test method specifies sampling, cleanup, and analysis procedures for the determination of polycyclic aromatic hydrocarbons (PAH) in ambient air.
1.2 This test method is designed to collect both gas-phase and particulate-phase PAH and to determine them collectively.
1.3 This test method is a high-volume sampling (100 to 250 L/min) method capable of detecting PAH at sub-nanograms per cubic metre (ng/m3) concentrations with sampling volumes up to 350 m3 of air.
1.4 This test method has been validated for sampling periods up to 24 h.
1.5 Precision and bias under normal conditions can be expected to be 35 to 50 %.
1.6 This test method describes a sampling and analysis procedure for PAH that involves collection from air on a combination fine-particle filter and sorbent trap and subsequent analysis by gas chromatography/mass spectrometry (GC/MS).
1.7 The range of this test method is approximately 0.05 to 1000 ng/m3 of air sampled.
1.8 The values stated in SI units shall be regarded as standard.
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. See also Section for additional safety precautions.
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Designation: D6209 − 98(Reapproved 2004)
Standard Test Method for
Determination of Gaseous and Particulate Polycyclic
Aromatic Hydrocarbons in Ambient Air (Collection on
Sorbent-Backed Filters with Gas Chromatographic/Mass
Spectrometric Analysis)
This standard is issued under the fixed designation D6209; 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 bility of regulatory limitations prior to use. See also Section 8
2 for additional safety precautions.
1.1 This test method specifies sampling, cleanup, and
analysis procedures for the determination of polycyclic aro-
2. Referenced Documents
matic hydrocarbons (PAH) in ambient air.
2.1 ASTM Standards:
1.2 This test method is designed to collect both gas-phase
D1356Terminology Relating to Sampling and Analysis of
and particulate-phase PAH and to determine them collectively.
Atmospheres
1.3 Thistestmethodisahigh-volumesampling(100to250
D1357Practice for Planning the Sampling of the Ambient
L/min)methodcapableofdetectingPAHatsub-nanogramsper
Atmosphere
cubic metre (ng/m ) concentrations with sampling volumes up
D3631Test Methods for Measuring Surface Atmospheric
to 350 m of air.
Pressure
E1Specification for ASTM Liquid-in-Glass Thermometers
1.4 This test method has been validated for sampling
periods up to 24 h.
3. Terminology
1.5 Precision and bias under normal conditions can be
3.1 Definitions—For definitions of terms used in this test
expected to be 635 to 50%.
method, refer to Terminology D1356.
1.6 This test method describes a sampling and analysis
3.2 Definitions of Terms Specific to This Standard:
procedure for PAH that involves collection from air on a
3.2.1 sampling effıciency (SE), n—ability of the sampler to
combinationfine-particlefilterandsorbenttrapandsubsequent
trap and retain PAH. The percent SE is the percentage of the
analysis by gas chromatography/mass spectrometry (GC/MS).
analyte of interest collected and retained by the sampling
1.7 The range of this test method is approximately 0.05 to
medium when it is introduced into the air sampler and the
1000 ng/m of air sampled.
sampler is operated under normal conditions for a period of
time equal to or greater than that required for the intended use.
1.8 The values stated in SI units shall be regarded as
standard.
3.2.2 dynamic retention effıciency, n—ability of the sam-
pling medium to retain a given PAH that has been added to the
1.9 This standard does not purport to address all of the
sorbenttrapinaspikingsolutionwhenairisdrawnthroughthe
safety concerns, if any, associated with its use. It is the
sampler under normal conditions for a period of time equal to
responsibility of the user of this standard to establish appro-
or greater than that required for the intended use.
priate safety and health practices and determine the applica-
4. Summary of Test Method
1 4.1 Sampling:
This test method is under the jurisdiction of ASTM Committee D22 on Air
Qualityand is the direct responsibility of Subcommittee D22.03 on Ambient 4.1.1 An air sample is collected directly from the ambient
Atmospheres and Source Emissions.
atmosphere by pulling air at approximately 225 L/min through
Current edition approved Oct. 1, 2004. Published December 2004. Originally
a fine particulate filter followed by a vapor trap containing
ε1
approved in 1997. Last previous edition approved in 1998 as D6209-98 . DOI:
10.1520/D6209-98R04.
This test method is based on U. S. Environmental ProtectionAgency Compen-
dum Method TO-13, Compendium of Methods for the Determination of Toxic For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Organic Compounds in Ambient Air, Report No. EPA/600-4-89/018, June 1988, contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
available from the National Technical Information Service, 5285 Port Royal Rd., Standards volume information, refer to the standard’s Document Summary page on
Springfield, VA 22161, Order No. PB90-11989/AS. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D6209 − 98 (2004)
TABLE 1 Formulae and Physical Properties of Selective PAH
Vapor
Melting
Boiling
Compound Molecular Pressure,
A
Formula Point, Point,
(Common Name) Weight kPa at
°C
°C
25°C
–2
Naphthalene C H 128.18 80.2 218 1.1 × 10
10 8
–3
Acenaphthylene C H 152.20 92-93 265-280 3.9 × 10
12 8
–2
Acenaphthene C H 154.20 90-96 278-279 2.1 × 10
12 10
–5
Fluorene C H 166.23 116-118 293-295 8.7 × 10
13 10
–5
9-Fluorenone C H O 180.21 84 341.5 ca.10
13 8
–6
Anthracene C H 178.24 216-219 340 3.6 × 10
14 10
–5
Phenanthrene C H 178.24 96-101 339-340 2.3 × 10
14 10
–7
Fluoranthene C H 202.26 107-111 375-393 6.5 × 10
16 10
–6
Pyrene C H 202.26 150-156 360-404 3.1 × 10
16 10
–7
Cyclopental[cd]pyrene C H 226.28 ca. 275? — ca. 10
18 10
–8
Benz[a]anthracene C H 228.30 157-167 435 1.5 × 10
18 12
–10
Chrysene C H 228.30 252-256 441-448 5.7 × 10
18 12
–6
Retene C H 234.34 101 390 ca. 10
18 18
–8
Benzo[b]fluoranthene C H 252.32 167-168 481 6.7 × 10
20 12
–8
Benzo[k]fluoranthene C H 252.32 198-217 480-481 2.1 × 10
20 12
–10
Perylene C H 252.32 273-278 500-503 7.0 × 10
20 12
–10
Benzo[a]pyrene C H 252.32 177-179 493-496 7.3 × 10
20 12
–10
Benzo[e]pyrene C H 252.32 178-179 493 7.4 × 10
20 12
–11
Benzo[ghi]perylene C H 276.34 275.278 525 1.3 × 10
22 12
–11
Indeno[1,2,3-cd]pyrene C H 276.34 162-163 — ca. 10
22 12
–11
Dibenz[ah]anthracene C H 278.35 266-270 524 1.3 × 10
22 14
–13
Coronene C H 300.36 438-440 525 2.0 × 10
24 12
A
Many of these compounds sublime.
polyurethane foam (PUF) or styrene/divinylbenzene polymer 5.5 PAH span a broad spectrum of vapor pressures (for
4 –2 –13
resin(XAD-2). Samplingtimesmaybevariedfrom1to24h, example,from1.1×10 kPafornaphthaleneto2×10 kPa
depending on monitoring needs and the detection limits for coronene at 25°C). Table 1 lists some PAH that are
required, so as not to exceed a total sample volume of 350 m . frequently found in ambient air. Those with vapor pressures
–8
above about 10 kPa will be present in the ambient air
4.2 Analysis:
substantially distributed between the gas and particulate
4.2.1 Aftersamplingafixedvolumeofair,theparticlefilter
phases. This test method will permit the collection of both
and sorbent cartridge are extracted together in a Soxhlet
phases. However, particulate-phase PAH will tend to be lost
extractor. The sample extract is concentrated by means of a
from the particulate filter during sampling due to desorption
Kuderna-Danish concentrator (or other validated method),
and volatilization.
followed by a further concentration under a nitrogen stream, if
5.5.1 The distribution between phases depends on ambient
necessary, and an aliquot is analyzed by gas chromatography/
temperature, humidity, types and concentrations of PAH and
massspectrometry.Theresultsderivedrepresentthecombined
particulate matter, and residence time in the air. PAH, espe-
gas-phase and particulate-phase air concentrations of each
–8
cially those having vapor pressures above 10 kPa, may
PAH analyzed.
vaporize from particulate filters during sampling.
5. Significance and Use Consequently, a back-up vapor trap must be used for efficient
sampling.
5.1 Polycyclic aromatic hydrocarbons (PAH) as defined by
this test method are compounds made up of two or more fused 5.6 Separate analyses of the filter and vapor trap will not
reflect the original atmospheric phase distributions and should
aromatic rings.
be discouraged.
5.2 Several PAH are considered to be probable human
carcinogens.
6. Limitations
5.3 PAH are emitted in the atmosphere primarily through
6.1 Particulate-phase PAH may be lost from the particle
wood or fossil fuel combustion.
filter during sampling due to desorption and volatilization
5.4 Two- and three-ring PAH are typically present in urban
(1-6).
air at concentrations ranging from 10 to several hundred 6.1.1 Loss of particulate-associated PAH from the filter
nanograms per cubic metre (ng/m ); those with four or more
depends on the ambient temperature during sampling,
rings are usually found at concentrations of a few ng/m or humidity, types and concentrations of PAH and particulate
lower.
matter, and residence time of the PAH on the filter.
6.1.2 During summer months, especially in warmer
4 climates, volatilization from the filter may be as great as 90%
XAD is a trademark of Rohm and Haas Co., Philadelphia, PA; it is available in
the United States solely from Supelco, Inc., Bellefonte, PA. If you are aware of
equivalent styrene/divinylbenzene polymer resins, please provide this information
to ASTM Headquarters. Your comments will receive careful consideration at a Theboldfacenumbersinparenthesesrefertothelistofreferencesattheendof
meeting of the responsible technical committee , which you may attend. this standard.
D6209 − 98 (2004)
–6
for PAH with vapor pressures above 10 kPa (3 and 6).At 7.4 Exposure to heat, ozone, nitrogen dioxide (NO ), and
ambient temperatures of 30°C and above, as much as 20% of ultraviolet (UV) light may cause PAH degradation during
–10
benzo[a]pyrene and perylene (v.p.=7×10 kPa) have been sampling, sample storage, and processing.
found in the vapor trap (7). 7.4.1 These problems should be addressed as part of a
standard operating procedure prepared by the user.
6.1.3 Separate analysis of the filter will not reflect the
concentrations of the PAH originally associated with particles, 7.4.2 Use incandescent or UV-filtered fluorescent lighting
norwillanalysisofthesorbentprovideanaccuratemeasureof where possible in the laboratory to avoid photodegradation
thegasphase.Consequently,thismethodcallsforcoextraction during analysis.
of the filter and sorbent to permit accurate measure of total
8. Safety Precautions
PAH air concentrations.
8.1 Benzo[a]pyrene and several other PAH have been clas-
6.2 This test method has been evaluated for the PAH shown
sified as probable human carcinogens. Exercise care when
in Table 1. Other PAH may be determined by this test method,
working with these substances.
but the user must demonstrate acceptable sampling and analy-
sis efficiencies.
8.2 Treat all PAH as potential carcinogens.
6.2.1 Naphthaleneandacenaphthenepossessrelativelyhigh
8.2.1 Weigh pure compounds in a glove box.
vapor pressures and may not be efficiently trapped by this test
8.2.2 Consider unused samples and standards to be toxic
method, especially when PUF is used.
waste and properly dispose of them in accordance with
6.2.2 The sampling efficiency for naphthalene has been
regulations.
determined to be about 35% for PUF and about 60% for
8.2.3 Regularly check laboratory bench tops and equipment
XAD-2.
withaUV“blacklight”forfluorescenceindicativeofcontami-
6.2.3 The user may estimate the sampling efficiencies for
nation.
PAHofinterestbydeterminingdynamicretentionefficiencyof
the sorbent. The percent RE generally approximates the per-
9. Apparatus
cent SE.
9.1 Sampling:
9.1.1 Sampling Module— A typical collection system con-
7. Interferences
sisting of a particle filter backed up by a sorbent trap is shown
7.1 Methodinterferencesmaybecausedbycontaminantsin in Fig. 1. It consists of the following:
solvents, reagents, on glassware, and other sample processing 9.1.1.1 Metal Filter Holder (Part 2), capable of holding a
hardwarethatresultindiscreteartifactsandelevatedbaselines, 104-mm circular particulate filter supported by a 1.2-mm
or both, in the detector profiles.Thoroughly clean glass before (16-mesh)stainless-steelscreenwith50%openarea.Thefilter
use (for example, by acid washing, followed by heating to holder is equipped with inert sealing gaskets (for example,
450°Cinamufflefurnace).Checksolventsandothermaterials
polytetrafluoroethylene) placed on either side of the filter.
routinely by running laboratory reagent blanks under the 9.1.1.2 Metal Cylinder(Part1),capableofholdinga65-mm
conditions of the analysis to establish that they are free of
o.d. (60-mm i.d.) by 125-mm borosilicate glass sorbent car-
interfering materials. tridge. Inert, pliable gaskets (for example, silicone rubber) are
used to provide an air-tight seal at each end of the sorbent
7.2 Matrix interferences may be caused by contaminants
cartridge. The glass sorbent cartridge is indented 20 mm from
that are coextracted from the sample. Additional clean-up by
the lower end to provide a support for a 1.2-mm (16-mesh)
column chromatography may be required.
stainless-steel screen that holds the sorbent.
7.3 The extent of interferences that may be encountered
9.1.1.3 The glass sorbent cartridge fits into Part 1, which is
using gas chromatographic techniques has not been fully
screwed onto Part 2 until the sorbent cartridge is sealed
assessed.
between the gaskets. The sampling module is described by
7.3.1 Although the GC/MS conditions described allow for
Lewis and Jackson (8) . Similar sampling modules are com-
resolution of most of the specific PAH compounds covered by
mercially available.
this test method, other PAH compounds may interfere.
9.1.2 High-volume Pumping System, capable of providing a
7.3.2 Some PAH isomers may not be chromatographically
constant air flow of up to 250 L/min (15 m /h) through the
resolvable and, therefore, can not be distinguished from each
sampling module (9.1.1). A typical air pumping system is
other by MS.
showninFig.2.Itisequippedwiththefollowingcomponents:
7.3.3 Interferences from some non-PAH compounds, espe-
9.1.2.1 Appropriate Flow-control Device:
cially oils and polar organic species, may be reduced or
9.1.2.2 Manometer, to measure pressure drop across the
eliminated by the use of column chromatography for sample
sampling module or other suitable flow measuring device.
clean-up prior to GC/MS analysis.
9.1.2.3 Interval Timer.
7.3.4 The analytical system must be routinely demonstrated
9.1.2.4 Exhaust hose, to carry exhausted air at least 3 m
to be free of internal contaminants such as contaminated
away from the sampler.
solvents, glassware, or other reagents that may lead to method
NOTE 1—The sampling system described in 9.1.1 to 9.1.2.4 has been
interferences.
showntoefficientlytrapPAHwiththreeormoreringsatsamplesvolumes
7.3.5 Analyze a laboratory reagent blank for each batch of
350 m and lower (8-16). Other samplers utilizing larger filters (for
reagents used to determine if reagents are contaminant-free. example, 200-mm by 250-mm) and higher capacity sorbent traps (for
D6209 − 98 (2004)
FIG. 1 Typi
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