ASTM D6209-98e1

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)

SCOPE
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 particular-phase PAH and to determine them collectively.
1.3 This test method is a high-volume sampling (100 to 250L/min) method capable of detecting PAH at sub-nanograms per cubic meter (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 S1 units shall be regarded as standard.
1.9 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 application.

General Information

• Status: Historical
• Publication Date: 02-Dec-1998
• ICS: 13.040.20 - Ambient atmospheres
• Technical Committee: D22 - Air Quality
• Drafting Committee: D22.03 - Ambient Atmospheres and Source Emissions

Relations

• Replaced By: ASTM D6209-98(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)
• Effective Date: 01-Oct-2004

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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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
e1
Designation:D6209–98
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 D 6209; 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.
e NOTE—Paragraph 11.2.2 was corrected editorially in December 1998.
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
D 1356 Terminology Relating to Sampling and Analysis of
and particulate-phase PAH and to determine them collectively.
Atmospheres
1.3 This test method is a high-volume sampling (100 to 250
D 1357 Practice for Planning the Sampling of the Ambient
L/min)methodcapableofdetectingPAHatsub-nanogramsper
Atmosphere
cubic meter (ng/m ) concentrations with sampling volumes up
D 3631 Test Methods for Measuring Surface Atmospheric
to 350 m of air.
Pressure
1.4 This test method has been validated for sampling
E 1 Specification for ASTM Thermometers
periods up to 24 h.
1.5 Precision and bias under normal conditions can be
3. Terminology
expected to be 635 to 50 %.
3.1 Definitions— For definitions of terms used in this test
1.6 This test method describes a sampling and analysis
method, refer to Terminology D 1356.
procedure for PAH that involves collection from air on a
3.2 Definitions of Terms Specific to This Standard:
combinationfine-particlefilterandsorbenttrapandsubsequent
3.2.1 sampling effıciency (SE), n—ability of the sampler to
analysis by gas chromatography/mass spectrometry (GC/MS).
trap and retain PAH. The percent SE is the percentage of the
1.7 The range of this test method is approximately 0.05 to
3 analyte of interest collected and retained by the sampling
1000 ng/m of air sampled.
medium when it is introduced into the air sampler and the
1.8 The values stated in SI units shall be regarded as
sampler is operated under normal conditions for a period of
standard.
time equal to or greater than that required for the intended use.
1.9 This standard does not purport to address all of the
3.2.2 dynamic retention effıciency, n—ability of the sam-
safety concerns, if any, associated with its use. It is the
pling medium to retain a given PAH that has been added to the
responsibility of the user of this standard to establish appro-
sorbenttrapinaspikingsolutionwhenairisdrawnthroughthe
priate safety and health practices and determine the applica-
sampler under normal conditions for a period of time equal to
or greater than that required for the intended use.
This test method is under the jurisdiction of ASTM Committee D–22 on
4. Summary of Test Method
Sampling and Analysis of Atmospheres and is the direct responsibility of Subcom-
mittee D22.03 on Ambient Atmospheres and Source Emissions.
4.1 Sampling:
Current edition approved May 10, 1998. Published July 1998. Originally
4.1.1 An air sample is collected directly from the ambient
published as D 6209-97. Last previous edition D 6209-97.
This test method is based on U. S. Environmental ProtectionAgency Compen- atmosphere by pulling air at approximately 225 L/min through
dum Method TO-13, Compendium of Methods for the Determination of Toxic
Organic Compounds in Ambient Air, Report No. EPA/600-4-89/018, June 1988,
available from the National Technical Information Service, 5285 Port Royal Rd., Annual Book of ASTM Standards, Vol 11.03.
Springfield, VA 22161, Order No. PB90-11989/AS. Annual Book of ASTM Standards, Vol 14.03.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D6209
a fine particulate filter followed by a vapor trap containing 5.5 PAH span a broad spectrum of vapor pressures (for
–2 –13
polyurethane foam (PUF) or styrene/divinylbenzene polymer example,from1.1 310 kPafornaphthaleneto2310 kPa
resin (XAD-2). Sampling times may be varied from 1 to 24 h, for coronene at 25°C). Table 1 lists some PAH that are
depending on monitoring needs and the detection limits re- frequently found in ambient air. Those with vapor pressures
3 –8
quired, so as not to exceed a total sample volume of 350 m . above about 10 kPa will be present in the ambient air
4.2 Analysis: substantially distributed between the gas and particulate
4.2.1 After sampling a fixed volume of air, the particle filter 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
mass spectrometry. The results derived represent the combined particulate matter, and residence time in the air. PAH, espe-
–8
gas-phase and particulate-phase air concentrations of each cially those having vapor pressures above 10 kPa, may
PAH analyzed. vaporize from particulate filters during sampling. Conse-
quently, a back-up vapor trap must be used for efficient
5. Significance and Use
sampling.
5.6 Separate analyses of the filter and vapor trap will not
5.1 Polycyclic aromatic hydrocarbons (PAH) as defined by
reflect the original atmospheric phase distributions and should
this test method are compounds made up of two or more fused
be discouraged.
aromatic rings.
5.2 Several PAH are considered to be probable human
6. Limitations
carcinogens.
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 meter (ng/m ); those with four or more
depends on the ambient temperature during sampling, humid-
rings are usually found at concentrations of a few ng/m or
ity, types and concentrations of PAH and particulate matter,
lower.
and residence time of the PAH on the filter.
6.1.2 During summer months, especially in warmer cli-
mates, volatilization from the filter may be as great as 90 % for
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
The boldface numbers in parentheses refer to the list of references at the end of
to ASTM Headquarters. Your comments will receive careful consideration at a
this standard.
meeting of the responsible technical committee , which you may attend.
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 3 10
10 8
–3
Acenaphthylene C H 152.20 92-93 265-280 3.9 3 10
12 8
–2
Acenaphthene C H 154.20 90-96 278-279 2.1 3 10
12 10
–5
Fluorene C H 166.23 116-118 293-295 8.7 3 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 3 10
14 10
–5
Phenanthrene C H 178.24 96-101 339-340 2.3 3 10
14 10
–7
Fluoranthene C H 202.26 107-111 375-393 6.5 3 10
16 10
–6
Pyrene C H 202.26 150-156 360-404 3.1 3 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 3 10
18 12
–10
Chrysene C H 228.30 252-256 441-448 5.7 3 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 3 10
20 12
–8
Benzo[k]fluoranthene C H 252.32 198-217 480-481 2.1 3 10
20 12
–10
Perylene C H 252.32 273-278 500-503 7.0 3 10
20 12
–10
Benzo[a]pyrene C H 252.32 177-179 493-496 7.3 3 10
20 12
–10
Benzo[e]pyrene C H 252.32 178-179 493 7.4 3 10
20 12
–11
Benzo[ghi]perylene C H 276.34 275.278 525 1.3 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 3 10
22 14
–13
Coronene C H 300.36 438-440 525 2.0 3 10
24 12
A
Many of these compounds sublime.
D6209
–6
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 3 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
7.4.2 Use incandescent or UV-filtered fluorescent lighting
concentrations of the PAH originally associated with particles,
where possible in the laboratory to avoid photodegradation
nor will analysis of the sorbent provide an accurate measure of
during analysis.
the gas phase. Consequently, this method calls for coextraction
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-
8.2 Treat all PAH as potential carcinogens.
sis efficiencies.
8.2.1 Weigh pure compounds in a glove box.
6.2.1 Naphthalene and acenaphthene possess relatively high
8.2.2 Consider unused samples and standards to be toxic
vapor pressures and may not be efficiently trapped by this test
waste and properly dispose of them according to regulations.
method, especially when PUF is used.
8.2.3 Regularly check laboratory bench tops and equipment
6.2.2 The sampling efficiency for naphthalene has been
with a UV“black light” for fluorescence indicative of contami-
determined to be about 35 % for PUF and about 60 % for
nation.
XAD-2.
6.2.3 The user may estimate the sampling efficiencies for
9. Apparatus
PAH of interest by determining dynamic retention efficiency of
9.1 Sampling:
the sorbent. The percent RE generally approximates the per-
9.1.1 Sampling Module— A typical collection system con-
cent SE.
sisting of a particle filter backed up by a sorbent trap is shown
in Fig. 1. It consists of the following:
7. Interferences
9.1.1.1 Metal Filter Holder (Part 2), capable of holding a
7.1 Method interferences may be caused by contaminants in
104-mm circular particulate filter supported by a 1.2-mm
solvents, reagents, on glassware, and other sample processing (16-mesh)stainless-steelscreenwith50 %openarea.Thefilter
hardware that result in discrete artifacts and elevated baselines,
holder is equipped with inert sealing gaskets (for example,
or both, in the detector profiles. Thoroughly clean glass before polytetrafluoroethylene) placed on either side of the filter.
use (for example, by acid washing, followed by heating to
9.1.1.2 Metal Cylinder (Part 1), capable of holding a
450°C in a muffle furnace). Check solvents and other materials
65-mm o.d. (60-mm i.d.) by 125-mm borosilicate glass sorbent
routinely by running laboratory reagent blanks under the
cartridge. Inert, pliable gaskets (for example, silicone rubber)
conditions of the analysis to establish that they are free of
are used to provide an air-tight seal at each end of the sorbent
interfering materials.
cartridge. The glass sorbent cartridge is indented 20 mm from
the lower end to provide a support for a 1.2-mm (16-mesh)
7.2 Matrix interferences may be caused by contaminants
that are coextracted from the sample. Additional clean-up by stainless-steel screen that holds the sorbent.
9.1.1.3 The glass sorbent cartridge fits into Part 1, which is
column chromatography may be required.
screwed onto Part 2 until the sorbent cartridge is sealed
7.3 The extent of interferences that may be encountered
between the gaskets. The sampling module is described by
using gas chromatographic techniques has not been fully
Lewis and Jackson (8) . Similar sampling modules are com-
assessed.
mercially available.
7.3.1 Although the GC/MS conditions described allow for
9.1.2 High-volume Pumping System, capable of providing a
resolution of most of the specific PAH compounds covered by
constant air flow of up to 250 L/min (15 m /h) through the
this test method, other PAH compounds may interfere.
sampling module (9.1.1). A typical air pumping system is
7.3.2 Some PAH isomers may not be chromatographically
shown in Fig. 2. It is equipped with the following components:
resolvable and, therefore, can not be distinguished from each
9.1.2.1 Appropriate Flow-control Device:
other by MS.
9.1.2.2 Manometer, to measure pressure drop across the
7.3.3 Interferences from some non-PAH compounds, espe-
sampling module or other suitable flow measuring device.
cially oils and polar organic species, may be reduced or
9.1.2.3 Interval Timer.
eliminated by the use of column chromatography for sample
9.1.2.4 Exhaust hose, to carry exhausted air at least 3 m
clean-up prior to GC/MS analysis.
away from the sampler.
7.3.4 The analytical system must be routinely demonstrated
NOTE 1—The sampling system described in 9.1.1 to 9.1.2.4 has been
to be free of internal contaminants such as contaminated
showntoefficientlytrapPAHwiththreeormoreringsatsamplesvolumes
solvents, glassware, or other reagents that may lead to method
350 m and lower (8-16). Other samplers utilizing larger filters (for
interferences.
example, 200-mm by 250-mm) and higher capacity sorbent traps (for
7.3.5 Analyze a laboratory reagent blank for each batch of
example, by tandem 77-mm by 62-mm PUF plugs) have been used to
reagents used to determine if reagents are contaminant-free. collect PAH from larger ai
...