1、Designation: D6209 98 (Reapproved 2012)D6209 13Standard Test Method forDetermination of Gaseous and Particulate PolycyclicAromatic Hydrocarbons in Ambient Air (Collection onSorbent-Backed Filters with Gas Chromatographic/MassSpectrometric Analysis)1This standard is issued under the fixed designation
2、 D6209; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reap
3、proval.1. Scope1.1 This test method2 specifies sampling, cleanup, and analysis procedures for the determination of polycyclic aromatichydrocarbons (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 tes
4、t method is a high-volume sampling (100 to 250 L/min) method capable of detecting PAH at sub-nanograms percubic 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 condition
5、s can be expected to be 635 to 50 %.1.6 This test method describes a sampling and analysis procedure for PAH that involves collection from air on a combinationfine-particle filter and sorbent trap and subsequent analysis by gas chromatography/mass spectrometry (GC/MS).1.7 The range of this test meth
6、od is approximately 0.05 to 1000 ng/m3 of air sampled.1.8 The values stated in SI 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 responsibilityof the user of this standard to establish appropria
7、te safety and health practices and determine the applicability of regulatorylimitations prior to use. See also Section 8 for additional safety precautions.2. Referenced Documents2.1 ASTM Standards:3D1356 Terminology Relating to Sampling and Analysis of AtmospheresD1357 Practice for Planning the Samp
8、ling of the Ambient AtmosphereD3631 Test Methods for Measuring Surface Atmospheric PressureE1 Specification for ASTM Liquid-in-Glass ThermometersE2251 Specification for Liquid-in-Glass ASTM Thermometers with Low-Hazard Precision Liquids3. Terminology3.1 DefinitionsFor definitions of terms used in th
9、is test method, refer to Terminology D1356.3.2 Definitions of Terms Specific to This Standard:1 This test method is under the jurisdiction of ASTM Committee D22 on Air Quality and is the direct responsibility of Subcommittee D22.03 on Ambient Atmospheresand Source Emissions.Current edition approved
10、Nov. 1, 2012April 1, 2013. Published November 2012April 2013. Originally approved in 1997. Last previous edition approved in 20042012 asD6209 - 98 (2004).(2012). DOI: 10.1520/D6209-98R12.10.1520/D6209-13.2 This test method is based on U. S. Environmental Protection Agency Compendum Method TO-13, Com
11、pendium of Methods for the Determination of Toxic OrganicCompounds in Ambient Air, Report No. EPA/600-4-89/018, June 1988, available from the National Technical Information Service, 5285 Port Royal Rd., Springfield, VA22161, Order No. PB90-11989/AS.3 For referencedASTM standards, visit theASTM websi
12、te, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication
13、 of what changes have been made to the previous version. Becauseit may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be conside
14、red the official document.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States13.2.1 sampling effciency (SE), nability of the sampler to trap and retain PAH. The percent SE is the percentage of the analyteof interest collected and retained
15、 by the sampling medium when it is introduced into the air sampler and the sampler is operatedunder normal conditions for a period of time equal to or greater than that required for the intended use.3.2.2 dynamic retention effciency, nability of the sampling medium to retain a given PAH that has bee
16、n added to the sorbenttrap in a spiking solution when air is drawn through the sampler under normal conditions for a period of time equal to or greaterthan that required for the intended use.4. Summary of Test Method4.1 Sampling:4.1.1 An air sample is collected directly from the ambient atmosphere b
17、y pulling air at approximately 225 L/min through a fineparticulate filter followed by a vapor trap containing polyurethane foam (PUF) or styrene/divinylbenzene polymer resin (XAD-2).4Sampling times may be varied from 1 to 24 h, depending on monitoring needs and the detection limits required, so as n
18、ot to exceeda total sample volume of 350 m3.4.2 Analysis:4.2.1 After sampling a fixed volume of air, the particle filter and sorbent cartridge are extracted together in a Soxhlet extractor.The sample extract is concentrated by means of a Kuderna-Danish concentrator (or other validated method), follo
19、wed by a furtherconcentration under a nitrogen stream, if necessary, and an aliquot is analyzed by gas chromatography/mass spectrometry. Theresults derived represent the combined gas-phase and particulate-phase air concentrations of each PAH analyzed.5. Significance and Use5.1 Polycyclic aromatic hy
20、drocarbons (PAH) as defined by this test method are compounds made up of two or more fusedaromatic rings.5.2 Several PAH are considered to be probable human carcinogens.5.3 PAH are emitted in the atmosphere primarily through wood or fossil fuel combustion.5.4 Two- and three-ring PAH are typically pr
21、esent in urban air at concentrations ranging from 10 to several hundred nanogramsper cubic metre (ng/m3); those with four or more rings are usually found at concentrations of a few ng/m3 or lower.5.5 PAH span a broad spectrum of vapor pressures (for example, from 1.1 102 kPa for naphthalene to 2 101
22、3 kPa forcoronene at 25C). Table 1 lists some PAH that are frequently found in ambient air. Those with vapor pressures above about 1084 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 equiv
23、alentstyrene/divinylbenzene polymer resins, please provide this information to ASTM Headquarters. Your comments will receive careful consideration at a meeting of theresponsible technical committee1, which you may attend.TABLE 1 Formulae and Physical Properties of Selective PAHCompound(Common Name)
24、FormulaMolecularWeightMeltingPoint,CBoilingPoint,ACVaporPressure,kPa at25CNaphthalene C10H8 128.18 80.2 218 1.1 102Acenaphthylene C12H8 152.20 92-93 265-280 3.9 103Acenaphthene C12H10 154.20 90-96 278-279 2.1 102Fluorene C13H10 166.23 116-118 293-295 8.7 1059-Fluorenone C13H8O 180.21 84 341.5 ca.105
25、Anthracene C14H10 178.24 216-219 340 3.6 106Phenanthrene C14H10 178.24 96-101 339-340 2.3 105Fluoranthene C16H10 202.26 107-111 375-393 6.5 107Pyrene C16H10 202.26 150-156 360-404 3.1 106Cyclopentalcdpyrene C18H10 226.28 ca. 275? ca. 107Benzaanthracene C18H12 228.30 157-167 435 1.5 108Chrysene C18H1
26、2 228.30 252-256 441-448 5.7 1010Retene C18H18 234.34 101 390 ca. 106Benzobfluoranthene C20H12 252.32 167-168 481 6.7 108Benzokfluoranthene C20H12 252.32 198-217 480-481 2.1 108Perylene C20H12 252.32 273-278 500-503 7.0 1010Benzoapyrene C20H12 252.32 177-179 493-496 7.3 1010Benzoepyrene C20H12 252.3
27、2 178-179 493 7.4 1010Benzoghiperylene C22H12 276.34 275.278 525 1.3 1011Indeno1,2,3-cdpyrene C22H12 276.34 162-163 ca. 1011Dibenzahanthracene C22H14 278.35 266-270 524 1.3 1011Coronene C24H12 300.36 438-440 525 2.0 1013AMany of these compounds sublime.D6209 132kPa will be present in the ambient air
28、 substantially distributed between the gas and particulate phases. This test method will permitthe collection of both phases. However, particulate-phase PAH will tend to be lost from the particulate filter during sampling dueto desorption and volatilization.5.5.1 The distribution between phases depe
29、nds on ambient temperature, humidity, types and concentrations of PAH andparticulate matter, and residence time in the air. PAH, especially those having vapor pressures above 108 kPa, may vaporize fromparticulate filters during sampling. Consequently, a back-up vapor trap must be used for efficient
30、sampling.5.6 Separate analyses of the filter and vapor trap will not reflect the original atmospheric phase distributions and should bediscouraged.6. Limitations6.1 Particulate-phase PAH may be lost from the particle filter during sampling due to desorption and volatilization (1-6).56.1.1 Loss of pa
31、rticulate-associated PAH from the filter depends on the ambient temperature during sampling, humidity, typesand concentrations of PAH and particulate matter, and residence time of the PAH on the filter.6.1.2 During summer months, especially in warmer climates, volatilization from the filter may be a
32、s great as 90 % for PAH withvapor pressures above 106 kPa (3 and 6). At ambient temperatures of 30C and above, as much as 20 % of benzoapyrene andperylene (v.p. = 7 1010 kPa) have been found in the vapor trap (7).6.1.3 Separate analysis of the filter will not reflect the concentrations of the PAH or
33、iginally associated with particles, nor willanalysis of the sorbent provide an accurate measure of the gas phase. Consequently, this method calls for coextraction of the filterand sorbent to permit accurate measure of total PAH air concentrations.6.2 This test method has been evaluated for the PAH s
34、hown in Table 1. Other PAH may be determined by this test method, butthe user must demonstrate acceptable sampling and analysis efficiencies.6.2.1 Naphthalene and acenaphthene possess relatively high vapor pressures and may not be efficiently trapped by this testmethod, especially when PUF is used.6
35、.2.2 The sampling efficiency for naphthalene has been determined to be about 35 % for PUF and about 60 % for XAD-2.6.2.3 The user may estimate the sampling efficiencies for PAH of interest by determining dynamic retention efficiency of thesorbent. The percent RE generally approximates the percent SE
36、.7. Interferences7.1 Method interferences may be caused by contaminants in solvents, reagents, on glassware, and other sample processinghardware that result in discrete artifacts and elevated baselines, or both, in the detector profiles. Thoroughly clean glass before use(for example, by acid washing
37、, followed by heating to 450C in a muffle furnace). Check solvents and other materials routinelyby running laboratory reagent blanks under the conditions of the analysis to establish that they are free of interfering materials.7.2 Matrix interferences may be caused by contaminants that are coextract
38、ed from the sample. Additional clean-up by columnchromatography may be required.7.3 The extent of interferences that may be encountered using gas chromatographic techniques has not been fully assessed.7.3.1 Although the GC/MS conditions described allow for resolution of most of the specific PAH comp
39、ounds covered by thistest method, other PAH compounds may interfere.7.3.2 Some PAH isomers may not be chromatographically resolvable and, therefore, can not be distinguished from each otherby MS.7.3.3 Interferences from some non-PAH compounds, especially oils and polar organic species, may be reduce
40、d or eliminatedby the use of column chromatography for sample clean-up prior to GC/MS analysis.7.3.4 The analytical system must be routinely demonstrated to be free of internal contaminants such as contaminated solvents,glassware, or other reagents that may lead to method interferences.7.3.5 Analyze
41、 a laboratory reagent blank for each batch of reagents used to determine if reagents are contaminant-free.7.4 Exposure to heat, ozone, nitrogen dioxide (NO2), and ultraviolet (UV) light may cause PAH degradation during sampling,sample storage, and processing.7.4.1 These problems should be addressed
42、as part of a standard operating procedure prepared by the user.7.4.2 Use incandescent or UV-filtered fluorescent lighting where possible in the laboratory to avoid photodegradation duringanalysis.8. Safety Precautions8.1 Benzoapyrene and several other PAH have been classified as probable human carci
43、nogens. Exercise care when workingwith these substances.8.2 Treat all PAH as potential carcinogens.5 The boldface numbers in parentheses refer to the list of references at the end of this standard.D6209 1338.2.1 Weigh pure compounds in a glove box.8.2.2 Consider unused samples and standards to be to
44、xic waste and properly dispose of them in accordance with regulations.8.2.3 Regularly check laboratory bench tops and equipment with a UV “black light” for fluorescence indicative ofcontamination.9. Apparatus9.1 Sampling:9.1.1 Sampling Module A typical collection system consisting of a particle filt
45、er backed up by a sorbent trap is shown in Fig.1. It consists of the following:9.1.1.1 Metal Filter Holder (Part 2), capable of holding a 104-mm circular particulate filter supported by a 1.2-mm (16-mesh)stainless-steel screen with 50 % open area. The filter holder is equipped with inert sealing gas
46、kets (for example, polytetrafluo-roethylene) placed on either side of the filter.9.1.1.2 Metal Cylinder (Part 1), capable of holding a 65-mm o.d. (60-mm i.d.) by 125-mm borosilicate glass sorbent cartridge.Inert, pliable gaskets (for example, silicone rubber) are used to provide an air-tight seal at
47、 each end of the sorbent cartridge. Theglass sorbent cartridge is indented 20 mm from the lower end to provide a support for a 1.2-mm (16-mesh) stainless-steel screenthat holds the sorbent.9.1.1.3 The glass sorbent cartridge fits into Part 1, which is screwed onto Part 2 until the sorbent cartridge
48、is sealed betweenthe gaskets. The sampling module is described by Lewis and Jackson (8)4. Similar sampling modules are commercially available.9.1.2 High-volume Pumping System, capable of providing a constant air flow of up to 250 L/min (15 m3/h) through the samplingmodule (9.1.1). A typical air pump
49、ing system is shown in Fig. 2. It is equipped with the following components:9.1.2.1 Appropriate Flow-control Device:9.1.2.2 Manometer, to measure pressure drop across the sampling module or other suitable flow measuring device.9.1.2.3 Interval Timer.9.1.2.4 Exhaust hose, to carry exhausted air at least 3 m away from the sampler.NOTE 1The sampling system described in 9.1.1 to 9.1.2.4 has been shown to efficiently trap PAH with three or more rings at samples volumes 350m3 and
