1、Designation: D 6209 98 (Reapproved 2004)Standard 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 D 6209
2、; 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 (e) indicates an editorial change since the last revision or reapprova
3、l.1. Scope1.1 This test method2specifies sampling, cleanup, andanalysis procedures for the determination of polycyclic aro-matic hydrocarbons (PAH) in ambient air.1.2 This test method is designed to collect both gas-phaseand particulate-phase PAH and to determine them collectively.1.3 This test meth
4、od is a high-volume sampling (100 to 250L/min) method capable of detecting PAH at sub-nanograms percubic metre (ng/m3) concentrations with sampling volumes upto 350 m3of air.1.4 This test method has been validated for samplingperiods up to 24 h.1.5 Precision and bias under normal conditions can beex
5、pected to be 635 to 50 %.1.6 This test method describes a sampling and analysisprocedure for PAH that involves collection from air on acombination fine-particle filter and sorbent trap and subsequentanalysis by gas chromatography/mass spectrometry (GC/MS).1.7 The range of this test method is approxi
6、mately 0.05 to1000 ng/m3of air sampled.1.8 The values stated in SI units shall be regarded asstandard.1.9 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and he
7、alth practices and determine the applica-bility of regulatory limitations prior to use. See also Section 8for additional safety precautions.2. Referenced Documents2.1 ASTM Standards:3D 1356 Terminology Relating to Sampling and Analysis ofAtmospheresD 1357 Practice for Planning the Sampling of the Am
8、bientAtmosphereD 3631 Test Methods for Measuring Surface AtmosphericPressureE1 Specification for ASTM Liquid-in-Glass Thermometers3. Terminology3.1 Definitions For definitions of terms used in this testmethod, refer to Terminology D 1356.3.2 Definitions of Terms Specific to This Standard:3.2.1 sampl
9、ing effciency (SE), nability of the sampler totrap and retain PAH. The percent SE is the percentage of theanalyte of interest collected and retained by the samplingmedium when it is introduced into the air sampler and thesampler is operated under normal conditions for a period oftime equal to or gre
10、ater than that required for the intended use.3.2.2 dynamic retention effciency, nability of the sam-pling medium to retain a given PAH that has been added to thesorbent trap in a spiking solution when air is drawn through thesampler under normal conditions for a period of time equal toor greater tha
11、n that required for the intended use.4. Summary of Test Method4.1 Sampling:4.1.1 An air sample is collected directly from the ambientatmosphere by pulling air at approximately 225 L/min througha fine particulate filter followed by a vapor trap containingpolyurethane foam (PUF) or styrene/divinylbenz
12、ene polymer1This test method is under the jurisdiction of ASTM Committee D22 onSampling and Analysis of Atmospheres and is the direct responsibility of Subcom-mittee D22.03 on Ambient Atmospheres and Source Emissions.Current edition approved October 1, 2004. Published December 2004. Originallyapprov
13、ed in 1997. Last previous edition approved in 1998 as D 6209 - 98e1.2This test method is based on U. S. Environmental Protection Agency Compen-dum Method TO-13, Compendium of Methods for the Determination of ToxicOrganic Compounds in Ambient Air, Report No. EPA/600-4-89/018, June 1988,available from
14、 the National Technical Information Service, 5285 Port Royal Rd.,Springfield, VA 22161, Order No. PB90-11989/AS.3For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the
15、standards Document Summary page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.resin (XAD-2).4Sampling times may be varied from 1 to 24 h,depending on monitoring needs and the detection limits re-quired, so as not
16、 to exceed a total sample volume of 350 m3.4.2 Analysis:4.2.1 After sampling a fixed volume of air, the particle filterand sorbent cartridge are extracted together in a Soxhletextractor. The sample extract is concentrated by means of aKuderna-Danish concentrator (or other validated method),followed
17、by a further concentration under a nitrogen stream, ifnecessary, and an aliquot is analyzed by gas chromatography/mass spectrometry. The results derived represent the combinedgas-phase and particulate-phase air concentrations of eachPAH analyzed.5. Significance and Use5.1 Polycyclic aromatic hydroca
18、rbons (PAH) as defined bythis test method are compounds made up of two or more fusedaromatic rings.5.2 Several PAH are considered to be probable humancarcinogens.5.3 PAH are emitted in the atmosphere primarily throughwood or fossil fuel combustion.5.4 Two- and three-ring PAH are typically present in
19、 urbanair at concentrations ranging from 10 to several hundrednanograms per cubic metre (ng/m3); those with four or morerings are usually found at concentrations of a few ng/m3orlower.5.5 PAH span a broad spectrum of vapor pressures (forexample, from 1.1 3 102kPa for naphthalene to 2 3 1013kPa for c
20、oronene at 25C). Table 1 lists some PAH that arefrequently found in ambient air. Those with vapor pressuresabove about 108kPa will be present in the ambient airsubstantially distributed between the gas and particulatephases. This test method will permit the collection of bothphases. However, particu
21、late-phase PAH will tend to be lostfrom the particulate filter during sampling due to desorptionand volatilization.5.5.1 The distribution between phases depends on ambienttemperature, humidity, types and concentrations of PAH andparticulate matter, and residence time in the air. PAH, espe-cially tho
22、se having vapor pressures above 108kPa, mayvaporize from particulate filters during sampling. Conse-quently, a back-up vapor trap must be used for efficientsampling.5.6 Separate analyses of the filter and vapor trap will notreflect the original atmospheric phase distributions and shouldbe discourage
23、d.6. Limitations6.1 Particulate-phase PAH may be lost from the particlefilter during sampling due to desorption and volatilization(1-6).56.1.1 Loss of particulate-associated PAH from the filterdepends on the ambient temperature during sampling, humid-ity, types and concentrations of PAH and particul
24、ate matter,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 % forPAH with vapor pressures above 106kPa (3 and 6).Atambient temperatures of 30C and above, as much as 20 % of4XAD is a trademark
25、of Rohm and Haas Co., Philadelphia, PA; it is available inthe United States solely from Supelco, Inc., Bellefonte, PA. If you are aware ofequivalent styrene/divinylbenzene polymer resins, please provide this informationto ASTM Headquarters. Your comments will receive careful consideration at ameetin
26、g of the responsible technical committee1, which you may attend.5The boldface numbers in parentheses refer to the list of references at the end ofthis standard.TABLE 1 Formulae and Physical Properties of Selective PAHCompound(Common Name)FormulaMolecularWeightMeltingPoint,CBoilingPoint,ACVaporPressu
27、re,kPa at25CNaphthalene C10H8128.18 80.2 218 1.1 3 102Acenaphthylene C12H8152.20 92-93 265-280 3.9 3 103Acenaphthene C12H10154.20 90-96 278-279 2.1 3 102Fluorene C13H10166.23 116-118 293-295 8.7 3 1059-Fluorenone C13H8O 180.21 84 341.5 ca.105Anthracene C14H10178.24 216-219 340 3.6 3 106Phenanthrene
28、C14H10178.24 96-101 339-340 2.3 3 105Fluoranthene C16H10202.26 107-111 375-393 6.5 3 107Pyrene C16H10202.26 150-156 360-404 3.1 3 106Cyclopentalcdpyrene C18H10226.28 ca. 275? ca. 107Benzaanthracene C18H12228.30 157-167 435 1.5 3 108Chrysene C18H12228.30 252-256 441-448 5.7 3 1010Retene C18H18234.34
29、101 390 ca. 106Benzobfluoranthene C20H12252.32 167-168 481 6.7 3 108Benzokfluoranthene C20H12252.32 198-217 480-481 2.1 3 108Perylene C20H12252.32 273-278 500-503 7.0 3 1010Benzoapyrene C20H12252.32 177-179 493-496 7.3 3 1010Benzoepyrene C20H12252.32 178-179 493 7.4 3 1010Benzoghiperylene C22H12276.
30、34 275.278 525 1.3 3 1011Indeno1,2,3-cdpyrene C22H12276.34 162-163 ca. 1011Dibenzahanthracene C22H14278.35 266-270 524 1.3 3 1011Coronene C24H12300.36 438-440 525 2.0 3 1013AMany of these compounds sublime.D 6209 98 (2004)2benzoapyrene and perylene (v.p. = 7 3 1010kPa) have beenfound in the vapor tr
31、ap (7).6.1.3 Separate analysis of the filter will not reflect theconcentrations of the PAH originally associated with particles,nor will analysis of the sorbent provide an accurate measure ofthe gas phase. Consequently, this method calls for coextractionof the filter and sorbent to permit accurate m
32、easure of totalPAH air concentrations.6.2 This test method has been evaluated for the PAH shownin Table 1. Other PAH may be determined by this test method,but the user must demonstrate acceptable sampling and analy-sis efficiencies.6.2.1 Naphthalene and acenaphthene possess relatively highvapor pres
33、sures and may not be efficiently trapped by this testmethod, especially when PUF is used.6.2.2 The sampling efficiency for naphthalene has beendetermined to be about 35 % for PUF and about 60 % forXAD-2.6.2.3 The user may estimate the sampling efficiencies forPAH of interest by determining dynamic r
34、etention efficiency ofthe sorbent. The percent RE generally approximates the per-cent SE.7. Interferences7.1 Method interferences may be caused by contaminants insolvents, reagents, on glassware, and other sample processinghardware that result in discrete artifacts and elevated baselines,or both, in
35、 the detector profiles. Thoroughly clean glass beforeuse (for example, by acid washing, followed by heating to450C in a muffle furnace). Check solvents and other materialsroutinely by running laboratory reagent blanks under theconditions of the analysis to establish that they are free ofinterfering
36、materials.7.2 Matrix interferences may be caused by contaminantsthat are coextracted from the sample. Additional clean-up bycolumn chromatography may be required.7.3 The extent of interferences that may be encounteredusing gas chromatographic techniques has not been fullyassessed.7.3.1 Although the
37、GC/MS conditions described allow forresolution of most of the specific PAH compounds covered bythis test method, other PAH compounds may interfere.7.3.2 Some PAH isomers may not be chromatographicallyresolvable and, therefore, can not be distinguished from eachother by MS.7.3.3 Interferences from so
38、me non-PAH compounds, espe-cially oils and polar organic species, may be reduced oreliminated by the use of column chromatography for sampleclean-up prior to GC/MS analysis.7.3.4 The analytical system must be routinely demonstratedto be free of internal contaminants such as contaminatedsolvents, gla
39、ssware, or other reagents that may lead to methodinterferences.7.3.5 Analyze a laboratory reagent blank for each batch ofreagents used to determine if reagents are contaminant-free.7.4 Exposure to heat, ozone, nitrogen dioxide (NO2), andultraviolet (UV) light may cause PAH degradation duringsampling
40、, sample storage, and processing.7.4.1 These problems should be addressed as part of astandard operating procedure prepared by the user.7.4.2 Use incandescent or UV-filtered fluorescent lightingwhere possible in the laboratory to avoid photodegradationduring analysis.8. Safety Precautions8.1 Benzoap
41、yrene and several other PAH have been clas-sified as probable human carcinogens. Exercise care whenworking with these substances.8.2 Treat all PAH as potential carcinogens.8.2.1 Weigh pure compounds in a glove box.8.2.2 Consider unused samples and standards to be toxicwaste and properly dispose of t
42、hem in accordance withregulations.8.2.3 Regularly check laboratory bench tops and equipmentwith a UV “black light” for fluorescence indicative of contami-nation.9. Apparatus9.1 Sampling:9.1.1 Sampling Module A typical collection system con-sisting of a particle filter backed up by a sorbent trap is
43、shownin Fig. 1. It consists of the following:9.1.1.1 Metal Filter Holder (Part 2), capable of holding a104-mm circular particulate filter supported by a 1.2-mm(16-mesh) stainless-steel screen with 50 % open area. The filterholder is equipped with inert sealing gaskets (for example,polytetrafluoroeth
44、ylene) placed on either side of the filter.9.1.1.2 Metal Cylinder (Part 1), capable of holding a65-mm o.d. (60-mm i.d.) by 125-mm borosilicate glass sorbentcartridge. Inert, pliable gaskets (for example, silicone rubber)are used to provide an air-tight seal at each end of the sorbentcartridge. The g
45、lass sorbent cartridge is indented 20 mm fromthe lower end to provide a support for a 1.2-mm (16-mesh)stainless-steel screen that holds the sorbent.9.1.1.3 The glass sorbent cartridge fits into Part 1, which isscrewed onto Part 2 until the sorbent cartridge is sealedbetween the gaskets. The sampling
46、 module is described byLewis and Jackson (8)4. Similar sampling modules are com-mercially available.9.1.2 High-volume Pumping System, capable of providing aconstant air flow of up to 250 L/min (15 m3/h) through thesampling module (9.1.1). A typical air pumping system isshown in Fig. 2. It is equippe
47、d with the following components:9.1.2.1 Appropriate Flow-control Device:9.1.2.2 Manometer, to measure pressure drop across thesampling 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 maway from the sampler.NOTE 1The sampli
48、ng system described in 9.1.1 to 9.1.2.4 has beenshown to efficiently trap PAH with three or more rings at samples volumes350 m3and lower (8-16). Other samplers utilizing larger filters (forexample, 200-mm by 250-mm) and higher capacity sorbent traps (forexample, by tandem 77-mm by 62-mm PUF plugs) h
49、ave been used tocollect PAH from larger air volumes (for example, by 700 m3) (17-26 and7). If larger sampling volumes or higher flow rates are used, thoroughlyevaluate their performance to ensure acceptable sampling efficiencies.D 6209 98 (2004)39.1.3 Flow Calibrator, a calibrated manometer or othersuitable flow measuring device capable of being attached to theinlet of the sampling module (9.1.1).9.1.4 Standard Audit Calibration Orifice:9.1.5 Positive-Displacement Rootsmeter:9.1.6 Barometer, ASTM Thermometer 33C, meet
