ASTM D6209-1998(2012) 6250 Standard Test Method for Determination of Gaseous and Particulate Polycyclic Aromatic Hydrocarbons in Ambient Air (Collection on Sorbent-Backed Filters w.pdf

1、Designation: D6209 98 (Reapproved 2012)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 D6209;

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 () indicates an editorial change since the last revision or reapproval.1

3、. 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 method

4、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 beexpec

5、ted 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 approximat

6、ely 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 healt

7、h 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:3D1356 Terminology Relating to Sampling and Analysis ofAtmospheresD1357 Practice for Planning the Sampling of the Ambient

8、AtmosphereD3631 Test Methods for Measuring Surface AtmosphericPressureE1 Specification for ASTM Liquid-in-Glass Thermometers3. Terminology3.1 DefinitionsFor definitions of terms used in this testmethod, refer to Terminology D1356.3.2 Definitions of Terms Specific to This Standard:3.2.1 sampling effc

9、iency (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 greater tha

10、n 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 than that r

11、equired 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 containing1This test method is under the jurisdiction of ASTM Co

12、mmittee D22 on AirQuality and is the direct responsibility of Subcommittee D22.03 on AmbientAtmospheres and Source Emissions.Current edition approved Nov. 1, 2012. Published November 2012. Originallyapproved in 1997. Last previous edition approved in 2004 as D6209 - 98 (2004).DOI: 10.1520/D6209-98R1

13、2.2This 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 the National Technical Information Service, 5285 Port Royal Rd.,S

14、pringfield, 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 standards Document Summary page onthe ASTM website.Copyright ASTM

15、International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1polyurethane foam (PUF) or styrene/divinylbenzene polymerresin (XAD-2).4Sampling times may be varied from 1 to 24 h,depending on monitoring needs and the detection limitsrequired, so as not to exceed a

16、 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 by a further

17、 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 hydrocarbons (PAH)

18、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 urbanair at

19、 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 102kPa for naphthalene to21013kPafor coronene at 25C). Ta

20、ble 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, particulate-phase PAH will

21、 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 those having vapor pre

22、ssures above 108kPa, mayvaporize from particulate filters during sampling.Consequently, 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 discouraged.6. Limitations6.1 P

23、articulate-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,humidity, types and concentrations of PAH and particulatematter, and residenc

24、e time of the PAH on the filter.6.1.2 During summer months, especially in warmerclimates, volatilization from the filter may be as great as 90 %4XAD is a trademark of Rohm and Haas Co., Philadelphia, PA; it is available inthe United States solely from Supelco, Inc., Bellefonte, PA. If you are aware

25、ofequivalent styrene/divinylbenzene polymer resins, please provide this informationto ASTM Headquarters. Your comments will receive careful consideration at ameeting of the responsible technical committee1, which you may attend.5The boldface numbers in parentheses refer to the list of references at

26、the end ofthis standard.TABLE 1 Formulae and Physical Properties of Selective PAHCompound(Common Name)FormulaMolecularWeightMeltingPoint,CBoilingPoint,ACVaporPressure,kPa at25CNaphthalene C10H8128.18 80.2 218 1.1 102Acenaphthylene C12H8152.20 92-93 265-280 3.9 103Acenaphthene C12H10154.20 90-96 278-

27、279 2.1 102Fluorene C13H10166.23 116-118 293-295 8.7 1059-Fluorenone C13H8O 180.21 84 341.5 ca.105Anthracene C14H10178.24 216-219 340 3.6 106Phenanthrene C14H10178.24 96-101 339-340 2.3 105Fluoranthene C16H10202.26 107-111 375-393 6.5 107Pyrene C16H10202.26 150-156 360-404 3.1 106Cyclopentalcdpyrene

28、 C18H10226.28 ca. 275? ca. 107Benzaanthracene C18H12228.30 157-167 435 1.5 108Chrysene C18H12228.30 252-256 441-448 5.7 1010Retene C18H18234.34 101 390 ca. 106Benzobfluoranthene C20H12252.32 167-168 481 6.7 108Benzokfluoranthene C20H12252.32 198-217 480-481 2.1 108Perylene C20H12252.32 273-278 500-5

29、03 7.0 1010Benzoapyrene C20H12252.32 177-179 493-496 7.3 1010Benzoepyrene C20H12252.32 178-179 493 7.4 1010Benzoghiperylene C22H12276.34 275.278 525 1.3 1011Indeno1,2,3-cdpyrene C22H12276.34 162-163 ca. 1011Dibenzahanthracene C22H14278.35 266-270 524 1.3 1011Coronene C24H12300.36 438-440 525 2.0 101

30、3AMany of these compounds sublime.D6209 98 (2012)2for PAH with vapor pressures above 106kPa (3 and 6).Atambient temperatures of 30C and above, as much as 20 % ofbenzoapyrene and perylene (v.p.=71010kPa) have beenfound in the vapor trap (7).6.1.3 Separate analysis of the filter will not reflect theco

31、ncentrations 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 measure of totalPAH air concentrations.6.2 This test method has been

32、 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 pressures and may not be efficiently trapped by this testmethod, especi

33、ally 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 retention efficiency ofthe sorbent. The percent RE generally approxi

34、mates 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 the detector profiles. Thoroughly clean glass beforeuse (for examp

35、le, 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 materials.7.2 Matrix interferences may be caused by contaminantstha

36、t 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 GC/MS conditions described allow forresolution of most of the speci

37、fic 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 some non-PAH compounds, espe-cially oils and polar organic species, m

38、ay 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, glassware, or other reagents that may lead to methodinterferences.7.3.

39、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, sample storage, and processing.7.4.1 These problems should be add

40、ressed 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 Benzoapyrene and several other PAH have been clas-sified as probable human

41、 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 them in accordance withregulations.8.2.3 Regularly check laboratory

42、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 shownin Fig. 1. It consists of the following:9.1.1.1 Metal Filter H

43、older (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,polytetrafluoroethylene) placed on either side of the filter.9.1.1.2 Metal Cylinder (

44、Part 1), capable of holding a 65-mmo.d. (60-mm i.d.) by 125-mm borosilicate glass sorbent car-tridge. Inert, pliable gaskets (for example, silicone rubber) areused to provide an air-tight seal at each end of the sorbentcartridge. The glass sorbent cartridge is indented 20 mm fromthe lower end to pro

45、vide 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 module is described byLewis and Jackson (8)4. Similar sampling m

46、odules 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 equipped with the following components:9.1.2.1 Appropriate Flow-control

47、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 sampling system described in 9.1.1 to 9.1.2.4 has beenshown to efficien

48、tly 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 (forD6209 98 (2012)3example, by tandem 77-mm by 62-mm PUF plugs) have been used tocollect PAH from larger air volum

49、es (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.9.1.3 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, meeting therequirements of Sp