1、Designation: D 4861 05Standard Practice forSampling and Selection of Analytical Techniques forPesticides and Polychlorinated Biphenyls in Air1This standard is issued under the fixed designation D 4861; the number immediately following the designation indicates the year oforiginal adoption or, in the
2、 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 reapproval.1. Scope1.1 This practice covers the sampling of air for a variety ofcommon pesticides and polychl
3、orinated biphenyls (PCBs) andprovides guidance on the selection of appropriate analyticalmeasurement methods. Other compounds such as polychlori-nated dibenzodioxins/furans, polybrominated biphenyls, poly-brominated diphenyl ethers, polycyclic aromatic hydrocarbons,and polychlorinated naphthalenes m
4、ay be efficiently collectedfrom air by this practice, but guidance on their analyticaldetermination is not covered by this practice.1.2 A complete listing of pesticides and other semivolatileorganic chemicals for which this practice has been tested isshown in Table 1.1.3 This practice is based on th
5、e collection of chemicalsfrom air onto polyurethane foam (PUF) or a combination ofPUF and granular sorbent.1.4 This practice is applicable to multicomponent atmo-spheres, 0.001 to 50-g/m3concentrations, and 4 to 24-hsampling periods. The limit of detection will depend on thenature of the analyte and
6、 the length of the sampling period.1.5 The analytical method(s) recommended will depend onthe specific chemical(s) sought, the concentration level, and thedegree of specificity required.1.6 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is th
7、eresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. For specific hazardsstatements, see 10.24 and A1.1.2. Referenced Documents2.1 ASTM Standards:2D 1193 Specification for Reagent W
8、aterD 1356 Terminology Relating to Sampling and Analysis ofAtmospheresD 3686 Practice for Sampling Atmospheres to Collect Or-ganic Compound Vapors (Activated Charcoal Tube Ad-sorption Method)D 3687 Practice for Analysis of Organic Compound VaporsCollected by the Activated Charcoal Tube AdsorptionMet
9、hodD 4185 Practice for Measurement of Metals in WorkplaceAtmosphere by Atomic Absorption SpectrophotometryE 355 Practice for Gas Chromatography Terms and Rela-tionships2.2 EPA Methods and Standards:3EPA 600/R-96/010b Compendium of Methods for the De-termination to Toxic Organic Compounds inAmbientAi
10、r4EPA 821/C-99-004 Methods and Guidance for Analysis ofWater, Versions 25EPA SW-846 Test Methods for Evaluating Solid WastePhysical Chemical Methods40 CFR 136 EPA Organic Chemical Analysis of Municipaland Industrial Wastewater62.3 NIOSH Methods:3NIOSH Manual of Analytical Methods73. Terminology3.1 D
11、efinitionsRefer to Terminology D 1356 and PracticeE 355 for definitions of terms used in this practice.3.2 Definitions of Terms Specific to This Standard:3.2.1 dynamic retention effciencyability of the samplingmedium to retain the solution spike when air or nitrogen isdrawn through the sampling cart
12、ridge under normal operatingconditions and for the duration of the test period. The dynamicRE is normally equal to or less than the SE.1This practice is under the jurisdiction of ASTM Committee D22 on Samplingand Analysis of Atmospheres and is the direct responsibility of SubcommitteeD22.05 on Indoo
13、r Air.Current edition approved March 1, 2005. Published March 2005. Originallyapproved in 1991. Last previous edition approved in 2000 as D 4861 - 00.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStand
14、ards volume information, refer to the standards Document Summary page onthe ASTM website.3Available from Superintendent of Documents, U.S. Government PrintingOffice, Washington, DC 20402.4Also available at http:/www.epa.gov/ttn/amtic/airtox.html5NTIS PB99-500209INQ (see http:/www.ntis.gov/product/ep
15、a-water-methods.htm)6Also available at http:/www.access.gpo.gov/nara/cfr/waisdx_03/40cfr136_03.html7Also available at http:/www.cdc.gov/niosh/nmam1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.3.2.2 relative retention time, (RRT)rat
16、io of RTs for twochemicals for the same chromatographic column and carriergas flow rate, where the denominator represents a referencechemical.3.2.3 retention effciency, (RE)ability of the samplingmedium to retain a compound added (spiked) to it in liquidsolution.3.2.4 retention time, (RT)time to elu
17、te a specific chemicalfrom a chromatographic column, for a specific carrier gas flowrate, measured from the time the chemical is injected into thegas stream until it appears at the detector.3.2.5 sampling effciency, (SE)ability of the samplingmedium to trap vapors of interest. The percentage of thea
18、nalyte of interest collected and retained by the samplingmedium when it is introduced as a vapor in air or nitrogen intothe air sampler and the sampler is operated under normalconditions for a period of time equal to or greater than thatrequired for the intended use is indicated by % SE.3.2.6 static
19、 retention effciencyability of the samplingmedium to retain the solution spike when the samplingcartridge is stored under clean, quiescent conditions for theduration of the test period.4. Summary of Practice4.1 A low-volume (1 to 5 L/min) sampler is used to collectvapors on a sorbent cartridge conta
20、ining PUF or PUF incombination with another solid sorbent.Airborne particles mayalso be collected, but the sampling efficiency is not known. Themethod is adopted from Ref (1)8and is the basis of EPA600/R-96/010b, Method TO-10A.4.2 Pesticides and other chemicals are extracted from thesorbent cartridg
21、e with 5 % diethyl ether in hexane and may bedetermined by gas-liquid chromatography (GC) coupled withan electron capture detector (ECD), nitrogen-phosphorus de-tector (NPD), flame photometric detector (FPD), Hall electro-lytic conductivity detector (HECD), or a mass spectrometer(MS). For some pesti
22、cides, high-performance liquid chroma-tography (HPLC) coupled with an ultraviolet (UV) detector orelectrochemical detector may be preferable.4.3 Interferences resulting from analytes having similar RTsduring GC are resolved by improving the resolution or sepa-ration, such as by changing the chromato
23、graphic column oroperating parameters, or by fractionating the sample by columnchromatography.5. Significance and Use5.1 This practice is recommended for use primarily fornon-occupational exposure monitoring in domiciles, publicaccess buildings, and offices.8The boldface numbers in parentheses refer
24、 to the list of references at the end ofthis standard.TABLE 1 Compounds for Which Procedure Has Been TestedCompound Recommended AnalysisACompound Recommended AnalysisAlachlor GC/ECD or MS Heptachlor GC/ECD or MSAldrin GC/ECD or MS Heptachlor epoxide GC/ECD or MSAllethrin HPLC/UV or GC/MS Hexachlorbe
25、nzene GC/ECD or MSAroclor 1242 GC/ECD or MS HexachlorocyclopentadieneB,CGC/ECD or MSAroclor 1254 GC/ECD or MS Lindane (g-HCH) GC/ECDAroclor 1260 GC/ECD or MS Linuron HPLC/UVAtrazine GC/NPD or MS Malathion GC/NPD or FPDBendiocarb HPLC/UV or GC/MS Methyl parathion GC/NPD or FPDHCH (a- and b-Hexachloro
26、cyclohexanes)GC/ECD or MS Methoxychlor GC/ECD or MSCaptan GC/ECD or MS Metolachlor GC/ECD or MSCarbaryl HPLC/UV or GC/MS MexacarbateCarbofuran HPLC/UV or GC/MS Mirex GC/ECD or MSChlordane, technical GC/ECD or MS Monuron HPLC/UVChlorothalonil GC/ECD or MS trans-Nonachlor GC/ECD or MSCholorotoluron HP
27、LC/UV or GC/MS Oxychlordane GC/ECD or MSChlorpyrifos GC/ECD or MS Parathion GC/NPD, FPD, or MSCyfluthrin GC/ECD or MS Pentachlorobenzine GC/ECD or MS2,4-D, acid, esters and salts GC/ECD or MSDPentachlorphenol GC/ECD or MSDacthal GC/ECD or MS Permethrin (cis and trans) GC/MSp,p-DDT GC/ECD or MS o-Phe
28、nylphenol HPLC/UV, GC/ECD, or MSp,p-DDE GC/ECD or MS Phorate GC/NPD, FPD, or MSDiazinon GC/NPD, FPD, or MS Propazine GC/NPD or MSDicloran GC/ECD or MS Propoxur (Baygon) GC/NPD or MSDieldrin GC/ECD or MS Pyrethrin GC/MSDichlorvos (DDVP) GC/ECD or MS Resmethrin GC/MSDicofol GC/ECD or MS Ronnel GC/ECD
29、or MSDicrotophos HPLC/UV or GC/MS Simazine HPLC/UV or GC/MSDiuron HPLC/UV or GC/MS Terbuthiuron HPLC/UV or GC/MSEndrin GC/ECD or MS 1,2,3,4-TetrachlorobenzeneBGC/ECD or MSFenvalerate HPLC/UV or GC/MS 1,2,3-TrichlorobenzeneBGC/ECD or MSFluometuron HPLC/UV or GC/MS 2,4,5-Trichlorophenol GC/ECD or MSFo
30、lpet GC/ECD or MS Trifluralin GC/ECD or MSFonophos GC/NPD, FPD, or MS Vinclozolin GC/ECD, NPD, or MSAGC = gas chromatography; ECD = electron capture detector; FPD = flame photometric detector; HPLC = high-performance liquid chromatography; NPD = nitrogen-phosphorus detector; UV = ultraviolet absorpt
31、ion detector. (GC/MS (gas chromatography/mass spectrometry) is always recommended, if available.)BUsing PUF/2,6-diphenyl-p-phenylene oxide “sandwich” trap.CCompound is very unstable in solution.DDerivatization necessary for free acid and salts.D48610525.2 The methods described in this practice have
32、beensuccessfully applied to measurement of pesticides and PCBs inoutdoor air and for personal respiratory exposure monitoring.5.3 A broad spectrum of pesticides are commonly used inand around the house and for insect control in public andcommercial buildings. Other semivolatile organic chemicals,suc
33、h as PCBs, are also often present in indoor air, particularlyin large office buildings. This practice promotes needed preci-sion and bias in the determination of many of these airbornechemicals.6. Interferences6.1 Any gas or liquid chromatographic separation of com-plex mixtures of organic chemicals
34、 is subject to seriousinterference problems due to coelution of two or more com-pounds. The use of capillary or microbore columns withsuperior resolution or two columns of different polarity willfrequently eliminate these problems.6.1.1 Selectivity may be further enhanced by use of a MS ina selected
35、 ion monitoring (SIM) mode as the GC detector. Inthis mode, coeluting compounds can often be determined.6.2 The ECD responds to a wide variety of organic com-pounds. It is likely that such compounds will be encountered asinterferences during GC-ECD analysis. The NPD, FPD, andHECD detectors are eleme
36、nt specific, but are still subject tointerferences. UV detectors for HPLC are nearly universal andthe electrochemical detector may also respond to a variety ofchemicals. Mass spectrometric analyses will generally providefor positive identification of specific compounds.6.3 PCBs and certain organochl
37、orine pesticides (for ex-ample, chlordane) are complex mixtures of individual com-pounds, which can cause difficulty in accurately quantifying aparticular formulation in a multiple component mixture. PCBsmay also interfere with the determination of pesticides.6.4 Contamination of glassware and sampl
38、ing apparatuswith traces of pesticides or PCBs can be a major source oferror, particularly at lower analyte concentrations. Carefulattention to cleaning and handling procedures is required in allsteps of the sampling and analysis to minimize this source oferror.6.5 General approaches that can be fol
39、lowed to minimizeinterferences are as follows:6.5.1 Polar compounds, including certain pesticides (forexample, organophosphorus and carbamate classes) can beremoved by column chromatography on alumina. This samplecleanup will permit the analysis of most organochlorine pesti-cides and PCBs (2).6.5.2
40、PCBs may be separated from organochlorine pesti-cides by column chromatography on silicic acid. See Refs (3)and (4).6.5.3 Many pesticides can be fractionated into groups bycolumn chromatography on Florisil-PR9(4).7. Apparatus7.1 Air Sampler:7.1.1 Sampling Pump, with a flow rate of 1 to 5 L/min. Thep
41、ump should provide a constant air flow (#65 %) and be quietand unobtrusive.7.1.2 Sampling Cartridge, constructed from a 20-mm (in-side diameter) by 10-cm borosilicate glass tube drawn down toa 7-mm (outside diameter) open connection for attachment tothe pump by way of flexible tubing (see Fig. 1).7.
42、1.3 Sorbent, PUF, cut into a cylinder 22 mm in diameterand 7.6-cm long, and fitted under slight compression inside thecartridge. The PUF should be of the polyether type, density0.022 g/cm3. This is the type of foam used for furnitureupholstery, pillows, and mattresses. The PUF cylinders (plugs)shoul
43、d be cut slightly larger in diameter than the internaldiameter of the cartridge. They may be cut by one of thefollowing means:7.1.3.1 With a high-speed cutting tool, such as a motorizedcork borer. Distilled Type II water should be used to lubricatethe cutting tool.7.1.3.2 With a hot-wire cutter. Car
44、e is required to preventthermal degradation of the foam.7.1.3.3 With scissors, while compressed between two22-mm circular templates.7.1.4 Alternatively, pre-extracted PUF plugs and glass car-tridges may be obtained commercially from one of severalvendors.7.1.5 Particle Filter, if desired, may be uti
45、lized. The col-lection efficiency of PUF for small-diameter (0.1 to 1 m)airborne particles is only about 20 % (5). However, mostpesticides and PCBs exist in air under steady-state conditions,primarily as vapors (6). Most particulate-associated pesticidesor PCBs, if any, will also tend to be vaporize
46、d from filters aftercollection (7). Collocated sampling with and without a quartz-fiber pre-filter has yielded indistinguishable results for a broadspectrum of pesticides and PCBs found in indoor air (8).7.1.5.1 An open-face filter may be attached to the samplingcartridge by means of a union for 1-i
47、n. 25.4-mm tubing. A9Florisil is a trademark of the U.S Silica Co., Berkeley Springs, WV. It is anatural magnesium silicate and is available from several commercial suppliers.FIG. 1 PUF Sampling Cartridge (a) and PUF “Sandwich” Sampling Cartridge (b)D486105332-mm diameter micro-quartz-fibre, binderl
48、ess, acid-washedfilter is placed in the open end of the union and supported bymeans of a screen or perforated metal plate for example, a 304stainless steel disk, 0.0312-in. 0.8-mm thick with116-in.1.6-mm diameter round perforations at 132 holes/in.220holes/cm2, 41 % open area. A 32-mm fluoroelastome
49、ric orpolytetrafluoroethylene (PTFE) O-ring is placed between thefilter and outer nut to effect a seal (see Fig. 2).7.1.6 Size-Selective Impactor Inlet with particle-size cut-points of either 2.5 or 10 m mean diameter at a sampling rateof 4 L/min may be used to exclude non-respirable airborneparticulate matter (9, 10). An example of a sampler with asize-selective inlet, particle filter support, sampling cartridgeholder is shown in Fig. 3. This sampling cartridge is availablecommercially.7.2 Equipment and Reagents for Sample Extraction andConcentration:7.2
