1、Designation: D4861 17Standard Practice forSampling and Selection of Analytical Techniques forPesticides and Polychlorinated Biphenyls in Air1This standard is issued under the fixed designation D4861; the number immediately following the designation indicates the year oforiginal adoption or, in the c
2、ase 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. Scope1.1 This practice covers the sampling of air for a variety ofcommon pesticides and polychlori
3、nated 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 may
4、be efficiently collectedfrom air by this practice, but guidance on their analyticaldetermination is not covered by this practice.1.2 The sampling and analysis of PCBs in air can be morecomplicated than sampling PCBs in solid media (for example,soils, building materials) or liquids (for example, tran
5、sformerfluids). PCBs in solid or liquid material are typically analyzedusing Aroclor2distillation groups in chromatograms. Incontrast, recent research has shown that analysis of PCBs in airsamples by GC/ECD has also been found to exhibit potentialuncertainties due to changes in the PCB patterns, dif
6、ferences inresponses in distillation groups, peak co-elutions and differ-ences in response factors within a homolog group (1, 2).3Assuch it is recommended that PCBs in air not be quantified usingAroclorTM distillation groups. In addition, it is recommendedthat analysis of PCBs in air be done using G
7、C/MS rather thanGC/ECD. Any mention, to outdated practices for “Aroclor”and GC/ECD analysis of PCBs herein are retained solely forhistorical perspective.1.3 A complete listing of pesticides and other semivolatileorganic chemicals for which this practice has been tested isshown in Table 1.1.4 This pr
8、actice is based on the collection of chemicalsfrom air onto polyurethane foam (PUF) or a combination ofPUF and granular sorbent (for example, diphenyl oxide,styrene-divinylbenzene), or a granular sorbent alone.1.5 This practice is applicable to multicomponentatmospheres, 0.001 to 50-g/m3concentratio
9、ns, and 4 to 24-hsampling periods. The limit of detection will depend on thenature of the analyte and the length of the sampling period.1.6 The analytical method(s) recommended will depend onthe specific chemical(s) sought, the concentration level, and thedegree of specificity required.1.7 The value
10、s stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.8 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 safe
11、ty, health, and environmental practices and deter-mine the applicability of regulatory limitations prior to use.For specific hazards statements, see 10.24 and A1.1.1.9 This international standard was developed in accor-dance with internationally recognized principles on standard-ization established
12、in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:4D1193 Specification for Reagent WaterD1356 Terminology Relating to Sam
13、pling and Analysis ofAtmospheresD3686 Practice for Sampling Atmospheres to Collect Or-ganic Compound Vapors (Activated Charcoal Tube Ad-sorption Method)D3687 Practice for Analysis of Organic Compound VaporsCollected by the Activated Charcoal Tube AdsorptionMethodD4185 Test Method for Measurement of
14、Metals in Work-place Atmospheres by Flame Atomic Absorption Spectro-photometry1This practice is under the jurisdiction ofASTM Committee D22 on Air Qualityand is the direct responsibility of Subcommittee D22.05 on Indoor Air.Current edition approved Dec. 15, 2017. Published March 2018. Originallyappr
15、oved in 1991. Last previous edition approved in 2011 as D4861 11. DOI:10.1520/D4861-17.2A trade name formerly used by Monsanto Corporation, Creve Coeur, MO.3The boldface numbers in parentheses refer to the list of references at the end ofthis standard.4For referenced ASTM standards, visit the ASTM w
16、ebsite, 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 International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United St
17、atesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to T
18、rade (TBT) Committee.1E355 Practice for Gas Chromatography Terms and Relation-ships2.2 EPA Methods and Standards:EPA600/R-96/010b Compendium of Methods for the Deter-mination to Toxic Organic Compounds in Ambient Air5EPA 821/C-99-004 Methods and Guidance for Analysis ofWater, Versions 26EPA SW-846 T
19、est Methods for Evaluating Solid WastePhysical Chemical Methods40 CFR 136 EPA Organic Chemical Analysis of Municipaland Industrial Wastewater72.3 NIOSH Methods:NIOSH Manual of Analytical Methods8NOTE 1ASTM does not recommend NIOSH 5503 for PCB analysisdue to Aroclor quantitation and GC-ECDGC/ECD ana
20、lysis.3. Terminology3.1 DefinitionsRefer to Terminology D1356 and PracticeE355 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 th
21、rough the sampling cartridge under normal operatingconditions and for the duration of the test period. The dynamicRE is normally equal to or less than the SE.3.2.2 relative retention time, (RRT)ratio of RTs for twochemicals for the same chromatographic column and carriergas flow rate, where the deno
22、minator 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 elute a specific chemicalfrom a chromatographic column, for a specific carrier gas flowrate, measured from
23、 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 the5Also available at http:/www.epa.gov/ttnamti1/files/ambient/airtox/tocomp99.pdf6NTIS PB99-500209 (see ht
24、tp:/www.ntis.gov/products/epa-water-methods.aspx)7Also available at http:/ecfr.gpoaccess.gov/cgi/t/text/text-idx?c=ecfr&tpl=/ecfrbrowse/Title40/40cfr136_main_02.tpl8Also available at http:/www.cdc.gov/niosh/docs/2003-154/TABLE 1 Compounds for Which Procedure Has Been TestedCompound Recommended Analy
25、sisACompound 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 Hexachlorbenzene GC/ECD or MSChlorobiphenyl Congeners or Homologs GC/MS HexachlorocyclopentadieneB,CGC/ECD or MSLindane (-HCH) GC/ECDLinuron HPL
26、C/UVAtrazine GC/NPD or MS Malathion GC/NPD or FPDBendiocarb HPLC/UV or GC/MS Methyl parathion GC/NPD or FPDHCH (- and -Hexachlorocyclohexanes) 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/E
27、CD or MSChlordane, technical GC/ECD or MS Monuron HPLC/UVChlorothalonil GC/ECD or MS trans-Nonachlor GC/ECD or MSCholorotoluron HPLC/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 a
28、nd 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-Phenylphenol 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) G
29、C/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 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 M
30、SFenvalerate HPLC/UV or GC/MS 1,2,3-TrichlorobenzeneBGC/ECD or MSFluometuron HPLC/UV or GC/MS 2,4,5-Trichlorophenol GC/ECD or MSFolpet 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
31、 photometric detector; HPLC = high-performance liquid chromatography; NPD = nitrogen-phosphorus detector; UV = ultraviolet absorption detector. (GC/MS (gas chromatography/mass spectrometry) is always recommended, if available.)BUsing PUF/2,6-diphenyl-p-phenylene oxide “sandwich” trap.CCompound is ve
32、ry unstable in solution.DDerivatization necessary for free acid and salts.D4861 172analyte 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
33、 or greater than thatrequired for the intended use is indicated by % SE.3.2.6 static 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
34、-volume (1 to 5 L/min) sampler is used to collectvapors on a sorbent cartridge containing PUF or PUF incombination with another solid sorbent, or another solidsorbent alone.Airborne particles may also be collected, but thesampling efficiency is not known. The method is adopted fromRef (3) and is the
35、 basis of EPA 600/R-96/010b, MethodTO-10A.4.2 Pesticides and other chemicals are extracted from thesorbent cartridge 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 phot
36、ometric detector (FPD), Hall electro-lytic conductivity detector (HECD), or a mass spectrometer(MS). For some pesticides, high-performance liquid chroma-tography (HPLC) coupled with an ultraviolet (UV) detector orelectrochemical detector may be preferable. For PCBs, MSdetection is the recommended de
37、tector with congener orhomolog based quantitation.4.3 Interferences resulting from analytes having similar RTsduring GC are resolved by improving the resolution orseparation, such as by changing the chromatographic columnor operating parameters, or by fractionating the sample bycolumn chromatography
38、, or by mass spectrometric analysis.5. Significance and Use5.1 This practice is recommended for use primarily fornon-occupational exposure monitoring in domiciles, publicaccess buildings, and offices.5.2 The methods described in this practice have beensuccessfully applied to measurement of pesticide
39、s 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,such as PCBs, are also often present in indoor air, par
40、ticularlyin 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 is subject to seriousinterference problems due to c
41、oelutions of two or morecompounds. 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 ion monitoring (SIM) mode as the GC detector. Inthis
42、 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 element specific, but are still subject tointerferences. U
43、V 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 organochlorine pesticides (forexample, chlordane) are complex
44、mixtures of individualcompounds, which can cause difficulty in accurately quantify-ing a particular formulation in a multiple component mixture.PCBs may also interfere with the determination of pesticides.The analysis of PCBs in air samples by GC/ECD is notrecommended.6.4 Contamination of glassware
45、and sampling 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 c
46、an be followed 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 (
47、4).6.5.2 PCBs may be separated from organochlorine pesti-cides by column chromatography on silicic acid. See Refs (5)and (6).6.5.3 Many pesticides can be fractionated into groups bycolumn chromatography on Florisil9(6).7. Apparatus7.1 Air Sampler:7.1.1 Sampling Pump, with a flow rate of 1 to 5 L/min
48、. Thepump 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.
49、1).7.1.3 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)should be cut slightly larger in diameter than the internaldiameter of the cartridge. They may be cut by one of thefollowing means:9Florisil is a trademark of the U.S Silica Co., Berkeley Springs, WV. It is anatural magnesium silicate and is available fro
