1、Designation: D 5075 01 (Reapproved 2007)Standard Test Method forNicotine and 3-Ethenylpyridine in Indoor Air1This standard is issued under the fixed designation D 5075; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of la
2、st 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 test method covers the sampling/analysis of nico-tine and 3-ethenylpyridine (3-EP) in indoor air. This testmethod
3、is based upon the collection of nicotine and 3-EP byadsorption on a sorbent resin, extraction of nicotine and 3-EPfrom the sorbent resin, and determination by gas chromatog-raphy (GC) with nitrogen selective detection. (1)21.2 The active samplers consist of an XAD-4 sorbent tubeattached to a samplin
4、g pump. This test method is applicable topersonal or area sampling.1.3 This test method is limited in sample duration by thecapacity of the XAD-4 tube for nicotine (about 300 g). Thistest method has been evaluated up to 24-h sample duration;however, samples are typically acquired for at least 1h(som
5、etimes only 1 h). (2)1.4 For this test method, limits of detection (LOD) andquantitation (LOQ) for nicotine at a sampling rate of 1.5 L/minare, respectively, 0.11 g/m3and 0.37 g/m3for 1-h sampleduration and 0.01 g/m3and 0.05 g/m3for 8-h sampleduration. The LOD and LOQ for 3-EP at a sampling rate of
6、1.5L/min are, respectively, 0.06 g/m3and 0.19 g/m3for 1-hsample duration and 0.01 g/m3and 0.02 g/m3for 8-h sampleduration (2). Both LOD and LOQ can be reduced by increasingthe sensitivity of the thermionic specific detector.1.5 The values stated in SI units are to be regarded asstandard.1.6 This sta
7、ndard 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 health practices and determine the applica-bility of regulatory limitations prior to use. Specific precau-tionary in
8、formation is given in 13.6.2. Referenced Documents2.1 ASTM Standards:3D 1356 Terminology Relating to Sampling and Analysis ofAtmospheresD 1357 Practice for Planning the Sampling of the AmbientAtmosphereD 3631 Test Methods for Measuring Surface AtmosphericPressureD 5337 Practice for Flow Rate Calibra
9、tion of PersonalSampling PumpsE 260 Practice for Packed Column Gas ChromatographyE 355 Practice for Gas Chromatography Terms and Rela-tionships3. Terminology3.1 DefinitionsFor definitions of terms used in this testmethod, refer to Terminology D 1356 and Practice E 355.3.2 Definitions of Terms Specif
10、ic to This Standard:3.2.1 environmental tobacco smoke (ETS)an aged, dilutecomposite of exhaled tobacco smoke and smoke from tobaccoproducts.3.2.2 nitrogen-phosphorus detector (NPD)a highly sensi-tive device selective for detection of nitrogen- and phosphorus-containing organic compounds.3.2.3 XAD-4
11、resinmacroreticular polystyrene-divinylbenzene copolymer beads.4. Summary of Test Method4.1 A known volume of air is drawn through a sorbentsampling tube containing XAD-4 resin to adsorb the nicotineand 3-EP present.4.2 The XAD-4 sorbent tube contents are transferred to a2-mL autosampler vial, and t
12、he nicotine and 3-EP are desorbedwith ethyl acetate containing 0.01 % triethylamine and aknown quantity of quinoline, the internal standard.4.3 An aliquot of the desorbed sample is injected into a gaschromatograph equipped with a thermionic-specific (nitrogen-phosphorus) detector.1This test method i
13、s under the jurisdiction of ASTM Committee D22 on AirQuality and is the direct responsibility of Subcommittee D22.05 on Indoor Air.Current edition approved April 1, 2007. Published June 2007. Originallyapproved in 1990. Last previous edition approved in 2001 as D 5075 - 01.2The boldface numbers in p
14、arentheses refer to a list of references at the end ofthe text.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 websit
15、e.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.4.4 The areas of the resulting nicotine and 3-EP peaks areeach divided by the area of the internal standard peak andcompared with area ratios obtained from the injection ofstandards.5
16、. Significance and Use5.1 In order to estimate ETS concentrations, there needs tobe a marker or tracer for ETS that is unique or highly specificto tobacco smoke, in sufficient concentrations in air to bemeasured easily at realistic smoking rates, and in constantproportion to the other components of
17、ETS for a variety oftobacco blends and environmental conditions. Nicotine and3-ethenylpyridine have been used as tracers of the vapor phaseof ETS. Nicotine is the major alkaloid of tobacco and a majorconstituent of ETS. The determination of nicotine concentra-tion has often been used to estimate the
18、 concentration of ETS;however, due to its unpredictable decay kinetics, nicotine maynot be an ideal tracer. Because nicotine readily adsorbs tobuilding materials and room furnishings and is depleted fromETS at a rate faster than most other components, some havesuggested that nicotine concentrations
19、underestimate ETSconcentrations. Although this is true in many environmentsduring the generation of smoke, the converse is true inenvironments with a recent past history of smoking. Theadsorbed nicotine slowly desorbs over time, resulting in anoverestimation of ETS concentrations.Thus, measured conc
20、en-trations of nicotine precisely assess only airborne nicotine andindicate only that smoking has taken place; they do notnecessarily indicate the presence, and certainly not the concen-trations, of other ETS constituents. 3-Ethenylpyridine, on theother hand, has been shown to track exactly the vapo
21、r phase ofETS as measured by CO and FID response (3). It is for thesereasons that 3-ethenylpyridine may be a better tracer of ETS(1,4,5). The ETS at high concentrations is known to beannoying and irritating to individuals, and concerns overpotential health effects have also been expressed. There is
22、adefinite need to have reliable methods for the estimation ofETS levels in order to evaluate its effect. The NIOSH haspreviously set a threshold limit value (TLV) for nicotine in theworkplace of 0.5 mg/m3.5.2 Studies show that more than 90 % of nicotine in indoorair is found in the vapor phase (6,7)
23、. The described test methodcollects vapor-phase nicotine quantitatively. Early studies onfreshly generated ETS indicated that some but not all of theparticulate phase was trapped on the XAD-4 resin (7). A morerecent investigation of the trapping of particulate materials bysorbent beds suggests that
24、the trapping of the particles fromindoor air may be nearly quantitative (8). 3-Ethenylpyridine isfound exclusively in the vapor phase.5.3 Nicotine concentrations typically range from ND (notdetected) to 70 g/m3in various indoor environments withvalues usually at the lower end of this range (9). Beca
25、use suchlow concentrations of nicotine are often encountered, sophis-ticated analytical procedures and equipment are required forquantifying nicotine in indoor air. Other methods for thedetermination of nicotine in indoor air have also been reported(6,10,11,12). 3-Ethenylpyridine concentrations typi
26、cally areabout one third the concentrations of nicotine in real-worldenvironments (13).6. Interferences6.1 Use of packed GC columns may result in readings lowerthan expected because nicotine can adsorb onto undeactivatedglass, metal, and solid support particles. Fused silica capillarycolumns and the
27、 modified extraction solvent prescribed herecan circumvent this problem.6.2 Quinoline (internal standard) is present in ETS at aconcentration approximately 1 % of that for nicotine and iscollected by the XAD-4 resin. If 10 g nicotine is collected onthe resin, there will be sufficient quinoline prese
28、nt to cause adetectable bias in results (approximately 1 %). (For example,this quantity of nicotine would be collected if a nicotineconcentration of 167 g/m3was sampled at 1 L/min for 1 h.) Inthese cases, one of the following alternative procedures shouldbe followed:6.2.1 Quantitatively dilute the s
29、ample with the same modi-fied solvent containing internal standard (described in 11.2)used to extract the original sample; that is, decrease the amountof quinoline (and also nicotine) present in the sample whilekeeping the quinoline concentration in the solvent constant. Toprevent significant interf
30、erence, the nicotine concentration inthe most concentrated sample should be less than or equal tothe quinoline concentration in the solvent.6.2.2 Use an alternate internal standard N8-ethylnornico-tine is recommended (14).7. Apparatus7.1 Sample Collection:7.1.1 XAD-4 Sorbent TubeGlass tube with both
31、 endsflame-sealed, approximately 7 cm long with 6-mm outsidediameter and 4-mm inside diameter, containing one section of120 mg of 20/40 mesh XAD-4 resin. A glass wool plug islocated at the front end (inlet) and back end of the tube. Theglass wool plug at the inlet end of the tube is held in place wi
32、tha metal lockspring.7.1.2 Tube Holder, with clip attachment for attaching tubeto clothing or objects.7.1.3 Tube Breaker, to break sealed ends from sampletubes.7.1.4 NIOSH-approved Plastic Caps, for capping tubes aftersampling.7.1.5 Barometer and Thermometer, for taking pressure andtemperature readi
33、ngs at the sampling site (optional).7.1.6 Bubble Flowmeter, for sample pump calibration.7.1.7 Personal Sampling Pump, portable constant-flowsampling pump calibrated for the flow rate desired (up to 1.5L/min).7.2 Analytical System:7.2.1 Gas Chromatograph, with a nitrogen-phosphorus(thermionic) detect
34、or and autosampler.7.2.2 GC ColumnA 30-m by 0.32-mm inside diameterfused silica capillary column, coated with a 1.0-m film of 5 %phenyl methylpolysiloxane (DB-5).7.2.3 Chromatography Data Acquisition System, for mea-suring peak areas electronically.7.2.4 Sample Containers, borosilicate glass autosam
35、plervials, 2-mL capacity, with PTFE-lined septum closures.7.2.5 Dispensing Pipets, 1.25-mL.D 5075 01 (2007)27.2.6 Triangular File, for scoring and breaking open sampletubes.7.2.7 Forceps, for assisting transfer of sorbent tube contentsfrom tube to autosampler vial.7.2.8 Glass Wool Removal Tool, for
36、assisting transfer ofsorbent tube contents from tube to autosampler vial.7.2.9 Wrist-action Shaking Device, for solvent extraction.8. Reagents and Materials8.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents conform to
37、the specifications of the Committee onAnalytical Reagents of the American Chemical Society wheresuch specifications are available. Other grades may be used,provided it is first ascertained that the reagent is of sufficientlyhigh purity to permit its use without lessening the accuracy ofthe determina
38、tion.8.2 Ethyl Acetate, chromatographic quality.8.3 Quinoline (internal standard), 99+ %.8.4 Triethylamine, 99+ %.8.5 Nicotine, 99+ %.8.6 4-Ethenylpyridine (4-EP), 95 %, commercially avail-able isomer of 3-ethenylpyridine.8.7 Helium Cylinders, for carrier or detector makeup gas, orboth, 99.995 % gra
39、de.8.8 Hydrogen Cylinders, for detector gas, 99.995 % grade.8.9 Air, for detector gas (5 % of tube contents found inbackup resin section) can occur after collecting approximately300 g nicotine in a single XAD-4 tube. A shorter samplingtime is necessary if sample concentration and duration ofsampling
40、 suggest a breakthrough occurrence.TABLE 1 Summary of Gas Chromatograph ConditionsTemperaturesInjector 225COvenInitial temperature 50CHold time 1 minProgram Step 1Rate 10C/minFinal temperature 215CHold time 0 minProgram Step 2Rate 20C/minFinal temperature 295CHold time 1 minDetector 300CGas flowsHe,
41、 carrier 4 mL/min (15 psig)H2, detector 3 mL/minAir, detector 75 mL/minHe, makeup 15 mL/minRetention times3-EP, 4-EP 8.5 minQuinoline 13.5 minNicotine 15 minD 5075 01 (2007)311. Procedure11.1 XAD-4 Sorbent Tube AnalysisThe analytical proce-dure for nicotine and 3-EP is performed by extracting theXAD
42、-4 resin with modified ethyl acetate solvent followed byGC/NPD analysis. Ethyl acetate extracts nicotine and 3-EPfrom the XAD-4 resin beads, but the solvent is modified with0.01 % v/v triethylamine to prevent any adsorption of nicotineon the glass walls of the vials (14). The solvent also containsth
43、e internal standard quinoline, at a concentration of approxi-mately 8 g/mL. Solvent henceforth will refer to this modifiedethyl acetate solvent.11.2 Preparation of Modified Ethyl Acetate Solvent:11.2.1 To a previously unopened 4-L bottle of ethyl acetate,add 0.5 mL triethylamine and 30 L quinoline.
44、Shake vigor-ously to mix.11.2.1.1 To a separate freshly opened 4-L bottle of ethylacetate, add 0.5 mL triethylamine; shake vigorously to mix.Use modified solvent containing no internal standard onlywhen specifically called for in the procedure.11.2.2 Store the modified ethyl acetate solvent containi
45、ngquinoline at 4C or less when not in use. Allow the solvent toreach room temperature before using it to prepare standardsolutions or samples.11.2.3 Prepare fresh modified solvent as needed. Deteriora-tion of the modified solvent has not been observed, and nodefinitive time interval has been establi
46、shed for its replace-ment; however, storage and use for more than 12 months is notrecommended.NOTE 3In order to keep the amount of internal standard constant forboth standards and samples, the same batch of modified solvent that isused to prepare standard solutions must be used to extract samples.Th
47、erefore, whenever a new batch of modified solvent is prepared, a newbatch of standard solutions must also be prepared. Otherwise, if standardsand samples contain different amounts of internal standard, the exactamounts in both solutions must be known precisely, and the regression andequations in 11.
48、6.1 and 12.1 must be modified to reflect the differentinternal standard concentrations.11.3 Preparation of Standard Solutions:11.3.1 Clean all volumetric flasks and screw-cap jars usedfor the preparation and storage of standard solutions withdetergent, thoroughly rinse with tap water followed by dis
49、tilledwater followed by ethyl acetate containing only 0.01 % triethy-lamine with no quinoline, and allow to air dry.11.3.2 Prepare a primary standard of nicotine containing400 g/mL by weighing 100 mg of nicotine directly into a250-mL volumetric flask, diluting to volume with solvent, andshaking to mix. Prepare a primary standard of 4-EP containing500 g/mL by weighing 100 mg of 4-EP into a 200-mLvolumetric flask, diluting to volume with solvent, and shakingto mix. Prepare a secondary standard containing 4.8 g/mLnicotine and 2.0 g/mL 4-EP by trans
