1、Designation: D 4413 98 (Reapproved 2003)Standard Test Method forDetermination of Ethylene Oxide in Workplace Atmospheres(Charcoal Tube Methodology)1This standard is issued under the fixed designation D 4413; the number immediately following the designation indicates the year oforiginal adoption or,
2、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 reapproval.1. Scope1.1 This test method describes the determination of ethyleneoxide (oxirane) in workp
3、lace atmospheres using charcoal tubemethodology.1.2 This test method is compatible with low flow ratepersonal sampling equipment: 10 to 200 mL/min. It can beused for personnel or area monitoring.1.3 The sampling method develops a time-weighted average(TWA) sample and can be used to determine short-t
4、ermexcursions (STE).1.4 The applicable concentration range for the TWA sampleis from 0.3 to 20 ppm(v).1.5 The applicable concentration range for the STE sampleranges from 1 to 1000 ppm(v).1.6 The values stated in SI units shall be regarded as thestandard. Inch-pound units are provided for informatio
5、n only.1.7 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 health practices and determine the applica-bility of regulatory limitations prior to use. (For mo
6、re specificsafety precautionary statements see Section 9 and 10.2.3 and11.1.3.)2. Referenced Documents2.1 ASTM Standards:2D 1356 Terminology Relating to Sampling and Analysis ofAtmospheresD 3686 Practice for Sampling Atmospheres to Collect Or-ganic Compound Vapors (Activated Charcoal Tube Ad-sorptio
7、n Method)E 355 Practice for Gas Chromatography Terms and Rela-tionships3. Terminology3.1 Definitions:3.1.1 For definitions of terms relating to this test method,refer to Terminology D 1356 and Practice E 355.4. Summary of Test Method4.1 Aknown volume of sample air is passed through a glasstube packe
8、d with activated charcoal. Ethylene oxide is re-moved from the air stream by adsorption on the charcoal.4.2 A two-section tube containing a front and a backupsection of adsorbent is used to collect the sample. The backupsection adsorbs vapors that penetrate the front section and isused to determine
9、if the collection capacity of the tube has beenexceeded.4.3 The ethylene oxide is desorbed with carbon disulfideand analyzed with a gas chromatograph equipped with a flameionization detector.4.4 Quantitation is based on the comparison of peak heightsor peak areas of the samples with those of standar
10、d solutions.4.5 Recovery factors are determined by the same techniquesused for the atmospheric analysis applied to known standards.5. Significance and Use5.1 Ethylene oxide is a major raw material used in themanufacture of numerous other bulk industrial chemicals aswell as a sterilizing agent.5.2 Th
11、is test method provides a means of evaluating expo-sure to ethylene oxide in the working environment at thepresently recommended exposure guidelines:5.2.1 OSHA PEL 1 ppm(v) 8-hr TWA.35.2.2 ACGIH TLV 1 ppm(v).46. Interferences6.1 Organic components that have the same or nearly thesame retention time
12、as ethylene oxide during gas chromato-graphic analysis will interfere.1This test method is under the jurisdiction of ASTM Committee D22 on AirQuality and is the direct responsibility of Subcommittee D22.04 on WorkplaceAtmospheres.Current edition approved April 10, 2003. Published June 2003. Original
13、lyapproved in 1985. Last previous edition approved in 1998 as D 4413 98e1.2For 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
14、ASTM website.3Title 29, Code of Federal Regulation (Section 1910.1047), U.S. Department ofLabor, revised 49FR 25797 June 22, 1984.4“Threshold Limit Values for Chemical Substances and Physical Agents in theWorkroom Environment with Intended Changes for 1997,”American Conference ofGovernmental Industr
15、ial Hygienists, P.O. Box 1937, Cincinnati, OH 45201.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.6.2 Other volatile organic compounds in the area wheresamples are taken should be considered.6.3 Such interferences can be minimized
16、by proper selectionof gas chromatographic columns. A mass spectrometric detec-tor can be used to confirm the presence of ethylene oxide.6.4 Water mists, high humidity, elevated temperatures, andhigh concentrations of other compounds affect adsorptionefficiencies by reducing the adsorptive capacity o
17、f the charcoalfor ethylene oxide.7. Apparatus7.1 Charcoal Sampling Tube:7.1.1 DescriptionA sampling tube consists of a length ofglass tubing containing two sections of activated charcoal thatare held in place by nonadsorbent material and sealed at eachend. The front section is retained by a plug of
18、glass wool andthe back section is retained by a second 2-mm portion ofurethane foam or other retainer, such as glass wool. The twocharcoal sections are separated by a 2-mm portion of urethanefoam. The ends of the tube are flame-sealed (refer to PracticeD 3686). The back section of the sample tube ad
19、sorbs vaporsthat penetrate the front section and is used to determine if thecollection capacity of the tube has been exceeded. Instead of asingle tube, two tubes in series may be used (see 11.1.12).7.1.2 Sampling tubes containing approximately1gofactivated charcoal are used for sampling ethylene oxi
20、de. Twotypes of sampling tubes have been found suitable.5,67.1.2.1 A sampling tube consisting of a glass tube 110-mmlong, 10 mm in outside diameter, 8 mm in inside diameter andcontaining two sections of activated charcoal (Pittsburgh Co-conut Base (PCB) 20/40 mesh),5800 and 200 mg, separated bya 2-m
21、m section of urethane foam. This tube is capable ofsampling 3 to 20 L of air, depending on the environmentalconditions, with no or with minimal breakthrough of ethyleneoxide into the back section (1,2).77.1.2.2 A sampling tube, consisting of a glass tube 150-mmlong, 8 mm in outside diameter, 6 mm in
22、 inside diameter andcontaining two sections of activated charcoal (Columbia JXC,20/48 mesh),6700 and 390 mg, separated by a 2-mm section ofurethane foam. This tube is capable of sampling 3 to 8 L of air,depending on the environmental conditions, with no or withminimal breakthrough of ethylene oxide
23、into the back section(3).7.1.2.3 When sampling under conditions of high humidity,elevated temperatures, or in the presence of high concentra-tions of other compounds, the lesser volume in 7.1.2.1 and7.1.2.2 should be used.7.1.3 The pressure drop across the charcoal tube should beno greater than 3.3
24、kPa 25 mm Hg at a flow rate of 1000mL/min.7.1.4 Glass tubes shall be held in suitable protective holdersto prevent breakage during sampling and to protect workers.7.1.5 Polyethylene end caps are used to reseal the charcoaltubes. Caps must fit tightly to prevent leakage.7.2 Syringes:7.2.1 Gas-Tight S
25、yringe, 1 and 2-mL capacity with a lowdead-volume needle.7.2.2 Microlitre Syringes, 10, 100, and 1000-L or otherconvenient sizes for making standards.7.3 Vials, glass, 4, 8, and 12 mL 1, 2, and 3 dram fordesorbing samples and holding standards, polyethylene orTFE-fluorocarbon-lined screw caps and se
26、ptum-valve caps.7.4 Styrene Foam Shipping Container, seamless polystyrenefoam container with a minimum wall thickness of 35 mm 138in. and approximately 12-L13-ft3 capacity. Other containers,such as vacuum bottles, may be suitable as long as they canmaintain the samples at dry-ice temperatures during
27、 shipping.7.5 Mechanical Shaker, or vibrator that will vigorouslyagitate the desorbing sample.7.6 Sampling Equipment:7.6.1 Any pump whose flow rate can be accurately deter-mined and set at the desired sampling rate is suitable.7.6.2 As a guideline, suitable pumps are those having stablelow flow rate
28、s, 610 % of the set flow rate, within the range of10 to 100 mL/min, for sampling periods of up to 8 h. Flowratesup to 200 mL/min can be used for STE (15 min) monitoring.7.6.3 All sampling pumps shall be carefully calibrated witha charcoal tube in the proper sampling position (see Fig. A2.1of Practic
29、e D 3686). The accuracy of determining the total airvolume sampled should be 100 6 5%.7.6.4 Tubing, rubber or plastic, 6-mm 14-in. bore, about90-cm 3-ft long equipped with a spring clip to hold the tubingand charcoal tube in place on workers lapel area.7.6.4.1 Caution: Sampling tubes shall not be us
30、ed withplastic or rubber tubing upstream of the charcoal. Absorptionby the tubing may introduce sampling errors.7.7 Gas Chromatograph:7.7.1 Gas chromatographs that employ either a flame ion-ization detector or a detector whose specifications are equiva-lent in sensitivity and selectivity should be u
31、sed. Detectorsshall be capable of determining ethylene oxide concentrationsof interest with a signal to noise ratio of at least 10 to 1.Suitable detectors are capable of detecting approximately1 3 1010g of ethylene oxide per injection. For example, 3.2g of ethylene oxide will be collected from a 6-L
32、 air samplecontaining 0.3-ppm ethylene oxide and the use of 5 mL ofdesorption solvent will result in a concentration of 0.65 g ofethylene oxide per millilitre of CS2.7.7.2 A gas chromatographic column capable of separatingethylene oxide from other components is required.Anumber ofsuitable columns ha
33、ve been discussed in the literature (1, 2, 3,4). Table 1 lists columns and the chromatographic conditionsused for ethylene oxide determination. Table 2 lists theretention lines of some potential interferences for three chro-matographic columns. Column suitability shall be verified by5Activated cocon
34、ut-shell charcoal (Pittsburgh Coconut Base, 20/40 mesh) hasbeen found to have adequate adsorption capacity and recovery properties. Preparedtubes containing activated coconut-shell charcoal (800 mg/200 mg) are availablefrom a number of sources.6Columbia activated (pelletized) carbon, grade-JXC (20/4
35、8 mesh) is no longeravailable. The sole supplier of JXC carbon (700 mg/390 mg) known to thecommittee at this time is SKC, Eighty Four, PA. If you are aware of alternatesuppliers, please provide this information to ASTM Headquarters. Your commentswill receive careful consideration at a meeting of the
36、 responsible technicalcommittee, which you may attend.7The boldface numbers in parentheses refer to the list of references at the end ofthis test method.D 4413 98 (2003)2testing two or more columns of dissimilar packings to mini-mize the possibility of interferences. If the chromatographicpeak for e
37、thylene oxide overlaps the peak for other componentsby no greater than 5 %, the separation is considered to besatisfactory.7.7.3 Gas chromatographic operating conditions for theinstrument being used should be optimized so that the separa-tion required for a successful analysis can be obtained in are
38、asonable time.8. Reagents8.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise noted, all reagents shallconform to the specifications of the Committee on AnalyticalReagents of the American Chemical Society, where suchspecifications are available.8Other reagents ma
39、y be usedprovided it can be demonstrated that they are of sufficientlyhigh purity to permit their use without decreasing the accuracyof determination.8.2 Carbon Disulfide (CS2), spectroquality, should containno major interferences at the retention time of ethylene oxide.8.3 Ethylene Oxide, commercia
40、lly available in lecturebottles at 99 % purity or better.9. Safety Precautions9.1 Carbon disulfide vapors are toxic and highly flammable.Usage should be restricted to a well-ventilated hood.9.2 Small waste quantities of carbon disulfide shall bedisposed of only in accordance with local regulations a
41、ndaccepted practices.9.3 Ethylene oxide may cause irritation and necrosis of theeyes, blistering, edema, and necrosis of the skin.9.3.1 Caution: Ethylene oxide is toxic, highly flammable,and should be handled under a hood.9.4 Avoid inhalation of, or skin contact with, carbon disul-fide, carbon disul
42、fide solutions of ethylene oxide, and ethyleneoxide gas.10. Calibration10.1 Pump Calibration:10.1.1 Calibrate the sample pump flow in accordance withPractice D 3686, Annex A2.10.1.2 Calibrate the flow rate of the pump from 10 to 100mL/min for TWA sampling and 100 to 200 mL/min for shortterm excursio
43、ns (STE) sampling depending on the duration ofthe sample and the volume of the sample needed (see 11.1).10.2 Gas Chromatograph Calibration:10.2.1 Prepare calibration standards containing microgramsof ethylene oxide per mL of carbon disulfide over the range ofinterest.10.2.2 Pipet 10 mL of carbon dis
44、ulfide into each of two12-mL 3-dram vials and seal with septum-valve caps. Placethe vials in dry ice or a wet-ice bath to cool.10.2.3 Adapt a valve on the ethylene oxide cylinder with a0.25-in. Swagelok tubing nut which contains a chromato-graphic septum. Caution: Ethylene oxide is toxic, highlyflam
45、mable, and therefore should be handled under a hood.10.2.4 Place the ethylene oxide cylinder in the hood andinsert a hypodermic needle through the septum on the cylinder.Open the valve and allow the ethylene oxide gas to ventthrough the needle for about 10 s to purge the air from thesystem. Remove t
46、he needle.10.2.5 Using a 1.0 or 2.0-mL gas syringe (equipped with alow-volume needle), insert the needle through the septum on8Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on testing of reagents not listedby theAmerican Chemic
47、al Society, see Analar Standards for Laboratory Chemicals,BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and NationalFormulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.TABLE 1 Gas Chromatographic Columns for Determination of Ethylene OxideColumn Length DiameterCa
48、rrier Flow Temperature C Ethylene OxideRetention Time(mL/min) Column Detector (min) Ref(1) Chromosorb 102 (60/80 mesh) 2 m6.6 ft3.17 mm18 in.30 140 250 1.4 (2)(2) Phenapiwax 12 % 6.1 m20 ft3.17 mm18 in.20 80 300 3.8 (2)(3) Porapak QS, (100/200 mesh) 2.0 m6.6 ft2mm0/078 in.30 140 250 1.5 (5)TABLE 2 R
49、etention Time for Ethylene Oxide and PossibleInterfering CompoundsCompoundRetention Time (min)Chromosorb102PhenapiwaxPorapakQSFreon120.88 2.2 1.12Methylchloride0.99 2.8 1.01Vinylchloride1.23 2.9 1.48Freon113.09 3.7 3.69Ethylchloride1.95 3.8 2.22Ethyleneoxide1.36 3.8 1.53Methylbromide1.67 3.9 1.76Propyleneoxide1.88 4.9 2.42Vinylidenechloride3.44 5.0 4.07Carbondisulfide2.89 7.0 3.08Butyleneoxide6.10 8.3 7.91Acrylonitrile 2.74 9.0 3.32Benzene 3.26 14.8 11.07D 4413 98 (2003)3the cylinder and withdraw ethylene oxide into the syringe.Flush the syrin
