ASTM D4413-98(2009)e1

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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´1
Designation: D4413 − 98(Reapproved 2009)
Standard Test Method for
Determination of Ethylene Oxide in Workplace Atmospheres
(Charcoal Tube Methodology)
This standard is issued under the fixed designation D4413; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
´ NOTE—Editorial changes were made throughout this test method in October 2009.
1. Scope D3686Practice for Sampling Atmospheres to Collect Or-
ganic Compound Vapors (Activated Charcoal Tube Ad-
1.1 Thistestmethoddescribesthedeterminationofethylene
sorption Method)
oxide (oxirane) in workplace atmospheres using charcoal tube
E355PracticeforGasChromatographyTermsandRelation-
sampling methodology. Subsequent analysis is carried out by
ships
gas chromatography.
1.2 This test method is compatible with low flow rate
3. Terminology
personal sampling equipment: 10 to 200 mL/min. It can be
3.1 Definitions:
used for personal or area monitoring.
3.1.1 For definitions of terms relating to this test method,
1.3 The sampling method develops a time-weighted aver-
refer to Terminology D1356 and Practice E355.
aged (TWA) sample and can be used to determine short-term
excursions (STE).
4. Summary of Test Method
1.4 The applicable concentration range for theTWAsample
is from 0.3 to 20 ppm(v). 4.1 Aknownvolumeofsampleairispassedthroughaglass
tube packed with activated charcoal. Ethylene oxide is re-
1.5 The applicable concentration range for the STE sample
moved from the air stream by adsorption on the charcoal.
ranges from 1 to 1000 ppm(v).
1.6 The values stated in SI units shall be regarded as the 4.2 A two-section tube containing a front and a backup
section of adsorbent is used to collect the sample. The backup
standard. Inch-pound units are provided for information only.
section adsorbs vapors that penetrate the front section and is
1.7 This standard does not purport to address all of the
usedtodetermineifthecollectioncapacityofthetubehasbeen
safety concerns, if any, associated with its use. It is the
exceeded.
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
4.3 The ethylene oxide is desorbed with carbon disulfide
bility of regulatory limitations prior to use. (For more specific
and analyzed with a gas chromatograph equipped with a flame
safety precautionary statements see Section 9 and 10.2.3 and
ionization detector.
11.1.3.)
4.4 Quantitationisbasedonthecomparisonofpeakheights
2. Referenced Documents
or peak areas of the samples with those of standard solutions.
2.1 ASTM Standards:
4.5 Recoveryfactorsaredeterminedbythesametechniques
D1356Terminology Relating to Sampling and Analysis of
used for the atmospheric analysis applied to known standards.
Atmospheres
5. Significance and Use
This test method is under the jurisdiction of ASTM Committee D22 on Air
5.1 Ethylene oxide is a major raw material used in the
Qualityand is the direct responsibility of Subcommittee D22.04 on WorkplaceAir
manufacture of numerous other bulk industrial chemicals, and
Quality.
Current edition approved Oct. 1, 2009. Published December 2009. Originally
is also used as a sterilizing agent.
approved in 1985. Last previous edition approved in 2003 as D4413–98(2003).
DOI: 10.1520/D4413-98R09E01.
5.2 This test method provides a means of evaluating expo-
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
sure to ethylene oxide in the working environment. Examples
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
ofrecommendedoccupationalexposurelimits(OELs)include:
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. aU.S.OccupationalSafetyandHealthAdministration(OSHA)
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
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D4413 − 98 (2009)
personal exposure limit (PEL) of 1 ppm(v) (8-hTWA) and an conditions, with no or with minimal breakthrough of ethylene
American Conference of Governmental Industrial Hygienists oxide into the back section (1,2).
(ACGIH) Threshold Limit Value (TLV) of 1 ppm(v). 7.1.2.2 Asampling tube, consisting of a glass tube 150-mm
long, 8 mm in outside diameter, 6 mm in inside diameter and
containing two sections of activated charcoal (for example,
6. Interferences
Columbia JXC, 20/48 mesh), 700 and 390 mg, separated by a
6.1 Organic components that have the same or nearly the
2-mm section of urethane foam. This tube is capable of
same retention time as ethylene oxide during gas chromato-
sampling 3 to 8 L of air, depending on the environmental
graphic analysis will interfere.
conditions, with no or with minimal breakthrough of ethylene
6.2 Other volatile organic compounds in the area where
oxide into the back section (3).
samples are taken should be considered.
7.1.2.3 When sampling under conditions of high humidity,
elevated temperatures, or in the presence of high concentra-
6.3 Suchinterferencescanbeminimizedbyproperselection
tions of other compounds, the lesser volume in 7.1.2.1 and
of gas chromatographic columns.Amass spectrometric detec-
7.1.2.2 should be used.
tor can be used to confirm the presence of ethylene oxide.
7.1.3 The pressure drop across the charcoal tube should be
6.4 Water mists, high humidity, elevated temperatures, and
no greater than 3.3 kPa (25 mm Hg) at a flow rate of 1000
high concentrations of other compounds affect adsorption
mL/min.
efficienciesbyreducingtheadsorptivecapacityofthecharcoal
7.1.4 Glasstubesshallbeheldinsuitableprotectiveholders
for ethylene oxide.
to prevent breakage during sampling and to protect workers.
7.1.5 Polyethylene end caps are used to reseal the charcoal
7. Apparatus
tubes. Caps must fit tightly to prevent leakage.
7.1 Charcoal Sampling Tube:
7.2 Syringes:
7.1.1 Description—A sampling tube consists of a length of
7.2.1 Gas-Tight Syringe, 1 and 2-mL capacity with a low
glass tubing containing two sections of activated charcoal that
dead-volume needle.
are held in place by nonadsorbent material and sealed at each
7.2.2 Microlitre Syringes, 10, 100, and 1000-µL or other
end. The front section is retained by a plug of glass wool and
convenient sizes for making standards.
the back section is retained by a second 2-mm portion of
7.3 Vials, glass, 4, 8, and 12 mL (1, 2, and 3 dram) for
urethane foam or other retainer, such as glass wool. The two
desorbing samples and holding standards, polyethylene or
charcoal sections are separated by a 2-mm portion of urethane
TFE-fluorocarbon-lined screw caps and septum-valve caps.
foam. The ends of the tube are flame-sealed (refer to Practice
D3686). The back section of the sample tube adsorbs vapors
7.4 Styrene Foam Shipping Container,seamlesspolystyrene
that penetrate the front section and is used to determine if the
foam container with a minimum wall thickness of 35 mm (1 ⁄8
collection capacity of the tube has been exceeded. Instead of a
in.)andapproximately12-L( ⁄3-ft )capacity.Othercontainers,
single tube, two tubes in series may be used (see 11.1.12).
such as vacuum bottles, may be suitable as long as they can
7.1.2 Sampling tubes containing approximately1gof
maintain the samples at dry-ice temperatures during shipping.
activated charcoal are used for sampling ethylene oxide. Two
7.5 Mechanical Shaker, or vibrator that will vigorously
5,6
types of sampling tubes have been found suitable.
agitate the desorbing sample.
7.1.2.1 Asampling tube consisting of a glass tube 110-mm
7.6 Sampling Equipment:
long, 10 mm in outside diameter, 8 mm in inside diameter and
7.6.1 Any pump whose flow rate can be accurately deter-
containing two sections of activated charcoal (Pittsburgh Co-
mined and set at the desired sampling rate is suitable.
conutBase(PCB)20/40mesh), 800and200mg,separatedby
7.6.2 Asaguideline,suitablepumpsarethosehavingstable
a 2-mm section of urethane foam. This tube is capable of
low flow rates, 610% of the set flow rate, within the range of
sampling 3 to 20 L of air, depending on the environmental
10to100mL/min,forsamplingperiodsofupto8h.Flowrates
up to 200 mL/min can be used for STE (15 min) monitoring.
7.6.3 All sampling pumps shall be carefully calibrated with
a charcoal tube in the proper sampling position (see Fig.A2.1
of Practice D3686). The accuracy of determining the total air
Title 29, Code of Federal Regulation (Section 1910.1047), U.S. Department of
Labor, revised 49FR 25797 June 22, 1984.
volume sampled should be 100 65%.
American Conference of Governmental Industrial Hygienists, Threshold Limit
7.6.4 Tubing, rubber or plastic, 6-mm ( ⁄4-in.) bore, about
Values for Chemical Substances and Physical Agents & Biological Exposure
90-cm(3-ft)longequippedwithaspringcliptoholdthetubing
Indices, ACGIH, Cincinnati, OH (2009; updated annually).
Activated coconut-shell charcoal (Pittsburgh Coconut Base, 20/40 mesh) has and charcoal tube in place on worker’s lapel area.
been found to have adequate adsorption capacity and recovery properties. Prepared
7.6.4.1 Caution: Sampling tubes shall not be used with
tubes containing activated coconut-shell charcoal (800 mg/200 mg) are available
plastic or rubber tubing upstream of the charcoal. Absorption
from a number of sources.
by the tubing may introduce sampling errors.
Columbia activated (pelletized) carbon, grade-JXC (20/48 mesh) is no longer
available. The sole supplier of JXC carbon (700 mg/390 mg) known to the
committee at this time is SKC, Eighty Four, PA. If you are aware of alternate
suppliers, please provide this information to ASTM International Headquarters.
Your comments will receive careful consideration at a meeting of the responsible Theboldfacenumbersinparenthesesrefertothelistofreferencesattheendof
technical committee, which you may attend. this test method.
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D4413 − 98 (2009)
TABLE 2 Retention Time for Ethylene Oxide and Possible
7.7 Gas Chromatograph:
Interfering Compounds
7.7.1 Gas chromatographs that employ either a flame ion-
Retention Time (min)
ization detector or a detector whose specifications are equiva-
Compound Chromosorb
Phenapiwax Porapak QS
lent in sensitivity and selectivity should be used. Detectors
shall be capable of determining ethylene oxide concentrations
Freon 12 0.88 2.2 1.12
Methyl chloride 0.99 2.8 1.01
of interest with a signal to noise ratio of at least 10 to 1.
Vinyl chloride 1.23 2.9 1.48
Suitable detectors are capable of detecting approximately
Freon 11 3.09 3.7 3.69
−10
1×10 gofethyleneoxideperinjection.Forexample,3.2µg Ethyl chloride 1.95 3.8 2.22
Ethylene oxide 1.36 3.8 1.53
of ethylene oxide will be collected from a 6-L air sample
Methyl bromide 1.67 3.9 1.76
containing 0.3-ppm ethylene oxide and the use of 5 mL of
Propylene oxide 1.88 4.9 2.42
desorption solvent will result in a concentration of 0.65 µg of Vinylidene 3.44 5.0 4.07
chloride
ethylene oxide per millilitre of CS .
Carbon disulfide 2.89 7.0 3.08
7.7.2 A gas chromatographic column capable of separating
Butylene oxide 6.10 8.3 7.91
ethyleneoxidefromothercomponentsisrequired.Anumberof Acrylonitrile 2.74 9.0 3.32
Benzene 3.26 14.8 11.07
suitable columns have been discussed in the literature (1, 2, 3,
4). Table 1 lists columns and the chromatographic conditions
used for ethylene oxide determination. Table 2 lists the
retention lines of some potential interferences for three chro-
9. Safety Precautions
matographic columns. Column suitability shall be verified by
testing two or more columns of dissimilar packings to mini- 9.1 Carbondisulfidevaporsaretoxicandhighlyflammable.
Usage should be restricted to a well-ventilated hood.
mize the possibility of interferences. If the chromatographic
peakforethyleneoxideoverlapsthepeakforothercomponents
9.2 Small waste quantities of carbon disulfide shall be
by no greater than 5%, the separation is considered to be
disposedofonlyinaccordancewithapplicableregulationsand
satisfactory.
accepted practices.
7.7.3 Gas chromatographic operating conditions for the
9.3 Ethylene oxide may cause irritation and necrosis of the
instrument being used should be optimized so that the separa-
eyes, blistering, edema, and necrosis of the skin. (Warning—
tion required for a successful analysis can be obtained in a
Ethylene oxide is toxic, highly flammable, and should be
reasonable time.
handled under a hood.)
8. Reagents
9.4 Avoid inhalation of, or skin contact with, carbon
disulfide, carbon disulfide solutions of ethylene oxide, and
8.1 Purity of Reagents—Reagent grade chemicals shall be
ethylene oxide gas.
used in all tests. Unless otherwise noted, all reagents shall
conform to the specifications of the Committee on Analytical
10. Calibration
Reagents of the American Chemical Society, where such
specifications are available. Other reagents may be used
10.1 Pump Calibration:
provided it can be demonstrated that they are of sufficiently
10.1.1 Calibrate the sample pump flow in accordance with
high purity to permit their use without decreasing the accuracy Practice D3686, Annex A2.
of determination.
10.1.2 Calibrate the flow rate of the pump from 10 to 100
mL/min for TWA sampling and 100 to 200 mL/min for short
8.2 Carbon Disulfide (CS ), spectroquality, should contain
term excursions (STE) sampling depending on the duration of
no major interferences at the retention time of ethylene oxide.
the sample and the volume of the sample needed (see 11.1).
8.3 Ethylene Oxide, commercially available in lecture
10.2 Gas Chromatograph Calibration:
bottles at 99% purity or better.
10.2.1 Prepare calibration standards containing micrograms
of ethylene oxide per mLof carbon disulfide over the range of
interest.
Reagent Chemicals, American Chemical Society Specifications, American
10.2.2 Pipet 10 mL of carbon disulfide into each of two
ChemicalSociety,Washington,DC.Forsuggestionsontestingofreagentsnotlisted
bytheAmericanChemicalSociety,seeAnalarStandardsforLaboratoryChemicals,
12-mL (3-dram) vials and seal with septum-valve caps. Place
BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
the vials in dry ice or a wet-ice bath to cool.
Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
TABLE 1 Gas Chromatographic Columns for Determination of Ethylene Oxide
Carrier Flow Temperature °C Ethylene Oxide
Column Length Diameter Retention Time
(mL/min) Column Detector (min) Ref
(1) Chromosorb 102 (60/80 mesh) 2 m 3.17 mm 30 140 250 1.4 (2)
(6.6 ft) ( ⁄8 in.)
(2) Phenapiwax 12 % 6.1 m 3.17 mm 20 80 300 3.8 (2)
(20 ft) ( ⁄
...