ASTM D4413-98e1
(Test Method)Standard Test Method for Determination of Ethylene Oxide in Workplace Atmospheres (Charcoal Tube Methodology)
Standard Test Method for Determination of Ethylene Oxide in Workplace Atmospheres (Charcoal Tube Methodology)
SCOPE
1.1 This test method describes the determination of ethylene oxide (oxirane) in workplace atmospheres using charcoal tube methodology.
1.2 This procedure is compatible with low flow rate personal sampling equipment: 10 to 200 mL/min. It can be used for personnel or area monitoring.
1.3 The sampling method develops a time-weighted average (TWA) sample and can be used to determine short-term excursions (STE).
1.4 The applicable concentration range for the TWA sample is from 0.3 to 20 ppm (v/v).
1.5 The applicable concentration range for the STE sample ranges from 1 to 1000 ppm (v/v).
1.6 The values stated in SI units shall be regarded as the standard. Inch-pound units are provided for information only.
1.7 This standard does not purport to address all of the safety problems, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. (For more specific safety precautionary statements see Section 9, 10.2.3, and 11.1.3.)
General Information
Relations
Standards Content (Sample)
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Designation: D 4413 – 98
Standard Test Method for
Determination of Ethylene Oxide in Workplace Atmospheres
(Charcoal Tube Methodology)
This standard is issued under the fixed designation D 4413; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
e NOTE—Footnote 7 was corrected editorially in March 1999.
1. Scope 3. Terminology
1.1 This test method describes the determination of ethylene 3.1 Definitions:
oxide (oxirane) in workplace atmospheres using charcoal tube 3.1.1 For definitions of terms relating to this test method,
methodology. refer to Terminology D 1356 and Practice E 355.
1.2 This test method is compatible with low flow rate
4. Summary of Test Method
personal sampling equipment: 10 to 200 mL/min. It can be
used for personnel or area monitoring. 4.1 A known volume of sample air is passed through a glass
tube packed with activated charcoal. Ethylene oxide is re-
1.3 The sampling method develops a time-weighted average
(TWA) sample and can be used to determine short-term moved from the air stream by adsorption on the charcoal.
4.2 A two-section tube containing a front and a backup
excursions (STE).
1.4 The applicable concentration range for the TWA sample section of adsorbent is used to collect the sample. The backup
section adsorbs vapors that penetrate the front section and is
is from 0.3 to 20 ppm(v).
1.5 The applicable concentration range for the STE sample used to determine if the collection capacity of the tube has been
exceeded.
ranges from 1 to 1000 ppm(v).
1.6 The values stated in SI units shall be regarded as the 4.3 The ethylene oxide is desorbed with carbon disulfide
and analyzed with a gas chromatograph equipped with a flame
standard. Inch-pound units are provided for information only.
1.7 This standard does not purport to address all of the ionization detector.
4.4 Quantitation is based on the comparison of peak heights
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- or peak areas of the samples with those of standard solutions.
4.5 Recovery factors are determined by the same techniques
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. (For more specific used for the atmospheric analysis applied to known standards.
safety precautionary statements see Section 9 and 10.2.3 and
5. Significance and Use
11.1.3.)
5.1 Ethylene oxide is a major raw material used in the
2. Referenced Documents
manufacture of numerous other bulk industrial chemicals as
well as a sterilizing agent.
2.1 ASTM Standards:
D 1356 Terminology Relating to Sampling and Analysis of 5.2 This test method provides a means of evaluating expo-
sure to ethylene oxide in the working environment at the
Atmospheres
D 3686 Practice for Sampling Atmospheres to Collect Or- presently recommended exposure guidelines:
5.2.1 OSHA PEL 1 ppm(v) 8-hr TWA.
ganic Compound Vapors (Activated Charcoal Tube Ad-
sorption Method) 5.2.2 ACGIH TLV 1 ppm(v).
E 355 Practice for Gas Chromatography Terms and Rela-
6. Interferences
tionships
6.1 Organic components that have the same or nearly the
same retention time as ethylene oxide during gas chromato-
graphic analysis will interfere.
This test method is under the jurisdiction of ASTM Committee D-22 on
Sampling and Analysis of Atmospheresand is the direct responsibility of Subcom-
mittee D22.04on Workplace Atmospheres.
Title 29, Code of Federal Regulation (Section 1910.1047), U.S. Department of
Current edition approved Oct. 10, 1998. Published December 1998. Originally
Labor, revised 49FR 25797 June 22, 1984.
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published as D 4413 – 85. Last previous edition D 4413 – 88 (1993) .
“Threshold Limit Values for Chemical Substances and Physical Agents in the
Annual Book of ASTM Standards, Vol 11.03.
Workroom Environment with Intended Changes for 1997,” American Conference of
Annual Book of ASTM Standards, Vol 14.02.
Governmental Industrial Hygienists, P.O. Box 1937, Cincinnati, OH 45201.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
D 4413
6.2 Other volatile organic compounds in the area where 7.1.3 The pressure drop across the charcoal tube should be
samples are taken should be considered. no greater than 3.3 kPa (25 mm Hg) at a flow rate of 1000
6.3 Such interferences can be minimized by proper selection mL/min.
of gas chromatographic columns. A mass spectrometric detec-
7.1.4 Glass tubes shall be held in suitable protective holders
tor can be used to confirm the presence of ethylene oxide. to prevent breakage during sampling and to protect workers.
6.4 Water mists, high humidity, elevated temperatures, and
7.1.5 Polyethylene end caps are used to reseal the charcoal
high concentrations of other compounds affect adsorption
tubes. Caps must fit tightly to prevent leakage.
efficiencies by reducing the adsorptive capacity of the charcoal
7.2 Syringes:
for ethylene oxide.
7.2.1 Gas-Tight Syringe, 1 and 2-mL capacity with a low
dead-volume needle.
7. Apparatus
7.2.2 Microlitre Syringes, 10, 100, and 1000-μL or other
7.1 Charcoal Sampling Tube:
convenient sizes for making standards.
7.1.1 Description—A sampling tube consists of a length of
7.3 Vials, glass, 4, 8, and 12 mL (1, 2, and 3 dram) for
glass tubing containing two sections of activated charcoal that
desorbing samples and holding standards, polyethylene or
are held in place by nonadsorbent material and sealed at each
TFE-fluorocarbon-lined screw caps and septum-valve caps.
end. The front section is retained by a plug of glass wool and
7.4 Styrene Foam Shipping Container, seamless polystyrene
the back section is retained by a second 2-mm portion of 3
foam container with a minimum wall thickness of 35 mm (1 ⁄8
urethane foam or other retainer, such as glass wool. The two 1
in.) and approximately 12-L ( ⁄3-ft ) capacity. Other containers,
charcoal sections are separated by a 2-mm portion of urethane
such as vacuum bottles, may be suitable as long as they can
foam. The ends of the tube are flame-sealed (refer to Practice
maintain the samples at dry-ice temperatures during shipping.
D 3686). The back section of the sample tube adsorbs vapors
7.5 Mechanical Shaker, or vibrator that will vigorously
that penetrate the front section and is used to determine if the
agitate the desorbing sample.
collection capacity of the tube has been exceeded. Instead of a
7.6 Sampling Equipment:
single tube, two tubes in series may be used (see 11.1.12).
7.6.1 Any pump whose flow rate can be accurately deter-
7.1.2 Sampling tubes containing approximately1gof
mined and set at the desired sampling rate is suitable.
activated charcoal are used for sampling ethylene oxide. Two
7.6.2 As a guideline, suitable pumps are those having stable
,
6 7
types of sampling tubes have been found suitable.
low flow rates, 610 % of the set flow rate, within the range of
7.1.2.1 A sampling tube consisting of a glass tube 110-mm
10 to 100 mL/min, for sampling periods of up to 8 h. Flowrates
long, 10 mm in outside diameter, 8 mm in inside diameter and
up to 200 mL/min can be used for STE (15 min) monitoring.
containing two sections of activated charcoal (Pittsburgh Co-
7.6.3 All sampling pumps shall be carefully calibrated with
conut Base (PCB) 20/40 mesh), 800 and 200 mg, separated by
a charcoal tube in the proper sampling position (see Fig. A2.1
a 2-mm section of urethane foam. This tube is capable of
of Practice D 3686). The accuracy of determining the total air
sampling 3 to 20 L of air, depending on the environmental
volume sampled should be 100 65%.
conditions, with no or with minimal breakthrough of ethylene
7.6.4 Tubing, rubber or plastic, 6-mm ( ⁄4-in.) bore, about
oxide into the back section (1,2).
90-cm (3-ft) long equipped with a spring clip to hold the tubing
7.1.2.2 A sampling tube, consisting of a glass tube 150-mm
and charcoal tube in place on worker’s lapel area.
long, 8 mm in outside diameter, 6 mm in inside diameter and
7.6.4.1 Caution: Sampling tubes shall not be used with
containing two sections of activated charcoal (Columbia JXC,
plastic or rubber tubing upstream of the charcoal. Absorption
20/48 mesh), 700 and 390 mg, separated by a 2-mm section of
by the tubing may introduce sampling errors.
urethane foam. This tube is capable of sampling 3 to 8 L of air,
7.7 Gas Chromatograph:
depending on the environmental conditions, with no or with
7.7.1 Gas chromatographs that employ either a flame ion-
minimal breakthrough of ethylene oxide into the back section
ization detector or a detector whose specifications are equiva-
(3).
lent in sensitivity and selectivity should be used. Detectors
7.1.2.3 When sampling under conditions of high humidity,
shall be capable of determining ethylene oxide concentrations
elevated temperatures, or in the presence of high concentra-
of interest with a signal to noise ratio of at least 10 to 1.
tions of other compounds, the lesser volume in 7.1.2.1 and
Suitable detectors are capable of detecting approximately
7.1.2.2 should be used.
−10
1 3 10 g of ethylene oxide per injection. For example, 3.2
μg of ethylene oxide will be collected from a 6-L air sample
containing 0.3-ppm ethylene oxide and the use of 5 mL of
Activated coconut-shell charcoal (Pittsburgh Coconut Base, 20/40 mesh) has
desorption solvent will result in a concentration of 0.65 μg of
been found to have adequate adsorption capacity and recovery properties. Prepared
tubes containing activated coconut-shell charcoal (800 mg/200 mg) are available ethylene oxide per millilitre of CS .
from a number of sources.
7.7.2 A gas chromatographic column capable of separating
Columbia activated (pelletized) carbon, grade-JXC (20/48 mesh) is no longer
ethylene oxide from other components is required. A number of
available. The sole supplier of JXC carbon (700 mg/390 mg) known to the
suitable columns have been discussed in the literature (1, 2, 3,
committee at this time is SKC, Eighty Four, PA. If you are aware of alternate
suppliers, please provide this information to ASTM Headquarters. Your comments
4). Table 1 lists columns and the chromatographic conditions
will receive careful consideration at a meeting of the responsible technical
used for ethylene oxide determination. Table 2 lists the
committee, which you may attend.
8 retention lines of some potential interferences for three chro-
The boldface numbers in parentheses refer to the list of references at the end of
this test method. matographic columns. Column suitability shall be verified by
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
D 4413
TABLE 1 Gas Chromatographic Columns for Determination of Ethylene Oxide
Carrier Ethylene Oxide
Temperature °C
Column Length Diameter Flow Retention Time
(mL/min) Column Detector (min) Ref
(1) 2 3.17 30 140 250 1.4 (2)
Chromosorb m mm
102 (6.6 ( ⁄8in.)
(60/80 ft)
mesh)
(2) 6.1 3.17 20 80 300 3.8 (2)
Phenapiwax m mm
12 % (20 ( ⁄8
ft) in.)
(3) 2.0 2 30 140 250 1.5 (5)
Porapak m mm
QS, (6.6 (0/078
(100/200 ft) in.)
mesh)
TABLE 2 Retention Time for Ethylene Oxide and Possible
specifications are available. Other reagents may be used
Interfering Compounds
provided it can be demonstrated that they are of sufficiently
Retention Time (min)
high purity to permit their use without decreasing the accuracy
Compound Chromosorb Porapak
Phenapiwax of determination.
102 QS
Freon 0.88 2.2 1.12 8.2 Carbon Disulfide (CS ), spectroquality, should contain
no major interferences at the retention time of ethylene oxide.
Methyl 0.99 2.8 1.01
8.3 Ethylene Oxide, commercially available in lecture
chloride
bottles at 99 % purity or better.
Vinyl 1.23 2.9 1.48
chloride
Freon 3.09 3.7 3.69 9. Safety Precautions
9.1 Carbon disulfide vapors are toxic and highly flammable.
Ethyl 1.95 3.8 2.22
chloride
Usage should be restricted to a well-ventilated hood.
Ethylene 1.36 3.8 1.53
9.2 Small waste quantities of carbon disulfide shall be
oxide
disposed of only in accordance with local regulations and
Methyl 1.67 3.9 1.76
bromide
accepted practices.
Propylene 1.88 4.9 2.42
9.3 Ethylene oxide may cause irritation and necrosis of the
oxide
eyes, blistering, edema, and necrosis of the skin.
Vinylidene 3.44 5.0 4.07
chloride
9.3.1 Caution: Ethylene oxide is toxic, highly flammable,
Carbon 2.89 7.0 3.08
and should be handled under a hood.
disulfide
9.4 Avoid inhalation of, or skin contact with, carbon disul-
Butylene 6.10 8.3 7.91
oxide
fide, carbon disulfide solutions of ethylene oxide, and ethylene
Acrylonitrile 2.74 9.0 3.32
oxide gas.
Benzene 3.26 14.8 11.07
10. Calibration
10.1 Pump Calibration:
10.1.1 Calibrate the sample pump flow in accordance with
Practice D 3686, Annex A2.
testing two or more columns of dissimilar packings to mini-
10.1.2 Calibrate the flow rate of the pump from 10 to 100
mize the possibility of interferences. If the chromatographic
mL/min for TWA sampling and 100 to 200 mL/min for short
peak for ethylene oxide overlaps the peak for other components
term excursions (STE) sampling depending on the duration of
by no greater than 5 %, the separation is considered to be
the sample and the volume of the sample needed (see 11.1).
satisfactory.
10.2 Gas Chromatograph Calibration:
7.7.3 Gas chromatographic operating conditions for the
10.2.1 Prepare calibration standards containing micrograms
instrument being used should be optimized so that the separa-
of ethylene oxide per mL of carbon disulfide over the range of
tion required for a successful analysis can be obtained in a
interest.
reasonable time.
10.2.2 Pipet 10 mL of carbon disulfide into each of two
12-mL (3-dram) vials and seal with septum-valve caps. Place
8. Reagents
the vials in dry ice or a wet-ice bath to cool.
8.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise noted, all reagents shall Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on testing of reagents not listed
conform to the specifications of the Committee on Analytical
by the American Chemical Society, see Analar Standards for Laboratory Chemicals,
Reagents of the American
...
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