ASTM D4443-19

Standard Test Method for Determining Residual Vinyl Chloride Monomer Content in PPB Range in Vinyl Chloride Homo- and Co-Polymers by Headspace Gas Chromatography

SIGNIFICANCE AND USE
5.1 Vinyl chloride-containing polymers are widely used to package a variety of materials, including foods.  
5.2 Vinyl chloride monomer has been shown to be a human carcinogen. Threshold toxicity value has not been established.  
5.3 Plastic manufacturers, food packagers, government agencies, etc. have a need to know the residual vinyl chloride monomer content of vinyl chloride-containing polymers.
SCOPE
1.1 This test method is suitable for determining the residual vinyl chloride monomer (RVM) content of homopolymer and copolymers of vinyl chloride down to a concentration of ∼5 µg/kg (ppb).  
1.2 This test method is applicable to any polymer form, such as resin, compound, film, bottle wall, etc. that can be dissolved in a suitable solvent.  
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use. Specific hazard statements are given in Section 9 and Note 10.  
Note 1: This standard is equivalent to ISO 6401.  
1.4 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

General Information

• Status: Published
• Publication Date: 31-Mar-2019
• ICS: 83.080.20 - Thermoplastic materials
• Technical Committee: D20 - Plastics
• Drafting Committee: D20.70 - Analytical Methods

Relations

• Replaces: ASTM D4443-13 - Standard Test Method for Determining Residual Vinyl Chloride Monomer Content in PPB Range in Vinyl Chloride Homo- and Co-Polymers by Headspace Gas Chromatography
• Effective Date: 01-Apr-2019
• Referred By: ASTM D3749-19 - Standard Test Method for Residual Vinyl Chloride Monomer in Poly(Vinyl Chloride) Resins by Gas Chromatographic Headspace Technique
• Effective Date: 01-Apr-2019

Overview

ASTM D4443-19 is the Standard Test Method for Determining Residual Vinyl Chloride Monomer Content in Parts per Billion (ppb) Range in Vinyl Chloride Homo- and Co-Polymers by Headspace Gas Chromatography. Developed and maintained by ASTM International, this method offers a validated approach to accurately measure residual vinyl chloride monomer (VCM) in a variety of polymer forms, including resins, compounds, films, and bottle walls. Residual VCM is a critical quality and safety concern-especially for materials intended for contact with food-due to its recognized status as a human carcinogen.

Key Topics

• Residual Vinyl Chloride Monomer (VCM) Detection: The method accurately determines VCM content as low as 5 µg/kg (ppb) in both homopolymer and copolymer forms of vinyl chloride.
• Headspace Gas Chromatography: Utilizes advanced analytical chemistry techniques, ensuring high sensitivity and specificity for detecting low levels of VCM.
• Sample Versatility: Suitable for all polymer forms that can be dissolved in a compatible solvent, such as N,N-dimethylacetamide (DMAc).
• Calibration and Accuracy: Employs standard addition or use of standards in nitrogen gas to achieve reliable quantitative results, essential for safety and regulatory compliance.
• Safety Considerations: The method highlights the importance of safety practices due to the hazardous nature of VCM and some solvents used.

Applications

This ASTM standard test method is crucial for a number of stakeholders involved with vinyl chloride-based polymers:

• Plastic Manufacturers: To assess and control residual VCM in PVC and related materials, optimizing manufacturing processes to meet safety and regulatory requirements.
• Food Packaging Industry: Ensuring compliance with stringent food safety guidelines by verifying that residual monomer levels in packaging materials are within acceptable limits.
• Quality Control Laboratories: Routine monitoring of VCM in resin, compounds, films, and finished packaging to guarantee product safety and consistency.
• Regulatory Agencies: Supports compliance verification and enforcement of health and safety standards related to vinyl chloride monomer exposure.
• Environmental and Occupational Health: Assists in risk assessments related to VCM exposure, helping to establish and maintain safe workplace and consumer practices.

The method adds practical value by allowing the quantification of very low levels of VCM, aiding in health risk mitigation and upholding consumer protection standards worldwide.

Related Standards

Adherence to international and national guidelines is often required for harmonization and regulatory acceptance. ASTM D4443-19 references and aligns with:

• ISO 6401: Plastics-Homopolymer and Copolymer Resins of Vinyl Chloride-Determination of Residual Vinyl Chloride Monomer-Gas Chromatographic Method. This equivalency supports consistent global practices.
• OSHA 29 CFR 1910.1017: U.S. Occupational Safety and Health regulations for vinyl chloride exposure, relevant for workplace safety.

Keywords: residual vinyl chloride monomer, VCM determination, PPB, headspace gas chromatography, ASTM D4443-19, PVC polymers, food packaging, quality control, safety testing, ISO 6401.

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By following ASTM D4443-19, organizations ensure robust, sensitive testing for residual VCM, supporting compliance, public health, and product integrity initiatives.

Standards Content (Sample)

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D4443 − 19
Standard Test Method for
Determining Residual Vinyl Chloride Monomer Content in
PPB Range in Vinyl Chloride Homo- and Co-Polymers by
Headspace Gas Chromatography
This standard is issued under the fixed designation D4443; 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.
1. Scope* 3. Terminology
3.1 Abbreviations:
1.1 This test method is suitable for determining the residual
vinyl chloride monomer (RVM) content of homopolymer and
3.1.1 DMAc—N,N-dimethylacetamide.
copolymers of vinyl chloride down to a concentration of ;5
3.1.2 VCM—Vinyl chloride monomer.
µg/kg (ppb).
1.2 Thistestmethodisapplicabletoanypolymerform,such
4. Summary of Test Method
asresin,compound,film,bottlewall,etc.thatcanbedissolved
4.1 Samples of vinyl chloride-containing polymers are dis-
in a suitable solvent.
solved in a suitable solvent in a closed system.
1.3 This standard does not purport to address all of the
4.2 The polymer solution and headspace are equilibrated at
safety concerns, if any, associated with its use. It is the
an elevated temperature.
responsibility of the user of this standard to establish appro-
priate safety, health, and environmental practices and deter-
4.3 Aliquots of headspace gas are injected into a gas
mine the applicability of regulatory limitations prior to use.
chromatograph and the vinyl chloride monomer is separated.
Specific hazard statements are given in Section 9 and Note 10.
The response of vinyl chloride monomer is determined by the
use of one of several suggested detectors.
NOTE 1—This standard is equivalent to ISO 6401.
1.4 This international standard was developed in accor-
4.4 Calibration is accomplished using either (a) vinyl chlo-
dance with internationally recognized principles on standard-
ride monomer in nitrogen gas standards, (b) standard solutions
ization established in the Decision on Principles for the
containingknownamountsofvinylchloridemonomer,or (c)a
Development of International Standards, Guides and Recom-
method of standard addition.
mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
5. Significance and Use
5.1 Vinyl chloride-containing polymers are widely used to
2. Referenced Documents
package a variety of materials, including foods.
2.1 ISO Standard:
5.2 Vinyl chloride monomer has been shown to be a human
ISO6401Plastics—Homopolymer and Copolymer Resins
carcinogen. Threshold toxicity value has not been established.
of Vinyl Chloride—Determination of Residual Vinyl
5.3 Plastic manufacturers, food packagers, government
Chloride Monomer—Gas Chromatographic Method
agencies, etc. have a need to know the residual vinyl chloride
2.2 OSHA Standard:
3 monomer content of vinyl chloride-containing polymers.
29 CFR 1919.1017Vinyl Chloride
6. Interferences
1 6.1 N,N-dimethylacetamideshouldbeanalyzedunderiden-
ThistestmethodisunderthejurisdictionofASTMCommitteeD20onPlastics
and is the direct responsibility of Subcommittee D20.70 on Analytical Methods. ticalconditionstodeterminetheabsenceofinterferencesatthe
Current edition approved April 1, 2019. Published May 2019. Originally
vinyl chloride monomer gas chromatography (GC) retention
approved in 1984. Last previous edition approved in 2013 as D4443–13. DOI:
time.
10.1520/D4443-19.
Available fromAmerican National Standards Institute (ANSI), 25 W. 43rd St.,
6.2 Other solvents, monomers, or compounding aids may
4th Floor, New York, NY 10036, http://www.ansi.org.
cause interference at the vinyl chloride monomer GC retention
Available from Superintendent of Documents, US Government Printing Office,
Washington, DC 20402, https://bookstore.gpo.gov. time.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4443 − 19
7. Apparatus properly functioning hood and septum-sealed sample contain-
ers are recommended.
7.1 Gas Chromatography, equipped with either, a mass
9.1.2 Avoid all contact with heated parts of the gas
spectrometricdetector,flameionizationdetector(FID),aphoto
chromatograph, hot syringes, and sample bottles. Handle all
ionization detector (PID), or a Hall electroconductivity detec-
electrical connections with care.
tor (HED), backflushing valve, and either automatic capability
9.1.3 Once heated, sample vials are under pressure. After
or manual sampling (Note 2) and ability to analyze the
analysis,relievethepressurewithahypodermicsyringeneedle
headspace vapors contained in a sealed vial.
vented into a charcoal slug or vent tube leading to a hood
NOTE 2—If the analyses are to be performed manually (that is, by
before removing vials from the water bath.
syringe injection), then the following equipment will also be needed:
(1)Constant-temperature bath or oven capable of maintaining a tem-
10. Sampling and Storage
perature of 90 6 1°C.
(2)Gas-tight GC syringes for sampling and injection.
10.1 Keep all polymer samples in tightly sealed jars or
(3)Sample bottles with fluoropolymer faces septa and caps (size
tightly wrapped aluminum foil prior to analysis. Dissolved
optional).
polymersamplesmustbekeptinseptum-sealedvialsorbottles
(4)Gloves for handling hot syringes.
until analyzed. Polymer solutions stored longer than 24 h
7.2 Chromatographic Column, 3% OV-101 on 80/100
should be maintained under refrigeration.
mesh Chromosorb WHP, ⁄8-in. (3.2-mm) outside diameter by
2 ft (0.6 m), stainless steel connected through ⁄8-in. “tee” to
11. Preparation of Gas Chromatograph
0.19%picricacidon80/100meshCarbopackC, ⁄8-in.outside
NOTE 5—All conditions in this section refer to a Headspace Analyzer.
diameter by 8 ft (2.4 m), stainless steel.
If analyses are performed manually, alter the operating procedures as
required by the instrumentation.
NOTE 3—Any column packing that will resolve VCM from interfer-
ences and elute VCM in a reasonable length of time (1 to 5 min) is
11.1 Install the chromatographic column and condition
satisfactory. For example, a 3-ft (0.9-m) by ⁄8-in. (3.2-mm) outside
overnight at 100°C, using normal carrier flow. Do not connect
diameter column containing 0.19% picric acid on 80/100 mesh Car-
the exit end of the column to the detector or turn on detector
bopack C can replace the recommended 3% OV−101 column. Settings
gases during column conditioning.
recommended in 11.3.1 may have to be modified to suit the packing
material being used.
11.2 Set the flow of detector gases as follows:
7.3 Detector Output Filter/Amplifier—Theextremesensitiv-
Detector Gas Flow
ity of this test method is best realized when the detector
FID Hydrogen 30 to 40 cm /min
Air 300 to 400 cm /min
(usually operated at the maximum sensitivity) output is (1)
PID Not required
filteredtoremovethehigh-frequencynoiseand(2)amplifiedto
HED Hydrogen 30 cm /min
give a visible or measurable signal.
11.3 Set other parameters as follows:
7.4 Sample Headspace Vials, glass, 23 mL, with
11.3.1 Oven Temperature—50 to 60°C.
fluoropolymer-lined septa and aluminum caps.
NOTE 6—Higher oven temperatures may be required when other
7.5 Vial Sealer.
chromatographic columns are used, or when high-boiling solvents and
late-eluting materials are being driven from the column.
7.6 Analytical Balance, capable of weighing to 60.001 g.
11.3.2 Dosing Needle—150°C.
8. Reagents and Materials
11.3.3 Injection Block Temperature—200°C.
11.3.4 Constant-Temperature Bath—90 6 1.0°C.
8.1 Vinyl Chloride Monomer (neat), pure, preferably in
11.3.5 Carrier-Gas Flow Rate—30 cm /min.
small cylinder.
NOTE 7—Backflushing the carrier gas after VCM elutes can consider-
8.2 Standard Cylinders,vinylchloridemonomerinnitrogen
ably shorten analysis time. After backflushing, allow adequate time for
at 1 and 10 mg/L by volume.
chromatographic conditions to stabilize before making another injection.
8.3 Hydrogen Cylinder, prepurified gas.
11.3.6 Detector Temperature:
8.4 Nitrogen, oxygen-free.
11.3.6.1 FID—250°C.
11.3.6.2 PID—150°C.
NOTE 4—Helium may replace nitrogen as the carrier gas.
11.3.6.3 HED—880°C.
8.5 Air, breathing or water-pumped.
11.3.7 Filter/Amplifier—Adjust as needed to remove high
8.6 N,N-Dimethylacetamide (DMAc), sparged with nitrogen
frequencynoiseandtoprovideadequateamplificationofVCM
gas for up to a
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D4443 − 13 D4443 − 19
Standard Test Method for
Determining Residual Vinyl Chloride Monomer Content in
PPB Range in Vinyl Chloride Homo- and Co-Polymers by
Headspace Gas Chromatography
This standard is issued under the fixed designation D4443; 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 (´) indicates an editorial change since the last revision or reapproval.
1. Scope*
1.1 This test method is suitable for determining the residual vinyl chloride monomer (RVM) content of homopolymer and
copolymers of vinyl chloride down to a levelconcentration of ;5 ppb.μg/kg (ppb).
1.2 This test method is applicable to any polymer form, such as resin, compound, film, bottle wall, etc. that can be dissolved
in a suitable solvent.
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use. Specific hazard statements are given in Section 9 and Note 10.
NOTE 1—This standard is equivalent to ISO 6401.
NOTE 1—This standard is equivalent to ISO 6401.
1.4 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
2. Referenced Documents
2.1 ISO Standard:
ISO 6401 Plastics—Homopolymer and Copolymer Resins of Vinyl Chloride—Determination of Residual Vinyl Chloride
Monomer—Gas Chromatographic Method
2.2 OSHA Standard:
29 CFR 1919.1017 Vinyl Chloride
3. Terminology
3.1 Abbreviations:
3.1.1 DMAc—N,N-dimethylacetamide.
3.1.2 VCM—Vinyl chloride monomer.
4. Summary of Test Method
4.1 Samples of vinyl chloride-containing polymers are dissolved in a suitable solvent in a closed system.
4.2 The polymer solution and headspace are equilibrated at an elevated temperature.
4.3 Aliquots of headspace gas are injected into a gas chromatograph and the vinyl chloride monomer is separated. The response
of vinyl chloride monomer is determined by the use of one of several suggested detectors.
4.4 Calibration is accomplished using either (a) vinyl chloride monomer in nitrogen gas standards, (b) standard solutions
containing known amounts of vinyl chloride monomer, or (c) a method of standard addition.
This test method is under the jurisdiction of ASTM Committee D20 on Plastics and is the direct responsibility of Subcommittee D20.70 on Analytical Methods.
Current edition approved Nov. 1, 2013April 1, 2019. Published November 2013May 2019. Originally approved in 1984. Last previous edition approved in 20122013 as
D4443 – 12.D4443 – 13. DOI: 10.1520/D4443-13.10.1520/D4443-19.
Available from American National Standards Institute (ANSI), 25 W. 43rd St., 4th Floor, New York, NY 10036, http://www.ansi.org.
Available from Superintendent of Documents, US Government Printing Office, Washington, DC 20402.20402, https://bookstore.gpo.gov.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4443 − 19
5. Significance and Use
5.1 Vinyl chloride-containing polymers are widely used to package a variety of materials, including foods.
5.2 Vinyl chloride monomer has been shown to be a human carcinogen. Threshold toxicity value has not been established.
5.3 Plastic manufacturers, food packagers, government agencies, etc. have a need to know the residual vinyl chloride monomer
content of vinyl chloride-containing polymers.
6. Interferences
6.1 N,N- dimethylacetamide should be analyzed under identical conditions to determine the absence of interferences at the vinyl
chloride monomer gas chromatography (GC) retention time.
6.2 Other solvents, monomers, or compounding aids may cause interference at the vinyl chloride monomer GC retention time.
7. Apparatus
7.1 Gas Chromatography, equipped with either a either, a mass spectrometric detector, flame ionization detector (FID), a photo
ionization detector (PID), or a Hall electroconductivity detector (HED), backflushing valve, and either automatic capability or
manual sampling (Note 2) and ability to analyze the headspace vapors contained in a sealed vial.
NOTE 2—If the analyses are to be performed manually (that is, by syringe injection), then the following equipment will also be needed:
(1) Constant-temperature bath or oven capable of maintaining a temperature of 90 6 1°C.
(2) Gas-tight GC syringes for sampling and injection.
(3) Sample bottles with fluoropolymer faces septa and caps (size optional).
(4) Gloves for handling hot syringes.
(1) Constant-temperature bath or oven capable of maintaining a temperature of 90 6 1°C.
(2) Gas-tight GC syringes for sampling and injection.
(3) Sample bottles with fluoropolymer faces septa and caps (size optional).
(4) Gloves for handling hot syringes.
7.2 Chromatographic Column, 3 % OV-101 on 80/100 mesh Chromosorb WHP, ⁄8-in. (3.2-mm) outside diameter by 2 ft (0.6
1 1
m), stainless steel connected through ⁄8-in. “tee” to 0.19 % picric acid on 80/100 mesh Carbopack C, ⁄8-in. outside diameter by
8 ft (2.4 m), stainless steel.
NOTE 3—Any column packing that will resolve VCM from interferences and elute VCM in a reasonable length of time (1 to 5 min) is satisfactory.
For example, a 3-ft (0.9-m) by ⁄8-in. (3.2-mm) outside diameter column containing 0.19 % picric acid on 80/100 mesh Carbopack C can replace the
recommended 3 % OV − 101 column. Settings recommended in 11.3.1 may have to be modified to suit the packing material being used.
7.3 Detector Output Filter/Amplifier—The extreme sensitivity of this test method is best realized when the detector (usually
operated at the maximum sensitivity) output is (1) filtered to remove the high-frequency noise and (2) amplified to give a visible
or measurable signal.
7.4 Sample Headspace Vials, glass, 23 mL, with fluoropolymer-lined septa and aluminum caps.
7.5 Vial Sealer.
7.6 Analytical Balance, capable of weighing to 60.001 g.
8. Reagents and Materials
8.1 Vinyl Chloride Monomer (neat), pure, preferably in small cylinder.
8.2 Standard Cylinders, vinyl chloride monomer in nitrogen at 1 and 10 ppmmg/L by volume.
8.3 Hydrogen Cylinder, prepurified gas.
8.4 Nitrogen, oxygen-free.
NOTE 4—Helium may replace nitrogen as the carrier gas.
8.5 Air, breathing or water-pumped.
8.6 N,N-Dimethylacetamide (DMAc), sparged with nitrogen gas for up to a week at room temperature to remove
chromatographic interferences.
9. Hazards
9.1 Safety Precautions:
9.1.1 Vinyl chloride monomer is a carcinogen and exposure by inhalation or dermal contact, or both, is to be avoided. Refer
to OSHA Standard 29 CFR 1919.1017 for regulated levels of exposure. N,N-dimethylacetamide is a teratogen. The use of a
properly functioning hood and septum-sealed sample containers are recommended.
9.1.2 Avoid all contact with heated parts of the gas chromatograph, hot syringes, and sample bottles. Handle all electrical
connections with care.
D4443 − 19
9.1.3 Once heated, sample vials are under pressure. After analysis, relieve the pressure with a hypodermic syringe needle vented
into a charcoal slug or vent tube leading to a hood before removing vials from the water bath.
10. Sampling and Storage
10.1 Keep all polymer samples in tightly sealed jars or tightly wrapped aluminum foil prior to analysis. Dissolved polymer
samples must be kept in septum-sealed vials or bottles until analyzed. Polymer solutions stored longer than 24 h should be
maintained under refrigeration.
11. Preparation of Gas Chromatograph
NOTE 5—All conditions in this section refer to the Perkin-Elmer a Headspace Analyzer. If analyses are performed manually, alter the operating
procedures as required by the instrumentation.
11.1 Install the chromatographic column and condition overnight at 100°C, using normal carrier flow. Do not connect the exit
end of the column to the detector or turn on detector gases during column conditioning.
11.2 Set the flow of detector gases as follows:
Detector Gas Flow
FID Hydrogen 30 to 40 cm /min
Air 300 to 400 cm /min
PID Not required
HED Hydrogen 30 cm /min
11.3 Set other parameters as follows:
11.3.1 Oven Temperature—50 to 60°C.
NOTE 6—Higher oven temperatures may be required when other chromatographic columns are used, or when high-boiling solvents and late-eluting
materials are being driven from the column.
11.3.2 Dosing Needle—150°C.
11.3.3 Injection Block Temperature—200°C.
11.3.4 Constant-Temperature Bath—90 6 1.0°C.
11.3.5 Carrier-Gas Flow Rate—30 cm /min.
NOTE 7—Backflushing the carrier gas after VCM elutes can c
...