ASTM D8133-23

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: D8133 − 21 D8133 − 23
Standard Test Method for
Determination of Low Level Phthalates in Poly(Vinyl
Chloride) Plastics by Solvent Extraction—Gas
Chromatography/Mass Spectrometry
This standard is issued under the fixed designation D8133; 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 provides a procedure to quantify six phthalates by solvent extraction of plasticized PVC articles followed by
analysis of the extract by gas chromatography/mass spectrometry. Six phthalates, BBP, DBP, DEHP, DNOP, DINP, and DIDP, are
used to illustrate how to implement the method.
NOTE 1—The method can be extended to other phthalates in a wide range of polymeric substrates.
1.2 Within the context of this method, “low level” is defined as 1000 ppm.
1.3 The values in SI units are to be regarded as standard.
1.4 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.
NOTE 2—There is no known ISO equivalent to this standard.
1.5 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 ASTM Standards:
D883 Terminology Relating to Plastics
D1600 Terminology for Abbreviated Terms Relating to Plastics
D3465 Guide for Purity of Monomeric Plasticizers by Gas Chromatography
D7083 Practice for Determination of Monomeric Plasticizers in Poly (Vinyl Chloride) (PVC) by Gas Chromatography
D7823 Test Method for Determination of Low Level Phthalates in Poly (Vinyl Chloride) Plastics by Thermal Desorption—Gas
Chromatography/Mass Spectrometry
D7993 Guide for Analyzing Complex Phthalates
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 Jan. 15, 2021March 15, 2023. Published February 2021April 2023. Originally approved in 2017. Last previous edition approved in 20202021
as D8133 – 20.D8133 – 21. DOI: 10.1520/D8133-21.10.1520/D8133-23.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
*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
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E177 Practice for Use of the Terms Precision and Bias in ASTM Test Methods
E355 Practice for Gas Chromatography Terms and Relationships
E594 Practice for Testing Flame Ionization Detectors Used in Gas or Supercritical Fluid Chromatography
E691 Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method
IEEE/ASTM SI-10 Practice for Use of the International System of Units (SI), the Modernized Metric System
2.2 ASTM Adjuncts:ADJD7823-EA
Vinyl Plasticizer Library—Total Ion Chromatograms and Mass Spectra
2.3 CPSC Standard:
CPSC-CH-C1001–09.3 Standard Operating Procedure for Determination of Phthalates
3. Terminology
3.1 Definitions:
3.1.1 For definition of plastic terms used in this standard, see Terminologies D883 and D1600.
3.2 For units, symbols, and abbreviations used in this standard refer to Practices E594, E355, or IEEE/ASTM SI-10.
3.3 Compounds and Instrumentation:
3.3.1 (DOA) Hexanedioic acid, 1,6-bis(2-ethylhexyl) ester CAS #103-23-1
3.3.2 (DINCH) 1,2-Cyclohexanedicarboxylic acid, dinonyl ester, branched and linear CAS #474919-59-0
3.3.3 (DBP) 1,2-Benzenedicarboxylic acid, 1,2-di-n-butyl ester CAS #84-74-2
3.3.4 (BBP) Benzyl butyl phthalate CAS #85-68-7
3.3.5 (DEHP) Bis(2-ethyhexyl) phthalate CAS #117-81-7
3.3.6 (DNOP) Di(n-octyl) phthalate CAS #117-84-0
3.3.7 (DINP) 1,2-Benzenedicarboxylic acid, di-C8-10-branched alkyl esters, C9-rich (Jayflex) CAS #68515-48-0
3.3.8 (DINP) 1,2-Benzenedicarboxylic acid, 1,2-diisononyl (Palatinol) CAS #28553-12-0
3.3.9 (DIDP) 1,2-Benzenedicarboxylic acid, di-C9-11-branched alkyl esters, C10-rich (Jayflex) CAS #68515-49-1
3.3.10 (DIDP) 1,2-Benzenedicarboxylic acid, 1,2-diisodecyl CAS #26761-40-0
3.3.11 GC Gas Chromatography
3.3.12 GC/MS Gas Chromatography/Mass Spectrometry
3.3.13 TD-GC/MS Thermal Desorption—Gas Chromatography/Mass Spectrometry
3.3.14 PVC Poly(vinyl chloride)
3.3.15 Heptane GC grade or higher
3.3.16 FTIR Fourier Transform Infrared Spectroscopy
3.3.17 TIC Total ion chromatogram
3.3.18 DQO Data quality objectives
Available from U.S. Consumer Product Safety Commission (CPSC), 4330 East West Hwy., Bethesda, MD 20814, http://www.cpsc.gov.
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4. Summary of Test Method
4.1 Test Method A—100 mg of the plasticized PVC sample along with 10 mL of heptane is extracted for 2 hours with the aid of
sonication. One milliliter of the heptane solution is placed in a GC vial and analyzed by GC/MS. Phthalates are identified by their
retention times and their mass spectra/SIM ions. Quantification is based on the area of a designated quantitative ion (SIM or full
scan) (see Table 1). The amount of each component is determined using a standard addition calibration method.
4.2 Test Method B—100 mg of the plasticized PVC sample are dissolved in THF. After the polymer is precipitated by adding 20
mL of hexane, 1.3 mL of the supernatant is filtered and placed in a GC vial and analyzed by GC/MS. Quantification is based on
the area of a designated quantitative ion (SIM or full scan) (see Table 1). The amount of each component is determined using an
internal calibration method.
NOTE 3—Standard addition calibration will correct for matrix affects (that is, response of the phthalates being different in solvent versus the solvent and
sample matrix).
5. Significance and Use
5.1 Identification and Quantification of Phthalates—DBP, BBP, DEHP, DNOP, DINP and DIDP are representative of the
phthalates either banned or being monitored by a variety of regulations. Regulations include: EU—Directive 2005/84/EC,
US—Consumer Product Safety Improvement Act of 2008 – section 108, Japan—Health, Labor and Welfare Ministry guideline No.
336 (2010) and IEC 62321-8:2017. These test methods provide a procedure to identify and quantify phthalates in PVC.
5.2 Other techniques successfully used to separate and identify phthalates in PVC include TD-GC/MS (ASTM D7823), GC/MS,
HPLC/UV, HPLC/MS, FTIR, and GC/FID (flame ionization detector).
6. Interferences
6.1 Retention times for GC are dependent on several variables and it is possible to have two or more components with identical
retention times. The analyst shall take the necessary steps to ensure that adequate separation of the plasticizer components is
achieved and or the ions used to monitor for a target phthalate are free of interference. This includes, but is not limited to changing
the selectivity of the chromatographic column or the heating profile of the GC column. Calibration by standard addition offers the
advantage of correcting for matrix affects.
6.2 When running the GC/MS method, care must be taken to ensure that the vials, septa, and containers are free of any phthalate
contamination. Also, all solvents used to prepare standards and sample solutions must be free of contamination.
6.3 The presence or absence of each phthalate is based upon three criteria:
(1) the relative retention time of the peak,
(2) the presence or absence of the Quant Ion and the two Confirm Ions, and
(3) the ratio of the Quant Ion and the Confirm Ion 1 in Table 1 must satisfy the established guideline.
6.4 Calculating the phthalate concentrations using the areas of compound specific ions significantly reduces interference from
non-target compounds, additionally using standard addition corrects for matrix affects.
TABLE 1 Ions and Ion Ratios Used to Identify Each Phthalate
NOTE 1—When DINP and DIDP are both present in a sample or standard, m/z 127 is used as a qualifying ion for DINP and m/z 289 for DIDP. This
is because DINP and DIDP partially co-elute and both produce m/z 149 and 167. If 149 qualifier ion ratios are set when DINP and DIDP are at equal
concentrations, then any samples with different ratios will produce substantially different 149/167 ratios, potentially leading to a false negative.
DBP BBP DEHP DNOP DINP DIDP
Quant ion 223 206 279 279 293 307
Confirm ion 1 149 149 149 149 149 149
Area ratio (±10%) <0.04 <0.23 <0.08 <0.06 <0.20 <0.12
(Quant/Confirm 1)
Confirm ion 2 167 167 167 167 167 167
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7. Safety and Precautions
7.1 Use organic solvents in a well-ventilated space.
TEST METHOD A—HEPTANE EXTRACTION PROCEDURE
8. Apparatus
8.1 Gas chromatograph/mass spectrometer capable of operating in the 100-260°C temperature range and equipped with
autosampler and injector.
8.2 GC vials, glass pipets, 4, and 20-mL vials.
8.3 Optional Recommended Equipment—10-mL volumetric flask.
8.4 GC Capillary Column—Carbowax capillary column, 30 m by 0.25 mm ID with a 0.25 μm film thickness, or equivalent.
8.5 Integrator or data handling system, capable of measuring peak areas and retention times.
8.6 Analytical balance, capable of weighing to 60.00001 g.
8.7 Pressure regulators, for all required gas cylinders.
8.8 Flow meter, or other means of measuring gas flow rates 60.1 mL/min.
9. Reagents and Materials
9.1 Helium carrier gas, chromatographic grade.
9.2 Heptane for preparing the phthalate standard solution (Stock Standard Solution, Standard Solution #1, 10.2 and 10.3; Sample
Solution, 10.4), spectral quality or chromatographic grade.
9.3 Standards of the appropriate phthalates for use when preparing the Stock Standard Solution (10.2) and Standard Solution #1
(10.3) used for standard addition. See Note 4.
NOTE 4—DINP and DIDP, when used in various PVC formulations are technical mixtures. Here is specific information on DINP and DIDP. For more
information, please refer to Appendix X3.
Jayflex DIDP: 1,2-Benzenedicarboxylic acid, di-C9-11-branched alkyl esters, C10-rich: CAS# 68515-49-1.
Jayflex DINP: 1,2-Benzenedicarboxylic acid, di-C8-10-branched alkyl esters, C9-rich: CAS# 68515-48-0.
10. Preparation of the Analytical Samples
10.1 Four solutions shall be prepared:
(1) a Stock Standard Solution of the target phthalate standards,
(2) a Standard Solution of the target phthalate standards used to spike the sample,
(3) a solution of the sample, and
(4) the sample solution spiked with the standard stock solution.
10.2 Stock Standard Solution—Prepare a stock standard solution of the phthalates by dissolving 0.10 g of each phthalate in 10 mL
of heptane (0.10 g/10 mL; this is conveniently performed by weighing the phthalates into a 10 mL volumetric flask and diluting
to the mark).
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10.3 Standard Solution #1A—Prepare a diluted (1:10) solution of the Stock Standard Solution to spike the sample solutions. To
test system performance and verify retention times a 10 μL aliquot of Standard Solution #1 is added to 1 mL of heptane and
analyzed.
10.4 Sample Solution—Cut each plasticized component part into small pieces (no dimension larger than 2 mm), or milled/ground
into a representative powder. Each cut/milled plasticized component part will be considered a sample for testing as described
below.
10.4.1 Weigh 100 mg (0.10 g) of the sample in a vial and add 10 mL heptane with a 10-mL volumetric pipet (100 mg/10 mL).
The vial with the sample and heptane is placed in a sonication bath and extracted for two hours at room temperature. Into a GC
vial, place 1.0 mL of the extracted sample solution (this is conveniently done with a 1 mL volumetric pipet). See Fig. 1 and Fig.
2 for example chromatograms.
10.5 Spiked Sample Solution—Place 1.0 mL of the sample solution (10.4) into a GC vial. Add 10 μL of the phthalate Standard
Solution #1 (10.3) to the sample solution with a GC syringe.
NOTE 5—A critical step in the accurate determination of phthalates is sample homogeneity. This is discussed in more detail in Appendix X1.
11. Procedure
11.1 Establish that the analytical system has an acceptable background of phthalate contamination by analyzing a heptane solvent
blank. Acceptable background contamination will be determined by the data quality specific objectives.
11.2 Establish the relative retention time and mass spectrum/SIM ions of each phthalate by analyzing a solution of 10 μL of
Standard Solution #1 (10.1(3)) added to 1.0 mL of heptane. The conditions in Table 2 were used to obtain the example
chromatograms shown in Figs. 1 and 2.
TABLE 2 Gas Chromatography/Mass Spectrometry Analysis Conditions
Column: Carbowax (Polyethylene glycol) stationary phase, 30 m × 0.25 mm i.d, 0.25 μm film thickness
Carrier Gas: Helium or other acceptable gas
Carrier 1.0 mL/min
Flow Rate:
Oven 150°C (0 min hold) to 250°C (at 10°C/min) (45 min hold)
Temperature
Program:
Injector 250°C
Temperature:
Injection Splitless injection
Conditions:
Injection Split or splitless injection depending on the sensitivity of the instrument. 20:1 split is recommended as a starting point
Conditions: for those wishing to run split.
Injection 1 μL
Volume:
MSD Transfer 250°C
Line Temp.:
Ion Source 230°C
(EI) Temp.:
MS Mode: SIM (scan mode is employed if sufficient detection sensitivity is met)
11.2.1 The mass spectrometer is run in scan mode for general identification of phthalates and other sample components.
11.3 Analyze the sample (Sample Solution – 10.4) and Spiked Sample (Spiked Sample Solution – 10.5) using the conditions
outlined in 11.2. A typical chromatogram is shown in Fig. 1 and Fig. 2.
11.4 Peak identifications are based on relative retention data, Scan mode (extracted ion) or single ion monitoring (SIM) mode of
the quant and confirming ions and the ion area ratios as indicated in Table 1. Phthalate quantification is based upon the peak areas
of the quant ions listed in Table 1. The assumption being made is that the sole source of the quant ion at a predetermined retention
time is the phthalate. Use the peak area of the quant ion to accurately determine the amount of the phthalate.
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FIG. 1 Sample Solution—Ion Extracted Chromatogram of DINCH Plasticizer with About 1000 ppm of Each Phthalate (see 10.4 and 11.3)
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FIG. 2 Sample Solution—Ion Extracted Chromatogram of DINCH Plasticizer with About 1000 ppm of Each Phthalate (see 10.4 and
11.3)—Expanded TIC
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11.4.1 Peak identification is based solely on the presence or absence of the quant ion and the two confirming ions at a
predetermined retention time. Quantification is based on the area of the quant ion.
NOTE 6—A typical ion extracted chromatogram obtained using the conditions specific in 11.2 is shown in Fig. 1. Because the absolute retention times
are dependent upon the entirety of the GC system; relative retention times are used to identify each phthalate.
11.5 Quantification is done using standard addition. Analyze a Sample Solution. A typical ion extracted chromatogram is shown
in Fig. 1 and Fig. 2. Standard addition is very useful to correct for difference in response of the analyte in the sample matrix. This
is often the case when analyzing PVC where DINCH, Mesamoll or both are present.
NOTE 7—A good overview of standard addition is found on page 476, LCGC North America, Volume 27, number 6, June 2009.
12. Example Calculations
12.1 The amount of each phthalate in the samples are determined by a single-point standard addition method. The amount of the
analyte spiked into the sample (in μg) is plotted versus the peak area (see Fig. 3). The line is used to calculate the amount of
phthalate in the sample. As only one-tenth of the sample solution is spiked (the weight of sample is about 0.100 g / 10 = 0.01 g).
12.1.1 To determine the amount of the analyte in the sample, determine the point where the line crosses the x-axis (this is the
amount of the analyte in the sample solution, DBP in this case).
y = 12202.3x + 116113.0 = 0
x (μg of analyte in sample solution) = 116113.0 / 12202.3 = 9.52
Amount of analyte in sample (ppm) = μg of analyte in sample solution / weight of sample in spiked sample
Weight of spiked sample = weight of sample / 10 =
0.1002 / 10 = 0.01002
Amount of BBP in sample (ppm) = 9.52 / 0.01002 = 947
13. Quality Control
13.1 Perform the quality checks outlined in Table 3.
13.2 Ensure that the system is free of phthalate contamination before analyzing samples. Prior to sample analysis the ability of
the system to perform properly shall be verified.
14. Report
14.1 The amount of each target phthalate in ppm.
FIG. 3 Plot of Micrograms of Phthalate Added to the Sample Solution Versus Phthalate Peak Area
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TABLE 3 System Performance Verificatio
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