1、Designation: D8133 18Standard Test Method forDetermination of Low Level Phthalates in Poly(VinylChloride) Plastics by Solvent ExtractionGasChromatography/Mass Spectrometry1This standard is issued under the fixed designation D8133; the number immediately following the designation indicates the year o
2、foriginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope*1.1 This test method provides a procedure to quantify sixphth
3、alates by solvent extraction of plasticized PVC articlesfollowed 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 themethod.NOTE 1The method can be extended to other phthalates in a widera
4、nge of polymeric substrates.1.2 Within the context of this method, “low level” is definedas 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 thesafety concerns, if any, associated with its use. It is theresponsibility of the user
5、 of this standard to establish appro-priate safety, health, and environmental practices and deter-mine the applicability of regulatory limitations prior to use.NOTE 2There is no known ISO equivalent to this standard.1.5 This international standard was developed in accor-dance with internationally re
6、cognized principles on standard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D883 Terminology R
7、elating to PlasticsD1600 Terminology forAbbreviated Terms Relating to Plas-ticsD3465 Test Method for Purity of Monomeric Plasticizers byGas ChromatographyD7083 Practice for Determination of Monomeric Plasticiz-ers in Poly (Vinyl Chloride) (PVC) by Gas Chromatogra-phyD7823 Test Method for Determinati
8、on of Low Level, Regu-lated Phthalates in Poly (Vinyl Chloride) Plastics byThermal DesorptionGas Chromatography/Mass Spec-trometryD7993 Guide for Analyzing Complex PhthalatesE177 Practice for Use of the Terms Precision and Bias inASTM Test MethodsE355 Practice for Gas Chromatography Terms and Relati
9、on-shipsE594 Practice for Testing Flame Ionization Detectors Usedin Gas or Supercritical Fluid ChromatographyE691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a Test MethodIEEE/ASTM SI-10 Practice for Use of the InternationalSystem of Units (SI), the Modernized Metri
10、c System2.2 ASTM Adjuncts:ADJD7823-EAVinyl Plasticizer LibraryTotal Ion Chromatograms andMass Spectra2.3 CPSC Standard:3CPSC-CH-C100109.3 Standard Operating Procedure forDetermination of Phthalates3. Terminology3.1 Definitions:3.1.1 For definition of plastic terms used in this standard,see Terminolo
11、gies D883 and D1600.3.2 For units, symbols, and abbreviations used in thisstandard refer to Practices E594, E355,orIEEE/ASTM SI-10.3.3 Compounds and Instrumentation:3.3.1 (DOA) Hexanedioic acid, 1,6-bis(2-ethylhexyl) esterCAS #103-23-11This test method is under the jurisdiction of ASTM Committee D20
12、 on Plasticsand is the direct responsibility of Subcommittee D20.70 on Analytical Methods.Current edition approved Nov. 1, 2018. Published November 2018. Originallyapproved in 2017. Last previous edition approved in 2017 as D8133 17. DOI:10.1520/D8133-18.2For referenced ASTM standards, visit the AST
13、M 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 ASTM website.3Available from U.S. Consumer Product Safety Commission (CPSC), 4330 EastWest Hwy., Bethesda, MD 20814, ht
14、tp:/www.cpsc.gov.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on sta
15、ndardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.13.3.2 (DINCH) 1,2-Cyclohexanedicarboxylic acid, dinonylester, branched and linear CAS #
16、474919-59-03.3.3 (DBP) 1,2-Benzenedicarboxylic acid, 1,2-di-n-butylester CAS #84-74-23.3.4 (BBP) Benzyl butyl phthalate CAS #85-68-73.3.5 (DEHP) Bis(2-ethyhexyl) phthalate CAS #117-81-73.3.6 (DNOP) Di(n-octyl) phthalate CAS #117-84-03.3.7 (DINP) 1,2-Benzenedicarboxylic acid, di-C8-10-branched alkyl
17、esters, C9-rich (Jayflex) CAS #68515-48-03.3.8 (DINP) 1,2-Benzenedicarboxylic acid, 1,2-diisononyl(Palatinol) CAS #28553-12-03.3.9 (DIDP) 1,2-Benzenedicarboxylic acid, di-C9-11-branched alkyl esters, C10-rich (Jayflex) CAS #68515-49-13.3.10 (DIDP) 1,2-Benzenedicarboxylic acid, 1,2-diisodecyl CAS #26
18、761-40-03.3.11 GC Gas Chromatography3.3.12 GC/MS Gas Chromatography/Mass Spectrometry3.3.13 TD-GC/MS Thermal DesorptionGasChromatography/Mass Spectrometry3.3.14 PVC Poly(vinyl chloride)3.3.15 Heptane GC grade or higher3.3.16 FTIR Fourier Transform Infrared Spectroscopy3.3.17 TIC Total ion chromatogr
19、am3.3.18 DQO Data quality objectives4. Summary of Test Method4.1 Test Method A100 mg of the plasticized PVC samplealong with 10 mL of heptane is extracted for 2 hours with theaid of sonication. One milliliter of the heptane solution isplaced in a GC vial and analyzed by GC/MS. Phthalates areidentifi
20、ed by their retention times and their mass spectra/SIMions. Quantification is based on the area of a designatedquantitative ion (SIM or full scan) (see Table 1). The amountof each component is determined using a standard additioncalibration method.4.2 Test Method B50 mg of the plasticized PVC sample
21、are dissolved in THF. After the polymer is precipitated byadding 10 mL of hexane, 1.3 mL of the supernatant is filteredand placed in a GC vial and analyzed by GC/MS. Quantifica-tion is based on the area of a designated quantitative ion (SIMor full scan) (see Table 1). The amount of each component is
22、determined using an internal calibration method.NOTE 3Standard addition calibration will correct for matrix affects(that is, response of the phthalates being different in solvent versus thesolvent and sample matrix).5. Significance and Use5.1 Identification and Quantification of PhthalatesDBP,BBP, D
23、EHP, DNOP, DINP and DIDP are representative of thephthalates either banned or being monitored by a variety ofregulations. Regulations include: EUDirective 2005/84/EC,USConsumer Product Safety Improvement Act of 2008 section 108, JapanHealth, Labor and Welfare Ministryguideline No. 336 (2010) and IEC
24、 62321-8:2017. These testmethods provide a procedure to identify and quantify phtha-lates in PVC.5.2 Other techniques successfully used to separate andidentify phthalates in PVC include TD-GC/MS (ASTMD7823), GC/MS, HPLC/UV, HPLC/MS, FTIR, and GC/FID(flame ionization detector).6. Interferences6.1 Ret
25、ention times for GC are dependent on several vari-ables and it is possible to have two or more components withidentical retention times. The analyst shall take the necessarysteps to ensure that adequate separation of the plasticizercomponents is achieved and or the ions used to monitor for atarget p
26、hthalate are free of interference. This includes, but isnot limited to changing the selectivity of the chromatographiccolumn or the heating profile of the GC column. Calibration bystandard addition offers the advantage of correcting for matrixaffects.6.2 When running the GC/MS method, care must be t
27、akento ensure that the vials, septa, and containers are free of anyphthalate contamination. Also, all solvents used to preparestandards and sample solutions must be free of contamination.6.3 The presence or absence of each phthalate is based uponthree criteria:(1) the relative retention time of the
28、peak,(2) the presence or absence of the Quant Ion and the twoConfirm Ions, and(3) the ratio of the Quant Ion and the Confirm Ion 1 inTable 1 must satisfy the established guideline.6.4 Calculating the phthalate concentrations using the areasof compound specific ions significantly reduces interference
29、from non-target compounds, additionally using standard addi-tion corrects for matrix affects.7. Safety and Precautions7.1 Use organic solvents in a well-ventilated space.TABLE 1 Ions and Ion Ratios Used to Identify Each PhthalateNOTE 1When DINP and DIDP are both present in a sample or standard, m/z
30、127 is used as a qualifying ion for DINP and m/z 289 for DIDP. Thisis 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 equalconcentrations, then any samples with different ratios will produce substantially differ
31、ent 149/167 ratios, potentially leading to a false negative.DBP BBP DEHP DNOP DINP DIDPQuant ion 223 206 279 279 293 307Confirm ion 1 149 149 149 149 149 149Area ratio (10%)(Quant/Confirm 1)0.04 0.23 0.08 0.06 0.20 0.12Confirm ion 2 167 167 167 167 167 167D8133 182TEST METHOD AHEPTANE EXTRACTIONPROC
32、EDURE8. Apparatus8.1 Gas chromatograph/mass spectrometer capable of op-erating in the 100-260C temperature range and equipped withautosampler and injector.8.2 GC vials, glass pipets, 4, and 20-mL vials.8.3 Optional Recommended Equipment10-mL volumetricflask.8.4 GC Capillary ColumnCarbowax capillary
33、column, 30m by 0.25 mm ID with a 0.25 m film thickness, or equivalent.8.5 Integrator or data handling system, capable of measur-ing 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 othe
34、r means of measuring gas flow rates60.1 mL/min.9. Reagents and Materials9.1 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 chromatographicgrad
35、e.9.3 Standards of the appropriate phthalates for use whenpreparing the Stock Standard Solution (10.2) and StandardSolution #1 (10.3) used for standard addition. See Note 4.NOTE 4DINP and DIDP, when used in various PVC formulations aretechnical mixtures. Here is specific information on DINP and DIDP
36、. Formore information, please refer to Appendix X3.Jayflex DIDP: 1,2-Benzenedicarboxylic acid, di-C9-11-branched alkylesters, C10-rich: CAS# 68515-49-1.Jayflex DINP: 1,2-Benzenedicarboxylic acid, di-C8-10-branched alkylesters, C9-rich: CAS# 68515-48-0.10. Preparation of the Analytical Samples10.1 Fo
37、ur solutions shall be prepared:(1) a Stock Standard Solution of the target phthalatestandards,(2) a Standard Solution of the target phthalate standardsused to spike the sample,(3) a solution of the sample, and(4) the sample solution spiked with the standard stocksolution.10.2 Stock Standard Solution
38、Prepare a stock standardsolution of the phthalates by dissolving 0.10 g of eachphthalate in 10 mL of heptane (0.10 g/10 mL; this is conve-niently performed by weighing the phthalates into a 10 mLvolumetric flask and diluting to the mark).10.3 Standard Solution #1APrepare a diluted (1:10) solu-tion o
39、f the Stock Standard Solution to spike the samplesolutions. To test system performance and verify retentiontimes a 10 L aliquot of Standard Solution #1 is added to 1 mLof heptane and analyzed.10.4 Sample SolutionCut each plasticized component partinto small pieces (no dimension larger than 2 mm), or
40、milled/ground into a representative powder. Each cut/milledplasticized component part will be considered a sample fortesting as described below.10.4.1 Weigh 100 mg (0.10 g) of the sample in a vial andadd 10 mL heptane with a 10-mL volumetric pipet (100 mg/10mL). The vial with the sample and heptane
41、is placed in asonication bath and extracted for two hours at room tempera-ture. Into a GC vial, place 1.0 mL of the extracted samplesolution (this is conveniently done witha1mLvolumetricpipet). See Fig. 1 and Fig. 2 for example chromatograms.10.5 Spiked Sample SolutionPlace 1.0 mL of the samplesolut
42、ion (10.4) into a GC vial. Add 10 L of the phthalateStandard Solution #1 (10.3) to the sample solution with a GCsyringe.NOTE 5A critical step in the accurate determination of phthalates issample homogeneity. This is discussed in more detail in Appendix X1.11. Procedure11.1 Establish that the analyti
43、cal system has an acceptablebackground of phthalate contamination by analyzing a heptanesolvent blank. Acceptable background contamination will bedetermined by the data quality specific objectives.11.2 Establish the relative retention time and massspectrum/SIM ions of each phthalate by analyzing a s
44、olution of10 L of Standard Solution #1 (10.1(3) added to 1.0 mL ofheptane. The conditions in Table 2 were used to obtain theexample chromatograms shown in Figs. 1 and 2.TABLE 2 Gas Chromatography/Mass Spectrometry AnalysisConditionsColumn: Carbowax (Polyethylene glycol) stationary phase, 30 m 0.25 m
45、m i.d, 0.25 m film thicknessCarrier Gas: Helium or other acceptable gasCarrierFlow Rate:1.0 mL/minOvenTemperatureProgram:150C (0 min hold) to 250C (at 10C/min) (45 min hold)InjectorTemperature:250CInjectionConditions:Splitless injectionInjectionVolume:1LMSD TransferLine Temp.:250CIon Source(EI) Temp
46、.:230CMS Mode: SIM (scan mode is employed if sufficient detectionsensitivity is met)11.2.1 The mass spectrometer is run in scan mode forgeneral identification of phthalates and other sample compo-nents.11.3 Analyze the sample (Sample Solution 10.4) andSpiked Sample (Spiked Sample Solution 10.5) usin
47、g theconditions outlined in 11.2. A typical chromatogram is shownin Fig. 1 and Fig. 2.11.4 Peak identifications are based on relative retentiondata, Scan mode (extracted ion) or single ion monitoring (SIM)mode of the quant and confirming ions and the ion area ratiosas indicated in Table 1. Phthalate
48、 quantification is based uponD8133 183FIG. 1 Sample SolutionIon Extracted Chromatogram of DINCH Plasticizer with About 1000 ppm of Each Phthalate (see 10.4 and 11.3)D8133 184FIG. 2 Sample SolutionIon Extracted Chromatogram of DINCH Plasticizer with About 1000 ppm of Each Phthalate (see 10.4 and11.3)
49、Expanded TICD8133 185the peak areas of the quant ions listed in Table 1. Theassumption being made is that the sole source of the quant ionat a predetermined retention time is the phthalate. Use the peakarea of the quant ion to accurately determine the amount of thephthalate.11.4.1 Peak identification is based solely on the presence orabsence of the quant ion and the two confirming ions at apredetermined retention time. Quantification is based on thearea of the quant ion.NOTE 6A typical ion extracted chromatogram obtained using
