1、Designation: D8133 17Standard Test Method forDetermination of Low Level, Regulated Phthalates inPoly(Vinyl Chloride) Plastics by Solvent ExtractionGasChromatography/Mass Spectrometry1This standard is issued under the fixed designation D8133; the number immediately following the designation indicates
2、 the year oforiginal 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. Scope1.1 This test method provides a procedure to quanti
3、fy sixphthalates by solvent extraction of plasticized PVC articlesfollowed by analysis of the extract by gas chromatography/mass spectrometry. The phthalates which are quantified areBBP, DBP, DEHP, DNOP, DINP, and DIDP.NOTE 1The method can be extended to other phthalates.1.2 Within the context of th
4、is 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 of this standard to establish appro-priate safety, heal
5、th, 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 recognized principles on standard-ization established in t
6、he 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 Relating to PlasticsD1600 Terminology forAbbreviated Term
7、s 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 Determination of Low Level, Regu-lated Phthalates in Poly (Vinyl Ch
8、loride) 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 Relation-shipsE594 Practice for Testing Flame Ionization Detec
9、tors 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 Metric System2.2 ASTM Adjuncts:ADJD7823-EAVinyl Plasticizer L
10、ibraryTotal 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 Terminologies D883 and D1600.3.2 For units, symbols, and abbrevia
11、tions 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 #103-23-13.3.2 (DINCH) 1,2-Cyclohexanedicarboxylic acid, dinonylester, branched and linear CAS #474919-59-03.3.3 (DBP) 1,2-Benzene
12、dicarboxylic acid, 1,2-di-n-butylester CAS #84-74-21This test method is under the jurisdiction of ASTM Committee D20 on Plasticsand is the direct responsibility of Subcommittee D20.70 on Analytical Methods.Current edition approved Aug. 1, 2017. Published November 2017. DOI:10.1520/D8133-17.2For refe
13、renced ASTM standards, visit the ASTM 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 E
14、astWest Hwy., Bethesda, MD 20814, http:/www.cpsc.gov.Copyright 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 standardization established in t
15、he Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.13.3.4 (BBP) Benzyl butyl phthalate CAS #85-68-73.3.5 (DEHP) Bis(2-Ethyhexyl) Phthalate CAS #117-81-73.3.6 (DNOP) Di(
16、n-Octyl) phthalate CAS #117-84-03.3.7 (DINP) 1,2-Benzenedicarboxylic acid, di-C8-10-branched alkyl 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, C
17、10-rich (Jayflex) CAS #68515-49-13.3.10 (DIDP) 1,2-Benzenedicarboxylic acid, 1,2-diisodecyl CAS #26761-40-03.3.11 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 G
18、C grade or higher3.3.16 FTIR Fourier Transform Infrared Spectroscopy3.3.17 TIC Total ion chromatogram3.3.18 DQO Data quality objectivesNOTE 3DINP and DIDP, when used in various PVC formulations aretechnical mixtures. Take care, when preparing the phthalate calibrationstandard to use the technical gr
19、ade. Here is specific information on DINPand DIDP. For more information, please refer to Appendix B and D7993.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 alkyl esters, C9-rich: CAS
20、#68515-48-0.4. 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 areidentified by their retention ti
21、mes 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 sampleare dissolved in THF. Af
22、ter 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 isdetermined using an inte
23、rnal calibration method.NOTE 4Standard 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, DEHP, DNOP, DINP and DIDP
24、 are required for regulatedarticles. Regulations include: EUDirective 2005/84/EC,USConsumer Product Safety Improvement Act of 2008 section 108, JapanHealth, Labor and Welfare Ministryguideline No. 336 (2010). This test method provides a proce-dure to identify and quantify regulated phthalates in PVC
25、.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 Retention times for GC are dependent on several vari-ables and it is possible to have two or more c
26、omponents 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 phthalate are free of interference. This includes, but isnot limited to changing the selectivity
27、of the chromatographiccolumn. Calibration by standard addition offers the advantageof correcting for matrix affects.6.2 When running the GC/MS method, care must be takento ensure that the vials, septa, and containers are free of anyphthalate contamination. Also, all solvents used to preparestandards
28、 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 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 inTa
29、ble 1 must satisfy the established guideline.6.4 Calculating the phthalate concentrations using the areasof compound specific ions significantly reduces interferencefrom non-target compounds, additionally using standard addi-tion corrects for matrix affects.7. Safety and Precautions7.1 Use organic s
30、olvents 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 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
31、 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 different 149/167 ratios, potentially leading to a false negative.DBP BBP DEHP DNOP DINP DIDPQuant ion 223 206 279 279 293 307Confirm ion 1 1
32、49 149 149 149 149 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 172TEST METHOD AHEPTANE EXTRACTIONPROCEDURE8. Apparatus8.1 Gas chromatograph/mass spectrometer capable of op-erating in the 100-260C temperature range and equipped withautos
33、ampler 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 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 pea
34、k 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 rates60.1 mL/min.9. Reagents and Materials9.1 Helium carrier gas, chromatographic grade.9.2 Heptane for p
35、reparing the phthalate standard solution(Stock Standard Solution, Standard Solution #1, 10.2 and 10.3;Sample Solution, 10.4), spectral quality or chromatographicgrade.9.3 Standards of the appropriate phthalates for use whenpreparing the Stock Standard Solution (10.2) and StandardSolution #1 (10.3) u
36、sed for standard addition. See Note 3.10. Preparation of the Analytical Samples10.1 Four 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) t
37、he sample solution spiked with the standard stocksolution.10.2 Stock Standard SolutionPrepare 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 an
38、d diluting to the mark).10.3 Standard Solution #1APrepare a diluted (1:10) solu-tion of 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 SolutionCu
39、t each plasticized component partinto small pieces (no dimension larger than 2 mm), ormilled/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 hept
40、ane with a 10-mL volumetric pipet (100 mg/10mL). The vial with the sample and heptane 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.
41、2 for example chromatograms.10.5 Spiked Sample SolutionPlace 1.0 mL of the samplesolution (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 i
42、s discussed in more detail in Appendix X1.11. Procedure11.1 Establish that the analytical 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 th
43、e relative retention time and massspectrum/SIM ions of each phthalate by analyzing a solution 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
44、AnalysisConditionsColumn: Carbowax (Polyethylene glycol) stationary phase, 30 m 0.25 mm 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:250CInjectionConditio
45、ns:Splitless injectionInjectionVolume:1LMSD TransferLine Temp.:250CIon Source(EI) Temp.: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
46、 the sample (Sample Solution 10.4) andSpiked Sample (Spiked Sample Solution 10.5) using 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 t
47、he quant and confirming ions and the ion area ratiosas indicated in Table 1. Phthalate quantification is based uponthe 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
48、 of the quant ion to accurately determine the amount of thephthalate.D8133 17311.4.1 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 ex
49、tracted chromatogram obtained using theconditions specific in 11.2 is shown in Fig. 1. Because the absoluteretention times are dependent upon the entirety of the GC system; relativeretention times are used to identify each phthalate.11.5 Quantification is done using standard addition.Analyzea Sample Solution. A typical ion extracted chromatogram isshown in Fig. 1 and Fig. 2. Standard addition is very useful tocorrect for difference in response of the analyte in the samplematrix. This is often the case when analyzing PVC whereDINCH, Mesa
