1、Designation: D7823 13D7823 14Standard Test Method forDetermination of Low Level, Regulated Phthalates in Poly(Vinyl Chloride) Plastics by Thermal DesorptionGasChromatography/Mass ChromatographySpectrometry1This standard is issued under the fixed designation D7823; the number immediately following th
2、e designation indicates 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. Scope Scope*1.1 This test method
3、provides a procedure to identify and quantify six phthalates by thermal desorption (TD) gaschromatography (GC) mass spectrometry (MS). The phthalates are BBP, DBP, DEHP, DNOP, DINP and DIDP.NOTE 1The method can be extended to include other phthalates.1.2 Within the context of this method, “low level
4、” is defined as 1000 ppm.1.3 The values in SI units are to be regarded as standard.1.4 This test method includes references, notes and footnotes that provide explanatory material. These notes and footnotes(excluding those in the tables and figures) shall not be considered as requirements of this met
5、hod.1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use.NOTE 2There i
6、s no known ISO equivalent to this test method.2. Referenced Documents2.1 ASTM Standards:2D883 Terminology Relating to PlasticsD1600 Terminology for Abbreviated Terms Relating to PlasticsD3465 Test Method for Purity of Monomeric Plasticizers by Gas ChromatographyD7083 Practice for Determination of Mo
7、nomeric Plasticizers in Poly (Vinyl Chloride) (PVC) by Gas ChromatographyE177 Practice for Use of the Terms Precision and Bias in ASTM Test MethodsE355 Practice for Gas Chromatography Terms and RelationshipsE594 Practice for Testing Flame Ionization Detectors Used in Gas or Supercritical Fluid Chrom
8、atographyE691 Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test MethodIEEE/ASTM SI10 Practice for Use of the International System of Units (SI), the Modernized Metric System3. Terminology3.1 DefinitionsFor definition of plastic terms used in this test method, see
9、Terminologies D883 and D1600.3.2 For units, symbols, and abbreviations used in this test method refer to Practices E594, E355, or SI10.3.3 Compounds and Instrumentation:3.3.1 (DOA) Hexanedioic acid, 1,6bis(2ethylhexyl) ester CAS #1032313.3.2 (DINCH) 1,2Cyclohexanedicarboxylic acid, dinonyl ester, br
10、anched and linear CAS #4749195903.3.3 (DBP) 1,2Benzenedicarboxylicacid, 1,2dinbutyl ester CAS #847423.3.4 (BBP) Benzyl butyl phthalate CAS #856871 This test method is under the jurisdiction of ASTM Committee D20 on Plastics and is the direct responsibility of Subcommittee D20.70 on Analytical Method
11、s.Current edition approved April 1, 2013Aug. 1, 2014. Published April 2013September 2013. Originally approved in 2013. Last previous edition approved in 2013 asD7823 - 13. DOI: 10.1520/D7823-13.10.1520/D7823-14.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Custo
12、mer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.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
13、 previous version. Becauseit 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 versionof the standard as published by ASTM is to be considered the official document.*A Summary o
14、f Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States13.3.5 (DEHP) Bis(2Ethyhexyl) Phthalate CAS #1178173.3.6 (DNOP) Di(nDioctyl)Di(noctyl) phthalate CAS #1178403.3.7 (DINP) 1,2Benzenedic
15、arboxylicacid, diC810branched alkyl esters, C9rich (Jayflex) CAS #685154803.3.8 (DINP) 1,2Benzenedicarboxylicacid, 1,2diisononyl (Palatinol) CAS #285531203.3.9 (DIDP) 1,2Benzenedicarboxylicacid, diC911branched alkyl esters, C10rich (Jayflex) CAS #685154913.3.10 (DIDP) 1,2Benzenedicarboxylicacid, 1,2
16、diisodecyl CAS #267614003.3.11 TD Thermal Desorption3.3.12 GC Gas Chromatography3.3.13 GC/MS Gas Chromatography/Mass Spectrometry3.3.14 PVC Poly (Vinyl Chloride)3.3.15 THF GC grade or higher “Tetrahydrofuran”3.3.16 DCM GC grade or higher “Methylene Chloride”3.3.17 EGAMS Evolved Gas Analysismass spec
17、trometry3.3.18 FTIR Fourier Transform Infrared Spectroscopy3.3.19 TIC Total ion chromatogram3.3.20 DQO Data quality objectivesNOTE 3DINPand DIDP, when used in various PVC formulations are technical mixtures. Take care, when preparing the phthalate calibration standardto use the technical grade. Here
18、 is specific information on DINP and DIDP. For more information, please refer to Appendix X3.Jayflex DIDP: 1,2Benzenedicarboxylicacid, diC911branched alkyl esters, C10rich: CAS# 68515491.Jayflex DINP: 1,2Benzenedicarboxylicacid, diC810branched alkyl esters, C9rich: CAS# 68515 480.4. Summary of Test
19、Method4.1 200 mg of the PVC sample are dissolved in 10 mL of THF. 10 L of the THF solution are analyzed usingTDGC/MS.TD-GC/MS. Phthalates are identified by their retention times and their mass spectra. Quantification is based on the areaof a designated quant ion (SIM or full scan)see Table 1. Standa
20、rd addition is the calibration method.NOTE 4Standard addition calibration will negate matrix interference. It also takes into account the overall performance of the instrumentation at thetime the samples are analyzed.5. Significance and Use5.1 Identification and quantificationquantitation of phthala
21、tes: DBP, BBP, DEHP, DNOP, DINP, and DIDP are required forregulated articles. Regulations include: EUDirective 2005/84/EC, USConsumer Product Safety Improvement Act of2008section 108, JapanHealth, Labor and Welfare Ministry guideline No.336 (2010). This test method provides a procedureto identify an
22、d quantify regulated phthalates in PVC.5.2 Other techniques successfully used to separate and identify phthalates in PVC include GC/MS, HPLC/UV, HPLC/MS,FTIR, and GC/FID (flame ionization detector).6. Interferences6.1 Retention times for GC are dependent on several variables and it is possible to ha
23、ve two or more components with identicalretention times. The analyst shall take the necessary steps to insure that adequate separation of the plasticizer components isachieved and or the ions used to monitor for a target phthalate are free of interference. This includes, but is not limited to changi
24、ngthe selectivity of the chromatographic column. Calibration by standard addition offers the advantage of minimizing interferences.6.2 When using a TDGC/MS method, care must be taken to ensure that the sample cups are inert and clean. Any and allsolvents used to prepare standards and sample solution
25、s 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) thepresence or absence of the quant ion and the two confirming ions and (3) the ratio of the quant and the confirming ion one mustsatisfy the es
26、tablished guideline (see Table 1).TABLE 1 Ions and Ion Ratios Used to Identify Each PhthalateDBP BBP DEHP DNOP DINP DIDPQuant ion 223 206 279 279 293 307Confirmion 1149 149 149 149 149 149Area ratio(10%)(Quant/Confirm1)0.04 0.23 0.08 0.06 0.20 0.12Confirmion 2167 167 167 167 167 167D7823 1426.4 Calc
27、ulating the phthalate concentrations using the areas of compound specific ions and standard addition significantlyreduces interference from nontarget compounds.7. Apparatus7.1 Gas chromatograph/mass spectrometer capable of operating in the 75 to 350C range.NOTE 5Optional but recommended: Ventfree GC
28、/MS Adapter. This facilitates the rapid conversion between detailed analysis and evolved gasanalysis.7.2 Thermal desorption unit capable of heating the sample from 100 to 350C at 20C/min.7.3 Inert, reusable or disposable sample containers or cups.7.4 GC capillary column: UA5 (5 % 5 % diphenyl95 % po
29、ly (dimethylsiloxane) stainless steel, 30 m by 0.25 mm ID with a0.25 m film thickness, or equivalent.7.5 Integrator or data handling system, capable of measuring peak areas and retention times to four significant figures.7.6 Analytical balance, capable of weighing to 60.000001 g (1 g). If using a ba
30、lance capable of weighing to 60.00001 g (10g), weight used in the sample and standard preparation must be scaled accordingly in order to ensure that the data isare accurateto three significant figures.7.7 Pressure regulators, for all required gas cylinders.7.8 Flow meter, or other means of measuring
31、 gas flow rates 60.1 mL/min.8. Reagents and Materials8.1 Helium carrier gas, chromatographic grade.8.2 Methylene chloride (DCM) or nhexane for preparing the phthalate standard solution (Solution #1, 10.2), spectral qualityor chromatographic grade.8.3 Tetrahydrofuran (THF), or a solvent suitable for
32、preparing the PVC sample (Solution #2, 10.3), spectral quality orchromatographic grade.8.4 Standards of the appropriate phthalates for use when constructing an external calibration curve or preparing Solution #3(10.4) used for standard addition. See Note 23.9. Safety and Precautions9.1 Use THF and m
33、ethylene chloride in a wellventilated space.10. Preparation of the Analytical Samples (based upon using a 1 g balance) Weights must be scaled up if using a10-g balance.10.1 Three solutions must be prepared: (1) a stock solution of the target phthalate standards, (2) a solution of the sample and(3) t
34、he sample solution spiked with the standard stock solution.10.2 Solution #1Prepare a stock standard solution of the phthalates by dissolving 0.30 mg of each phthalate in 10 mL ofmethylene chloride (0.30 mg/10 mL). Nhexane has also been used with success. See Fig. 1 for a typical chromatogram.10.3 So
35、lution #2Dissolve 200 mg of the sample in 10 mL THF (200 mg/10 mL). Shake (or sonicate) the solution for fiveminutessee Note 6. The solution may is likely to range from clear to slightly cloudy. Place 10 L of the sample solution in aclean sample cup. Evaporate the solvent; the sample is ready to ana
36、lyze. See Figs. 2 and 3 for example chromatograms.NOTE 6A critical step in the accurate determination of phthalates is sample homogeneity. This is discussed in more detail in Appendix X2.NOTE 7The THF sample solution mayIt is possible that the solution will contain inorganic material. Studies have s
37、hown that the presence of insolubleinorganic material will not affect either the accuracy or precision of the phthalate determination.10.4 Solution #3Place 10 Lof the sample solution (#2) into a clean sample cup.Add 10 Lof the phthalate standard solution(#1). Evaporate the solvent.NOTE 8To expedite
38、the evaporation process, pass a steady stream of a high purity inert gas using clean, (plasticizer- and additive-free) tubing overthe sample cup.11. Procedure11.1 Establish that the analytical system is freecontains concentrations of phthalate contamination by analyzing 10 L of THF.Acceptable levels
39、 of background contamination will be determined by that are lower than the background contaminationacceptable to the project specific Data Quality Objectives. Objectives by analyzing 10 L of THF.11.2 Establish the relative retention time and mass spectrum of each phthalate using Solution #110.2: The
40、 followingconditions were used to obtain the example chromatograms shown in Figs. 1-4:D7823 143Thermal Desorption (TD)GC/MS AnalysisTD temperature: 100 20C/min 320C (5 min hold)Py interface: 320C (Auto mode),GC injector : 300CGC oven: 80 (1 min hold) to 200C (at 50C/min) to 320C (15C/min, 2 min hold
41、)Solvent delay: 6 minColumn: UA5 (5 % Diphenyl95 % dimethyl polysiloxane) 30 m by 0.25 mm i.d, 0.25 mfilm) or equivalentColumn He flow: 1.2 mL/min, Split ratio: 1/20Mass range: 29600 m/z,Scan speed: 2.57 scans/sec,Threshold: 50MSD Transfer Line Temp.: 300CIon Source (EI) temp.: 230CNOTE 9Confirm the
42、 TD zone using Evolved Gas Analysis (EGA)MS. The total ion chromatogram of the sample (Solution #2, 10.3) needs to besimilar to that presented in Appendix X1.11.2.1 Confirm the TD zone using Evolved Gas Analysis (EGA)MS. The total ion chromatogram of the sample (Solution #2,10.3) needs to be similar
43、 to that presented in Appendix X1.NOTE 10The use of alternative GC columns or chromatographic conditions normally results in adequate separation of the phthalates. Thosetechniques are allowed as long as the same or a similar separation is achieved.11.3 Analyze the sample (Solution #2, 10.3) using th
44、e conditions outlined in 11.2. Typical chromatograms are shown in Figs.2 and 3. The precision of the TD method is shown in Fig. 3.FIG. 1 Solution #1Phthalates Standard Mixture (see 10.2)D7823 14411.4 Peak identifications are based on relative retention data, full scan extracted ion chromatograms of
45、both the quant andconfirming ions and the ion area ratios as indicated in Table 1. Phthalate quantificationquantitation is based upon the peak areasof the quant ions listed in Table 1. The assumption being made is that the sole source of the quant ion at a predetermined retentiontime is the phthalat
46、e and therefore phthalate. Use the peak area of the quant ion can be used to accurately determine the amountof the phthalate.11.5 If using selected ion monitoring (SIM), peak identification is based solely on the presence or absence of the quant ion andthe two confirming ions at a predetermined rete
47、ntion time. QuantificationQuantitation is based on the area of the quant ion.11.6 When DINP and DIDP are copresent both present in a sample or standard, use m/z 127 should be used as a qualifyingion for DINP and m/z 289 for DIDP. This is because DINP and DIDP partialpartially coelute and both produc
48、e m/z 149 and 167.FIG. 2 Solution #2Chromatograms (TIC) of PVC with Three Different Plasticizers, TD-GC/MS Analysis (see 10.3 and 11.3)D7823 145If 149 qualifier ion ratios are set when DINP and DIDP are at equal concentrations, then any samples with different ratios willproduce substantially differe
49、nt 149/167 ratios, potentially leading to a false negative.NOTE 9A typical total ion chromatogram obtained using the conditions specified in 11.2 is shown in Fig. 1. Because the absolute retention times aredependent upon the entirety of the GC system; relative retention times can be used to identify each phthalate. The choice of the base phthalate is left tothe laboratory.11.7 QuantificationQuantitation is done using standard addition. Analyze Sol
