1、Designation: D7823 14D7823 16Standard Test Method forDetermination of Low Level, Regulated Phthalates in Poly(Vinyl Chloride) Plastics by Thermal DesorptionGasChromatography/Mass Spectrometry1This standard is issued under the fixed designation D7823; the number immediately following the designation
2、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*1.1 This test method provides a procedure
3、 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” is defined as 1000
4、 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 method.1.5 This standar
5、d 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 is no known ISO equiv
6、alent to this test method.standard.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 Monomeric Pla
7、sticizers 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 ChromatographyE6
8、91 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 System2.2 ASTM Adjuncts:Adjunct to D7823 Vinyl Plasticizer LibraryTotal Ion Chromatograms and Mass Spectra33
9、. Terminology3.1 DefinitionsFor definition of plastic terms used in this test method, see 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(2eth
10、ylhexyl) ester CAS #1032313.3.2 (DINCH) 1,2Cyclohexanedicarboxylic acid, dinonyl ester, branched and linear CAS #4749195901 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 appro
11、ved Aug. 1, 2014May 1, 2016. Published September 2013May 2016. Originally approved in 2013. Last previous edition approved in 20132014 asD7823 - 13.D7823 - 14. DOI: 10.1520/D7823-14.10.1520/D7823-16.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service
12、at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.3 Available from ASTM International Headquarters. Order Adjunct No. ADJD7823S-EA. Original adjunct produced in 2016.This document is not an ASTM standard and is i
13、ntended only to provide the user of an ASTM standard an indication of what changes have been made to the 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 cu
14、rrent versionof the standard as published by ASTM is to be considered the official document.*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 States13.3.3 (DBP) 1,2Benzenedicarbo
15、xylicacid, 1,2dinbutyl ester CAS #847423.3.4 (BBP) Benzyl butyl phthalate CAS #856873.3.5 (DEHP) Bis(2Ethyhexyl) Phthalate CAS #1178173.3.6 (DNOP) Di(noctyl) phthalate CAS #1178403.3.7 (DINP) 1,2Benzenedicarboxylicacid, diC810branched alkyl esters, C9rich (Jayflex) CAS #685154803.3.8 (DINP) 1,2Benze
16、nedicarboxylicacid, 1,2diisononyl (Palatinol) CAS #285531203.3.9 (DIDP) 1,2Benzenedicarboxylicacid, diC911branched alkyl esters, C10rich (Jayflex) CAS #685154913.3.10 (DIDP) 1,2Benzenedicarboxylicacid, 1,2diisodecyl CAS #267614003.3.11 TD Thermal Desorption3.3.12 GC Gas Chromatography3.3.13 GC/MS Ga
17、s 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“Methylene Chloride”3.3.17 EGAMS Evolved Gas Analysismass spectrometry3.3.18 FTIR Fourier Transform Infrared Spectroscopy3.3.19 TIC Total ion chrom
18、atogram3.3.20 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 is specific information on DINP and DIDP. For more information, please refer to Appe
19、ndix X3Appendix X3Jayflex DIDP: 1,2Benzenedicarboxylicacid, diC911branched alkyl esters, C10rich: CAS# 68515491.Jayflex DINP: 1,2Benzenedicarboxylicacid, diC810branched alkyl esters, C9rich: CAS# 68515 480.4. Summary of Test Method4.1 200 mg of the PVC sample are dissolved in 10 mL of THF. 10 L of t
20、he THF solution are analyzed using TD-GC/MS.Phthalates are identified by their retention times and their mass spectra. Quantification is based on the area of a designated quantion (SIM or full scan)see Table 1. Standard addition is the calibration method.NOTE 4Standard addition calibration will nega
21、te 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 quantitation of phthalates: DBP, BBP, DEHP, DNOP, DINP, and DIDP are required for regulated articles.Regulations include
22、: EUDirective 2005/84/EC, USConsumer Product Safety Improvement Act of 2008section 108,JapanHealth, Labor and Welfare Ministry guideline No.336 (2010). This test method provides a procedure to identify andquantify regulated phthalates in PVC.5.2 Other techniques successfully used to separate and ide
23、ntify 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 have two or more components with identicalretention times. The analyst shall take the necessary ste
24、ps 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 changingthe selectivity of the chromatographic column. Calibration by standard addition offers the adva
25、ntage 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 solutions must be free of contamination.TABLE 1 Ions and Ion Ratios Used to Identify Each PhthalateDBP BB
26、P 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 1626.3 The presence or absence of each phthalate is based upon three criteria: (1) the relative retention time
27、 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 established guideline (see Table 1).6.4 Calculating the phthalate concentrations using the areas of compound specific ions and standard addit
28、ion 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/MS Adapter. This facilitates the rapid conversion between detailed analysis and evolved gasanaly
29、sis.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: 5 % diphenyl95 % poly (dimethylsiloxane) stainless steel, 30 m by 0.25 mm ID with a 0.25 m filmthickness, or equivalent.7.5 I
30、ntegrator 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 balance capable of weighing to 60.00001 g (10g), weight used in the sample and standard preparation must be
31、scaled accordingly in order to ensure that the data are accurateto three significant figures.7.7 Pressure regulators, for all required gas cylinders.7.8 Flow meter, or other means of measuring gas flow rates 60.1 mL/min.8. Reagents and Materials8.1 Helium carrier gas, chromatographic grade.8.2 Methy
32、lene 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 preparing the PVC sample (Solution #2, 10.3), spectral quality orchromatographic grade.8.4 Standards of the
33、appropriate phthalates for use when constructing an external calibration curve or preparing Solution #3(10.4) used for standard addition. See Note 3.9. Safety and Precautions9.1 Use THF and methylene chloride in a wellventilated space.10. Preparation of the Analytical Samples (based upon using a 1 g
34、 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) the sample solution spiked with the standard stock solution.10.2 Solution #1Prepare a stock standard solution
35、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 Solution #2Dissolve 200 mg of the sample in 10 mL THF (200 mg/10 mL). Shake (or sonicate) the solution for five
36、minutessee Note 6. The solution is likely to range from clear to slightly cloudy. Place 10 L of the sample solution in a cleansample cup. Evaporate the solvent; the sample is ready to analyze. See Figs. 2 and 3 for example chromatograms.NOTE 6A critical step in the accurate determination of phthalat
37、es is sample homogeneity. This is discussed in more detail in Appendix X2.NOTE 7It is possible that the solution will contain inorganic material. Studies have shown that the presence of insoluble inorganic material will notaffect either the accuracy or precision of the phthalate determination.10.4 S
38、olution #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 the evaporation process, pass a steady stream of a high purity inert gas using clean, (plasticizer- and additive-free) tubing overthe sample
39、 cup.11. Procedure11.1 Establish that the analytical system contains concentrations of phthalate contamination that are lower than the backgroundcontamination acceptable to the project specific Data Quality Objectives by analyzing 10 L of THF.D7823 16311.2 Establish the relative retention time and m
40、ass spectrum of each phthalate using Solution #110.2: The followingconditions were used to obtain the example chromatograms shown in Figs. 1-4:Thermal 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) t
41、o 200C (at 50C/min) to 320C (15C/min, 2 min hold)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.:
42、300CIon Source (EI) temp.: 230C11.2.1 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 to that presented in Appendix X1.11.3 Analyze the sample (Solution #2, 10.3) using the conditions outlined in 11.2. Typical ch
43、romatograms are shown in Figs.2 and 3. The precision of the TD method is shown in Fig. 3.11.4 Peak identifications are based on relative retention data, full scan extracted ion chromatograms of both the quant andconfirming ions and the ion area ratios as indicated in Table 1. Phthalate quantitation
44、is based upon the peak areas of the quantFIG. 1 Solution #1Phthalates Standard Mixture (see 10.2)D7823 164ions listed in Table 1. The assumption being made is that the sole source of the quant ion at a predetermined retention time is thephthalate. Use the peak area of the quant ion can be used to ac
45、curately determine the amount of 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 retention time. Quantitation is based on the area of the quant ion.11.6 When DINP
46、and DIDP are both present in a sample or standard, use m/z 127 as a qualifying ion for DINP and m/z 289for DIDP. This is because DINP and DIDP partially coelute and both produce m/z 149 and 167. If 149 qualifier ion ratios are setwhen DINP and DIDP are at equal concentrations, then any samples with
47、different ratios will produce substantially different149/167 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 areFIG. 2 Solution #2Chromatograms (TIC) of PVC
48、 with Three Different Plasticizers, TD-GC/MS Analysis (see 10.3 and 11.3)D7823 165dependent 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 Quantitation is done using standard addition
49、. Analyze Solution #3. A typical total ion chromatogram is shown in Fig. 4.Analytical precision is presented in the table at the bottom of Fig. 4. Standard addition is very useful when it is difficult to eliminateinterferences from the sample matrix. This is often the case when analyzing PVC where DINCH, Mesamoll or both are present.FIG. 3 Solution #2Reproducibility of PVC-DINCH (n=6) (see 10.3 and 11.3)D7823 16611.8 Pay attention to the chromatograp
