1、Designation: D8143 17Standard Test Method forDetermination of the EU-8 List of PAH Compounds inCarbon Black1This standard is issued under the fixed designation D8143; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last
2、 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 covers the qualitative and quantitativedetermination of the EU-8 list of polycyclic aromatic hydro-carbon
3、s (PAH) on carbon black. The EU-8 list of PAHcompounds is given in Table 1.The procedure involves Soxhletextraction with toluene followed by extract analysis using gaschromatography with mass spectrometry (GC/MS). Thismethod is not intended to test for U.S. Food and DrugAdministration (FDA21 CFR 178
4、.3297) compliance of carbonblacks used for indirect food contact applications.1.2 UnitsThe values stated in SI units are to be regardedas the standard. No other units of measurement are included inthis standard.1.3 This standard does not purport to address all of thesafety concerns, if any, associat
5、ed with its use. It is theresponsibility of the user of this standard to establish appro-priate safety, health, and environmental practices and deter-mine the applicability of regulatory limitations prior to use.1.4 This international standard was developed in accor-dance with internationally recogn
6、ized 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 Federal Standard:221 CFR 178.3297 Indi
7、rect Food Additives: Adjuvants, Pro-ductions Aids, and Sanitizers, Colorants for Polymers3. Terminology3.1 Definitions of Terms Specific to This Standard:3.1.1 polycyclic aromatic hydrocarbon, PAH, norganiccompound(s) that consist of chemical structures of alternatingsingle and double bonds of a rin
8、g like nature (for example,benzene), with no heteroatom or other substituents; frequentlythe rings are fused to make larger chemical structures.3.1.1.1 DiscussionPAH naturally occur in oil, coal, and tardeposits; are produced by the incomplete combustion ofhydrocarbons; and occur in many other produ
9、cts and processes.3.1.2 EU-8 PAH compound list, na list of eight polycyclicaromatic hydrocarbons that are specified by the CommissionRegulation (EU) 1272/2013 (December 6, 2013)3amendingAnnex XVII to Regulation (EC) 1907/2006 of the EuropeanParliament and of the Council on the Registration, Evaluati
10、on,Authorisation and Restriction of Chemicals (REACH) asregards polycyclic aromatic hydrocarbons (2013) OJ L328/69.3.1.2.1 DiscussionRegulation (EU) No. 1272/2013 setsPAH concentration limits on finished products specified bytheir application. The regulation does not refer directly tocarbon black, t
11、hough in many instances and for formulationpurposes there is a need to know the quantitative, extractablePAH content present in carbon black that will become part ofthe finished product. In addition, no specific test method hasbeen defined by the regulation for testing finished products orraw materi
12、als used in the finished products.4. Summary of Test Method4.1 A portion of carbon black is Soxhlet-extracted withtoluene for 48 h. The extract is concentrated and subsequentlyanalyzed for specific PAH compounds by gas chromatographywith mass spectrometry (GC/MS). Each PAH compound isquantified indi
13、vidually using internal and external standards.5. Significance and Use5.1 This test procedure is used to determine the individualconcentrations of the PAH compounds in the EU-8 list ex-tracted from carbon black by the means of a Soxhlet extractionapparatus with toluene.1This test method is under the
14、 jurisdiction of ASTM Committee D24 on CarbonBlack and is the direct responsibility of Subcommittee D24.66 on Environment,Health, and Safety.Current edition approved Oct. 1, 2017. Published November 2017. DOI:10.1520/D8143-17.2Available from U.S. Government Printing Office, Superintendent ofDocument
15、s, 732 N. Capitol St., NW, Washington, DC 20401-0001, http:/www.access.gpo.gov.3Commission Regulation (EU) No 1272/2013 of 6 December 2013.Available athttp:/eur-lex.europa.eu/eli/reg/2013/1272/oj.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. Unit
16、ed StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers
17、 to Trade (TBT) Committee.16. Apparatus6.1 Soxhlet Extractor with Reflux Condenser, 50 or 100 cm3capacity.6.2 Extraction Thimbles, glass or cellulose, approximately50 to 70 cm3capacity. For instance, glass extraction thimble of35 mm diameter by 90 mm height with course porosity (70 to100 m similar t
18、o Ace Glass Size C, Porosity B, Code-14).6.3 Heating Mantle, compatible with boiling flask describedin 6.4.6.4 Boiling Flasks for Soxhlet, for example, 250 cm3.6.5 Glass Beads, approximately 180 to 250 m (60/80mesh) if glass thimbles are used. Need to be very clean ortoluene extracted.6.6 Glass Boil
19、ing Beads, approximately 3 mm.6.7 Glass Wool, need to be very clean or toluene extracted.6.8 Rotary Evaporator, with temperature-controlled waterbath, automatic pressure regulation, and solvent-proof mem-brane vacuum pump. Other evaporators may be used if theyproduce acceptable results.6.9 Nitrogen
20、Blow-Down Apparatus, equipped with a con-trolled water bath and nitrogen pressure control.6.10 Pear-Shaped Flasks for Rotary Evaporator, forexample, 25, 50, and 100 cm3.6.11 GC/MS, with autosampler.6.11.1 Mass Spectrometer (MS), with electron impact capa-bility and Selected Ion Monitoring (SIM) mode
21、.6.11.2 GC Capillary Column, usually a nonpolar GC col-umn composed of 5 % diphenyl/95 % dimethyl polysiloxanecoating is used for PAH analysis. Other similar column phasesmay be used if they provide acceptable peak resolutions.6.11.3 Deactivated Straight Borosilicate Liner with SmallPiece of Deactiv
22、ated Glass WoolThis liner may be used aslong as peak resolution is satisfactory.6.11.4 Alternative liner is a split/splitless nondeactivatedliner with glass wool (4 mm internal diameter, straight liner).This shall be deactivated with a silanizing agent before use.Another alternative is a split/split
23、less liner with fluorocarbonliner seals. Such a liner will already contain conditionedsilanized glass wool. Other liners can be used if they produceacceptable results.6.11.5 Gold-Plated Seal, for GC injector port or similarnonreactive seal.6.11.6 GC/MS Amber Autosampler Vials, with polytetra-fluoroe
24、thylene (PTFE)-coated caps.6.12 Adjustable Micropipettes, for example 1000, 200, and20 L, or similar analytical-grade volume measuring equip-ment.6.13 Microliter Syringes of Different Volumes, for example,10 and 100 L.6.14 Volumetric Flasks, for example 10 and 100 cm3.6.15 Analytical Balance, with a
25、n accuracy of 0.1 mg.6.16 Furnace, capable of temperature regulation of 500 625C, used to burn off organic contamination from glasssurfaces.6.17 Manometer, capable of pressure readings in the rangeof 5 6 0.3 kPa for controlling vacuum evaporators.7. Reagents and Materials7.1 Purity of ReagentsReagen
26、t-grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents conform to the specifications of the Committee onAnalytical Reagents of the American Chemical Society wheresuch specifications are available.4Other grades may be used,provided it is first ascerta
27、ined that the reagent is of sufficientlyhigh purity to permit its use without lessening the accuracy ofthe determination.7.2 Stock solutions or mixtures of the native PAH standardsand of the internal standard (deuterated PAH compounds) canbe purchased as premade solutions or prepared from solidmater
28、ials (Table 1).7.2.1 Aconcentration range of 80 to 100 g/cm3for each ofthe native PAH analytes is recommended for a stock solutionmixture.7.2.2 A similar concentration range of 80 to 100 g/cm3foreach of the deuterated internal standard compounds is recom-mended for the internal standard (IS) stock s
29、olution.7.2.3 All purchased standard materials shall be 98 % pure orbetter and certified with respect to their purity and concentra-tion by the manufacturer. Follow the manufacturers recom-mendation on how to store the standard solutions and theirrecommended expiration date. Typically, the stock sol
30、utionsare protected from light and stored at room temperature. Theyshould be checked for signs of degradation or evaporation. The4Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For Suggestions on the testing of reagents notlisted by the America
31、n Chemical Society, see Annual Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.TABLE 1 EU-8 PAH Compounds and Internal StandardsNative PAH CAS# Deuterated Internal Sta
32、ndard CAS#Benzaanthracene 56-55-3 Chrysene-d12 1719-03-5Chrysene 218-01-9 Benzoapyrene-d12 63466-71-7Benzobfluoranthene 205-99-2 1,12-Benzoperylene-d12 93951-66-7Benzojfluoranthene 205-82-3 Perylene-d12 1520-96-3Benzokfluoranthene 207-08-9Benzoepyrene 192-97-2Benzoapyrene 50-32-8Dibenza,hanthracene
33、53-70-3D8143 172standard stock solutions shall be replaced/recertified on ayearly basis or sooner if comparisons with quality control (QC)samples indicate a problem.7.3 Toluene, suitable for high resolution gas chromatogra-phy analysis (99.99 % pure).7.4 Cyclohexane, suitable for high resolution gas
34、 chroma-tography analysis (99.99 % pure).7.5 Helium, GC/MS purity grade.7.6 Nitrogen, analytical purity grade.7.7 Silica gel columns for Solid Phase Extraction (SPE)removal of polar compounds.7.7.1 Silica SPE Cartridges, single-use application, having avolume capacity of approximately 1 to 10 cm3.57
35、.7.1.1 Preparation of Silica SPE CartridgeFollow themanufacturers instruction for preparation and use. The typicalmethod of preparation is to wet the cartridge with approxi-mately 10 cm3of the elution solvent. Discard the wettingsolvent.7.7.2 Alternative SPE Method: Silica Gel/13 % H2O Grav-ity Colu
36、mn:7.7.2.1 Preparation of a Silica Gel/13 % H2O AdsorbentPour 200 g silica gel (high purity grade, type 60, particle size0.063 to 0.200 mm) into a screw cap glass bottle and add 30 gof deionized water in small portions (for example, 2 cm3) usinga suitable pipette. After addition of each portion of w
37、ater, thesilica gel bottle is shaken to evenly distribute the wetted silicagel. No aggregation should occur during this process. If so,shaking must be continued until a homogeneous material isobtained. Finally, the closed bottle is shaken for8hbymeansof an overhead shaker. If properly closed and sto
38、red, theadsorbent should be viable for at least 6 months.7.7.2.2 Preparation of a Silica Gel/13 % H2O GravityColumnInsert a glass wool plug into the bottom of a pipettetip (for example, 8 to 10 mm inner diameter and 5 cm3capacity). Place1gofthesilica gel/13 % H2O in the columnand tap the column gent
39、ly to settle the silica gel. Cover theadsorbent layer with a glass wool plug and pre-elute thecolumn with 5 cm3of cyclohexane. Discard the cyclohexaneeluate.8. Hazards8.1 This test involves hazardous materials, operations, andequipment. This procedure does not attempt to address thesafety problems a
40、ssociated with this test. A hazards reviewshall be conducted by all personnel performing the test. It is theresponsibility of the user to review all material safety datasheets (MSDS), manuals, and hazards procedures and establishthe appropriate safety measures. Some PAH compounds havebeen shown to p
41、ossess mutagenic as well as carcinogenic andteratogenic properties.As such, concentrated extracts of carbonblacks containing PAHs also may possess the same harmfulproperties. Solvents used are flammable. Appropriate personalprotection equipment (PPE) shall be used.9. Preparation of Standard Solution
42、s9.1 The GC/MS instrument is calibrated using five solutionsof the PAH mixture in which internal standards (IS) have alsobeen added. The recommended external standard concentra-tions are to cover a range of 0.0125 to 1.0 g/cm3. Otherconcentrations may be used as needed for the application. TheIS con
43、centration is kept constant within the calibration range.Preferably the IS concentration is in the middle of the selectedcalibration range (for example, 0.3 to 0.6 g/cm3). A lowerPAH concentration range can be used for high-purity carbonblacks. However, the IS concentration should maintain an S/Nrat
44、io of at least 15/1 for routine instrument performance.Subsections 9.2 9.4 describe the preparation of the varioussolutions required.9.2 Preparation of PAH Standard Solutions forCalibrationUsing the native PAH standard stock solutiondescribed in 7.2, prepare at least 10 cm3of five toluenesolutions a
45、t the concentrations suggested in the following list.Other concentrations may be used but the difference betweenany two concentration levels shall not exceed a factor of four.Before diluting to the final solution volume, spike eachstandard with the appropriate volume (for example, 100 L ISsolution d
46、escribed in 9.3 into 10 cm3volumetric flask to givea final IS concentration of 0.500 g/cm3). Other aliquotvolumes and final volumes may be used to obtain the desiredconcentrations. Cap the standard solutions securely, mix thor-oughly and label. Store all standard solutions in the dark.Native PAH Sta
47、ndard 5 1.00 g/cm3Native PAH Standard 4 0.500 g/cm3Native PAH Standard 3 0.200 g/cm3Native PAH Standard 2 0.0500 g/cm3Native PAH Standard 1 0.0125 g/cm39.3 Preparation of Diluted IS SolutionUsing the IS stocksolution described in 7.2, prepare at least 10 cm3of dilutedinternal standard solution for a
48、dding to samples and calibrationstandards. A concentration of 50 g/cm3is suggested for thissolution but other concentrations can be used. For example,when adding 100 L of a 50 g/cm3IS solution to a 10 cm3final extract volume, the IS concentration will be 0.500 g/cm3.9.4 All standard solutions shall
49、be stored in a refrigerator(6C) when not in use. Care has to be taken not to exceedtheir shelf life. If any indication of degradation is perceived,then new standards have to be prepared.10. Carbon Black Sample Preparation and Extraction10.1 All glassware coming into contact with the sampleshall be free of PAH on the basis of the limits of quantification.It is recommended to use separate glassware and extractionunits for high-purity carbon blacks and carbon blacks in whichhigher PAH levels are expected. Blanks should be run on aregul
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