1、BSI Standards PublicationWB11885_BSI_StandardCovs_2013_AW.indd 1 15/05/2013 15:06Footwear - Critical substances potentially present in footwear and footwear components - Determination of phenol in footwear materials (ISO 20536:2017)BS EN ISO 20536:2017National forewordThis British Standard is the UK
2、 implementation of EN ISO 20536:2017. It is identical to ISO 20536:2017.The UK participation in its preparation was entrusted to Technical Committee TCI/69, Footwear analytical grade for the solvents.5.1.1 Phenol CAS: 108-95-2 (target compound).5.1.2 Phenol-D6 CAS: 13127-88-3 (extraction surrogate).
3、5.1.3 Anthracene-D10 CAS: 1719-06-8 (internal standard).5.1.4 Toluene CAS: 108-88-3 (solvent).5.1.5 Acetone CAS: 67-64-1 (solvent).5.1.6 Mixture toluene/acetone (80/20) percent by volume (extraction mixture).The composition of the mixture is based on the volume. For example, to make 100 ml of the mi
4、xture, mix 80 ml of toluene with 20 ml of acetone.5.1.7 Methanol CAS: 67-56-1 (solvent).5.2 Stock solutions5.2.1 Internal standard Anthracene-D10 stock solution (1 000 mg/l).Weigh 10 mg of Anthracene-D10 in a 10 ml volumetric flask and fill to the mark with acetone. Transfer the content to an amber
5、10 ml vial with a polytetrafluoroethylene (PTFE) stopper and store at 4 C.5.2.2 Internal standard Anthracene-D10 working solution (10 mg/l).Prepare a 1:100 dilution of the stock solution (5.2.1). For example, take 100 l of the stock solution in a 10 ml volumetric flask and fill to the mark with acet
6、one.5.2.3 Extraction surrogate Phenol-D6 stock solution (1 000 mg/l).Weigh 10 mg of Phenol-D6 in a 10 ml volumetric flask and fill to the mark with acetone. Transfer the content to an amber 10 ml vial with PTFE stopper and store at 4 C.5.2.4 Extraction surrogate Phenol-D6 working solution (10 mg/l).
7、Prepare a 1:100 dilution of the stock solution (5.2.3). For example, take 100 l of the stock solution in a 10 ml volumetric flask and fill to the mark with acetone.5.2.5 Target compound phenol stock solution (1 000 mg/l).Weigh 10 mg of phenol in a 10 ml volumetric flask and fill to the mark with ace
8、tone. Transfer the content to an amber 10 ml vial with PTFE stopper and store at 4 C.2 ISO 2017 All rights reservedBS EN ISO 20536:2017ISO 20536:2017(E)5.2.6 Phenol + Phenol-D6 intermediate calibration solution (10 mg/l).Take a volume of 100 l of the stock solution of the extraction surrogate (5.2.3
9、) and the target compound (5.2.5) in a 10 ml volumetric flask and fill to the mark with the mixture of toluene/acetone (80/20).5.2.7 Phenol + Phenol-D6 working calibration solution (1 mg/l).Take a volume of 1 000 l of the intermediate calibration solution (5.2.6) in a 10 ml volumetric flask and fill
10、 to the mark with the mixture of toluene/acetone (80/20).6 ApparatusUsual lab equipment and the following. Use laboratory glassware in accordance with ISO 4787.6.1 Analytical balance, with an accuracy of at least 0,1 mg.6.2 Glass vial, which can be tightly sealed, 40 ml.6.3 Ultrasonic bath, with adj
11、ustable temperature.6.4 PTFE-membrane filter, pore width 0,45 m.6.5 2 ml sample vials, PTFE-capped.6.6 20 ml sample vials, PTFE-capped.6.7 Gas chromatograph with a mass selective detector (MSD). Other chromatographic technics may be used provided that they have been validated for this analysis.7 Sam
12、plingIn the footwear, the upper and the complex lining plus the insock shall be tested.The test piece consists of a single material (leather, textile or polymer). Homogenous textile, leather and polymer samples are cut into pieces with an edge length of up to 5 mm.The sample should not be subjected
13、to grinding as it results in the loss of volatile phenol.8 Test method8.1 ExtractionWeigh 1 g of the sample in a 20 ml glass vial (6.6). Then add 9,8 ml of the extraction mixture (5.1.6) and 200 l of the extraction surrogate working solution (5.2.4).The extraction is conducted with an ultrasonic dev
14、ice at 60 C 5 C during 60 min 2 min.NOTE It has been proven that acetone is efficient as extraction solvent. However, its high polarity (compared to the extraction mixture) can conduct to a high amount of co-extracted compounds (such as dyes or other polar compounds like glycols) which could disturb
15、 the analysis.Some polymeric materials can be dissolved in the extraction mixture and can cause problems during the quantification. In these cases, precipitation by methanol could be necessary. Precipitate the solution obtained by adding 20 ml of methanol (5.1.7) and allow the precipitate to settle
16、for at least 5 min. Filtrate, if necessary, using a 0,45 m PTFE filter. ISO 2017 All rights reserved 3BS EN ISO 20536:2017ISO 20536:2017(E)8.2 AnalysisTake an aliquot of exactly 1 ml of the extract and add 50 l of the internal standard working solution (5.2.2).Analyse with GC-MS (6.7) according to C
17、lause 9.8.3 CalibrationFor practical reasons the calibration is based on a solution containing the target compound and the extraction surrogate.Within the linear range use at least five measurements at different concentrations. The calibration is conducted directly in 2 ml sample vials, see Table 1.
18、Table 1 Calibration solutionsStandard L1 L2 L3 L4 L5Volume of the working calibration solution (l) (5.2.7)50 100 250 500 1 000Volume of extracting mixture (l) (5.1.6)950 900 750 500 0Concentration of phenol and Phenol-D6 (g/l) 50 100 250 500 1 000Volume of the internal standard working solution (l)
19、(5.2.2)50Concentration of the internal standard (g/l) 5009 Determination with GC-MS9.1 Measuring methodValidated analysis methods other than the method described in Annex A are permitted, provided a comparable precision and quantification limit (9.3.1) can be reached.The ions given in Table 2 shall
20、be used.Examples are given in Annex A.Table 2 Monitoring ionsCompounds IonsPhenol9466Phenol-D69971Anthracene-D10 1884 ISO 2017 All rights reservedBS EN ISO 20536:2017ISO 20536:2017(E)9.2 Quantification9.2.1 Calibration curveSet up the linear regression function by using the following ratio (A e/A is
21、) and (C e/C is) with the help of Formula (1):AAabCCeiseis=+ (1)whereAeis the area of the target of phenol based on the monitoring ions;Aisis the area of the peak of Anthracene-D10 based on the monitoring ions;Ceis the concentration of phenol in the calibration standard, in g/l;Cisis the concentrati
22、on of Anthracene-D10 in the calibration standard, in g/l;a is the slope of the linear function;b is the ordinate intercept of the calibration curve. The units depend on the evaluation.The same calculation shall be conducted for Phenol-D6.9.2.2 Recovery rateThe use of an extraction surrogate permits
23、the calculation of an extraction yield using Formula (2):RCC%()=calculatedtheoretical100 (2)whereCcalculatedis the concentration of Phenol-D6 analysed in the sample after the extraction;Ctheoreticalis the concentration of Phenol-D6 initially introduced before the extraction (200 l of a 10 mg/l solut
24、ion into 10 ml of extraction mixture; in this case Ctheoreticalis 200 g/l).If the extraction is below 75 % or above 125 %, the sample shall be reanalysed.9.2.3 Determination of the phenol contentThe content of phenol is calculated according to Formula (3) as a mass fraction W in mg/kg:WVmaCAAb=(/)ec
25、hisis(3)whereW is the content of the phenol in the specimen, in mg/kg;V is the volume of extraction mixture used for the extraction, in ml (in most cases this value will be equal to 10 ml);m is the mass of the test specimen, in kg;Aechis the area of the peak of phenol in the sample;Aisis the area of
26、 the peak of Anthrancene-D10 in the sample;Cisis concentration of Anthrancene-D10 in the sample, in g/l;a is the slope of the linear function determined in (9.2.1);b is the ordinate intercept of the calibration curve determined in (9.2.1). ISO 2017 All rights reserved 5BS EN ISO 20536:2017ISO 20536:
27、2017(E)9.3 Performances of the test method9.3.1 Quantification limit of the GC-MS methodThe quantification limit of the method should be 0,5 mg/kg considering a mass of sample of 1 g and an extraction volume of 10 ml.It can be lowered by concentrating the sample solution. This is done by reducing th
28、e extraction volume to 1 ml under a gentle stream of nitrogen.9.3.2 Interlaboratory testsThe results of the interlaboratory tests are given in Annex B.10 Test reportThe test report shall contain the following information:a) a reference to this document, i.e. ISO 20536;b) the date of the test;c) all
29、the details necessary for complete identification of the sample tested;d) the different material types (see Clause 7) that have been tested;e) the condition of storage before the test, if available;f) a determination of the extracted phenol as calculated in 9.2.3;g) deviations from the method specif
30、ied in this document.6 ISO 2017 All rights reservedBS EN ISO 20536:2017ISO 20536:2017(E)Annex A (informative) Example of an instrumental methodA.1 GeneralThe phenol and Phenol-D6 are analysed by gas chromatography/mass spectrometry on a single quad/MS use in a simultaneous SIM/SCAN mode.A.2 Chromato
31、graphic conditionsColumn: DB-5MS (or equivalent-5 %phenyl-95 %dimethylpolysiloxane).Dimension: 30 m 0,25 mm 0,25 m.Carrier gas: Helium with a linear velocity of 36 cm/s.Oven:50 C during 1 min.245 C at 15 C/min.300 C at 25 C/min during 4 min.Injector: 265 C in pulse splitless mode with an injection v
32、olume of 1 l.Pulse pressure: 120 kPa during 1,5 min.Split flow: 60 ml/min at 1,5 min.NOTE In order to get a suitable separation between toluene and phenol, another column with a more polar phase could be used, such as DB-35 (35 % phenyl), VF-17 (50 % phenyl) or DB-WAX (100 % polyethylene glycol).A.3
33、 Detection conditionsTransfer line: 280 C.The single quad MS works in simultaneous SIM/SCAN mode.The mass SCAN range is between 50 m/z and 300 m/z.The SIM mode focus on the ions is given in Table 2. ISO 2017 All rights reserved 7BS EN ISO 20536:2017ISO 20536:2017(E)Key1 phenol and Phenol-D62 Anthran
34、cene-D10Figure A.1 Total ion chromatogram (TIC) of a standard at 500 g/l8 ISO 2017 All rights reservedBS EN ISO 20536:2017ISO 20536:2017(E)Annex B (informative) Results of the interlaboratory testsThe results obtained from two separate interlaboratory trials are given in Table B.1.Table B.1 Precisio
35、n data from trialsMaterialDate of the ILTNumber of laboratoryMean valueamg/kgRobust standard deviationamg/kgUncertainty type , u(x)amg/kgTex tile 06/2015 9 13,2 0,7 3,1Leather 03/2016 7 15,3 1,9 0,9Leather 03/2016 7 12,5 1,6 0,8Coated textile 03/2016 9 15,1 4,4 1,8Key ILT: Interlaboratory trial.aIn
36、accordance with ISO 13528:2015, Annex C using a robust algorithm. ISO 2017 All rights reserved 9BS EN ISO 20536:2017ISO 20536:2017(E)Bibliography1 ISO/TR 16178:2012, Footwear Critical substances potentially present in footwear and footwear component2 ISO 13528:2015, Statistical methods for use in pr
37、oficiency testing by interlaboratory comparisons10 ISO 2017 All rights reservedBS EN ISO 20536:2017This page deliberately left blankThis page deliberately left blankBSI is the national body responsible for preparing British Standards and other standards-related publications, information and services
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