1、BSI Standards PublicationBS EN 16778:2016Protective gloves The determination ofDimethylformamide in glovesBS EN 16778:2016 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN 16778:2016.The UK participation in its preparation was entrusted to Technical Committee PH/
2、3/8, Protective gloves.A list of organizations represented on this committee can be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2016.
3、Published by BSI Standards Limited 2016ISBN 978 0 580 87150 4 ICS 13.340.40 Compliance with a British Standard cannot confer immunity from legal obligations.This British Standard was published under the authority of the Standards Policy and Strategy Committee on 30 April 2016.Amendments/corrigenda i
4、ssued since publicationDate T e x t a f f e c t e dBS EN 16778:2016EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16778 March 2016 ICS 13.340.40 English Version Protective gloves - The determination of Dimethylformamide in gloves Gants de protection - Dtermination de la teneur en dimthylformam
5、ide dans les gants Schutzhandschuhe - Bestimmung von Dimethylformamid in Handschuhen This European Standard was approved by CEN on 30 January 2016. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of
6、 a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official versions (English, French, German)
7、. A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, C
8、yprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United
9、Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2016 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 167
10、78:2016 EBS EN 16778:2016EN 16778:2016 (E) 2 Contents Page European foreword . 3 1 Scope 3 2 Normative references 4 3 Principle . 4 4 Consumables . 4 4.1 Reagents . 4 4.2 Stock solutions . 4 4.2.1 Internal standard Stock solution (1000 mg/l) 4 4.2.2 Internal standard working solution (200 mg/l). 4 4
11、.2.3 Target compound Stock solution (1000 mg/l) 5 4.2.4 Target compound working solution (200 mg/l) 5 4.2.5 Extraction solution containing 20 mg/l internal standard 5 5 Equipment . 5 6 Test procedure . 5 6.1 Sampling . 5 6.2 Conditioning 5 6.3 Preparation . 6 6.4 Extraction . 6 6.5 Determination wit
12、h GC-MS 7 6.5.1 Calibration . 7 6.5.2 Examples of instrumental method 7 6.6 Quantification . 8 6.7 Results . 9 7 Performance of the method . 9 8 Test report . 9 Annex A (informative) Results of the interlaboratory trial . 10 Bibliography . 11 BS EN 16778:2016EN 16778:2016 (E) 3 European foreword Thi
13、s document (EN 16778:2016) has been prepared by Technical Committee CEN/TC 162 “Protective clothing including hand and arm protection and lifejackets”, the secretariat of which is held by DIN. This European Standard shall be given the status of a national standard, either by publication of an identi
14、cal text or by endorsement, at the latest by September 2016, and conflicting national standards shall be withdrawn at the latest by September 2016. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN shall not be held responsible
15、for identifying any or all such patent rights. According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, For
16、mer Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. BS EN 16778:2016EN 16778:2016 (E) 4 1 Sc
17、ope This document specifies a test method for the determination of Dimethylformamide (DMFa CAS N 68-12-2) in glove materials. NOTE For Dimethylformamide the following abbreviations can be used: DMF, DMFa DMFo. The test method is applicable for the following materials: polyurethane (PU) materials (ex
18、cept elastane), PU Coated material (textile, leather), PU foam, PU blended materials; adhesives; all materials manufactured with a dipping process using DMFa. 2 Normative references Not applicable. 3 Principle The sample is cut into small pieces and extracted with methanol in a sealed flask in an ul
19、trasonic bath. An aliquot of the extract is analysed with GC-MS. 4 Consumables 4.1 Reagents The substances are given in Table 1. Table 1 Reagent used in analysis N Substances CAS-Nr. purity 1 N, N-Dimethylformamide (DMFa) 68122 Certified standard (purity 95 % at least) 2 Dimethylformamide-d7 (DMFa-d
20、7) 4472417 Certified standard (purity 95 % at least) 3 Methanol 67561 analytical grade (purity 99 % at least) 4.2 Stock solutions 4.2.1 Internal standard Stock solution (1000 mg/l) 100 mg of DMFa-d7 is weighed with an accuracy of 0,1 mg in a 100 ml volumetric flask and filled with methanol to the ma
21、rk and stored at 4 C, for maximum 1 month. 4.2.2 Internal standard working solution (200 mg/l) The solution is prepared by 1:5 dilution of the stock solution (4.2.1) with methanol. Storage conditions maximum of 1 month at 4 C. BS EN 16778:2016EN 16778:2016 (E) 5 4.2.3 Target compound Stock solution
22、(1000 mg/l) 100 mg of DMFa is weighed with an accuracy of 0,1 mg in a 100 ml volumetric flask and filled up to the mark with methanol and stored at 4 C for maximum 1 month. 4.2.4 Target compound working solution (200 mg/l) The solution is prepared by 1:5 dilution of the stock solution (4.2.3) with m
23、ethanol. Storage conditions maximum of 1 month at 4 C. 4.2.5 Extraction solution containing 20 mg/l internal standard Add 100 ml internal standard working solution (4.2.2) in a 1000 ml volumetric flask and fill it with Methanol to the 1000 ml calibration mark. This solution can be stored in a vessel
24、 at 4 C for 6 months. 5 Equipment Usual lab equipment, in addition: 5.1 analytical balance (precision at least 0,1 mg); 5.2 sealed flask (for instance, Erlenmeyer) with screw cap and polytetrafluoroethylene (PTFE) seal, 250 ml; 5.3 ultrasonic bath capable of maintaining a temperature of (70 5) C; 5.
25、4 PTFE-membrane filter pore width 0,45 m; 5.5 suitable sample vials with PTFE-capped for GC-MS analysis; 5.6 volumetric flask, 10 ml, 100 ml, 1000 ml; 5.7 range of micropipettes and dispenser with volume between 20 l to 200 ml; 5.8 gas chromatograph with mass detector. 6 Test procedure 6.1 Sampling
26、The sample shall consist of a least a pair of gloves. 6.2 Conditioning When the gloves are received, the laboratory shall package them into an airtight plastic sealed bag (e.g. polyethylene bag) before the start of the preparation steps. Vacuum sealer shall not be used. If stored for more than 24 h
27、before testing, the gloves shall be kept at (4 3) C. NOTE During the validation interlaboratory test, it has been demonstrated that a15 days storage in sealed plastic bag at 4 C has shown no significant difference in results. The sample (in the seal plastic bag) shall be conditioned (24 1) hours at
28、(23 2) C prior to the preparation. BS EN 16778:2016EN 16778:2016 (E) 6 6.3 Preparation The sample is removed from the plastic bag. Cut a piece as shown in Figure 1 from each glove of the pair to have 2 test pieces. Each test pieces is a full finger including the strips from the palm and the back of
29、the glove. The sampling is carried out so that all materials are included. Cut each of the 2 test pieces into pieces of about 10 mm by 10 mm. Immediately after use an analytical balance (5.1) to weigh each of the 2 cut up test pieces to an accuracy of 0,1 g. Key: 1 cut d (30 5) mm NOTE The shaded ar
30、ea is the test piece Figure 1 Cutting of the test piece 6.4 Extraction The extraction shall be started maximum (30 5) minutes after the weighing of the tests pieces. Each test piece is put in a 250 ml Erlenmeyer flask. (5.2). Add the stored extraction solution (4.2.5) at a ratio of 10,0 ml per 1,0 g
31、 cut up test piece. The closure is to maintain safe and gas tight, throughout the complete extraction. The sample is then extracted 30 min at a temperature of 70 C in an Ultrasonic bath. BS EN 16778:2016EN 16778:2016 (E) 7 WARNING Extraction at 70 C leads to overpressure and the risk of uncontrolled
32、 emission of Methanol and loss of DMFa. After cooling to room temperature, the solution is filtered through a PTFE membrane filter (5.4). An aliquot of the extract is transferred to a GC-MS vial and sealed with a PTFE-cap (5.5). The sealing should be done by well-trained operator to avoid any leakag
33、e. 6.5 Determination with GC-MS 6.5.1 Calibration Five calibrations points are used to establish the calibration curve, they are all prepared in 10 ml volumetric flasks, as stated in Table 2. A 6th point, L0,a blank, shall be included in the calibration curve. Table 2 Preparation of calibration Stan
34、dard L1 L2 L3 L4 L5 Volume of target compound working solution (4.2.4) in l 25 50 100 250 500 Conc. of target compound in the solution in mg/l 0,5 1 2 5 10 Volume of the of internal standard working solution (4.2.2) in l 1000 1000 1000 1000 1000 Concentration of the internal standard in mg/l 20 20 2
35、0 20 20 Standard L1L2L3L4L5Volumetric flasks are filled to the mark with methanol 6.5.2 Examples of instrumental method 6.5.2.1 Measuring method Suggested parameters for GC-MS determination of DMFa. Measuring parameter: The DMFa is analysed by gas chromatography/mass spectrometry on a single quad/MS
36、 use in a simultaneous SIM/SCAN mode. 6.5.2.2 Chromatographic conditions a) COLUMN: polar stationary phase based on Polyethylene Glycol; length: 30 m; internal diameter: 250 m; BS EN 16778:2016EN 16778:2016 (E) 8 film thickness: 0,5 m; (alternative column possible as long as it has the same properti
37、es). b) CARRIER GAS: helium. c) OVEN: 60 C during 2 min; 250 C at 20 C/min; 250 C during 2 min. d) INJECTOR: 240 C in splitless mode with an injection volume of 1 l. 6.5.2.3 Detection conditions a) TRANSFER LINE: 240 C: The single quad MS work in simultaneous SIM/SCAN mode; The mass SCAN range is be
38、tween 40 to 200 uma. Table 3 The SIM mode focus on the following ions Compounds Ions DMFa 73 (quantifier) 44 (qualifier) DMFa-d7 80 (quantifier) 6.6 Quantification The DMFa content is calculated according to the following equation as a mass fraction w in mg/kg of glove. Set up the linear regression
39、function by using the following ratio (Ae/Ais) and (Ce/Cis) with the help of the formula: =+ eeis isACab Where: Aeis the area of the peak of Dimethylformamide; Aisis the area of the peak of Dimethylformamide-D7; Ceis concentration of Dimethylformamide in the calibration standard in microgram per lit
40、ter; CISis concentration of Dimethylformamide-D7 in the calibration standard in microgram per litter; a is the slope of the linear function; BS EN 16778:2016EN 16778:2016 (E) 9 b is the ordinate intercept of the calibration curve, in mg/l. The content of DMFa is calculated according to the following
41、 equation as a mass fraction w in mg/l: =echisisAbAVWCmaWhere: W is the content of the Dimethylformamide in the specimen (mg/l); V is the volume of the solvent use for the extraction (ml) (in most cases, this value will be equal to 10 ml); m is the mass of the tested specimen (g); Aechis the area of
42、 the peak of Dimethylformamide in the sample; Aisis the area of the peak of Dimethylformamide-D7 in the sample; CISis concentration of Dimethylformamide-D7 in the sample in microgram per litter; a is the slope of the linear function; b is the ordinate intercept of the calibration curve. The units de
43、pend of the evaluation. 6.7 Results Each determination result shall be reported. The final result is the average (Mv) of the 2 values obtained on the 2 test pieces. 7 Performance of the method Quantification limit of this test method is 5 mg/kg of DMFa in gloves or glove components. 8 Test report Th
44、e test report shall include at least the following: reference to this standard; description of the packaging at reception; all details necessary for complete identification of the sample tested; date of reception of the sample in the laboratory; date of the test; condition and time of storage before
45、 the test in the laboratory; used analytical technic; the determined content of the extracted DMFa is given in ppm (see 6.7); any deviation from the present standard. BS EN 16778:2016EN 16778:2016 (E) 10 Annex A (informative) Results of the interlaboratory trial The following data have been obtained
46、 in a collaborative correlation trial organized by CEN/TC 162 WG 8 in November/December 2013 with a group of relevant laboratories (on demand from CEN/TC 162 secretariat). Table A.1 Results of correlation trial Number of laboratories Number of measurement per laboratory Average value Standard deviat
47、ion Spiked sample with 10ppm 8 1 12,5 7,0 Spiked sample with 200ppm 5 1 197,7 8,0 Dipped Polyurethane test pieces with dynema 5 4 33,7 5,3 Dipped Polyurethane test pieces with nylon 7 4 761,4 130,9 BS EN 16778:2016EN 16778:2016 (E) 11 Bibliography CEN ISO/TS 16189, Footwear - Critical substances pot
48、entially present in footwear and footwear components - Test method to quantitatively determine dimethylformamide in footwear materials (ISO/TS 16189:2013) This page deliberately left blankThis page deliberately left blankBSI is the national body responsible for preparing British Standards and other
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