Substances Limits - Testing methods

Transcription

1 Ref. Ares(2017) /02/2017 Substances Limits - Testing methods Technical Workshop Brussels 07 February 2017 Karin Kilian DG ENV, Unit B2, Sustainable Chemicals 1

2 Formaldehyde Substance Suggested limit Testing method Formaldehyde 75 ppm - 75ppm for apparel with skin contact feasible - Different limit needed for clothing that does not come into direct and prolonged contact with the skin - recommendation 300 ppm - Proposed test method is o.k. EN ISO (2014) Textiles - Determination of formaldehyde -Part 1: Free and hydrolysed formaldehyde (water extraction method) Measures free and hydrolysed formaldehyde between 16 mg/kg and mg/kg The lower limit is 16 mg/kg. Below this limit, the result is reported as "not detectable" What is measured is extractable formaldehyde, not total formaldehyde 2

3 Formaldehyde key points discussed 75 ppm is feasible for clothing It might be more problematic for other kind of textiles (upholstery), due to FA-containing glues, flame retardants Testing method is well established Difficult to have formaldehyde free resins for textile applications, risk of regrettable substitution, negative environmental impact in production countries Risk of contamination during production and distribution (but for children clothing limits are much lower in some standards and seem to be observed) 3

4 Heavy metals Cd Substance Suggested limit Testing method Cadmium sulphate Cadmium/cadmium (pyrophoric) Cadmium chloride Cadmium oxide/cadmium oxide (non-pyrophoric) Cadmium sulphide 1 ppm Cd (extractable?) - limit should refer to extractable amount. - Remove compounds with no role in textile processing - 1 ppm extractable Cd is reasonable/technically feasible limit. - EN method for extractable cadmium content. Preparation via ISO 105-E04, extractable cadmium content via EN Extraction: ISO 105-E04, measurement ISO EN Textiles - Determination of metal content. - Part 1: Determination of metals using microwave digestion - Part 2: Determination of metals extracted by acidic artificial perspiration solution 4 Pre-treatment total Cd: - EN 1122 Plastics. Determination of cadmium. Wet decomposition method. Range of 10 mg to mg Cd/kg. - Microwave digestion with H 2 O 2 /HNO 3 - Total digestion with acid Pre-treatment - extractable Cd: - ISO 105-E04:2013 Textiles -Tests for colour fastness -Part E04: Colour fastness to perspiration Measurement - BS EN ISO 11885:2009 Water quality. Determination of selected elements by inductively coupled plasma optical emission spectrometry (ICP- OES) - DIN EN ISO 5961 Water quality - Determination of cadmium by atomic absorption spectrometry - ISO :2016 Water quality - Application of inductively coupled plasma mass spectrometry (ICP- MS). Part 2: Determination of selected elements - Inductively coupled plasma-optical emission spectrometry (ICP-OES), atomic absorption spectroscopy (AAS) (total heavy metals)

5 Cadmium key points discussed Split opinions on use of total or extractable fraction, arguments exist for both Different limits would need to apply in the two cases 1ppm extractable, 100 mg/kg total content Support to regulate metal and not individual substances Some methods are easier to implement: need to consider possibility of recommending testing methods. EN methods contain all conditions, for extraction and measurement 5

6 Heavy metals Cr Substance Suggested limit Testing method Ammonium dichromate Calcium chromate Chromium (VI) trioxide Chromyl dichloride Dichromium tris(chromate); chromium III chromate; chromic chromate Sodium chromate Sodium dichromate Strontium chromate Potassium chromate Potassium dichromate Chromic acid, lead(2+) salt (1:1) 1 ppm Cr VI (extractable) - Use limit of 3 ppm Cr VI (extractable) - below reliable extraction and detection is hardly feasible - Limit used in leather supply chain - reliable analytical test method for textiles has to be made available - restriction should refer to Na/K (di)chromate - other Chromium VI compounds not used - Extractable chromium: EN ISO 105-EO4 (sample preparation), EN ISO (measurement) - Cr-VI: EN ISO 105-EO4 (sample preparation), EN ISO (measurement) - difficulty reliably testing down to 1 ppm Cr-VI using this methods? - Cr VI determination by indirect colorimetric methods may produce false positive results (organic acids and amines may produce coloured reactions with diphenylcarbazide )- alternative method needed to verify positive cases. Pre-treatment - ISO 105-E04:2013 Textiles - Tests for colour fastness -- Part E04: Colour fastness to perspiration Measurement - Inductively coupled plasma-optical emission spectrometry (ICP-OES), atomic absorption spectroscopy (AAS) (total heavy metals) - Detection with ICP-MS DIN :1987? 6

7 Chromium key points discussed Restriction needs to be specific for CrVI Therefore only limit for extractable fraction possible Different methods are available recommended to use the one for leather. 3ppm is limit for leather, some recommended to use the same for textile Different views on possibility to reliably measure down to 1 ppm for textiles (technically difficult for leather, easier for textiles?) Experience from test labs indicate there are very few cases above 1ppm 7

8 Heavy metals As, Pb Substance Suggested limit Testing method Lead hydrogen arsenate lead 2,4,6-trinitrom-phenylene dioxide; lead 2,4,6- trinitroresorcinoxide; lead styphnate lead di(acetate) lead diazide; lead azide Chromic acid, lead(2+) salt (1:1) 1 ppm As 1ppm Pb (extractable?) - analyse lead not arsenic to reduce necessary testing. - Limit should refer to extractable amount. - If the arsenic limit is intended to be total content, limit of 100 ppm proposed - 1ppm extractable Pb is reasonable limit. - method to detect extractable Pb should be identified - Proposed limits are technically feasible for extractable arsenic and lead. Test ISO 105-EO4: (sample preparation), EN ISO (measurement) - Pb azide (explosive) should be removed from the list. Pre-treatment - ISO 105-E04:2013 Textiles -Tests for colour fastness - Part E04:Colour fastness to perspiration - Total digestion with acid Measurement - ISO :2016 Water quality. Application of inductively coupled plasma mass spectrometry (ICP-MS). Part 2: Determination of selected elements - BS EN ISO 11885:2009 Water quality. Determination of selected elements by inductively coupled plasma optical emission spectrometry (ICP-OES) -DIN 38406, E6, German standard methods for the examination of water, waste water and sludge - Cations (group E) - Part 6: Determination of lead by atomic absorption spectrometry (AAS) 8

9 Arsenic, lead key points discussed Arguments for both extractable and total content Methods are available for both, different levels should be considered Rarely found in textiles, sometimes in metal or plastic parts, could however be a problem for imported articles because of process contamination Consider possible double regulation with existing restriction 9

10 Chlorinated aromatic hydrocarbons Substance Suggested limit Testing method a,a,a,4-tetrachlorotoluene a,a,a-trichlorotoluene a-chlorotoluene 1 ppm each - Limit o.k. - DIN method ok. Chlorobenzenes/chlorotoluenes: - DIN Textiles - Determination of the content of bonds based on chlorobenzene and chlorotoluene - Extraction with methylene chloride, detection with GC-MS 10

11 Chlorinated aromatic hydrocarbons - key points discussed 1 ppm is feasible Test method is available, under development as EN method 11

12 Phthalates Substance Suggested limit Testing method 1,2-Benzenedicarboxylic acid, di-c6-8-branched alkyl esters Bis(2-methoxyethyl) phthalate diisopentylphthalate Di-n-hexyl phthalate (DnHP) Dipentyl phthalate (DPP) 1000 ppm (individually or in in combination) - proposed limit is reasonable/technically feasible - proposed test methods o.k. EN ISO 14389:2014 Textiles -Determination of the phthalate content - Tetrahydrofuran method (Detection by GC-MS) 12

13 Phthalates - key points discussed Limit for individual compounds or combination? Limit needs to refer to the part of the article made of plastic, not to the whole article This needs to be specified in the text of the restriction 13

14 Polar aprotic solvents Substance Suggested limit Testing method N-methyl-2-pyrrolidone; 1-methyl-2-pyrrolidone (NMP) N,N-dimethylacetamide (DMAC) Dimethylformamide (DMF) 3000 ppm - proposed limit is reasonable/technically feasible. - EN for DMF in protective gloves, ultrasonic extraction in methanol, 70 C 30min (2016) is the best method. - For DMAC and DMF, the method should be DIN CEN ISO/TS For NMP, lab consultation is needed to determine appropriate test method. Solvent extraction / GC-MS or LC-MS degrees C for one hour headspace solvent extraction (VOC) - Methanol extraction at 60 degrees; GC-MS Solvent extraction / GC-MS or LC-MS - Extraction with methanol 30min 70 C, Detection with GC-MS - DIN CEN ISO/TS 16189:2013 Footwear - Critical substances potentially present in footwear and footwear components - Test method to quantitatively determine dimethylformamide in footwear materials- Solvent extraction / GC-MS or LC-MS 14

15 Polar aprotic solvents key points discussed Substances cannot be completely avoided, there will be traces in finished products Limits could be lower than 0.3%, but it would be difficult Is this limit giving incentive to improve the process? Is there a feasible lower limit? It is very difficult to extract the full content of the substance The method currently used for shoes for the 3 solvents is being adapted for textiles, EN method under development 15

16 Benzene and PAHs Substance Suggested limit Testing method Benzene 1 ppm each Benz[a]anthracene Benz[e]acephenanthrylene Benzo[a]pyrene Benzo[e]pyrene Benzo[j]fluoranthene Benzo[k]fluoranthene Chrysene Dibenz[a,h]anthracene - Benzene: for practical reasons limit of 20 ppm: False positive results due to cracking processes in analyses occur and distort test results. Proposed methods ok for 20 ppm. - Benzene: align with the EU Toy Safety Directive/ AFIRM RSL, limit of 5ppm proposed - PAH: The proposed limit is reasonable/technially feasible. Proposed test methods are o.k. - Test method should be AFPS GS DIN ISO 18287:2006 Soil quality - Determination of polycyclic aromatic hydrocarbons (PAH) -Gas chromatographic method with mass spectrometric detection (GC-MS) - AFPS GS 2014 Testing and assessment of polycyclic aromatic hydrocarbons (PAHs) in the course of GS mark certification - ISO DIN 13877:2000 Soil quality - Determination of polynuclear aromatic hydrocarbons - Method using highperformance liquid chromatographic 16

17 Benzene and PAHs key points discussed 1 ppm feasible for PAHs Benzene: 1 ppm has risk of false positives; 5 ppm limit is also used in Toys Benzene not used as such, but contaminant in other solvents Achievable limit depends on the method (and extraction method) Potential problem for PAH limit in recycling of footwear: case should be described and sent to COM, to consider the need for an exemption 17

18 Azodyes and arylamines Substance Suggested limit Testing method Basic violet 3 Disperse Blue 1 Basic Red 9 30 mg/kg Basic violet 3: - Classification is based on content of Michler's ketone/base, add ">0.1% of Michler's ketone/base" to the description of the substance All: - Experiences with a limit of 50ppm in the textile supply chain e.g. in OecoTex Entry 43 method not feasible - Reliable analytical test method should be made available. - Proposed limit of 30 ppm is too low, may not be technically feasible. Substances can be present as impurities at concentrations above 30 ppm. Current RSL programs prohibit them, but allow impurities up to 75 ppm. - Suggested test methodology for these substances: DIN 54231: Suggested method ISO : HPLC-DAD-MS/MS For substances currently in entry 43 of Annex XVII: EN ISO According to CEN/TC 248/WG 26, it is not possible to measure all the azo dyes in the list with this method, because it has been developed for the aromatic amines (degradation products). When azodyes cannot be measured with this method, ISO part 2 may be used for some of them (detection limit of 150 mg/kg). Some cannot be measured because the structure does not contain an aromatic amine with an azo-bound. 18

19 Key points discussed These 3 substances are not covered by entry 43: they do not cleave to restricted aromatic amines Old dyes, no longer used in EU but could still be found in imported articles Basic violet 3 is registered for textile use under REACH DIN method is preferred, has limit of 75 ppm General support to keep the substances in the list, also to avoid they are used again 19

20 Azodyes and arylamines Substance Suggested limit Testing method Disperse orange 149 Direct Red 28 Direct Blue 6 Direct Black 38 Direct Brown mg/kg DO149 - limit of 30 ppm too low, may not be technically feasible. May be present as impurities at >30 ppm. Current RSL programs prohibit, but allow impurities up to 75 ppm. - Suggested test DIN 54231:2005 DR28/DB6/DB38/DB95 - already covered by Entry 43 of Annex XVII - 30 mg/kg limit acceptable, aligns with existing legal requirements - Suggested test: EN ISO :2015. All: - Potential cleavage to already restricted amine in entry 43 of Annex XVII - remove to avoid double regulation - Entry 43 analytical method is o.k. for the amine - Method ISO : HPLC-DAD-MS/MS 20 For substances currently in entry 43 of Annex XVII: EN ISO According to CEN/TC 248/WG 26, it is not possible to measure all the azo dyes in the list with this method, because it has been developed for the aromatic amines (degradation products). When azodyes cannot be measured with this method, ISO part 2 may be used for some of them (detection limit of 150 mg/kg). Some cannot be measured because the structure does not contain an aromatic amine with an azo-bound.

21 Key points discussed These azodyes cleave to aromatic amines regulated in entry 43 Consistent request to remove them to avoid double regulation 21

22 Azodyes and arylamines Substance Suggested limit Testing method 4-chloro-o-toluidinium chloride 2- Naphthylammoniumacetate 4-methoxy-m-phenylene diammonium sulphate 2,4,5-trimethylaniline hydrochloride N,N,N',N'-tetramethyl-4,4'- methylenedianiline (Michler's base) 4,4'- bis(dimethylamino)benzoph enone (Michler's ketone) azobenzene 30 mg/kg - Arylamin salts - equivalent to restricted amine, covered by entry 43 - Entry 43 test method is o.k. /may be analysed with : determining whether these substances can be properly analysed and differentiated using available, standard test methods is critical may not be enforceable - evidence of their existence in apparel and footwear? - Not a dyestuff by itself, impurity - No test method available, has to be developed - Base: to be analysed as free contaminant (no cleavage) - Keton: : determining whether these substances can be properly analysed and differentiated using available, standard test methods is critical may not be enforceable - evidence of their existence in apparel and footwear? - Not relevant for dye synthesis and textile processing - determining whether these substances can be properly analysed and differentiated using available, standard test methods is critical may not be enforceable - evidence of their existence in apparel and footwear? For substances currently in entry 43 of Annex XVII: EN ISO According to CEN/TC 248/WG 26, it is not possible to measure all the azo dyes in the list with this method, because it has been developed for the aromatic amines (degradation products). When azodyes cannot be measured with this method, ISO part 2 may be used for some of them (detection limit of 150 mg/kg). Some cannot be measured because the structure does not contain an aromatic amine with an azo-bound. 22

23 Key points discussed First 4 substances: Already covered by entry 43 if they are degradation products, but, due to wording of the restriction, not when used as dyes themselves Can be added with same limit and method of entry 43 MB and MK Can be impurities in dyestuff, drive carc. classification No reliable testing method available Azobenzene Not a colorant No use in textile production 23

24 Miscellaneous Substance Suggested limit Testing method 1 mg/kg Quinoline - No info on presence or contamination in textiles - No established analytical method - a reliable method would be precondition for setting a limit - impurity in certain dyestuffs. - persistent in the environment, the proposed 1 ppm limit may not be realistic - additional data needed to evaluate the feasibility of this limit/whether the substance poses a risk to consumers - Risk Management Option Analysis was completed by in 2015 with a conclusion of no need for regulatory follow-up action Extraction with Toluene//GCMS 24

25 Quinoline key points discussed Potentially relevant for textiles, impurity in dye stuff Not a lot of experience in measuring in finished products No established analytical method If considered, limit should be higher Claimed to be used as food colorant in higher concentrations 25

26 Miscellaneous Substance dibutyltin dichloride (DBTC) Suggested limit 1 mg/kg - 2ppm (OekoTex 100 limit) is reasonable. - No need to restrict, already restriction on dibutyltin compounds of 1000 ppm by weight of tin in textile articles. - If a stricter restriction is intended, recommend 10 ppm which is safely below a risk-based limit. - It is unclear whether DBTC can be maesures individually individually. Test method for analyzing dibuyltin compounds generally is DIN ISO/TS 16179: Testing method DIN ISO/TS 16179: ; ISO (2004) 26

27 DBTC key points discussed Cannot be measured as individual substance, test method for dibutyltin compounds in general 2 ppm limit (e.g. Oekotex) is for all dibutyltin compounds 27

28 Thank For further information please visit: you eec.europa.eu/environment/chemicals/reach c.europa.eu/enterprise/reach echa.europa.eu This presentation does not necessarily reflect the official opinion of the Commission. 28