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Ares(2017)700206 - 08/02/2017

Substances – Limits - Testing methods

Technical Workshop
Brussels 07 February 2017

Karin Kilian
DG ENV, Unit B2, Sustainable Chemicals

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 Substances included in the restriction
248 substances in the initial list for public consultation
58 selected as most relevant for the first step

• Formaldehyde
• Heavy metals
– Cadmium compounds
– Chromium compounds
– Arsenic compounds
– Lead compounds
• Chlorinated aromatic hydrocarbons
• Phthalates
• Polar aprotic solvents
• Benzene and PAHs
• Azodyes and arylamines

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 Proposed limits

Proposed limits are based on:

• Contributions from public consultation

• Existing limits set by existing legislation

• Existing limits set by different textile schemes/labels

• Existing limits set by industry

• Available information on performance of testing methods

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 Questions to workshop participants

• Are the proposed limits for substances

– Technically feasible? If not, why?
– Enforceable with the available testing methods?

• Are limits for heavy metals more appropriately

set for total content or extractable fraction?
Same approach for all proposed metals?

• Azodyes: which testing method are applicable?

Are they sensitive enough?

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 Formaldehyde

Substance Suggested limit Testing method

EN ISO 14184-1 (2014) Textiles -

75 ppm Determination of formaldehyde -Part 1:
Free and hydrolysed formaldehyde (water
extraction method)
Comments:
- 75ppm for apparel with Measures free and hydrolysed
Formaldehyde skin contact feasible formaldehyde between 16 mg/kg and 3
- Different limit needed for 500 mg/kg
clothing that does not The lower limit is 16 mg/kg. Below this
come into direct and
limit, the result is reported as "not
prolonged contact with the
detectable"
skin - recommendation
300 ppm What is measured is extractable
- Proposed test method is formaldehyde, not total formaldehyde
o.k.

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 Heavy metals – Cd
Substance Suggested limit Testing method
Pre-treatment – total Cd:
Cadmium sulphate 1 ppm Cd - EN 1122 Plastics. Determination of cadmium. Wet
(extractable?) decomposition method. Range of 10 mg to 3 000
mg Cd/kg.
Comments: - Microwave digestion with H2O2/HNO3
Cadmium/cadmium - limit should refer to extractable
amount. - Total digestion with acid
(pyrophoric) - Remove compounds with no role Pre-treatment - extractable Cd:
in textile processing
- ISO 105-E04:2013 Textiles -Tests for colour
- 1 ppm extractable Cd is
fastness -Part E04: Colour fastness to perspiration
reasonable/technically feasible
Cadmium chloride limit. Measurement
- EN method for extractable
- BS EN ISO 11885:2009 Water quality.
cadmium content. Preparation
Determination of selected elements by inductively
via ISO 105-E04, extractable
coupled plasma optical emission spectrometry (ICP-
cadmium content via EN 1122.
Cadmium OES)
- Extraction: ISO 105-E04,
oxide/cadmium oxide measurement ISO 17294-2 - DIN EN ISO 5961 Water quality - Determination of
(non-pyrophoric) - EN 16711 Textiles - cadmium by atomic absorption spectrometry
Determination of metal content. - ISO 17294-2:2016 Water quality - Application of
- Part 1: Determination of metals inductively coupled plasma mass spectrometry (ICP-
using microwave digestion MS). Part 2: Determination of selected elements
- Part 2: Determination of metals
Cadmium sulphide extracted by acidic artificial - Inductively coupled plasma-optical emission
perspiration solution spectrometry (ICP-OES), atomic absorption
spectroscopy (AAS) (total heavy metals)
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 Heavy metals – Cr
Substance Suggested limit Testing method

Ammonium dichromate 1 ppm Cr VI

(extractable)
Calcium chromate Pre-treatment
Comments:
- ISO 105-E04:2013
Chromium (VI) trioxide - Use limit of 3 ppm Cr VI (extractable) - below Textiles - Tests for colour
reliable extraction and detection is hardly fastness -- Part E04:
Chromyl dichloride feasible - Limit used in leather supply chain Colour fastness to
Dichromium tris(chromate); - reliable analytical test method for textiles has to perspiration
be made available
chromium III chromate; Measurement
chromic chromate - restriction should refer to Na/K (di)chromate -
other Chromium VI compounds not used - Inductively coupled
Sodium chromate plasma-optical emission
- Extractable chromium: EN ISO 105-EO4 (sample spectrometry (ICP-OES),
preparation), EN ISO 17294-2 (measurement)
Sodium dichromate atomic absorption
- Cr-VI: EN ISO 105-EO4 (sample preparation), spectroscopy (AAS) (total
Strontium chromate EN ISO 17294-2 (measurement) - difficulty heavy metals)
reliably testing down to 1 ppm Cr-VI using this
Potassium chromate methods? - Detection with ICP-MS

Potassium dichromate - Cr VI determination by indirect colorimetric

methods may produce false positive results DIN 38405-24:1987 ?
(organic acids and amines may produce coloured
Chromic acid, lead(2+) salt reactions with diphenylcarbazide )- alternative
(1:1) method needed to verify positive cases.

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 Heavy metals – Ar, Pb
Substance Suggested limit Testing method
1 ppm Ar
Lead hydrogen
1ppm Pb Pre-treatment
arsenate
(extractable?) - ISO 105-E04:2013 Textiles -Tests for colour
fastness - Part E04:Colour fastness to
lead 2,4,6-trinitro- Comments: perspiration
m-phenylene
- analyse lead not arsenic to reduce - Total digestion with acid
dioxide; lead 2,4,6- necessary testing.
trinitroresorcinoxide; Measurement
- Limit should refer to extractable
lead styphnate amount. - ISO 17294-2:2016 Water quality.
Application of inductively coupled plasma mass
- If the arsenic limit is intended to be
total content, limit of 100 ppm spectrometry (ICP-MS). Part 2: Determination
lead di(acetate) of selected elements
proposed
- 1ppm extractable Pb is reasonable - BS EN ISO 11885:2009 Water quality.
limit. Determination of selected elements by
inductively coupled plasma optical emission
- method to detect extractable Pb
lead diazide; lead spectrometry (ICP-OES)
should be identified
azide -DIN 38406, E6, German standard methods
- Proposed limits are technically feasible
for extractable arsenic and lead. Test for the examination of water, waste water and
ISO 105-EO4: (sample preparation), sludge - Cations (group E) - Part 6:
EN ISO 17294-2 (measurement) Determination of lead by atomic absorption
Chromic acid,
- Pb azide (explosive) should be spectrometry (AAS)
lead(2+) salt (1:1)
removed from the list.

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 Chlorinated aromatic hydrocarbons

Substance Suggested limit Testing method

a,a,a,4-tetrachlorotoluene Chlorobenzenes/chlorotoluenes:
1 ppm each
- DIN 54232 Textiles - Determination of
a,a,a-trichlorotoluene the content of bonds based on
chlorobenzene and chlorotoluene
Comments:

- Limit o.k. - Extraction with methylene chloride,

a-chlorotoluene detection with GC-MS
- DIN 54232 method ok.

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 Phthalates

Substance Suggested limit Testing method

1,2-Benzenedicarboxylic
acid, di-C6-8-branched
alkyl esters
1000 ppm
Bis(2-methoxyethyl) (individually or in
EN ISO 14389:2014 Textiles -Determination
phthalate in combination) of the phthalate content - Tetrahydrofuran
method

diisopentylphthalate (Detection by GC-MS)

Comments:

- proposed limit is
Di-n-hexyl phthalate reasonable/technically
(DnHP) feasible
- proposed test methods
o.k.
Dipentyl phthalate (DPP)

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 Polar aprotic solvents
Substance Suggested limit Testing method

N-methyl-2-pyrrolidone;
1-methyl-2-pyrrolidone 3000 ppm Solvent extraction / GC-MS or LC-MS
(NMP)
Comments: - 120 degrees C for one hour headspace
- proposed limit is solvent extraction (VOC)
N,N-dimethylacetamide reasonable/technically
(DMAC) feasible. - Methanol extraction at 60 degrees; GC-MS

- EN 16778 for DMF in Solvent extraction / GC-MS or LC-MS

protective gloves, ultrasonic
extraction in methanol, 70°C
30min (2016) is the best - Extraction with methanol 30min 70°C,
method. Detection with GC-MS
- For DMAC and DMF, the - DIN CEN ISO/TS 16189:2013 Footwear
Dimethylformamide method should be DIN CEN - Critical substances potentially present in
(DMF) ISO/TS 16189. footwear and footwear components - Test
- For NMP, lab consultation is method to quantitatively determine
needed to determine dimethylformamide in footwear materials-
appropriate test method. Solvent extraction / GC-MS or LC-MS

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 Benzene and PAHs
Substance Suggested limit Testing method

Benzene 1 ppm each

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

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 Azodyes and arylamines
Substance Suggested limit Testing method

30 mg/kg
Basic violet 3 For substances currently in
Comments:
entry 43 of Annex XVII: EN
Basic violet 3: ISO 14362.
- Classification is based on content of Michler's ketone/base, According to CEN/TC 248/WG
add ">0.1% of Michler's ketone/base" to the description of 26, it is not possible to measure
the substance all the azo dyes in the list with
Disperse Blue 1
this method, because it has
All: been developed for the
aromatic amines (degradation
- Experiences with a limit of 50ppm in the textile supply chain products).
e.g. in OecoTex 100.
When azodyes cannot be
- Entry 43 method not feasible
measured with this method,
- Reliable analytical test method should be made available. ISO 16373 part 2 may be
- Proposed limit of 30 ppm is too low, may not be technically used for some of them
feasible. Substances can be present as impurities at (detection limit of 150 mg/kg).
Basic Red 9
concentrations above 30 ppm. Current RSL programs
Some cannot be measured
prohibit them, but allow impurities up to 75 ppm.
because the structure does not
- Suggested test methodology for these substances: DIN contain an aromatic amine with
54231:2005 an azo-bound.
- Suggested method ISO 16373-2:2014 + HPLC-DAD-MS/MS

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 Azodyes and arylamines
Substance Suggested limit Testing method

For substances currently in

30 mg/kg entry 43 of Annex XVII: EN
Comments: ISO 14362.
Disperse orange 149
DO149 According to CEN/TC
248/WG 26, it is not possible
- limit of 30 ppm too low, may not be technically feasible.
to measure all the azo dyes
May be present as impurities at >30 ppm. Current RSL
programs prohibit, but allow impurities up to 75 ppm. in the list with this method,
Direct Red 28
because it has been
- Suggested test DIN 54231:2005 developed for the aromatic
Direct Blue 6
DR28/DB6/DB38/DB95 amines (degradation
Direct Black 38 - already covered by Entry 43 of Annex XVII products).

- 30 mg/kg limit acceptable, aligns with existing legal When azodyes cannot be
requirements measured with this method,
ISO 16373 part 2 may be
- Suggested test: EN ISO 14362-1:2015.
used for some of them
All: (detection limit of 150
Direct Brown 95 - Potential cleavage to already restricted amine in entry 43 mg/kg).
of Annex XVII - remove to avoid double regulation Some cannot be measured
- Entry 43 analytical method is o.k. for the amine because the structure does
- Method ISO 16373-2:2014 + HPLC-DAD-MS/MS
not contain an aromatic
amine with an azo-bound.
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 Azodyes and arylamines
Substance Suggested limit Testing method
4-chloro-o-toluidinium 30 mg/kg
chloride For substances currently in
Comments:
2- - Arylamin salts - equivalent to restricted amine, covered
entry 43 of Annex XVII: EN
Naphthylammoniumacetate by entry 43 ISO 14362.
- Entry 43 test method is o.k. /may be analysed with
14362-1:2014 According to CEN/TC 248/WG
4-methoxy-m-phenylene
26, it is not possible to
diammonium sulphate - determining whether these substances can be properly measure all the azo dyes in
analysed and differentiated using available, standard test
2,4,5-trimethylaniline methods is critical – may not be enforceable the list with this method,
hydrochloride - evidence of their existence in apparel and footwear? because it has been developed
Comments:
for the aromatic amines
N,N,N',N'-tetramethyl-4,4'- - Not a dyestuff by itself, impurity (degradation products).
methylenedianiline - No test method available, has to be developed
When azodyes cannot be
- Base: to be analysed as free contaminant (no cleavage)
(Michler's base) - Keton: 14362-1:2014 measured with this method,
ISO 16373 part 2 may be
4,4'- - determining whether these substances can be properly
analysed and differentiated using available, standard test used for some of them
bis(dimethylamino)benzoph methods is critical – may not be enforceable (detection limit of 150 mg/kg).
enone (Michler's ketone) - evidence of their existence in apparel and footwear?
Some cannot be measured
Comments:
- Not relevant for dye synthesis and textile processing because the structure does not
- determining whether these substances can be properly contain an aromatic amine
azobenzene analysed and differentiated using available, standard test with an azo-bound.
methods is critical – may not be enforceable
- evidence of their existence in apparel and footwear?

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 Miscellaneous
Testing
Substance Suggested limit
method

1 mg/kg

Comments:
- No info on presence or contamination in textiles
- No established analytical method - a reliable method would be
precondition for setting a limit Extraction with
Quinoline Toluene//GCMS
- 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

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 Miscellaneous
Testing
Substance Suggested limit
method
dibutyltin 1 mg/kg DIN ISO/TS
dichloride 16179: 2012-08;
ISO 17353
(DBTC)
Comments: (2004)

- 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: 2012-08.

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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.

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