Chromium VI and Azo-Dye Content of Leather

Products Available to UK Consumers

A joint initiative between Trading Standards, the Health

and Safety Executive and the British Safety Industry

Federation

Executive Summary Report

Contents

Introduction ............................................................................................................................................ 3

Review of Intelligence as of 2016 ....................................................................................................... 4

Method ................................................................................................................................................... 5

Results ..................................................................................................................................................... 5

Conclusions ............................................................................................................................................. 8

Recommendations .................................................................................................................................. 9

Appendix 1 Example Costs .................................................................................................................... 12

Bibliography ...................................................................................................................................... 14

Introduction

Various consumer goods are made from leather: bracelets, fashion gloves, baby

shoes and protective gloves. This process involves the use of processing agents

which may produce Chromium VI and Azo Dyes. The Chromium VI and Azo-Dyes

(which cleave to aromatic amines) content of leather products are a concern due to

the safety risks they present, and are therefore restricted by Annex XVII of Regulation

(EC) No 1907/2006.

The data below is reproduced from the RAPEX database.

Chromium VI

Product Category Number of

Notifications

Number Generated by UK

Leather Fashion Gloves 30 0

Baby Shoes/ Children's

Footwear

58 0

Protective Gloves 43 0

Straps and Bracelets 4 0

TOTAL 135 0

Table 1: RAPEX Data 2005-2016. Extracted from 437 Notifications for Chromium VI covering 11 Product Categories

Azo-Dye

Product Category Number of

Notifications

Number Generated by UK

Leather Fashion Gloves 6 2

Baby Shoes/ Children's

Footwear

4 0

Protective Gloves 11 0

Straps and Bracelets 6 0

TOTAL 27 2

Table 2: RAPEX Data 2005-2016. Extracted from 305 Notifications for Azo-Dyes covering 11 Product Categories

In 2015, the British Safety Industry Federation (BSIF) sampled leather rigger gloves

for Chromium VI and Azo-Dye content. All of the products originated in India,

Pakistan and China. The suppliers of the samples were all established businesses in

the UK with a recognised international quality system.

Sample

Number Azo-Dye or Chromium VI

Concentration

(ppm)

Limit

(ppm)

Pass/Fail

1 Azo-Dye 135 30 Fail

2 Chromium VI 3.8 3 Fail

3 Azo-Dye 115 30 Fail

4 Chromium VI 18 3 Fail

5 Azo-Dye 91 30 Fail

6

Chromium VI

Azo-Dye

3.9

40

3

30

Fail

Fail

7 Chromium VI 3.8 3 Fail

8 Azo-Dye 142 30 Fail

Table 3: Sampling Data Produced by British Safety Industry Federation, 2015.

Review of Intelligence as of 2016

Based on the RAPEX and BSIF information, it is expected that leather baby shoes,

fashion gloves, protective gloves and bracelets/straps on sale to consumers in the

UK will contain excessive levels of Chromium VI and Azo-Dyes. The BSIF study

suggests that some protective gloves sold to the trade are also likely to be unsafe.

Whilst the EU has laws prohibiting Chromium VI and Azo-Dyes in leather articles

above specified levels, this does not necessarily protect consumers who purchase

products directly from 3rd Countries. It is important to establish whether or not

consumers are protected to the same degree when purchasing products from 3rd

Countries compared to purchasing products from the EU. The information currently

available is not specific enough to address this point.

Method

157 samples consisting of leather bracelets, fashion gloves, baby shoes and

protective gloves were analysed. Samples were obtained from the EU and from 3rd

Countries via the internet. Protective gloves included those sold to the public and

those sold directly to the trade. The samples were tested using methods described

in national standards EN ISO 17234-1:2016 Determination of certain aromatic amines

derived from azo colourants followed by GC-MS Analysis, and Chromium VI was

assessed using BS EN ISO 17075 :2007 by UV-VIS Spectrophotometer.

Results

Table 4: Total number of samples complying and in breach of REACH restrictions

Figure 1: Compliance with REACH restriction limits

Total Number of

Samples

Number of Samples within

REACH Restriction Limits

Number of Samples

Over CrVi Limit

(≥3ppm)

Number of Samples Over Azo Dyes Limit

(≥30ppm)

157 132 19 6

0 10 20 30 40

Baby Shoes

PPE Gloves

Trade PPE Gloves

30

30

32

11

29

6

4

6

3

1

2

1

2

Number of Products

Product Type

Number of Products Within and Exceeding REACH

Restriction Limits

Within Limits CrVi (≥3ppm) Azo Dyes (≥30ppm)

Figure 2: Number of samples falling within ranges of Chromium VI detected across the samples. Maximum permitted

concentration shown at 3ppm.

Table 5: Concentrations of amines found in samples which breached the REACH restriction for Azo Dyes

Sample Type Country of Sale Product Claims Restricted Substance Detected

PPE Gloves EU EN388 compliant Chromium VI

PPE Gloves EU EN388 EN420 Chromium VI

Trade PPE Gloves EU EN388 & EN407. CE Mark. Benzidine

Trade PPE Gloves EU CE marked on label. Chromium VI

Baby Shoes 3rd Country EN71-3 compliant, Intertek tested Chromium VI

Trade PPE Gloves EU CE marked (typeA), EN388 (mech

4,1,2,2), EN407Therm (4,1,3,X,X)

4-Aminobiphenyl, Benzidine, 3,3’-

Dimethoxybenzidine

Table 6: Further details of samples which breached REACH restrictions and were sold with claims relating to

compliance with the law

4-Aminobiphenyl

(ppm)

Benzidine

(ppm)

3,3’-Dimethoxybenzidine

(ppm)

Specific Sam

ple

Baby Shoes 185

Bracelet/Strap 583 418

Fashion Gloves 148

Trade PPE Gloves 55

Trade PPE Gloves 35 1200 92

Fashion Gloves 36 585

0 1 2 3 4 5 6 7 8

1-1.9

2-2.9

3-3.9

4-4.9

5-5.9

6-6.9

7-7.9

8-8.9

9-9.9

26-26.9

Number of Samples within Range

Cr V

i C

on

cen

tratio

n R

an

ge (p

pm

)

Chromium Vi Concentration Range by Sample Type

Trade PPE Gloves PPE Gloves

Fashion Gloves Baby Shoes

Maximum Permitted Concentration

Sample

Reference

Follow-up Action Details

Dudley/3 Internal Inspection

by business.

Request for

technical

documents by

authority.

The business quarantined and inspected

stock of 8,127 pairs of gloves. Work is

ongoing together with the Primary

Authority. Technical documents for the

product were compliant. Business has

issued a warning notice in all stores at the

till point.

Dudley/1 Internal Inspection

by business.

Request for

technical

documents by

authority.

Work is ongoing together with the Home

Authority.

Suffolk

Imports/1

Internal Inspection

by business.

Request for

technical

documents by

authority.

The business inspected their stock and sent

a sample to Intertek. That sample passed

testing.

Suffolk

Imports/2

Home authority

referral

Home authority referral

Staffordshire/3 Suspension notice.

RAPEX notice.

ICSMS record.

After the suspension notice was issued, the

business voluntarily destroyed the seven

remaining items in stock. The batch was

produced in 2001. The authority decided

against requiring a product recall.

Hereford/3 & 6 Contacted ebay The products were supplied from a 3rd

country via eBay. A request was sent to eBay

to remove the listings

Southend/2 & 4 Refer to Primary

Authority

The primary authority confirmed that the

product listings had been taken down from

Amazon and Ebay, and the sellers informed

of the reasons.

HSE/8 & 21 &

26 & 33 & 34

Co-operation with

supplier

Voluntarily removed from market - ongoing

discussions with supplier and supply chain

to establish QA procedures

Suffolk/3 & 8 &

10 & 11

Contacted ebay The products were supplied from a 3rd

country via eBay. A request was sent to eBay

to remove the listings

Table 7: Descriptions of action taken by authorities or businesses

Conclusions

Due to statistical analysis, the following conclusions were reached: 1) there is no

significant different of compliance in the products purchased from the EU compared

to products from 3rd

Countries and 2) there is no significant difference of compliance

in the leather PPE gloves intended for consumers and those intended for trade use.

Table 8: Summary Findings of Statistical Analysis

The results reflect the pattern in the RAPEX information. Most failures are Chromium

VI, and within that most Chromium VI failures are with baby shoes and PPE gloves,

followed by fashion gloves and then bracelets.

It is possible to produce leather which will not form Chromium VI and can therefore

be avoided (Deivkavathi, Suresh, Rose, & Muralidharan, 2014). Detecting Chromium

VI in 32% of the samples suggests a general issue with the tanning methods and

controls in place at those manufacturers.

Protective gloves can contain Chromium VI and Azo Dyes, even though they are CE

marked and sometimes claim compliance with EN 388. The PPE gloves sampled

during this project were ‘category II PPE’. Category II PPE does not require ongoing

quality assurance by a 3rd

party, and this could contribute to the supply of leather PPE

gloves which contain Chromium VI and/or Azo Dyes. This reflects the findings in the

BSIF sampling exercise.

Failure rate (Number, %)

Chemical test type

Group 1 Group2 Statistical significance test

CrVI testing 3rd Country, 7(17%) EU, 12(11%) p-value=0.310 >0.05 Not statistically significant

Azo Dye testing

3rd Country, 3(7%) EU, 3(3%) p-value=0.349 >0.05 Not statistically significant

CrVI testing PPE Gloves, 6(16%) Trade PPE Gloves, 3(9%)

p-value=0.485 >0.05 Not statistically significant

Azo Dye testing

PPE Gloves, 0 Trade PPE Gloves, 2(6%)

p-value=0.220 >0.05 Not statistically significant

Recommendations

1. The sampling method did not take in to account the time lapse in obtaining

the sample and carrying out analysis. Chromium VI formation can take place

at any time. Sampling methods should control and reduce the time between

obtaining and analysing the sample.

2. Future sampling projects should identify the quantity of samples, and

statistically sound methods, needed to draw proper conclusions. This type of

conclusion requires statistical analysis, therefore advice should be obtained

advice from experts e.g. statisticians.

3. Only a basic statistical analysis was possible. This was due to the number of

unknown variables in the sampling method. In designing projects, advice

should be obtained from the statistician experts to ensure that the method is

sufficiently robust to allow proper statistical analysis.

4. During the course of this project, an authority carried out a sampling exercise

to examine leather belts, wallets/purses, hand bags and phone cases. This

exercise consisted of eight samples and all of them passed analysis for

Chromium VI and Azo-Dyes. All of the products were purchased from high-

street suppliers in the UK. The RAPEX data does support targeted sampling of

these products, and reveals a lack of information from the UK. It is

recommended that further sampling takes place with these product categories

on a wider scale.

5. Future projects should investigate where the leather was dyed and not just

where the final product originated, as well as the age of the product. This will

help build a picture of where the breaches originate. This could be as part of

a wider investigation of the leather supply chain.

6. BEIS and the relevant ADCO groups should consider the following issues:

a) Responsibility for the formation of Chromium VI

Because the background document to the opinion on the Annex XV dossier

proposing restrictions on chromium VI leather articles used by the Committee for

Risk Assessment (RAC) and Committee for Socio-economic Analysis (SEAC)1 states

that chromium VI compounds can be formed during:

a) the tanning/re-tanning of leather;

b) the formation of articles made from tanned leather; and

c) in finished articles.

It may not be possible to establish at which point in the supply chain the breach

first occurred, if indeed it did (i.e. is it the tanner of the leather who triggers the

offence; the producer of the article; the importer/supplier or the article; the

retailer, or did the breach occur between sample collection and analysis?). The

REACH Regulation doesn’t include any due diligence defence. However, factors

may exist to mitigate why the breach has occurred. (e.g. testing may have been

undertaken to check compliance, and the chromium VI may have formed post-

testing). Whilst this doesn’t remove the breach, issues may exist which may need

to be taken into consideration.

b) Timescale for exposure with respect to chromium VI compounds

The issue of timescales for “exposure” was considered during the drafting of the

Chromium VI compounds in leather restriction. The decision of the Committee for

Risk Assessment was, that, based on the scientific evidence available, the risks

were such that it was appropriate to state that the restriction should apply to

“leather articles or leather parts of articles coming into contact with the skin”. The

wording “prolonged” was NOT included.

c) Definitions for exposure with respect to the azo dyes restriction

The azo dyes restriction uses the phrase “may come into direct and prolonged

contact”. No definition of “prolonged” is provided with regard to the restriction,

nor has one subsequently been prepared.

Work has been done at an EU level to produce a definition for “nickel”, as that

substance also contained the wording “direct and prolonged contact with skin” in

its restriction.

For Nickel, a Q&A7 (number 0935 on the ECHA website) has been produced which

states that:

“Prolonged contact with the skin is defined as contact with the skin to articles

containing nickel of potentially more than:

>10 minutes on three or more occasion within two weeks, or

>30 minutes on one of more occasions with two weeks.

The skin contact time of 10 minutes applies when there are three or more

occasions of skin contacts within a two week period. The skin contact time of 30

minutes applies when there is at least one occasion within a two-week time

period".

Whilst this definition has not been prepared for the azo dyes, it may serve as an

example of how the word “prolonged” could be interpreted. However, attention is

drawn to the fact that the “clarification” took account of recent scientific data on

nickel allergy and a similar consideration has not been conducted for azo

dyes/colourants. Therefore direct read-across of the definition is not appropriate.

d) Test methods

The REACH legal text states that the test methods referred to in Appendix 10,

Annex XVII of REACH must be used to assess compliance of an article with respect

to restriction 43 (azo dyes and colourants).

The wording of the chromium VI compounds restriction2 does not reference a

specific method. However, at the point the restriction came into force, the

Regulation stated that EN ISO 17075 was the only internationally recognised

analytical method currently available to detect chromium VI in leather, including

leather in articles.

e) Issues with test methods

Testing and analysis of azo dyes should follow the method prescribed in Appendix

10, to Annex XVII of the REACH legal text. This refers to the EN ISO 17234-1:2010

test method, even though the method itself has been replaced by a 2015 version.

7. The same groups could also consider developing a standardised sampling

method for analysis of Chromium VI in leather products, to mitigate the issue

with Chromium VI forming after the sample is obtained.

8. The wording used for REACH restrictions is different and some are more

difficult to assess than others. For example, the restrictions in this project use

phrases such as ‘prolonged skin contact’ which does not have a definitive

meaning. The wording of the REACH restriction should be considered at the

project initiation stage, to resolve any ambiguities. The testing methodology

should also be researched as there may be inconsistencies in the method

referenced in REACH and the current state of scientific knowledge.

Appendix 1 Example Costs

Bibliography

Assem, L. Z. (2007). Chromium Toxicology Overview. Retrieved April 25, 2016, from

https://www.gov.uk/government/uploads/system/uploads/attachment_data/file/338694/C

hromium_toxicological_overview.pdf. Last accessed 25/04/2016

CSTEE. (1999). Assessment of the Report by LGC "The risk of cancer caused by textiles and leather

goods coloured with Azo-Dyes". Retrieved March 3, 2017, from

http://ec.europa.eu/health/scientific_committees/environmental_risks/opinions/sctee/sct_

out27_en.htm. Last accessed 28/04/2016.

Deivkavathi, G., Suresh, S., Rose, C., & Muralidharan, C. (2014, January Vol 21). Prevention of

carcinogenic Cr (VI) formation in leather - A three pronged approach for leather products.

Indian Journal of Chemical Technology, pp. 7-13.

EU Commission. (2014, March 25). Commission Regulation (EU) No 301/2014. Retrieved March 03,

2017, from http://eur-lex.europa.eu/legal-

content/EN/TXT/?uri=uriserv%3AOJ.L_.2014.090.01.0001.01.ENG.

EU Commission. (2016, June). Trade Report Comparisson per Year. Retrieved March 9, 2017, from

https://circabc.europa.eu/sd/a/0c7774ff-c3e8-4171-9835-f08238cb77ef/EDW%20-

%20ITI%20TEX%20-

%20Trade%20YTD%20Report%20NC%20Product%201st%20Level%20Groups%20-

%2006%20June%20-%20Leather.pdf

Marks and Spencer. (2014, March). Chromium VI Management A Practical Guide. Retrieved March

03, 2017, from http://corporate.marksandspencer.com/documents/policy-documents/ecp-

modules/module-7.pdf