How REACH Annex XVII affects the manufacture of consumer products

Restricted substances included within REACH Annex XVII, the materials these apply to, and where they may be used.

The purpose of REACH (Registration, Evaluation, Authorisation and restriction of Chemicals) Annex XVII is to place restrictions upon harmful chemicals in consumer products. There are currently 70 entries under Annex XVII, each with its own specific restrictions, and suppliers of consumer goods have a legal obligation to ensure that their products are compliant with any limits laid down in these restrictions. The responsibility for compliance with these requirements lies primarily with the manufacturer, or the importer if the goods are made outside the EU. However, retailers also have a duty to make certain that goods are compliant before placing them on the market, and this can be managed using an approach based on risk assessment.

Compliance can be demonstrated through a programme of check testing, or by a comprehensive audit of the raw materials and production processes used. In either case, it is essential to have a clear understanding of the product and good communication and cooperation throughout the supply chain. This is because not all of the 70 entries are applicable to all product types. Some entries are specific to certain types of material, due to the chemical reactions involved in the production process, while others will only be present if certain treatments have been applied. It is therefore crucial to have an understanding of how various materials are used in the construction of a product in order to develop a targeted approach to check testing, or to organise a thorough and efficient audit.

The key entries in Annex XVII for textiles, leathers and polymers are summarised in table 1. Although this is not an exhaustive list, these substances provide a good starting point for technical audits and testing programmes.

Restricted substances in textiles

For textile materials, the notable restricted substances in REACH Annex XVII are azo dyes, organotin compounds and nonylphenol ethoxylates. Azo dye colourants are frequently used to dye leathers and textiles, and the majority pose no risk to human health. However, a small subset of azo dyes can break down to form aromatic amines, which are classified as carcinogens, meaning that they can alter the genetic structure of human cells, leading to the development of cancers. Because of this, these amines are restricted to a maximum of 30mg/kg in dyed textiles and leathers which come into contact with the wearer’s skin. This restriction could therefore apply to linings in footwear, clothing, handbags and soft furnishings. Nevertheless, the restriction does not apply to undyed or bleached materials, as the azo colourants from which the restricted amines are derived would not be used.

In addition to restricting chemicals which have adverse effects upon human health, REACH Annex XVII aims to reduce the environmental impact of harmful chemicals. This is the primary reason for the restrictions imposed upon organotin compounds and nonylphenol ethoxylates (NPEs). Organotin compounds are a family of molecules containing the metallic element tin bonded to a chain of hydrocarbons. They can be used as stabilisers during the production of polymers (such as polyvinyl chloride), and can also be applied as an antimicrobial treatment for textiles and leathers. Organotins are highly toxic to aquatic organisms, so they are restricted to a maximum permitted level of 1,000 mg/kg. Nonylphenol ethoxylates are also severely toxic to aquatic life, and are classified as ‘persistent pollutants’. This means that they are not easily broken down, and therefore pose a significant long-term risk. These compounds are commonly used as wetting agents and detergents in the production of textiles and leathers.

In February 2021, restrictions entered into force restricting the allowable concentration of NPEs to a maximum of 100 mg/kg in textiles that would reasonably be washed during their lifespan. This regulation aims to reduce the levels of NPEs that enter aquatic ecosystems through waste water from domestic washing machines, and so limit the harmful impact of this substance upon aquatic life. While the Annex XVII requirement applies only to textiles, NPEs may also be present in leathers, and it is not uncommon for brands to include restrictions on NPEs in leather materials in their restricted substances lists.

Restricted substances in leather

The leather tanning process can introduce additional harmful chemicals that would not be present in textile materials. One example is the use of chromium sulphate salts as tanning agents. These contain chromium in its trivalent state (chromium III), which is not a restricted substance and is a trace element required in the human diet. However, under certain conditions, chromium III can oxidise and form chromium VI, which is a severe skin irritant and carcinogen. This reaction could theoretically occur during leather processing after tanning or during storage. There is an increased probability of the reaction occurring at high temperatures or alkaline conditions, so it is important to consider storage conditions during compliance audits. The maximum permitted concentration of chromium VI in finished leather is 3 mg/kg. This requirement applies to leathers which come into direct contact with the wearer’s skin. It is recommended, though, that any leather present is compliant with the restrictions, regardless of whether or not it comes into contact with the skin.

Restricted substances in plastics and polymers

Polymeric materials such as plastics and rubbers have very different compositions than textiles and leathers and, as a result, different chemicals are used in their manufacture. One notable distinction is the use of pigments rather than dyes to add colour to polymeric materials. This means that testing for aromatic amines derived from azo dyes is not applicable. The pigments used may, though, contain other restricted chemicals, such as the metallic element cadmium. This is commonly used in certain pigments, and can also be used as a stabiliser in the formulation. Cadmium is toxic to humans and is classified as a carcinogen. Like PCP, it is also a bioaccumlator, and so presents environmental concerns. Because of these factors, it is restricted to less than 100 mg/kg in plastics and synthetic rubbers.

Another family of restricted substances which may be present in polymeric materials are polycyclic aromatic hydrocarbons (PAHs). These occur naturally in coal, crude oil and petrol, and they can also be formed during the incomplete combustion of fossil fuels, so could be present as impurities in carbon black pigment or extender oils. They would not be deliberately introduced during manufacturing, but arise as contaminants. As a result, chemical testing is recommended to show compliance. PAHs are suspected of causing cancer through long-term exposure, and they are restricted in materials which come into prolonged contact with the skin, as well as in materials which have repeated, short-term skin contact. There are eight PAHs listed in REACH Annex XVII, all of which are restricted to less than 1 mg/kg. However, certain countries have additional, more stringent requirements which include restrictions on a broader range of chemicals within the PAH family.

Although restrictions on these substances are primarily relevant to plastics and polymers, they are also applicable to textiles and leathers which have a polymer coating. This should be considered when conducting compliance audits or developing a testing programme.

Treatments

The majority of the substances listed in REACH Annex XVII are incorporated into products as a result of contamination, or from chemical reactions occurring during or after the production process. A select few of the chemicals listed may be, however, intentionally added to the product in order to confer desirable characteristics. Examples include the use of dimethyl fumarate (DMFu) as a biocide to prevent mould growth during transportation and the application of perfluorooctanoic acid (PFOA) as a water or stain repellency treatment. In 2009, DMFu was considered to be the cause of a series of very severe allergic skin reactions in upholstered leather furniture, and an immediate ban on the substance was implemented. Following evaluation, DMFu was added to REACH Annex XVII in 2012, with a maximum permitted limit of 0.1 mg/kg. PFOA is one of the more recent additions to Annex XVII. This chemical is a carcinogen, and is also highly persistent in the environment and within the human body. As a result, it has been restricted to a maximum of 25 µg/kg in final products since July 2020.

Another notable example is the use of flame retardants to improve flammability performance. The use of these chemicals is often needed to safeguard consumers against the risks of flammable materials in products such as domestic furniture or protective garments for firefighters. However, studies have shown that certain brominated flame retardants have toxic properties and can build up in fatty tissues within the human body. For this reason, two of these flame retardants, octabromodiphenyl ether and decabromodiphenyl ether, are restricted to a maximum of 1,000 mg/kg in final products.

Because chemicals present in treatments will only be present in products if they have been deliberately introduced, they do not need to be considered if the supplier can confirm they have not been used. This is a good example of a case where cooperation across the supply chain can help to inform the strategy for demonstrating compliance.

REACH Annex XVII is continuously evolving, and additional substances are regularly added to the list as ‘substances of very high concern’ (SVHCs) are evaluated and other potentially hazardous chemicals are identified. A significant update to Annex XVII was the addition of entry 72, which was published in October 2018, and came into force in November 2020. This imposes restrictions on a number of chemicals that are carcinogenic, mutagenic or toxic for reproduction in clothing, footwear and textiles which come into contact with the user’s skin.

One of the most significant additions to Annex XVII included within entry 72 is formaldehyde, as this is the first European-wide restriction imposed on this substance in articles. Formaldehyde may be used in the textile industry to improve the resistance to creasing, and can also be used as a preservative – particularly for natural textiles. Nevertheless, at high concentrations, formaldehyde is capable of causing severe skin burns or damage to the eyes, and it is also highly toxic by ingestion, inhalation and skin contact. Even at low concentrations, formaldehyde presents a risk to human health, as it is a widespread allergen, with some individuals displaying sensitivity at very low concentrations. The maximum permitted amount of formaldehyde in textiles is 75mg/kg under entry 72.

Table 1: Key restricted substances relevant to consumer goods
Material	Applicable restricted substances	Annex XVII entry number	Maximum permitted limit	Test methods
Textiles	Aromatic amines (azo dyes)	43	30 mg/kg	EN ISO 14362-1:2017
	Organotin compounds	20	1,000 mg/kg	SATRA TM277:2020 PD CEN ISO/TS 16179:2012
	Perfluorooctanoic acid (PFOA) – only applicable if a repellency treatment has been applied	68	25 µg/kg	Extraction with an organic solvent and quantification by LC-MS/MS
	Formaldehyde	72	75 mg/kg	EN ISO 14184-1:2011
	Nonylphenol ethoxylates	46	100 mg/kg	EN ISO 18254-1:2016
Leather	Aromatic amines (azo dyes)	43	30 mg/kg	EN ISO 17234-1:2020
	Organotin compounds	20	1,000 mg/kg	SATRA TM277:2020 PD CEN ISO/TS 16179:2012
	Perfluorooctanoic acid (PFOA) – only applicable if a repellency treatment has been applied	68	25 µg/kg	Extraction with an organic solvent and quantification by LC-MS/MS
	Dimethyl fumarate (only applicable if a biocide has been applied)	61	0.1 mg/kg	PD CEN ISO/TS 16186:2012
	Chromium VI	47	3 mg/kg	EN ISO 17075-2:2017
Polymers	Organotin compounds	20	1,000 mg/kg	SATRA TM277:2020 PD CEN ISO/TS 16179:2012
	Cadmium	23	100 mg/kg	EN 16711-1:2015
	PAHs	50	100 mg/kg	PD CEN ISO/TS 16190:2013

In conclusion

As highlighted in this article, the purpose of REACH Annex XVII is to protect consumer health and the environment by placing restrictions upon harmful chemicals in consumer products. Manufacturers, importers and distributors have a legal obligation to meet the requirements specified in Annex XVII, and retailers also have a responsibility to make sure that they only place compliant products on the market. Compliance may be demonstrated either by a technical audit, or through a programme of check testing. In either case, a comprehensive understanding of the product is essential in order to determine which restricted substances should be assessed.

---