Which nanoparticles in which cosmetic products?

Virtually all cosmetics are likely to contain nanos, either as colorants or texture agents (toothpastes, make-up products, hair dyes, soaps, shower gels, etc.), as antibacterial agents (in deodorants) or as UV filters (in sun creams, day creams, foundations, etc.).

At the beginning of 2018, the French authorities (DGCCRF) indicated that they had identified more than 11,000 product references and in 2021, the European Commission specified that on average, about 3620 new cosmetics containing nanomaterials were notified each year between 2016 and 2020. Every day, about ten new cosmetic products containing nanomaterials are placed on the market in the EU, but the product references, identified in the “Cosmetic Products Notification Portal” (CPNP) of the European Commission, are not publicly available.

In fact, the precise identification of nanos in cosmetics is still very difficult for the consumer – the labeling obligation, in force since 2013, is indeed rarely respected. Various initiatives have been put in place to identify cosmetics that contain nanos, but unfortunately, they are currently too limited.

Which cosmetics contain nanos?

The cosmetics best known for containing nanomaterials are:

• toothpastes¹Sources:
  – Assessment of cosmetic products inspections at ANSM, ANSM, Perfumes & Cosmetics Congress, November 4, 2020: ANSM presented the results of tests it had conducted in 2019 on 12 toothpastes of different brands, complementing the analyses conducted by the DGCCRF on 5 other toothpastes
  – Are toothpastes hazardous to your health, The Daily, May 6, 2019
  – Investigation report on the presence of titanium dioxide in toothpastes, Act for the Environment, March 2019
  – Nanoparticles – Attention, elles se cachent partout, UFC-Que Choisir, Mensuel n° 566, February 2018: Aquafresh toothpaste (GlaxoSmithKline) contains titanium dioxide (TiO2), 40% of whose particles are smaller than 100 nmwhich often contain silica and/or nanoparticulate titanium dioxide
• sun creams with mineral filters²This is evidenced by:
  – analyses conducted by the DGCCRF (which unfortunately does not publish the references of the tested products)
  – tests conducted by Agir pour l’Environnement and WECF and available in the report Produits solaires pour enfants – Trop de substances préoccupantes, Wecf France and Agir pour l’Environnement, June 2020
  – the test of Lavera Sunscreen 100% mineral SPF 30 (organic) of Que Choisir which showed the presence of 100% nano titanium dioxide (but not labeled). Cf. Nanoparticles – Beware, they are hiding everywhere! UFC-Que Choisir, Monthly n° 566, February 2018 nanoparticulate titanium dioxide or zinc oxide compounds
• make-up products³See in particular:
  – the analyses conducted by the DGCCRF (which unfortunately does not publish the references of the tested products)
  – the Bourjois 3D effect gloss test, Que Choisir, January 2018: the iron oxide (Fe₂O₃) it contained was 100% nano (but not labeled) , composed of colorants containing nanoparticles of titanium dioxide, iron oxides, carbon black, etc.

However, unless we resort to laboratory tests, it is currently impossible to obtain reliable information on the presence of nanos in specific cosmetics.

No precise, exhaustive and reliable inventory

Official inventories do exist, but they are not sufficiently accurate and reliable – and not accessible to the general public:

Declarations in R-nano without the identification of finished products (yet)

In 2017, some 20 “nanoparticulate substances” for cosmetic use had been the subject of 616 declarations in the r-nano register, where nano substances manufactured, imported or placed on the market in France must be declared each year⁴See list of ~20 grants on page 220 of the 2017 Report. (These figures will be updated when the Official Report Card 2020 is published).

The “cosmetics, personal care products” product category (PC 39) is the second most declared category in the register.

However, as the register currently stands, products containing these nano substances cannot be identified (hence the need for improvements to the declaration procedure).

In the European Union: a “catalog” of nanos in cosmetics to be improved

• A first version of the catalog of nanomaterials used in cosmetics marketed in the European Union was put online by the European Commission mid-June 2017 (three and a half years after the date provided for by the Cosmetics Regulation⁵According to the Cosmetic Regulation, “by January 11, 2014, the Commission (should have made) available a catalog of all nanomaterials used in cosmetic products placed on the market, including those used as colorants, UV filters and preservatives, mentioned in a separate section, indicating the categories of cosmetic products and the reasonably foreseeable exposure conditions. This catalog shall be regularly updated thereafter and shall be made available to the public”. In a letter dated September 3, 2015, Internal Market Commissioner Elzbieta Bienkowska had indicated that industry had provided inaccurate information and that the Commission had asked them to verify their notifications. It had also asked Member States to monitor the market and contact operators by October 2015 to conduct verifications. “Once accurate and complete information is received, the Commission intends to publish the catalog.” In a February 18, 2016 article, Chemical Watch announced the publication of the catalog for mid-2016 (Cosmetics nanomaterials inventory expected mid-2016, Chemical Watch, February 18, 2016). Questioned by the NGO Client Earth, the Commission had once again called for patience and promised that the catalog would be published “in the coming weeks” on the page https://ec.europa.eu/growth/sectors/cosmetics_en (see EU cosmetics nano inventory hits three-year delay, Chemical Watch, January 11, 2017 and Three-year wait for nanomaterial risk data promised ‘in the next few weeks’, Vito Buonsante, Client Earth, January 11, 2017). It contained many unauthorized nano substances (such as TiO₂ in toothpastes for example):

• The 2^nd version of the “catalog” was published by the European Commission in November 2019. It highlights once again the use of nanoparticles, some of which are not authorized.
  Curiously though, the number of nanomaterials is clearly reduced compared to the first version of the catalog, especially concerning the colorants⁶For the rest, the number of nano UV filters has been reduced from 6 to 4, and the number of nano substances with other functions has been reduced from 25 to 22.: there were 12 listed in 2017 but only 3 in 2019 – iron oxides for example have disappeared… while the DGCCRF has identified some in makeup products since 2019.
  
  The “catalog” is not a catalog in the sense that it does not actually give precise names of products or brands, it just provides a list of substances in the nano state and the (generic) categories of products in which they have been declared – without them necessarily being authorized… far from it. This is the case of TiO₂ nanoparticles used as a colorant, for example.

• These catalogs are produced from the European Commission’s Cosmetic Products Notification Portal (CPNP).

An inventory of nano pigments

In September 2018, more than 80 nano-sized pigments were identified on the European market by the European Chemicals Agency (ECHA). Many are likely to be present in cosmetic products, especially make-up products (lipsticks, mascaras, eyeliners, blushes, powders, etc.) or toothpastes.

Some inventories conducted by associations (but not updated)

• In 2019, the association Agir pour l’Environnement (APE) launched the website https://dentifrice-infoconso.agirpourlenvironnement.org, a database listing, initially, 271 toothpastes suspected of containing titanium dioxide nanoparticles. By the end of 2021, the number had dropped to 224, so nearly 50 fewer toothpastes. The database has not been updated since.

• Several other “guides” or “applications”⁷“The Safe Sunscreen Guide summer 2010-2011 of Friends of the Earth Australia, December 2010 and the “Skin Deep Cosmetic Safety database “created by the American NGO Environmental Working Group (EWG) for example propose to identify nanos in cosmetics or, alernatively, “nano-free” cosmetics, but their reliability is limited, either because they are too old or because they rely on the (sometimes misleading) declarations of manufacturers.

• The “Yuka” or “Quel produit ?” (from Que Choisir) apps do not allow you to search for the products with or without nanos.

Tests have revealed the presence of unlabeled and/or unauthorized nanomaterials in many cosmetic products

The obligation to label nanomaterials in cosmetics is applied by some brands… but not by all, far from it.

Tests carried out initially by associations, then by the regulatory authorities (DGCCRF), have revealed the presence of unlabeled (or even unauthorized) nanoparticles in many cosmetics, in varying proportions – in some cases, with up to 100% of particles below 100 nm:

Which nanomaterials for which cosmetic purpose?

The nanomaterials present in cosmetic products are mainly colorants, texture agents, antibacterial agents or UV filters.

According to a report published in 2021 by the Commission, the most notified nano substances in the European CPNP portal – which account for more than 70% of all nanomaterial notifications – are:

• titanium dioxide
• silicas
• carbon black.

As an indication, here are the main nanomaterials identified as being used or likely to be present in cosmetics (although they are not necessarily authorized), with their supposed functions (non-exhaustive list):

For a given substance (e.g. “titanium dioxide”, “zinc oxide”, “iron oxide”, …), the proportion of nanometric particles, having a size at least under the 100 nm mark, can vary significantly. The higher the proportion of “nano” particles, the higher the associated risks are likely to be (due to the greater mobility and reactivity of small particles)¹²On the risks associated with nanos in cosmetics, see in particular:
In French :
– Evaluating and anticipating the risks associated with nanoparticulate UV filters used in sunscreens: a life cycle oriented study, thesis by Riccardo Catalano, June 2020 (abstract in French, thesis in English)
– Titanium dioxide nanoparticles, their place in the cosmetic industry and its dangers, Laura Daragnes, Thesis for the obtention of the State Diploma of Doctor of Pharmacy, under the direction of Isabelle Bestel, University of Bordeaux, September 2018
– Les nanos dans les cosmétiques: bénéfice ou risque?”, in Faut-il avoir peur des nanos? Francelyne Marano, Buchet Chastel, April 2016
In English:
– Influence of _TiO2 nanocomposite UV filter surface chemistry and their interactions with organic UV filters on uptake and toxicity toward cultured fish gill cells, Martin N et al, Ecotoxicology and Environmental Safety, 243, 113984, September 2022
– Safety Assessment of Nanomaterials in Cosmetics: Focus on Dermal and Hair Dyes Products, Cosmetics, Coimbra SC et al, 9, 83, 2022
– Scientific advice on the safety of nanomaterials in cosmetics, Scientific Committee on Consumer Safety (SCCS), January 2021 (Corrigendum of 8 March 2021)
– Titanium Dioxide Nanoparticles in Food and Personal Care Products-What Do We Know about Their Safety, Joanna Musial et al, Nanomaterials, June 2020
– NanoTiO2 Sunscreen Does Not Prevent Systemic Oxidative Stress Caused by UV Radiation and a Minor Amount of NanoTiO2 is Absorbed in Humans, Pelclova D et al, Nanomaterials, 9(6), 888, 2019
And more info here.

Nano-free cosmetics: how to differentiate the real from the fake?

More and more brands are using the “nano-free” label as a selling point to attract customers who do not want to buy cosmetics containing nanoparticles. However, as of July 1, 2019, restrictions for “without…” claims in cosmetics came into effect¹³Cf. “Without” claims in cosmetic products: clarifications from the control authorities, ANSM & DGCCRF, April 16, 2020. The terms “nanoparticle-free”, “nanomaterial-free”, “titanium dioxide-free” (among others) should no longer appear on cosmetics.

Apart from the regulatory requirement, experience shows that the total absence of nanoparticles is difficult to guarantee anyway. Some raw material suppliers do not indicate the nanometric dimension of the ingredients they sell to cosmetics manufacturers and others have even gone so far as to sell ingredients as “non-nano” when they are actually nano – ECOCERT learned this the hard way in 2012¹⁴ In August 2012, ECOCERT had to suspend its organic certification of the ingredient ZinClear of the brand Antaria Ltd: composed of zinc oxide, it was presented by the brand as “nano-free” while Friends of the Earth Australia had revealed that other documents of the company proved that it knew its nanometric composition (Cf. Antaria finally admits its sunscreen ingredient is a nanomaterial, Friends of the Earth Australia, 4 March 2013) before the start of product tests performed in France from 2017 by associations and the DGCCRF (see above).

Cosmetic brands should conduct frequent tests to monitor particle size in their raw materials and finished products – a challenge for smaller companies with fewer resources. One possible solution lies in the hands of the professional federations: pooling resources to carry out regular analyses of suppliers’ raw materials and creating “sets” of very well-characterized raw materials that are not harmful to health or the environment. A major challenge nonetheless.