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VeilleNanos - Which nanoparticles in which cosmetic products?

Which nanoparticles in which cosmetic products?

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The use of nanos in cosmetic products: state of play

By the AVICENN team – Last updated December 2022

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:

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 "nano" substances catalogued in the 1st version

Nano substances listed in the1st version of the “catalog” put online mid-June 2017 (only those marked with an asterisk* being  authorized in the nano state) :

  • 12 colorants: CI15850 (red) – CI19140 (yellow) – CI77120 (white) – CI77266* (carbon black) – CI77288 (green dye) – CI77400 (brown) – CI77480 (yellow) – CI77491 (iron oxide; red) – CI77499 (iron oxide; black) – CI77510 (blue) – CI77820 (silver) – CI77891 (titanium dioxide; white)
  • 6 UV filters: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine , Ethylhexyl Methoxycinnamate, MBBT*, Titanium dioxide (TiO2)*, TBPT*, Zinc oxide (ZnO)*
  • 25 other substances: Alumina, Cellulose, Colloidal Copper, Colloidal Gold, Colloidal Platinum, Colloidal Silver, Fullerenes, Gold Thioethylamino Hyaluronic Acid, Hydrated Silica, Hydroxyapatite, Lithium Magnesium Sodium Silicate, Platinum, Platinum Powder, Retinol, Sapphire Powder, Silica, Silica Dimethicone Silylate, Silica Dimethyl Silylate, Silica Silylate, Sodium Magnesium Fluorosilicate, Sodium Magnesium Silicate, Sodium Propoxyhydroxypropyl Thiosulfate Silica, Styrene/Acrylates Copolymer, Tin Oxide, Tocopheryl Acetate.
  • The 2nd 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:

Tests conducted by the DGCCRF from 2017 to 2022

Since 2017, the DGCCRF has been monitoring the European obligation to label nanomaterials in cosmetics, conducting tests whose results show that the labeling obligation is insufficiently respected and that unauthorized nanomaterials are present in cosmetics8See in particular:
2021 controls on regulated substances in cosmetics: too many anomalies, DGCCRF, December 2022: “In 2021, 44 cosmetic products were sampled and analyzed by the joint laboratory service (common to the DGCCRF and the DGDDI). The analyses showed that 86% had anomalies related to the presence of nanomaterials (similar to the 85% rate found in 2020).”
Bilan d’activités 2021, DGCCRF, 2022: “The 2021 survey targeted makeup and sunscreen products and raw material suppliers. The audits of 127 establishments revealed the following In addition to the above, there is evidence of mislabeling, the use of colorants in the form of unauthorized nanomaterials (only carbon black is allowed), and the failure to comply with certain regulatory size limits. These shortcomings often result from defects in the characterization of ingredients due to inadequate analytical methods or to a questionable reading of the texts.
Of the 35 products with a high risk of non-compliance analyzed, more than three quarters were indeed non-compliant.
The consequences were proportionate to the risks incurred by the consumer. Requests for re-labeling, product withdrawal or to bring products back into compliance have been addressed to professionals (16 warnings, 15 injunctions). Information from the products that belonged to foreign manufacturers was requested from these operators and reported to their national authorities”.
Nanomaterials in cosmetic products: the DGCCRF reports, DGCCRF, 22 February 2021
Composition of cosmetics: the requirement of clear information for consumers, DGCCRF, October 15, 2019
Control of the presence of nanoparticles in food products and cosmetics by the DGCCRF, DGCCRF, January 2018
:

  • carbon black for mascaras and eyeliners,
  • iron, aluminum and copper nanoparticles not authorized at the nano scale as colorants or preservatives
  • silica nanoparticles, not authorized as texturing agents
  • nanoparticles of titanium dioxide not labeled and/or present in proportions exceeding the authorized thresholds for UV filters

The DGCCRF continues its investigations with manufacturers, whether just on documents or with on-site inspections, to find out why these substances are present and to take appropriate actions (from “raising operators’ awareness” to penal sanctions in particular).

Tests conducted by Agir pour l'Environnement and WECF France in 2020

In the summer of 2020, the associations WECF and Agir pour l’Environnement published their analysis of 71 sunscreens for children9Cf. Produits solaires pour enfants – Trop de substances préoccupantes, Wecf France et Agir pour l’Environnement, June 2020. The NGO found nanoparticulaes in 3 of the targeted products with no [nano] mention on the packaging.

The Federation of Beauty Companies (FEBEA) immediately reacted by way of a press release, denying the fact that manufacturers did not respect the law, but without any supporting evidence. Biarritz Laboratories also published a press release to “categorically refute the results of this survey” (although it was conducted by the most advanced laboratory on the subject and according to methods recommended at the European and French level) and denounced the “stigmatization of AlgaMaris® SPF50+ children’s sunscreen”.

Tests conducted by ANSM in 2019 (but what next?)

ANSM presented at the November 2020 Perfumes & Cosmetics Congress the results of tests it had conducted by the LNE in 2019 on 12 different brands of toothpastes, complementing the analyses conducted by the DGCCRF on 5 other toothpastes.

The results show 21 to 54% (by number) of titanium dioxide (TiO2) particles smaller than 100 nm.

Unfortunately, these results have not been made public outside the conferences reserved for cosmetic brands and ANSM has never responded to AVICENN’s requests for clarification.

Tests conducted by UFC Que Choisir in 2017

In January 2018, UFC-Que Choisir announced that it had found unlabeled nanomaterials in the nine cosmetic products it had tested in 2017. It has filed complaints against manufacturers for non-compliance with the legal labeling requirement as only three products were labeled [nano]. In the other six cosmetics, nanoparticles were detected in very significant proportions:

  • Lavera sun cream (organic) (TiO2 – 100% nano)
  • Avene nourishing lip balm (TiO2 – 100% nano)
  • Bourjois gloss ( iron oxide Fe₂O₃ – 100% nano)
  • Aquafresh toothpaste (GlaxoSmithKline) (TiO2 – 40% nano)
  • Sanex deodorant (Colgate-Palmolive) (aluminum oxide – 31% nano)
  • Dove body milk (TiO2 – 6% nano)

Avene responded that “Our Cold cream lip stick does not contain any nanomaterial in the sense of the European regulation on cosmetics as evidenced by the certificates issued to us by our suppliers of raw materials”, according to the Moniteur des Pharmacies.

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):

Authorized in nano form
  • Titanium dioxide
      (TiO2) as a UVB filter in rutile form (or rutile/anatase mixture); the use of TiO2 nanoparticles makes it possible to obtain sunscreens that are less opaque, more transparent and more fluid, but also more effective at filtering UV rays (larger particles or agglomerates causing a decrease in the “specific surface” and therefore in their absorption efficiency)10The anti-UV efficiency would be related to the larger reaction surface of small particles compared to larger particles (the surface/volume ratio is more important for nanoparticles than for microparticles); see for example:
    Fueling a Hot Debate on the Application of TiO2 Nanoparticles in Sunscreen, Sharma S et al, Materials, July 2019
    – “De l’intérêt des nanoparticules en cosmétiques”, Devers T, Head of the GIM Department IUT de Chartres, ICMN UMR 7374, presentation at the Nano and Cosmetics Technical Day, LNE, 29 March 2018
    Use of titanium dioxide nanoparticles in cosmetic emulsions. Impact on human health and the environment, Rossano M., Thesis, University of Le Havre, Speciality: Physico-Chemistry of colloids, 2014 (page 54)
  • Zinc oxide (ZnO) as a UVA filter
  • MBBT* (Methylene bis-benzotriazolyl tetramethylbutylphenol) as a UV filter
  • TBPT as a UV filter
  • HAA299 (Bis-(Diethylaminohydroxybenzoyl Benzoyl) Piperazine) as a UV filter
  • Carbon black: as a colorant (CI 77266) used in mascaras, eyeliners, …
Other nanomaterials commonly used in cosmetics but not authorized

Soon to be banned:

– Not allowed:

  • Titanium dioxide (TiO2) as white colorant (CI 77891) > not allowed in nano form
    → beware: even when the TiO2 ingredient is white, it contains a nanoparticle fraction; in June 2019, the consumer association Que Choisir revealed that it had identified nearly 7,000 cosmetic products (toothpastes, mouthwashes, lipsticks and balms) containing TiO2
  • Zinc oxide (ZnO) as a colorant (CI 77947)
  • Silica (SiO2): abrasive agent for toothpaste, texture and preservative agent, anti-caking additive (anti-coagulant) in powders (also declared in the R-nano register for “hair cosmetics”)
  • Iron oxide: mineral colorant (black CI 77499; yellow CI 77492; red CI 77491) used in eye shadow, foundation and powder, mascara, pencil and eye liner, lipstick, etc.
  • Cerium dioxide (CeO2): UV filter
  • Calcium carbonate (CaCO3): thickener
  • Silver (Ag): antibacterial; silver dye (CI 77820)
  • Fullerenes: anti-aging cream
  • Calcium peroxide: toothpaste
  • Calcium carbonate: thickener
  • Chromium oxide (Cr2O3): green dye (CI 77288)
  • Clay: matifying
  • Nanocellulose: rheological agent
  • Methyl-alkenoic (C=3-6) acid, polymers with alkyl(C=1-4) acrylate, polyalkylene glycol methacrylate alkyl ethers and polyalkylenepolyalkylene( C=2-4) glycol methacrylate (disubstitutedcarbopolycyclic) ethyl ether : a thickener, declared to the R-nano register and marketed under the name Aculyn
  • CI 11710: 2-[(4-chloro-2-nitrophenyl)azo]-N-(2-chlorophenyl)-3-oxobutyramide : yellow dye declared in the R-nano register for cosmetic use
  • CI 11680: 2-[(4-methyl-2-nitrophenyl)azo]-3-oxo-Nphenylbutyramide : yellow dye declared in the R-nano register for cosmetic use
  • CI 74160: 29H,31H-phthalocyaninato(2-)-N29,N30,N31,N32 copper : blue dye declared in the R-nano register for cosmetic use ; antibacterial
  • CI 51319: 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo[3,2-b:3′,2′-m]triphenodioxazine: violet dye declared in the R-nano register for cosmetic use
  • CI 12490: N-(5-chloro-2,4-dimethoxyphenyl)-4-5-[(diethylamino)sulphonyl]-2-methoxyphenyl]azo]-3-hydroxynaphthalene-2-carboxamide : red dye declared to the DeclarationObligatoireNanoFrance register R-nano for cosmetic use
  • 2,2′-[ethylenebis(oxyphenyl-2,1-eneazo)]bis[N-(2,3-dihydro-2-oxo-1H-benzimidazol-5-yl)-3-oxobutyramide: yellow dye registered in the R-nano register for cosmetic use
  • CI 74260: polychloro copper phthalocyanine : green colorant declared in the R-nano register for cosmetic use

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.

Elsewhere on the web

For more references, see our “nano & cosmetics” biblio

Any questions or comments? This information sheet compiled by AVICENN is intended to be completed and updated. Please feel free to contribute.

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Information sheet initially created in April 2018


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