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WatchNanos - 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 AVICENN Team – Last added December 2022

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

In early 2018, the French authorities (DGCCRF) indicated that they had identified more than 11000 product references and in 2021, the European Commission specified that on average, approximately 3620 new cosmetics containing nanomaterials were notified every year between 2016 and 2020. Every day around ten new cosmetic products containing nanomaterials are placed on the market in the EU. Problem: the references in question, identified via the “Cosmetic Products Notification Portal” (CPNP) of the European Commission, are not publicly accessible.

In fact, the precise identification of nanos in cosmetics is still very difficult for the consumer today – thelabeling requirement, in force since 2013 is indeed little respected. Various initiatives have been put in place to identify cosmetics that contain nanos, but they are unfortunately too limited as things stand.

In which cosmetics are nanos found?

The cosmetics best known to contain nanomaterials are:

But, except to resort to laboratory tests, it is today impossible to have reliable information on the presence of nanos in such or such precise cosmetic.

No precise, exhaustive and reliable census

Official censuses exist, but they are insufficiently precise and reliable – and inaccessible to the general public:

Declarations in R-nano but not (yet) information on finished products 

In 2017, about twenty "substances in nanoparticle state" for cosmetic use had been the subject of 616 declarations in the r-nano register where must be declared each year the nano substances manufactured, imported or placed on the market in France4See the list of ~20 substances on page 220 of the 2017 review. (These figures will be updated when the Official 2020 Report is published).

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

But, in the current state of the register, the products which contain these nano substances cannot be identified (hence the need for improvements to the reporting procedure).

A “catalogue” of nanos in cosmetics in the European Union, to be improved

  • A first version of catalog nanomaterials used in cosmetics marketed in the European Union had been posted online by the European Commission in mid-June 2017 (i.e. three and a half years after the date set by the Cosmetics Regulations5According to Cosmetics Regulations, “by 11 January 2014 at the latest, the Commission (should have made) available a catalog of all nanomaterials used in cosmetic products placed on the market, including those used as colorants, ultraviolet filters and preservatives, mentioned in a separate section, indicating the categories of cosmetic products and reasonably foreseeable exposure conditions. This catalog is regularly updated thereafter and is made available to the public.. In one letter dated September 3, 2015, Internal Market Commissioner Elzbieta Bienkowska had indicated that the manufacturers had provided imprecise information and that the Commission had asked them to check their notifications. It also asked Member States to monitor the market and contact operators by October 2015 to carry out checks. “Once accurate and complete information is received, the Commission intends to publish the catalogue”. In one February 18, 2016 article, the magazine Chemical Watch announced the publication of the catalog for mid-2016 (Cosmetics nanomaterials inventory expected mid-2016ChemicalWatch, 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 next weeks " on the page https://ec.europa.eu/growth/sectors/cosmetics_en (Cf. EU cosmetics nano inventory hits three-year delayChemicalWatch, January 11, 2017 and Three-year wait for nanomaterial risk data promised 'in the next weeks', Vito Buonsante, Client Earth, January 11, 2017), with many unauthorized nano substances (such as TiO2 in toothpaste for example):
The "nano" substances cataloged in the 1st version

Nano substances listed in the 1st version of the "catalogue" put online in mid-June 2017 (only those marked with an asterisk * being allowed in nano state):

  • 12 dyes : CI15850 (red) – CI19140 (yellow) – CI77120 (white) – CI77266* (carbon black) – CI 77288 (green colorant) – 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
  • La 2nd version of the "catalogue" was published by the European Commission in November 2019. It again highlights the use of nanoparticles for some unauthorized.
    But curiously, the number of nanomaterials is significantly reduced compared to the first version of the catalog, especially concerning dyes6For the rest, from 6 the number of nano UV filters has increased to 4, and from 25 the number of nano substances performing other functions has increased to 22 : there were 12 listed in 2017, there were only 3 left in 2019: iron oxides, for example, have disappeared... while the DGCCRF has identified them in make-up products since 2019!

    The "catalogue" 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 necessarily being authorised… far from it! This is the case of TiO nanoparticles2 used as a dye for example.
  • These catalogs are produced from the “Cosmetic Products Notification Portal” (CPNP) of the European Commission.

An inventory of nano pigments

In September 2018, more than 80 nano-sized pigments have been identified on the European market by the European Chemicals Agency (ECHA). Many are likely to be present in cosmetic products, especially make-up products (lipstick, mascara, eyeliner, make-up, powder and blush, etc.) or toothpaste.

Censuses carried out by associations (not updated)

  • In 2019, the association Agir pour l'Environnement (APE) launched the site https://dentifrice-infoconso.agirpourlenvironnement.org, a database initially listing 271 toothpastes suspected of containing titanium dioxide nanoparticles. By the end of 2021, the figure had dropped to 224, or nearly 50 fewer toothpastes. The database has not been updated since.
  • Several other “guides” or “applications”7Le Safe Sunscreen Guide summer 2010-2011 Friends of the Earth Australia, December 2010 and the database “ Skin Deep Cosmetic Safety database created by the American NGO Environmental Working Group (EWG) for example propose to identify nanos in cosmetics or, conversely, "nano-free" cosmetics, but their reliability is limited, either because they are too dated or because they rely on declarations (sometimes misleading) from the manufacturers.
  • The apps " Yuka " or " Which product ? » (from Que Choisir) do not allow to carry out a search on the presence or not of nanos in the products.

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

THEmandatory labeling of nanomaterials in cosmetics, is applied by some brands… but not by all, far from it.

Tests carried out first by associations, then by the control authorities (DGCCRF), have revealed the presence of unlabeled (or even unauthorized) nanoparticles in many cosmetics, in variable proportions… which can go up to 100% particles below 100 nm:

Tests carried out by the DGCCRF from 2017 to 2022

The DGCCRF control theEuropean labeling obligation nanomaterials in cosmetics, conducts tests whose results show that the labeling obligation is insufficiently respected and that unauthorized nanomaterials are present in cosmetics8See in particular:
2021 checks on controlled substances in cosmetics: too many anomalies, DGCCRF, December 2022: “ In 2021, 44 cosmetic products were sampled and analyzed by the common laboratory service (common to the DGCCRF and the DGDDI). The analyzes showed that 86% had anomalies related to the presence of nanomaterials (similar to the rate of 85% observed in 2020)”.
2021 activity report, DGCCRF, 2022: “The survey conducted in 2021 targeted make-up and sunscreen products and raw material suppliers. The checks carried out at 127 establishments revealed evidence of labeling defects, the use of dyes in the form of unauthorized nanomaterials (only carbon black is authorized), and non-compliance with certain regulatory size limits. These shortcomings often come from defects in the characterization of ingredients due to unsuitable analysis methods. or 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 follow-up provided was proportionate the risks incurred by the consumer. Requests for relabelling, withdrawal of products or restoration of conformity have been addressed to professionals (16 warnings, 15 injunctions). Products that came from foreign manufacturers were the subject of requests to these operators and a report to their national authorities”.
- Nanomaterials in cosmetic products: the DGCCRF takes stock, DGCCRF, February 22, 2021
- Composition of cosmetics: the requirement for clear consumer information, DGCCRF, October 15, 2019
- Control of the presence of nanoparticles in food products and cosmetics by the DGCCRF, DGCCRF, January 2018
:

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

The DGCCRF is continuing its documentary and on-site investigations with manufacturers to find out the reasons for the presence of these substances and take the appropriate action (from “operator awareness” to criminal penalties in particular).

Tests carried out 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 children9See Sunscreen products for children – Too many substances of concern, Wecf France and Acting for the Environment, June 2020. For 3 targeted products in particular, the NGOs still found nanoparticles, but without mentioning [nano] on the packaging:

The Federation of Beauty Companies (FEBEA) immediately reacted by way of communicated, denying that manufacturers would not comply with the law, but without supporting evidence. Biarritz laboratories have also published a communicated to "categorically refute the results of this investigation" (although conducted by the most advanced laboratory on the subject and according to methods recommended at European and French level) and the “stigmatization of AlgaMaris® SPF50+ children’s sunscreen”.

Tests carried out by the ANSM in 2019 (and then?)

The ANSM presented at the Perfumes & Cosmetics Congress in November 2020 the results of the tests it had carried out by the LNE in 2019 on 12 toothpastes of different brands, supplementing the analyzes carried out by the DGCCRF on 5 other toothpastes.

Results show 2-21% (by number) titanium dioxide (TiO54) particles smaller than 100 nm.

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

Tests carried out by the UFC Que Choisir in 2017

In January 2018, UFC-Que Choisir has announced that it has found nanomaterials (unlabelled) in the nine cosmetic products she had tested in 2017. She filed complaints against manufacturers for non-compliance with the legal obligation to report on the packaging: only three products were labeled [nano] . In the six other cosmetics, nanoparticles were detected in very high proportions:

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

“Our Cold cream lip stick does not contain any nanomaterial within the meaning of the European cosmetic regulations, as evidenced by the certificates issued to us by our raw material suppliers”, had replied Avène, according to the Pharmacy Monitor.

Which nanomaterials for which cosmetic functions?

The nanomaterials present in cosmetic products are mainly dyes, texture agents, antibacterials or UV filters.

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

  • titanium dioxide
  • silicas
  • carbon black.

As an indication, here are the main nanomaterials identified as used or likely to be present in cosmetics (without necessarily being authorized), with their supposed functions (non-exhaustive list):

Authorized in nano form
  • Titanium dioxide (TiO2) as UVB filter ; in rutile form (or rutile/anatase mixture); the use of TiO2 nanoparticles makes it possible to obtain sun creams that are less opaque, more transparent and fluid but also more effective in filtering out UV rays (larger particles or agglomerates causing a reduction in the "specific surface" and therefore in their absorption efficiency)10The anti-UV efficiency would be linked to the larger reaction surface of the particles of small sizes compared to the larger particles (the surface/volume ratio is greater for the nanoparticles than for the microparticles); see for example:
    - Fueling a Hot Debate on the Application of TiO2 Nanoparticles in Sunscreen, Sharma S et al., MaterialsJuly 2019
    – "The interest of nanoparticles in cosmetics", Devers T, Head of the GIM IUT Department of Chartres, ICMN UMR 7374, presentation during the Nano and Cosmetics Technical Day, LNE, March 29, 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 UV filterA
  • MBBT* (Methylene bis-benzotriazolyl tetramethylbutylphenol) as UV filter
  • TBPT as UV filter
  • HAA299 (Bis-(Diethylaminohydroxybenzoyl Benzoyl)Piperazine) as UV filter
  • Carbon black : inasmuch as colorant (CI 77266) used in mascaras, eyeliners, …
Other nanomaterials commonly used in cosmetics but not authorized

- Soon banned :

  • Copper (Cu): antibacterial; brown colorant (CI 77400) > banned in 2022

– Not allowed:

  • Titanium dioxide (TiO2) as white colorant (CI 77891) > not permitted in nano form
    → caution: 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 7000 cosmetic products (toothpastes, mouthwashes, lipsticks and lip balms) containing TiO2
  • Zinc oxide (ZnO) as 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 (CI black 77499; CI yellow 77492; CI red 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: mattifying
  • 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 R-nano register and marketed as Aculyn
  • CI 11710: 2-[(4-chloro-2-nitrophenyl)azo]-N-(2-chlorophenyl)-3-oxobutyramide: yellow dye declared in R-nano register for cosmetic use
  • CI 11680: 2-[(4-methyl-2-nitrophenyl)azo]-3-oxo-Nphenylbutyramide: yellow dye declared in R-nano register for cosmetic use
  • CI 74160: 29H,31H-phthalocyaninato(2-)-N29,N30,N31,N32 copper: blue dye declared in R-nano register for cosmetic use; antibacterial
  • CI CI 51319: 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo[3,2-b:3′,2′-m]triphenodioxazine: violet dye declared in 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 in 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 declared in R-nano register for cosmetic use
  • CI 74260: polychloro copper phthalocyanine: green dye declared in R-nano register for cosmetic use

For a given substance (for example "titanium dioxide", "zinc oxide", iron oxide, etc.), the proportion of nanometric particles, having a dimension at least below the 100 nm bar can be very variable. The greater the proportion of "nano" particles, the greater the risks associates are likely to be significant (due to the greater mobility and reactivity of small particles)12On the risks associated with nanos in cosmetics, see in particular:
In French :
- Assessing and anticipating the risks associated with nanoparticle UV filters used in sunscreens: a life cycle-oriented study, thesis by Riccardo Catalano, June 2020 (summary in French, thesis in English)
- Titanium dioxide nanoparticles, their place in the cosmetics industry and their dangers, Laura Daragnes, Thesis for obtaining the state diploma of doctor of pharmacy, under the supervision of Isabelle Bestel, University of Bordeaux, September 2018
– “Nanos in cosmetics: benefit or risk?” », in Should we be afraid of 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 for Consumer Safety (CSSC / SCCS), January 2021 (Corrigendum of March 8, 2021)
- Titanium Dioxide Nanoparticles in Food and Personal Care Products—What Do We Know about Their Safety?, Joanna Musial et al.NanomaterialsJune 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
.

Cosmetics "without nano", how to distinguish the true from the false?

More and more brands have opted for "nano-free" to attract customers who do not want to buy cosmetics with nanoparticles. However, on July 1, 2019, restrictions came into force for “free from…” claims in cosmetics.13See "Free" claims in cosmetic products: details from the control authorities, ANSM & DGCCRF, April 16, 2020. The mentions “without nanoparticles”, “without nanomaterials”, “without titanium dioxide” (among others) should no longer appear on cosmetics.

In addition to the regulatory obligation, experience shows that the total absence of nanoparticles is in any case difficult to guarantee. Some suppliers of raw materials do not report the nanometric dimension of the ingredients they sell to cosmetics manufacturers and others have even gone so far as to sell them as "non-nano" ingredients that are nevertheless nano - ECOCERT had learned this from its costs from 201214 In August 2012, ECOCERT had to suspend its organic certification of the ZinClear ingredient of the Antaria Ltd brand: composed of zinc oxide, it was presented by the brand as "nano-free" while Friends of the Earth Australia had revealed that other company documents 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 brands tested in France since 2017 by associations and the DGCCRF (see above).

Cosmetics brands would have to conduct frequent tests to control the particle size in their raw materials and finished products – a challenge for “smaller” companies with fewer resources. One possible solution to explore lies in the hands of professional federations: the pooling of resources to carry out regular analyzes of suppliers' raw materials and create "pools" of very well characterized raw materials that are safe for health and the environment. . A tall order – literally and figuratively!

Elsewhere on the web

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

A question, a remark ? This sheet produced by AVICENN is intended to be supplemented and updated. Please feel free to contribute.

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Sheet initially created in April 2018


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