Formaldehyde analysis of seized cosmetic products by HS-GC-MS of methylal, ethoxymethoxymethane, and ethylal derivatives
DOI:
https://doi.org/10.1590/s2175-97902020000X2e20253%20%20Keywords:
Formaldehyde, Cosmetics, GC-MS, AcetalsAbstract
Formaldehyde is a carcinogenic compound used as preservative in cosmetic products. In this study, a derivatization procedure using MeOH, EtOH and HCl (25:25:1), and incubation at 60ºC for 4 hours was optimized, and the derivatized products - methylal, ethoxymethoxymethane (EMM), and ethylal - were directly analyzed by headspace-gas chromatography-mass spectrometry (HS-GC-MS) to determine formaldehyde concentrations. The validated method provided good linearity of the standard curve, selectivity, recovery (89.6-106.6%), repeatability, and intermediate precision (RSD < 12%), with an LOD of 0.0015% and an LOQ of 0.005% for all derivatized analytes. The validated method showed to be fast, clean, and easy to implement in a laboratory. To the best of our knowledge, this is the first reported HS-GC-MS procedure to determine formaldehyde as methylal, ethylal, and EMM as derivatized compounds. The method was satisfactorily applied for the analysis of nine hair-straightener cream samples seized by the Civil Police of the Federal District, Brazil. Eight samples contained formaldehyde, at levels ranging from 0.33 to 4.02 %, higher than the legal levels, indicating the need to control the levels of this toxic compound in cosmetic products.
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Anvisa - Agência Nacional de Vigilância Sanitária; Formulário Nacional da Farmacopéia Brasileira, 2a ed. 2012. [Accessed July 18, 2022] Available at: Available at: https://www.gov.br/anvisa/pt-br/assuntos/farmacopeia
» https://www.gov.br/anvisa/pt-br/assuntos/farmacopeia
Anvisa - Agência Nacional de Vigilância Sanitária. RDC nº 15, de 26/03/2013. Aprova o Regulamento Técnico “lista de substâncias de uso cosmético: acetato de chumbo, pirogalol, formaldeído e paraformaldeído” e dá outras providências. 2013. [Accessed July 18, 2022]. Available at: Available at: https://www. gov.br/anvisa/pt-br/assuntos/cosmeticos
» https://www. gov.br/anvisa/pt-br/assuntos/cosmeticos
Anvisa - Agência Nacional de Vigilância Sanitária. RDC n° 166, de 24/07/2017. Dispõe sobre a validação de métodos analíticos e dá outras providências. 2017. [ Accessed July 18, 2022]. Available at: Available at: http://antigo.anvisa.gov.br/documents/10181/2721567/RDC_166_2017_COMP.pdf/ d5fb92b3-6c6b-4130-8670-4e3263763401
» http://antigo.anvisa.gov.br/documents/10181/2721567/RDC_166_2017_COMP.pdf/ d5fb92b3-6c6b-4130-8670-4e3263763401
Brandão PF, Ramos RM, Rodrigues JA. GDME-based methodology for the determination of free formaldehyde in cosmetics and hygiene products containing formaldehyde releasers. Anal Bioanal Chem. 2018;410(26):6873-80.
Brasil, 2019. [ Accessed July 18, 2022]. Available at: Available at: https://g1.globo.com/sp/sao-jose-do-rio-preto-aracatuba/noticia/2019/12/17/policia-abre-inquerito-para-apurar- morte-de-mulher-apos-fazer-escova-progressiva-em-ilha- solteira.ghtml
» https://g1.globo.com/sp/sao-jose-do-rio-preto-aracatuba/noticia/2019/12/17/policia-abre-inquerito-para-apurar- morte-de-mulher-apos-fazer-escova-progressiva-em-ilha- solteira.ghtml
Cao SJ, Hao AY, Sun HY, Sun T. A convenient preparation of ethoxymethoxymethane and its effect on the solubility of methanol/gasoline blends. Chinese Chem Lett. 2009;20(8):973-6.
Chang CJ, Cheng SF, Chang PT, Tsai SW. Indoor air quality in hairdressing salons in Taipei. Indoor Air. 2018;28(1):173-180.
Chopade SP, Sharma MM. Reaction of ethanol and formaldehyde: Use of versatile cation-exchange resins as catalyst in batch reactors and reactive distillation columns. React Funct Polym. 1997;32(1):53-65.
Cogliano V, Grosse Y, Baan R, Straif K, Secretan B, El Ghissassi F, et al. Advice on formaldehyde and glycol ethers. Lancet Oncol. 2004;5(9):528.
Commission Regulation (EU) 2019/831. Amending Annexes II, III and V to Regulation (EC) No 1223/2009 of the European Parliament and of the Council on cosmetic products. Official Journal of the European Union. 2019; L137, 29-63.
Daoudy BDAD, Al-Khayat MA, Karabet F, Al-Mardini MA. A robust static headspace GC-FID method to detect and quantify formaldehyde impurity in pharmaceutical excipients. J Anal Methods Chem. 2018;2018:13-7.
De Groot AC, White IR, Flyvholm MA, Lensen G, Coenraads PJ. Formaldehyde-releasers in cosmetics: relationship to formaldehyde contact allergy. Part 1. Characterization, frequency and relevance of sensitization, and frequency of use in cosmetics. Contact Dermatitis. 2010;62(1600-0536):2-17.
Del Barrio MA, Hu J, Zhou P, Cauchon N. Simultaneous determination of formic acid and formaldehyde in pharmaceutical excipients using headspace GC/MS. J Pharm Biomed Anal. 2006;41(3):738-43.
EWG - Environmental Working Group. Brands that hide formaldehyde; 2011. [Accessed July 18. 2022]. Available at: Available at: https://www.ewg.org/hair-straighteners/our-report/hair- straighteners-that-hide-formaldehyde/
» https://www.ewg.org/hair-straighteners/our-report/hair- straighteners-that-hide-formaldehyde/
Golden R, Valentini M. Formaldehyde and methylene glycol equivalence: Critical assessment of chemical and toxicological aspects. Regul Toxicol Pharmacol. 2014;69(2):178-86.
Hauksson I, Pontén A, Isaksson M, Hamada H, Engfeldt M, Bruze M. Formaldehyde in cosmetics in patch tested dermatitis patients with and without contact allergy to formaldehyde. Contact Dermatitis. 2016;74(3):145-51.
Health Canada; Cosmetics Ingredient Hotlist. 2019. [ Accessed July 18. 2022]. Available at: Available at: https://www.canada. ca/en/health-canada/services/consumer-product-safety/ cosmetics/cosmetic-ingredient-hotlist-prohibited-restricted- ingredients/hotlist.html
» https://www.canada. ca/en/health-canada/services/consumer-product-safety/ cosmetics/cosmetic-ingredient-hotlist-prohibited-restricted- ingredients/hotlist.html
Horev L, Isaksson M, Engfeldt M, Persson L, Ingber A, Bruze M. Preservatives in cosmetics in the Israeli market conform well to the EU legislation. J Eur Acad Dermatology Venereol. 2015;29(4):761-6.
IARC. Working Group on the Evaluation of Carcinogenic Risks to Humans. Chemical agents and related occupations. IARC Monogr Eval Carcinog Risks Hum. 2012;100:9-562.
Li Z, Jacobus LK, Wuelfing WP, Golden M, Martin GP, Reed RA. Detection and quantification of low-molecular- weight aldehydes in pharmaceutical excipients by headspace gas chromatography. J Chromatogr A. 2006;1104(1-2):1-10.
Magalhães AFA, Caldas ED. Two health information systems to characterize poisoning in Brazil - a descriptive study. J Public Health. 2018;(March):1-9.
Malinauskiene L, Blaziene A, Chomiciene A, Isaksson M. Formaldehyde may be found in cosmetic products even when unlabelled. Open Med. 2015;10(1):323-8.
Miralles P, Chisvert A, Alonso MJ, Hernandorena S, Salvador A. Determination of free formaldehyde in cosmetics containing formaldehyde-releasing preservatives by reversed-phase dispersive liquid-liquid microextraction and liquid chromatography with post-column derivatization. J Chromatogr A. 2018;1543:34-9.
Oiye EN, Ribeiro MFM, Okumura LL, Saczk AA, Ciancaglini P, de Oliveira MF. Forensic investigation of formaldehyde in illicit products for hair treatment by DAD- HPLC: A case study. J Forensic Sci. 2016;61(4):1122-5.
Pexe ME, Marcante A, Luz MS, Fernandes PHM, Neto FC, Sato APS, et al. Hairdressers are exposed to high concentrations of formaldehyde during the hair straightening procedure. Environ Sci Pollut Res Int. 2019;26(26):27319- 27329.
Pierce JS, Abelmann A, Spicer LJ, Adams RE, Glynn ME, Neier K, et al. Characterization of formaldehyde exposure resulting from the use of four professional hair straightening products. J Occup Environ Hyg. 2011;8(11):686-699.
Soman A, Qiu Y, Chan LQ. HPLC-UV method development and validation for the determination of low level formaldehyde in a drug substance. J Chromatogr Sci. 2008;46(6):461-5.
Wu Y, Levons J, Narang AS, Raghavan K, Rao VM. Reactive impurities in excipients: Profiling, identification and mitigation of drug-excipient incompatibility. AAPS PharmSciTech. 2011;12(4):1248-63.
Zhang X, Zhang S, Jian C. Synthesis of methylal by catalytic distillation. Chem Eng Res Des. 2011;89(6):573-80.
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