ORIGINAL ARTICLE Elevated formaldehyde concentration in ‘‘Brazilian keratin type’’ hair-straightening products: A cross-sectional study Mbulelo H. Maneli, PhD,a Peter Smith, PhD,b and Nonhlanhla P. Khumalo, FCDerm, PhDa Cape Town, South Africa Background: Brazilian keratin treatment (BKT) and similar straightening products fix and retain a straight shape even when the hair is wet. Unacceptably high concentrations of formaldehyde have been reported in such products. Objective: We sought to measure the formaldehyde concentration in all BKT brands marketed in South Africa in 2012. Methods: We quantified formaldehyde by high-performance liquid chromatography with ultraviolet light detection after derivatization with dinitrophenylhydrazine. All components of 7 identified commercial brands were each tested 3 times. Results: The maximum safe concentration of formaldehyde set by the US Cosmetic Ingredient Review Expert Panel is less than 0.2%. Of the 7 commercial BKT brands, 6 had formaldehyde levels that ranged from 0.96% to 1.4%, ie, 5 times higher than the recommended level; these included 5 brands labeled formaldehyde-free. Limitations: The study is limited by not including all internationally available BKT products. Conclusions: Formaldehyde concentrations in BKT products may exceed recommended levels and serve as a health hazard. Industry monitoring is needed to improve compliance and protection of hairdressers and consumers. ( J Am Acad Dermatol 10.1016/j.jaad.2013.10.023.) Key words: Brazilian keratin treatments; formaldehyde; hair; hairdressing; public health. H eat straightens hair by breaking down temporary hydrogen bonds found between keratin filaments, but the effect is lost when the hair gets wet. A Brazilian mortician is said to have invented a method where keratin fibers in heatstraightened hair are cross-linked to retain a straight, water-resistant shape for up to 3 months. The convenience and popularity of long-lasting straight hair has resulted in a flood of products. These brands are known by various names.1 Brazilian keratin treatments (BKT) and similar products internationally and in the United States have been reported to contain unacceptably high From the Division of Dermatologya and Division of Pharmacology,b Groote Schuur Hospital, University of Cape Town. Supported by the National Research Foundation (South Africa). Conflicts of interest: None declared. Accepted for publication October 11, 2013. Reprint requests: Nonhlanhla P. Khumalo, FCDerm, PhD, Division of Dermatology, Ward G23, Groote Schuur Hospital, Abbreviations used: BKT: DNPH: DNPHF: HPLC: Brazilian keratin treatment dinitrophenylhydrazine formaldehyde dinitrophenylhydrazone high-performance liquid chromatography levels of formaldehyde.1,2 The Cosmetic Ingredient Review was established in 1976 by the industry trade association (now the Personal Care Products Council), with the support of the US Food and Drug Administration and the Consumer Federation University of Cape Town, Observatory 7925, South Africa. E-mail: [email protected]. Published online December 8, 2013. 0190-9622/$36.00 Ó 2013 by the American Academy of Dermatology, Inc. http://dx.doi.org/10.1016/j.jaad.2013.10.023 1 J AM ACAD DERMATOL 2 Maneli, Smith, and Khumalo of America.3 According to the Cosmetic Ingredient Sampling Review Expert Panel, formaldehyde is safe to use at a Samples were stored at ambient temperature maximum concentration of 0.2% as a preservative in until formaldehyde measurements, which occurred consumer products.4 Formaldehyde may cause within 2 months of delivery. Three samples respiratory irritation, contact dermatitis, headaches, (treatment, shampoo, and conditioner) of each and pregnancy complications.5 Formaldehyde is brand were analyzed for formaldehyde concentraclassified as a carcinogen; chronic exposure to high tion. Each sample was tested 3 times and a mean concentration is associated and SD calculated for with respiratory and hemocomparison. CAPSULE SUMMARY poietic malignancies.6,7 Methods of formaldehyde Preparation of 2,4-DNPH Formaldehyde concentrations of up to detection in cosmetics are solutions: Brady reagent 0.2% are recommended for use in well established and include The solution of 0.18-mol/ consumer products. High concentrations microdiffusion apparatus L 2,4-DNPH reagents was increase risks of cancers and of with fluorescent illuminaprepared following protocol respiratory and pregnancy abnormalities. tion, polarography, thinby Ruekberg and Rossini.8 A Using high-performance liquid layer chromatography, total of 3.0 g of powdered chromatography; 6 of 7 ‘‘Brazilian keratin colorimetry that involves 2,4-DNPH was suspended in type’’ hair brands had formaldehyde reaction of formaldehyde 20 mL of water and 70 mL of concentrations of 0.96% to 1.4%. This with chromotropic acid, 95% ethanol followed by included 5 brands labeled formaldehyde2,4-dinitrophenylhydrazine slow addition of 15 mL of free. (DNPH) or acetylacetone, concentrated sulfuric acid at high-performance liquid 108C. Dissolution of 2,4Protective clothing is recommended for chromatography (HPLC), DNPH was completed by occupations with high formaldehyde and mass spectrometry. heating the resulting exposure; this is currently not available Measurement of formalreddish-yellow solution until to hairdressers. Use of these products dehyde that relies on the all 2,4-DNPH particles has requires regulatory review and reaction of formaldehyde dissolved or until temperamonitoring. with 2,4-DNPH8 (condensature reached 608C. tion reaction) to form a stable complex and quantification by HPLC is most reliDerivatization of formaldehyde in BKT hair able.8 HPLC is the technique of choice as it permits care product and extraction both instrumentation and quantification to be autoA total of 1 g of cosmetic product was suspended in mated. It is highly specific and has a selective excess (approximately 6.0 mL) of 0.18 mol/L of detection limit, in water, of approximately 6 parts 2,4-DNPH. The resulting emulsion, containing a red per billion. Further, derivative maximum absorbance or yellow precipitate of the formaldehyde derivative at wavelength 365 nm greatly reduces interferences.9 or formaldehyde 2,4-dinitrophenylhydrazones (2,4We aimed to determine concentrations of formalDNPHF), was vortexed and left standing at ambient dehyde in BKT brands sold on the South African temperature for at least 10 minutes. The 2,4-DNPHF market by HPLC with ultraviolet detection after was vigorously extracted into 10.0-mL dichloromethane derivatization with 2,4-DNPH. and 2,4-DNPHF was diluted 50 times to 1.0-mL volume with methanol before HPLC injection. d d d METHODS Material An attempt was made to identify all BKT products sold in South Africa from catalogs of large retailers and local World Wide Web sites that advertise hair products. Samples of identified product were purchased through the Internet in the first quarter of 2012. Chemistry reagents 2,4-DNPH, dichloromethane, acetonitrile, and sulfuric acid were analytical grade, and methanol was HPLC grade purchased from Merck (Pty) Ltd South Africa (Modderfontein, South Africa). Formaldehyde 2,4-DNPH standard was obtained from Sigma-Aldrich South Africa (Aston Manor, South Africa). HPLC analysis The HPLC column method by Benassi et al9 was used on Shimadzu LC 10A instrument series (Tokyo, Japan). Briefly, 2,4-DNPHF was subjected to flow through Agilent Eclipse XDB-C18 column (Agilent Technologies, New Castle, DE), 5 m, 150 3 4.6 mm, where acetonenitrile and water (60:40, vol/vol), with a flow rate of 1 mL/min, served as mobile phase. The volume of sample injected was 20 L and the absorption wavelength of a detector was set at 365 nm. The signal peak area was used for quantitative calculation of formaldehyde. The calibration curve, J AM ACAD DERMATOL Maneli, Smith, and Khumalo 3 Fig 1. High-performance liquid chromatography of 2,4-dinitrophenylhydrazones (DNPHF) (2,4-dinitrophenylhydrazine [DNPH] formaldehyde derivative) showing retention times (x-axis) and concentration for detected signals (y-axis). A, Positive control. Peak detected with the retention time of 16.0 minutes, which represents 2,4-DNPHF (sample: commercial 2,4-DNPHF). B, Negative control. Very low peak at 16.0-minute retention time reflecting little (or no) 2,4-DNPHF and high peak at 12.8 minutes reflects excess or unused 2,4-DNPH (sample: shampoo). C, Positive test result. Peak detected at 16.0-minute retention time represent 2,4-DNPHF (sample: Brazilian keratin treatment, brand B [Table I]). in the concentration range of 0 to 25 g/mL, was constructed by plotting 2,4-DNPHF peak area against its concentrations. The detection and quantitative limit to the formaldehyde standard solution were determined to be 3.31 g/L and 10.0 g/L, respectively. The linear regression of y = 81,072x was obtained with the correlation coefficient very close to unity (R2 = 0.995). The 2,4-DNPHF peak area was corrected for any interference found in blank sample by subtracting the average peak area of the interference in blanks from the 2,4-DNPHF peak areas in peaked samples. J AM ACAD DERMATOL 4 Maneli, Smith, and Khumalo Table I. Formaldehyde concentration in Brazilian keratin type hair products This included 5 brands labeled formaldehyde-free and 1 labeled formaldehyde less than 0.2%. BKT brand DISCUSSION A B C D E F G Formaldehyde label Concentration, mg/mL Formaldehyde-free 0.27 Formaldehyde-free 0.28 Formaldehyde-free 0.27 0.2% Formaldehyde 0.26 Formaldehyde-free 0.31 None 0.18 Formaldehyde-free 0.055 6 6 6 6 6 6 6 0.018 0.00 0.0047 0.014 0.016 0.014 0.010 Concentration, % 1.08 1.08 1.11 1.15 0.96 1.40 0.17 6 6 6 6 6 6 6 0.16 0.00 0.094 0.021 0.11 0.51 0.040 Formaldehyde was quantified by high-performance liquid chromatography with ultraviolet light detection after derivatization with 2,4-dinitrophenylhydrazine. Formaldehyde concentration was determined from a calibration curve constructed by plotting the formaldehyde 2,4-dinitrophenylhydrazone peak area against its concentrations (Fig 1, C ). BKT, Brazilian keratin treatment. Confirmatory tests Nuclear magnetic resonance and Fourier transformed infrared spectroscopy10 techniques were used to confirm the presence of formaldehyde in tested samples before quantification (data available on request). RESULTS HPLC analysis Free formaldehyde concentration in BKT cosmetics was determined from known concentration of 2,4-DNPHF. Fig 1, A, shows HPLC chromatogram of 2,4-DNPHF standard solution. One main peak was detected at the retention time of 16.0 minutes, which represents a 2,4-DNPH formaldehyde derivative (2,4-DNPHF). The peak area of 2,4-DNPHF is used to construct the standard curve from which the formaldehyde concentration is calculated. Cosmetics (eg, shampoos and conditioners) with low formaldehyde concentration display low peak for 2,4-DNPHF and high peak for free 2,4-DNPH (Fig 1, B), which indicate lower amount of 2,4-DNPH required to derivatize formaldehyde; the rest remains in excess. The opposite is true for the treatment product that contains high formaldehyde concentration (Fig 1, C ). Formaldehyde concentrations Concentration of formaldehyde based on 2,4DNPHF derivatives in shampoos, conditioners, and one of the treatment products was shown to be less than 0.2%. Formaldehyde levels detected from BKT products are tabulated below (Table I). For 6 BKT, formaldehyde concentration ranged from 0.96% to 1.4%, which is 5 times higher that the concentration set by the Cosmetic Ingredient Review Expert Panel. Formaldehyde is ubiquitous in household products; in cosmetics it is used as a preservative at low concentration (up to 0.2%). It is essentially used in BKT products as a fixative that cross-links keratin amino acid side chains retaining the straight shape in hair. Initial reports of high formaldehyde concentrations preceded a flood of newer brands that claim to contain low and no formaldehyde. Although concentrations seem lower in newer brands, they are still more than 1% formaldehyde10; and there are still reports of high concentration (eg, an average of 8% was reported in US products advertized as containing no formaldehyde).11 The popularity of BKT products is increasing worldwide. We tested 7 brands sold in the South African market at the time of the study. All advertised as international brands. We have not been able to confirm that all were imported from Brazil. The concentration of formaldehyde in the products we tested confirms recent international data,10 in spite of much media attention and regulatory concern. This study has limited generalizability because it did not including all internationally available BKT products. However, the false labeling of products as formaldehyde-free exposes unsuspecting consumers and hairdressers to adverse effects. Formaldehyde is unstable in its gaseous state and exists as a liquid (formalin) in cosmetic products. At high temperatures, such as occurs when applying BKT products, formaldehyde gas is released. A recent simulated air-quality study tested brands (including those labeled formaldehyde-free) and found them to have ‘‘.concentrations that meet or exceed occupational exposure limits.’’12 At high concentrations formaldehyde is listed as a carcinogen and its use in industries is regulated under strict air control. This is not the case in most hairdressing salons where BKT products are used daily. Finally, high concentrations of formaldehyde were found even in products labeled formaldehyde-free. Unlike pharmaceutical companies, there is no requirement to produce evidence of rigorous safety testing before marketing new cosmetics. However, perhaps it is time that products known to contain (or to have mechanisms that function through) potentially harmful ingredients should be required to clearly list concentrations on labels. Random tests could then be used to monitor and influence industry practice in the interest of consumer safety and occupational health. Compliance with and the adequacy of the J AM ACAD DERMATOL recommendation that hair salons use air-monitoring equipment requires evaluation.11 Decisions about whether to enforce lower concentrations of formaldehyde in products or recommend appropriate air-flow control and/or protective garments need to be made by cosmetic regulators. The authors are grateful to Anwar Jardine, PhD, and Lutete Khonde, MSc, from the Department of Chemistry at University of Cape Town for assisting with nuclear magnetic resonance tests. REFERENCES 1. Anderson A. Brazilian hair straightening: the curly-haired girls’ quest for smooth, shiny, straight hair has added a treatment to its choice of products. The hair smoothing procedure goes under various names. 2011. Available from: URL:http://suite101.com/ article/brazilian-hair-straightening-a113357. Accessed November 12, 2011. 2. Oregon Occupational Safety and Health Administration. A Division of the Oregon Department of Consumer and Business Services and Center for Research on Occupational and Environmental Toxicology at Oregon Health & Science University. ‘‘Keratin-based’’ hair smoothing products and the presence of formaldehyde. 2010. Available from: URL:http: //www.orosha.org/pdf/Final_Hair_Smoothing_Report.pdf. Accessed June 28, 2011. 3. Cosmetic Ingredient Review, 2013. Available from: URL:http:// www.cir-safety.org/about. Accessed January 20, 2013. Maneli, Smith, and Khumalo 5 4. Cosmetic Ingredient Review Expert Panel. Final report on the safety assessment of formaldehyde. J Am Coll Toxicol 1984;39: 157-84. 5. Duong A, Steinmaus C, McHale CM, Vaughan CP, Zhang L. Reproductive and developmental toxicity of formaldehyde: a systematic review. Mutat Res 2011;728:118-38. 6. Hauptmann M, Stewart PA, Lubin JH, Beane Freeman LE, Hornung RW, Herrick RF, et al. Mortality from lymphohematopoietic malignancies and brain cancer among embalmers exposed to formaldehyde. J Natl Cancer Inst 2009;101:1696-708. 7. Schwilk E, Zhang L, Smith MT, Smith AH, Steinmaus C. Formaldehyde and leukemia: an updated meta-analysis and evaluation of bias. J Occup Environ Med 2010;52:878-86. 8. Ruekberg B, Rossoni E. An improved preparation of 2,4-dinitrophenylhydrazine reagent. J Chem Educ 2005;82:1. 9. Benassi CA, Semenzato A, Bettero A. High performance liquid chromatographic determination of free formaldehyde in cosmetics. J Chromatogr 1989;464:387-93. 10. National Institute of Occupational Safety and Health. Brazilian blowout. In: health hazard evaluation HETA 2011-0014. Cincinnati, (Ohio): National Institute of Occupational Safety and Health; 2011. 11. Occupational Safety and Health Administration. Hazard alert: hair smoothing products and formaldehyde. 2011. Available from: URL:http://www.cbs.state.or.us/external/osha/pdf/hazards/299326.pdf. Accessed September 19, 2011. 12. 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;8:686-99.
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