2009 International Nuclear Atlantic Conference - INAC 2009 Rio de Janeiro,RJ, Brazil, September27 to October 2, 2009 ASSOCIAÇÃO BRASILEIRA DE ENERGIA NUCLEAR - ABEN ISBN: 978-85-99141-03-8
COSMETICS CHEMICAL COMPOSITION CHARACTERIZATION BY INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS
Ana Paula Alves*, Gustavo José Pereira, Ângela Maria Amaral, Andréa Vidal Ferreira
Centro de Desenvolvimento da Tecnologia Nuclear CDTN/CNEN, Caixa Postal 941 30123-970 Belo Horizonte, Brazil *e-mail: [email protected]
ABSTRACT
Brazil is in the 3rd position in the world’s cosmetics market. It is an expanding and growing market where new products and manufacturing processes are in a constant and steady expansion. Therefore, it is mandatory that the composition of the products is well known in order to guarantee safety and quality of daily used cosmetics. The Brazilian National Health Surveillance Agency (ANVISA) has issued a resolution, RDC No48, March 16, 2006, which defines a “List of Substances which can not be used in personal hygiene products, cosmetics and perfumes”. In this work, samples of locally manufactured and imported cosmetics (lipsticks, eye shadows, etc.) were analyzed using the Instrumental Neutron Activation Analysis technique. The samples were irradiated in the TRIGA IPR-R1 reactor of the Centro de Desenvolvimento da Tecnologia Nuclear CDTN/CNEN, on a 100kW thermal power, with a thermal neutron fluence rate about 8x1011ncm-2s-1. The analysis has detected the chemical elements Br, Ba, Ga, Na, K, Sc, Fe, Cr, Zn, Sm, W, La, Rb, Cs, Ta, Ge, Co, U, Ti, V, Cl, Al, Mn and Cu. The concentrations of these elements are on a range from 5 to 3000µg.g-1. Some chemical elements observed in samples (Cl, Br, Cr, U) are included at ANVISA prohibitive list.
1. INTRODUCTION
The modern term “cosmetic” originated in the ancient Roman public baths, which were used for an elaborate system of personal hygiene [1]. The men’s bath contained an unctuarium in which ointments for skin and facial care were applied to bathers by aliptes (masseuses). In the women’s bath, female slaves styled and dyed hair, applied facial makeup, performed manicures, and applied ointments to the skin. These slaves were called cosmetae - derived from the Greek cosmetikos, which means to arrange or to order. The name evolved into our modern word “cosmetic” meaning “to beautify the body”.
The modern use of cosmetics was greatly facilitated by several practical yet powerful inventions: the toothpaste container, the compact makeup, the safety razor, the aerosol can, and lately the retractable lipstick container [2].
The beauty is certainly an obsession to many people and this big concern with appearance caused many disasters with the unleash of the use of chemicals. For example, in the Middle Ages, women used lead in a facial cream to make their faces pale [3]. Later it was discovered that lead was toxic and that practice should have caused some deaths.
According to ABIHPEC - Brazilian Association of the Industry of Personal Hygiene, Perfumery and Cosmetics - Brazil has shown over the past ten years a cumulative growth of 357.6% in exports between 1999 and 2008 [4]. In 1996, Brazil had a net revenue on sales of 4.9 billion reais which increased to 21.7 billion in 2008. Currently on the world market for Personal Hygiene, Perfumery and Cosmetics, as data from Euromonitor, 2008, Brazil occupies the third position with an 8.6% world market, Japan is the second with 10.6% participation and the United States is the first with 15.2% participation. As far as new products and manufacturing processes are constantly in development, it is necessary to know the composition of the cosmetics to ensure the consumer safety and quality.
In Brazil, ANVISA - Brazilian National Health Surveillance Agency - has issued a resolution, RDC No48, March 16, 2006, which prohibits, in cosmetic products, the use of carcinogenic, mutagenic or toxic substances [5]. These substances are defined in the “LIST OF SUBSTANCES THAT CAN NOT BE USED IN PERSONAL HYGIENE PRODUCTS, COSMETICS AND PERFUMES”.
The aim of this work is to analyze the chemical composition of samples of national and imported cosmetics to verify the presence of any chemical element listed in the prohibitive list issued by the health’s national authority. It is intended to provide an initial assessment of the adequacy of cosmetics purchased in popular trade to the recommendations of ANVISA, RDC n ° 48.
2. MATERIALS AND METHODS
In this work, 21 national and imported cosmetics, randomly purchased in a local popular market were analyzed. The analyzed cosmetics comprehend seven lipsticks, five nail polishes, eight eye shadows and one exfoliating cream for feet. Cosmetic aliquots about 200mg were taken for neutron activation analysis. The aliquots were encapsulated on polystyrene vials. From each cosmetic, three aliquots were analyzed: one for short half-life radionuclides, other for medium half-life radionuclides and the last for long half-life radionuclides.
The eye shadows samples were obtained from a case with 18 different colors, from which seven colors were chosen randomly to be analyzed. The colors of the samples are white, light blue, pink, purple, black and dark blue. A sample from another manufacturer consisted in a roll-on type light blue eye shadow. All of the samples came from international manufacturers.
Samples of nail polish consisted of an imported pink sample and a total of four national samples in the colors white, silver, and two shades of red.
Six samples of lipsticks in blue, green, orange, red, purple and black have come from an international manufacturer. Another pink sample was obtained from a national manufacturer.
The sample of an exfoliating cream for feet comes from a national manufacturer.
The cosmetic samples were submitted to neutron activation analysis NAA to perform the chemical analysis. The samples were irradiated in the TRIGA IPR-R1 reactor of the Centro de Desenvolvimento da Tecnologia Nuclear CDTN/CNEN. The thermal neutron fluence rate was about 8x1011ncm-2s-1. The gamma spectrometry was performed in a gamma spectrometer supplied with HPGe detector (Canberra®, Model 1518 GC, counting efficiency of 15%,
INAC 2009, Rio de Janeiro, RJ, Brazil. resolution FWHM 1.85 keV for the 1332keV from 60Co). The chemical elements quantitative analysis was performed using the k0 method [6] implemented in the Neutron Activation Analysis Laboratory LAAN of CDTN/CNEN since 1995 [7]. At present, routinely, the LAAN can analyze: Dy, Ba, Sm, Ti, Mo, Cl, Mg, V, Al and Mn short half-life radioisotopes; La, Ho, Ga, Na, K, Au, As, Cd, Ca, U, W and Br medium half-life radioisotopes; Hf, Ag, Sb, Se, Ce, Th, Cr, Cs, Sc, Rb , Yb, Fe, Zr, Co, Hg, Ta, Tb and Zn long half-life radioisotopes. The experimental conditions of neutron irradiation and gamma spectrometry are presented in the Table 1.
Table 1: NAA experimental conditions
Short half-life Medium half-life Long half-life Irradiation Time 5 minutes 4 hours 8 hours Decay Time ~10 minutes ~3 days ~2 weeks Counting Time 600 seconds ~1 hour 4 hours
3. RESULTS AND DISCUSSIONS
The results obtained from the radiochemical analysis are presented in Figures 1, 2, 3 and 4. The results on Figure 1 are the mean value and standard deviation of the set of seven lipsticks samples. Figure 2 presents the mean value and standard deviation of the set of five nail polishes. Figure 3 presents the mean value and standard deviation of the set of eight eye shadows. Figure 4 presents the result for the exfoliating cream for feet.
4000 Lipstick 2000
)
-1
gg
µ
(
200
100
Concentration
0 Br Ba Na K Fe Ti Cl Al Mn Chemical Element
Figure 1. Average concentration of chemical elements detected in 7 lipstick samples
INAC 2009, Rio de Janeiro, RJ, Brazil.
50 700
Nail Polish Nail Polish 600 40 500
-1
gg
µ 30 400
300 20
200
Concentration 10 100
0 0 Br Ba Na Cr Zn Ti Cl Al Chemical Element Chemical Element Figure 2. Average concentration of chemical elements detected in 5 nail polish samples.
Figure 3. Average concentration of chemical elements detected in 8 eye shadow samples.
1200 Exfoliating Cream
1000
)
-1
gg 800
µ
600
400
Concentration ( 200
0 Na Cr Zn Al Chemical Element
Figure 4 – Chemical Elements detected in the exfoliating cream for feet.
INAC 2009, Rio de Janeiro, RJ, Brazil.
The radiochemical analyses have detected traces and even significant concentrations of some chemical elements included in the prohibitive list issued by ANVISA. These substances will be discussed on the next paragraphs. The ANVISA list does not specify concentration limits. 423 substances (organic compounds at majority) are listed and the text just says that it is prohibited the use of listed substances in personal hygiene products, cosmetics and perfumes.
In lipstick samples, as shown in Figure 1, the chemical elements Cl and Br were detected in significant concentrations: 2600±100 µgg-1 and 1357± 86 µgg-1 respectively. At the ANVISA prohibitive list, the chemical element Cl appears as elemental chlorine and also in specific compounds as, for example, chlormezanona, chlorpropamide, chloroethane and others, while Br appears only in specific compounds as, for example, bromisoval, benzilonium bromide, tetrylammonium bromide and others.
In the nail polish samples, besides Cl (380±32 µgg-1) and Br (0.6±0.2 µgg-1), a significant concentration of Cr, 11.86±0.84 µgg-1, was observed. At ANVISA prohibitive list, Cr appears as chromium, chromic acid and its salts.
In the eye shadow samples, traces of U were detected as shown in Figure 3. At ANVISA prohibitive list, radioactive substances are included. The exfoliating cream for feet presented a significant concentration of Cr, 720 ±10 µgg-1.
4. CONCLUSIONS
This preliminary work using neutron activation analysis NAA observed that some cosmetic samples contain substances of the ANVISA prohibitive list, as for example uranium (a radioactive substance) in trace level. This fact reveals the need for further analysis with a larger number of cosmetic samples from different manufacturers and batches for a more representative work.
The preliminary results show that our effort in analyze cosmetic samples is very important to provides an efficient tool to verify if the cosmetics composition is in accordance with Resolution Nº48 published by ANVISA, in order to guarantee safety and quality of daily used cosmetics.
The results also suggest the need to use other analytical techniques to determine chemical compounds belonging to the ANVISA prohibitive list.
ACKNOWLEDGMENTS
The authors express their thanks to the IPR-R1 operational staff: M.Sc Fausto Maretti Júnior, and Amir Zacarias Mesquite, supervisors of the IPR-R1 reactor, and Paulo Fernando Oliveira and Luiz Otávio Ivanenko Sette Câmara, reactor operators.
The authors also thank CDTN/CNEN, CNPq and FAPEMIG for their support.
INAC 2009, Rio de Janeiro, RJ, Brazil.
REFERENCES
1. Johnston, H.W.(Ed.),“The Private Life of the Romans”, New York: Cooper Square Publishers, (1973). 2. Vail,G.A, “A History of Cosmetics in America”, New York: Toilet Goods Association, (1947). 3. Nardello-Rataj, V. and Bonté, F. ,“Chimie et cosmétiques. Une longue histoire ponctuée d’innovations”, l’Actualité Chimique , v.323-324, pp.10-12 (2008) 4. “Dados do mercado brasileiro, 2006”, http://www.abihpec.org.br/conteudo/material/panoramadosetor/panorama_2008_2009_pt3.pdf. 5. “Resolução n. 48, de 16 de Março de 2006” http://e-legis.anvisa.gov.br/leisref/public/showAct.php?id=21253&word= 6. De Corte, F., “The k0 - standardization method; A move to the optimization of neutron activation analysis”, Gent: Rijksuniversiteit Gent, pp.464, (1986). 7. Menezes, MÂ.B.C., Sabino,C.V.S., Franco,M.B., Kastner, G.F., Rossi, E.H.M., “k0 Instrumental Neutron Activation Establishment at CDTN, Brazil: A Successful Story”, Journal of Radioanalytical and Nuclear Chemistry, 257, pp.627-632 (2003).
INAC 2009, Rio de Janeiro, RJ, Brazil.