STUDY OF HEAVY METAL IMPURITIES IN COSMETIC PRODUCTS AVAILABLE IN LOCAL MARKET OF INDONESIA

1SAPTONO HADI, 2ARDIANTI, J.A., 3IRAWAN, I., 4ISTININGSIH, I.J., 5PERMATASARI, D.A.C., 6SULANDARI, I.

Department of Pharmacy, Faculty of Mathematics and Natural Sciences, UniversitasSebelasMaret, Indonesia E-mail: [email protected]

Abstract - The presence of heavy metals impurities in facial has becomes current issue in developing countries. Concern is mainly due to potential long-term toxic effects of heavy metals in cosmetics products to humans. In this study, the levels of toxic metal cadmium (Cd) in different facial cosmetic products sold at in local shop in Surakarta, Indonesia were assessed. The cosmetic items included , , face powder, face whitening cream and face cream of various prices. The cosmetics were acid digested and analyzed for heavy metal cadmium in triplicate using a flame atomic absorption spectrophotometer. The method was validated for linearity and range, precision, accuracy, limit of detection (LOD) and limit of quantification (LOQ). The results of this study showed that metals impurities Cd was detected in all cosmetics samples at level of the concentrations of mg kg−1. The detectable Cd level however was found below the acceptable limit. Furthermore test showed no statistical significant difference in concentrations of Cd between the expensive and cheap cosmetic products. The results indicate that the concentrations of toxic metal Cd in these facial cosmetic pose no considerable risk to the users. However, chronic exposure of the metal might possible from the continued use of the products.

Keywords - Cadmium, facial cosmetics products, atomic absorption spectrophotometer

I. INTRODUCTION is primarily toxic to the kidney and can cause renal failure. Cadmium can also cause bone A cosmetic is a substance or preparation used in demineralization. Cadmium is also classified as a contact with various parts of the human body such as human carcinogen [5]. epidermis, hair, nails, lips and external genital organs Dermal exposure is considered to be the most (external parts) or applied to the teeth or mucous significant route for cosmetic products since the membranes of the oral cavity with a view or for the majority of cosmetics are applied topically. The purpose of cleaning, perfuming, protection, changing absorption of individual metals is influenced by some their outlook, converting body odours and keeping factors which include physical and chemical the surfaces in good condition [1]. Cosmetics are properties of the mixtures. Oral exposure can also mixtures of some ingredients such as surfactants, oils occur especially for cosmetics used in and around the and they need to be effective, long lasting, stable and mouth as well as from hand-to-mouth contact after safe to human use[2]. exposure to cosmetics containing these heavy The various forms of cosmetic include lipstick (used metals[6]. to colour the lips), face powder (used to colour the In most countries, it is legally prohibited to use heavy face, lighten and remove flaws to produce an metals in skin cosmetic products, for example impression of youth and health), eye shadow (used to cadmium is prohibited as part of cosmetic colour the eye lids), face whitening creams (used to compositions in Korea, the European Union, China, lighten the face), face moisturizer cream etc. [3]. and Indonesia. The maximum allow able level of Many cosmetic products contain heavy metals such cadmium is 5 mg·kg-1 in Indonesia jurisdiction set by as cadmium, , arsenic, mercury, cobalt, etc. as the National Agency of Drug and Food Control of impurities. An impurity is a substance not Republic of Indonesia (NADFC) [7]. intentionally added to a product, but rather is either a Considering the different conditions of byproduct of the manufacturing process or an manufacturing and distribution, which could possibly environmental contaminant of raw ingredients [4]. As affect the heavy metals content of these cosmetics, their persistence and their natural presence, heavy coupled with the lack of regulations on cosmetics metals might bepresent in raw materials used in many studies have been reported the presence of toxic cosmetics industry. Although the presence of the metals in cosmetic products. However, the complete toxic metals in cosmetic products were in trace profile of heavy metals in cosmetics in Indonesia is amount, the slow release of these metals into the lacking. Therefore, the need arises to investigate the human system may be harmful to the biological heavy metal contents of cosmetics in thestate. system if allowed to accumulate in the body organs This research was aimed at determining the due to their long half-life. Furthermore, studies have concentration of heavy metal in cosmetic products in indicated an association between heavy metals local market of Indonesia through the determination exposure and a variety of health problems. Cadmium of the concentration of cadmium as it is among the

Proceedings of 142nd The IRES International Conference, Madrid, Spain, 10th-11th October, 2018 13 Study of Heavy Metal Impurities in Facial Cosmetic Products Available in Local Market of Indonesia most toxic heavy metals and their role in cosmetics from local market in Surakarta, Indonesia. Total 30 preparation. Selected samples , eye shadow, samples of different class of facial cosmetic products face powder, skin moisturizer cream, and skin were taken for study, viz. lipstick, eye shadow, face lightening creams were used for thisstudy. powder, skin lightening creams and face moisturizer cream. The samples were of different qualities with II. MATERIALS ANDMETHODS different price ranges from expensive and cheap products (that is higher and lower prices).The 2.1 Collection of samples information about test items and their quantities is Samples were collected from the various retail shops summarized in Table1.

Table 1:Summarization of test items and their quantity used in the study Number of test Sample No. Brand Code Sample name Code Name items* Lipstick LS-A 3 Eye shadow ES-A 3 1. Lower price (A) Compactpowder CP-A 3 Face whitening cream FW-A 3 Face moisturizer FM-A 3 Lipstick LS-B 3 Eye shadow ES-B 3 2. Higher price (B) Compactpowder CP-B 3 Face whitening cream FW-B 3 Face moisturizer FM-B 3 *Total number of samples = 30

2.2 Reagents andchemicals temperature ± 70 C for 1-2 hrs or until the Analytical grade nitric acid (65%, Sigma Aldrich) formation of white fumes, marking the end of the and perchloric acid (70%, Sigma Aldrich) were used digestion process. On completion of digestion, the for sample preparation. Standard solution of samples were allowed to cool to room temperature Cadmium was prepared from 1000 ppm standard then the samples were filtered (Whatmann filter paper stock solution. These stock solutions were serially No. 42) and made up to 10 ml with distilled water diluted with deionized water to give concentrations of into a calibrated flask. The clear solution was used for 0.025, 0.05, 0.1, 0.5, and 1 ppm cadmium standard. metal quantification.

2.3 Preparation ofsamples 2.4 Heavy metalmeasurement All the samples were digested using the standard Each sample was subsequently transferred into method [8]. 5 g of homogenized sample were volumetric flask for analysis by flame atomic weighed and carefully transferred into flask and wet absorption spectroscopy (Shimadzu AA-6650). The digested with 10 ml of acid (HNO3 65% and H2O2 instruments working conditions and parameters were 30%). Digestion process were run on a hot plate set at presented in Table2.

Table 2:Working conditions for determination of concentration of heavy metal Cd using Atomic absorption spectrophotometer. Parameter Value Wavelength (nm) 228.8 Fuel gas Acetylene Oxidant gas Air Fuel gas flow rate (L/min) 0.2 Oxidant gas flow rate (L/min) 2.5 Lamp current (mA) 4 Burner height (mm) 9 Flame type AA 1994) [9], namely linearity and range, precision, limit 2.5 Method Validation Method validation was performed by assessing of detection (LOD) and limit of quantification (LOQ), several analytical figures of merit according to and accuracy. International Conference on Harmonization (ICH,

Proceedings of 142nd The IRES International Conference, Madrid, Spain, 10th-11th October, 2018 14 Study of Heavy Metal Impurities in Facial Cosmetic Products Available in Local Market of Indonesia 2.6 StatisticalAnalysis study was demonstrated by analyzing six different Results of the research were analyzed for statistical concentrations of standard solution of Cd. significance by using SPSS v.21 (IBM Corp., USA). The sensitivity of the method was assesed by Student t-test was conducted to determine significant determining limit of detection (LOD) and limit of differences in level of metals between the two quantification (LOQ). LOD is the lowest categories of each class of cosmetic. Values in the concentration of analyte that can be detected and text are shown in tabulated form as mean ±SD. This reliably distinguished from zero, but not necessarily research was performed in triplicate analysis. quantified, while LOQ is defined as the lowest concentration of analyte that can be determined III. RESULTS AND DISCUSSION quantitatively with an acceptable level of precision and accuracy. The linearity parameter and range for 3.1 Method validation Cd is compiled in Table 3. As shown in the Table 3, For quantitative determination of heavy metal Cd in the corresponding linear regression equation obtained cosmetics, several parameters have been taken into has correlation coefficient of 0.9999. According to account and evaluated for the validation of the Eurachem (1998) [10], the analytical was linier over analytical methods, i.e. range and linearity, the certain concentration ranges if R2 obtained is higher minimum detection limit, the minimum limit of than0.995. quantification, accuracy, and precision. Linearity

Table 3: Analytical parameters of merit for the determination of Cd in cosmetics Parameters Values found Aqueous calibration curve y = 0.2277x-0.0014 R2 0.9999 Working range (mg·L-1 ) 0.025 – 0.25 LOD (mg·L-1) 0.015 LOQ (mg·L-1) 0.051 studies were performed in order to confirm the losses The precision was evaluated in terms of repeatability of cadmium or contamination during sample and expressed as relative standard deviation (RSD) of preparation as well as matrix interferences during the a set of measurement, which are performed under the measurement step. In this study, the recovery studies similar conditions (day, analyst, instrument, and were carried out by adding a known quantity of sample). In this study, precision was tested at three analyteat three different levels of concentrations. All different concentrations: low, medium, and high. The precision and accuracy studies were performed in accuracy of the analytical method was determined by three replicates. The results of precision and accuracy calculating recoveries of target compound. Recovery studies were compiled in Table4.

Table 4: Precision and accuracy studies data for determination of Cd in cosmetics Spiked concentration Repeatability Recovery [mg L-1] [RSD, %] [% ±SD] 0.1 2.00 100.98 ± 0.00 1 3.06 98.36 ± 0.02 Therefore, the proposed AAS method was accurate The repeatability was found to range from 2.00% to for quantification of cadmium in cosmetics.3.2 Cd 3.06% (Table 4). According to the International determination in cosmetics samples Conference on Harmonization (ICH, 1994), the In this study, we have tested the five different maximum RSD value acceptable for the level analyte cosmetic products for the presence of cadmium. of 1 mg L-1is 16%. Therefore, it can be concluded These samples were further categorized according to that the developed method exhibited a good precision. their price e.g. brand A was for lower price brand and Recovery rates between 98.36% and 100.98% were B for higher price brand. For each sample items, obtained (Table 4). These findings are considered triplicate samples were taken during sampling. The adequate according to the acceptance criteria set by cadmium concentration in different cosmetic products ICH which requires recovery range of 80-110 %. has depicted in Table 5. −1 Table 5:Concentrations (in mg·kg ) of heavy metal Cd in cosmetic products in Surakarta Lowerprice Higher price Cosmetic products Mean ± SD Median Range Mean ± SD Median Range Lipstick 0.10 ± 0.04 0.09 0.09 0.12 ± 0,03 0.13 0.05 Eye shadow 0.16 ± 0.03 0.15 0.05 0.13 ± 0,01 0.13 0.01

Proceedings of 142nd The IRES International Conference, Madrid, Spain, 10th-11th October, 2018 15 Study of Heavy Metal Impurities in Facial Cosmetic Products Available in Local Market of Indonesia Compact powder 0.15 ± 0.09 0.11 0.17 0.09 ± 0.01 0.10 0.02 Face whitening 0.06 ± 0.01 0.06 0,02 0.09 ± 0.00 0.09 0.00 cream Face moisturizer 0.07 ± 0.01 0.07 0.01 0.09 ± 0.02 0.09 0.03

From Table 5, the mean ± SD concentration of lipstick > compact powder > face moisturizer = face cadmium in cosmetics samples were ranged from whitening cream. From Table 5, Cd was detected in (0.06 ± 0.01) mg kg−1 in face whitening cream to all samples in both sample groups. However, the −1 concentration level is not exceeded the WHO and (0.16 ± 0.03) mg kg in eye shadow. Among the −1 analyzed samples, the highest concentration of NADFC permissible limit which are 5 mg·kg . cadmium was detected in colored decorative Comparison between same products with different cosmetics products, eye shadow, face powder, and brand, brand A (lower price products) showed the lipstick. While whitening and moisturizer cream higher concentration of cadmium than brand B showed lowest cadmium content. The median (higher price products) for eye shadow lipstick, and concentration of the heavy metal Cd analyzed in compact powder. (Figure 1). Furthermore, for face lower price product are in the order of eye shadow > moisturizer and face whitening cream, T test showed compact powder > lipstick > face moisturizer > face no significant difference statistically between the whitening cream. The similar pattern are shown also higher and lower price cosmetics in terms of the for higher price product, which are eye shadow = concentration of the heavy metal Cd analyzed (p < 0.05).

Figure 1: Comparative mean ± SD concentration of cadmium in cosmetics products (n=3). A = lower price cosmetics products; B = higher price cosmetics products; LS = lipstick, ES = eye shadow, CP = compact powder, FW = Face whitening cream, FM = Facemoisturizer

Proceedings of 142nd The IRES International Conference, Madrid, Spain, 10th-11th October, 2018 16 Study of Heavy Metal Impurities in Facial Cosmetic Products Available in Local Market of Indonesia CONCLUSION [2] N. Roa, S. Pathriba, Cosmetics and Personal Care Products, I Elsevier Inc, 1998, pp.380–382. [3] S.O. Ajayi, M.O.A. Oladipo, H.O. Ogunsuyil, A.O. Adebayo, In the present study, cadmium was determined in Determination of Minor & trace elements in Birniwatin pyrite various brand of cosmetics products sold in local and ornamental lead/zinc ore Using neutron activation market of Indonesia. From the results, the cadmium analysis, Bull. Chem. Soc. Ethiopia 16 (2) (2002) 207–211. was present in low quantities. It might possible that [4] S. Kumar, J. Singh, M. Garg, AAS Estimation of heavy metals and trace elements in Indian herbal cosmetics preparations, the continuous use of cosmetic products contaminated Res. J. Chem. Sci. 2 (3) (2012)46–51. with cadmium may however cause slow release of [5] M.A. Gondal, Z.S. Seddigi, M.M. Nasir, B. Gondal, these metals into the human body and cause harmful Spectroscopic detection of Health hazardous contaminant in effects to the consumers over time. Given the lipstick using Laser induce breakdown Spectroscopy, J. Hazard. Mater. 175 (1) (2010)726–732. significant and relatively uncontrolled human [6] E. Sainio, R. Jolanki, E. Hakala, L. Kanerva, Metals and exposure to cosmetics, these products must be arsenic in eye shadows, Contact Dermat. 42 (I) (2000)5–10. thoroughly evaluated for their safety prior to [7] US FDA, United State Food Drug & Cosmetic Act on marketing. Hazardous Chemicals in Cosmetics. Available at: accessed from: http://www.fda.gov/opacom/laws/fdcact/fdctoc.htm.21/04/201 ACKNOWLEDGEMENT [8] G.J. Nohynek, E. Antignac, T. Re, H. Toutain, Safety assessment of personal care products/cosmetics and Their The authors are grateful to the Indonesian Directorate ingredients, Toxicol. Appl. Pharmacol. 243 (2010)239–259. [9] International Conference on Harmonisation (ICH), 1994. of Higher Education Ministry of National Education Validation of Analytical Procedures: Text and Methodology, for financial support by providing BLSN DIKTI accessed from: grant. http://www.ich.org/fileadmin/Public_Web_Site/ICH_Products /Guidelines/ Quality/Q2_R1/Step4/Q2_R1_Guideline.pdf.,19/04/2017 REFERENCES [10] Eurachem, 1998. The fitness for purpose of analytical method: A laboratory guide to method validation and related topics, [1] F.O. Oyedeji, G.O. Hassan, B.B. Adeleke, Hydroquinone and accessed from: http://www.eurachem.org/guides/pdf., heavy metals levels in cosmetics marketed in Nigeria, Trends 18/04/2017 Appl. Sci. Res. 6 (2011)622–639.

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