Cosmetic products since ancient civilizations were indicated the power and beautiful . Many found Egyptian burial furniture consisting of containers filled with makeup dated from 1200 BC . Since cosmetics are daily used by millions of consumers from all over the world, the security of these products and their components has drawn raising consideration due to their toxicology evaluation . Several studies have revealed that some used materials can penetrate human skin and cause many problems; this leads to improve the analysis of cosmetic products ingredients besides examination of their possible regular toxicity . Some metals are added on purpose as ingredients, whereas others are impurities. Applying to metals has been joined to health concerns including reproductive disorders, immune and nervous system toxicity. A group, heavy metals like arsenic (As), chromium (Cr), nickel (Ni), lead (Pb), cobalt (Co), copper (Cu), and Zi-Nc (Zn) can cause an adverse effect. Ingested or inhaled heavy metal will cause poisoning in the form of various diseases . Lead venenosity is an international problem, it is one of the great environmental diseases in pregnant women and children even the exposure to low levels of it  . Since cosmetic products are very used by women in Saudi Arabia, these cosmetics contain various chemicals which include heavy metals. The latter are known to be responsible for many allergic problems and health risk to consumers. This study is a target to the determination for heavy metals concentrations and detection of some dangerous components in eye makeup (eye shadow) available in the Saudi market using XRF, XRD and ICP techniques.
2.1. Materials and Methods
A total of 12 samples of eye shadow makeup were selected from products available in the shops at Jeddah markets in Saudi Arabiain May 2016. Samples were chosen depending on the results of the questionnaire for Saudi women about the most brands they use. The analyzed colored eye shadow samples were divided into 4 groups, manufactured in different countries. Three of the selected samples were locally manufactured while the 9 others were produced in China, Italy, Canada, and USA. To achieve this work many techniques were used for analysis, included; ICP-OES, X-Ray Fluorescence (XRF) for quantitative multi-elemental analysis, X-Ray Powder Diffraction (XRD) to investigate the structural information on the crystalline content.
2.2. Powder X-Ray Diffraction PXRD
Sample Analysis: powdered eye shadow samples were analyzed using a Powder XRD diffractometer (Model Equinox1000 ? INEL (France) with Co Kα (λ = 1.7890 Å) radiation at 30 kV and 30 mA. Minimal eye shadow powder sample was preparation, fixed into sample holders and located into the instrument. Sample was scanned over a 2θ range 0˚ - 120˚. PXRD data was used to detect the crystalline phases present in the samples and comparing them to the ICDD (International Centre for Diffraction Data) database. Data Processing: To describe the components that present in eye shadow samples, MATCH software (Ver. 12.0, Crystal Impact, Germany) was used to achieve a search/match analysis by balance sample diagram to reference diagram from an ICDD Powder Diffraction Files (PDF) and COD (Crystallographic Open Databases) databases.
2.3. Energy Dispersive X-Ray Fluorescence Spectrometry EDXRF
For EDXRF analysis, finely grounded powder was mounted in sample cups. Diffraction data were collected by Amptek spectrometer with X-123 Silicon Drift Detector SDD and 22 KeV Ag X-Ray source (50 KV, 60 uA). These data were used to determine the elemental composition, as percent by weight of the element, present in samples. The detection was qualitative and the elemental range covered all elements from Si to UU.
Reagents and standards: Great pureness HNO3 and HClO4 (65% - 60%, Sigma Aldrich) were adjusted to digesting the eye shadow samples . Calibration curve for every heavy metal (stock standards of ICP-OES-68B Solution A, 100 mg/L in 4% HNO3 in the field of (0.5 to 10 ppm) were created daily, dilution correction was applied. Sample preparation and analysis: followed precedent issued methods  . Accurate assessment of heavy metal concentration in eye shadow products is very considerable due to close range betwixt toxic and safe levels. This study made use of ICP-OES (Perkin Elmer-Optima 7300DV) for copper, nickel and lead. The situation for the ICP-OES work was: power, 1550 W; plasma gas, 15 L/min; aux gas, 0.2 L/min; nebulizer, 0.8 L/min; sampling rate, 0.3 mL/min. The analysis was performed in triplicate, standard deviation was calculate.
3. Results and Discussions
Lead concentration is summarized in (Table 1). The results range from 1.2 μg∙g−1 (S6) to 16.6 μg∙g−1 (S3).
Samples S5 and S8 are lead-free. The analyzed samples had content of lead less than 20 μg∙g−1, which represents the highest lead limit as contaminant in color additives in the cosmetics for outer treatment, according to US FDA (United
Table 1. Concentration of Pb in eye shadow samples (μg∙g−1).
(ND = Not Detectable).
States Food and Drugs Administration), but exceeds the limits of SASO (Saudi Standards, Metrology and Quality Org.) and health Canada organisms which limits are 10 ppm (Table 2). The maximum amounts in eye shadows reported for Pb are 41.1  , 58.7  and 81.5 μg∙g−1 .
The concentrations of copper and nickel are showed in (Table 3). Copper amount ranges from 0.6 μg∙g−1 (S5) to 337.4 μg∙g−1 (S2). 6 out of 12 samples had undetectable cupper level. The highest value corresponds to eye shadow sample from china. Greatest of the nickel concentration ranged betwixt 1.4 μg∙g−1 (S4) and 14.8 μg∙g−1 (S11). The maximum levels in eye shadows reported for Ni is 49.7 μg∙g−1. Hopefully, the levels of heavy metals obtained from the present work are below results obtained from precedent studies .
In order to minimize allergic risks related to cosmetic products use, preferred amounts of heavy metals represent as copper and nickel are less than 5 μg∙g−1   . Analyzed sample results had copper and nickel levels largely
Table 2. Recommended limits and toxicity for some metals.
Table 3. Copper and Nickel concentrations in eye shadow samples (μg∙g−1).
(ND = Not Detectable).
under this limit, so they consider as harmless and safe. However, several Chinese samples had a concentration of copper and nickel over this limit. XRF instrument usually used to detect many elements of cosmetic products . The XRF analysis of the 12 eye-shadow samples reveals the presence of heavy metals: Ti, Cr, Fe, Ni, Cu, Co, Mn, Pb, and Znas mentioned in (Figure 1). The XRD pattern of the twelve samples is presented in (Figure 2), S11-S12 examined samples, are Bismuth containing. These samples are manufactured in Canada and USA respectively. Energy Dispersive X-Ray Fluorescence Spectrometry EDXRF pattern of sample S11 is presented in (Figure 3).
Figure 1. Summary of XRF results of the 12 eye-shadow samples.
Figure 2. XRD patterns of the 12 eye shadow samples.
Figure 3. EDXRF pattern of sample S11.
Bi is identified at levels of product weight as 47.65% in S11 and 8.47% in S12 (Table 4). Bi is joined with the additive BiOCl as evidenced by XRD. The diffraction pattern as diffraction peaks match those of BiOCl at 2θ angles 13.94˚, 28.1˚, 30.14˚, 37.87˚ and 39.7. (ICDD, PDF number 01-085-0861). The phase identification in S11 sample is shown in (Figure 4). BiOCl which is used in cosmetics and known as a skin irritant. Iron is present in all samples with different concentrations. Fe levels of product weight range from 1.69% to 82.9% (Table 4).
Figure 4. XRD pattern of S11 with phase identification.
Table 4. XRF % weight composition.
Greatest levels were detected in dark Italian and American samples S10 and S12. The iron-based sample, contained hematite (Fe2O3) has assigned by PXRD results. The search matched diffraction patterns of iron oxide Fe2O3, titanium dioxide TiO2, bismuth oxychloride, zinc oxide ZnO, and lead sulfide PbS to sample diffraction pattern in the structure of Hematite, anatase, BiOCl, zincite, and Galena respectively. Compared these results to the relative elemental concentrations of zinc, titanium and Fe, Bi and Pb obtained by XRF analysis.
The amounts of heavy metals in various eye shadow products were achieved by X-ray Fluorescence and ICP-OES in this work. The composition of some samples was studied by PXRD. The overall results of these study reported that heavy metals present in eye shadow are within acceptable limits while some of those imported from China can be harmful, the prolonged use of such products can be a potential threat to human health since heavy metals can accumulate in human tissues over time and induce allergic problems. To minimize health risks related to cosmetic products use, it is highly recommended to control the quality of these products.
We would like to thank Dr. Hafedh Driss Assistant Professor at King Abdulaziz University for his precious help in performing XRF and XRD experiment and analysis.
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