Elemental Compositions of Some Eye Shadow Products Marketed in Saudi Arabia

This study focuses on the determination, as well as, the composition of some heavy metals contained in 12 eye shadow cosmetic samples. An elemental analysis of heavy metals (Ti, Cr, Fe, Ni, Cu, Co, Mn, Pb, and Zn) was performed by X-ray Fluorescence. The constitution of some samples was studied by Powder X-Ray Diffraction. Heavy metals exist as zinc oxide, Titanium dioxide, Iron oxide, Bismuth oxychloride, and lead sulfide. The quantification of selected toxic heavy metals lead, copper and nickel were achieved by Inductively Coupled Plasma-Optical Emission Spectrometry after digestion with concentrated acids. In all analyzed samples lead had a concentration less than 20 ppm, which indicated good manufacturing practice. Copper and nickel levels were within 
acceptable concentrations, but overpasses the safe limit appeared in China samples. The prolonged use of cosmetics case an allergic problem for consumers. Therefore, quality controls are highly controlled for imported products with different regulations.


Introduction
Cosmetic products since ancient civilizations were indicated the power and beautiful [1]. Many found Egyptian burial furniture consisting of containers filled with makeup dated from 1200 BC [2]. 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 [3]. 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 tox- icity [4]. 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 [5]. 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 [6] [7]. 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.

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.

Energy Dispersive X-Ray Fluorescence Spectrometry EDXRF
For EDXRF analysis, finely grounded powder was mounted in sample cups. Dif-

ICP-OES
Reagents and standards: Great pureness HNO 3 and HClO 4 (65% -60%, Sigma Aldrich) were adjusted to digesting the eye shadow samples [8]. Calibration curve for every heavy metal (stock standards of ICP-OES-68B Solution A, 100 mg/L in 4% HNO 3 in the field of (0.5 to 10 ppm) were created daily, dilution correction was applied. Sample preparation and analysis: followed precedent is-
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 [16].
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 [17] [18] [19]. Analyzed sample results had copper and nickel levels largely FDA --20 μg•g −1 [7] Health Canada --10 μg•g −1 [7] Toxicities Liver damage, insomnia, Wilson disease dermatitis, nausea, chronic asthma, coughing, a human carcinogen fetal brain damage, kidney disease, circulatory system, nervous system, and autoimmunity problems [15]  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 [20]. 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).   Bi is identified at levels of product weight as 47.65% in S11 and 8.47% in S12 ( 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).

Conclusion
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.