Evaluation of Metals Content among Different Cosmetic Products in the Arabian Market
- 1. Department of Forensic Medicine and Clinical Toxicology, Alexandria University, Egypt
Abstract
Cosmetics’ use is very popular all over the world including Arabian countries. The use of some cosmetics as Kohl is part of culture and traditions in some countries, and is used since very young ages. This makes detection of heavy metal content in cosmetics marketed in Egypt and other Arabian markets of crucial importance.
Objective: To evaluate the levels of heavy metals content among different cosmetic products in the Arabian market.
Methods: Different brands of anti-freckle creams, eye shadows, eyeliners, facial powders, foundation, henna and lipsticks were purchased from open markets in Egypt and Saudi Arabia. Sample preparation and analysis was conducted, to estimate levels of twelve different metals (Pb, As, Cd, Ag, Ba, Al, Cr, Mn, Co, Ni, Cu, and Zn) using Inductively Coupled Plasma Mass Spectrometry (ICP-MS).
Results: The mean concentration of some studied metals as Aluminium, lead, arsenic, copper and nickel were higher than permissible levels for cosmetics in some of the studied samples.
Conclusion: In conclusion, cosmetics’ contamination with metals above permissible levels is very common in most of the products available in the developing world and Arabian markets. Physicians and users must be aware of the probable toxicity of these elements and of the clinical signs of systemic poisoning. Considering popular use of cosmetics by different age groups, the hazardous cumulative effects of prolonged exposure to low concentrations of metals like; Aluminium, lead, Arsenic, nickel and copper especially in children, cannot be ruled out. Further studies are recommended in addition, cosmetic market control and legislation procedures should be thoroughly implemented.
Keywords
• Cosmetics
• Henna
• Lipstick
• Heavy metals
• Aluminum
• Lead
• ICP-MS
• Traditional herbs
• Allergic dermatitis
• Poisoning
• Toxicity
• Arabian market
Citation
Ibrahim SY, Maguid RA (2016) Evaluation of Metals Content among Different Cosmetic Products in the Arabian Market. J Pharmacol Clin Toxicol 4(1):1062.
ABBREVIATIONS
DDW: Distilled and De-ionized Water; FDA: United State Food and Drug Administration; HNO3 : Nitric acid; HF: Hydrofluoric acid; HCl: Hydrochloric acid; PPD: Para- Phenylenediamine; ICPMS: Inductively Coupled Plasma Mass Spectrometry; HPLC: High Performance Liquid Chromatography; IS: Internal Standard; SD: Standard Deviation; Pb, As, Cd, Ag, Ba, Al, Cr, Mn, Co, Ni, Cu, and Zn: Lead, Arsenic, Cadmium, Silver, Barium, Aluminum, Chromium, Manganese, Cobalt, Nickel, Copper and Zinc consecutively
INTRODUCTION
The definition of a cosmetic identifies the site of application (epidermis, hair system, nails, lips, eyes) and the intended functions (cleaning, perfuming, changing the appearance, correcting body odours, protecting and keeping in good condition) [1]. During the past decades the safety of cosmetic products and their ingredients had attracted greater than ever attention; thus their toxicological safety evaluation is a relatively young discipline, which evolved in the second half of the 20th century. Up to the 1960s it was commonly believed that cosmetic products will never go beyond the surface of the human body. Therefore, local effects were the primary safety concern. The first consistent in vivo tests for skin and eye irritation were developed in the 1940s. Oral exposure can occur from wearing of cosmetic products containing heavy metal impurities around the mouth and also from hand to mouth contact [2,3].
Cosmetics products have infrequently been associated with severe health hazards; however, this does not mean that the use of cosmetics per se is safe. Particular attention needs to be paid to long-term safety aspects, since cosmetics products may be used extensively over a large part of the human lifespan and sensitive groups of the population such as children, old people, pregnant women, etc., may be affected. Therefore, safety-inuse for cosmetics products has been established in Europe by controlling the ingredients via their chemical structures, toxicity profiles, and patterns of exposure [4].
Some heavy metals have been used as cosmetics ingredients previously. Examples include the preservative thimerosal (mercury), the hair dye lead acetate and a number of tattoo pigments such as red cinnabar (mercuric sulphide). As the issue of heavy metals as intentional cosmetics ingredients has been thoroughly studied, awareness turns nowadays to the presence of these substances as impurities [5]. It is therefore evident that any action devoted to the definition of the possible risks for the consumer due to the presence of toxic substances in a cosmetic formulation is to be robustly supported. That’s why, many countries legalized the procedures to be followed for the commercialization of cosmetic products [6].
METHODS
Heavy metals
Accurately weighed portion (0.1 – 0.2g) of each cosmetic sample was transferred to a TEFLON digestion tube (120 mL) and 7.0 mL of the acid mixture Nitric/ Hydrofluoric/hydrochloric acids (HNO3 /HF/HCl, 4.5:2:0.5) was introduced. The tube was sealed and the sample was digested inside a microwave oven (Milestone ETHOS 1600). After being cooled to ambient temperature, the tube was opened; the inside of the lid was rinsed with distilled and de-ionized water (DDW) and the mixture heated on a hotplate (120 °C) for 30 minutes to drive off the residual HF and HCl. The resulting digest was filtered in a polypropylene flask using 1% HNO3 and made up to 50ml volume. For ICPMS measurement the clear digest obtained were diluted 10 times using DDW. Samples and standard reference materials (SRM) were prepared in a batch of six including a blank (HNO3 /HF/HCl) digest [7]. Twelve different metals (Pb, As, Cd, Ag, Ba, Al, Cr, Mn, Co, Ni, Cu, and Zn) in all prepared solutions were quantified subsequently by ICP-MS.
Chemicals
High purity water (Specific resistivity 18 MΩ cm-1) obtained from a Milli Q - pure water purification system (Millipore SAS, France) was used throughout the work. All solvents, chemicals and, reagents used were purchased from MERCK, (Darmstadt, Germany).
Samples
Different brands of anti-freckle creams, eye shadows, eyeliners, facial powders, foundation, lipsticks and henna were purchased from local markets in Egypt, and Saudi Arabia. All the samples were purchased by different commercial suppliers located in the local markets of both countries. The brand names were blinded and given the codes 1 to 25. The other details are presented in Table 1.
Table 1: Details of purchased cosmetic products.
Sample Code | Type | Uses as written on the product |
1- 3 | Anti-freckle creams | Depigmentation, skin cleansing and fairness. |
4 - 6 | Eye shadows | Cosmetic colouring of eye lids. |
7 - 9 | Eye liners | Eye Demarcation. |
10 - 12 | Facial powders | Improve the complexion. |
13 - 15 | Foundations | Anti-aging, tone up the skin, tighten the pores. |
16 - 18 | Lip sticks | Lip colour, and moisturizer. |
19 - 25 | Henna powder | Skin pigmentation and Tattooing. |
Statistical analysis
Data for metal estimation have been tabulated and the results were analyzed statistically and expressed as mean ± SD. The concentrations of metals were presented in table (2),
Table 2: Concentrations of metals in cosmetic products.
Sample Number | Metals studied (Mean ± SD) | |||||||||||
Pb | As | Cd | Ag | Ba | Al | Cr | Mg | Co | Ni | Cu | Zn | |
1 | 33.100±1.975 | 1.563±0.038 | 0.625±0.000 | 0.076±0.010 | ND | 230±21.63 | 27.07 ± 6.15 | 112±0 | 2.06± 0.19 | 2.14± 0.18 | 20.5±0.7 | 6.6±0.00 |
2 | 20.580±3.746 | 1.430±0.035 | 0.658±0.058 | 0.083±0.010 | 38.58± 3.26 | 275±55.75 | 7.3± 4.97 | 3508±115 | 1.06± 0.12 | 3.74± 0.68 | 21.9±0.3 | 4.8±0.15 |
3 | 16.630±3.992 | 1.887±0.021 | 0.625±0.000 | 0.278±0.011 | ND | 325±69.50 | 5.60 ± 4.12 | 1358±14 | ND | 23.1± 0.25 | 22.2±0.5 | 6.89±0.09 |
4 | 6.750±2.479 | 3.423±0.045 | 0.992±0.321 | 2.183±0.026 | 66.15± 3.06 | 3780±95.09 | 12.0± 3.50 | 2071±566 | ND | 9.65± 1.53 | 24.3±0.5 | 21.11±0.24 |
5 | 12.030±3.995 | 2.923±0.045 | 0.692±0.115 | 0.157±0.021 | 21.30± 4.02 | 806±90.27 | 1.40 ± 2.20 | 475±38 | ND | ND | 19.5±0.1 | 31.4±0.34 |
6 | 9.390±3.438 | 3.683±0.181 | 1.158±0.208 | 0.309±0.021 | 54.15± 3.10 | 1122±87.40 | 3.74 ± 1.70 | 8317±83 | 3.34 ±0.61 | 3.41± 0.74 | 22.0±0.6 | 18.69±0.40 |
7 | 11.350±2.963 | 2.237±0.038 | 1.092±0.252 | 0.072±0.014 | ND | 313±32.01 | 1.15 ± 0.22 | 5316±101 | ND | 8.45± 12.30 | 19.9±0.2 | 49.26±0.26 |
8 | 96.430±1.975 | 1.557±0.042 | 1.875±0.499 | 0.065±0.010 | 1.1± 0.05 | 582±12.86 | 0.69 ± 0.15 | 7917±196 | ND | ND | 22.9±0.2 | 50.78±0.41 |
9 | 21.400±1.302 | 2.927±0.047 | 1.258±0.551 | 1.095±0.031 | ND | 4779±82.56 | 4.70 ± 0.95 | 8350±307 | 1.06± 0.09 | ND | 23.2±0.5 | 56.57±0.57 |
10 | 11.300±1.988 | 3.213±0.040 | 0.758±0.153 | 0.311±0.012 | ND | 5311±66.58 | 0.69 ± 2. 13 | 8112±481 | ND | ND | 20.4±0.1 | 46.12±0.26 |
11 | 6.750±0.563 | 2.637±0.038 | 0.725±0.173 | 0.041±0.007 | ND | 4825±77.03 | 24.70 ± 5.20 | 10681±900 | 0.4± 0.21 | 3.2± 0.34 | 48.5±0.4 | 50.49±0.58 |
12 | 10.040±1.158 | 3.077±0.191 | 0.792±0.231 | 0.041±0.004 | 32.07± 3.51 | 4268±36.83 | 8.72± 0.04 | 4929±97 | ND | 7.1± 0.30 | 49.1±0.8 | 54.01±0.14 |
13 | 7.400±1.975 | 2.927±0.047 | 0.858±0.343 | 0.168±0.007 | 18.1± 1.05 | 4917±109.8 | 4.30± 0.12 | 5146±159 | 1.30 ±0.3 | ND | 10.0±0.3 | 50.46±2.51 |
14 | 1.470±0.852 | 2.263±0.021 | 0.825±0.100 | 0.118±0.004 | ND | 4511±89.61 | 0.44 ± l.35 | 475±38 | ND | 18.1± 2.30 | 10.4±0.3 | 39.65±0.30 |
15 | 12.850±0.577 | 2.013±0.006 | 0.785±0.115 | 0.278±0.011 | 2.07± 0.51 | 5505±31.64 | 2.16±0.32 | 5108±97 | ND | 1.53± 0.15 | 9.4±0.3 | 35.66±6.99 |
16 | 11.12±2.64 | 1.42±0.031 | l.1 7 ± 1.20 | 0.14±0.032 | 28.18± 3.14 | ND | 25.41 ± 5.20 | 15±3.24 | 1.11 ±0.5 | ND | 41.1±0.4 | 4.1±0.17 |
17 | 7.214±1.21 | 3.021±0.133 | 0.07 ± 0.65 | 0.141±0.09 | ND | 344±12.47 | 9.50 ± 2.43 | ND | ND | 3.22± 0.64 | 19.1±0.5 | ND |
18 | 9.350±2.963 | 1.651±0.035 | 1.40 ± 0.46 | 0.321±0.024 | ND | 52±10.16 | 0.69 ± 0.15 | 19±4.211 | ND | ND | 22.1±0.64 | 14.8±0.11 |
19 | 6.430±1.975 | 2.470±0.124 | 0.08 ± 1.25 | 0.355±0.018 | 2.18± 1.14 | 12±14.81 | 12.06 ± 3.50 | ND | 1.04 ±0.7 | ND | 4.12±0.2 | 24.1±0.16 |
20 | 8.400±1.302 | 1.830±0.120 | 0.09 ± 1.35 | 0.214±0.054 | 3.22± 1.02 | ND | 26.07 ± 6.15 | 25±7.29 | ND | 7.21± 0.14 | 16.1±0.8 | 3.2±0.14 |
21 | 11.300±1.988 | ND | 3.50 ± 0.70 | 0.147±0.025 | 2.14± 0.19 | 82±12.71 | 5.60 ± 4.12 | 79±13.24 | ND | ND | 39.1±0.5 | ND |
22 | 8.400±1.975 | 3.927±0.047 | 0.958±0.343 | 0.268±0.007 | 17.1± 1.05 | 494±109.8 | 4.60± 0.12 | 524±159 | 1.80 ±0.3 | 7.11± 0.14 | 11.0±0.3 | 50.15±2.51 |
23 | 1.240±0.85 | 2.215±0.021 | 0.425±0.100 | 0.248±0.004 | ND | 421±89.61 | 0.31 ± l.35 | 275±38 | ND | 15.7± 2.30 | 7.4±0.3 | 24.65±0.30 |
24 | 14.850±0.577 | 2.013±0.006 | 0.715±0.115 | 0.278±0.011 | 2.07± 0.51 | 545±31.64 | 2.16±0.32 | 547±24 | ND | 1.85± 0.15 | 9.1±0.3 | 35.25±6.99 |
25 | 17.4±2.64 | 1.42±0.031 | l.1 7 ± 1.20 | 0.14±0.032 | 28.11± 3.14 | ND | 20.41 ± 5.20 | 11±3.24 | 1.11 ±0.5 | ND | 32.1±0.4 | 7.1±0.17 |
and were expressed as mean ± SD.
RESULTS
Laboratory studies
In this study, we have tested twenty five cosmetic products for the presence of twelve different metals (Pb, As, Cd, Ag, Ba, Al, Cr, Mn, Co, Ni, Cu, and Zn) using ICP-MS. The distribution of heavy metals in samples studied is shown in Table 2 expressed as mean ± SD. Metals were detected in most of the samples in varying concentrations. However, clear patterns indicating that metal concentrations were related to specific brands, cost, or color were not detected. The result of this experiment revealed that the distribution frequency of metals among the studied samples were; Pb, As, Cd, Ag >Zn, Mg > Al > Ba, Ni > Co. The distribution frequency of Cobalt was the least among the studied elements (detected in 10 samples only). Aluminium was detected in most of the studied samples (22 samples).
DISCUSSION
Back in ancient Egypt, Greece, and Roman Empire times, women had been applying some reddish mineral or plant pigment to their cheeks and lips for the purpose of beautification. Therefore, the history of lip cosmetics might have been over thousands of years [8]. To ensure safety and efficacy, cosmetic products are regulated and controlled worldwide. However, harmonization of laws dealing with cosmetics is far from being achieved and regulatory frameworks vary greatly between countries making it practically impossible for a global industry to sell the same product on all markets [1]. Cosmetics have often been considered by many dermatologists, more dangerous than good [9]. They may contain more than 10,000 ingredients which are related to many diseases like cancer, birth defects, developmental and reproductive harms. Knowing such poisonous effects the [10] completely forbidden the presence of nine ingredients including coal tar colors, formaldehyde, glycol ethers, lead, mercury, Phenylenediamine, phthalates in cosmetic products.
The density of heavy metals is five folds more than that of water [11]. These includes: antimony, arsenic, bismuth, cadmium, cerium, chromium, cobalt, copper, gallium, gold, iron, lead, manganese, mercury, nickel, platinum, silver, tellurium, thallium, tin, uranium, vanadium and zinc. Essential metals when present in higher concentration show toxic effects as well [10].
Exposure to metals may occur through the diet, medications environmental exposure and cosmetics use [12]. The use of underarm anti-perspirant has been investigated as a possible cause of breast cancer. Basis for breast carcinogenesis may be due to the binding of various chemical constituents including metals to DNA and promotion of damaged cells growth, that’s why some directives banned the use or presence of the heavy metals, Cd, Co, Cr, Ni, and Pb as impurities in the preparation of cosmetics [13]. Information about dermal exposure to metal toxins is very scanty, and few data exist on the personal care products and their role in inducing toxicities [14].
The study of metal content in some cosmetic products raise the concern about potential public health hazards; though, metals in cosmetic products are not currently regulated by the FDA. Although metal concentrations in cosmetic products have been reported by studies performed in many countries [15-17] interpreting how these reported concentrations may be related to potential health risk is challenging.
The increasing health awareness and, the increased availability of cosmetic products in different markets draws the attention of researchers and clinicians to find adverse effects related to heavy metal contamination [18,19]. Although some cosmetics are benign; others can cause or are supposed to cause harmful effects such as cancer, allergic reaction, mutations, as well as respiratory, developmental and reproductive problems [20]. High levels of cadmium have been linked to DNA mismatches. Increased zinc levels has been reported to produce clinical illness similar to that caused by lead toxicity, and can easily be mistakenly diagnosed as lead poisoning [21].
There are currently no international standards for impurities in cosmetics. Limits have been established in Germany. Rather than taking a risk-based approach, the German limits are based on levels that could be technically avoided. Thus, heavy metal impurities were limited to anything above normal background levels. Heavy metal levels in cosmetic products above the values listed later are considered technically avoidable. Lead: 20 ppm, Arsenic: 5 ppm, Cadmium: 5 ppm, Mercury: 1 ppm, Antimony: 10 ppm [22].
Health Canada has taken a similar approach in the establishment of heavy metal impurity limits, as the department has always maintained that impurities in cosmetics should be reduced to the extent that is technically feasible [23]. Most of the cosmetic samples in this study were found to contain high concentration of metals, particularly; Pb, Al, Cu, Ni, Mg and Zn which showed a wide variation among the samples and products. The differences in concentration of the studied metals between the samples may be attributed to the difference in the origin of the cosmetic samples.
Aluminium was detected in nearly most of the studied samples (22 samples), whereas Pb, As, Cd, Cr, Cu and Ag were detected in all the studied samples. Significant concentrations of aluminium (5505± 31.64 ppm) have been found in one product (sample 15) and 5311± 66.58 ppm in sample number (10). Worth mentioning, [16] had highlighted the adverse developmental effects of aluminium toxic exposure on children and infants.
Cobalt, Barium and Nickel were the least detected elements. Cadmium, chromium and Silver were detected in all samples, while Cobalt was only detected in ten samples. Some directives banned the use of heavy metals, Cd, Co, Cr, Ni, and Pb as impurities in the preparation of cosmetics [24,25].
Very high lead concentration was measured also in four samples which reached 96.43, 21.4, 17.4 and 14.85 ppm in samples number (8, 9, 25, and 24) respectively. This high lead value poses an alert for all users of such products, as any cosmetic product is considered technically avoidable when they exceed the 10 ppm Pb limits [23]. It is likely that an exposure to more than 0.005 ppm of cadmium can be hazardous to human health. However, level of exposure that is well thought-out as a high limit is diverse because the cadmium effect may increase or decrease depending on other factors as the form, type and duration of exposure [25].
Arsenic was detected in all the studied samples, the highest level detected was 3.927 (sample 22), six of the studied samples showed results for As higher than 3 ppm which is the permissible As level in cosmetics [23] Fifteen (15) of the tested samples contained nickel, with levels ranging from 1.53 ppm in sample (15) to 23.1 ppm in sample number (3). The presence of high concentrations of nickel (more than 5 ppm) was detected in eight samples of studied cosmetic products. Usually, nickel salts are used as dye mordant and pigments. Nickel allergy caused by eye shadow has been reported by [2], who reported that even 1 ppm may set off a pre-existing allergy.
Maximum concentration of Copper was 49.1 ppm detected in sample (12) which is higher than many of the studies conducted for cosmetic products [26,21]. The maximum value of cobalt (3.34 ppm) obtained in this study in sample number (6) was found to be lower than those reported elsewhere [26].
The metals analyzed in this study were not listed as ingredients on any of the tested products. Due to absence of manufacturer testing and regulatory monitoring of such products, it is possible that the producing companies are not even attentive that their commercial final products are contaminated. These metal contaminants likely get into the products when below standard ingredients are used. Manufacturers should test the used raw ingredients before using them in making the final products to be able to track the origin of such contaminants [27].
CONCLUSION
The current study revealed that the continuous use of such contaminated cosmetics could result in an increase in some metal levels in the human body beyond acceptable limits. Such findings call for instant mandatory regular testing programs to check metals’ concentration in cosmetic products that are imported to Egypt, Saudi Arabia and other parts of the Arabian markets in order to limit their plethora and hence protect the consumers’ health. Further efforts are needed to enlighten the users and the general public on the dangers of using unknown misbranded products that are pumped in large quantities to many markets in the Arab world.
REFERENCES
8. Brown VJ. Metals in lip products: a cause for concern? Environ Health Perspect. 2013; 121: 196.
10. US FDA. United State Food Drug and Cosmetic Act on Hazardous Chemicals in Cosmetics. 2011.
12. Adal A, Tarabar A. Heavy Metal Toxicity. 2013.
13. Darbre PD. Underarm cosmetics and breast cancer. J Appl Toxicol. 2003; 23: 89-95.
23. Health Canada, Consumer product safety. Draft guidance on heavy metal impurities in cosmetics. 2011