| Abstract|| |
Background: Nowadays, eye shadows have become common cosmetics used by consumers. Previous studies proved that some of the eye shadows used had excessive levels of heavy metals. Objectives: The aims of this study are to (i) quantify the heavy metals concentration of lead and chromium in the eye shadows based on the color categories and types of eye shadows and (ii) assess potential non-carcinogenic health risk due exposure to heavy metals concentrations in eye shadows by using Hazard Quotient (HQ). Methodology: A conventional method using oven heating was applied to extract heavy metals from the samples. The analysis of heavy metals in the samples was performed using the Graphite Furnace Atomic Absorption Spectrophotometer (GF-AAS). The chronic non-carcinogenic health effect was evaluated quantitatively using HQ. Results: Both lead and chromium concentrations were found to be the highest in blue color category with the mean concentration of 161.8 ± 101.6 µg kg−1 and 149.4 ± 53.1 µg kg−1, respectively. The chromium levels were higher in the shimmering shade compared to the matte shade. The lead concentrations in all the samples analyzed were below the standard set by Health Canada (10 mg kg−1) and United States Food and Drug Administration (20 mg kg−1). The HQ values for chromium in all samples were less than 1. Conclusion: Lead concentrations were present within the permitted levels stated by the international standards in cosmetics intended for external use. The HQ values for chromium were less than 1 in all samples, indicating there was no significant chronic non-carcinogenic health risk to eye shadow users.
Keywords: Eye shadows, Graphite Furnace Atomic Absorption Spectrophotometer (GF-AAS), health risk assessment, heavy metals
|How to cite this article:|
Lim JS, Ho YB, Hamsan H. Heavy metals contamination in eye shadows sold in Malaysia and user's potential health risks. Ann Trop Med Public Health 2017;10:56-64
|How to cite this URL:|
Lim JS, Ho YB, Hamsan H. Heavy metals contamination in eye shadows sold in Malaysia and user's potential health risks. Ann Trop Med Public Health [serial online] 2017 [cited 2019 Nov 14];10:56-64. Available from: http://www.atmph.org/text.asp?2017/10/1/56/205541
| Introduction|| |
The cosmetic industry is growing fast due to the high demand from the consumers especially female. Despite any age groups, it has become a trend that the consumers will apply cosmetics in their daily life. Nowadays, eye shadows have become one of the common cosmetics widely used by consumers. It was found that eye shadows actually existed 12 thousand years ago, where Ancient Egyptians applied kohl as an eye shadow and liner. Eye shadows sold in the local markets are available in various forms, such as pressed powders, anhydrous creams, emulsions, sticks, and pencils. The most common form of eye cosmetics used by consumers is powdered eye shadows. In addition, eye shadows also come with various colors to meet the different purposes of the consumers. Basically, it can be divided into two types: the matte colors and the shimmery colors.
It has been reported that heavy metals are found as inorganic pigments in some of the cosmetic products including eye shadows. Heavy metals such as cadmium, cobalt, chromium, nickel, and lead are retained as impurities in the pigments of eye shadows. There is also possibility that they are released by the metallic devices used during the manufacturing of the products. A study reported by Ziarati et al. stated that the brown and golden colors in all brands of eye shadow samples assessed have the highest concentrations of lead, whereas blue and green colors have the lowest lead content. Other than lead, the study also found that golden and blue color eye shadow samples have the highest and lowest concentration of cadmium, respectively. According to Mansor and Yaacob, some women have to apply eye shadows for prolong period due to the nature of their career, for instance, stewardess, artists, and cosmetic promoters, in order to enhance their appearance and look attractive all the time. They might have to reapply the eye shadow few times a day as the color fades away. Heavy metals in the eye shadows are of great concern as they are applied directly to the skin and may cause health effects to the users. Although the skin provides protective barrier, the use of cosmetics may expose human to the heavy metals through penetration into the skin and produce systemic effects. The sweat can promote the absorption of these heavy metal compounds into the skin. Considering the prolonged contact time of cosmetic products with the skin, the risk of allergic dermatitis contact might be increased.
In Malaysia, there was no study performed on the heavy metal concentration in local and imported brands of eye shadows available in cosmetic shops. Besides, there was a lack of study on the safety from the prolonged use of eye shadows and its subsequent health effect on the consumers. Thus, there was a need to conduct a study on the heavy metals in eye shadows and its association with human health due to a prolonged period of usage. Hence, the aims of this study were to: (i) quantify the heavy metals (lead and chromium) concentration in the eye shadows based on the color categories (pinks, blues, greens, browns, and grays) and types of eye shadows (shimmering and matte) and (ii) assess potential non-carcinogenic health risk due exposure to heavy metals concentrations in eye shadow by using hazard quotient (HQ) as proposed by United States Environmental Protection Agency (2005).
| Materials and Methods|| |
The colors of the eye shadows sample were divided into five categories: pinks, blues, greens, browns, and grays. For each color category, eight popular local and imported brands of eye shadows used by consumers were conveniently picked and purchased at the local drugstores (Watsons and Guardian) and markets (low-cost shops, cosmetic shops, and street vendors). Hence, it made up to a total of 40 eye shadow samples. Samples were stored at room temperature until analysis.
The method by Al-Saleh et al. was applied for the digestion of sample. 0.2 g of the eye shadow samples was weighted using four decimal electronic balance. It was then placed into a 100 mL Pyrex glass beaker where 4 mL concentrated HNO3was added. It was left at room temperature for 4 h before placing in the oven overnight at 85°C. After digestion, the sample was taken out and allowed to cool at room temperature. In addition, 1 mL of 30% H2O2 was added to oxidize completely the organic matter of residues, the sample was heated for another hour at 85 °C. Then, the clear supernatant was filtered with the Whatman filter paper No. 1 (Sigma Aldrich, Germany) into a 10 mL volumetric flask. Ultrapure water was added to dilute the sample to a volume of 10 mL before transferring to polypropylene tubes. Sample blanks were prepared using the same procedure. The blanks and the digested samples were stored in the refrigerator at 4 °C until analysis. Metal contents were expressed as microgram per kilogram (µg kg−1).
Analysis of heavy metals, lead and chromium, in eye shadow samples was performed using the Perkin-Elmer AAnalyst 600 Graphic Furnace Atomic Absorption Spectrophotometer (GF-AAS), equipped with transversely heated graphite atomizer (THGA), AS 800 autosampler and hollow cathode lamp for different metals. The GF-AAS was controlled through the Winlab 32 Software Version 6.5. The graphs of absorbance against concentration were plotted in order to calculate the heavy metal concentration found in the samples. The concentrations of heavy metals found in the samples extract were computed using the following equation:
Concentration in solid sample
where Cex is the concentration of the compound in the extract (µg mL−1), Vex is the extract volume (mL), Ws is the sample weight (kg), and DF is the dilution factor.
Quality control (QC)
All the apparatus and glass wares were soaked in acid bath, thoroughly cleaned with detergent, rinsed abundantly with ultrapure water and air dried to prevent any contamination of the samples. Blank extraction was included for every batch of sample extraction to obtain an accurate measurement of heavy metals. The calibration standards were prepared in a concentration range of 1– 6 µg L−1 for lead and 0.8–4 µg L−1 for chromium. Calibration curve was constructed for each metal by plotting the graph of the concentrations of heavy metals lead and chromium against the absorbance of the standard solutions. The range of linearity was determined by referring to the linear regression coefficient (R2) of the calibration curve.
The standard reference material (SRM) is required to determine the percentage of extraction recovery, and it must be free from any contaminant. However, due to the unavailability of the certified SRM for heavy-metal-free eye shadow, the sample matrix was used. The extraction recovery was conducted in order to validate the analytical procedure, and this was done by spiking the samples with known amount of standard solutions of each metal. The percentage of recovery was calculated by comparing the concentration of each heavy metal spiked before sample digestion (Cp) to its concentration spiked after sample digestion (Ca) in the same sample matrix using Eq. 2, where Cqc is the concentration of analyte in the blank sample:
Health risk assessment
The non-carcinogenic chronic health risk due to exposure to heavy metals in eye shadows was evaluated quantitatively using Hazard Quotient (HQ). HQ is the ratio of Average Daily Dose (ADD) to the Reference Dose (RfD) (see Eq. 3):
ADD for dermal exposure was calculated using the following equation:
where C is the contaminant concentration (mg kg−1), SA is the surface area (24 cm2), AF is the adherence factor (6.9 mg cm2−1event−1), ABS is the absorption factor (0.001), ED is the exposure duration (30 years), EF is the exposure frequency (730 events year−1), BW is the body weight (60 kg), and AT is the average time (10 950 days).
The recommended value for the dermal adherence factor and absorption factor of skin whiteners in the study of Murphy et al. was used in estimating the ADD of exposure to heavy metals in eye shadows. The recommended value for the surface area of eyes was adapted from the study from Bremmer. There was no RfDs or slope factors available for the dermal route of exposure; however, United States Environmental Protection Agency stated that non-carcinogenic or carcinogenic risks associated with dermal exposure can be evaluated using an oral RfD oral slope factor, respectively. The RfD for chromium is 0.003 mg kg−1 day−1,  whereas the RfD for lead is not available from Integrated Risk Information System (IRIS) United States Environmental Protection Agency.
The data were analyzed using the software Statistical Package for the Social Sciences (SPSS) for Windows, version 20. Descriptive statistics was used to determine mean, standard deviation, minimum, and maximum values of heavy metal concentration in selected eye shadows purchased from local drugstores or market.
One way analysis of variance (ANOVA) was used to compare the differences of heavy metal mean concentration among the five color categories (pinks, blues, greens, browns, and grays) of eye shadows at a significant level of P < 0.05.
Independent sample t-test was conducted to compare the differences of heavy metal mean concentration among types of eye shadows, which are shimmering shade and matte shade at a significant level of P < 0.05.
| Results|| |
Determination of linearity, range of the calibration curve, and percent recovery
Calibration curves were obtained for lead and chromium to determine the concentration of heavy metals in the eye shadows analyzed. [Table 1] shows the percentage of recovery, linearity, and regression coefficient (R2) obtained for lead and chromium.
Heavy metal content in eye shadow samples
[Table 2] illustrates the levels of heavy metals analyzed in the eye shadow samples. As given in table, lead was found in all the analyzed samples. The lead concentrations found in this study varied through a wide range of values, ranging from 14.2 to 284.9 µg kg−1. The highest lead concentration was found in sample B5 (284.4 ± 6.2 µg kg−1) with shimmering light blue color and the lowest concentration in sample Br6 (14.2 ± 0.1 µg kg−1), which was dark brown in color.
|Table 2: Concentration of lead and chromium in eye shadow samples (n = 40) and non-carcinogenic health risk based on hazard quotient (HQ) for the exposure to chromium concentration in eye shadow samples|
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On the other hand, chromium was not detected in samples G4 and G5 that were having color of shimmering dark green and light green, respectively.
The chromium concentrations found in the samples were ranged from 1.2 to 197.2 µg kg−1. Sample B1 (shimmering dark blue) was found to have the highest concentration of chromium, which was 197.2 ± 0.4 µg kg−1. On the other hand, the lowest chromium concentration was detected in sample Gy6 (1.2 ± 0.2 µg kg−1), which was light gray in color.
Health risk of heavy metals in the eye shadow samples
The non-carcinogenic health risk due to the exposure to heavy metals lead and chromium was estimated using HQ. The HQ for chromium concentration is shown in [Table 2]. As shown in the table, the HQ values for chromium in all eye shadow samples analyzed were less than 1, indicating there was no non-carcinogenic health risk expected as a result of dermal exposure to chromium.
| Discussion|| |
Determination of linearity, range of the calibration curve, and percent recovery
A five-point calibration curves were obtained for lead and chromium with the concentration range from 1 to 6 µg L−1 and 0.8 to 4 µg L−1, respectively. Both curves showed good linearity with R2 of more than 0.999. A calibration curve with R2 more than 0.995 is usually considered to be linear. The percentage of recovery obtained for lead was 80%, whereas chromium had a recovery value of 93% [Table 1].
Heavy metal content in eye shadow samples
Previous studies found a measurable level of heavy metals in facial cosmetics such as mascara, eye shadows, lipsticks, eye liners, foundation, and cream, as well as nail polish.,,,,, Based on the descriptive analysis, the mean lead concentration in the 40 eye shadow samples analyzed was 113.3 ± 74.0 µg kg−1. The maximum and minimum lead concentrations were 284.4 and 14.2 µg kg−1, respectively. The median of lead concentration obtained indicates that at least 50% of the eye shadow samples had a concentration of more than 91.9 µg kg−1. As for chromium, the mean concentration in the eye shadow samples was 120.4 ± 77.3 µg kg−1. The maximum chromium concentration was 197.2 µg kg−1, whereas the lowest concentration was 1.2 µg kg−1. From the statistical analysis, the median of chromium concentration indicates that at least 50% of the eye shadow samples had a concentration of more than 142.8 µg kg−1.
The concentrations of heavy metals in the eye shadow samples of different brands are summarized in [Table 2]. The concentration of lead found in the eye shadow samples was ranged from 14.2 to 284.9 µg kg−1. The finding by Al-Saleh et al. reported that eye shadows imported from China, France, and USA analyzed had lead concentrations of 420 to 58 700 µg kg−1. Besides, Volpe et al. reported lead concentrations of 250 to 81 500 µg kg−1 in the Chinese eye shadow samples, which were higher than the findings from this study. As for chromium, the concentration found in this study was ranged as low as 1.2–197.2 µg kg−1. About 58% of the samples analyzed had chromium concentration of more than 100 µg kg−1. Similar results have been obtained in previous study by Volpe et al., which reported that the range of chromium concentrations found in the eye shadow samples was from 15.0 to 287.0 µg kg−1. The results obtained were comparable to that obtained in this study. Besides, the chromium concentrations reported by Omolaoye et al. in all seven brands of the eye shadows imported from China were far higher than the values obtained in this study and exceeded the standards (ranging from 16 700 to 150 000 µg kg−1). The high levels of lead and chromium found in the eye shadow samples could be due to the contamination from the metallic machines used during the manufacturing processes. There is also possibility that these metals are being retained as impurities in the pigments added to the eye shadows.
Concentration of heavy metals among the five color categories of eye shadows
An ANOVA was conducted to compare the mean difference in lead and chromium concentrations and the color category of the eye shadow samples. In [Table 3], the mean lead concentration for pink category was122.4 ± 54.2 µg kg−1, blue category was 161.8 ± 101.6 µg kg−1, green category was 118.9 ± 58.7 µg kg−1, brown category was 94.2 ± 88.0 µg kg−1, and gray category was 69.1 ± 24.8 µg kg−1. The mean chromium concentration for pink category was 121.4 ± 65.0 µg kg−1, blue category was149.4 ± 53.1 µg kg−1, green category was 115.5 ± 90.9 µg kg−1, brown category was 91.2 ± 91.6 µg kg−1, and gray category was 124.8 ± 87.2 µg kg−1. From the result, for both lead and chromium, blue color eye shadow showed the highest concentration of heavy metals content.
|Table 3: Results from the non-parametric Kruskal–Wallis test between lead and chromium concentration (µg kg−1) and the five color categories of the eye shadows|
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The non-parametric Kruskal-Wallis test was conducted to evaluate the differences in lead and chromium concentrations among the color category by estimating differences in ranks among them. The P-value from the non-parametric Kruskal-Wallis test for both lead and chromium was more than 0.05, indicating that there was no significant difference in lead and chromium concentrations between color categories of the eye shadows.
Both lead and chromium concentrations were found to be the highest in blue color category of the eye shadows with mean concentration of 161.8 ± 101.6 and 149.4 ± 53.1 µg kg−1, respectively. Besides, gray color eye shadows were found to have the lowest lead concentration (69.1 ± 24.8 µg kg−1). This finding was in contrast with the study by Ziarati et al. that stated that blue color eye shadows had the lowest lead mean concentration (10 500 µg kg−1) among the seven color groups. In addition, the lowest concentration of chromium was detected in brown color, which was 91.2 ± 91.6 µg kg−1 compared to other color categories. Previous study by Volpe et al. also detected a low chromium concentration (21.7 ± 2.8 µg kg−1) in brown color eye shadows of all brands.
Chromium oxide greens are commonly found as one of the ingredients in the labeling of the eye shadows. They are mineral pigments that are added to the eye shadows as coloring agents. This color additive is permitted for use in eye cosmetics, which are intended for external application in the eye area and in an amount consistent with good manufacturing practice. The detection of heavy metals in the samples might be due to the color additive added to the eye shadows. It also could be due to the unavoidable condition in which the eye shadows were contaminated with heavy metals during the manufacturing process when in contact with the manufacturing tools.
Concentration of heavy metals in types of eye shadows
Independent sample t-test was conducted to test the mean difference between the shimmering shade and the matte shade. As shown in [Table 4], the P-value of the test for lead is 0.065, which is more than 0.05. Hence, there was no significant difference in lead concentration between the shimmering shade and matte shade. Based on the result for chromium, the P-value for the independent sample t-test was 0.007, which was less than 0.05. Thus, there was a significant difference in mean chromium concentration between shimmering shade and matte shade eye shadow samples. The chromium level among the shimmering shade types of eye shadows was higher than that of matte shade eye shadows. The mean chromium concentration in the shimmering shade was 152.8 ± 68.8 µg kg−1, whereas the mean concentration in the matte shade was 88.2 ± 73.1 µg kg−1. There was no previous study that reported the higher concentration of heavy metals in the shimmering shade in comparison to matte shade. However, the finding from this study demonstrated that shimmering types of eye shadows contained higher level of heavy metals. The ingredient used to produce shimmery effect of the eye shadows may contribute to a higher concentration of heavy metals. According to Al-Saleh et al., the shiny and metallic shimmering effects of the lipsticks might be due to the presence of mica as one of the ingredients that is used in the manufacturing process. Mica is a naturally occurring group of silicate minerals that may contain trace amount of heavy metals.
|Table 4: Results from independent sample t-test between lead and chromium concentration (µg kg−1) and the types of eye shadows|
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Under Annex II Part 1 of the Guidelines for Control of Cosmetic Products in Malaysia, lead and its compound and chromium should not be present as one of the ingredients in the cosmetic products provided that such presence is technically unavoidable in good manufacturing practice. There were no current international standards for impurities such as heavy metals in cosmetics except 10 mg kg−1 for lead by Health Canada and maximum specified lead levels of not more than 20 mg kg−1 as impurities in color additive by US Food and Drug Administration., The findings from this study showed that the lead concentrations in all the eye shadow samples analyzed were below the standards.
Health risk of heavy metals in the eye shadow samples
Most of the previous studies focused solely on the assessment of heavy metals and found detectable levels of the metals in various brands of eye shadows. Little research is available to determine the safety or health risks of low-dose repeated exposures to cosmetics.
Based on the study of heavy metals contamination in lipsticks by Zakaria and Ho (2015), the concentrations of lead, cadmium, and chromium in lipsticks were ranged from 0.77 to 15.44 mg kg−1, 0.06 to 0.33 mg kg−1 and 0.48 to 2.50 mg kg−1, respectively, and the health risk was estimated using HQ where the HQ for cadmium and chromium in all lipsticks were below 1. To the best of the author's knowledge, no health risk assessment has been studied before for the chronic exposure to heavy metals in eye shadows. In this study, the health risks posed by the presence of heavy metals in the eye shadows were assessed for the first time. To date, few studies have been conducted on the health risk associated with exposure to heavy metals in fish samples,, particulate matter samples,, soil samples,, vegetable samples, and water samples.
Chronic exposures to heavy metals in cosmetics involve frequent doses at relatively low levels over a period of time ranging from months to years. The health risk estimated in this study was made for the worst-case scenario assuming the application of eye shadows for 30 years. The non-carcinogenic health risk due to dermal exposure tochromium was estimated using HQ. However, the HQ for exposure to lead in eye shadows was excluded in this study due to the unavailability of reference dose (RfD) from IRIS US EPA as the degree of uncertainty about the health effects of lead was still low. The HQ value obtained for chromium was less than 1 in all the eye shadow samples analyzed, indicating that there was no chronic non-carcinogenic health risk expected due to dermal exposure to chromium in eye shadows.
The inorganic lead compounds and chromium (IV) compounds have been classified as carcinogenic to human health by IARC. However, considering the unavailability of the cancer slope factors for the metals in the database, the carcinogenic health risks due to exposure to the metals were not assessed. The main route of entry of heavy metals into human body is through inhalation and ingestion. However, the absorption of the metals via dermal contact due to prolong exposure should not be ignored. The cumulative property of the heavy metals can cause chronic damage to the nervous system and organs. Although the heavy metals are present in a trace amount in the cosmetics, the slow releasing rate of the metals may harm the human health if they accumulate in the body over time. Heavy metals have long half-life, which indicates that it may take a longer period to excrete the heavy metals from the body.
Inorganic lead was demonstrated to be permeable to the skin with a median penetration of 2.9 ng cm-1 and substantially increase the blood lead concentration after a prolonged period of exposure. The use of leaded eye powder such as surma and kohl was found to be associated with elevated blood lead levels in children and women. Long-term exposure to lead can affect the normal function of organs such as kidney and liver and ultimately cause severe damage. Under conditions of continual exposure to lead, some of its compounds are not eliminated from the body and may accumulate in body tissues, especially bone. Exposure to the relatively low level of lead can cause irreversible effect to the nervous system. Children are more susceptible to the adverse effect of lead in which their intellectual abilities, cognitive function, visual motor, and psychomotor development are impaired.
Study by Filon et al. revealed that chromium is able to permeate through intact human skin, and its concentration was found to be significantly higher in the damaged skin compared to that in the intact skin. Chromium can be easily absorbed by the skin probably due to its strong binding capacity to the skin proteins. Sweat increases the absorption rate of chromium into the skin and cause sensitizing effects. Contact allergies are also observed in sensitive individuals via dermal contact with the chromium compound.
| Conclusions|| |
Concentrations of lead and chromium were found in a wide range in all the eye shadow samples analyzed except in samples G4 and G5, in which chromium was not detected. Lead concentrations in all the samples were within the permitted levels stated by the international standards in cosmetics intended for external use. The findings from the study showed that there was no significant difference between the lead and chromium levels in different color categories of eye shadows. Both mean lead and chromium concentrations were found to be the highest in the blue color category, whereas lowest lead and chromium concentrations were found in gray and brown colors, respectively. There was no significant difference between the lead concentrations in the types of eye shadows. However, there was a significant difference between the chromium concentration levels in the types of eye shadows, in which the chromium levels were higher in the shimmering shades compared to the matte shades. The HQ values for chromium were below 1 for all samples, indicating that there was no significant chronic non-carcinogenic health risk expected due to dermal exposure to chromium for eye shadow users.
This study was financially supported by Universiti Putra Malaysia Grant (project number 9423900). We would like to thank Laboratory of Environmental Health, Department of Environmental and Occupational Health for the use of GF-AAS.
No ethical approval is required for this study.
Financial support and sponsorship
This study was financially supported by Universiti Putra Malaysia Grant (project number 9423900).
Conflicts of interest
There are no conflicts of interest.
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Yu Bin Ho
Department of Environmental and Occupational Health, Faculty of Medicine and Health Sciences, Universiti Putra Malaysia, UPM Serdang, Selangor
Source of Support: None, Conflict of Interest: None
[Table 1], [Table 2], [Table 3], [Table 4]