1 Introduction
For people all over the world, beauty makeup forms an important part of their daily lives. Cosmetics; It consists of substances or mixtures of substances used to clean, heal or change the skin, hair, lips, nails and teeth (EC 1976). Cosmetic and personal care products are preferred all over the world to improve skin quality and appearance. Intentional use of toxic elements in cosmetics is prohibited, but these may be foreign matter in the raw materials or by-product residue during the production step (EWG 2007; Nohynek et al. 2010).
In ancient civilizations, such as Egypt, Greece and the Roman Empire, women would apply reddish mineral or plant pigments to their cheeks and lips for beautification purposes. There has been a huge increase in cosmetic products in the last few decades (Al-Dayel et al. 2011). Women's exposure to organic and inorganic pollutants in cosmetic products due to their personal habits and environment may pose carcinogenic and non-carcinogenic risks after daily exposure through ingestion and dermal absorption. Besides the demand of cosmetics in the markets, exposure to toxic elements is alluring the attention of investigator to search their distribution and adverse effects (Liu et al. 2013; Gardner et al. 2013; Atz and Pozebon 2009; Piccinini et al. 2013; Loretz et al. 2005; Becker 2011). The sources and toxic effects of various contaminants in cosmetic products have been discussed previously (Foster Mesko et al. 2020). Color cosmetics are particularly interesting for women and girl children. Eye shadow, lipstick and nail polish are a group of cosmetic products that have been most commonly used in various parts of the world (Farrag et al. 2015).
Anzeige
While there are such thoughts for cosmetic products, very little information is available about toy make-up products. Widely available commercially, these products are applied to the thin skin of children's faces and are often used for a long time. Toy cosmetics for children are usually available in the market in the form of kits and boxes containing different toy makeup products such as eye shadow, lipstick, lip gloss, nail polish. The kit is a toy and each item in the kit is a cosmetic item.
Qualified cosmetics do not affect the health of users. Despite this, some risks still exist for low-quality cosmetics that can affect the health of users, manufacturers and distributors. Most cosmetic companies can market their products by targeting health-conscious consumers with trending phrases such as vegan, naturally sourced, environmentally friendly and products not tested on animals (Maamoun 2022). Therefore, product choices are very important for health (Corazza et al. 2009; Liu et al. 2020). Many studies have found that cosmetic products contain high concentrations of heavy metals (Al-Saleh et al. 1999; Nourmoradi et al. 2013; Gao et al. 2015). Because toxic metals in cosmetics can be ingested or absorbed through the skin, they can accumulate in the body over time and give rise to adverse effects even at low levels (Bellinger 2008). Pb, Hg, and As are considered the toxic elements of most concern. Pb can affect all systems in the body, including reproductive, neurological and hepatic systems (Meyer et al. 2008; Al-Ashban et al. 2004). Prolonged exposure to low levels in children damages the brain and nervous system. Exposure to inorganic Hg can cause encephalopathy and interstitial kidney diseases (Soo et al. 2003). As awareness about the safety of cosmetic products increases, tests have begun to be carried out to determine the toxic element contents of commercially sold cosmetic products. (Al-Saleh and Al-Enazi 2011; Ng et al. 2015).
For example, the widespread use of lip cosmetics in daily life causes the introduction of non-dietary metals into the body to become widespread. Metals from lip cosmetics are sent to the stomach and intestinal fluids after ingestion (Loretz et al. 2005; Reiner and Kannan 2006). Ultimately, information on the bioabsorbability of metals in lip cosmetics and the magnitude of exposure in China is limited (Hepp et al. 2009).
Analytical techniques based on atomic spectrometric and chromatographic analyzes are an important factor in the quantitative determination of toxic elements in cosmetic products. Investigation of heavy metal concentrations is critical in cosmetic production. A number of traditional analytical techniques have been performed to the determination of heavy metals in cosmetics production, containing atomic absorption spectroscopy (AAS) (Corazza et al. 2009), graphite furnace atomic absorption spectroscopy (GF-AAS), flame atomic absorption spectrophotometry (FAAS), inductively coupled plasma mass spectrometry (ICP-MS) (De la Calle et al. 2017; Guerranti et al. 2023), inductively coupled plasma optical emission spectrometry (ICP-OES) (Batista et al. 2016; Kilic et al. 2021) is available. However, some disadvantages of cosmetic analysis still need to be overcome in order to reach new aims in analytical chemistry such as higher sample yield, lower reagent consumption and lower residue production (Flores et al. 2014). Other techniques have also been used to identify toxic or potentially toxic elements in cosmetics applied to the lip and eye area. Systems that provide direct analysis are used as an alternative to the determination of metals, metalloids and nonmetals in cosmetics. Energy dispersive X-ray fluorescence (EDXRF) (Sogut et al. 2016), neutron activation analysis (NAA) (El-Shazly et al. 2004), laser-induced breakdown spectroscopy (LIBS) (Gondal et al. 2010) were used.
Anzeige
In this study, trace element analyzes of pink, blue, green, yellow, orange, purple, brown colored eye shadow, pink and red lipstick and nail polish samples of different colors in 3 different brands of children's cosmetics were performed using ICP-MS after microwave digestion.
2 Experimental
2.1 Instrumentation
Inductively coupled plasma mass spectrometer (ICP-MS, Agilent 7900), contains an autosampler, Babington nebulizer, Ni cones and a peristaltic sample delivery pump, was used for the detection of elements. High purity ICP-MS multi element standard solution obtained from Merck was used for the preparation of calibration curves in the quantitative analysis of the elements. Double distilled water (18.2 MΩ cm−1) was used in all solutions. Internal solution containing 145Sc, 103Rh and 209Bi with a concentration of 200 µg L−1 was used to correct for changes in sampling rate and plasma conditions for ICP-MS analysis.
High purity argon gas (99.99%) was employed to form the plasma in the ICP-MS. The pulse/analog detector factor adjustment was made daily before analyses and ICP-MS tuning solution of 10 μg L−1 (Ce, Co, Li, Tl, and Y) was used for the tuning setting of the instrument before each experiment. The ICP-MS operating conditions for analyses of the analytes are shown in Table 1.
Table 1
Optimal ICP-MS operating conditions for analysis of samples
Parameter | Value |
|---|---|
Radio frequency power | 1550 W |
Radio frequency Matching | 1.80 V |
Sample depth | 8.0 mm |
Torch-H | − 0.3 mm |
Torch-V | 0.8 mm |
Carrier gas | 1.20 L/min |
Nebulizer gas | 1 L/min |
Auxiliary gas flow rate | 0.9 L/min |
Plasma gas flow rate | 15 L/min |
Nebulizer pump | 0.10 rps |
Spray chamber temperature | 2 °C |
2.2 Reagents and standards
All reagents were used in analytical purity. The high-quality distilled water was acquired Millipore, Milli-Q system. HCl (37% w/w) and HNO3 (65% w/w) (Merck) were also used for digestion and diluting the samples. The standard stock solutions including 1000 µg L−1 of multi-element calibration standard were supplied from the Merck (Darmstadt, Germany). Stock solution and standard solutions were diluted in HNO3. A calibration curve was prepared containing the elements aluminum, chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, selenium, mercury, cadmium and lead in the range of 0–50 µg L−1. Standard reference material NCS ZC 81002b Human Hair was analyzed for metallic elements utilizing the same procedure to check the effectiveness of the digestion and analytical procedure. The results are shown in Table 2.
Table 2
Analysis of certified reference material NCS ZC 81002b Human Hair
Element | Concentration (μg g−1) | Recovery (%) | |
|---|---|---|---|
Certified | Found | ||
Al | 23.2 ± 2.0 | 22.2 ± 0.3 | 96 |
Cr | 8.7 ± 0.9 | 9.0 ± 0.05 | 103 |
Mn | 3.8 ± 0.4 | 3.7 ± 0.3 | 97 |
Fe | 160 ± 16 | 163 ± 3 | 102 |
Co | 0.15 ± 0.01 | 0.148 ± 0.001 | 99 |
Ni | 5.7 | 5.8 ± 0.1 | 101 |
Cu | 33.6 ± 2.3 | 33.4 ± 0.3 | 99 |
Zn | 191 ± 16 | 190 ± 2 | 99 |
As | 0.19 ± 0.02 | 0.20 ± 0.01 | 105 |
Se | 0.59 ± 0.04 | 0.58 ± 0.01 | 98 |
Cd | 0.07 ± 0.01 | 0.075 ± 0.002 | 107 |
Hg | 1.06 ± 0.28 | 1.00 ± 0.01 | 94 |
Pb | 3.83 ± 0.18 | 3.85 ± 0.05 | 101 |
2.3 Method calibration parameters
The limit of detection (LOD) and limit of quantification (LOQ) for the determination of the analytes in eye shadow, lipstick and nail polish samples were determined as 3 times and 10 times the standard deviation (s) of 10 repetitive analyses of the blank, i.e., 3 s/slope of calibration graphs and 10 s/slope of calibration graphs (Flores et al. 2014). LOD and LOQ (μg L−1) values for elements are shown in Table 3.
Table 3
Instrumental detection (LOD) and quantification limits (LOQ) (mg L−1), N = 3
LOD (μg L−1) | LOQ (μg L−1) | |
|---|---|---|
Al | 0.03 | 0.12 |
Cr | 0.02 | 0.08 |
Mn | 0.05 | 0.22 |
Fe | 0.12 | 0.45 |
Co | 0.002 | 0.009 |
Ni | 0.01 | 0.05 |
Cu | 0.1 | 0.5 |
Zn | 0.03 | 0.10 |
As | 0.01 | 0.03 |
Se | 0.001 | 0.004 |
Cd | 0.001 | 0.005 |
Hg | 0.002 | 0.007 |
Pb | 0.04 | 0.16 |
2.4 Sample collection
In this study, the most frequently used products in children's cosmetics were collected for analysis. Eye shadow, lipstick and nail polish samples sold in Turkey as children's cosmetics in 3 different brands toy make-up kits, numbered 1–3, including pink, blue, green, yellow, orange, purple, brown eye shadow, pink and red lipstick and nail polish samples, were provided.
2.5 Digestion of the samples
The sample preparation step is the most critical part in analytical studies and should be studied carefully to minimize errors. Digestion methods using conventional or microwave-heated concentrated acids are widely recommended for sample preparation. A mixture of HNO3 and HF is still used in some studies and the use of hydrofluoric acid is avoided during sample preparation due to its high toxicity and damage to sample introduction systems (e.g. ICP-MS analysis) (Foster et al. 2020; Mesko et al. 2017).
Cosmetics have a dense matrix for metal analysis because they consist of various components such as oil, dye and pigments. Pigments may also contain refractory minerals such as alumina, silica, titanium dioxide and mica. In the studies, pre-treatments such as dissolution or calcination were performed using the cosmetic matrix, concentrated acids (i.e. HNO3, H2SO4 and HF) and high temperatures and pressures. Although hot plate mineralization has been used in some studies, digestion of samples has repeatedly been accomplished by microwave digestion (Bocca et al. 2014). In this study, microwave digestion technique was applied.
All samples were digested using the cosmetic method with the ETHOS Easy™ Microwave digestion system (Milestone Advanced Digestion Inc., USA). For determination of total element concentration in cosmetic samples microwave (MW) digestion method was used because it is short, fast and the most recently developed dissolution method, for sample digestion. 0.20 g of the samples were weighed in 3 parallel to 100 ml PTFE containers. Samples were dissolved by adding an acid mixture of HNO3 (65%)/H2O2 (35%) (9:1). After crushing, PTFE vessels were cooled to room temperature. Digested children's cosmetic samples were filtered using Whatman 40 filter paper to remove undissolved particles. After cooling, the extracted samples were transferred to a 25 mL flask and diluted with distilled water before they were analyzed with ICP-MS. Blank solutions were prepared in the same way. The microwave program for samples was operated under microwave conditions with a power of 1800 W for 20 min at a temperature of 210˚C. Second step was applied as 1800 W for 15 min at a temperature of 210˚C (Milestone App.).
3 Results and discussion
Cosmetics is a term that contains more than makeup. These "personal care products", as defined by the National Poison Data System (NPDS), include products as diverse as perfumes, nail polishes, moisturizers, and eye shadows and share a common purpose: they cleanse, beautify, stimulate attractiveness, or alter appearance. Cosmetics contains substances and mixtures used to clean, heal or change the skin, hair, lips, nails or teeth. (Foster et al. 2020; EC 1976).
According to the definition recommended by the European Council Directive 76/768/EEC, products such as skin care cream, lotion, sprays, perfumes, lipsticks, nail polishes, eye and face make-up, toothpaste and sunscreen are used for men and women. It contains many products used by men. Although a cosmetic product is not harmful when used as directed by an adult, accidental exposure to a child may cause injury or death. The Environmental Protection Agency has now stated that blood lead levels of just 10 μg dL−1 can cause decreased intelligence, hearing impairment, decreased attention span, hyperactivity, antisocial behavior and other harmful effects.
Cosmetic products consist of different organic and inorganic substances, including hydrophilic and hydrophobic substances. In the production of colored cosmetics, mineral pigments that cause contamination with heavy metals such as cobalt, nickel, copper, lead and other elements are widely used. The addition of additives and color minerals, as the type of raw material used in production, causes contamination. Additionally, the water used for their preparation may also contain metallic impurities. In addition, the use of different instrumentation in the sorting, production and packaging processes in the cosmetics industries can also cause metal contamination (Ahmed et al. 2017; Łodyga-Chruścińska et al. 2018).
Trace amounts of some toxic metals (Cadmium and lead), It has been detected in many products, including face make up products and lipsticks (Eltegani et al. 2013). It has also been concluded that cosmetics with natural ingredients, such as plant-based products, are the main source of heavy metal pollution (Bocca et al. 2014). Measurement of the levels of toxic metals in plants used as raw materials and in final products has been recommended by International Organizations. According to reports, toxic metals may be present in plants due to previous use of fertilizers, pesticides or their cultivation near industrial areas.
This is why lip cosmetics may have existed for more than thousands of years (Brown 2013). Lip cosmetics are one of the non-dietary exposure sources for metals. Lipstick products sold on the market in different colors as children's cosmetics can pose a health risk due to the toxic elements in their content. The toxic element contents of cosmetics, especially the Pb distribution in lipstick, are noteworthy. Each type of lipstick has different properties in terms of its content of various waxes, oils, polishes, antioxidants, softeners, dye pigments and fillers such as mica, silica, fish scale, titanium dioxide, which give different colors, properties and appearance. The US Food and Drug Administration (FDA) detect that the lead content of a variety of 400 lipsticks ranged from < 0.026 ng mg−1 (limit of detection) to a high of 7.19 ng mg−1 (Gunduz and Akman 2013).
Metallic-based color containing lead is used as a dye in most cosmetics, including lipstick. (US FDA 2014; Al-Saleh et al. 2009). Pb is a neurotoxin known to be the cause of learning, language, and behavior problems such as low IQ, poor school performance, and increased aggression. Pb accumulates in the body over time, and lead-containing lipsticks applied several times a day can reach significant exposure levels when combined with lead from water and other sources. Pb is among the most destructive poisons for children (Divrikli et al. 2007; Haque et al. 2023; Rosner and Markowitz 2007).
According to a study, Pb poisoning is not just a problem for post-industrial urban children, analysis of the bones of samurai children who lived 400 years ago suggested that high Pb levels in children came from their mothers' makeup. Samurai children in Japan's Edo period faced serious Pb contamination. While mothers are breastfeeding their children, children may involuntarily swallow their mother's white lead. The study found evidence of serious Pb contamination among the children of samurai families living in a castle town during Japan's Edo period (1603–1867). Pb concentration values in their bones were found to be 14.3 μg g−1 in adult males, 1241.0 μg g−1 in children aged 3 and under, 462.5 μg g−1 in children aged 4–6 years, and 23.6 μg g−1 in females. The average Pb value in the bones of children aged 3 and under was fifty times higher than that of their mothers (Nakashima et al. 2011). There are many studies of lead found at measurable levels in many brands of lipstick, but few quantitative exposure analysis studies to assess potential Pb exposures and health risks associated with lipstick use. It has been assumed that exposure to lipstick products in children is usually due to accidental ingestion or use as a toy, but also from use and adults using lipstick through oral contact from mother to child (e.g. kisses) (Monnot et al. 2015).
Another cosmetic that attracts the attention of children with a different matrix is nail polishes produced in different colors. Various colored nail polishes of different brands were measured for the same elements and the results are shown in Tables 4 and 5. Colors alternated between pink and red. Again, most polishes contain small amounts of metal and can cause exposure if fingernails are bitten or chewed and the polish is swallowed (Grosser et al. 2011). The use of nail polish is quite common, the chemicals used, coloring pigments, acrylates can cause allergic reactions (Warshaw et al. 2020). Eye shadow is generally a cosmetic product that mostly contains pigment in its composition. Percutaneous absorption of elements occurring as impurities in pigments can occur in moist skin when some toxic elements are dissolved in water. The auxiliary substances in its composition are also effective in its absorption through the skin. When eye shadow is applied dry to the skin, the risk of percutaneous absorption of pigments and toxic elements is reduced. The skin of the eyelids is thin and eczema is more common on the eyelids. It is possible for elements to be absorbed into the circulation, but the absorption of elements is slower than that of fat-soluble substances (Guarneri et al. 2010).
Table 4
Determined element concentrations (µg g−1) for Brand-1 of child cosmetic samples (N = 3)
Brand | Al | Cr | Mn | Fe | Co | Ni | Cu | Zn | As | Se | Cd | Hg | Pb |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Brand 1 | |||||||||||||
Eye shadows | |||||||||||||
Green | 527.4 ± 2.8 | 4.1 ± 0.2 | 10.3 ± 0.9 | 27.2 ± 0.3 | 0.53 ± 0.008 | <0.001 | <0.005 | 4.1 ± 1.3 | 0.63 ± 0.04 | 0.21 ± 0.01 | 0.25 ± 0.04 | 0.65 ± 0.04 | 12.2 ± 1.4 |
Yellow | 761.8 ± 1.4 | 6.5 ± 0.3 | 3.5 ± 1.4 | 5.6 ± 3.8 | 0.30 ± 0.02 | 1.4 ± 0.6 | 4.3 ± 0.4 | 2.2 ± 0.9 | 0.82 ± 0.01 | 0.05 ± 0.03 | 0.008 ± 0.004 | 0.004 ± 0.001 | 0.20 ± 0.06 |
Orange | 822.8 ± 10.8 | 4.4 ± 0.3 | 13.2 ± 2.3 | 29.4 ± 0.5 | 0.49 ± 0.01 | <0.001 | <0.005 | 3.7 ± 1.0 | 0.7 ± 0.1 | 0.09 ± 0.04 | 0.18 ± 0.02 | 0.90 ± 0.04 | 9.9 ± 0.5 |
Purple | 802.1 ± 3.1 | 4.32 ± 0.01 | 11.9 ± 1.6 | 28.8 ± 6.3 | 0.53 ± 0.006 | <0.001 | <0.005 | 2.3 ± 0.5 | 0.84 ± 0.06 | 0.17 ± 0.05 | 0.21 ± 0.05 | 0.57 ± 0.06 | 0.5 ± 0.1 |
Silvery eye shadows | |||||||||||||
Pink | 122.9 ± 1.8 | 5.2 ± 0.6 | 0.260 ± 0.009 | 16.5 ± 0.04 | 0.020 ± 0.007 | 0.08 ± 0.01 | 0.03 ± 0.01 | 0.7 ± 0.1 | 0.02 ± 0.01 | 0.11 ± 0.04 | <0.001 | 0.16 ± 0.02 | 0.100 ± 0.001 |
Green | 86.1 ± 2.4 | 15.9 ± 0.8 | 0.23 ± 0.02 | 2.6 ± 1.2 | 0.02 ± 0.01 | 0.2 ± 0.1 | 1.4 ± 0.4 | 2.3 ± 0.7 | 0.020 ± 0.004 | 0.08 ± 0.01 | 0.08 ± 0.03 | 0.14 ± 0.03 | 0.14 ± 0.02 |
Yellow | 80.4 ± 2.9 | 2.7 ± 0.3 | 0.24 ± 0.02 | 13.5 ± 0.4 | 0.04 ± 0.01 | 0.9 ± 0.6 | 3.7 ± 1.7 | 4.1 ± 0.4 | 0.03 ± 0.01 | 0.09 ± 0.01 | 0.03 ± 0.01 | 0.12 ± 0.03 | 0.45 ± 0.05 |
Blue | 81.7 ± 0.9 | 2.6 ± 0.3 | 0.9 ± 0.5 | 25.2 ± 1.3 | 0.11 ± 0.02 | 0.4 ± 0.2 | 2.7 ± 0.2 | 0.08 ± 0.03 | <0.001 | 0.05 ± 0.003 | <0.001 | 0.10 ± 0.05 | 0.07 ± 0.02 |
Orange | 153.5 ± 1.0 | 51.8 ± 3.0 | 0.57 ± 0.02 | 12.1 ± 3.0 | 0.04 ± 0.01 | 0.28 ± 0.03 | <0.005 | 2.4 ± 0.6 | 0.05 ± 0.02 | 0.07 ± 0.01 | <0.001 | 0.11 ± 0.01 | 0.05 ± 0.04 |
Purple | 106.8 ± 0.9 | 16.5 ± 2.5 | 0.18 ± 0.06 | 14.2 ± 1.2 | 0.03 ± 0.01 | 0.3 ± 0.2 | 0.18 ± 0.02 | 1.31 ± 0.01 | 0.06 ± 0.02 | 0.07 ± 0.01 | 0.02 ± 0.001 | 0.110 ± 0.006 | 0.38 ± 0.1 |
Lipsticks | |||||||||||||
Red | 14.3 ± 0.4 | 4.15 ± 0.03 | 0.86 ± 0.02 | 26.2 ± 0.4 | 0.58 ± 0.05 | <0.001 | <0.005 | 1.51 ± 0.05 | 0.71 ± 0.01 | 0.13 ± 0.03 | 0.17 ± 0.01 | 0.50 ± 0.02 | 10.7 ± 0.9 |
Pink | 156.3 ± 0.8 | 7.0 ± 0.5 | 2.22 ± 0.08 | 67.8 ± 6.0 | 0.20 ± 0.05 | 1.1 ± 0.6 | 0.4 ± 0.2 | 1.5 ± 0.3 | 0.5 ± 0.1 | 0.15 ± 0.03 | 0.200 ± 0.003 | 0.37 ± 0.03 | 2.5 ± 0.7 |
Nail polish | |||||||||||||
Pink | 107.8 ± 1.4 | 4.3 ± 0.2 | 11.3 ± 4.1 | 24.4 ± 5.4 | 0.48 ± 0.04 | <0.001 | <0.005 | 2.8 ± 1.2 | 0.70 ± 0.03 | 0.11 ± 0.02 | 0.17 ± 0.01 | 0.48 ± 0.02 | 12.10 ± 0.05 |
Table 5
Determined element concentrations (µg g−1) for Brand 2–3 of child cosmetic samples (N = 3)
Brand | Al | Cr | Mn | Fe | Co | Ni | Cu | Zn | As | Se | Cd | Hg | Pb |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Brand 2 | |||||||||||||
Eye shadows | |||||||||||||
Pink | 345.3 ± 12.2 | 1.36 ± 0.08 | 19.2 ± 0.06 | 46.5 ± 8.4 | 0.13 ± 0.01 | 0.06 ± 0.03 | < 0.005 | 0.3 ± 0.1 | < 0.001 | 0.12 ± 0.01 | 0.020 ± 0.003 | 0.2 ± 0.1 | 0.24 ± 0.01 |
Green | 277.6 ± 2.5 | 3.72 ± 0.02 | 15.9 ± 0.4 | 30 ± 15 | 0.11 ± 0.03 | 0.05 ± 0.02 | < 0.005 | 0.11 ± 0.05 | 0.06 ± 0.001 | 0.100 ± 0.004 | 0.003 ± 0.001 | 0.08 ± 0.01 | 0.11 ± 0.03 |
Yellow | 212.2 ± 3.6 | 1.13 ± 0.03 | 16.6 ± 0.4 | 46.2 ± 2.2 | 0.08 ± 0.002 | < 0.001 | < 0.005 | 0.07 ± 0.1 | 0.05 ± 0.02 | 0.05 ± 0.01 | 0.008 ± 0.003 | 0.17 ± 0.05 | 1.09 ± 0.02 |
Purple | 278.2 ± 9.3 | 0.11 ± 0.01 | 10.03 ± 0.02 | 37.1 ± 1.3 | 0.06 ± 0.01 | < 0.001 | < 0.005 | 0.15 ± 0.02 | 0.07 ± 0.01 | 0.040 ± 0.002 | 0.003 ± 0.001 | 0.2 ± 0.1 | 0.84 ± 0.03 |
Orange | 243 ± 2 | 0.20 ± 0.06 | 15.80 ± 0.02 | 44.6 ± 3.4 | 0.07 ± 0.02 | 0.03 ± 0.01 | < 0.005 | 0.2 ± 0.1 | 0.030 ± 0.001 | 0.020 ± 0.005 | 0.004 ± 0.001 | 0.14 ± 0.03 | 0.16 ± 0.05 |
Lipsticks | |||||||||||||
Red | 124 ± 4 | 0.33 ± 0.06 | 0.90 ± 0.05 | 35.7 ± 5.1 | 0.016 ± 0.004 | 0.39 ± 0.05 | < 0.005 | 1.02 ± 0.16 | 0.010 ± 0.003 | 0.008 ± 0.003 | 0.013 ± 0.001 | 0.15 ± 0.02 | 0.17 ± 0.07 |
Nail polish | |||||||||||||
Pink | 312.8 ± 2.8 | 0.30 ± 0.02 | 1.2 ± 0.3 | 10.8 ± 0.3 | 0.04 ± 0.02 | 0.07 ± 0.02 | 0.41 ± 0.02 | 3.85 ± 0.04 | 0.04 ± 0.01 | 0.015 ± 0.001 | 0.010 ± 0.007 | 0.08 ± 0.03 | 0.02 ± 0.01 |
Purple | 363.4 ± 4.6 | 4.2 ± 0.6 | 1.5 ±
0.1 | 32.0 ± 1.7 | 0.20 ± 0.02 | 1.11 ± 0.01 | 2.60 ± 0.05 | 3.08 ± 0.08 | 0.08 ± 0.01 | 0.07 ± 0.01 | 0.26 ± 0.05 | 0.50 ± 0.04 | 0.65 ± 0.08 |
Brand 3 | |||||||||||||
Eye shadows | |||||||||||||
Pink | 221.2 ± 2.0 | 1.2 ± 0.15 | 9.80 ± 0.01 | 28.8 ± 0.13 | 0.11 ± 0.04 | 0.25 ± 0.05 | 0.10 ± 0.03 | 8.0 ± 0.2 | 0.60 ± 0.003 | 0.30 ± 0.01 | < 0.002 | 0.063 ± 0.008 | 1.30 ± 0.02 |
Green | 170.1 ± 3.1 | 1.2 ± 0.2 | 10.6 ± 0.1 | 38.4 ± 0.7 | 0.13 ± 0.01 | 0.32 ± 0.05 | 9.46 ± 0.02 | 7.9 ± 1.2 | 0.66 ± 0.002 | 0.35 ± 0.02 | < 0.002 | 0.080 ± 0.009 | 1.3 ± 0.1 |
Yellow | 180.0 ± 1.2 | 1.15 ± 0.09 | 10.52 ± 0.05 | 30.2 ± 0.4 | 0.11 ± 0.02 | 0.34 ± 0.09 | 0.40 ± 0.03 | 6.02 ± 0.03 | 0.55 ± 0.04 | 0.28 ± 0.03 | 0.06 ± 0.05 | 0.06 ± 0.001 | 1.7 ± 0.1 |
Blue | 175.7 ± 0.3 | 1.5 ± 0.2 | 11.20 ± 0.03 | 32.5 ± 0.2 | 0.14 ± 0.01 | 0.64 ± 0.04 | 1.20 ± 0.04 | 7.3 ± 0.2 | 0.60 ± 0.07 | 0.32 ± 0.02 | 0.07 ± 0.03 | 0.48 ± 0.05 | 1.5 ± 0.8 |
Orange | 267.4 ± 0.4 | 1.9 ± 0.2 | 14.1 ± 0.6 | 43.6 ± 0.1 | 0.16 ± 0.01 | 0.5 ± 0.3 | 0.5 ± 0.1 | 13.3 ± 0.8 | 0.76 ± 0.06 | 0.38 ± 0.04 | 0.09 ± 0.02 | 0.09 ± 0.01 | 0.32 ± 0.03 |
Purple | 202.4 ± 0.8 | 1.50 ± 0.09 | 10.6 ± 0.1 | 33.2 ± 0.4 | 0.17 ± 0.02 | 0.7 ± 0.3 | 1.8 ± 0.1 | 6.6 ± 0.5 | 0.52 ± 0.001 | 0.3 ± 0.1 | < 0.002 | 0.04 ± 0.01 | 1.5 ± 0.1 |
Brown | 118.3 ± 3.7 | 1.3 ± 0.1 | 17.8 ± 0.04 | 31.4 ± 0.3 | 0.150 ± 0.004 | 0.3 ± 0.1 | < 0.005 | 7.4 ± 0.2 | 0.48 ± 0.006 | 0.22 ± 0.05 | < 0.002 | 0.05 ± 0.01 | 2.2 ± 0.4 |
Lipstick | |||||||||||||
Pink | 113.4 ± 0.6 | 0.22 ± 0.04 | 0.08 ± 0.03 | 0.24 ± 0.02 | 0.013 ± 0.007 | 0.4 ± 0.2 | < 0.005 | 3.0 ± 0.6 | 0.02 ± 0.01 | 0.003 ± 0.001 | < 0.002 | 0.03 ± 0.01 | 0.13 ± 0.04 |
Nail polish | |||||||||||||
Purple | 8.2 ± 0.8 | 0.23 ± 0.01 | 0.09 ± 0.04 | 1.4 ± 0.5 | 0.015 ± 0.003 | 1.1 ± 0.7 | < 0.005 | 0.3 ± 0.1 | 0.03 ± 0.01 | 0.013 ± 0.004 | 0.015 ± 0.001 | 0.06 ± 0.03 | 0.45 ± 0.06 |
It has been reported that toxic metals are found in eye shadow products, especially those used by women and children. Eye shadows typically come in the form of talc, mica, titanium oxide, zinc oxide, micronized silk powder, calcium or magnesium carbonate, magnesium or zinc stearate, rice powder, kaolin, and pigment. Eye shadows are cosmetic products that have a wide range of colors and are highly pigmented make-up products due to the pigments such as iron oxide, TiO2, Cu powder, emulsions, sticks and pressed powders in their composition (Foster et al. 2020; Pawlaczyk et al. 2021).
In cosmetics, some metals are used as colorants, for example Cr is used as colorants in eye shadows and blushes. Additionally, some color additives may be contaminated with metals, such as D&C Red 6, which can be contaminated with As, Pb and Hg. Among these pollutants, heavy metals are extremely dangerous. Pb can easily cross the placenta of mothers and damage the brain of fetuses, damaging the brain, kidney and nervous system, which is extremely harmful to adults, children and babies (Soylak et al. 2002). Symptoms include anemia, insomnia, headache, dizziness and irritability, muscle weakness, hallucinations and kidney damage. Children's exposure to Pb and Hg can cause learning disabilities, memory impairment, damage to the nervous system, and aggression and hyperactivity (EWG 2007; Omenka et al. 2016).
Cadmium is also one of the most toxic elements that cause bone demineralization and kidney dysfunction and high levels of exposure result in death (Sesli et al. 2008; Ozaytekin and Dedeoglu 2023; Billah et al. 2023). Overexposure to Cd affects lung function and increases the risk of lung cancer. Due to the high toxicity of lead and Cadmium, various countries such as Germany have established strict standards stipulating the concentration of heavy metals in cosmetic products. But many manufacturers may break the rules to benefit. Some may use lower-quality ingredients and introduce Cd into these products to reduce costs. Some manufacturers add Pb to their products because lead compounds make the skin smoother and brighter (Oyaro et al. 2007).
Nickel is a human carcinogen metal that can cause to kidney problems, gastrointestinal distress, pulmonary fibrosis and skin dermatitis (Saracoglu et al. 2007; Parlak et al. 2023). Chronic exposure to Ni is known to be associated with an increased risk of lung cancer, cardiovascular and neurological disorders, childhood developmental deficits and high blood pressure (Omenka et al. 2016; Chervona et al. 2012). It is also known that nickel causes allergic effects that sensitize the skin (Contado and Pagnoni 2012). The repeated skin exposure to low Ni concentration had an effect on vesicle formation and blood flow (Ozbek and Akman 2016). Zn has been reported to cause diseases in the same way as Pb can cause other health problems such as stomach cramping, vomiting, nausea, skin irritation and anemia. Other health effects associated with Cd, Cu and Zn poisoning include gastrointestinal disorders, diarrhea, stomatitis, tremors, ataxia, paralysis, vomiting and convulsions, depression and pneumonia (Oyaro et al. 2007; Duruibe and Egwurugwu 2007).
In order to protect the health of consumers, some countries have imposed some restrictions on cosmetic production. The German Federal Government conducted tests to determine the levels of metal content in various cosmetic products, and metal impurities were limited to anything above their normal levels. According to studies, it has been determined that metal levels as impurities in cosmetic products are 5 μg g−1 for Arsenic and Cadmium, 1 μg g−1 for mercury and 20 μg g−1 for lead (BfR 2006). Heavy metal analysis on some cosmetic products sold in Canada was performed by Health Canada Product Safety Laboratory. It has set appropriate limits for arsenic, cadmium and mercury (3 μg g−1) and lead (10 μg g−1) as metal content in cosmetic products (HC-SC 2012).
However, there is scientific debate about what constitutes a "safe" level. Some metals are known to accumulate in the body over time and cause various long term health effects such as cancer, reproductive and developmental disorders, neurological disorders, cardiovascular and kidney problems. Arsenic, cadmium, mercury, lead and antimony are highly toxic and cobalt, chromium and nickel are particularly potent skin sensitizers (Forte et al. 2008; Thyssen and Menné 2010). So, there's a difference between what's safe and what's technically preventable. Because the testing is voluntary and controlled by the manufacturers, many ingredients in cosmetic products have not been tested for safety.
As a result of the evaluation for this work; the highest concentration of Al used as pigment was found in the eye shadow, lipstick and nail polish samples for the 3 brands, while the Se concentrations were the lowest in lipstick samples. In addition to Pb, as a non-essential element, Aluminium might also be toxic at both environmental and therapeutic levels. Al exposure, apart from causing cholinotoxicity, can induce changes in other neurotransmitter levels since neurotransmitter levels are closely inter-related (Venturini-Soriano et al. 2001; Kumar 2002). In the study conducted by Mercan et al., the Al concentration in lipstick and eye shadow products was detected in the range of 10.98–694.50 and 20.00–50.00 µg g−1, respectively, while in our study the amount of Al in eye shadow products was It ranges from 80.4 to 822.8 µg g−1 in products and 14.3 to 156.3 µg g−1 in lipsticks. While the amount of Al in eye shadow samples was higher in our study, Al in lipstick was found to be lower (Mercan et al. 2023).
By inhibiting melanin production, mercury is used as a skin whitening agent in cosmetic products. For all the eye shadows we studied, the highest Hg concentration was 0.9 μg g−1 and was observed in brand 1, orange eyeshadow (ED 2011). Found Hg concentration < LOD in various eye area cosmetic products sourced from Canada, Europe, Korea, USA. In lipstick samples, the Hg concentration range is 0.03–0.5 μg g−1 and Adepoju-Bello et al. 2012 on lip gloss, lipstick, and skin cream, the mercury concentration range was 0.009–0.207 μg g−1, which was lower than our study. Hg concentration of nail polish samples for 3 brands is in the range of 0.06–0.5 μg g−1. Hg concentration was in the range of < 0.0037–0.00965 μg g−1 (Grosser et al. 2011). However, according to FDA (2000) (FDA (2000), cosmetics must contain Hg at a concentration of less than 1 μg g−1. Health Canada has a limit value of 3 μg g−1 for Hg as an impurity in cosmetic products (HC-SC 2012). In Germany, the limit for Hg as an impurity in cosmetic products is 1 μg g−1 (BfR 2006). In this regard, the Hg concentration is below the limit value.
Lipstick samples element concentrations, respectively; Brand 1- In Red lipstick; Ni and Cu was found below the LOD. Fe > Al > Pb > Cr > Zn > Mn > As > Co > Hg > Cd > Se. In Pink lipstick; Al > Fe > Cr > Pb > Mn > Zn > Ni > As > Cu > Hg > Cd = Co > Se, Brand 2- In Red lipstick; Cu was found below the LOD. Al > Fe > Zn > Mn > Ni > Cr > Pb > Hg > Co > Cd > As > Se, Brand 3- In Pink lipstick; Cd and Cu was found below the LOD. Al > Zn > Ni > Fe > Cr > Pb > Mn > Hg > As > Co > Se.
The maximum levels in lipstick samples for 3 brands; 156.3 μg g−1 Al, 7.0 μg g−1 Cr, 2.22 μg g−1 Mn, 67.8 μg g−1 Fe, 0.58 μg g−1 Co, 1.1 μg g−1 Ni, 0.4 μg g−1 Cu, 3.0 μg g−1 Zn, 0.7 μg g−1 As, 0.13 μg g−1 Se, 0.17 μg g−1 Cd, 0.5 μg g−1 Hg. Pb level was found to be higher than brands 2 and 3. In brand 1 it is in the range of 2.5–10.7 μg g−1, in brands 2 and 3 it is in the range of 0.13–0.17 μg g−1.
Nail polish samples element concentrations, respectively; Brand 1- In Pink Nail polish; Ni and Cu was found below the LOD. Al > Fe > Pb > Mn > Cr > Zn > As > Hg = Co > Cd > Se Brand-2- In Pink Nail polish; Al > Fe > Zn > Mn > Cr > Ni > Hg > Cu > Co = As > Pb > Se > Cd In Purple Nail polish; Al > Fe > Cr > Zn > Cu > Mn > Ni > Pb > Hg > Cd > Co > As > Se. Brand-3-In Purple Nail polish; Cu was found below the LOD. Al > Fe > Ni > Pb > Zn > Cr > Mn > Hg > As > Co > Se > Cd. The maximum levels in nail polish samples, 363.4 μg g−1 Al, 4.3 μg g−1 Cr, 11.34 μg g−1 Mn, 32.0 μg g−1 Fe, 0.48 μg g−1 Co, 1.11 μg g−1 Ni, 2.6 μg g−1 Cu, 3.85 μg g−1 Zn, 0.7 μg g−1 As, 0.11 μg g−1 Se, 0.26 μg g−1 Cd, 0.5 μg g−1 Hg, 12.1 μg g−1 Pb.
Eye shadow samples element concentrations, respectively; Brand 1- Ni and Cu was found below the LOD for green, orange, purple eye shadow. Silvery eye shadows Al concentrations are lower than the other not silvery eye shadows. For green eye shadow; Al > Fe > Pb > Mn > Cr = Zn > Hg > As > Co > Cd > Se, orange eye shadow, Al > Fe > Mn > Pb > Cr > As > Hg > Co > Cd > Pb > Se, yellow eye shadow; Al > Cr > Fe > Cu > Mn > Zn > As > Co > Pb > Se > Cd > Hg, Purple eye shadow; Al > Fe > Mn > Cr > Zn > As > Hg > Co > Pb > Cd > Se.
Brand 2 eye shadow samples Cu was found below the LOD. Brand 3 pink, green, purple, brown eye shadow samples Cd was found below the LOD. The maximum levels in eye shadows are 822.8 μg g−1 Al, 16.5 μg g−1 Cr (for only brand 1 orange eye shadow 51.8 μg g−1 Cr), 19.2 μg g−1 Mn, 46.5 Fe μg g−1, 0.53 μg g−1 Co, 1.4 μg g−1 Ni, 9.46 μg g−1 Cu, 13.3 μg g−1 Zn, 0.82 μg g−1 As, 0.38 μg g−1 Se, 0.26 μg g−1 Cd, 0.65 μg g−1 Hg.
There are studies in the literature on the Pb content in cosmetic samples (Al-Saleh et al. 2009, Soares and Nascentes 2013; Zakaria et al. 2015; US FDA 2002; Volpe et al. 2012). Pb was found in 25 lipstick samples; Pb values vary between 0.11 and 4.48 mg kg−1 by Gunduz and Akman’s study (2013) (Soares and Nascentes 2013). The concentration of lead in our study for brand 1 was higher than the concentration reported by Gunduz and Akman (2013). But the Pb levels in all lipstick samples in this study was below the FDA limit (20 μg g−1) (US FDA 2002). The concentrations of heavy metals in lipsticks reported in this work Cd and Cr values are lower than in the study by Gondal (Gondal et al. 2010). The values of Pb, Cd and Cr ranged from 6.4 to 9.9 mg kg−1, 5.4–10.6 mg kg−1, and 9.3–39.4 mg kg−1, respectively for lipstick samples at Gondal et al. (2010). Lead is at similar values with our study.
Women and children are particularly vulnerable to lead exposure (Demirel et al. 2008). The use of lead contaminated lipstick or eye shadows by women and child could expose the fetus and infants to the risk of Pb poisoning. Pb was detected in all tested for eye shadow samples of 3 different brands and different colors in the range of 0.05–12.2 μg g−1 wet wt. This range is below in all brands with lead content above 20 μg g−1 the US FDA limit for lead as impurities in color additives used in cosmetics (US FDA 2002).
The highest concentrations were detected in eye shadow samples lead concentration imported from China by Volpe (Volpe et al. 2012). The range of 9.53–81.50 μg g − 1 in Chinese cosmetic products was reported by Volpe et al. (2012) reported. These products require particular attention because they are applied to the very thin part of the facial skin, to the area around the eyes, where the risk of percutaneous absorption of pigments and the development of irritants is very high, and allergic skin reactions may develop.
In terms of Cd concentration, Omolaoye (Omolaoye et al. 2010) study, the eye shadow samples were < LOD-8.89 μg g−1. In the same study, Cd concentration was found to be 4.9–10.6 μg g−1 in lipstick samples. In our study, Cadmium concentration in eye shadow samples was in the range of < 0.002–0.25 μg g−1, and in lipstick samples was in the range of 0.01–0.26 μg g−1 Omolaoye according to the study, it has low concentration values. In the study conducted by Volpe Cd was found to be in the range of 0.0006–0.033 μg g−1, therefore it is at high values.
Grosser et al. (2011), Cd in nail polish samples were 0.0110–0.0832 μg g−1, the limits determined by Health Canada were 3 μg g−1 for Cd, according to the German Federal Government, metal limits as impurity in cosmetics were 5 μg g−1. In our study, it was found to be 0.015–0.26 μg g−1, but it was observed to be higher. It is below the specified limits.
There are various studies that show that allergenic metals such as Ni, Co and Cr are found at the highest levels in cosmetic products, especially colored eye shadows. Volpe et al. (2012), Ni concentration in eyeshadow samples was 0.0218–4.148 μg g−1, Sainio et al. (2000) study, it was found to be 0.5–49.7 μg g−1, and in Contado and Pagnoni (2012) study, it was found to be 7.9–344 μg g−1. In our study, it was found to be < 0.001–1.4 μg g−1, which is lower than other studies. Ni concentration in lipstick samples (Nnorom al. 2005) it was in the range of 7.0–22.8 μg g−1. In this work, Ni concentration was found to be < 0.001–1.1 μg g−1 for lipstick samples.
In this study, Co concentration was found to be 0.02–0.53 μg g−1 in eye shadow samples, 0.13–0.58 μg g−1 in lipsticks, and 0.015–0.48 μg g−1 in nail polish. A study conducted on eye shadows produced in different countries (Italy, China, USA) reported Co concentration of 0.00015–0.3037 μg g−1 (Volpe et al. 2012). In another study, Co in toy make-up kits used by children ranged above 10 μg g−1 in 4 eye shadows and between 1 and 10 μg g−1 in 15 eye shadows (Corazza et al. 2009).
Chromium has two valences, Cr(III) and Cr(VI) valences (Karatepe et al. 2010). Cr(III) valence is an essential nutrient required for normal energy metabolism. Cr(VI) valence is not found naturally in the environment and is highly toxic to human health. Both are used in dyes and pigments in the textile industry (ATDSR 2008). Cr(III) oxide green is allowed to be used as a colorant in cosmetic products. Cr is not limited to cosmetics as an impurity. However, it is known that the occurrence of ACD (allergic contact dermatitis) is extremely low when Cr is present in consumer products at a concentration lower than 1 μg g-1 Cr. Cr concentration is in the range of 0.11–51.8 μg g−1 for all samples in this study. Compared to other studies, Omolaoye et al. (2010) report, Cr concentration in eyeshadow samples was found to be < LOD-150 μg g−1, and in Contado and Pagnoni (2012) study, it was found to be 2.9–149,500 μg g−1. The results we obtained are below these values.
Arsenic element concentration range was found to be < 0.001–0.84 μg g−1 for all samples in our study (Sneyers et al. 2009), in eye shadows, it was 0.181–1.58 μg g−1, and Sainio et al. (2000) obtained a result of < 0.3–2.3 μg g−1. The maximum concentration we found in lipstick samples was 0.71 μg g−1, while Grosser et al. (2011) it has a lower value in the range of 0.0571–0.828 μg g−1. In the same study, the As concentration in nail polish samples was found to be < 0.014–1.91 μg g−1, and in our study it was found to be 0.03–0.7 μg g−1, which is a low value. It is at a low level according to The German Federal Government (< 1.0 μg g−1).
4 Conclusions
Cosmetics are products widely used by people all over the world. The safety of some cosmetic products is of concern as they have been found to contain ingredients banned or restricted under US and EU legislation. Cosmetic products are often packaged and designed to be colorful, visually appealing, and easy to open and use. Ingredients in cosmetics are often designed to look like sweet-smelling fruit or colorful foods, so a young child may mix cosmetics into food or drinks. Children are curious and also explore their environment. They may be curious about the parent or caregiver's cosmetic product and use it. The properties of both children's and cosmetic products may increase children's interest in these products, which may endanger them. While a cosmetic product will not be harmful when used properly by an adult, unintentional exposure by a child may cause injury.
When eye shadow, lipstick and similar facial cosmetics containing heavy metals are applied to human skin, there is direct exposure to toxic and carcinogenic chemicals. When the eyelids are blinked, pigments and toxic metals enter the body. Metals can also be absorbed into the organism through healthy skin. Although the absorption of metals through the skin is often overlooked, studies have shown that Pb can actually be absorbed through the skin. The skin is considered a protective barrier, but constant use of cosmetics, facial makeup, eating, and sweating on the face, lips, and eye skin result in increased exposure and absorption of toxic heavy metals, primarily Cd and Pb. In most regulations, cosmetic products are prohibited from containing certain substances due to their negative effects on the liver. Therefore, for all cosmetic products, the safety of consumer products should be assessed by determining the presence and amounts of hazardous ingredients, as well as examining the hazards in terms of exposure and comparing them with health-based standards.
In this study, different three brands, 22 eye shadows, 4 lipsticks and 4 nail polishes samples were analyzed the concentration of trace (Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Hg, Cd and Pb) elements of child cosmetic products in Turkey were investigated. The mean trace element contents and standard deviations for child cosmetic products (eye shadow, lipstick, and nail polish) were analyzed by using ICP-MS and the concentrations (μg g−1) of each element were shown in Tables 4 and 5. This study is the first research on children's cosmetics with ICP-MS device in Turkey.
In cosmetics, reliable analytical techniques come to the fore in terms of product quality, detection of prohibited substances and protection of human health. There are different techniques for analyzing hazardous compounds in cosmetics. ICP-MS is a good choice for the detection of low analyte concentrations, enabling the evaluation of toxic components in cosmetics. It has the advantage of achieving the lowest detection limit by eliminating molecular interference in the mass of interest by using interference correction.
Declarations
Conflict of interest
We declare that the authors have no competing interests as defined by Springer, or other interests that might be perceived to influence the results and/or discussion reported in this paper.
Ethical approval
This work is not applicable for both human and/or animal studies.
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