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Biol Trace Elem Res (2016) 170:476484

DOI 10.1007/s12011-015-0477-2

A Study of the Possible Harmful Effects of Cosmetic Beauty


Products on Human Health
Biljana Kalianin 1 & Dragan Velimirovi 1

Received: 5 May 2015 / Accepted: 12 August 2015 / Published online: 23 August 2015
# Springer Science+Business Media New York 2015

Abstract The origins of the usage of different substances in contact with skin or mucous membranes and are often used in
beauty, skin, body, hair, and nails care products can be found daily life.
in ancient times. To achieve better quality and enhance their
effects, some additives such as preservatives, stabilizers, min- Keywords Cosmeticproducts . Lead . Cadmium . Zinc . PSA
eral pigments, dye, and shine were added to these products.
Some of these substances may also have allergic, irritating,
and harmful effects on human health. The aim of this study Introduction
was the optimization of the potentiometric stripping analysis
(PSA) for the purpose of determining the content of heavy Humans are exposed to naturally occurring metals released by
metals (lead, cadmium, zinc), in some commercial cosmetic the environment via a broad range of routes every day.
beauty products (lipsticks, lip glosses, eye shadows, and hen- Atmospheric emissions tend to be of greatest concern in terms
na hair dye). In addition, in order to monitor the potential of human exposure and health effects, both because of the
adverse effects of henna dye on hair quality, as well as the amount of metals involved and the widespread dispersion.
total body burden of heavy metals (Pb, Cd), the paper ana- Exposure to metals may also occur through a diet, receiving
lyzed hair samples before and after henna dye treatment. medication, or in the course of work or play [1]. However,
Beauty products used for cosmetic purposes can have adverse other less essential sources of exposure have to be considered,
effects to human health due to the fact that they contain lead, a including the use of cosmetic products [2].
highly toxic metal. The lead content in the tested samples Since the dawn of civilization, cosmetic products have con-
varied depending on the additives used along with the method stituted a part of routine body care not only by the upper strata
of production. The cosmetic products that were analyzed in of society but also by middle and low class people [3].
this study contained a certain amount of zinc, which is an Cosmetic products include a very large number of products
essential element, although its content above the prescribed that are used for the care, cleaning, protection, and beautifica-
limit may lead to side effects. Highly toxic metal, cadmium, tion of skin, hair, teeth, and nails. On todays market, there is a
was not detected in the tested samples. The presence of these large number of these products that are of different quality and
metals in cosmetic products certainly indicate that it is neces- from a different manufacturer. Lipstick, lip gloss, mascara,
sary to monitor and determinate the content of toxic heavy nail polish, and make-up powder are cosmetic beauty products
metals in these products, especially because they are in direct which are common in everyday use.
In recent years, more and more importance is given to
testing and monitoring the possible harmful effects of these
* Biljana Kalianin cosmetic products because they are in direct and frequent con-
bkalicanin@yahoo.com tact with the skin and mucous membranes. The basic compo-
Dragan Velimirovi nents of cosmetic beauty products frequently contain a com-
dravel08@yahoo.com pound of different metals, which are added in order to achieve
1
Department of Pharmacy, University of Ni, Faculty of Medicine, a better effect, or may be present as impurities. Compounds of
81dr Zoran ini Boulevard, Ni 18000, Serbia some essential metals (Cu, Zn, Fe, Cr) which are added to
A Study of the Possible Harmful Effects of Cosmetic Products 477

cosmetic products to improve their quality, in addition to their this Annex, several metals, such as antimony (Sb), arsenic
positive effect, may also lead to skin irritation if their content (As), cadmium (Cd), chromium (Cr), cobalt (Co), mercury
is above the prescribed. Also, in order to obtain a wider color (Hg), nickel (Ni), and lead (Pb) are prohibited ingredients in
palette and better shine, some mineral pigments, dye, and cosmetic products because they are considered unsafe. On the
glitter are added to these products. These auxiliary compo- other hand, in the USA, The US Food Drug and Cosmetic Act
nents may contain certain metals (Al, Zn, Si, Ti, Pb), which offers a somewhat narrower definition of cosmetics than in the
may appear as their integral parts or as contaminants [4]. EU, but certain products regarded in the EU as cosmetics have
Heavy metals that are present in applied cosmetic products been classified by the US FDA as Over-the-Counter drugs,
can cause epithelium damage as well as skin rash. Due to including sunscreen products, anti-cavity toothpastes, antiper-
the cumulative effects of these metals, severe conditions spirants, antidandruff products, skin protectant products, and
may appear on the skin and mucous membranes. hair restorers [14]. The FDA has banned nine chemicals in-
Furthermore, heavy metals can be absorbed by the skin and cluding only one toxic metal, namely Hg (with the exception
enter bodily fluids. Via bodily fluids, these toxins can reach of its use as a preservative in the eye area cosmetics). For
vital organs. cosmetic color additives, a maximum Pb concentration of
Many studies of different authors have shown that cosmetic 20 g/g has been established by the FDA [15]. However,
products may be potential routes of entry of toxic metals into the Regulation applicable in the Republic of Serbia prescribed
the body [13, 510]. the amount of heavy metals allowed per 1 kg of a specific
Cosmetic products can contain more than 10,000 ingre- product used for lips and eye coloring, which must not be
dients which can be linked to many diseases like cancer, exceeded [16].
birth defects, developmental and reproductive impair- In relation to cumulative and toxic effects of lead and cad-
ments. Because of that, US FDA (Food and Drug mium [1719], this study observed the influence of auxiliary
Administration) banned nine ingredients including coal components (mineral pigments, dye, and glitter), on the total
tar colors, formaldehyde, glycol ethers, lead, mercury, content of these heavy metals, in analyzed decorative cosmet-
parabens, phenylenediamine, and phthalates in cosmetic ic products. The content of essential metal zinc is also deter-
products [1]. mined since, present in high concentrations, it can also have
Dermal exposure is the most significant route, because adverse effects on human health [20, 21].
most of the cosmetic products are directly applied to the In order to monitor the potential adverse effects of henna
skin. On the other hand, oral exposure can occur from dye on hair quality, as well as the total body burden of heavy
applying cosmetic products that contain heavy metal im- metals (Pb, Cd), the paper analyzed hair samples before and
purities around the mouth and also from hand to mouth after henna dye treatment.
contact [11]. In contact with human body, heavy metal Lead, cadmium, and zinc content in the analyzed samples
ions get absorbed and form complexes with carboxylic was determined using a highly sensitive microanalytical tech-
acid (COOH), amine (NH2), and thiol (SH) of pro- niquepotentiometric stripping analysis (PSA).
teins resulting in malfunctioning or death of the cells
and consequently lead to variety of diseases. The treat-
ment for metal intoxication is achieved by using a chelat-
ing agent that binds with the metal ions, and thus, the Materials and Method
complexes are eliminated from the body [12].
Due to the harmful effects of heavy metals that are Chemicals and Solutions
presented in cosmetic products, many world countries
have agreed on the appropriate Regulations governing Hydrochloric acid (36 %, suprapur grade), nitric acid (65 %,
the amount of these toxins in particular cosmetic products. suprapur grade), acetic acid (suprapur grade), sodium hydrox-
It should be said that there is no one uniformed directive ide (suprapur grade), acetone, EXTRAN (cleaning agent,
that would be globally applied; rather, each state has its MA-02, neutral), hydrogen peroxide (30 %, suprapur grade),
corresponding Regulations. solution of lead (1 g/L, Titrisol), standard solution of cadmium
The European Commission (EC) Scientific Committee on (1 g/L, Titrisol), standard solution of zinc (1 g/L, Titrisol), and
Consumer Safety released its Guidance on the safety assess- standard solution of mercury (1 g/L, Titrisol) were purchased
ment of nanomaterials in cosmetics in 2012, which is now from Merck company (Darmstadt, Germany) and have been
widely applied throughout EU [13]. Annex II of the used in the condition they were received in.
Guidance (BList of substances which must not form part of Working solutions were prepared by dilution of standard
the composition of cosmetic products^) lists more than 1000 solutions with doubly distilled water.
chemical substances which ought not to be used in cosmetic All containers, utensils, and cells were cleaned by nitric
products, due to their toxicological properties. According to acid and doubly distilled water (1:1) before being used.
478 Kalianin and Velimirovi

Samples temperatures of 6070 C, for a period of 1 h. Finally, the


samples were analyzed for the content of heavy metals (Pb,
Twenty-five different samples of cosmetic beauty products (7 Cd).
lipsticks, 5 lip glosses, 10 eye shadows, and 3 henna hair dyes)
of different colors and produced by different manufactures Instrumentation
were analyzed in this study after being obtained from local
shops of the city of Ni. All the analyses were performed by using a commercially
To monitor the impact of the heavy metal content (Pb, Cd) available computerized Stripping analyzer M1 (Faculty of
in henna dye on treated hair, we used hair samples of 10 Technology, Novi Sad and Elektrouniverzal, Leskovac,
female test subjects. The samples were either of natural, un- Serbia). The analyzer has a program for automatic qualitative
treated hair (before henna dye treatment), or samples of hair 1 and quantitative analysis, involving the element contents
and 3 years after henna dye treatment. assessment.

Sample Preparation
Lead, Cadmium, and Zinc Contents Measured by PSA
Cosmetic Products
The PSA modification with oxygen as an oxidant was applied
with the diffusion conditions of the mass transfer during the
Wet digestion method was employed in order to determine the
analytical step. This PSA modification was the simplest since
total lead, cadmium, and zinc content in tested samples of
it used the already present diluted oxygen as a means of oxi-
cosmetic products. Weighted samples (23 g) were treated
dation that reduces the contamination risk by applying other
with a mixture of concentrated nitric and hydrochloric acids,
oxidation means. For the PSA analysis of lead, cadmium, and
respectively 1:1.5 (V:V) and heated at a temperature of 60
zinc, it was necessary that the analyzed sample was in soluble
80 C for the duration of 2 h, in order to complete the miner-
form, and the pH value needed to be within the range of 2.0 to
alization of the samples. After the mineralization process, the
4.0. Acetate buffer was used to achieve this range of pH.
resulting solution was diluted with doubly distilled water and
then filtered through a quantitative filter paper (black belt)
until a volume of 50 mL was obtained [22]. Formation of a Working Electrode

Henna Dye Treatment The working electrode was prepared as follows: a thin layer
mercury electrode on glassy carbon was used as an inert sup-
Two hundred milligrams of hot water (40 C) was poured over port. Before the preparation of the electrode, the glassy carbon
100 g of red henna powder, and the mixture was applied on surface was wiped with filter paper soaked first in acetone and
dry hair. After 34 h, the hair was rinsed with water and then then in distilled water. The mercury film was formed electro-
washed using shampoo. lytically from a solution containing 100 mg/L mercury (II)
ions and 0.02 mol/L hydrochloric acid (pH value 2), at a
Hair Samples constant current of 50 A for a deposition time of 240 s.
Once deposited, the mercury film was used for 2530 analyses
Hair samples (untreated and treated with henna), weighing of different sample types [24].
approximately 1.00 g, were obtained using scissors made of
stainless steel and stored in plastic bags. All hair samples were
treated according to the Miekeley et al. procedure. [23]. Hair Results and Discussion
samples were first treated with 20 mL of acetone over a period
of 10 min. Each sample was then rinsed three times with In order to determine the optimal conditions of the PSA of
20 mL of 1 % EXTRAN solution. Ultra-pure water 0.05 lead, cadmium, and zinc, in the chosen supporting electrolyte,
S/cm (MicroMed high purity water system, TKA the effects of time of the electrodeposition, of the electrolysis
Wasseraufbereitungssysteme GmbH) was used to remove potential, and of the solution stirring rate were examined.
the cleaning agent. After washing, the samples were then dried After the optimization of the determination conditions, both
at a temperature of 60 C. Wet digestion was applied for the the linearity and the reproductivity of the analytical signal
dissolution of samples. Thus, prepared samples were placed in were defined.
the crucible and treated with 2.5 mL 65 % HNO3 at room The most reproductive values were obtained at potential
temperature for the duration of 12 h and then burned at the electrolysis of 1.530 mV, while the electrolysis time
temperature of 6070 C for a period of 1 h. Treated samples depended on the content of lead, cadmium, and zinc in the
were cooled with 1 mL of H2O2 and again subjected to analyzed samples, namely 240 s for zinc, 300 s for lead, and
A Study of the Possible Harmful Effects of Cosmetic Products 479

900 s for cadmium. Optimal solution stirring rate for all sam-
ples was 4000 rpm.
Under defined optimal experimental conditions, linearity
of analytical signal in PSA for lead, cadmium, and zinc was
examined, in the solution model of mass concentrations in the
range from 5 to 15 g/L, 1 to 9 g/L, and 2 to 12 g/L,
respectively. Obtained equations for tested metals had high
values of correlation coefficient (Figs. 1, 2, and 3) which in-
dicates a good agreement of tested linearity with given linear
dependence.
Under defined experimental conditions, the analysis of the
samples of cosmetic products was performed. The total con-
tent of metals in the samples was determined using the ade-
quate calibration curve (Figs. 1, 2, and 3), and the values
obtained were presented as the mean of five measurements.
The detected total lead and zinc contents in the tested sam- Fig. 2 Linearity of the analytical signal of PSA for cadmium in the
model of solution of mass concentrations from 1 to 9 g/L
ples of cosmetic products are given in Figs. 4, 5, 6, 7, 8, 9, 10,
and 11.
Cadmium (Cd) is one of the most toxic metal ions in envi- These findings are in line with the studies of authors who also
ronment, and it can be found in air, food, and water. Cd ions did not detect this metal in the tested samples of lipsticks and
are absorbed by most tissues of the body and become concen- lip glosses [2629]. On the other hand, a high concentration of
trated mainly in liver and kidneys. The most dangerous char- Cd (from 5 g/g to 10 g/g) was found in both unbranded
acteristic of cadmium is that it accumulates throughout a life- (low-cost samples) and branded lipsticks during the study
time. Chronic human exposure to Cd results in renal dysfunc- conducted by Gondal et al. [10]. In eye shadows, Cd levels
tion, anemia, hepatic dysfunction, osteotoxicities, and cancer varied from only traces (0.0006 g/g) [30] to high concentra-
in multiple organs, potentially including the kidneys [17, 18]. tions (8.89 g/g) [31].
Because of its carcinogenic properties, cadmium has been Lead is a toxic metal with cumulative deleterious effect and
classified as the first in the category of human carcinogens can be introduced into the human body by inhalation, inges-
by the International Agency for Research on Cancer (IARC) tion, or cutaneous absorption [19]. Although its concentration
[25]. Cadmium is a potent human carcinogen and has been can be relatively high in liver and kidneys, lead is mainly
associated with lung, prostate, pancreas, and kidney cancer. deposited in bones. The total lead content in normal human
Cadmium can cause osteoporosis, anemia, non-hypertrophic bodies ranges from 100 to 400 mg and increases with age. The
emphysema, irreversible renal tubular injury, eosinophilia, an- normal level of lead in blood is below 400 ng/mL [32]. The
osmia, and chronic rhinitis [12]. deleterious properties of lead are particularly noticeable in the
A highly toxic metal cadmium was not detected in the central nervous system, kidneys, and liver. The toxicity of lead
samples of cosmetic beauty products analyzed in this study.

Fig. 1 Linearity of the analytical signal of PSA for lead in the model of Fig. 3 Linearity of the analytical signal of PSA for zinc in the model of
solution of mass concentrations from 5 to 15 g/L solution of mass concentrations from 2 to 12 g/L
480 Kalianin and Velimirovi

Fig. 6 The total lead content in lip gloss samples


Fig. 4 The total lead content in lipstick samples
content in the tested lipstick samples can be the consequence of
to the human body arises from its ability to bond with SH lead contaminated dust and water that was used in the process
groups of enzymes and cellular proteins, which leads to of production of these cosmetic products. Inadequate treatment
changes in their functions or their inactivation. In addition, during the production, storing, and transporting the final prod-
lead interacts metabolically with essential metals (Ca, Fe, ucts can also present a potential route of lead contamination.
Cu, Zn), which can cause disorders in kidney function, ner- The lead content in lipstick samples analyzed in this study
vous and cardiovascular system, and heme biosynthesis [19]. is high and above some international standards, which pre-
In the analyzed samples, a highly toxic metal, lead, was scribe a maximum level of 20 g/g of this heavy metal in
detected. The content of toxic metal lead in the tested lipsticks cosmetic products [1]. According to these recommended
ranged from 16.67 to 105.60 g/g (Fig. 4), depending on the values, it can be said that the lead contents in the lipstick
color of the sample. The highest lead content was detected in samples tested in this study can be seen as toxic. Only the
light pink pearly shine lipsticks, and the lowest in beige lip- beige lipstick can be considered safe for usage, because the
sticks. The difference in the content of this metal in the tested content of lead in this sample was below 20 g/g.
lipstick samples may be due to the addition of auxiliary com- Total lead content in the tested lip gloss samples ranged
ponents such as Mica, various pearls and Pb chromate, which from 12.77 to 20.17 g/g which was about 2 to 5 times lower
are used basically to provide pigment in lipsticks, though they compared to the content of this metal detected in lipsticks.
may contain some toxic metals, as well as contaminants [33]. Differences in detected lead concentrations in these prod-
Results of the study conducted by Al-Saleh et al. showed that ucts may be due to fact that some cosmetic dyes and pigments
lipsticks with pearl shine contain significantly more lead com- are added to lipsticks in greater quantity in relation to lip
pared to the matte color lipsticks [9]. These results suggest that glosses [9]. The results of this study indicated that color agents
the added auxiliary components can be a potential source of
metal contamination in lipsticks. Additionally, the increased Pb

Fig. 5 The total zinc content in lipstick samples Fig. 7 The total zinc content in lip gloss samples
A Study of the Possible Harmful Effects of Cosmetic Products 481

Fig. 10 The total lead content in henna dye samples

According to the detected lead content, it can be concluded


Fig. 8 The total lead content in eye shadow samples that all eye shadow samples tested in this study can be poten-
tially toxic.
which essentially contain metal oxides and are used in cos- In recent years, henna hair dye has been improved by
metic industry could be potential sources of toxic metals. adding various herbs or substances in order to provide a stron-
In the group of lip glosses, only samples of light orange lip ger color to the final product and to shorten the time of its
glosses can be considered potentially harmful to human health, application. The added material can include various mineral
because the lead content in this product is higher than 20 g/g. products which can be very rich in metals such as Pb [3].This
The lead content in eye shadows ranged from 26.43 to study showed that in the samples of henna hair dye, the con-
95.55 g/g (Fig. 8). As in the case of lipsticks, it was detected tent of lead ranged from 8.52 to 19.61 g/g (Fig. 10). The
that pearl shine eye shadows have greater lead content (from highest lead content was detected in red henna dye and the
53.19 to 95.55 g/g) compared to the eye shadows without lowest content in brown henna dye. This difference in lead
this addition (from 26.43 to 50.41 g/g). Studies of some content in samples of henna hair dye may be the result of the
authors have shown that eye shadows, which contain mineral addition of metal salts, which are often used to obtain different
pigments (iron oxides and zinc), have a high lead content that color henna dyes (red, black, brown). Results obtained in this
ranged from 0.42 to 58.7 g/g, which is in line with the results study are in accordance with the study of Lekouch et al., in
of our work [6, 9]. which the lead content in henna hair dye ranged from 2.2 to
19.9 g/g [34]. On the other hand, in their own study, Jallada
and Espada-Jallada detected the lead content that ranged from

Fig. 9 The total zinc content in eye shadow samples Fig. 11 The total zinc content in henna dye samples
482 Kalianin and Velimirovi

2.29 to 65.98 g/g [8], which indicates that henna dye samples with henna during 1 to 3 years represents only the Bcurrent^
tested in their study may have adverse effects on human load of this heavy metal in the hair.
health. The content of detected lead in most analyzed samples of
In the Republic of Serbia, mainly red henna is used in hair cosmetic beauty products was high and above 20 g/g which
treatment. By analyzing samples of red henna dye in this is the allowed maximum content for this contaminant in this
study, the highest total lead content was detected in relation type of products. Only samples of lip gloss and henna hair dye
to other henna dye types (Fig. 10). For this reason, we had lead content below 20 g/g. Due to its highly toxic and
researched the influence of red henna on the total lead content cumulative effects, it is necessary to monitor and control the
in the hair that was treated with it. content of this metal in cosmetic products.
Table 1 shows total Pb content in the tested samples of Zinc is an essential element necessary for growth, develop-
untreated hair and hair treated with red henna (for the duration ment, and normal functioning of human bodies. However,
of 1 and 3 years) and the percentage of lead increase in hair increased concentrations of zinc in the body can adversely
samples after being treated with henna. affect human health. Some tests have shown that increased
Total lead content in the samples of natural, untreated hair intake of zinc in the body leads to a deficiency of copper in
(Table 1) ranged from 5.21 to 10.36 g/g. Variations in the the liver, serum, and heart and reduced activity of copper
content of this metal in the hair samples resulted from different metalloenzymes [20, 21]. Also, increased intake of zinc in
places of residence, life styles, and ages of the subjects tested the body may have a detrimental effect on the storage of iron
[35]. The lead content in hair samples treated with henna over and can cause anemia [36].
the period of 1 year was about 510 % higher than the lead Compared to the detected lead content, the content of zinc
content detected in the samples of natural, untreated hair. In in all of the tested samples was higher. The higher zinc content
hair samples treated with henna dye over a longer period of in relation to lead may be due to the addition of zinc com-
time (3 years), there was a temporary increase in lead content pounds (oxides, stearate) to cosmetic products, in order to
in relation to the total lead content in hair samples treated for a reduce their irritability and increase water resistance [4].
year (about 215 %) and about 1020 % in relation to the lead The content of zinc in tested samples of lipsticks
content in the untreated hair (Table 1). These results indicate ranged from 0.35 to 3.81 mg/g (Fig. 5). The highest con-
that hair samples tend to retain lead traces that can be found in tent of zinc was detected in bright pink colored lipstick
henna, and that the total lead content increases if the product is with a pearly shine and the lowest in the matte orange
used over a longer period of time. Thus, besides its good lipstick. The usage of different auxiliary substances which
qualities of nourishing and strengthening the hair, and giving improve quality and allow color diversity in lipsticks can
it a healthy shine, henna can also have adverse effects due to contribute to the detected difference in Zn content in dif-
prolonged use. The results of this study show that henna lead ferent colored lipsticks.
contents eventually lead to an increase in the total lead content Zinc compounds that are added to eye shadows in or-
in the hair, which can then become a potential source of toxic der to achieve greater durability and lessen skin irritability
metals released in the body. can contribute to a total zinc content of the analyzed sam-
Bearing in mind the cumulative toxic effects of lead, the ples, with the said content ranging from 0.21 to 4.24 mg/g
detected total lead content in the analyzed hair samples treated (Fig. 9).

Table 1 Total Pb content in the


tested samples of untreated and Samples Total Pb content (g/g) Variations of Pb Total Pb Variations of Pb
hair treated with red henna (for contents N T1y (%) content (g/g) contents N T3y (%)
the duration of 1 and 3 years) and N T (1 year) T (3 years)
the percentage of lead increase in
hair samples after being treated 1 5.21 0.01 5.47 0.03 4.99 6.20 0.02 19.00
with henna 2 5.84 0.03 6.42 0.07 9.93 6.73 0.04 15.23
3 6.43 0.04 6.97 0.02 8.40 7.59 0.03 18.04
4 6.85 0.02 7.28 0.05 6.28 7.96 0.03 16.20
5 7.81 0.01 8.58 0.07 8.97 8.97 0.01 14.85
6 8.29 0.07 8.83 0.03 9.86 9.92 0.08 19.66
7 8.44 0.04 9.04 0.05 7.11 9.98 0.02 18.25
8 9.07 0.03 9.54 0.04 5.18 10.98 0.05 21.06
9 10.11 0.06 11.10 0.02 9.79 11.39 0.04 12.66
10 10.36 0.08 10.95 0.06 5.69 12.38 0.08 19.50

N non-treated hair samples, T treated hair samples


A Study of the Possible Harmful Effects of Cosmetic Products 483

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