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Scholars Research Library
Archives of Applied Science Research, 2010, 2 (5): 76-84
(http://scholarsresearchlibrary.com/archive.html)
ISSN 0975-508X
CODEN (USA) AASRC9
76
Scholar Research Library
Heavy metal assessment of some eye shadow products imported into
Nigeria from China
*Omolaoye J.A., Uzairu A., and Gimba C.E.
Chemistry Department, Ahmadu Bello University Zaria, Nigeria
_____________________________________________________________________________
ABSTRACT
Chinese made eye shadows (cosmetic commonly used by women and children) were analysed to
determine the levels of heavy metals (Pb, Cd, Ni, Cu, Zn, Cr, Co, and Mn) in the products.
Different samples of eye shadow were randomly selected from products available in the shops at
Zaria, Kano and Kaduna markets in Nigeria. After digestion with concentrated acids (HNO3 and
HCl), concentrations of the selected heavy metals were determined in triplicate using a flame
atomic absorption spectrophotometer. Nickel, copper, zinc, cobalt and manganese were detected
in all the colours of eye shadow in varying concentrations. Chromium was also detected in all
the colours except one (Diamond pink). The regulations relating to cosmetics products gave no
limit values for toxic elements such as metals occurring as impurities in cosmetics products.
However, it has been proposed that the levels of nickel, cobalt and chromium should preferably
be less than 170 µgg-1
and Lead should not exceed 20 µgg-1
. 85% of the colours have Ni and Co
concentrations above 170 µgg-1
but Cr concentrations were below this limit in all the colours.
Only 2 brands (3 colours) have lead content higher than 20 µgg-1
. 7 out of 20 colours (35%) of
the brands of eye shadows contain cadmium at low concentrations. It is obvious from the present
study that the use of facial cosmetics like eye shadow exposes users to low levels of heavy metals.
Keywords: Heavy metal; Eye shadow; cosmetics.
______________________________________________________________________________
INTRODUCTION
China is the source of 60 percent of recent cosmetics and other product recalls because of the
presence of heavy metals in levels toxic to human in these products [1]. Some heavy metals have
been used as cosmetics ingredients in the past. Examples include the preservative thimerosal
(mercury), the progressive hair dye lead acetate and a number of tattoo pigments such as red
cinnabar (mercuric sulfide). As the issue of heavy metals as deliberate cosmetics ingredients has
been addressed, attention turns to the presence of these substances as impurities. Eye shadow, a
Omolaoye J.A., et al Arch. Appl. Sci. Res., 2010, 2 (5): 76-84
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cosmetic commonly used by women and children has been reported to contain toxic metals [2,
3]. It is a typical example of a group of cosmetic products in which the significance of pigment is
great. Some toxic elements and their compounds are water-soluble and moist skin can therefore
promote the percutaneous absorption of elements occurring as impurities in pigments [4].
The excipients used also affect the absorption through the skin [5]. On the other hand, eye
shadow is applied dry to the skin, lowering the risk of percutaneous absorption of pigments and
thus also of toxic elements. The skin of the eyelid is thin and eczemas of the eyelids are
common. Absorption of elements into the circulation is possible but percutaneous absorption of
elements is slower than that of fat-soluble substances. Some facial (make-up) cosmetics
commonly used in Nigeria were analyzed for their contents of the heavy metals; lead, cadmium,
chromium, nickel, zinc and iron [6]. The study showed that the continuous use of these cosmetics
may enhance the absorption of especially Cd and Pb during eating for lipsticks and during
sweating for the other facial make-ups. Exposure to lead by dermal contact can contribute to
significant toxicity [7].
The use of leaded eye cosmetics have been observed to be strongly correlated with elevated
blood lead levels [8, 9]. The environmental and public health implications of exposure to lead in
Africa have been reviewed and the use of local herbal remedies and cosmetics has been indicated
as sources of lead exposure [10]. A study of the use of skin lightening creams containing
hydroquinone, corticosteroid and mercury in Nigeria revealed a prevalence of dermatological
side effects with exogenous ochronosis as the commonest [11]. Under arm cosmetics are being
investigated as possible cause of breast cancer. A biological basis for breast carcinogenesis could
result from the ability of the various constituent chemicals to bind to DNA and to promote
growth of the damaged cells [12]. There is a growing concern about the physiological and
behavioural effects of environmental trace metals in human population. The toxicity of lead at
high levels of exposure is well known but a major concern of today is the possibility that
continual exposure to relatively low levels of lead may entail adverse health effects [13].
One study in Italy investigated the connection between children’s makeup with nickel, cobalt and
chromium and skin irritation. They found that children do react to these metals, especially if they
are prone to skin allergies or have damaged skin, such as from scrapes or cuts [14]. The book
Contact Dermatitis, a standard text for specialists in the field, also notes that researchers “have
seen patients with strong nickel sensitivity that seems to have reactions from some cosmetics”
[15].The question of skin reactions to cosmetics is much broader than just face paints. Numerous
other cosmetics have been linked to Dermatitis and allergic reactions, [16] including perfumes,
[17] children’s bath products [18], mascara [19] and other eye-care products, hair dye
(especially in children), [20, 21] facial care products, body care products and shampoo [22].
Fragrance chemicals and preservatives are some of the most significant allergens. One study in
India found that reactions to cosmetics, toiletries and topical applications are the most common
single reason for hospital referrals with allergic contact dermatitis [23]. However, no known
work has been done to investigate the heavy metals content of Chinese eye shadows which are
available in cosmetics shops in Nigeria, hence the need for this study. Therefore, this study was
designed to ascertain the levels of lead, cadmium, chromium, nickel, zinc, copper, cobalt and
manganese in Eye shadow. The samples were collected from Zaria, Kano, and Kaduna markets
in Nigeria.
Omolaoye J.A., et al Arch. Appl. Sci. Res., 2010, 2 (5): 76-84
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MATERIALS AND METHODS
Samples of eye shadow were homogenized in acid washed mortar and pestle. 300mg of the
processed sample was weighed into a beaker for acid digestion. After the digestion and cooling,
the solution was filtered through a Whatman 41 filter to remove the insoluble particles and
brought to a final volume of 50ml with de-ionized water. Blank sample was also prepared
similarly. Glass wares, crucibles and plastic containers were washed with liquid soaps, rinsed
with distilled water and soaked in 10% HNO3 for 24hours; cleaned with distilled-deionized water
and in such a manner that no contamination occurred [24]. Standards were prepared with serial
dilution technique within the range of 0.5-2.5ppm for lead, cadmium, nickel and manganese, 1-
5ppm for copper and cobalt, 0.5-2ppm for zinc and 2-10ppm for chromium. The instrument was
first calibrated with stock solutions of the prepared standards before analysis. The final processed
samples were quantitatively analyzed using Buck Scientific VGP 210 Flame Atomic Absorption
Spectrophotometer. After every five samples analyzed using AAS, the first sample was repeated
for quality check. Only when the results were within 10% of earlier readings did the analysis
proceed further.
RESULTS AND DISCUSSION
The distribution of heavy metals in the Eye shadows studied is shown in Table 1. 7 brands of eye
shadows were randomly selected for analysis but a single brand may contain several colours
which have been analyzed separately. Altogether, the study covered 20 colours of 7 brands,
nickel, copper, zinc, cobalt and manganese were detected in all the colours in varying
concentrations. The concentration of lead and cadmium are generally low compared to other
metals. Chromium was also detected in all the colours except one (Diamond pink). The lowest
concentration for lead and cadmium were below the detection limit (3 colours for Pb and 13
colours for Cd). In the majority of the products, the lead content was lower than 20 µgg-1
. Only 2
brands (3 colours) have lead content higher than 20µgg-1
. 7 out of 20 colours (35%) of the brands
of eye shadows contain cadmium at low concentrations. The fact that cadmium and lead were not
detected in some of the products shows that it is possible to eliminate these impurities from eye
shadows.
The regulations relating to cosmetics products gave no limit values for toxic elements such as
metals occurring as impurities in cosmetics products. However, it has been proposed that the
levels of nickel, cobalt and chromium should preferably be less than 170 µgg-1
and lead should
not exceed 20 µgg-1
[5]. Some of the colours analyzed have concentrations of nickel, cobalt and
chromium above this limit. For nickel, only 4 colours ((Diamond(Pink), Qiany(White),
Midle(Purple) and Qianny(White)) have concentration below 200 µgg-1
. The highest nickel
concentrations were measured in Ladyhood (Brown (359.44 µgg-1
), Yellow (306.67 µgg-1
),
Darkgrey (285.00 µgg-1
) and Purple (359.44 µgg-1
). The levels of nickel were generally higher
than those of other metals.
Copper contents were generally low except in FBI (blue). This shows that Cu might have been
used as a pigment in this particular colour because another colour (Ash) of the same product had
copper content as low as 27.78 µgg-1
. 6 out of the 20 colours studied have zinc content below
200 µgg-1
. The highest levels of zinc were observed in 2 brands of the eye shadows (Ladyhood
Omolaoye J.A., et al Arch. Appl. Sci. Res., 2010, 2 (5): 76-84
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and Diamond). In Ladyhood [Yellow (305 µgg-1
), Darkgrey (342.22 µgg-1
), and Purple (332.22
µgg-1
)], In Diamond [Pink (318.89 µgg-1
), and Blue (334.44 µgg-1
)].
The chromium concentrations were generally below 100 µgg-1
except in Qiany (Black (150 µgg-
1
) and Brown (133.33 µgg-1
)]. Chromium was below detection limit in Diamond (Pink). The
levels of chromium are generally within the acceptable limit. Cobalt concentrations were higher
than 200 µgg-1
in 45% of the colours. The lowest Cobalt concentration was observed in Diamond
(blue) while its highest concentration was observed in Shas (Army green). Only 3 out 20 colours
(15%) of the eye shadows had manganese content higher than 100 µgg-1
. This implies that
manganese content were generally low in the products.
Analysis of Variance (ANOVA) (Table 2-Table 4) was done on each brand of the eye shadow to
see if there is significant variation in the concentrations of heavy metals in different colours of
each brand. In Ladyhood, there is significant difference in the levels of nickel in all the four
colours analyzed. This shows that the type of pigment used in eye shadow contributes to its
heavy metal content. In Diamond, four colours were also analyzed and the concentrations of
nickel and zinc show significant differences of these metals in the colours. Other metals also
show significant differences (P< 0.05).
The concentrations of 5 metals (lead, cobalt, nickel, chromium and arsenic) were determined in
25 brands of eye shadows [2]. The levels of these metals observed were generally lower than
those observed in this study except for chromium. The highest concentration of chromium
obtained was 5470 µgg-1
which is far higher than the highest obtained in this study. Some facial
cosmetics available in Nigeria were also analyzed for their contents of heavy metals (lead,
cadmium, chromium, nickel, zinc and iron) [6]. The results obtained are comparable to that
obtained in this study. High levels of nickel, zinc and iron were observed as observed in this
study.
The campaign for safe cosmetics published a report on heavy metals in face paints [25]. All the
10 products studied contained lead, 4 contained nickel, 2 contained cobalt and 5 contained
chromium (ranging from 1.6 to 120ppm). The levels found in all the products exceeded the
recommendation of several industries [26]. The metals analyzed in this study are not listed as
ingredients on any of the products. Due to a lack of manufacturer testing and regulatory
oversight, it is possible that the companies are not even aware that the products are
contaminated. These contaminants likely get into the products when poor-quality ingredients are
used. Most likely the metals are contaminants from one or more of the inorganic base materials.
Since all the metals are found in various environments, manufacturers would have to test the raw
ingredients before they are assembled into the final products in order to track the origin of these
contaminants.
Eczema of the eyelids is common and may be caused by cosmetics. Mascara, eye-liner, eye
shadow, and eyebrow pencil or powders are the most commonly used eye make-ups [15]. The
metals which may be present in the colouring agents are often overlooked as causes of allergic
contact dermatitis of the eyelids. Eye shadow should not be applied to broken skin. Eye shadows
contain particles which differ in size and have various types of edges. The eyelids can therefore
be mechanically broken, enabling the penetration of pigment and thus also of metals into the
Omolaoye J.A., et al Arch. Appl. Sci. Res., 2010, 2 (5): 76-84
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body. Metals are also absorbed into the organism through healthy skin [4]. Although absorption
of metals through the skin is often ignored, studies show that lead actually can be absorbed
through the skin [27]. One study found that skin-absorbed lead can be detected in sweat, blood
and urine within six hours of skin application [28] though more research is needed in other to
understand just how skin absorbed lead is distributed in the body. In a study of nine adult males
who applied hair dye containing lead acetate for 90 days, it was found that seven out of nine of
them had elevated lead levels in hair on other parts of their bodies [29].
Three of the metals found in this study-nickel, cobalt and chromium-are well known triggers for
contact dermatitis [30]. These metals are widely understood to be skin allergens in children [31].
Though the number of scientific studies on Allergic Contact Dermatitis in children is growing,
routine testing at doctors’ offices is infrequent. As a result, children are often misdiagnosed with
eczema or other health problems and treated with unnecessary pharmaceuticals [32].
Understanding the consequences of low level human lead poisoning will depend upon an
accurate assessment of the pervasiveness of toxicity in the global population. This will require
that toxicity thresholds be determined as well as an understanding of the mechanisms underlying
toxicity [33].
Table 2: Duncan’s one way Analysis of Variance (ANOVA) of Means for heavy metal concentration
(ugg-1
) in different colours of Ladyhood brand of eye shadow.
Metals Ladyhood ( Sample colours)
Brown Yellow Darkgrey Purple
Pb 12.22ab
8.33a
15.56bc
18.89c
Cd 2.78a
NDb
8.89 1.67ab
Ni 359.44a
306.67b
285.00c
359.44d
Cu 5.56a
21.11b
1.67a
21.67b
Zn 83.33a
305.00b
342.22c
332.22c
Cr 38.89ab
61.11bc
83.33c
33.33a
Co 217.22a
122.78b
192.77c
221.11a
Mn 37.78a
270.56b
63.33c
42.78ac
ND-Not Detected
(P<0.05); Means with the same superscript in the same row are not significantly different.
Omolaoye J.A., et al Arch. Appl. Sci. Res., 2010, 2 (5): 76-84
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Table 1: Mean (+SD) heavy metal concentration (ugg-1
) in Eye shadow
Samples Metals
Brand Colour Pb Cd Ni Cu Zn Cr Co Mn
Ladyhood Brown 12.22±1.92 2.78±0.96 359.44±5.85 5.56±1.92 83.33±6.01 38.89±19.24 217.22±4.19 37.78±0.96
Yellow 8.33±1.67 0.00±0.00 306.67±4.41 21.11±1.92 305.00±6.01 61.11±9.62 122.78±9.08 270.56±22.38
Darkgrey 15.56±2.55 8.89±1.92 285.00±4.41 1.67±0.00 342.22±13.57 83.33±16.67 192.77±17.51 63.33±6.01
Purple 18.89±2.55 1.67±0.00 359.44±3.85 21.67±4.41 332.22±8.22 33.33±0.00 221.11±5.09 42.78±5.36
Diamond Pink 55.00±11.67 6.67±1.67 153.89±5.85 18.89±0.46 318.89±8.39 ND 217.78±2.55 30.56±5.85
Blue 46.67±5.00 3.33±0.00 230.56±19.53 75.56±3.47 334.44±10.72 16.67±0.00 162.78±18.58 25.56±3.47
Green 19.44±4.19 3.89±1.92 282±1.97 136.67±19.65 211.67±7.64 22.22±9.62 176.67±4.41 15.00±3.33
Golden
Brown
11.11±0.96 ND 206.67±3.33 4.44±0.96 103.33±4.41 51.67±6.01 190.56±5.09 59.44±4.19
Qiany1 White 12.22±2.55 ND 80.56±5.36 1.67±0.00 109.44±7.51 38.89±9.62 253.33±6.67 67.22±10.84
Black 6.11±2.55 ND 350.00±1.67 6.11±0.96 81.67±3.33 150.00±16.67 200.56±11.10 131.11±23.82
Brown 12.78±2.55 ND 213.33±10.41 8.89±1.93 112.78±2.55 133.33±33.33 188.33±3.33 95.00±9.28
Pink 13.89±2.55 ND 217.22±21.43 3.89±0.96 28.33±1.67 33.33±0.00 184.44±4.81 56.11±4.81
Shas Army
green
ND ND 228.89±2.55 88.98±19.20 208.89±6.94 72.22±9.62 258.33±6.01 32.22±2.55
Brown ND ND 227.2±21.1 21.11±2.55 210.56±5.09 77.8±19.20 201.11±5.09 36.67±2.89
Midle Purple ND ND 192.22±3.47 8.33±1.67 274.40±17.70 22.22±9.62 190.00±10.10 27.78±3.47
Light
Yellow
23.33±1.67 ND 262.22±1.92 2.22±0.96 288.89±5.09 44.44±9.62 167.78±6.94 58.33±4.41
Qianny White 17.78±2.55 ND 77.22±3.47 1.67±0.00 208.30±10.40 33.33±0.00 197.78±5.85 50.00±8.82
Light
Brown
8.89±1.92 ND 352.22±5.09 137.22±9.18 203.33±1.67 122.22±9.62 211.11±6.94 107.22±1.92
FBI Blue 5.00±0.00 4.44±0.96 278.89±6.31 465.00±5.00 257.20±17.80 16.67±0.00 201.11±6.74 34.44±2.55
Ash 9.44±0.96 ND 222.78±3.47 27.78±2.55 218.30±20.20 27.78±9.62 193.33±9.28 32.22±0.96
Omolaoye J.A., et al Arch. Appl. Sci. Res., 2010, 2 (5): 76-84
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Table 3: Duncan’s one way Analysis of Variance (ANOVA) of Means for heavy metal concentration
(ugg-1
) in different colours of Diamond brand of eye shadow.
Metals Diamond ( Sample colours)
Pink Blue Green Golden Brown
Pb 55.00a
46.67a
19.44b
11.11b
Cd 6.67a
3.33b
3.89b
NDab
Ni 153.89a
230.56b
282.22c
206.67d
Cu 18.89a
75.56b
136.67c
4.44a
Zn 318.89a
334.44b
211.67c
103.33d
Cr NDa
16.67a
22.22a
51.67b
Co 217.78a
162.78b
176.67bc
190.56c
Mn 30.56a
25.56a
15.00b
59.44c
ND-Not Detected
(P<0.05); Means with the same superscript in the same row are not significantly different.
Table 4: Duncan’s one way Analysis of Variance (ANOVA) of Means for heavy metal concentration
(ugg-1
) in different colours of Qiany brand of eye shadow.
Metals Qiany ( Sample colours)
Brown Yellow Darkgrey Purple
Pb 12.22ab
6.11b
12.78a
13.89a
Cd NDa
NDa
NDa
NDa
Ni 80.56a
350.00b
213.33c
217.22c
Cu 1.67a
6.11b
8.89c
3.89d
Zn 109.44a
81.67b
112.78a
28.33c
Cr 38.89a
150.00b
133.33b
33.33a
Co 253.33a
200.56.b
188.33bc
184.44c
Mn 67.22a
131.11b
95.00c
56.11a
ND-Not Detected
(P<0.05); Means with the same superscript in the same row are not significantly different.
CONCLUSION
It is obvious from the present study that the use of facial cosmetics like eye shadow exposes
users to low levels of heavy metals. Continuous use of these cosmetics could result in an increase
in the heavy metal level in human body beyond acceptable limits.
Acknowledgement
The authors are indebted to Mrs Iyun of Ahmadu Bello University, Zaria and Mr Muacu of
Kaduna State University, Nigeria for their technical assistance.
Omolaoye J.A., et al Arch. Appl. Sci. Res., 2010, 2 (5): 76-84
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[15] Rietschel, R.L., Fowler, J.F. and Fisher, A.A., Fisher’s Contact Dermatitis, Sixth Edition.
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[29] Mazuli, F.N., Watlington, P.M. and Maibach, H.I., Curr Probl Dermatol, 7: (1978), 196-
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21-23.

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Heavy Metal Assessment of Some Eye Shadow

  • 1. Available online at www.scholarsresearchlibrary.com Scholars Research Library Archives of Applied Science Research, 2010, 2 (5): 76-84 (http://scholarsresearchlibrary.com/archive.html) ISSN 0975-508X CODEN (USA) AASRC9 76 Scholar Research Library Heavy metal assessment of some eye shadow products imported into Nigeria from China *Omolaoye J.A., Uzairu A., and Gimba C.E. Chemistry Department, Ahmadu Bello University Zaria, Nigeria _____________________________________________________________________________ ABSTRACT Chinese made eye shadows (cosmetic commonly used by women and children) were analysed to determine the levels of heavy metals (Pb, Cd, Ni, Cu, Zn, Cr, Co, and Mn) in the products. Different samples of eye shadow were randomly selected from products available in the shops at Zaria, Kano and Kaduna markets in Nigeria. After digestion with concentrated acids (HNO3 and HCl), concentrations of the selected heavy metals were determined in triplicate using a flame atomic absorption spectrophotometer. Nickel, copper, zinc, cobalt and manganese were detected in all the colours of eye shadow in varying concentrations. Chromium was also detected in all the colours except one (Diamond pink). The regulations relating to cosmetics products gave no limit values for toxic elements such as metals occurring as impurities in cosmetics products. However, it has been proposed that the levels of nickel, cobalt and chromium should preferably be less than 170 µgg-1 and Lead should not exceed 20 µgg-1 . 85% of the colours have Ni and Co concentrations above 170 µgg-1 but Cr concentrations were below this limit in all the colours. Only 2 brands (3 colours) have lead content higher than 20 µgg-1 . 7 out of 20 colours (35%) of the brands of eye shadows contain cadmium at low concentrations. It is obvious from the present study that the use of facial cosmetics like eye shadow exposes users to low levels of heavy metals. Keywords: Heavy metal; Eye shadow; cosmetics. ______________________________________________________________________________ INTRODUCTION China is the source of 60 percent of recent cosmetics and other product recalls because of the presence of heavy metals in levels toxic to human in these products [1]. Some heavy metals have been used as cosmetics ingredients in the past. Examples include the preservative thimerosal (mercury), the progressive hair dye lead acetate and a number of tattoo pigments such as red cinnabar (mercuric sulfide). As the issue of heavy metals as deliberate cosmetics ingredients has been addressed, attention turns to the presence of these substances as impurities. Eye shadow, a
  • 2. Omolaoye J.A., et al Arch. Appl. Sci. Res., 2010, 2 (5): 76-84 _____________________________________________________________________________________ 77 Scholar Research Library cosmetic commonly used by women and children has been reported to contain toxic metals [2, 3]. It is a typical example of a group of cosmetic products in which the significance of pigment is great. Some toxic elements and their compounds are water-soluble and moist skin can therefore promote the percutaneous absorption of elements occurring as impurities in pigments [4]. The excipients used also affect the absorption through the skin [5]. On the other hand, eye shadow is applied dry to the skin, lowering the risk of percutaneous absorption of pigments and thus also of toxic elements. The skin of the eyelid is thin and eczemas of the eyelids are common. Absorption of elements into the circulation is possible but percutaneous absorption of elements is slower than that of fat-soluble substances. Some facial (make-up) cosmetics commonly used in Nigeria were analyzed for their contents of the heavy metals; lead, cadmium, chromium, nickel, zinc and iron [6]. The study showed that the continuous use of these cosmetics may enhance the absorption of especially Cd and Pb during eating for lipsticks and during sweating for the other facial make-ups. Exposure to lead by dermal contact can contribute to significant toxicity [7]. The use of leaded eye cosmetics have been observed to be strongly correlated with elevated blood lead levels [8, 9]. The environmental and public health implications of exposure to lead in Africa have been reviewed and the use of local herbal remedies and cosmetics has been indicated as sources of lead exposure [10]. A study of the use of skin lightening creams containing hydroquinone, corticosteroid and mercury in Nigeria revealed a prevalence of dermatological side effects with exogenous ochronosis as the commonest [11]. Under arm cosmetics are being investigated as possible cause of breast cancer. A biological basis for breast carcinogenesis could result from the ability of the various constituent chemicals to bind to DNA and to promote growth of the damaged cells [12]. There is a growing concern about the physiological and behavioural effects of environmental trace metals in human population. The toxicity of lead at high levels of exposure is well known but a major concern of today is the possibility that continual exposure to relatively low levels of lead may entail adverse health effects [13]. One study in Italy investigated the connection between children’s makeup with nickel, cobalt and chromium and skin irritation. They found that children do react to these metals, especially if they are prone to skin allergies or have damaged skin, such as from scrapes or cuts [14]. The book Contact Dermatitis, a standard text for specialists in the field, also notes that researchers “have seen patients with strong nickel sensitivity that seems to have reactions from some cosmetics” [15].The question of skin reactions to cosmetics is much broader than just face paints. Numerous other cosmetics have been linked to Dermatitis and allergic reactions, [16] including perfumes, [17] children’s bath products [18], mascara [19] and other eye-care products, hair dye (especially in children), [20, 21] facial care products, body care products and shampoo [22]. Fragrance chemicals and preservatives are some of the most significant allergens. One study in India found that reactions to cosmetics, toiletries and topical applications are the most common single reason for hospital referrals with allergic contact dermatitis [23]. However, no known work has been done to investigate the heavy metals content of Chinese eye shadows which are available in cosmetics shops in Nigeria, hence the need for this study. Therefore, this study was designed to ascertain the levels of lead, cadmium, chromium, nickel, zinc, copper, cobalt and manganese in Eye shadow. The samples were collected from Zaria, Kano, and Kaduna markets in Nigeria.
  • 3. Omolaoye J.A., et al Arch. Appl. Sci. Res., 2010, 2 (5): 76-84 _____________________________________________________________________________________ 78 Scholar Research Library MATERIALS AND METHODS Samples of eye shadow were homogenized in acid washed mortar and pestle. 300mg of the processed sample was weighed into a beaker for acid digestion. After the digestion and cooling, the solution was filtered through a Whatman 41 filter to remove the insoluble particles and brought to a final volume of 50ml with de-ionized water. Blank sample was also prepared similarly. Glass wares, crucibles and plastic containers were washed with liquid soaps, rinsed with distilled water and soaked in 10% HNO3 for 24hours; cleaned with distilled-deionized water and in such a manner that no contamination occurred [24]. Standards were prepared with serial dilution technique within the range of 0.5-2.5ppm for lead, cadmium, nickel and manganese, 1- 5ppm for copper and cobalt, 0.5-2ppm for zinc and 2-10ppm for chromium. The instrument was first calibrated with stock solutions of the prepared standards before analysis. The final processed samples were quantitatively analyzed using Buck Scientific VGP 210 Flame Atomic Absorption Spectrophotometer. After every five samples analyzed using AAS, the first sample was repeated for quality check. Only when the results were within 10% of earlier readings did the analysis proceed further. RESULTS AND DISCUSSION The distribution of heavy metals in the Eye shadows studied is shown in Table 1. 7 brands of eye shadows were randomly selected for analysis but a single brand may contain several colours which have been analyzed separately. Altogether, the study covered 20 colours of 7 brands, nickel, copper, zinc, cobalt and manganese were detected in all the colours in varying concentrations. The concentration of lead and cadmium are generally low compared to other metals. Chromium was also detected in all the colours except one (Diamond pink). The lowest concentration for lead and cadmium were below the detection limit (3 colours for Pb and 13 colours for Cd). In the majority of the products, the lead content was lower than 20 µgg-1 . Only 2 brands (3 colours) have lead content higher than 20µgg-1 . 7 out of 20 colours (35%) of the brands of eye shadows contain cadmium at low concentrations. The fact that cadmium and lead were not detected in some of the products shows that it is possible to eliminate these impurities from eye shadows. The regulations relating to cosmetics products gave no limit values for toxic elements such as metals occurring as impurities in cosmetics products. However, it has been proposed that the levels of nickel, cobalt and chromium should preferably be less than 170 µgg-1 and lead should not exceed 20 µgg-1 [5]. Some of the colours analyzed have concentrations of nickel, cobalt and chromium above this limit. For nickel, only 4 colours ((Diamond(Pink), Qiany(White), Midle(Purple) and Qianny(White)) have concentration below 200 µgg-1 . The highest nickel concentrations were measured in Ladyhood (Brown (359.44 µgg-1 ), Yellow (306.67 µgg-1 ), Darkgrey (285.00 µgg-1 ) and Purple (359.44 µgg-1 ). The levels of nickel were generally higher than those of other metals. Copper contents were generally low except in FBI (blue). This shows that Cu might have been used as a pigment in this particular colour because another colour (Ash) of the same product had copper content as low as 27.78 µgg-1 . 6 out of the 20 colours studied have zinc content below 200 µgg-1 . The highest levels of zinc were observed in 2 brands of the eye shadows (Ladyhood
  • 4. Omolaoye J.A., et al Arch. Appl. Sci. Res., 2010, 2 (5): 76-84 _____________________________________________________________________________________ 79 Scholar Research Library and Diamond). In Ladyhood [Yellow (305 µgg-1 ), Darkgrey (342.22 µgg-1 ), and Purple (332.22 µgg-1 )], In Diamond [Pink (318.89 µgg-1 ), and Blue (334.44 µgg-1 )]. The chromium concentrations were generally below 100 µgg-1 except in Qiany (Black (150 µgg- 1 ) and Brown (133.33 µgg-1 )]. Chromium was below detection limit in Diamond (Pink). The levels of chromium are generally within the acceptable limit. Cobalt concentrations were higher than 200 µgg-1 in 45% of the colours. The lowest Cobalt concentration was observed in Diamond (blue) while its highest concentration was observed in Shas (Army green). Only 3 out 20 colours (15%) of the eye shadows had manganese content higher than 100 µgg-1 . This implies that manganese content were generally low in the products. Analysis of Variance (ANOVA) (Table 2-Table 4) was done on each brand of the eye shadow to see if there is significant variation in the concentrations of heavy metals in different colours of each brand. In Ladyhood, there is significant difference in the levels of nickel in all the four colours analyzed. This shows that the type of pigment used in eye shadow contributes to its heavy metal content. In Diamond, four colours were also analyzed and the concentrations of nickel and zinc show significant differences of these metals in the colours. Other metals also show significant differences (P< 0.05). The concentrations of 5 metals (lead, cobalt, nickel, chromium and arsenic) were determined in 25 brands of eye shadows [2]. The levels of these metals observed were generally lower than those observed in this study except for chromium. The highest concentration of chromium obtained was 5470 µgg-1 which is far higher than the highest obtained in this study. Some facial cosmetics available in Nigeria were also analyzed for their contents of heavy metals (lead, cadmium, chromium, nickel, zinc and iron) [6]. The results obtained are comparable to that obtained in this study. High levels of nickel, zinc and iron were observed as observed in this study. The campaign for safe cosmetics published a report on heavy metals in face paints [25]. All the 10 products studied contained lead, 4 contained nickel, 2 contained cobalt and 5 contained chromium (ranging from 1.6 to 120ppm). The levels found in all the products exceeded the recommendation of several industries [26]. The metals analyzed in this study are not listed as ingredients on any of the products. Due to a lack of manufacturer testing and regulatory oversight, it is possible that the companies are not even aware that the products are contaminated. These contaminants likely get into the products when poor-quality ingredients are used. Most likely the metals are contaminants from one or more of the inorganic base materials. Since all the metals are found in various environments, manufacturers would have to test the raw ingredients before they are assembled into the final products in order to track the origin of these contaminants. Eczema of the eyelids is common and may be caused by cosmetics. Mascara, eye-liner, eye shadow, and eyebrow pencil or powders are the most commonly used eye make-ups [15]. The metals which may be present in the colouring agents are often overlooked as causes of allergic contact dermatitis of the eyelids. Eye shadow should not be applied to broken skin. Eye shadows contain particles which differ in size and have various types of edges. The eyelids can therefore be mechanically broken, enabling the penetration of pigment and thus also of metals into the
  • 5. Omolaoye J.A., et al Arch. Appl. Sci. Res., 2010, 2 (5): 76-84 _____________________________________________________________________________________ 80 Scholar Research Library body. Metals are also absorbed into the organism through healthy skin [4]. Although absorption of metals through the skin is often ignored, studies show that lead actually can be absorbed through the skin [27]. One study found that skin-absorbed lead can be detected in sweat, blood and urine within six hours of skin application [28] though more research is needed in other to understand just how skin absorbed lead is distributed in the body. In a study of nine adult males who applied hair dye containing lead acetate for 90 days, it was found that seven out of nine of them had elevated lead levels in hair on other parts of their bodies [29]. Three of the metals found in this study-nickel, cobalt and chromium-are well known triggers for contact dermatitis [30]. These metals are widely understood to be skin allergens in children [31]. Though the number of scientific studies on Allergic Contact Dermatitis in children is growing, routine testing at doctors’ offices is infrequent. As a result, children are often misdiagnosed with eczema or other health problems and treated with unnecessary pharmaceuticals [32]. Understanding the consequences of low level human lead poisoning will depend upon an accurate assessment of the pervasiveness of toxicity in the global population. This will require that toxicity thresholds be determined as well as an understanding of the mechanisms underlying toxicity [33]. Table 2: Duncan’s one way Analysis of Variance (ANOVA) of Means for heavy metal concentration (ugg-1 ) in different colours of Ladyhood brand of eye shadow. Metals Ladyhood ( Sample colours) Brown Yellow Darkgrey Purple Pb 12.22ab 8.33a 15.56bc 18.89c Cd 2.78a NDb 8.89 1.67ab Ni 359.44a 306.67b 285.00c 359.44d Cu 5.56a 21.11b 1.67a 21.67b Zn 83.33a 305.00b 342.22c 332.22c Cr 38.89ab 61.11bc 83.33c 33.33a Co 217.22a 122.78b 192.77c 221.11a Mn 37.78a 270.56b 63.33c 42.78ac ND-Not Detected (P<0.05); Means with the same superscript in the same row are not significantly different.
  • 6. Omolaoye J.A., et al Arch. Appl. Sci. Res., 2010, 2 (5): 76-84 _____________________________________________________________________________________ 81 Scholar Research Library Table 1: Mean (+SD) heavy metal concentration (ugg-1 ) in Eye shadow Samples Metals Brand Colour Pb Cd Ni Cu Zn Cr Co Mn Ladyhood Brown 12.22±1.92 2.78±0.96 359.44±5.85 5.56±1.92 83.33±6.01 38.89±19.24 217.22±4.19 37.78±0.96 Yellow 8.33±1.67 0.00±0.00 306.67±4.41 21.11±1.92 305.00±6.01 61.11±9.62 122.78±9.08 270.56±22.38 Darkgrey 15.56±2.55 8.89±1.92 285.00±4.41 1.67±0.00 342.22±13.57 83.33±16.67 192.77±17.51 63.33±6.01 Purple 18.89±2.55 1.67±0.00 359.44±3.85 21.67±4.41 332.22±8.22 33.33±0.00 221.11±5.09 42.78±5.36 Diamond Pink 55.00±11.67 6.67±1.67 153.89±5.85 18.89±0.46 318.89±8.39 ND 217.78±2.55 30.56±5.85 Blue 46.67±5.00 3.33±0.00 230.56±19.53 75.56±3.47 334.44±10.72 16.67±0.00 162.78±18.58 25.56±3.47 Green 19.44±4.19 3.89±1.92 282±1.97 136.67±19.65 211.67±7.64 22.22±9.62 176.67±4.41 15.00±3.33 Golden Brown 11.11±0.96 ND 206.67±3.33 4.44±0.96 103.33±4.41 51.67±6.01 190.56±5.09 59.44±4.19 Qiany1 White 12.22±2.55 ND 80.56±5.36 1.67±0.00 109.44±7.51 38.89±9.62 253.33±6.67 67.22±10.84 Black 6.11±2.55 ND 350.00±1.67 6.11±0.96 81.67±3.33 150.00±16.67 200.56±11.10 131.11±23.82 Brown 12.78±2.55 ND 213.33±10.41 8.89±1.93 112.78±2.55 133.33±33.33 188.33±3.33 95.00±9.28 Pink 13.89±2.55 ND 217.22±21.43 3.89±0.96 28.33±1.67 33.33±0.00 184.44±4.81 56.11±4.81 Shas Army green ND ND 228.89±2.55 88.98±19.20 208.89±6.94 72.22±9.62 258.33±6.01 32.22±2.55 Brown ND ND 227.2±21.1 21.11±2.55 210.56±5.09 77.8±19.20 201.11±5.09 36.67±2.89 Midle Purple ND ND 192.22±3.47 8.33±1.67 274.40±17.70 22.22±9.62 190.00±10.10 27.78±3.47 Light Yellow 23.33±1.67 ND 262.22±1.92 2.22±0.96 288.89±5.09 44.44±9.62 167.78±6.94 58.33±4.41 Qianny White 17.78±2.55 ND 77.22±3.47 1.67±0.00 208.30±10.40 33.33±0.00 197.78±5.85 50.00±8.82 Light Brown 8.89±1.92 ND 352.22±5.09 137.22±9.18 203.33±1.67 122.22±9.62 211.11±6.94 107.22±1.92 FBI Blue 5.00±0.00 4.44±0.96 278.89±6.31 465.00±5.00 257.20±17.80 16.67±0.00 201.11±6.74 34.44±2.55 Ash 9.44±0.96 ND 222.78±3.47 27.78±2.55 218.30±20.20 27.78±9.62 193.33±9.28 32.22±0.96
  • 7. Omolaoye J.A., et al Arch. Appl. Sci. Res., 2010, 2 (5): 76-84 _____________________________________________________________________________________ 82 Scholar Research Library Table 3: Duncan’s one way Analysis of Variance (ANOVA) of Means for heavy metal concentration (ugg-1 ) in different colours of Diamond brand of eye shadow. Metals Diamond ( Sample colours) Pink Blue Green Golden Brown Pb 55.00a 46.67a 19.44b 11.11b Cd 6.67a 3.33b 3.89b NDab Ni 153.89a 230.56b 282.22c 206.67d Cu 18.89a 75.56b 136.67c 4.44a Zn 318.89a 334.44b 211.67c 103.33d Cr NDa 16.67a 22.22a 51.67b Co 217.78a 162.78b 176.67bc 190.56c Mn 30.56a 25.56a 15.00b 59.44c ND-Not Detected (P<0.05); Means with the same superscript in the same row are not significantly different. Table 4: Duncan’s one way Analysis of Variance (ANOVA) of Means for heavy metal concentration (ugg-1 ) in different colours of Qiany brand of eye shadow. Metals Qiany ( Sample colours) Brown Yellow Darkgrey Purple Pb 12.22ab 6.11b 12.78a 13.89a Cd NDa NDa NDa NDa Ni 80.56a 350.00b 213.33c 217.22c Cu 1.67a 6.11b 8.89c 3.89d Zn 109.44a 81.67b 112.78a 28.33c Cr 38.89a 150.00b 133.33b 33.33a Co 253.33a 200.56.b 188.33bc 184.44c Mn 67.22a 131.11b 95.00c 56.11a ND-Not Detected (P<0.05); Means with the same superscript in the same row are not significantly different. CONCLUSION It is obvious from the present study that the use of facial cosmetics like eye shadow exposes users to low levels of heavy metals. Continuous use of these cosmetics could result in an increase in the heavy metal level in human body beyond acceptable limits. Acknowledgement The authors are indebted to Mrs Iyun of Ahmadu Bello University, Zaria and Mr Muacu of Kaduna State University, Nigeria for their technical assistance.
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