SCREENING TOXIC METAL IN COSMETIC

Chai Mui Man

Bachelor of Education with Honours

TP 983

(Chemistry) 2005

C434 2005

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Pusat Khidmat Makfumat Akad UNIVERSITI MALAYSIA SARA'

94"'00 KOla Samarahan

SCREENING TOXIC METAL IN COSMETIC

P.KHIDMAT MAKLUMAT AKADEMIK UNIMAS

1111111111111111111111111 1000133724

CHAIMUIMAN

This dissertation is submitted in partial fulfillment of the requirements for the degree of

Bachelor of Education with Hours in Chemistry

Faculty of Resource Sciences and Technology

UNIVERSITI MALAYSIA SARAWAK

March 2005

DECLARATION

No portion of the work referred to in this dissertation has been submitted in support of an

application for another degree of qualification of this or any university or institution of

higher learning.

Chai Mui Man Programme of Resource Chemistry Facul ty of Resource Science and Technology Universiti Malaysia Saniwak

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ACKNOWLEDGEMENT

Special thanks to my supervisor, Miss Devagi alp Kanakaraju and co-supervisor, Madam

Sim Siong Fong for there advise, guidance and constructive criticism throughout this

re earch. I also would like to gratefully thank the lab assistants especially Mr. Send Takuk

and Mr. Zahina Bidi for their help and assist.

My acknowledgement would not be completed without mentioning my family for their

positive encouragement, mental and financial support.

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ACKNOWLEDGEMENT

TABLE OF CONTENT

LIST OF TABLE

LIST OF FIGURE

ABSTRACT

CHAPTER ONE

CHAPTER TWO

CHAPTER THREE

TABLE OF CONTENTS

III

IV-V

VI

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INTRODUCTION 2-4

LITERATURE REVIEW 5-8

MATERIAL AND METHODS

3.1 Sample Collection 9

3.2 Digestion procedure 11

3.2.1 Compact Powder 11 and Foundation

3.2.2 Lipstick 11

3.3 Sample Analysis 12

3.4 Statistical Analysis 12

IV

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CHAPTER FOUR RESULT AND DISCUSSION

4.1 Metal concentration in 13 cosmetic product against regulation

4.2 Comparison of metal 14-15 concentration in cosmetic products against manufacturing country

4.3 Comparison of mean concentration 16-18 between low and high price cosmetic products

CHAPTER FIVE CONCLUSION AND RECOMMENDATION 19-20

REFERENCES 21-22

APPENDICES

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Table 2.1:

Table 3.1:

Table 4.1:

Table 4.2:

Table 4.3:

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LIST OF TABLE

Effect of metals and other ingredients found in cosmetic products 6

Detail of the cosmetic samples analyzed

The recommended permissible limit for selected metals 14

Mean metal concentration in cosmetic samples from 16 different countries

Mean metal concentration between low and high price 19 cosmetic samples

VI

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LIST OF FIGURE

Figure 4.1: Comparison of mean concentration of Pb in cosmetic 15 sample with recommended limit

Figure 4.2: Metals concentration in cosmetic products in 16 different countries

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Screening Heavy Metal In Cosmetics

Chai Mui Man

Programme of Resource Chemistry Falculty of Resource Science and Technology

Universiti Malaysia Sarawak

ABSTRACT

Three different types of commercially available cosmetic products namely compact powder, foundation and lipstick obtained from the local shops in Sarawak were analyzed for their heavy metal contents. Wet digestion method was employed to all samples and subsequently analyzed for toxic metals (Pb, Zn, Co, Cu) by using FAAS. The results indicated that Zn is the common metal present in the entire cosmetic products. The concentration of Pb in all cosmetic samples was found to be in the safe level. As compared between countries, the highest concentration ofZn was detected in compact powder from Indonesia. Cu present only in compact powder from Malaysia in trace amount. No Cu found in foundation and lipstick samples at any price. Analysis of metals for compact powder with low price showed that the samples from china have the same content of metal detected (Pb, Co, Cu) with Indonesia samples (Zn, Co, Cu) and the least in the standard sample, A von (Zn, Cu). There was no significant trend observed for the heavy metal contents in all types ofcosmetic samples from different countries and price range.

Key words: Heavy metal, compact powder, foundation , lipstick, wet digestion

ABSTRAK

Tiga jenis sampel kosmetik iaitu bedak pad at, krim asas dan gincu yang boleh didapati di pasaran Sarawak telah dianalisis bagi penentuan kandungan logam berat Sampel yang dikaji telah dihadam melalui proses peghadaman berasid dan seterusnya dianalisis dengan Spektroskopi Serapan Atom Nyala bagi menentukan kepekatan logam berat ( Pb, Zn, Co, Cu) yang hadir dalam setiap sampel. Keputusan yang diperolehi menunjukkan bahawa Zn ialah logam yang biasanya hadir dalam semua produk kosmetik. Kepekatan logam Pb pula didapati berada dalam tahap yang selamat dalam semua sampel yang dianalisis. Perbandingan antara negara pula menunjukkan kandungan Zn yang tinggi dalam bedak Indonesia. Cu hanya terdapat dalam sampel Malaysia sahaja. Cu tidak terdapat dalam sam pel krim asas dan gincu walaupun dalam harga tinggi atau rendah. Oaripada analisis, didapati bahawa bedak padat China mempunyai bilangan logam berat (Pb, Co, Cu) yang sarna dengan Indonesia (Zn, Co, Cu) dan paling kurang dalam standard (Zn, Cu). Tren yang signifikan tidak diperolehi bagi kandungan logam berat dalam semua produk kosmetik yang dianalisis dari negara yang berlainan dan harga tinggi dan rendah.

Kata kund: Logam Berat, bedak padat, krim asas, gincu, penghadaman basah.

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CHAPTER ONE

INTRODUCTION

To date, there are a lot of cosmetic products available in the market and new products

are also mushrooming the Malaysia cosmetic market whether it is produced locally or

those imported ones. Cosmetics products are getting very popular and have become

part and parcel among working women and housewives in Malaysia. There are

different types of cosmetic products that are available in the market with different

range of brands, prices and manufacturing countries. The Food, Drug, and Cosmetic

Act section 201 (i), defines cosmetics, as "articles intended to be rubbed, poured,

sprinkled, or sprayed on, introduced into, or otherwise applied to the human body for

cleansing, beautifying, promoting attractiveness, or altering the appearance". Among

the products included in this definition are skin moisturizers, perfumes, lipsticks,

fingernail polishes, eye and facial makeup preparations, shampoos, permanent waves,

hair colors toothpastes, and deodorants, as well as any material intended for the use as

a component of a cosmetic product (Mitchell, 1990).

Although cosmetics for the purpose of beautifying, perfuming, cleansing or rituals have

been existed since the origin of civilization, but only in the 20th century it has a great

progress in the diversities of products and also in the safety and protection of the

consumers (Jackson, 1995).

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Recently, a lot of local cosmetic industries had been set up in Malaysia. The root

question that arises and need to be addressed is whether the cosmetics products

produced locally are safe and comply with the Federal Food, Drug, and Cosmetic Act

and also whether those products are registered with the Ministry of Health. Consumers

would face high risk if they were not aware of the ingredients used in the cosmetic

production. Consumers should seek for some consultancy advice from the beautician to

minimize the risk of toxic effect if they are to tryon new cosmetic products available in

the market. (Norainon Othman and Zahirah Noor Abidin, 2004).

There are few regulations that has been established by Malaysian government several

for metals concentration in the cosmetic products. To ensure that the cosmetics are safe

to use, a special cod called "MAL" must be printed by the Health Ministry of Malaysia

behind the container or the boxes of the cosmetics to prove its safety and warranty. A

product, which does not registered under this regulation, would be banned from the

market (Najibah Hassan, 2004).

The main objective of this project is to determine and to compare the toxic metal

content (Pb, Zn, Co, and Cu) in the non-registered cosmetic products available in

Sarawak market. The non-registered cosmetic products from our neighbor countries are

also mushrooming in Malaysia beside those produced locally. Samples chosen for this

study are foundation, compact powder and lipsticks with different prices (low and

high) and manufacturing countries (Malaysia, Indonesia and China).

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The results obtained from the non-registered samples will be compared with one

established and widely used brand, which is Avon and the permissible limit provided

by Federal German Health Authority (FGHA). Face powders are available in loose and

pressed form. Foundations could be described as powder base suspended in liquid

emulsion or gel base. Lipsticks are molded in the form of a crayon and are dispersed

from a swivel-up case (Andre, 2001). Due to the little information is available on the

toxic metal contamination in cosmetics in Malaysia; it is therefore crucial to study the

level of toxic metal in the selected cosmetics.

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CHAPTER TWO

LITERATURE REVIEW

We are exposed to toxic metals on a day-to day basis in our environment. "Heavy

metals" is the term applied to large group of trace elements that are both industrially

and biologically important. All trace elements including heavy metals are toxic to

living organisms when present in excess (Alloway, 1990).

The number of toxic effects associated with the use of cosmetics is relatively low,

although the number of individuals throughout the world exposed to cosmetic is

staggering. The apparent safety of cosmetic products may reflect both the relatively

low inherent toxicity of most cosmetic ingredient, as well as the effectiveness of the

skin in preventing the absorption of exogenous chemicals. However, this does not

conclude that cosmetics are totally devoid of toxicity (William et aI., 2002). Table 2.1

shows the effects of few metals and other ingredients in cosmetics to human beings.

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Table 2.1: Effect of metals and other ingredients found in cosmetic products

Metals Effects

Mercury Skin irritation or sensitizes

Arsenic Red skin at contact point, mucosal irritation

Lead Allergies

Octyl methooxycinnamate Irritation associated with burning and stringing

Capryloyl salicylic acid Sensory irritation

Ascorbic acid Sensory irritation on the face

Aluminum chloride Sensory irritation and inflammation

Calcium chioglycelate Sensory irritation on the leg

Alpha-hydroxy acid (AHAs) Irritation

Hydroquinone Irritant dermatitis, nail discoloration and post

inflammatory heperpigmentation

Methyl paraben Sensitivity associated with cutaneous exposure

Regulations related to cosmetic products provide no limit values for toxic elements such as

arsenic occurring as impurities in the cosmetic products. A study was done in Finland to

assess the metals (pb, Co, Ni, Cr and As) in eye shadows in 88 colors of 25 brands and 49

products. 66 out of 88 (75%) of the colors contained more than 5 ppm of at least one of the

elements, and all 49 products contained more than 1 ppm of at least one of those elements.

The highest levels of Co and Ni were 41 and 49 ppm, respectively. These levels were high

enough to cause allergic symptoms in those previously sensitized.

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The concentrations of As were extremely low, 2.3 ppm. The level of Pb was less than 20

ppm in all products. Accordingly the concentration of As and Pb seemed safe. The overall

results indicated that eye shadows probably have no significant systemic toxicological

effects (Sainio et at. 2000).

The majority of adverse effects of cosmetics have been attributed to soaps in Dutch and

English studies, but not to eye makeup in a recent Swedish study. The reactions may be

caused by irritants or by sensitizing substances. The study was aimed to evaluate the

irritation potential of commercially available mascaras. The mascaras were exposed to the

skin in aluminums chambers. The skin reaction was evaluated using both visual

assessments of erythema tic and non-invasive measurements of the skin reaction. Seven

mascaras were tested on 15 healthy individuals in a randomized and blinded fashion. 2 of

the 7 tested mascaras induced pronounced skin inflammation, when applied to normal skin

under occlusion. These two mascaras were based on volatile petroleum distillate, in

contrast to the other five mascaras that were conventional emulsions with stearate as the

main emulsifier. The findings suggest that solvent-based mascaras might induce contact

dennatitis due to its content of irritating substances (Loden et at, 2002).

A study was done on 23 eye cosmetic (Kohls) samples in the Arabian Gulf countries using

X-ray powder diffraction and scanning electron microscopy. 19 samples were obtained in

Abu Dhabi and 4 in Dubai. The main component of 11 samples was found to be galena

(PbS). For the remaining 12 samples, the main components were found to be one of the

following that is amorphous carbon, zincite (ZnO), sassolite (H3B03) or calcite (CaC03).

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The kohl samples were analyzed with the aim of determining their 'heavy metal" content,

namely metal with a density of more than 5 glcc, and to determine the percentage of metals

in lead-based samples. A total of 19 kohl samples were obtained in Abu Dhabi city, 10

were lead-based. 10 of this kohl samples, all of which contain galena as the major phase,

only one had an estimated percentage of galena of less than 90 %. Pb was found to be the

main constituent of almost half the kohl samples examined in this study. For the 4 Dubai

city purchased kohls, 1 was based on galena, 2 on amorphous carbon and 2 sassolite. For

the 19 kolhs purchased from Abu Dhabi city, 9 were based on galena, 1 on amorphous

carbon, 5 on zincite, 1 on calcite and 2 on sassolite. Thus, of the 23 kohls studied, it was

found out that 48 % contained Pb (Hardy et aI., 2001).

Instrumental neutron activation analysis (INAA) was used to determine some trace, minor

elements in some cosmetic samples in Egypt. These samples were randomly selected from

the Egypt market. Some of these cosmetics are imported from the world market and the

others were manufactured in Egypt. Up to 25 elements have been quantitatively

detennined in selected cosmetic samples. Two certified standard reference materials have

been use to assure the accuracy and the technique, which are IAEA-405 and SL-l. Two

different 1- radioactivity counting systems had used to compare. Some of the analyzed

samples contain orne elements, which according to the European Union must not presence

in cosmetics. Moreover, some of these elements are presence in high concentration. Thus,

some of the analyzed samples contained As, Sb and Cr with the concentration ranges from

0.37- 3.67ppm, 0.14 - 5.36ppm and 0.52 - 4.12 ppm respectively (EI-Shazly, et aI., 2004).

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CHAPTER THREE

MATERIALS AND METHODS

3.1 Samples Collection

The samples of foundation, compact powder and lipstick were randomly obtained from

local shops in Kuching. A total of 18 samples were purchased from local shops in Kota

Samarahan, Serian and Kuching. The samples were chosen based on two major factors

namely the price range (low or high) and manufacturing countries (Malaysia,

Indonesia, China). The registered sample, Avon was obtained from one of its registered

outlet in Kuching. Two items of compact powder, foundation and lipstick were

purchased respectively for comparison reason with the non-registered samples. Table

3.1 represents the details of the cosmetic samples analyzed in this study.

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Table 3.1: Details of the cosmetic samples analyzed

Sample Manufacturi ng country

Price Category of price

Brand Texture

Non registered

Compact powder

Indonesia 2.90 **L Tumerik Powder

13.50 **H Pixy Powder

China 1.50 L CapAmoi Powder

4.90 H * N.P II Powder

Foundation

Indonesia 2.00 L Viva Liquid

7.00 H II

Pixy Cream

China 2.00 I L C&F Powder

8.90 H * N.P Powder

Lipstick

Indonesia

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1.20 L Tumerik Cream

9.00 H Temulawak Cream

China 1.80 L Xing He Cream

4.90 H *N.P Cream

Registered Sample

Compact powder

Malaysia

13.70 L

Avon

Powder

I 22.90

I

H Powder

Foundation

24.40

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L Powder

45.90 H Cream

Lip tick

10.20 L Cream

25.20 H Cream

• N.P - Not ProvIded •• L-Low price and H- High price

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3.2 Digestion Procedure

3.2.1 Compact Powder and Foundation

Approximately 1 g of homogenized sample was weighed and dissolved in 10 ml of 37

% HCI. The sample was allowed to stand prior to digestion. Then, the sample was

heated using hot plate for about 10 minutes. The samples were then filtered into 100

ml of volumetric flasks and the solutions were topped up with deionized water to 100

ml (Karkhais et al. 1973). All compact powder and foundation samples were digested

in three replicates.

3.2.2 Lipstick

The freeze-dried samples were homogenized and ground prior to digestion. Wet

digestion were performed using 19 of sample and 10 ml of concentrated HCI (37 %).

The mixture was digested on a hot plate for one hour to ensure complete dissolution.

After cooling to ambient temperature, the samples were filtered and diluted using

deionized water to 100 ml (Chen et aI., 2001).

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All

3.3 Sample Analysis

All samples were analyzed using Flame Atomic Absorption Spectrophotometer

(FAAS), (Model Perkin, Elmer, P3000). Commercially available standard solutions for

FAAS (lOOOmg/L) were used for the preparation of working standard solutions. For

quality assurance, four concentrations of each standard metal solution and a blank were

prepared.

3.4 Statistical Analysis

data obtained from FAAS were calculated usmg Microsoft Excel program.

Analysis of variance (ANOVA) was performed to identify the significant difference in

metal contents with the two different prices and manufacturing country.

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CHAPTER FOUR

RESULTS AND DISCUSSIONS

4.1 Metal Concentration in Cosmetic Products Against Regulation

The guideline of the Federal German Health Authority (FGHA) was adopted in this

study for comparison of the metals concentrations. The Federal German Health

Authority (FGHA) ha recommended the heavy metal limits for finished cosmetic

products (fable 4.1). The concentrations of Pb obtained for all cosmetic samples were

in the range of 2.83 ± 1.15 mglkg - 15.00 ± 1.71 mglkg. Based on Table 4.1, it was

observed that the concentrations of Pb in all cosmetic samples from three different

countries analyzed are below the recommended permissible limit, 20 mg/kg (Figure

4.1). Hence, the concentrations of Pb in the cosmetic products seem to be in the safe

level. However, higher concentration of Pb was detected in the compact powder

samples followed by foundation samples and Pb was not

Detected in all the lipstick samples (Table 4.2).

Table 4.1: The recommended permissible limit for selected metals Metal

Hg Recommended limit (mglkg)

<1

As, Cd

Sb, Ni

<5

<10

I

Ph < 20

13

20

15

Concentration 10 (mg/kg)

Msia

. Indo5 China 0 China

Compact , Foundation L' . k

IpstlC Permitted

level

Figure 4.1: Comparison of mean concentration of Pb in cosmetic samples with recommended limit

4.2 Comparison of Metal Concentration in Cosmetic Products Against Manufacturing Country

Table 4.2 and Figure 4.2 represents the mean metal concentrations in compact powder,

lipstick and foundation between three different countries, Malaysia, Indonesia and

China. Zn is a common metal present in almost all cosmetic products in the range of

15.17 ± 8.01 mg/kg - 299.30 ± 98.57 mg/kg except in compact powder manufactured

from China. The highest concentration of Zn was detected in compact powder from

Indonesia. Cu present only in compact powder from Malaysia in trace amount, which

is 16.39 ± 1.99 mg/kg (Figure 4.2). There was no significant trend observed for the

heavy metal contents in all types of cosmetic samples between countries. This is

further proved by ANOV A single factor at 95% confidence limit (Appendix 1).

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Pusat Khidmat Makiumat Akade UNIVERSITI MALAYSIA SARAWA}(

Qd,()() KOla Samarahan

Table 4.2: Mean metal concentrations in cosmetic samples from different countries

Sample

NO NO

143.25 ± 48.20 6.83 ± 3.77

2.83 ± 1.15 15.17 ± .67 ± 0.71 NO

14.00 ± 0.59 0.41 ± 6.01 NO7.5 ± .32

17.75 ± 1.29 15.08 ± 1.06

(Avon)

(Avon)

Lipstick

15

350

1300

250

200

o

Pb Zn Co Metals in cosmetic products

I_ Malaysia - Indonesia 0 China I

Cu

L

Figure 4.2: Metals concentration in cosmetic products in different countries

4.3 Comparison of Mean Metal Concentrations Between Low and High Price Cosmetic Products

The mean metal concentrations in low price and high price cosmetic samples studied

are shown in Table 4.3. Analysis of metals for compact powder with low price shows ·

that the samples from China have the most metal detected (Pb, Co, Ni, Cu) followed by

Indonesia samples (Zn, Co, Cu) and the least in the standard sample, Avon (Zn, Cu).

While for the high price compact powder, Pb is used in the manufacturing process of

compact powder. It was also observed that Pb was not present on lower range compact

powder.

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